CN116769274A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN116769274A
CN116769274A CN202310235278.6A CN202310235278A CN116769274A CN 116769274 A CN116769274 A CN 116769274A CN 202310235278 A CN202310235278 A CN 202310235278A CN 116769274 A CN116769274 A CN 116769274A
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CN
China
Prior art keywords
resin composition
group
ring
carbon atoms
mass
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Pending
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CN202310235278.6A
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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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Priority claimed from JP2023019158A external-priority patent/JP2023135613A/en
Application filed by Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Publication of CN116769274A publication Critical patent/CN116769274A/en
Pending legal-status Critical Current

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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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B27/36—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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0254—High voltage adaptations; Electrical insulation details; Overvoltage or electrostatic discharge protection ; Arrangements for regulating voltages or for using plural voltages
    • H05K1/0256—Electrical insulation details, e.g. around high voltage areas
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a resin composition and the like, which can obtain a cured product with suppressed warpage, excellent cracking resistance and copper adhesion. A resin composition comprising: an epoxy resin (A), an active ester curing agent (B), and a bismaleimide compound having a partial structure represented by the following formula (C-1). [ chemical formula 1 ]]

Description

Resin composition
Technical Field
The present invention relates to a resin composition. Further, the present invention relates to 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 Build-up (Build-up) method is known, in which insulating layers and conductor layers are alternately stacked. In the production method by the lamination method, the insulating layer is generally formed by curing a resin composition.
Heretofore, various maleimide compounds having a non-aromatic ring skeleton have been known (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2019-203122.
Disclosure of Invention
Problems to be solved by the invention
In recent years, suppression of occurrence of warpage and crack resistance have been demanded.
The subject of the invention is to provide: a resin composition which is a cured product having excellent crack resistance and which is suppressed in warpage, a sheet-like laminate obtained using the resin composition, a resin sheet, a printed wiring board, and a semiconductor device can be obtained.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the object of the present invention, and as a result, have found that: the present invention has been completed by combining an epoxy resin, an active ester-based curing agent, and a bismaleimide compound having a partial structure represented by the formula (C-1) as components of a resin composition to be contained in the resin composition, whereby a cured product having suppressed warpage and excellent crack resistance can be obtained.
Namely, the present invention includes the following.
[1] A resin composition comprising:
(A) An epoxy resin;
(B) An active ester compound; and
(C) A bismaleimide compound having a partial structure represented by the following formula (C-1).
[ chemical formula 1]
Wherein A is 1 Represents a 4-valent organic group comprising 2 or more aromatic or aliphatic rings, ring X C Represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent, A 2 Represents an alkylene group having 1 to 20 carbon atoms. m represents an integer of 1 or more. And represents a bonding site.
[2] The resin composition according to [1], wherein the component (C) has a partial structure represented by the formula (C-2),
[ chemical formula 2]
Wherein A is 21 Represents an alkylene group having 1 to 20 carbon atoms, R 21 Each independently represents an alkyl group having 1 to 20 carbon atoms. n2 represents an integer of 0 to 4. m1 represents an integer of 1 or more.
[3] The resin composition according to [1] or [2], wherein maleimide groups in the component (C) are located at both ends.
[4] The resin composition according to any one of [1] to [3], wherein the component (C) has a structure represented by the formula (C-3).
[ chemical formula 3]
Wherein A is 31 And A 36 Each independently represents a 4-valent organic group containing 2 or more aromatic or aliphatic rings, a ring X C1 Ring X C2 And ring X c3 Each independently represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent, A 33 And A 34 Each independently represents an alkylene group having 1 to 20 carbon atoms, A 32 、A 35 And A 37 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms which may have a substituent. m2 represents an integer of 0 or more, and m3 represents an integer of 1 or more.
[5] The resin composition according to any one of [1] to [4], wherein the component (C) comprises a compound represented by the formula (C-4).
[ chemical formula 4]
Wherein A is 41 And A 42 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, A 43 And A 44 R is independently an alkylene group having 1 to 20 carbon atoms 41 、R 42 And R is 43 Each independently represents an alkyl group having 1 to 20 carbon atoms. n41, n42 and n43 each independently represent an integer of 0 to 4. m4 represents an integer of 0 or more, and m5 represents an integer of 1 or more. Wherein A is 43 And the nitrogen atom is directly bonded by a single bond.
[6] The resin composition according to any one of [1] to [5], which further comprises (D) a radical polymerizable compound.
[7] The resin composition according to any one of [1] to [6], further comprising (E) an inorganic filler.
[8] The resin composition according to item [7], wherein the content of the component (E) is 40% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
[9] The resin composition according to any one of [1] to [8], further comprising (F) a curing agent.
[10] The resin composition according to any one of [1] to [9], wherein a glass transition temperature of a cured product obtained by curing the resin composition at 190℃for 90 minutes, as measured by a DMA method, is 130℃or higher.
[11] A sheet laminate comprising the resin composition according to any one of [1] to [10 ].
[12] A resin sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of [1] to [10 ].
[13] A printed wiring board comprising an insulating layer composed of a cured product of the resin composition according to any one of [1] to [10 ].
[14] A semiconductor device comprising the printed wiring board of [13 ].
Effects of the invention
According to the resin composition of the present invention, there can be provided: a resin composition which is a cured product having excellent crack resistance and which is suppressed in warpage, a sheet-like laminate obtained using the resin composition, a resin sheet, a printed wiring board, and a semiconductor device can be obtained.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and may be implemented by arbitrarily changing the scope of the claims and the equivalents thereof without departing from the scope of the present invention. In the present invention, unless otherwise specified, the content of each component in the resin composition refers to a value obtained by taking 100 mass% of the nonvolatile components in the resin composition, and the nonvolatile components refer to the entire nonvolatile components in the resin composition except the solvent.
[ resin composition ]
The resin composition of the present invention comprises: an epoxy resin (A), an active ester compound (B) and a bismaleimide compound (C) having a partial structure represented by the following formula (C-1). By using such a resin composition, a cured product having excellent crack resistance can be obtained while suppressing the occurrence of warpage. In addition, the resin composition generally provides a cured product having a low relative dielectric constant (Dk) and dielectric loss tangent (Df), excellent copper adhesion, and a high glass transition temperature (Tg).
[ chemical formula 5]
Wherein A is 1 Represents a 4-valent organic group comprising 2 or more aromatic or aliphatic rings, ring X C Represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent, A 2 Represents an alkylene group having 1 to 20 carbon atoms. m represents an integer of 1 or more. And represents a bonding site.
The resin composition of the present invention may further comprise optional components in combination with the components (a) to (C). Examples of the optional components include: (D) A radical polymerizable compound, (E) an inorganic filler, (F) a curing agent, (G) a curing accelerator, (H) other additives, and (I) a solvent. The components contained in the resin composition will be described in detail below.
Epoxy resin (A)
The resin composition contains an epoxy resin (A) as the component (A). The epoxy resin is a curable resin having an epoxy group.
Examples of the epoxy resin (a) include: bixylenol type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidol amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic type epoxy resin, heterocyclic type epoxy resin, spiro-ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane type epoxy resin, isocyanurate type epoxy resin, phenol benzo [ c ] pyrrolidone (phenolphthalein) type epoxy resin, phenoltype epoxy resin, and the like. (A) The epoxy resin may be used alone or in combination of 1 or more than 2.
The resin composition preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule as the (a) epoxy resin. 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, relative to 100% by mass of the nonvolatile component of the (a) epoxy resin.
Examples of the epoxy resin include 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 epoxy resin in the resin composition may be a liquid epoxy resin alone, a solid epoxy resin alone, or a combination of a liquid epoxy resin and a solid epoxy resin.
As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
The liquid epoxy resin is preferably 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, or epoxy resin having a butadiene structure, and more preferably naphthalene type epoxy resin.
Specific examples of the liquid epoxy resin include: "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", "825", "Epikote 828EL" 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" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ED-523T" (glycyrrhizic alcohol type epoxy resin) manufactured by ADEKA company; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Co; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co; "ZX1059" manufactured by Nissan Chemical & Material Chemical Co., ltd. (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 Daicel corporation; "PB-3600" manufactured by Daicel corporation, "JP-100" and "JP-200" manufactured by Nippon Caesada corporation (epoxy resin having butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nissan Chemical & Material Chemical Co., ltd.) and the like. These 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.
The solid epoxy resin is preferably a xylenol-type epoxy resin, a naphthalene-type 4-functional 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 tetraphenylethane-type epoxy resin, a phenol benzo [ c ] pyrrolidone-type epoxy resin, a phenolphthalein-type epoxy resin, more preferably a naphthalene-type epoxy resin or a biphenyl-type epoxy resin.
As specific examples of the solid epoxy resin, there may be mentioned: "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Co; "HP-4700", "HP-4710" (naphthalene type 4-functional epoxy resin) manufactured by DIC company; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "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 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 medicine corporation; "ESN475V", "ESN4100V" manufactured by Nissan Chemical & Material Co., ltd. (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nissan Chemical & Material company; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nissan Chemical & Material Co; "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" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "PG-100", "CG-500" manufactured by Osaka gas chemistry 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 benzo [ c ] pyrrolidone type epoxy resin) manufactured by Japanese chemical Co., ltd.) and the like. These may be used alone or in combination of 1 or more than 2.
In the case where a solid epoxy resin is used as the (a) epoxy resin in combination with a liquid epoxy resin, their mass ratio (solid epoxy resin: liquid epoxy resin) is preferably 1:0.01 to 1:50, more preferably 1:0.05 to 1: 10. particularly preferably 1:0.1 to 1:3. by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin to such a range, the following effects and the like can be obtained: 1) When the resin sheet is used in the form of a resin sheet, moderate adhesion can be achieved; 2) When the resin sheet is used in the form of a resin sheet, sufficient flexibility can be obtained, and the operability can be improved; and 3) a cured product having sufficient breaking strength can be obtained.
(A) The epoxy 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 group. The epoxy equivalent can be measured in accordance with JIS K7236.
(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene equivalent by Gel Permeation Chromatography (GPC).
From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (a) epoxy resin is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition. The upper limit of the content of the epoxy resin is preferably 25 mass% or less, more preferably 20 mass% or less, and further preferably 15 mass% or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (a) epoxy resin is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, and the upper limit thereof is preferably 60 mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less, based on 100 mass% of the resin component in the resin composition.
In the present invention, the term "resin component" of the resin composition means a component other than the inorganic filler (E) described below among the nonvolatile components constituting the resin composition.
Active ester compound (B)
The resin composition contains an active ester compound (B) as a component (B). (B) The active ester compound has a function of curing the epoxy resin (a). The active ester compound (B) as the component (B) does not contain a substance corresponding to the component (a). (B) The active ester compound may be used alone or in combination of 1 or more than 2.
As the (B) active ester compound, a compound having an active ester group as a reactive group reactive with the (A) epoxy resin can be used. Specifically, it is preferable that the component (B) contains any one of a compound having a structure represented by the formula (B-1) and a compound containing an aromatic ester skeleton and an unsaturated bond.
(Compound having a structure represented by the formula (B-1))
As one embodiment of the component (B), a compound having a structure represented by the formula (B-1) is preferable.
[ chemical formula 6]
Wherein R is 1 、R 2 And R is 3 The following are provided: (1) R is R 1 Represents a hydrogen atom, a halogen atom, a methyl group or R 11 -A-, and R 2 And R is 3 Each independently represents a hydrogen atom or a substituent; or (2) R 1 And R is 2 Bonded together to form an aromatic carbocyclic ring which may have substituents, and R 3 Represents a hydrogen atom or a substituent; or (3) R 2 And R is 3 Bonded together to form an aromatic carbocyclic ring which may have substituents, and R 1 Represents a hydrogen atom, a halogen atom, a methyl group or R 11 -A-；R 4 And R is 5 Each independently represents a hydrogen atom or a substituent; r is R 11 Represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent; a represents-CH 2 -、-CH(CH 3 ) -, -CO-or-O-; and represents a bonding site.
R 1 Represents a hydrogen atom, a halogen atom, a methyl group or a methyl group without forming an aromatic carbocyclic ringR 11 -A-。R 1 In the case of no aromatic carbocycles, it is preferred in one embodiment to be a hydrogen atom, methyl or R 11 -a-; more preferably a hydrogen atom or R 11 -A-。
A represents-CH 2 -、-CH(CH 3 ) -, -CO-or-O-. In one embodiment, A is preferably-CH 2 -or-CH (CH) 3 ) -; more preferably-CH (CH) 3 )-。
R 11 Represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent.
R 11 The alkyl, alkenyl and aryl groups represented may have substituents. Examples of the substituent include: halogen atoms, alkyl groups, alkenyl groups, aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl-aryl-alkyl groups (alkyl groups substituted with aryl groups substituted with alkyl groups), alkenyl-aryl-alkyl groups (alkyl groups substituted with aryl groups substituted with alkenyl groups), aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl-aryl groups, alkenyl-aryl groups, aryl-aryl groups, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, alkyl-carbonyl groups, alkenyl-carbonyl groups, aryl-carbonyl groups, alkyl-oxy-carbonyl groups, alkenyl-carbonyl-oxy groups, aryl-carbonyl-oxy groups, and the like.
In one embodiment, R 11 Aryl groups which may have a substituent are preferable; more preferably aryl; phenyl is particularly preferred.
R 2 And R is 3 In the case where an aromatic carbocyclic ring is not formed, each independently represents a hydrogen atom or a substituent.
As R 2 And R is 3 The substituent represented is with R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
R 2 And R is 3 In the case where no aromatic carbocyclic ring is formed, in one embodiment each is independently preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an alkyl-aryl group; more preferably a hydrogen atom, an alkyl group, an aryl group, or an aryl-alkyl group.
R 1 、R 2 And R is 3 In the case of an aromatic carbocyclic ring, R 1 And R is 2 Or R is 2 And R is 3 Together, to form an aromatic carbocyclic ring which may have substituents.
As R 1 、R 2 And R is 3 Substituents in the aromatic carbocycles formed, with R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
R 1 、R 2 And R is 3 In the case of an aromatic carbocyclic ring, in one embodiment, R 1 And R is 2 Or R is 2 And R is 3 Bonded together, preferably forming a benzene ring which may have a substituent; more preferably, a benzene ring which may be substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl and alkyl-aryl; it is further preferred to form an (unsubstituted) benzene ring.
R 4 And R is 5 Each independently represents a hydrogen atom or a substituent.
As R 4 And R is 5 The substituent represented is with R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
In one embodiment, R 4 And R is 5 Each independently is preferably a hydrogen atom, alkyl, alkenyl, aryl-alkyl, or alkyl-aryl; more preferably a hydrogen atom, an alkyl group, an aryl group, or an aryl-alkyl group.
In the first embodiment, R is preferably 1 、R 2 、R 4 And R is 5 Is a hydrogen atom, and R 3 Is alkyl or aryl; more preferably R 1 、R 2 、R 4 And R is 5 Is a hydrogen atom, and R 3 Is methyl or phenyl.
In the second embodiment, R is preferably 1 Is a hydrogen atom or R 11 -A-, A is-CH 2 -or-CH (CH) 3 )-，R 11 Is aryl, and R 2 、R 3 、R 4 And R is 5 Is a hydrogen atom, or an aryl-alkyl group (R is particularly preferred 1 Is R 11 -A-and/or R 2 、R 3 、R 4 And R is 5 At least 1 of which is aryl-alkyl); more preferably R 1 Is a hydrogen atom or R 11 -A-, A is-CH (CH) 3 )-，R 11 Is phenyl, and R 2 、R 3 、R 4 And R is 5 Is a hydrogen atom or an alpha-methylbenzyl group (R is particularly preferred 1 Is R 11 -A-and/or R 2 、R 3 、R 4 And R is 5 At least 1 of which is an alpha-methylbenzyl group).
In the third embodiment, R is preferably 1 And R is 2 Bonded together to form a benzene ring, and R 3 、R 4 And R is 5 Is a hydrogen atom, or R 2 And R is 3 Bonded together to form a benzene ring, and R 1 、R 4 And R is 5 Is a hydrogen atom.
In a preferred embodiment, the component (B) is a compound having a structure represented by the formula (B-2).
[ chemical formula 7]
In which ring X 1 Each independently represents an aromatic carbocycle which may have a substituent, or a non-aromatic carbocycle which may have a substituent; ring Y 1 And ring Z 1 Each independently represents an aromatic carbocyclic ring which may have a substituent; x is X b Each independently represents a single bond, -C (R) b ) 2 -、-O-、-CO-、-S-、-SO-、-SO 2 -, -CONH-or-NHCO-; r is R b Each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, or 2R b Bonded together to form a non-aromatic carbocyclic ring which may have substituents; b' represents an integer of 0 or 1 or more; c' each independently represents 0, 1, 2 or 3; d' each independently represents 0 or 1; the other symbols are as described above. The b 'and c' units may each be the same or different in each structural unit.
Ring X 1 Each independently represents an aromatic carbocyclic ring which may have a substituent or a non-aromatic which may have a substituentCarbocycles.
As ring X 1 Substituents in the aromatic carbocycle represented, with R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
In one embodiment, ring X 1 Each independently is preferably a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a non-aromatic carbocyclic ring having 5 to 12 carbon atoms which may have a substituent; more preferably: (1) a benzene ring which may be substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl and alkyl-aryl, (2) a naphthalene ring which may be substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl and alkyl-aryl, or (3) a non-aromatic carbocyclic ring having 5 to 12 carbon atoms which may be substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, alkyl-aryl and oxy (particularly preferably a tetrahydrodicyclopentadiene ring).
Ring Y 1 Each independently represents an aromatic carbocyclic ring which may have a substituent.
As ring Y 1 Substituents in the aromatic carbocycle represented, with R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
In one embodiment, ring Y 1 Each independently is preferably a benzene ring which may have a substituent or a naphthalene ring which may have a substituent; more preferably: (1) A benzene ring which may be substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl and alkyl-aryl, or (2) a naphthalene ring which may be substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl and alkyl-aryl.
Ring Z 1 Each independently represents an aromatic carbocyclic ring which may have a substituent.
As ring Z 1 Substituents in the aromatic carbocycle represented, with R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
In one embodiment, ring Z 1 Each independently is preferably a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent; more preferably: (1) Benzene rings which may be substituted with groups selected from alkyl, alkenyl, aryl-alkyl and alkyl-aryl, or (2) benzene rings which may be substituted with groups selected fromAlkyl, alkenyl, aryl-alkyl and alkyl-aryl groups.
X b Each independently represents a single bond, -C (R) b ) 2 -、-O-、-CO-、-S-、-SO-、-SO 2 -, -CONH-or-NHCO-. In one embodiment, X b Each independently is preferably a single bond, -C (R) b ) 2 -or-O-; more preferably a single bond or-O-.
R b Each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, or 2R b Together, to form a non-aromatic carbocyclic ring which may have substituents. As R b Substituents in the alkyl group represented, and R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
In one embodiment, R b Each independently is preferably a hydrogen atom or an alkyl group which may have a substituent; more preferably a hydrogen atom or an alkyl group; particularly preferred is a hydrogen atom or a methyl group.
b' represents an integer of 0 or 1 or more. In one embodiment, b' is preferably 0 or an integer from 1 to 100; more preferably 0 or an integer of 1 to 10; particularly preferably 0 or an integer of 1 to 5.
c' each independently represents 0, 1, 2 or 3. In one embodiment, c' is each independently preferably 0, 1 or 2; more preferably 0 or 1.
d' independently represent 0 or 1.
Examples of the partial structure represented by the formula (Y') in the formula (B-2) include: the structures represented by the formulae (Y-1) to (Y-12) and the like.
[ chemical formula 8]
Wherein Y is 1 Represents an aromatic carbocyclic ring which may have a substituent.
[ chemical formula 9]
Wherein R is y Each independently represents alkyl, alkenyl, aryl-alkyl or alkyl-aryl; y each independently represents 0, 1 or 2; the other symbols are as described above.
(B) The component (B-2) may contain a resin represented by the formula (B-2) and a resin (for example, a resin having a hydroxyl group and/or a carboxyl group at one or both terminals) which is a reaction intermediate produced during synthesis, a resin derived from a raw material impurity, and the like.
The compound having the structure represented by the formula (B-1) may be synthesized by a known method or a method based on the same, using a commercially available product. Examples of the commercially available compounds having the structure represented by the formula (B-1) include: "EXB9451", "EXB9460S", "HPC-8000-65T", "HPC-8000L-65TM", "HPC-8000H-65TM" (manufactured by DIC corporation) as an active ester compound comprising a dicyclopentadiene type diphenol structure; "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "EXB-8", "HPC-8150-62T" (manufactured by DIC corporation) as an active ester compound comprising a naphthalene structure; "EXB9401" (manufactured by DIC Co.) as a phosphorus-containing active ester compound, "DC808" (manufactured by Mitsubishi chemical corporation) as an active ester compound which is an acetyl compound of a phenol novolac, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation) as an active ester compound which is a benzoyl compound of a phenol novolac, and "PC1300-02-65MA" (manufactured by AIR WATER Co.) as an active ester compound containing a styryl group and a naphthalene structure.
(Compound having an aromatic ester skeleton and an unsaturated bond)
In another embodiment of the component (B), the component (B) is a compound having an aromatic ester skeleton and an unsaturated bond.
The compound having an aromatic ester skeleton and an unsaturated bond has an aromatic ester skeleton. An aromatic ester skeleton means a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Among them, a skeleton having an aromatic ring at both ends of an ester bond is preferable. Examples of the group having such a skeleton include: arylcarbonyloxy, aryloxycarbonyl, arylenecarbonyloxy, aryleneoxycarbonyl, arylenecarbonyloxy arylene, aryleneoxycarbonyl arylene, etc. The number of carbon atoms of the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and still more preferably 7 to 11. Aromatic hydrocarbon groups such as aryl groups and arylene groups may have a substituent.
The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include: phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, Azolyl, iso->An azole group, a thiazole group, an isothiazole group, a pyridine group, a pyrimidine group, a pyridazine group, a pyrazine group, a triazine group, or the like, from which 1 hydrogen atom is removed from the monocyclic aromatic compound; naphthyl, anthryl, phenalenyl (phenalenyl), phenanthryl, quinolinyl, isoquinolinyl, quinazolinyl, phthalazinyl, pteridinyl, coumarin, indolyl, benzimidazolyl, benzofuranyl, acridinyl, and the like, groups from which 1 hydrogen atom has been removed from the fused ring aromatic compound.
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, biphenylene (-C) 6 H 4 -C 6 H 4 (-), etc.
The compound having an aromatic ester skeleton and an unsaturated bond contains an unsaturated bond. This makes the dielectric constant of the cured product excellent. In addition, the unsaturated bond contributes to the curing reaction of the resin composition. Since the unsaturated bond contributes to the curing reaction, a part of the ester site of the aromatic ester skeleton is suppressed from being used for the curing reaction, and as a result, the curing shrinkage is suppressed.
The unsaturated bond is preferably a carbon-carbon unsaturated bond such as an ethylenic unsaturated bond. The unsaturated bond is preferably contained in a substituent having at least 1 unsaturated bond. Examples of the unsaturated bond include: unsaturated bonds contained in unsaturated hydrocarbon groups such as alkenyl groups having 2 to 30 carbon atoms and alkynyl groups having 2 to 30 carbon atoms. The unsaturated bond is preferably contained in the substituent of the terminal aromatic hydrocarbon group, more preferably contained in the substituent of the both terminal aromatic hydrocarbon group.
Examples of the alkenyl group having 2 to 30 carbon atoms include: vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1, 3-butadienyl, 1, 4-butadienyl, hex-1, 3-dienyl, hex-2, 5-dienyl, pentadec-4, 7-dienyl, hex-1, 3, 5-trienyl, pentadec-1, 4, 7-trienyl and the like.
Examples of the alkynyl group having 2 to 30 carbon atoms include: ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-pentynyl, 4-pentynyl, 1, 3-butadiynyl and the like.
Among these, an alkenyl group having 2 to 30 carbon atoms is preferable, an alkenyl group having 2 to 10 carbon atoms is more preferable, an alkenyl group having 2 to 5 carbon atoms is more preferable, an allyl group, an isopropenyl group, a 1-propenyl group are more preferable, and an allyl group is particularly preferable.
The compound having an aromatic ester skeleton and an unsaturated bond may have any one of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a group composed of a combination thereof, in addition to the aromatic ester skeleton. The term "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring, which may be any of monocyclic, polycyclic, heterocyclic.
The aromatic hydrocarbon group is preferably a 2-valent aromatic hydrocarbon group, more preferably an arylene group or an aralkylene group, and still more preferably an arylene group. 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, biphenylene, and the like. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Among these, phenylene is preferable.
The aliphatic hydrocarbon group is preferably a 2-valent aliphatic hydrocarbon group, more preferably a 2-valent saturated aliphatic hydrocarbon group, and further preferably an alkylene group or a cycloalkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include: methylene, ethylene, propylene, 1-methyl methylene, 1-dimethyl methylene, 1-methyl ethylene, 1-dimethyl ethylene, 1, 2-dimethyl ethylene, butylene, 1-methyl propylene, 2-methyl propylene, pentylene, hexylene, and the like.
The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and still more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include: and (c) a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, a cycloalkylene group represented by the following formulae (a) to (d), and the like. In the formulae (a) to (d), the term "" represents a bonding site.
[ chemical formula 10]
The aromatic ester skeleton, aromatic hydrocarbon group, aliphatic hydrocarbon group, and unsaturated hydrocarbon group may have a substituent. The substituent is with R 11 The alkyl, alkenyl and aryl groups represented may have the same substituents.
The compound having an aromatic ester skeleton and an unsaturated bond is preferably any one of a compound represented by the following general formula (B-3) and a compound represented by the following general formula (B-4).
[ chemical formula 11]
(in the general formula (B-3), ar 11 Each independently represents a 1-valent aromatic hydrocarbon group which may have a substituent, ar 12 Each independently represents a 2-valent aromatic hydrocarbon group which may have a substituent, ar 13 Each independently represents a substituent-capable 2-valent aromatic hydrocarbon group, a substituent-capable 2-valent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a 2-valent group composed of a combination thereof. n represents an integer of 0 to 10)
[ chemical formula 12]
(in the general formula (B-4), ar 21 Represents an m-valent aromatic hydrocarbon group which may have a substituent, ar 22 Each independently represents a 1-valent aromatic hydrocarbon group which may have a substituent. m represents an integer of 2 or 3)
Ar in the general formula (B-3) 11 Each independently represents a 1-valent aromatic hydrocarbon group which may have a substituent. Examples of the 1-valent aromatic hydrocarbon group include: phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl,Azolyl, iso->An azole group, a thiazole group, an isothiazole group, a pyridine group, a pyrimidine group, a pyridazine group, a pyrazine group, a triazine group, or the like, from which 1 hydrogen atom is removed from the monocyclic aromatic compound; naphthyl, anthryl, phenalenyl (phenalenyl), phenanthryl, quinolinyl, isoquinolinyl, quinazolinyl, phthalazinyl, pteridinyl, coumarin, indolyl, benzoAn imidazole group, a benzofuranyl group, an acridine group, or the like, from which 1 hydrogen atom is removed from the condensed ring aromatic compound, and among them, a phenyl group is preferable from the viewpoint of significantly obtaining the effect of the present invention. Ar (Ar) 11 The represented 1-valent aromatic hydrocarbon group may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have. Wherein Ar is 11 The substituent of (2) preferably contains an unsaturated bond.
Ar 12 Each independently represents a 2-valent aromatic hydrocarbon group which may have a substituent. Examples of the 2-valent aromatic hydrocarbon group include: arylene, aralkylene, and the like, with arylene being preferred. 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, biphenylene, and the like. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Among these, phenylene is preferable.
Ar 12 The represented 2-valent aromatic hydrocarbon group may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.
Ar in the general formula (B-3) 13 Each independently represents a substituent-capable 2-valent aromatic hydrocarbon group, a substituent-capable 2-valent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a 2-valent group composed of a combination thereof, preferably a 2-valent group composed of a combination thereof. As aromatic hydrocarbon groups of valence 2, with Ar 12 The 2-valent aromatic hydrocarbon groups represented are the same.
The 2-valent aliphatic hydrocarbon group is more preferably a 2-valent saturated aliphatic hydrocarbon group, and is preferably an alkylene group or a cycloalkylene group, and is more preferably a cycloalkylene group.
The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include: methylene, ethylene, propylene, 1-methyl methylene, 1-dimethyl methylene, 1-methyl ethylene, 1-dimethyl ethylene, 1, 2-dimethyl ethylene, butylene, 1-methyl propylene, 2-methyl propylene, pentylene, hexylene, and the like.
The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and still more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include: the cycloalkylene group represented by the above formulas (a) to (d) is preferably a cycloalkylene group represented by the formula (c).
The 2-valent group formed by a combination of these groups is preferably a 2-valent group formed by combining a 2-valent aromatic hydrocarbon group which may have a substituent and a 2-valent aliphatic hydrocarbon group which may have a substituent, and more preferably a 2-valent group formed by alternately combining a plurality of 2-valent aromatic hydrocarbon groups which may have a substituent and a plurality of 2-valent aliphatic hydrocarbon groups which may have a substituent. Specific examples of the above-mentioned 2-valent group include: the following (B1) to (B8) are 2-valent groups. Wherein b1 to b7 are integers of 0 to 10, preferably 0 to 5. The "onium" represents a bonding site, and the wavy line represents a structure obtained by reacting an aromatic compound, an acyl halide of an aromatic compound, or an ester of an aromatic compound, which are used in the synthesis of the component (B).
[ chemical formula 13]
[ chemical formula 14]
Ar 13 The represented 2-valent aromatic hydrocarbon group and 2-valent aliphatic hydrocarbon group may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.
In the general formula (B-3), n represents an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3. In the case where the compound represented by the general formula (B-3) is an oligomer or a polymer, n represents an average value thereof.
Ar in the general formula (B-4) 21 Represents an m-valent aromatic hydrocarbon group which may have a substituent. The m-valent aromatic hydrocarbon group is preferably an m-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an m-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and still more preferably an m-valent aromatic hydrocarbon group having 6 to 10 carbon atoms. Ar (Ar) 21 The m-valent aromatic hydrocarbon group represented may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.
Ar in the general formula (B-4) 22 Each independently represents a 1-valent aromatic hydrocarbon group which may have a substituent. Ar (Ar) 22 Ar in the general formula (B-3) 11 The aromatic hydrocarbon groups represented are the same. Ar (Ar) 22 The represented 1-valent aromatic hydrocarbon group may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.
In the general formula (B-4), m represents an integer of 2 or 3, preferably 2.
Specific examples of the compound having an aromatic ester skeleton and an unsaturated bond include the following compounds. In addition, specific examples of the compound containing an aromatic ester skeleton and an unsaturated bond include: compounds described in paragraphs 0068 to 0071 of International publication No. 2018/235424 and paragraphs 0113 to 0115 of International publication No. 2018/235425. However, the compound containing an aromatic ester skeleton and an unsaturated bond is not limited to these specific examples. Wherein s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10.
[ chemical formula 15]
As the compound having an aromatic ester skeleton and an unsaturated bond, a compound synthesized by a known method can be used. The synthesis of the compound having an aromatic ester skeleton and an unsaturated bond can be performed, for example, by a method described in International publication No. 2018/235424 or International publication No. 2018/235425.
The weight average molecular weight of the compound having an aromatic ester skeleton and an unsaturated bond is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, preferably 3000 or less, still more preferably 2000 or less, still more preferably 1500 or less, from the viewpoint of significantly obtaining the effect of the present invention. The weight average molecular weight of the compound having an aromatic ester skeleton and an unsaturated bond is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
From the viewpoint of remarkably obtaining the effect of the present invention, the unsaturated bond equivalent of the compound containing an aromatic ester skeleton and an unsaturated bond is preferably 50g/eq or more, more preferably 100g/eq or more, still more preferably 150g/eq, preferably 2000g/eq or less, more preferably 1000g/eq or less, still more preferably 500g/eq or less. The unsaturated bond equivalent means the mass of the component (B) containing 1 equivalent of unsaturated bond.
The ratio of the amount of the epoxy equivalent of the (a) epoxy resin to the amount of the active ester equivalent of the (B) active ester compound (active ester equivalent of the active ester compound/epoxy equivalent of the epoxy resin) is preferably 0.4 or more, more preferably 0.5 or more, still more preferably 0.6 or more, preferably 1.8 or less, still more preferably 1.5 or less, still more preferably 1.3 or less. The term "epoxy equivalent of the epoxy resin" refers to a value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent, and summing up all the values. The term "active ester group equivalent of the active ester compound" refers to a value obtained by dividing the mass of the non-volatile component of the active ester compound present in the resin composition by the active ester group equivalent, and summing up all the values. The effect of the present invention can be remarkably obtained by setting the amount ratio of the component (B) to the epoxy resin within such a range.
The content of the component (B) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, or 15% by mass, based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of significantly obtaining the effect of the present invention.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (B) is preferably 30 mass% or more, more preferably 35 mass% or more, further preferably 45 mass% or more, and the upper limit thereof is preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 55 mass% or less, based on 100 mass% of the resin component in the resin composition.
(C) bismaleimide Compound having a partial Structure represented by the formula (C-1)
The resin composition contains (C) a bismaleimide compound having a partial structure represented by the formula (C-1) as the component (C). The bismaleimide compound having a partial structure represented by the formula (C-1) as the component (C) does not contain any substances corresponding to the components (A) to (B). By adding the component (C) to the resin composition, a cured product having excellent crack resistance and copper adhesion can be obtained while suppressing warpage. (C) The components may be used alone or in combination of at least 2.
[ chemical formula 16]
Wherein A is 1 Represents a 4-valent organic group comprising 2 or more aromatic or aliphatic rings, ring X C Represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent, A 2 Represents an alkylene group having 1 to 20 carbon atoms. m represents an integer of 1 or more. And represents a bonding site.
(C) As the component (C), a compound having a partial structure represented by the formula (C-1) and having 2 maleimide groups in 1 molecule of the component (C) can be used. It is preferable that the component (C) has maleimide groups at both ends.
A in the formula (C-1) 1 Represents a 4-valent organic group containing 2 or more aromatic or aliphatic rings, preferably represents a 4-valent organic group containing an aromatic ring. Aromatic or aliphatic rings are concepts that include single or fused rings. As an aromatic ring or containing more than 2Examples of the 4-valent organic group of the aliphatic ring include: the following groups (C1) to (C9) are preferably groups (C1).
[ chemical formula 17]
Ring X C Represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent. Monocycloalkane ring means a monocyclic aliphatic saturated hydrocarbon ring. The monocycloalkane ring is preferably a monocycloalkane ring having 4 to 14 carbon atoms, more preferably a monocycloalkane ring having 4 to 10 carbon atoms, further preferably a monocycloalkane ring having 5 or 6 carbon atoms, particularly preferably a monocycloalkane ring having 6 carbon atoms. Examples of the monocycloalkane ring include: cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, and the like. Cycloolefin ring means a monocyclic aliphatic unsaturated hydrocarbon ring having at least 1 carbon-carbon double bond. The monocyclic olefin ring is preferably a monocyclic olefin ring having 4 to 14 carbon atoms, more preferably a monocyclic olefin ring having 4 to 10 carbon atoms, particularly preferably a monocyclic olefin ring having 5 or 6 carbon atoms. Examples of the monocyclic olefin ring include: cyclobutene ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclopentadiene ring, cyclohexadiene ring, isophorone diamine ring, and the like.
A 2 Represents an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear, branched or cyclic. The alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group. Examples of such alkylene groups include: straight-chain alkylene groups such as methylene, ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, heptamethylene, 1, 8-octylene, 1, 9-nonylene, and 1, 10-decylene; ethylene (-CH (CH) 3 ) -) propylene (-CH (CH) 2 CH 3 ) (-), isopropylidene (-C (CH) 3 ) 2 (-), ethylmethylmethylene (-C (CH) 3 )(CH 2 CH 3 ) (-), diethyl methylene (-C (CH) 2 CH 3 ) 2 (-) branched alkylene; cyclic alkylene groups such as cyclopentylene and cyclohexylene.
A 1 ((C1) - (C9) groups), ring X C And A 2 With or without substituents. Wherein ring X C Preferably, the monocycloalkane ring or monocycloalkene ring has a substituent, and may have a plurality of substituents. Examples of the substituent include: alkyl, alkenyl, aryl-alkyl (alkyl substituted with aryl), alkyl-oxy, alkenyl-oxy, aryl-oxy, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-carbonyl-oxy, aryl-carbonyl-oxy, and the like, and if substituted, may further contain a 2-valent substituent such as oxo (=o). As the substituent, an alkyl group is preferable.
Alkyl (radical) means a straight-chain, branched and/or cyclic aliphatic saturated hydrocarbon radical of valence 1. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 14 carbon atoms. Examples of the alkyl (group) include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl and the like. Alkenyl (group) refers to straight, branched and/or cyclic 1-valent aliphatic unsaturated hydrocarbon groups having at least 1 carbon-carbon double bond. Unless otherwise specified, the alkenyl group is preferably an alkenyl group having 2 to 14 carbon atoms. Examples of the alkenyl group (group) include: ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, cyclohexenyl and the like. Aryl (group) refers to a 1-valent aromatic hydrocarbon group. Aryl (group) is preferably aryl (group) having 6 to 14 carbon atoms unless otherwise specified. Examples of the aryl group include: phenyl, 1-naphthyl, 2-naphthyl, and the like.
m represents an integer of 1 or more, preferably an integer of 1 or more, more preferably an integer of 2 or more, and still more preferably an integer of 3 or more. The upper limit preferably represents an integer of 200 or less, more preferably an integer of 150 or less, and still more preferably an integer of 100 or less.
(C) The component (C-2) preferably has a partial structure represented by the formula (C).
[ chemical formula 18]
Wherein A is 21 Represents an alkylene group having 1 to 20 carbon atoms, R 21 Each independently represents an alkyl group having 1 to 20 carbon atoms. n2 represents an integer of 0 to 4. m1 represents an integer of 1 or more.
A in the formula (C-2) 21 Represents an alkylene group having 1 to 20 carbon atoms, and A in the formula (C-1) 2 The same applies.
R 21 Each independently represents an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear, branched or cyclic. R is R 21 The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. Examples of such alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl and the like.
n2 represents an integer of 0 to 4, preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and even more preferably an integer of 2 or 3. In the case where n2 represents 2 to 4, a plurality of R's may be bonded to 1 carbon atom forming a cyclohexane ring 21 。
m1 represents an integer of 1 or more, and is the same as m in formula (C-1).
(C) The component (C-3) preferably has a structure represented by the formula (C).
[ chemical formula 19]
Wherein A is 31 And A 36 Each independently represents a 4-valent organic group containing 2 or more aromatic or aliphatic rings, a ring X C1 Ring X C2 And ring X c3 Each independently represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent, A 33 And A 34 Each independently represents an alkylene group having 1 to 20 carbon atoms, A 32 、A 35 And A 37 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms which may have a substituent. m2 represents an integer of 0 or more, and m3 represents an integer of 1 or more.
A 31 And A 36 Each independently represents a 4-valent organic group containing 2 or more aromatic or aliphatic rings, and A in the formula (C-1) 1 The same applies.
Ring X C1 Ring X C2 And ring X c3 Each independently represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent, and a ring X in the formula (C-1) C The same applies.
A 33 And A 34 Each independently represents an alkylene group having 1 to 20 carbon atoms, and A in the formula (C-1) 2 The same applies.
A 32 、A 35 And A 37 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms which may have a substituent. The number of carbon atoms does not include the number of carbon atoms of the substituent. The alkylene group may be linear, branched or cyclic, and is preferably linear or cyclic. The alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 3 to 20 carbon atoms, more preferably an alkylene group having 3 to 15 carbon atoms, and still more preferably an alkylene group having 3 to 10 carbon atoms or 5 to 10 carbon atoms. Examples of such alkylene groups include: methylene, ethylene, 1, 3-propylene, 1, 4-butylene,Linear alkylene groups such as 1, 5-pentylene, 1, 6-hexylene, heptamethylene, 1, 8-octylene, 1, 9-nonylene, and 1, 10-decylene; ethylene (-CH (CH) 3 ) -) propylene (-CH (CH) 2 CH 3 ) (-), isopropylidene (-C (CH) 3 ) 2 (-), ethylmethylmethylene (-C (CH) 3 )(CH 2 CH 3 ) (-), diethyl methylene (-C (CH) 2 CH 3 ) 2 (-) branched alkylene; cyclic alkylene groups such as cyclopentylene and cyclohexylene. Wherein A is 32 Preferably, each independently represents an alkylene group having 1 to 20 carbon atoms, A 35 And A 37 Preferably represents a single bond.
A 31 、A 32 、A 33 、A 34 And ring X C1 And ring X C2 The monocycloalkane ring or monocycloalkene ring of (2) may or may not have a substituent. As a substituent, with A in the formula (C-1) 2 May have the same substituent.
m2 represents an integer of 0 or more, preferably 0, more preferably 1 or more, still more preferably 2 or more, and 3 or more. The upper limit preferably represents an integer of 200 or less, more preferably an integer of 150 or less, and still more preferably an integer of 100 or less.
m3 represents an integer of 1 or more, and is the same as m in formula (C-1).
(C) The component (C-4) preferably has a structure represented by the formula (C).
[ chemical formula 20]
Wherein A is 41 And A 42 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, A 43 And A 44 R is independently an alkylene group having 1 to 20 carbon atoms 41 、R 42 And R is 43 Each independently represents an alkyl group having 1 to 20 carbon atoms. n41, n42 and n43 each independently represent an integer of 0 to 4. m4 represents an integer of 0 or more, and m5 represents an integer of 1 or more. Wherein A is 43 And the nitrogen atom is directly bonded by a single bond.
A 43 And A 44 Each independently represents an alkylene group having 1 to 20 carbon atoms, and A in the formula (C-1) 2 The same applies.
A 41 And A 42 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and A in the formula (C-3) 32 And A 33 The same applies.
R 41 And R is 42 Each independently represents an alkyl group having 1 to 20 carbon atoms. R is R 41 The alkyl group having 1 to 20 carbon atoms is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 15 or less. Examples of such alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl and the like.
R 43 Represents an alkyl group having 1 to 20 carbon atoms, and R in the formula (C-2) 21 The same applies.
n41, n42 and n43 each independently represent an integer of 0 to 4, and are the same as n2 in formula (C-2).
m3 represents an integer of 0 or more, and is the same as m2 in formula (C-3). In addition, m4 represents an integer of 1 or more, and is the same as m in formula (C-1).
(C) The component (C-5) preferably has a structure represented by the formula (C).
[ chemical formula 21]
Wherein A is 51 And A 56 Separately and independently from each otherRepresents a 4-valent organic group comprising 2 or more aromatic or aliphatic rings, ring X C11 Ring X C12 And ring X c13 Each independently represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent, A 52 、A 53 And A 54 Each independently represents an alkylene group having 1 to 20 carbon atoms. m6 represents an integer of 0 or more, and m7 represents an integer of 1 or more.
A 51 And A 56 Each independently represents a 4-valent organic group containing 2 or more aromatic or aliphatic rings, and A in the formula (C-1) 1 The same applies.
Ring X C11 Ring X C12 And ring X c13 Each independently represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent, and a ring X in the formula (C-1) C The same applies.
A 52 、A 53 And A 54 Each independently represents an alkylene group having 1 to 20 carbon atoms, and A in the formula (C-1) 2 The same applies.
m6 represents an integer of 0 or more, and is the same as m2 in formula (C-3). M7 represents an integer of 1 or more, and is the same as m in formula (C-1).
(C) The component (C-6) preferably has a structure represented by the formula (I).
[ chemical formula 22]
Wherein A is 63 And A 64 R is independently an alkylene group having 1 to 20 carbon atoms 61 、R 62 And R is 63 Each independently represents an alkyl group having 1 to 20 carbon atoms. n61, n62 and n63 each independently represent an integer of 0 to 4. m8 represents an integer of 0 or more, and m9 represents an integer of 1 or more. Wherein A is 63 And the nitrogen atom is directly bonded by a single bond.
A 63 And A 64 Each independently represents an alkylene group having 1 to 20 carbon atoms, and A in the formula (C-1) 2 Identical to。
R 61 And R is 62 Each independently represents an alkyl group having 1 to 20 carbon atoms, and R in the formula (C-4) 41 The same applies. In addition, R 63 Represents an alkyl group having 1 to 20 carbon atoms, and R in the formula (C-2) 21 The same applies.
n61, n62 and n63 each independently represent an integer of 0 to 4, and are the same as n2 in formula (C-2).
m8 represents an integer of 0 or more, and is the same as m2 in formula (C-3). M9 represents an integer of 1 or more, and is the same as m in formula (C-1).
Specific examples of the component (C) include: the following compounds. However, the component (C) is not limited to these specific examples.
[ chemical formula 23]
[ chemical formula 24]
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m5 and m6 represent integers of 1 or more, and "" represents a bonding site.
(C) The components may be synthesized by a known method or a method based on the same. Examples of the commercial products of the component (C) include: "SLK-2700" manufactured by Xinyue chemical industry Co., ltd.
From the viewpoint of remarkably obtaining the effect of the present invention, the functional group equivalent of the component (C) is preferably 500g/eq. Or more, more preferably 700g/eq. Or more, still more preferably 1000g/eq. Or more, preferably 10000g/eq. Or less, more preferably 5000g/eq. Or less, still more preferably 2500g/eq. Or less. (C) The functional group equivalent of the component (C) means the mass of the component (C) per 1 equivalent of maleimide group.
The molecular weight of the component (C) is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, preferably 20000 or less, more preferably 10000 or less, further preferably 5000 or less, from the viewpoint of significantly obtaining the effect of the present invention.
The content of the component (C) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of significantly obtaining the effect of the present invention.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (C) is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% or more, and the upper limit thereof is preferably 15 mass% or less, more preferably 10 mass% or less, further preferably 8 mass% or less, based on 100 mass% of the resin component in the resin composition.
From the viewpoint of significantly obtaining the effect of the present invention, the mass ratio of the (C) component to the (a) epoxy resin in the resin composition ((a) component/(C) component) is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less.
From the viewpoint of significantly obtaining the effect of the present invention, the mass ratio of the (C) component to the (B) active ester compound in the resin composition ((B) component/(C) component) is preferably 1 or more, more preferably 3 or more, particularly preferably 5 or more, preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.
(D) radical polymerizable Compound
The resin composition may contain (D) a radical polymerizable compound as an optional component. The radical polymerizable compound (D) as the component (D) does not contain any substances corresponding to the components (a) to (C). In addition, the component (D) generally does not have a partial structure represented by the formula (C-1). (D) The components may be used alone or in combination of at least 2.
(D) The radical polymerizable compound may be, for example, a compound having a radical polymerizable unsaturated group. The radical polymerizable unsaturated group is not particularly limited as long as it can be radical polymerized, and an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or in the interior is preferable, and specifically, may be: unsaturated aliphatic groups such as allyl and 3-cyclohexenyl; aromatic groups containing an unsaturated aliphatic group such as p-vinylphenyl, m-vinylphenyl, and styryl; an α, β -unsaturated carbonyl group such as an acryl group, a methacryl group, a maleimide group in the case of imidization, a fumaryl group, and the like. (D) The radical polymerizable compound preferably has 1 or more radical polymerizable unsaturated groups, and more preferably has 2 or more radical polymerizable unsaturated groups.
As the other radical polymerizable compound (D), known radical polymerizable compounds can be widely used, and examples thereof include, but are not particularly limited to: maleimide-based radical polymerizable compounds having 2 or more maleimide groups, vinylphenyl-based radical polymerizable compounds having 2 or more vinylphenyl groups, and (meth) acrylic-based radical polymerizable compounds having 2 or more acryl groups and/or methacryl groups, other than the component (C).
The maleimide-based radical polymerizable compound is not particularly limited, and may be an aliphatic maleimide compound having an aliphatic amine skeleton or an aromatic maleimide compound having an aromatic amine skeleton, and examples of the commercially available product include: "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure) manufactured by Designer Molecules company, "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules company, "MIR-5000-60T", "MIR-3000-70MT" (biphenylaralkyl type maleimide compound) manufactured by Japanese chemical company, "BMI-70", "BMI-80" manufactured by K.I. chemical company, "BMI-2300", "BMI-TMH" manufactured by Dai chemical industry company, and "SLK-2600" manufactured by Xin Yue chemical industry company, etc. Further, as the maleimide-based radical polymerizable compound, a maleimide resin (a maleimide compound having an indane ring skeleton) disclosed in technical publication No. 2020-500211 of the institute of Electrical and electronics Endoconcha may be used.
The vinylphenyl radical polymerizable compound is not particularly limited, and in one embodiment, a thermoplastic resin having a vinylphenyl group is preferable, and a resin selected from a modified polyphenylene ether resin having a vinylphenyl group and a modified polystyrene resin having a vinylphenyl group is more preferable, and examples of the commercially available products include: "OPE-2St1200", "OPE-2St 2200" manufactured by Mitsubishi gas chemical corporation (vinylbenzyl modified polyphenylene ether resin); "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene/styrene copolymer) manufactured by Nissan Chemical & Material Co., ltd; "A-DOG" manufactured by Xinzhongcun chemical industry Co., ltd., and "DCP-A" manufactured by co-Rong chemical Co., ltd.
The (meth) acrylic radical polymerizable compound is not particularly limited, and in one embodiment, a thermoplastic resin having an acryl group and/or a methacryl group is preferable, and a resin selected from a modified polyphenylene ether resin having an acryl group and/or a methacryl group, and a modified polystyrene resin having an acryl group and/or a methacryl group is more preferable, and examples of the commercially available products include: and "SA9000" and "SA9000-111" manufactured by SABIC Innovative Plastics company (methacrylic acid-modified polyphenylene ether resin).
(D) The functional group equivalent of the component is preferably 100g/eq to 20000g/eq, more preferably 200g/eq to 15000g/eq, still more preferably 300g/eq to 10000g/eq. (D) The functional group equivalent of the component (D) means the mass of the (D) other radical polymerizable compound per 1 equivalent of the radical polymerizable unsaturated group (i.e., maleimide group, vinylphenyl group, acryl group, methacryl group, etc.).
(D) The weight average molecular weight (Mw) of the component (A) is preferably 500 to 50000, more preferably 700 to 20000. (D) The number average molecular weight (Mn) of the other radically polymerizable compound is preferably 500 to 50000, more preferably 700 to 20000. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (D) is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, still more preferably 0.3 mass% or more, preferably 3 mass% or less, still more preferably 2 mass% or less, still more preferably 1.5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (D) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1 mass% or more, preferably 5 mass% or less, still more preferably 3 mass% or less, still more preferably 2.5 mass% or less, based on 100 mass% of the resin component in the resin composition.
From the viewpoint of significantly obtaining the effect of the present invention, the mass ratio of the (C) component to the (D) component in the resin composition ((D) component/(C) component) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 3 or less, more preferably 1 or less, and particularly preferably 0.8 or less.
Inorganic filler (E)
The resin composition of the present invention sometimes contains (E) an inorganic filler as an optional ingredient. (E) The inorganic filler is contained in the resin composition in a particulate state.
As the material of the inorganic filler (E), an inorganic compound is used. Examples of the material of the inorganic filler (E) 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, zirconium phosphotungstate, and the like. Among these, silica is particularly suitable. Examples of the silica include: amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, spherical silica is preferable as silica. (E) The inorganic filler may be used alone or in combination of at least 2 kinds in any ratio.
The average particle diameter of the inorganic filler (E) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, further preferably 1 μm or less, particularly preferably 0.7 μm or less. The lower limit of the average particle diameter of the inorganic filler (E) 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. (E) The average particle size of the inorganic filler material can be determined by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced by volume-based measurement using a laser diffraction scattering particle size distribution measuring apparatus, and the measurement can be performed by using the median diameter as the average particle size. As a measurement sample, a sample obtained by weighing 100mg of an inorganic filler and 10g of butanone into a vial and dispersing the mixture with 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 used light source was set to blue and red, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method, and the average particle size was calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring apparatus include: LA-960 manufactured by horiba manufacturing company.
The specific surface area of the inorganic filler (E) is not particularly limited, but is preferably 0.1m 2 Preferably at least/g, more preferably 0.5m 2 Preferably 1m or more, more preferably per gram 2 Preferably 3m or more per gram 2 And/g. The upper limit of the specific surface area of the inorganic filler (E) is not particularly limited, but is preferably 100m 2 Less than/g, more preferably 70m 2 Preferably less than/g, more preferably 50m 2 Preferably less than/g, particularly preferably 40m 2 And/g or less. The specific surface area of the inorganic filler is according to the BET method,the specific surface area was calculated by the BET multipoint method by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech).
(E) The inorganic filler may be a non-hollow inorganic filler (preferably, non-hollow silica) having a porosity of 0% by volume, or a hollow inorganic filler (preferably, hollow silica) having a porosity of more than 0% by volume, or both may be contained. The porosity of the hollow inorganic filler is preferably 70% by volume or less, more preferably 50% by volume or less, and particularly preferably 30% by volume or less. (E) The lower limit of the porosity of the inorganic filler may be, for example, more than 0% by volume, 1% by volume or more, 5% by volume or more, 10% by volume or more, or the like. The porosity P (volume%) of the inorganic filler is defined as a volume-based ratio (total volume of pores/volume of particles) of the total volume of 1 or 2 or more pores existing inside the particles to the volume of the whole particles based on the outer surface of the particles, for example, a measured value D of the actual density using the inorganic filler M (g/cm 3 ) And theoretical value D of the mass density of the material forming the inorganic filler material T (g/cm 3 ) Calculated by the following formula (1).
[ mathematics 1]
(E) The actual density of the inorganic filler can be measured, for example, using a true density measuring device. Examples of the true density measuring device include: ULTRAPYCOMETER 1000 manufactured by QUANTACHOME Co. As the measurement gas, for example, nitrogen is used.
(E) As the inorganic filler, commercially available ones can be used. Examples of the commercial products of the inorganic filler (E) include: "UFP-30" manufactured by electrochemical industries; "SP60-05", "SP507-05" manufactured by Nissan gold Materials, inc.; "YC100C", "YA050C-MJE", "YA010C" manufactured by Admatechs company; "UFP-30" manufactured by Denka corporation; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Co; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs; "DAW-03", "FB-105FD" manufactured by Denka corporation; and "BA-S" manufactured by Nissan catalyst formation Co.
(E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include: fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of 2 or more kinds.
Examples of the commercial products of the surface treatment agent include: "KBM403" manufactured by Xinyue chemical industry Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" manufactured by Xinyue chemical industry Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" manufactured by Xinyue chemical industry Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" manufactured by Xinyue chemical industry Co., ltd. (N-phenyl-3-aminopropyl trimethoxysilane), "SZ-31" hexamethyldisilazane manufactured by Xinyue chemical industry Co., ltd., "KBM103" manufactured by Xinyue chemical industry Co., ltd. (phenyl trimethoxysilane), "KBM-4803" manufactured by Xinyue chemical industry Co., ltd. (long-chain epoxy silane coupling agent), and "KBM-7103" 3, 3-trifluoropropyl trimethoxysilane "manufactured by Xinyue chemical industry Co., ltd., etc.
From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent preferably falls within a predetermined range. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface treatment agent, more preferably 0.2 to 3 mass%, and even more preferably 0.3 to 2 mass%.
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. From the slaveFrom the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m 2 The above, more preferably 0.1mg/m 2 The above, more preferably 0.2mg/m 2 The above. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin composition or in melt viscosity in a sheet form, it is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The following is more preferably 0.5mg/m 2 The following is given.
(E) The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is subjected to a washing treatment using a solvent such as Methyl Ethyl Ketone (MEK). Specifically, MEK as a sufficient amount of solvent was added to the inorganic filler after the surface treatment with the surface treatment agent, and the mixture was subjected to ultrasonic washing at 25 ℃ for 5 minutes. The supernatant may be removed, and after drying the solid component, the carbon amount per unit surface area of the inorganic filler may be measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba manufacturing company can be used.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (E) inorganic filler is preferably 40 mass% or more, more preferably 50 mass% or more, further preferably 60 mass% or more, or 70 mass% or more, preferably 90 mass% or less, more preferably 85 mass% or less, further preferably 80 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The mass ratio of the component (C) to the inorganic filler (E) (component (E)/component (C)) in the resin composition is preferably 10 or more, more preferably 20 or more, further preferably 30 or more, 40 or more, or 50 or more, preferably 80 or less, more preferably 70 or less, further preferably 60 or less.
Curing agent (F)
The resin composition may contain (F) a curing agent (excluding the material corresponding to the component (B)) as an optional component. The curing agent (F) as the component (F) does not contain any substances corresponding to the components (A) to (E). (F) The components may be used alone or in combination of at least 2.
Examples of the component (F) include: phenol-based curing agent, naphthol-based curing agent, and benzoAnd an oxazine-based curing agent, a cyanate-based curing agent, a carbodiimide-based curing agent, and the like. Among them, from the viewpoint of remarkably obtaining the effect of the present invention, the component (F) is preferably any one of 1 or more of a phenol-based curing agent, a naphthol-based curing agent, a cyanate-based curing agent and a carbodiimide-based curing agent, more preferably any one of a phenol-based curing agent and a naphthol-based curing agent, and even more preferably contains a phenol-based curing agent.
As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.
Specific examples of the phenol-based curing agent and the naphthol-based curing agent include: "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He chemical Co., ltd., japan, "NHN", "CBN", "GPH", and "SN170", "SN180", "SN190", "SN475", "SN485", "SN 495V", "SN375", "SN395" manufactured by Nissan chemical Co., ltd., DIC "," TD-2090"," LA-7052"," LA-7054"," LA-1356"," LA-3018-50P "," EXB-9500 "manufactured by Nissan chemical Co., ltd.
As benzo (a) toSpecific examples of the oxazine-based curing agent include: "HFB2006M" manufactured by Showa Polymer Co., ltd., and "P-d" and "F-a" manufactured by Sichuangji chemical industry Co., ltd.
Examples of the cyanate-based curing agent include: 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) phenylpropane, 1-bis (4-cyanate phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 2-functional cyanate resins such as 1, 3-bis (4-cyanate phenyl-1- (methylethylene)) benzene, bis (4-cyanate phenyl) sulfide and bis (4-cyanate phenyl) ether, multifunctional cyanate resins derived from phenol novolac and cresol novolac, prepolymers obtained by triazinizing a part of these cyanate resins, and the like. Specific examples of the cyanate-based curing agent include: "PT30" and "PT60" manufactured by Lonza Japan (phenol novolac type multifunctional cyanate resin), "ULL-950S" (multifunctional cyanate resin), "BA230", "BA230S75" (prepolymer obtained by triazining part or all of bisphenol A dicyanate into a trimer), and the like.
Specific examples of the carbodiimide-based curing agent include: "V-03", "V-07", etc. manufactured by Niqing textile chemical company.
When the curing agent is contained as the component (F), the ratio of the amount of the component (A) to the amount of the component (B) to the amount of the component (F) is represented by [ (total count of epoxy groups of the component (A)) ]: the ratio of [ (total count of active groups of component (B) and component (F) ] is preferably 1:0.01 to 1: range of 5, more preferably 1:0.05 to 1: 3. further preferably 1:0.1 to 1:2. the "(epoxy number of component (a)" means a value obtained by summing all values obtained by dividing the mass of the nonvolatile component (a) existing in the resin composition by the epoxy equivalent weight. The "(active base number of component (B) and component (F)" means a value obtained by dividing the mass of the non-volatile components of component (B) and component (F) existing in the resin composition by the active base equivalent, and summing up the total. The effects of the present invention can be significantly obtained by setting the amount ratio of the component (B) to the component (A) within the above range.
When the curing agent is contained as the component (F), the ratio of the amount of the component (A) to the total amount of the components (F) is represented by [ (total count of epoxy groups of the component (A)) ]: the ratio of [ (total count of active groups of component (F) ] is preferably 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, further preferably 1:0.05 to 1:0.3. the "(active base number of component (F)" means a value obtained by dividing the mass of the nonvolatile component (F) contained in the resin composition by the active base equivalent weight, and summing up the total. The effect of the present invention can be remarkably obtained by setting the amount ratio of the component (a) to the component (F) within the above range.
The content of the component (F) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, still more preferably 0.5 mass% or more, preferably 5 mass% or less, still more preferably 3 mass% or less, and still more preferably 1.5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of significantly obtaining the desired effect of the present invention.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (F) is preferably 2 mass% or more, more preferably 3 mass% or more, still more preferably 3.5 mass% or more, preferably 8 mass% or less, still more preferably 6 mass% or less, still more preferably 5 mass% or less, based on 100 mass% of the resin component in the resin composition.
(G) curing accelerator
The resin composition may contain (G) a curing accelerator as an optional ingredient. The (G) curing accelerator as the (G) component does not contain any substances corresponding to the (a) to (F) components. (G) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (a) epoxy resin. (G) The curing accelerator may be used alone or in combination of 2 or more.
Examples of the curing accelerator (G) include: phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. Among them, a curing accelerator selected from the group consisting of amine-based curing accelerators and metal-based curing accelerators is preferable, and an amine-based curing accelerator is particularly preferable.
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-butyldimethylphosphonium 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) ethylphosphonium tetraphenyl borate, tris (2-methoxyphenyl) ethylphosphonium tetraphenyl borate, (4-methylphenyl) triphenylphosphine thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenylphosphine thiocyanate; 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 (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; 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 ' -dimethyltoluene) urea, 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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, and, 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 can be used, and examples thereof include: "1B2PZ", "2MZA-PW", "2PHZ-PW", "C11Z-A", manufactured by Mitsubishi chemical corporation, and "P200-H50", manufactured by Mitsubishi chemical corporation.
Examples of the metal-based curing accelerator include: organometallic complexes or salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, and the like. 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, zinc stearate, and the like.
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 products can be used, and examples thereof include: "MY-25" manufactured by Fine-Techno Co., ltd.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (G) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, preferably 1.5 mass% or less, still more preferably 1 mass% or less, and still more preferably 0.5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (G) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, still more preferably 0.5 mass% or more, preferably 3 mass% or less, still more preferably 1.5 mass% or less, and still more preferably 1 mass% or less, based on 100 mass% of the resin component in the resin composition.
(H) other additives
The resin composition of the present invention may further contain an optional additive as a non-volatile component. Examples of such additives include: a thermoplastic resin; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; phenol-based curing agent, acid anhydride-based curing agent, thiol-based curing agent, and benzo Epoxy curing agents other than active ester compounds, such as an oxazine curing agent, a cyanate curing agent, a carbodiimide curing agent, an imidazole curing agent, and an amine curing agent; thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyetheretherketone resin, and polyester resin; organic filler 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; triazole-based adhesion-imparting agent, tetrazole-based adhesion-imparting agent, and triazineAn adhesion imparting agent such as an adhesion imparting agent; antioxidants such as hindered phenol 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, phosphonic acid compounds, 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 acetylene 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 of 2 or more kinds in any ratio. (H) The content of the other additives can be appropriately set by those skilled in the art.
Solvent (I)
The resin composition may contain an optional solvent as a volatile component in addition to the above-mentioned nonvolatile components. The solvent (I) is not particularly limited in kind, and a known solvent may be suitably used, and an organic solvent is preferable. Examples of the solvent (I) include: ketone solvents such as acetone, butanone, 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; tetrahydropyran, tetrahydrofuran, 1, 4-diEther solvents such as alkyl, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, etc.; 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, ethyldiglycol acetate, γ -butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; 2-methoxypropanol, 2-methoxyethanol and 2-ethoxylEther alcohol solvents such as ethyl alcohol, 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 hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The solvent may be used alone or in combination of 2 or more kinds in any ratio.
In one embodiment, the content of the solvent (I) is not particularly limited, and when the total content of the components in the resin composition is 100% by mass, it may be 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, for example. The lower limit is not particularly limited, and may be set to 0.0001 mass% or more.
Method for producing resin composition
The resin composition of the present invention can be produced, for example, by adding and mixing the components (a) to (C) and, if necessary, the components (D) to (I) in any order and/or partially or completely simultaneously in any preparation vessel. In addition, the temperature may be set appropriately during the mixing of the components, and heating and/or cooling may be performed temporarily or constantly. In addition, 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, during or after the addition and mixing. The defoaming may be performed under low pressure such as vacuum while stirring or shaking.
< Properties of resin composition >
By using the resin composition containing the components (a) to (C), a cured product having excellent crack resistance and suppressed occurrence of warpage can be obtained. In addition, the resin composition generally provides a cured product having a low relative dielectric constant (Dk) and dielectric loss tangent (Df), excellent copper adhesion, and a high glass transition temperature (Tg).
The cured product obtained by curing the resin composition at 190℃for 90 minutes generally exhibits a low dielectric constant (Dk) at ordinary temperature. Thus, an insulating layer excellent in dielectric constant is formed. The dielectric constant (Dk) of the cured product of the resin composition is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.5 or less when measured at 5.8GHz and 23 ℃. The lower limit is not particularly limited, and may be set to 0.1 or more. The dielectric constant at 23℃can be measured by the method described in examples described below.
The cured product obtained by curing the resin composition at 190℃for 90 minutes generally exhibits a low dielectric constant (Dk) characteristic at high temperatures. Thus, an insulating layer excellent in dielectric constant is formed. The dielectric constant (Dk) of the cured product of the resin composition is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.5 or less when measured at 5.8GHz and 90 ℃. The lower limit is not particularly limited, and may be set to 0.1 or more. The dielectric constant at 90℃can be measured by the method described in examples described below.
The cured product obtained by curing the resin composition at 190℃for 90 minutes generally exhibits a low dielectric loss tangent (Df) at ordinary temperature. Thus, an insulating layer excellent in dielectric loss tangent is formed. The dielectric loss tangent (Df) of the cured product of the resin composition is preferably 0.005 or less, 0.004 or less, more preferably 0.003 or less, when measured at 5.8GHz and 23 ℃. The lower limit is not particularly limited, and may be set to 0.00001 or more. The dielectric loss tangent at 23℃can be measured by the method described in examples below.
The cured product obtained by curing the resin composition at 190℃for 90 minutes generally exhibits a low dielectric loss tangent (Df) at high temperatures. Thus, an insulating layer excellent in dielectric loss tangent is formed. The dielectric loss tangent (Df) of the cured product is preferably 0.005 or less, 0.004 or less, more preferably 0.003 or less, when measured at 5.8GHz and 90 ℃. The lower limit is not particularly limited, and may be set to 0.00001 or more. The dielectric loss tangent at 90℃can be measured by the method described in examples described below.
The cured product obtained by curing the resin composition at 190℃for 90 minutes generally exhibits a characteristic of high glass transition temperature (Tg). The glass transition temperature of the cured product represents the glass transition temperature measured by the DMA method. The glass transition temperature (Tg) of the cured product is preferably 130℃or higher, more preferably 140℃or higher, and still more preferably 150℃or higher. The upper limit is not particularly limited, and may be set to 500℃or lower. The glass transition temperature can be measured by the method described in examples described below.
The cured product obtained by curing the resin composition at 130℃for 30 minutes and then at 170℃for 30 minutes showed excellent crack resistance. Thus, an insulating layer excellent in crack resistance is formed. Specifically, a layer made of a cured product of the resin composition was formed on a core material having 100 copper pad portions. The layer made of the cured product was roughened, and 100 copper pad portions after the roughening were observed to confirm the presence or absence of cracks. In this case, the number of cracks is preferably 10 or less. The evaluation of the crack resistance can be measured by the method described in examples described below.
The cured product obtained by curing the resin composition at 190℃for 90 minutes exhibited a characteristic that the occurrence of warpage was suppressed. Thus, an insulating layer in which occurrence of warpage is suppressed is formed. The warpage amount is preferably 20mm or less, more preferably 10mm or less, and further preferably 5mm or less. The lower limit is not particularly limited, and may be 0mm or more. The evaluation of the warpage amount can be measured by the method described in examples described later.
The cured product obtained by curing the resin composition at 190℃for 90 minutes generally exhibits excellent copper adhesion properties. Thus, an insulating layer excellent in adhesion with copper is formed. The adhesion strength with the copper foil is preferably 0.2kgf/cm or more, more preferably 0.3kgf/cm or more, still more preferably 0.4kgf/cm or more, or 0.5kgf/cm or more, when measured in accordance with JIS C6481. The upper limit is not particularly limited, and may be 10kgf/cm or less. The evaluation of the adhesion can be measured by the method described in examples described below.
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, it can be suitably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) formed on an insulating layer (including a rewiring layer). In addition, in a printed wiring board described later, the resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of a printed wiring board) can be suitably used. 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, a primer material, a die bonding material, a semiconductor sealing material, a hole-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 a re-wiring layer (resin composition for forming a re-wiring layer) as an insulating layer for forming a re-wiring layer, and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). In manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer.
Step (1): laminating a temporary fixing film on a base material;
step (2): temporarily fixing the semiconductor chip on the temporary fixing film;
step (3): forming a sealing layer on the semiconductor chip;
step (4): peeling the substrate and the temporary fixing film from the semiconductor chip;
step (5): 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 off; and
step (6): and forming a rewiring layer as a conductor layer on the rewiring layer.
The resin composition of the present invention can be suitably used even when the printed wiring board is a component-embedded circuit board because it also forms an insulating layer excellent in component embedding property.
[ sheet laminate ]
The resin composition of the present invention can be used by coating in the form of a varnish, but is industrially generally suitable for use 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, the resin sheet comprises 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 and 10 μm or more.
Examples of the support include: the film, metal foil and release paper made of plastic material are preferable.
In the case of using a film made of a plastic material as a support, examples of the plastic material include: polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET"), polyethylene naphthalate (hereinafter, abbreviated as "PEN") and the like, polycarbonates (hereinafter, abbreviated as "PC") and the like, acrylics such as polymethyl methacrylate (PMMA) and the like, cyclic polyolefins, cellulose Triacetate (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, aluminum foil, etc., preferably copper foil. As the copper foil, a foil composed of a single metal of copper or a foil composed 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. Examples of the release agent used for the release layer of the support with a release layer include: and 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. The support with a release layer may be commercially available, and examples thereof include: PET films having a release layer composed mainly of an alkyd-based release agent, namely, "SK-1", "AL-5", "AL-7" manufactured by LINTEC, and "Lumiror T60" manufactured by Toray, inc., and "PUREX" manufactured by Di people, and "Unipel" manufactured by UNITKA, etc.
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. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
In one embodiment, the resin sheet may further comprise an optional layer as desired. Examples of such an optional layer include: a protective film provided on a surface of the resin composition layer which is not bonded to the support (i.e., a surface opposite to the support) and based on 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, adhesion or damage of dust or the like on the surface of the resin composition layer can be suppressed.
The resin sheet can be produced, for example, by preparing a resin varnish by directly dissolving a liquid resin composition or by dissolving a resin composition in an organic solvent, coating the resin varnish on a support by a die coater (die coater) or the like, and drying the resin varnish to form 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 at least 2 kinds.
Drying can be performed by a known method such as heating and blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. The boiling point of the organic solvent in the resin composition or the resin varnish varies depending on the boiling point, and 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 rolled into a cylindrical shape 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 substrate with the resin composition of the present invention.
The sheet-like fibrous base material used for the prepreg is not particularly limited, and materials commonly used as a base material for the prepreg, such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, and the like, 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, still more preferably 30 μm or less, 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.
The sheet-like laminate of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be suitably 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, for example, by a method comprising the following steps (I) and (II) using the resin sheet described above:
step (I): laminating a resin sheet on the inner layer substrate to bond the resin composition layer of the resin sheet to the inner layer substrate;
step (II): the resin composition layer is cured (e.g., thermally cured) to form an insulating layer.
The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include: glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene oxide substrates, 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 sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, intermediate products to be formed with an insulating layer and/or a conductor layer in the production of a printed wiring board are also included in the "inner layer substrate" in the present invention. In the case where the printed wiring board is a component-embedded circuit board, an inner layer substrate having a component embedded therein may be used.
Lamination of the inner layer substrate and the resin sheet can be performed by, for example, heat-pressing the resin sheet onto the inner layer substrate from the support side. As a member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as a "heat-pressing member"), there may be mentioned, for example: heated metal plates (SUS mirror plates, etc.), metal rollers (SUS rollers), etc. The heating and pressing member is preferably 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, instead of directly pressing the resin sheet.
Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and pressing pressure is preferably in the range of 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and pressing time is preferably in the range of 20 to 400 seconds, more preferably 30 to 300 seconds. Lamination may preferably be performed 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 pressure laminators manufactured by Ming machine manufacturing company, vacuum applicators manufactured by Nikko-Materials company, intermittent vacuum pressure laminators, and the like.
After lamination, the laminated resin sheets can be smoothed by pressurizing the heating and pressing member from the support body side at normal pressure (atmospheric pressure), for example. The pressurizing conditions for the smoothing treatment may be the same as the heating and pressing conditions for the lamination described above. The smoothing treatment may be performed using 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 composed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.
The heat curing conditions of the resin composition layer also vary 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 ℃, and even more preferably 170 to 210 ℃. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.
The resin composition layer may be preheated to a temperature below the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes at a temperature of 50 ℃ to 120 ℃, preferably 60 ℃ to 115 ℃, more preferably 70 ℃ to 110 ℃ 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) may be performed according to various methods known to those skilled in the art for manufacturing a printed wiring board. In the case where 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). Further, the insulating layer and the conductor layer in the steps (II) to (V) may be repeatedly formed as necessary to form a multilayer wiring board.
In other embodiments, the printed wiring board of the present invention may be manufactured using the above-described prepreg. The manufacturing 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, and thus holes such as a via hole and a through hole can be formed in the insulating layer. The step (III) may be performed by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition for forming the insulating layer. The size or shape of the hole may 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, the stain is removed also in this step (IV). 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 neutralization liquid.
The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include: the alkali solution and the surfactant solution are preferably alkali solutions, and sodium hydroxide solution and potassium hydroxide solution are more preferable as the alkali solution. Examples of commercially available swelling liquids include: "Swelling dip.Securiganth P", "Swelling dip.Securiganth SBU", etc. manufactured by Atotech Japan. The swelling treatment with the swelling solution is not particularly limited, and for example, the insulating layer may be immersed in the swelling solution 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 for the roughening treatment is not particularly limited, and examples thereof include: and dissolving potassium permanganate or sodium permanganate in sodium hydroxide water solution to obtain an alkaline permanganate solution. 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", "Dosing Solution Securiganth P" manufactured by Atotech Japan corporation.
The neutralizing liquid used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercial products include: "Reduction Solution Securigant P" manufactured by Atotech Japan Inc.
The treatment with the neutralizing solution may be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to impregnate the object roughened with the oxidizing agent in a neutralization solution at 40 to 70 ℃ for 5 to 20 minutes.
In one embodiment, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500nm or less, more preferably 400nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.
The step (V) is a step of forming a conductor layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises 1 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 2 or more metals selected from the group described above (for example, nichrome, cupronickel, and cupronickel). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of pattern formation, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nichrome, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nichrome, and still more preferably a single metal layer of copper is preferable.
The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more single metal layers or alloy layers each made of a different metal or alloy are stacked. In the case where 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 nichrome.
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 electroplating. For example, the conductor layer having a desired wiring pattern may be formed by electroplating on the surface of the insulating layer by a conventionally known technique such as a half-addition method or a full-addition method, and it is preferably formed 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 given.
First, an electroplating 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. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer may be removed by etching or the like to form a conductor layer having a desired wiring pattern.
In another embodiment, 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 resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described in relation to the step (I). Then, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive process or a modified semi-additive process 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 company, JXUT-III foil, 3EC-III foil manufactured by Sanjing metal mine company, TP-III foil, etc.
[ 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.
As the semiconductor device, there may be mentioned: various semiconductor devices are supplied to electric products (for example, computers, cellular 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 to these examples. In the following, unless otherwise specified, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively. In particular, in the case where the temperature and pressure are not specified, the temperature conditions and pressure conditions refer to room temperature (23 ℃) and atmospheric pressure (1 atm).
Synthesis example 1: synthesis of active ester Compound (B-1)
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 320g (2.0 mol) of 2, 7-dihydroxynaphthalene, 184g (1.7 mol) of benzyl alcohol and 5.0g of p-toluenesulfonic acid monohydrate, and stirred while nitrogen was blown in at room temperature. Then, the temperature was raised to 150℃and the water thus produced was distilled off from the system and stirred for 4 hours. After completion of the reaction, 900g of methyl isobutyl ketone and 5.4g of a 20% aqueous sodium hydroxide solution were added for neutralization, and then the aqueous layer was removed by separation, and water washing was performed 3 times with 280g of water, whereby methyl isobutyl ketone was removed under reduced pressure, and 460g of benzyl-modified naphthalene compound (A-1) was obtained. The obtained benzyl-modified naphthalene compound (A-1) was a black solid, and the hydroxyl equivalent was 180 g/equivalent.
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 nitrogen substitution under reduced pressure to dissolve the isophthaloyl dichloride. 113.9g (0.67 mol) of o-phenylphenol and 240g of benzyl-modified naphthalene compound (A-1) (molar number of phenolic hydroxyl groups: 1.33 mol) were then charged, and the system was dissolved by nitrogen substitution under reduced pressure. Then, 0.70g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60℃or lower by purging with nitrogen gas, and 400g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Then, 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. Then, water was added to the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for 15 minutes, and the mixture was allowed to stand for separation to remove the water layer. This operation was repeated until the pH of the aqueous layer was 7. Then, the water was removed by dehydration in a decanter to obtain an active ester compound (B-1) in the form of a toluene solution having a nonvolatile content of 61.5% by mass. The active ester equivalent of the active ester compound (B-1) obtained was 238g/eq.
< synthetic example 2: synthesis of active ester Compound (B-2)
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 165g of a resin for addition polymerization of dicyclopentadiene and phenol (hydroxyl equivalent: 165g/eq., softening point: 85 ℃ C.), 134g (1.0 mol) of o-allylphenol and 1200g of toluene, and the inside of the system was subjected to nitrogen substitution under reduced pressure. Then, 203g (1.0 mol) of isophthaloyl dichloride was charged, and the inside of the system was subjected to nitrogen substitution under reduced pressure. 0.6g of tetrabutylammonium bromide was added thereto, and the inside of the system was controlled to 60℃or lower while purging with nitrogen gas, and 412g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dripping, the mixture was stirred for 1.0 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the toluene layer obtained, 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 was 7. Then, the nonvolatile matter was adjusted to 70 mass% by heat drying, whereby an active ester compound (B-2) represented by the following formula was obtained. Wherein s is an integer of 0 or 1 or more, and the average value of r calculated from the filler ratio is 1. The dotted line in the formula is a structure obtained by reacting isophthaloyl dichloride, and a resin for addition polymerization of phenol and/or o-allylphenol. 214g/eq of the ester group equivalent weight of the active ester resin obtained was calculated from the filler ratio.
[ chemical formula 25]
< manufacture of resin varnish >
The components were weighed according to the parts by weight described in the following table, 10 parts of MEK and 10 parts of cyclohexanone were further mixed and uniformly dispersed by using a high-speed rotary mixer, to obtain a resin varnish. The details of the components described in the table are as follows.
(A) The components are as follows:
HP-4032-SS: functional group equivalent 144g/eq., manufactured by DIC corporation;
ESN-475V: functional group equivalent 330g/eq., manufactured by Nissan iron Chemical & Material Co; NC-3100: functional group equivalent 258g/eq., manufactured by japan chemical company;
(B) The components are as follows:
HPC-8150-62T: functional group equivalent 223g/eq., toluene solution with a nonvolatile matter of 62 mass%, manufactured by DIC Co., ltd;
HPC-8000-65T: functional group equivalent 229g/eq., toluene solution with a nonvolatile matter of 65 mass%, manufactured by DIC corporation;
active ester compound (B-1): the active ester compound synthesized in synthesis example 1;
active ester compound (B-2): the active ester compound synthesized in synthesis example 2;
PC1300-02: functional group equivalent 199g/eq., a methyl amyl ketone solution having a nonvolatile matter of 65 mass%, manufactured by AIR WATER PERFORMANCE CHEMICAL company;
(C) The components are as follows:
SLK-2700: the following structure is shown, and the nonvolatile matter is 50 mass% toluene solution manufactured by Xinyue chemical industry Co., ltd;
[ chemical formula 26]
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m5 and m6 represent integers of 1 or more, and "" represents a bonding site.
(D) The components are as follows:
SLK-2600: the nonvolatile matter was 50 mass% anisole solution, manufactured by Xinyue chemical industry company;
BMI-689: designer Molecules company;
BMI-1500: designer Molecules company;
maleimide a: a compound represented by the following formula (1) (Mw/mn=1.81, t "=1.47 (mainly 1, 2 or 3)), which is synthesized according to the method described in synthesis example 1 of technical publication No. 2020-500211 of the institute of technology and field, and a MEK solution having a nonvolatile content of 62 mass%;
[ chemical formula 27]
MIR-5000-60T: the nonvolatile matter was 60 mass% toluene solution, manufactured by japan chemical company;
a-DOG: manufactured by japan chemical medicine corporation;
OPE-2St-1200: the nonvolatile matter was a 65 mass% toluene solution manufactured by Mitsubishi gas chemical corporation;
(E) The components are as follows:
SO-C2: spherical silica surface-treated with an amine-based alkoxysilane compound (KBM 573 manufactured by Xinyue chemical Co., ltd.) having an average particle diameter of 0.5 μm and a specific surface area of 5.8m 2 /g, manufactured by Admatechs company;
BA-S: spherical silica having a hollow portion and surface-treated with an amine-based alkoxysilane compound (KBM 573 manufactured by Xinyue chemical Co., ltd.) and having an average particle diameter of 2 to 3 μm, manufactured by Nitro catalyst formation Co., ltd;
(F) The components are as follows:
LA-3018-50P: a 1-methoxy-2-propanol solution having a functional group equivalent of 151g/eq and a nonvolatile matter of 50 mass%;
(G) The components are as follows:
1B2PZ: manufactured by four chemical industry companies;
TABLE 1
< determination of dielectric constant/dielectric loss tangent >)
(1) Preparation of resin sheet A having a thickness of 40 μm in the layer of the resin composition
A polyethylene terephthalate film (AL 5, 38 μm in thickness, manufactured by LINTEC Co.) having a release layer was prepared as a support. 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 was 40. Mu.m. Thereafter, 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) Production of cured product
The resin sheets A obtained in examples and comparative examples were cured in an oven at 190℃for 90 minutes. The support was peeled off 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, and the resultant was used as a cured product for evaluation. (3) Determination of dielectric constant/dielectric loss tangent
For each cured product for evaluation, the dielectric constant/dielectric loss tangent (Dk value. Df value) was measured at a measurement frequency of 5.8GHz, a measurement temperature of 23℃and 90℃by a cavity resonance perturbation method using "HP8362B" manufactured by Agilent technologies. The average value of the 2 test pieces was calculated by measuring them.
Production of resin sheet B having a thickness of 25 μm of the resin composition layer
A polyethylene terephthalate film (AL 5, 38 μm in thickness, manufactured by LINTEC Co.) having a release layer was prepared as a support. The resin varnishes obtained in examples and comparative examples were uniformly applied to the release layer of the support, and the dried resin composition layer was dried at 70℃to 80℃for 2.5 minutes to give a resin sheet B comprising the support and the resin composition layer.
< evaluation of crack resistance after decontamination treatment >
A circular copper pad (copper thickness: 35 μm) having a diameter of 350 μm was formed at 400 μm intervals so as to have a copper residue ratio of 60%, and both sides of a lattice-shaped core material (E705 GR, thickness: 400 μm, manufactured by Hitachi chemical Co., ltd.) were laminated on both sides of an inner layer substrate using a batch vacuum pressure laminator (CVP 700, manufactured by Nikko-Materials Co., ltd.) to bond a resin composition layer to the inner layer substrate by laminating the resin sheet B having a thickness of 25 μm on both sides of the inner layer substrate. The lamination was performed by reducing the pressure to 13hPa or less for 30 seconds and then pressing at 100℃under a pressure of 0.74MPa for 30 seconds. It was put into an oven at 130 ℃ for 30 minutes and then transferred into an oven at 170 ℃ for 30 minutes. The support layer was peeled off again, and the obtained circuit board was immersed in a Swelling solution, called Swelling dip, of swolling dip.security P, manufactured by Atotech Japan, for 10 minutes at 60 ℃. Next, the polishing composition was prepared in a polishing composition of Concentrate Compact P (KMnO 4 :60g/L, naOH:40g/L in water) at 80℃for 30 minutes. Finally, in Atotech Japan Co., ltdIn the resulting Reduction Solution Securigant P, it was immersed at 40℃for 5 minutes. 100 copper pad portions of the roughened circuit board were observed, and the presence or absence of cracking in the resin composition layer was confirmed, and evaluated according to the following criteria.
And (2) the following steps: the number of cracks is less than 10;
x: more than 10 cracks.
< evaluation of warpage >
The resin sheet A having a thickness of 40 μm produced as described above was cut into 110 mm. Times.150 mm pieces, and the resultant pieces were laminated on a copper foil (3 EC-III, 35 μm thick, manufactured by Mitsui metal mining Co., ltd.) cut into 120 mm. Times.160 mm pieces using a batch vacuum pressure laminator (two-stage lamination laminator "CVP700", manufactured by Nikko-Materials Co., ltd.) to bring the resin composition layer into contact with the copper foil. The resulting mixture was then fixed to a SUS-made backing plate with a Kapton tape, and after peeling the PET film, the mixture was heated in an oven at 190℃for 90 minutes. The sheet was peeled off from the backing sheet, and the amount of warpage was measured and evaluated according to the following criteria.
And (2) the following steps: the warpage amount is below 20 mm;
x: the warpage amount exceeds 20mm.
< evaluation of adhesion to surface-treated copper foil >
The resin sheet A having a thickness of 40 μm produced as described above was laminated on a copper foil (3 EC-III, 35 μm in thickness, manufactured by Mitsui metal mining Co., ltd.) having a glossy surface subjected to surface treatment (CZ 8401 and AP3006, manufactured by MEC Co., ltd.) using a batch vacuum pressure laminator (two-stage lamination laminator "CVP700", manufactured by Nikko-Materials Co., ltd.), and the resin composition layer was brought into contact with the copper foil. After PET was peeled off, a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.4 mm) having an inner layer circuit formed thereon was laminated using a batch vacuum pressure laminator (two-stage laminator "CVP700" manufactured by Nikko-Materials Co., ltd.), and the double-sided laminate having "R1515A" manufactured by Song corporation was etched 1 μm with a microetching agent (CZ 8101 "manufactured by MEC Co., ltd.) to roughen the copper surface, and then heated in an oven at 130℃for 30 minutes, in an oven at 170℃for 30 minutes, and further heated in an oven at 190℃for 90 minutes, to produce an evaluation substrate.
The fabricated samples were cut into 150X 30mm pieces. A portion of a small piece of copper foil was cut into a portion having a width of 10mm and a length of 100mm using a cutter, one end of the copper foil was peeled off, and the copper foil was clamped by a jig ("AC-50C-SL" manufactured by TSE Co., ltd.) and the load [ kgf/cm ] at a speed of 50 mm/min in the vertical direction was measured at room temperature using an Instron universal tester according to JIS C6481.
< determination of glass transition temperature (Tg) ]
The cured product for evaluation of the resin composition obtained above was cut into a length of 50mm and a width of 7mm, and used as an evaluation sample. For this evaluation sample, a DMA apparatus (thermo-mechanical analysis apparatus) manufactured by hitachi High Technologies was used to measure the glass transition temperature (Tg) from 25 ℃ to 250 ℃ at a temperature rising rate of 5 ℃/min. The same test piece was measured 2 times, and the value of the 2 nd time was recorded.
TABLE 2
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Claims (14)

1. A resin composition comprising:
(A) An epoxy resin;
(B) An active ester compound; and
(C) A bismaleimide compound having a partial structure represented by the following formula (C-1),
[ chemical formula 1]
Wherein A is 1 Represents a 4-valent organic group comprising 2 or more aromatic or aliphatic rings, ring X C Represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent, A 2 Represents an alkylene group having 1 to 20 carbon atoms, m represents an integer of 1 or more, and x represents a bonding site.
2. The resin composition according to claim 1, wherein the component (C) has a partial structure represented by the formula (C-2),
[ chemical formula 2]
Wherein A is 21 Represents an alkylene group having 1 to 20 carbon atoms, R 21 Each independently represents an alkyl group having 1 to 20 carbon atoms, n2 represents an integer of 0 to 4, and m1 represents an integer of 1 or more.
3. The resin composition according to claim 1, wherein maleimide groups in the component (C) are located at both ends.
4. The resin composition according to claim 1, wherein the component (C) has a structure represented by the formula (C-3),
[ chemical formula 3]
Wherein A is 31 And A 36 Each independently represents a 4-valent organic group containing 2 or more aromatic or aliphatic rings, a ring X C1 Ring X C2 And ring X c3 Each independently represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent, A 33 And A 34 Each independently represents an alkylene group having 1 to 20 carbon atoms, A 32 、A 35 And A 37 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms which may have a substituent, m2 represents an integer of 0 or more, and m3 represents an integer of 1 or more.
5. The resin composition according to claim 1, wherein the component (C) comprises a compound represented by the formula (C-4),
[ chemical formula 4]
Wherein A is 41 And A 42 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, A 43 And A 44 R is independently an alkylene group having 1 to 20 carbon atoms 41 、R 42 And R is 43 Independently represent an alkyl group having 1 to 20 carbon atoms, n41, n42 and n43 independently represent an integer of 0 to 4, m4 represents an integer of 0 or more, and m5 represents an integer of 1 or more, wherein A 43 And the nitrogen atom is directly bonded by a single bond.
6. The resin composition according to claim 1, further comprising (D) a radical polymerizable compound.
7. The resin composition according to claim 1, further comprising (E) an inorganic filler.
8. The resin composition according to claim 7, wherein the content of the component (E) is 40% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
9. The resin composition according to claim 1, further comprising (F) a curing agent.
10. The resin composition according to claim 1, wherein a cured product obtained by curing the resin composition at 190℃for 90 minutes has a glass transition temperature of 130℃or higher as measured by a DMA method.
11. A sheet-like laminate comprising the resin composition according to any one of claims 1 to 10.
12. A resin sheet having a support and a resin composition layer provided on the support and formed of the resin composition according to any one of claims 1 to 10.
13. A printed wiring board comprising an insulating layer composed of the cured product of the resin composition according to any one of claims 1 to 10.
14. A semiconductor device comprising the printed wiring board according to claim 13.
CN202310235278.6A 2022-03-15 2023-03-13 Resin composition Pending CN116769274A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2022-040601 2022-03-15
JP2023-019158 2023-02-10
JP2023019158A JP2023135613A (en) 2022-03-15 2023-02-10 resin composition

Publications (1)

Publication Number Publication Date
CN116769274A true CN116769274A (en) 2023-09-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
CN (1) CN116769274A (en)

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