CN117881715A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN117881715A
CN117881715A CN202280057106.8A CN202280057106A CN117881715A CN 117881715 A CN117881715 A CN 117881715A CN 202280057106 A CN202280057106 A CN 202280057106A CN 117881715 A CN117881715 A CN 117881715A
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China
Prior art keywords
resin composition
optionally substituted
group
mass
substituent
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CN202280057106.8A
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Chinese (zh)
Inventor
川合贤司
长冈二朗
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN117881715A publication Critical patent/CN117881715A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

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

Abstract

The invention aims to provide a resin composition capable of obtaining a cured product with excellent crack resistance. The resin composition of the present invention is a resin composition comprising (A) an epoxy resin, (B) an active ester-based curing agent, and (C) an inorganic filler, wherein the content of the (C) component is 60% by mass or more, and the (B) component comprises: (B1) An active ester curing agent having a structure represented by the formula (B1-1). The definition of each symbol is as described in the attached specification.

Description

Resin composition
Technical Field
The present invention relates to a resin composition comprising an epoxy resin. The invention also relates to a resin sheet, a printed wiring board and a semiconductor device obtained by using the resin composition.
Background
As a technique for manufacturing a printed wiring board, a manufacturing method using a stacking method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method using the stacked method, the insulating layer is generally formed by curing a resin composition. In recent years, further improvement in dielectric characteristics such as dielectric loss tangent of an insulating layer has been demanded.
Heretofore, as a resin composition for forming an insulating layer, there has been known a resin composition which can further reduce the dielectric loss tangent of the insulating layer by using an epoxy resin composition highly filled with an inorganic filler or an epoxy resin composition incorporating an active ester compound instead of a general phenolic curing agent (patent document 1). In addition, various active ester curing agents have been known heretofore (patent documents 2 and 3).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2020-23714
Patent document 2: japanese patent No. 6862701
Patent document 3: japanese patent application laid-open No. 2021-14545.
Disclosure of Invention
Technical problem to be solved by the invention
However, when an active ester compound is used in an epoxy resin composition with a high degree of inorganic filler, the dielectric loss tangent can be further suppressed, but cracks tend to be easily generated after the desmear treatment.
The invention aims to provide a resin composition capable of obtaining a cured product with excellent crack resistance.
Technical proposal adopted for solving the technical problems
As a result of intensive studies to solve the problems of the present invention, the present inventors have found that, in an epoxy resin composition containing (B) an active ester curing agent in which the content of (C) an inorganic filler is 60% by mass or more, a cured product excellent in crack resistance can be unexpectedly obtained by using, as (B) the active ester curing agent, an active ester curing agent having a bulky group introduced at the para position of the terminal phenoxycarbonyl moiety, and have completed the present invention.
Namely, the present invention includes the following.
[1] A resin composition comprising (A) an epoxy resin, (B) an active ester-based curing agent, and (C) an inorganic filler, wherein,
when the nonvolatile content in the resin composition is set to 100 mass%, the content of the component (C) is 60 mass% or more,
(B) The components comprise: (B1) An active ester curing agent having a structure represented by the formula (B1-1) (hereinafter sometimes referred to as "(B1) terminal sterically hindered active ester curing agent"),
[ chemical formula 1]
In the method, in the process of the invention,
R 1a r is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents;
R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 2 each independently represents a substituent;
a represents 0, 1 or 2;
* Indicating the binding site.
[2] The resin composition according to the above [1], wherein the component (B1) contains an active ester curing agent having a structure represented by the formula (B1-2B) in addition to the structure represented by the formula (B1-1),
[ chemical formula 2]
In the method, in the process of the invention,
R 1a R is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents;
R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 2 each independently represents a substituent;
R 3 each independently represents a hydrogen atom or a methyl group;
ring X 1 Represents an aromatic carbocyclic ring optionally having a substituent;
a represents 0, 1 or 2;
* Indicating the binding site.
[3] The resin composition according to the above [1] or [2], wherein the component (B1) comprises a resin represented by the formula (B1 c),
[ chemical formula 3]
In the method, in the process of the invention,
R 1a r is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents;
R 1c each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 2 each independently represents a substituent;
R 3 each independently represents a hydrogen atom or a methyl group;
Ring X 1 Ring Y 1 Each independently represents an aromatic carbocyclic ring optionally having a substituent;
a each independently represents 0, 1 or 2;
b represents 0 or an integer of 1 or more.
[4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (B1) is 3 to 20% by mass based on 100% by mass of the nonvolatile component in the resin composition.
[5] The resin composition according to any one of the above [1] to [4], wherein the component (B) further comprises: (B2) An active ester curing agent having a structure represented by the formula (B2-1),
[ chemical formula 4]
In the method, in the process of the invention,
with respect to R 4 、R 5 R is R 6 ，(1)R 4 Represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-, and R 5 R is R 6 Each independently represents a hydrogen atom or a substituent, (2) R 4 R is R 5 Taken together to form an optionally substituted aromatic carbocyclic ring, and R 6 Represents a hydrogen atom or a substituent, or (3) R 5 R is R 6 Taken together to form an optionally substituted aromatic carbocyclic ring, and R 4 Represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-；
R 7 R is R 8 Each independently represents a hydrogen atom or a substituent;
R 41 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
A represents-CH 2 -、-CH(CH 3 ) -, -CO-, or-O-;
* Indicating the binding site.
[6] The resin composition according to any one of the above [1] to [5], wherein the content of the component (A) is 1 to 20% by mass based on 100% by mass of the nonvolatile component in the resin composition.
[7] The resin composition according to any one of the above [1] to [6], wherein the content of the component (B) is 12% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition.
[8] The resin composition according to any one of the above [1] to [7], wherein the component (C) is silica.
[9] The resin composition according to any one of the above [1] to [8], wherein the content of the component (C) is 70% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition.
[10] The resin composition according to any one of the above [1] to [9], further comprising (D) a curing accelerator.
[11] The resin composition according to any one of [1] to [10], further comprising a curing agent selected from a phenolic curing agent and a carbodiimide curing agent.
[12] The resin composition according to any one of [1] to [11], wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.003 or less when measured at 5.8GHz and 23 ℃.
[13] The resin composition according to any one of the above [1] to [12], wherein a glass transition temperature (Tg) of a cured product of the resin composition is 140℃or higher.
[14] The resin composition according to any one of [1] to [13] above, which is used for forming an insulating layer for forming a conductor layer.
[15] The resin composition according to any one of [1] to [13] above, which is used for forming an insulating layer of a printed wiring board.
[16] A cured product of the resin composition according to any one of the above [1] to [15 ].
[17] A sheet laminate comprising the resin composition according to any one of the above [1] to [15 ].
[18] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [15] provided on the support.
[19] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [15 ].
[20] A semiconductor device comprising the printed wiring board of [19 ].
ADVANTAGEOUS EFFECTS OF INVENTION
When the resin composition of the present invention is used, a cured product having excellent crack resistance can be obtained.
Brief description of the drawings
FIG. 1 shows GPC chart of active ester A (terminal sterically hindered ester curing agent) of Synthesis example 1.
FIG. 2 shows an IR chart of an active ester A (terminal sterically hindered ester curing agent) of Synthesis example 1.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified within the scope not departing from the scope of the claims and the equivalents thereof.
< resin composition >
The resin composition of the present invention comprises (A) an epoxy resin, (B) an active ester-based curing agent, and (C) an inorganic filler, wherein the content of the component (C) is 60 mass% or more, and the component (B) comprises the (B1) terminal sterically hindered active ester-based curing agent, when the nonvolatile component in the resin composition is 100 mass%. By using such a resin composition, a cured product having excellent crack resistance can be obtained.
The resin composition of the present invention may contain any component in addition to (a) the epoxy resin, (B) the active ester-based curing agent, and (C) the inorganic filler. Examples of the optional components include (D) a curing accelerator, (E) other additives, and (F) an organic solvent.
The components contained in the resin composition will be described in detail below.
Epoxy resin (A)
The resin composition of the present invention contains (A) an epoxy resin. (A) The epoxy resin is a curable resin having an epoxy group.
Examples of the epoxy resin (a) include a bisxylenol type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol novolac type epoxy resin, a phenol novolac type epoxy resin, a tert-butylcatechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidylester type epoxy resin, a cresol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthalene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenyl ethane type epoxy resin, an isocyanurate type epoxy resin, a phenol benzopyrrolidone (phenol phthalimidine) type epoxy resin, and the like. (A) The epoxy resin may be used alone or in combination of 1 kind or 2 or more kinds.
The resin composition preferably contains (a) an epoxy resin having 2 or more epoxy groups in 1 molecule as the 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, based on 100% by mass of the nonvolatile component of the (a) epoxy resin.
Examples of the epoxy resin include an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter also referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter also referred to as "solid epoxy resin"). In the resin composition of the present invention, the epoxy resin may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination, but it is preferable to contain a liquid epoxy resin and a solid epoxy resin in combination.
As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
As the liquid epoxy resin, a GLYCIROL type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a cyclic aliphatic glycidyl ether, and an epoxy resin having a butadiene structure are preferable, and a GLYCIROL type epoxy resin, a cyclic aliphatic glycidyl ether, a bisphenol A type epoxy resin, and a bisphenol F type epoxy resin are more preferable.
Specific examples of the liquid epoxy resin include "EX-992L" manufactured by Daiko Kagaku (Nagase ChemteX), "YX7400" manufactured by Mitsubishi chemical Co., ltd., "HP4032" manufactured by DIC, HP4032D "," HP4032SS "(naphthalene type epoxy resin)," 828US "manufactured by Mitsubishi chemical Co., ltd.," 828EL "," jER828EL "," 825"," EPIKOTE 828EL "(bisphenol A type epoxy resin)," jER "manufactured by Mitsubishi chemical Co., ltd.," 1750 "(bisphenol F type epoxy resin)," jER152 "manufactured by Mitsubishi chemical Co., ltd.," phenol novolac type epoxy resin ", and" 630LSD "604" manufactured by Mitsubishi chemical Co., ltd., "ED-523" manufactured by Mitsubishi chemical Co., ADEKA "(GLYCIROL type epoxy resin)," EP-3950L "manufactured by ADEKA (a" glycidyl amine type epoxy resin "), and" EP-4088S "manufactured by ADEKA (a" dicyclopentadiene type epoxy resin "), ZX1059" manufactured by Niday iron chemical materials (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), EX-721 "manufactured by Daiki Kagaku (a" glycidyl ester type epoxy resin ")," EX-991L "(epoxy resin having an alkylene oxide skeleton and a butadiene skeleton) manufactured by Kagaku Co., ltd.," CELLOXIDE 2021P "(alicyclic epoxy resin having an ester skeleton) made by Daxiu corporation," PB-3600 "made by Daxiu corporation, and" JP-100 "made by Japanese Sea corporation, "JP-200" (epoxy resin having butadiene structure), "ZX1658" manufactured by Nikka Chemicals Co., ltd., "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin), "EG-280" manufactured by Osaka gas Chemicals Co., ltd., "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Kagaku Co., ltd.).
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
As the solid epoxy resin, there are preferable a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthalene-ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenyl ethane-type epoxy resin, and a phenol benzopyrrolone-type epoxy resin.
Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Co., ltd., "HP-4700" manufactured by DIC Co., ltd., and "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Co., ltd., and "N-695" manufactured by DIC Co., ltd., and "cresol novolak type epoxy resin", and "HP-7200" manufactured by DIC Co., ltd., and "HP-7200" and "HP-7200H" and "HP-7200L" manufactured by DIC Co., ltd., and "EXA-7311" G3", and" EXA-7311 "G4S" and "HP6000" manufactured by DIC Co., ltd., and "dicyclopentadiene type epoxy resin", "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kagaku Co., ltd., "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kagaku Co., ltd., "NC3000H", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nitro Kagaku Co., ltd., "ESN475V", "ESN4100V" (naphthalene type epoxy resin) manufactured by Nitro Kagaku Co., ltd., "ESN485" (naphthol type epoxy resin) manufactured by Nitro Kagaku Co., ltd., "ESN375" (dihydroxy naphthalene type epoxy resin) manufactured by Nitro Kagaku Co., ltd., "YX4000H", "YX4000HK", "YL7890" (bina xylenol type epoxy resin) manufactured by Mitsubishi Kagaku Co., ltd., "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation, "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi chemical corporation, "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi chemical corporation, "PG-100", "CG-500" manufactured by Osaka gas chemical corporation, "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 corporation, "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi chemical corporation, "WHR991S" (phenol benzopyrrolone type epoxy resin) manufactured by Japan chemical corporation, and the like. These resins may be used alone or in combination of 1 or more than 2.
When the solid epoxy resin and the liquid epoxy resin are used in combination as the epoxy resin (A), the mass ratio thereof (solid epoxy resin: liquid epoxy resin) is preferably 10:1 to 1:50, more preferably 5:1 to 1:20, particularly preferably 2:1 to 1:10.
(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5000g/eq, more preferably 60g/eq to 2000g/eq, still more preferably 70g/eq to 1000g/eq, still more preferably 80g/eq to 500g/eq. The epoxy equivalent is the mass of the resin corresponding to each 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 5000, more preferably 250 to 3000, still more preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
The content of the epoxy resin (a) in the resin composition is not particularly limited, but is preferably 30 mass% or less, more preferably 25 mass% or less, still more preferably 20 mass% or less, still more preferably 15 mass% or less, particularly preferably 12 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the component (a) in the resin composition is not particularly limited, but is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, still more preferably 1 mass% or more, still more preferably 5 mass% or more, particularly preferably 10 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition.
Active ester curing agent (B)
The resin composition of the present invention contains (B) an active ester curing agent. (B) The active ester-based curing agent may have a function as an epoxy resin curing agent that reacts with (a) the epoxy resin to cure it. (B) The active ester curing agent may be used alone or in combination of at least 2 kinds in any ratio.
As the active ester curing agent (B), compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, are generally preferably used. (B) The active ester curing agent is preferably a compound obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the Phenolic compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene type bisphenol compounds, and Novolac (Phenolic Novolac).
(B) The active ester group equivalent (reactive group equivalent as a curing agent) of the active ester curing agent is preferably 50 g/eq.) to 500g/eq., more preferably 50 g/eq.) to 400g/eq., still more preferably 100 g/eq.) to 300g/eq. The active ester equivalent weight is the mass of the active ester curing agent corresponding to 1 equivalent of ester groups that can react with the epoxy resin.
The content of the active ester curing agent (B) in the resin composition is not particularly limited, but is preferably 0.1 mass% or more, more preferably 1 mass% or more, still more preferably 5 mass% or more, still more preferably 10 mass% or more, still more preferably 12 mass% or more, still more preferably 14 mass% or more, particularly preferably 15 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition. The upper limit of the content of the (B) active ester curing agent in the resin composition is not particularly limited, but is preferably 50 mass% or less, more preferably 40 mass% or less, still more preferably 30 mass% or less, still more preferably 25 mass% or less, particularly preferably 20 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
(B1) terminal sterically hindered active ester curing agent
(B) The active ester curing agent includes (B1) an active ester curing agent having a structure represented by the formula (B1-1).
[ chemical formula 5]
Wherein R is 1a R is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents; r is R 1c Represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group; r is R 2 Each independently represents a substituent; a represents 0, 1 or 2; * Indicating the binding site.
R 1a R is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents.
Alkyl means a straight, 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, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl and the like.
Alkenyl 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, more preferably an alkenyl group having 2 to 10 carbon atoms, and still more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of the alkenyl group include vinyl group, propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotonyl group, etc.), pentenyl group (1-pentenyl group, etc.), hexenyl group (1-hexenyl group, etc.), heptenyl group (1-heptenyl group, etc.), octenyl group (1-octenyl group, etc.), cyclopentenyl group (2-cyclopentenyl group, etc.), cyclohexenyl group (3-cyclohexenyl group, etc.), and the like.
Aryl refers to a 1-valent aromatic hydrocarbon group from which 1 hydrogen atom of an aromatic carbocyclic ring is removed. Unless otherwise specified, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include phenyl, 1-naphthyl and 2-naphthyl.
Non-aromatic carbocycles refer to rings other than aromatic carbocycles in which the ring as a whole is aromatic. Non-aromatic carbocycles have only carbon atoms as ring-forming atoms. The non-aromatic carbocycle may be a saturated carbocycle formed only by a single bond, or an unsaturated carbocycle having at least any one of a double bond and a triple bond. The non-aromatic carbon ring is preferably a non-aromatic carbon ring having 4 to 20 carbon atoms, more preferably a non-aromatic carbon ring having 5 to 12 carbon atoms Aromatic carbocycles. As preferable specific examples of the non-aromatic carbocycle, there may be mentioned, for example, a monocyclic saturated carbocycle such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring and the like, and a bicyclo [2.2.1]Heptane ring (norbornane ring), bicyclo [4.4.0]Decane ring (decalin ring), bicyclo [5.3.0]Decane Ring and bicyclo [4.3.0]Nonane ring (indene ring), bicyclo [3.2.1]Octane ring, bicyclo [5.4.0]Undecane ring, bicyclo [3.3.0]Octane ring, bicyclo [3.3.1]Bicyclic saturated carbocycles such as nonane ring, tricyclic [5.2.1.0 2,6 ]Decane ring (tetrahydrodicyclopentadiene ring), tricyclo [3.3.1.1 3,7 ]Decane ring (adamantane ring), tricyclo [6.2.1.0 ] 2,7 ]Tricyclic saturated carbocycles such as undecane ring, tetracyclic [6.2.1.1 ] 3,6 .0 2,7 ]Tetracyclic saturated carbocycles such as dodecane ring and pentacyclic [9.2.1.1 ] 4,7 .0 2 ,1 .0 3,8 ]Pentadecane ring, pentacyclic [6.5.1.1 ] 3,6 .0 2,7 .0 9,13 ]Pentadecane ring (tetrahydrotricyclopentadiene ring) and other pentacyclic saturated carbocycles. In addition, non-aromatic carbocycles may condense 1 or 2 or more aromatic carbocycles at a position where condensation is possible. Examples of the non-aromatic carbocycle condensed with the aromatic carbocycle include an indane ring, an indene ring, a tetrahydronaphthalene ring, a 1, 2-dihydronaphthalene ring, a 1, 4-dihydronaphthalene ring, a fluorene ring, a 9, 10-dihydroanthracene ring, and a 9, 10-dihydrophenanthrene ring.
An aromatic carbocyclic ring refers to a carbocyclic ring that follows the shock rule and contains 4p+2 electrons in the pi electron system on the ring, p being a natural number. Aromatic carbocycles have only carbon atoms as ring-forming atoms. In one embodiment, the aromatic carbocycle is preferably a 6-14 membered aromatic carbocycle, more preferably a 6-10 membered aromatic carbocycle. As preferable specific examples of the aromatic carbocycle, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like are given, preferably benzene ring or naphthalene ring, particularly preferably benzene ring.
By R as 1a R is R 1b The "substituent" in the alkyl group and alkenyl group represented is not particularly limited, and examples thereof include a halogen atom, an aryl group, an alkyl-aryl group (aryl group substituted with an alkyl group), an alkenyl-aryl group (aryl group substituted with an alkenyl group), and an aryl-aryl group (aryl group substituted with an alkenyl group)Aryl-substituted 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. By R as 1a R is R 1b The "substituent" in the aryl group represented is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), an alkyl-aryl-alkyl group (an alkyl group substituted with an aryl group substituted with an alkyl group), an alkenyl-aryl-alkyl group (an alkyl group substituted with an alkenyl group), an aryl-aryl group (an alkyl group substituted with an aryl group), an alkyl-aryl group, an alkenyl-aryl group, an aryl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-carbonyl-oxy group, and the like. As R 1a R is R 1b The "substituent" in the formed non-aromatic carbocyclic ring is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, an alkyl-aryl-alkyl group, an alkenyl-aryl-alkyl group, an aryl-aryl group, an alkyl-aryl group, an alkenyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, and an oxo group (=o).
The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.
In one embodiment, R 1a R is R 1b Each independently is preferably an optionally substituted alkyl group, or an optionally substituted aryl group, more preferably an optionally substituted alkyl group, still more preferably an alkyl group, still more preferably R 1a Is methyl and R 1b Is alkyl, still more preferably R 1a Is methyl and R 1b Alkyl groups having 2 or more carbon atoms are particularly preferableR 1a Is methyl and R 1b Is ethyl.
R 1c Represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
By R as 1c The "substituent" in the alkyl group and alkenyl group represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the same groups as those exemplified for "substituents" in the alkyl group and alkenyl group are shown. By R as 1c The "substituent" in the aryl group represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, R 1c Preferably an optionally substituted alkyl group, or an optionally substituted aryl group, more preferably an optionally substituted alkyl group, further more preferably an alkyl group, particularly preferably a methyl group.
As represented by R 1a 、R 1b R is R 1c The groups formed with the carbon atoms to which they are bound, i.e. in (R1):
[ chemical formula 6]
In the formula, each symbol is as described above. ]
Specific examples of the 1-valent group include tertiary alkyl groups such as tertiary butyl, tertiary amyl, 1-methylcyclobutyl, 1-dimethylbutyl, 1-ethyl-1-methylpropyl, 1-methylcyclopentyl, 1-ethylcyclobutyl, 1-dimethylpentyl, 1, 2-trimethylbutyl, 1-ethyl-1-methylbutyl and the like, 1-alkenyl-substituted secondary alkyl groups such as 1, 1-dimethyl-2-propenyl and the like, and 1-aryl-substituted secondary alkyl groups such as α -cumyl and the like.
R 2 Each independently represents a substituent.
By R as 2 The "substituent" represented by the formula (R1) is not particularly limited, and examples thereof include a 1-valent group represented by the formula (R1), and a halogen atom, an alkyl group, an alkenyl group, an aryl group, and an aryl-alkaneAlkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl-alkyl, alkyl-aryl, alkenyl-aryl, aryl-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.
In one embodiment, R 2 Each independently is preferably alkyl, alkenyl, aryl-alkyl, alkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl-alkyl, alkyl-aryl, alkenyl-aryl, or aryl-aryl.
a represents 0, 1 or 2. In one embodiment, a is preferably 0 or 1, more preferably 0.
(B1) The component (C) preferably contains an active ester curing agent having a structure represented by the formula (B1-2 a) in addition to the structure represented by the formula (B1-1),
[ chemical formula 7]
Wherein R is 1 Each independently represents a substituent, R 3 Each independently represents a hydrogen atom or a methyl group, a ring X 1 Represents an optionally substituted aromatic carbocyclic ring, e represents 0, 1, 2, 3 or 4 independently of one another, and represents a binding site.
By R as 1 The "substituent" represented by R is not particularly limited, and may be represented by R 2 The same examples of the groups exemplified by the "substituents" indicated.
R 1 Each independently represents a substituent. In one embodiment, R 1 Each independently is preferably an alkyl group, an alkenyl group, an aryl-alkyl group, an alkyl-aryl-alkyl group, an alkenyl-aryl-alkyl group, an aryl-alkyl group, an alkyl-aryl group, an alkenyl-aryl group, an aryl-aryl group, or a 1-valent group represented by the formula (R1), more preferably a 1-valent group represented by the formula (R1).
R 3 Respectively and independently representA hydrogen atom or a methyl group. In one embodiment, R 3 Each independently is preferably a hydrogen atom.
Ring X 1 Represents an aromatic carbocyclic ring optionally having substituents.
As a ring X 1 The "substituent" in the aromatic carbocycle represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, ring X 1 Preferably a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent, more preferably (1) a benzene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, or (2) a naphthalene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, further more preferably (1) a benzene ring optionally substituted with an alkyl, or (2) a naphthalene ring optionally substituted with an alkyl, still further more preferably a benzene ring optionally substituted with an alkyl, particularly preferably a (unsubstituted) benzene ring.
e each independently represents 0, 1, 2, 3 or 4. In one embodiment, e is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, still more preferably 0 or 1, particularly preferably 0, independently of one another.
(B1) The component (C) preferably contains an active ester curing agent having a structure represented by the formula (B1-2B) in addition to the structure represented by the formula (B1-1),
[ chemical formula 8]
Wherein each symbol is as described above.
In a preferred embodiment, the component (B1) contains a resin represented by the formula (B1 a).
[ chemical formula 9]
Wherein, each ring X independently represents an aromatic carbocycle optionally having a substituent or a non-aromatic carbocycle optionally having a substituent; ring Y 1 Ring Z 1 Each independently represents an aromatic carbocyclic ring optionally having a substituent; x is X a Each independently represents a single bond, -C (R) a ) 2 -、-O-、-CO-、-S-、-SO-、-SO 2 -, -CONH-, or-NHCO-; r is R a Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, or 2R a Taken together to form a non-aromatic carbocyclic ring optionally having 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 previously. The b unit and the c unit may be the same or different in each structural unit.
The rings X each independently represent an aromatic carbocyclic ring optionally having a substituent, or a non-aromatic carbocyclic ring optionally having a substituent.
The "substituent" in the aromatic carbocyclic ring represented by the ring X is not particularly limited, and examples thereof include R 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above. The "substituent" in the non-aromatic carbocyclic ring formed as the ring X is not particularly limited, and examples thereof include R 1a R is R 1b The same examples of groups illustrated for "substituents" in the non-aromatic carbocyclic ring formed.
In one embodiment, ring X is preferably an aromatic carbocyclic ring optionally having a substituent, more preferably a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent, further more preferably (1) a benzene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, or (2) a naphthalene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, still further more preferably a benzene ring optionally substituted with an alkyl group, particularly preferably an (unsubstituted) benzene ring.
Ring Y 1 Each independently represents an aromatic carbocyclic ring optionally having a substituent.
As a ring Y 1 The "substituent" in the aromatic carbocycle represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, ring Y 1 Each independently is preferably a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent, more preferably (1) a benzene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, or (2) a naphthalene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, further more preferably (1) a benzene ring optionally substituted with an alkyl, or (2) a naphthalene ring optionally substituted with an alkyl, still further more preferably a benzene ring optionally substituted with an alkyl, particularly preferably an (unsubstituted) benzene ring.
Ring Z 1 Each independently represents an aromatic carbocyclic ring optionally having a substituent.
As a ring Z 1 The "substituent" in the aromatic carbocycle represented by R is not particularly limited, and examples thereof include 2 The same examples of the groups exemplified by the "substituents" indicated.
In one embodiment, ring Z 1 Each independently is preferably a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent, more preferably (1) a benzene ring optionally substituted with a group selected from the group consisting of an alkyl group, an alkenyl group, an aryl-alkyl group, an alkyl-aryl-alkyl group, an alkenyl-aryl-alkyl group, an aryl-alkyl group, an alkyl-aryl group, an alkenyl-aryl group, an aryl-aryl group, and a 1-valent group represented by the formula (R1), or (2) a naphthalene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, alkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl-alkyl, alkyl-aryl, alkenyl-aryl, aryl-aryl, and a 1-valent group represented by the formula (R1), more preferably further optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, alkyl-aryl-alkyl, alkenyl-aryl-alkyl, aryl-alkyl, alkyl-arylThe group, alkenyl-aryl group, aryl-aryl group, and benzene ring substituted with the group of 1 valence represented by formula (R1), and even more preferable is a benzene ring optionally substituted with the group of 1 valence represented by formula (R1), and particularly preferable is a benzene ring substituted with the group of 1 valence represented by formula (R1).
X a Each independently represents a single bond, -C (R) a ) 2 -、-O-、-CO-、-S-、-SO-、-SO 2 -, -CONH-, or-NHCO-. In one embodiment, X a Preferably independently of one another is a single bond, -C (R) a ) 2 -, or-O-, more preferably-C (R a ) 2 -, particularly preferably-C (R 3 )(CH 3 )-。
R a Each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or 2R a Taken together to form a non-aromatic carbocyclic ring optionally having substituents.
By R as a The "substituent" in the alkyl group represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the same groups as those exemplified for "substituents" in the alkyl group and alkenyl group are shown. By R as a The "substituent" in the aryl group represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above. As R a The "substituent" in the formed non-aromatic carbocyclic ring is not particularly limited, and examples thereof include R 1a R is R 1b The same examples of groups illustrated for "substituents" in the non-aromatic carbocyclic ring formed.
In one embodiment, R a Each independently is preferably a hydrogen atom, or an alkyl group optionally having a substituent, more preferably a hydrogen atom, or an alkyl group optionally having a substituent, still more preferably a hydrogen atom or an alkyl group, particularly preferably 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 from 1 to 10, particularly preferably 0 or an integer from 1 to 5.
c each independently represents 0, 1, 2 or 3. In one embodiment, c is preferably 0, 1 or 2, more preferably 0 or 1, particularly preferably 1, independently of one another.
d each independently represents 0 or 1. In one embodiment, d is preferably 1 each independently.
In a more preferred embodiment, the component (B1) includes a resin represented by the formula (B1B).
[ chemical formula 10]
Wherein each symbol is as described above.
In a more preferred embodiment, the component (B1) includes a resin represented by the formula (B1 c).
[ chemical formula 11]
Wherein each symbol is as described above.
As examples of the partial structure represented by the formula (X) in the formulae (B1-2 a), (B1-2B), (B1B) and (B1 c),
[ chemical formula 12]
In the formula, other symbols are as described above. ]
The structures represented by the formulas (X-1) to (X-12) and the like are given.
[ chemical formula 13]
[ formula, R x Each independently represents alkyl, alkenyl, aryl-alkyl, or alkyl-aryl, x independently represents 0, 1, or 2, and the other symbols are as previously described.]
Wherein,the structures represented by the formulas (X-1) to (X-3) are preferable, and in one embodiment, the structure represented by the formula (X-2) is particularly preferable. In one embodiment, R x Each independently is preferably an alkyl group. In one embodiment, x is preferably 0 or 1, more preferably 0, independently of each other.
As examples of the partial structure represented by the formula (Y) in the formulas (B1 a), (B1B) and (B1 c),
[ chemical formula 14]
In the formula, other symbols are as described above. ]
The structures represented by the formulae (Y-1) to (Y-12) and the like are given.
[ chemical formula 15]
[ formula, R y Each independently represents alkyl, alkenyl, aryl-alkyl, or alkyl-aryl, y independently represents 0, 1, or 2, and the other symbols are as previously described.]
Of these, the structure represented by the formula (Y-2) is preferable. In one embodiment, R y Each independently is preferably an alkyl group. In one embodiment, y is preferably 0 or 1, more preferably 0, independently of each other.
(B1) In the component (a), a resin containing a reaction intermediate produced during synthesis (for example, a resin having hydroxyl groups and/or carboxyl groups at one or both terminals) and a resin derived from a raw material impurity may be contained together with the resin represented by the formula (B1 a), (B1B) or (B1 c).
(B1) The components may be commercially available ones, or synthesized by a known method or a method based thereon.
The content of the component (B1) in the resin composition is not particularly limited, but is preferably 50 mass% or less, more preferably 30 mass% or less, still more preferably 20 mass% or less, and even more preferably 15 mass% or less, particularly preferably 10 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of further increasing the glass transition temperature of the cured product. The lower limit of the content of the component (B1) in the resin composition is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, the content of the nonvolatile component in the resin composition is preferably 0.1 mass% or more, more preferably 1 mass% or more, still more preferably 3 mass% or more, still more preferably 5 mass% or more, and particularly preferably 7 mass% or more, based on 100 mass%.
When the content of the component (B1) in the active ester-based curing agent is 100% by mass, the content of the component (B1) in the active ester-based curing agent may be 100% by mass, and is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, still more preferably 70% by mass or less, particularly preferably 60% by mass, from the viewpoint of further increasing the glass transition temperature of the cured product. (B) The lower limit of the content of the component (B1) in the active ester-based curing agent is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, the content of the active ester-based curing agent (B) is preferably 1 mass% or more, more preferably 10 mass% or more, still more preferably 20 mass% or more, still more preferably 30 mass% or more, and particularly preferably 40 mass% or more, based on 100 mass%.
The mass ratio of the component (B1) to the epoxy resin (a) ((component B1)/(component a)) in the resin composition is not particularly limited, but is preferably 0.05 or more, more preferably 0.1 or more, and still more preferably 0.5 or more. The upper limit of the mass ratio of the component (B1) to the epoxy resin (a) (component (B1)/component (a)) in the resin composition is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and further preferably 1 or less from the viewpoint of further increasing the glass transition temperature of the cured product.
(B2) other active ester curing agent
(B) The active ester curing agent may further include an active ester curing agent other than the component (B1) (hereinafter also referred to as "(B2) other active ester curing agent").
(B) Among the active ester curing agents, the other active ester curing agents (B2) include those having a structure represented by the formula (B2-1).
[ chemical formula 16]
[ wherein, regarding R ] 4 、R 5 R is R 6 ，(1)R 4 Represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-, and R 5 R is R 6 Each independently represents a hydrogen atom or a substituent, (2) R 4 R is R 5 Taken together to form an optionally substituted aromatic carbocyclic ring, and R 6 Represents a hydrogen atom or a substituent, or (3) R 5 R is R 6 Taken together to form an optionally substituted aromatic carbocyclic ring, and R 4 Represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-；R 7 R is R 8 Each independently represents a hydrogen atom or a substituent; r is R 41 Represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group; a represents-CH 2 -、-CH(CH 3 ) -, -CO-, or-O-; * Indicating binding sites]。
R, without formation of aromatic carbocycles 4 Represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-. In one embodiment, R, without forming an aromatic carbocyclic ring 4 Preferably hydrogen, methyl, or R 41 A-, preferably a hydrogen atom, or R 41 -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 41 Represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
By R as 41 The "substituents" in the alkyl and alkenyl groups represented are not particularly specifiedThe term "R" is defined as 1a R is R 1b Examples of the same groups as those exemplified for "substituents" in the alkyl group and alkenyl group are shown. By R as 41 The "substituent" in the aryl group represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, R 41 Aryl optionally having a substituent is preferable, aryl is more preferable, and phenyl is particularly preferable.
R, without formation of aromatic carbocycles 5 R is R 6 Each independently represents a hydrogen atom or a substituent.
By R as 5 R is R 6 The "substituent" represented by R is not particularly limited, and may be represented by R 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, R, without forming an aromatic carbocyclic ring 5 R is R 6 Each independently is 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 4 、R 5 R is R 6 In the case of aromatic carbocycles, R 4 R is R 5 Or R is 5 R is R 6 Taken together to form an optionally substituted aromatic carbocyclic ring.
As R 4 、R 5 R is R 6 The "substituent" in the aromatic carbocycle to be formed is not particularly limited, and examples thereof include R 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
R 4 、R 5 R is R 6 In the case of forming an aromatic carbocyclic ring, in one embodiment, R 4 R is R 5 Or R is 5 R is R 6 Taken together, preferably forms a benzene ring optionally substituted, more preferably forms a ring optionally substituted with a substituent selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkylThe phenyl ring substituted by groups in the aryl group, more preferably forms an (unsubstituted) phenyl ring.
R 7 R is R 8 Each independently represents a hydrogen atom or a substituent.
By R as 7 R is R 8 The "substituent" represented by R is not particularly limited, and may be represented by R 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, R 7 R is R 8 Each independently is 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.
In the first embodiment, R is preferably 4 、R 5 、R 7 R is R 8 Is a hydrogen atom, and R 6 Is alkyl or aryl; more preferably R 4 、R 5 、R 7 R is R 8 Is a hydrogen atom, and R 6 Is methyl or phenyl.
In the second embodiment, R is preferably 4 Is a hydrogen atom, or R 41 -A-, A is-CH 2 -, or-CH (CH) 3 )-，R 41 Is aryl, and R 5 、R 6 、R 7 R is R 8 Is a hydrogen atom, or an aryl-alkyl group (particularly preferably R 4 Is R 41 -A-and/or R 5 、R 6 、R 7 R is R 8 At least 1 of which is aryl-alkyl); more preferably R 4 Is a hydrogen atom, or R 41 -A-, A is-CH (CH) 3 )-，R 41 Is phenyl, and R 5 、R 6 、R 7 R is R 8 Is a hydrogen atom, or an alpha-methylbenzyl group (particularly preferably R 4 Is R 41 -A-and/or R 5 、R 6 、R 7 R is R 8 At least 1 of which is an alpha-methylbenzyl group).
In the third embodiment, R is preferably 4 R is R 5 Are combined together to form a benzene ring, and R 6 、R 7 R is R 8 Is a hydrogen atom, or R 5 R is R 6 Are combined together to form a benzene ring, and R 4 、R 7 R is R 8 Is a hydrogen atom.
In a preferred embodiment, the component (B2) includes a resin represented by the formula (B2 a).
[ chemical formula 17]
[ wherein, the rings X' each independently represent an aromatic carbocycle optionally having a substituent, or a non-aromatic carbocycle optionally having a substituent; ring Y 2 Ring Z 2 Each independently represents an aromatic carbocyclic ring optionally having 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 optionally substituted alkyl group, or an optionally substituted aryl group, or 2R b Taken together to form a non-aromatic carbocyclic ring optionally having 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 previously.]
The b 'unit and the c' unit may be the same or different in each structural unit.
The rings X' each independently represent an aromatic carbocycle optionally having a substituent or a non-aromatic carbocycle optionally having a substituent.
The "substituent" in the aromatic carbocyclic ring represented by the ring X' is not particularly limited, and examples thereof include R 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above. The "substituent" in the non-aromatic carbocyclic ring represented by the ring X' is not particularly limited, and examples thereof include R 1a R is R 1b The same examples of groups illustrated for "substituents" in the non-aromatic carbocyclic ring formed.
In one embodiment, each ring X' is independently preferably a benzene ring optionally having a substituent, a naphthalene ring optionally having a substituent, or a non-aromatic carbon ring optionally having a substituent of 5 to 12 carbon atoms; more preferably, (1) a benzene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, (2) a naphthalene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, or (3) a non-aromatic carbocyclic ring (particularly preferably a tetrahydrodicyclopentadiene ring) of 5 to 12 carbon atoms optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, alkyl-aryl, and oxo.
Ring Y 2 Each independently represents an aromatic carbocyclic ring optionally having a substituent.
As a ring Y 2 The "substituent" in the aromatic carbocycle represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, ring Y 2 Each independently is preferably a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent; more preferably, (1) a benzene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, or (2) a naphthalene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl.
Ring Z 2 Each independently represents an aromatic carbocyclic ring optionally having a substituent.
As a ring Z 2 The "substituent" in the aromatic carbocycle represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above.
In one embodiment, ring Z 2 Each independently is preferably a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent; more preferably, (1) a benzene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl, or (2) a naphthalene ring optionally substituted with a group selected from the group consisting of alkyl, alkenyl, aryl-alkyl, and alkyl-aryl.
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 Preferably independently of one another is 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 optionally substituted alkyl group, or an optionally substituted aryl group, or 2R b Taken together to form a non-aromatic carbocyclic ring optionally having substituents. By R as b The "substituent" in the alkyl group represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the same groups as those exemplified for "substituents" in the alkyl group and alkenyl group are shown. By R as b The "substituent" in the aryl group represented by R is not particularly limited, and examples thereof include 1a R is R 1b Examples of the "substituent" in the aryl group are the same as those exemplified above. As R b The "substituent" in the formed non-aromatic carbocyclic ring is not particularly limited, and examples thereof include R 1a R is R 1b The same examples of groups illustrated for "substituents" in the non-aromatic carbocyclic ring formed.
In one embodiment, R b Each independently is preferably a hydrogen atom, or an optionally substituted alkyl group, more preferably a hydrogen atom, or an alkyl group, particularly preferably a hydrogen atom or a methyl group.
b' represents 0 or an integer of 1 or more. In one embodiment, b' is preferably 0, or an integer from 1 to 100, more preferably 0, or an integer from 1 to 10, particularly preferably 0, or an integer from 1 to 5.
c' each independently represents 0, 1, 2, or 3. In one embodiment, c' is preferably 0, 1 or 2, more preferably 0 or 1, respectively and independently.
d' independently represent 0 or 1.
As an example of the partial structure represented by the formula (Y') in the formula (B2 a),
[ chemical formula 18]
In the formula, other symbols are as described above. ]
The structures represented by the formulae (Y-1) to (Y-12) and the like are given.
(B2) The resin represented by the formula (B2 a) may contain a resin that is a reaction intermediate produced during synthesis (for example, a resin having hydroxyl groups and/or carboxyl groups at one or both ends), a resin derived from a raw material impurity, and the like.
(B2) The components may be commercially available ones, or synthesized by a known method or a method based thereon. Examples of the commercial products of the component (B2) include "EXB9451", "EXB9460S", "HPC-8000-65T", "HPC-8000L-65TM", "HPC-8000H-65TM" (manufactured by DIC Co., ltd.), as active ester compounds containing dicyclopentadiene, and "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "EXB-8", "HPC-8150-62T" (manufactured by DIC Co., ltd.), as active ester compounds of acetyl compounds which are novolac resins, "DC" (manufactured by Mitsubishi chemical Co., ltd.), as "YLH", "1026", "YLH1048" (manufactured by Mitsubishi chemical Co., ltd.), as active ester compounds of benzoyl compounds which are naphthalene structures, and "WAMA" manufactured by WAMA "1300", which are naphthalene structures of active ester compounds which are naphthalene structures (manufactured by Mitsubishi-Kagaku Co., ltd.).
The content of the component (B2) in the resin composition is not particularly limited, but is preferably 40 mass% or less, more preferably 20 mass% or less, still more preferably 15 mass% or less, still more preferably 10 mass% or less, particularly preferably 8 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the component (B2) in the resin composition is not particularly limited, but is preferably not less than 0 mass% and not less than 0.1 mass% when the nonvolatile component in the resin composition is 100 mass%, and more preferably not less than 1 mass%, particularly preferably not less than 5 mass% from the viewpoint of further increasing the glass transition temperature of the cured product.
The mass ratio of the component (B2) to the epoxy resin (a) (component (B2)/component (a)) in the resin composition is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and still more preferably 1 or less. The lower limit of the mass ratio of the component (B2) to the epoxy resin (a) (component (B2)/component (a)) in the resin composition is not particularly limited, but is, for example, 0 or more, preferably 0.1 or more, more preferably 0.5 or more, from the viewpoint of further increasing the glass transition temperature of the cured product.
(B') other curing agent
The resin composition of the present invention may further contain (B') a curing agent other than the (B) component as an optional component. The other curing agents (B') may be used alone or in combination of at least 2 kinds. The other curing agent (B') may have the same function as the epoxy resin curing agent (B) for curing the epoxy resin by reacting with the epoxy resin (A).
The other curing agent (B') is not particularly limited, and examples thereof include phenol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate curing agents and thiol curing agents. Among them, a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents is preferably used.
As the phenolic curing agent, a phenolic curing agent having a phenolic structure is preferable from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. Among them, a novolak resin having a triazine skeleton is preferable from the viewpoint of satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He Chemicals, japan, and "NHN", "CBN", "GPH", and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Miq Kagaku, DIC, and "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD2090", "KA-1160", etc.
Examples of the carbodiimide curing agent include aliphatic polycarbodiimides having 1 or more, preferably 2 or more, carbodiimide structures in 1 molecule, for example, aliphatic polycarbodiimides such as tetramethylenebis (t-butylcarbodiimide), cyclohexanedis (t-butylenecarbodiimide), aromatic bisphenylenecarbodiimides such as phenylenediimide, polyhexamethylene carbodiimides, polytrimethylenehexamethylenecarbodiimides, polycyclohexylenecarbodiimides, aliphatic polycarbodiimides such as poly (methylenedicyclohexyl carbodiimides), poly (isophorone carbodiimides), poly (phenylene carbodiimides), poly (naphthylenecarbodiimides), poly (toluene carbodiimides), poly (methyl diisopropylphenylene carbodiimides), poly (triethylphenylene carbodiimides), poly (diethylphenylene carbodiimides), poly (triisopropylenecarbodiimides), poly (diisopropylenecarbodiimides), poly (xylylenecarbodiimides), poly (tetramethylenecarbodiimides), poly (xylylenecarbodiimides).
Examples of the commercially available carbodiimide curing agents include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nigrossedente chemical Co., ltd., "Stabaxol P", "Stabaxol P400" and "Hycasyl 510".
The acid anhydride-based curing agent may be a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenyl sulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), and styrene-maleic anhydride obtained by copolymerizing styrene with maleic acid. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Nippon chemical Co., ltd., and "YH306", "YH307" manufactured by Mitsubishi chemical Co., ltd., and "HN-2200", "HN-5500" manufactured by Hitachi chemical Co., ltd., and "EF-30", "EF-40", "EF-60", "EF-80" manufactured by g Lei Weili Co., ltd.
The amine curing agent may be a curing agent having 1 or more, preferably 2 or more amino groups in 1 molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among these, aromatic amines are preferable from the viewpoint of exhibiting the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. As a specific example of the amine-based curing agent, examples thereof include 4,4' -methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine 4,4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. As the amine curing agent, commercially available products can be used, and examples thereof include "SEIKACURE-S" manufactured by Seika corporation, and "EPICURE W" manufactured by Mitsubishi chemical corporation, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", manufactured by Japan chemical corporation.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" made by JFE chemical Co., ltd. "ODA-BOZ", made by Showa Polymer Co., ltd. "HFB2006M" and "P-D" made by four-country chemical industry Co., ltd. "F-a".
Examples of the cyanate ester curing agent include difunctional cyanate ester resins such as bisphenol a dicyanate, polyphenol cyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate-phenyl methane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylene)) benzene, bis (4-cyanate-phenyl) sulfide, and bis (4-cyanate-phenyl) ether, polyfunctional cyanate ester resins derived from phenol novolac resins and cresol novolac resins, and prepolymers obtained by partially triazinizing these cyanate ester resins. Specific examples of the cyanate curing agent include "PT30" and "PT60" manufactured by LONZA japan corporation (each of which is a phenol novolac type polyfunctional cyanate resin), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol a dicyanate is triazinized to form a trimer).
Examples of the thiol curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.
The equivalent weight of the reactive group of the other curing agent (B') is preferably 50g/eq to 3000g/eq, more preferably 100g/eq to 1000g/eq, still more preferably 100g/eq to 500g/eq, particularly preferably 100g/eq to 300g/eq. The equivalent of the reactive group is the mass of the curing agent corresponding to each 1 equivalent of the reactive group. The reactive group is a group that reacts with the epoxy resin, and is a phenolic hydroxyl group in the case of a phenolic curing agent, and is a carbodiimide group in the case of a carbodiimide curing agent, and varies depending on the type of curing agent.
The content of the other curing agent (B') in the resin composition is not particularly limited, but is preferably 15 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, particularly preferably 3 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the other curing agent (B') in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is set to 100 mass%, it may be, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 1 mass% or more, 1.5 mass% or more, or the like.
When the total amount of the (B) active ester curing agent and the (B') other curing agents in the resin composition is 100% by mass, the content of the (B) active ester curing agent in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more.
The ratio of the total molar equivalent number of the (B) active ester curing agent and (B') the curing agent reactive groups in the other curing agent in the resin composition to the total molar equivalent number of the epoxy groups in the (A) epoxy resin (curing agent reactive groups/epoxy groups) is preferably in the range of 0.2 to 2, more preferably in the range of 0.5 to 1.8, still more preferably in the range of 1 to 1.5. The "(total molar equivalent number of epoxy groups in the (a) epoxy resin" means the sum of the values obtained by dividing the mass of the (a) epoxy resin present in the resin composition by the epoxy equivalent number. Further, "(B) total molar equivalent number of curing agent reactive groups in the active ester curing agent and (B ') other curing agent" means the sum of the value obtained by dividing the mass of the active ester curing agent (B) present in the resin composition by the active ester group equivalent amount and the value obtained by dividing the mass of the (B') other curing agent by the reactive group equivalent amount.
Inorganic filler (C)
The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the form of particles.
As the material of the inorganic filler (C), an inorganic compound is used. Examples of the material of the inorganic filler (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone in 1 kind, or may be used in combination of 2 or more kinds in any ratio.
Examples of the commercial products of the inorganic filler (C) include "SP60-05", "SP507-05", made by Nikka chemical materials Co., ltd., "YC100C", "YA050C-MJE", "YA010C", made by DENKA Co., ltd., "UFP-30", made by Denka Co., ltd., "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N", made by Nikka Co., ltd., "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", made by DENKA Co., ltd., "DAW-03", "FB-105FD", made by Denka Co., ltd., "BA-S" made by Nikka Co., ltd., etc.
(C) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 4 μm or less, still more preferably 3 μm or less, particularly preferably 2.7 μm or less. (C) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, particularly preferably 0.2 μm or more. (C) 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 a laser diffraction scattering type particle size distribution measuring apparatus on a volume basis, and the median particle size can be measured as the average particle size. As a measurement sample, a sample obtained by weighing 100mg of an inorganic filler and 10g of methyl ethyl ketone into a vial and dispersing by ultrasonic waves for 10 minutes was used. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus was used, blue and red were used as light source wavelengths, a volume-based particle size distribution of the inorganic filler was measured by a flow cell method, and an average particle size was calculated from the obtained particle size distribution as a median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1m 2 Preferably at least 0.5m 2 Preferably at least/g, more preferably at least 1m 2 Preferably at least 3m 2 And/g. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100m 2 Preferably less than or equal to/g, more preferably 70m 2 Preferably less than or equal to/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 can be obtained by adsorbing nitrogen gas onto the surface of a sample by a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., ltd.) according to the BET method, and calculating the specific surface area by the BET multipoint method.
(C) The inorganic filler may be a non-hollow inorganic filler having a porosity of 0% by volume, preferably a non-hollow silica, or a hollow inorganic filler having a porosity of more than 0% by volume, preferably a hollow silica, or both of them may be contained. From the viewpoint of further lowering the dielectric constant, (C) the inorganic filler preferably includes only the hollow inorganic filler (preferably hollow silica) or includes both the non-hollow inorganic filler (preferably non-hollow silica) and the hollow inorganic filler (preferably hollow silica). The hollow inorganic filler has a porosity of preferably 70% by volume or less, more preferably 50% by volume or less, particularly preferably 30% by volume or less. (C) The lower limit of the porosity of the inorganic filler may be, for example, more than 0 vol%, 1 vol% or more, 5 vol% or more, 10 vol% or more % or more, etc. The porosity P (volume%) of the inorganic filler is defined as a volume reference ratio (total volume of voids/volume of particles) of a total volume of 1 or 2 or more voids existing in the interior of the particle relative to the volume of the entire particle based on the outer surface of the particle, and is, for example, a measured value D of an 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]
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 ULTRAPYCNOMETER 1000 manufactured by Kanta corporation. As the measurement gas, for example, nitrogen gas can be used.
From the viewpoint of improving moisture resistance and dispersibility, (C) the inorganic filler is preferably treated with a surface treating agent. Examples of the surface treating agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. In addition, 1 kind of the surface treating agent may be used alone, or 2 or more kinds may be used in any combination.
Examples of the commercial products of the surface treatment agent include "KBM403" (3-glycidoxypropyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., "KBM803" (3-mercaptopropyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., KBE903 "(3-aminopropyl triethoxysilane) manufactured by Shimadzu chemical Co., ltd., KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., SZ-31 "(hexamethyldisilazane) manufactured by Shimadzu chemical Co., ltd., KBM103" (phenyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., KBM-4803 "(long chain epoxy silane coupling agent) manufactured by Shimadzu chemical Co., ltd., KBM-7103" (3, 3-trifluoropropyl trimethoxysilane) and the like.
The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface-treating agent, more preferably 0.2 to 3 mass% of a surface-treating agent, and even more preferably 0.3 to 2 mass% of a surface-treating agent.
The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving the dispersibility of the inorganic filler 2 The above is more preferably 0.1mg/m 2 The above is more preferably 0.2mg/m 2 The above. On the other hand, from the viewpoints of melt viscosity of the resin composition and prevention of rise in melt viscosity in sheet form, it is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The following is more preferable to be 0.5mg/m 2 The following is given.
(C) 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 with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with the surface treating agent, and the mixture was ultrasonically cleaned at 25 ℃ for 5 minutes. After the supernatant is removed and the solid component is dried, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.
The content of the inorganic filler (C) in the resin composition is not particularly limited, but may be preferably 90 mass% or less, more preferably 85 mass% or less, still more preferably 80 mass% or less, particularly preferably 75 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the inorganic filler (C) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is set to 100% by mass, for example, it is preferably 5% by mass or more, or 10% by mass or more, more preferably 20% by mass or more, or 30% by mass or more, still more preferably 40% by mass or more, or 50% by mass or more, still more preferably 55% by mass or more, or 60% by mass or more, particularly preferably 65% by mass or more, or 70% by mass or more.
Curing accelerator (D)
The resin composition of the present invention may contain (D) a curing accelerator as an optional component. (D) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (a) epoxy resin.
Examples of the curing accelerator (D) 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. (D) The curing accelerator preferably includes an imidazole-based curing accelerator. (D) The curing accelerator may be used alone or in combination of 1 or more than 2.
Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalate hydrogen salt, tetrabutylphosphonium 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenolate, 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) ethyl phosphonium tetraphenyl borate, tris (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenyl phosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridyl phosphine, 1, 2-bis (diphenyl) phosphino-ethane, 1, 3-bis (diphenyl) phosphine, 2 '-diphenyl) phosphine, bis (2, 2' -diphenyl) phosphine, bis (2, 2-diphenyl) phosphine, etc.
Examples of the urea curing accelerator 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-tolylguanidine), 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, and 1- (o-tolylguanide).
Examples of the imidazole 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-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 '-methylimidazole- (1') ] -ethyl-s triazine, 2, 4-diamino-6- [2 '-undecylimidazole- (1') ] -ethyl-s triazine, 2, 4-diamino-6- [2 '-methyl-2' -undecylimidazole ] -2 '-ethyl-4-methylimidazole, 1' -cyanoethyl-2-cyanoethyl-phenylimidazole, 1 '-cyanoethyl-4-cyanoethyl-2-cyanoethyl-phenylimidazole and 1' -iminotriazine Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 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, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins. As the imidazole 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 curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include cobalt (II) acetylacetonate, organic cobalt complexes such as cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyl dimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo [5.4.0] undecene.
As the amine curing accelerator, commercially available products can be used, and examples thereof include "MY-25" manufactured by Weisu Fine technology Co., ltd.
The content of the curing accelerator (D) in the resin composition is not particularly limited, but is preferably 15 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, particularly preferably 2 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the (D) curing accelerator in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is set to 100 mass%, it may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, or the like.
(E) other additives
The resin composition of the present invention may further contain any additives. Examples of such additives include radical polymerizable compounds having a vinylphenyl group, an acryl group, a methacryl group, a maleimide group (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl) and the like, radical polymerization initiators such as a peroxide radical polymerization initiator and an azo radical polymerization initiator, thermosetting resins other than epoxy resins such as an epoxy acrylate resin, a urethane acrylate resin, a polyurethane resin, a cyanate resin, a benzoxazine resin, an unsaturated polyester resin, a phenol resin, a melamine resin, a silicone resin and the like, thermoplastic resins such as a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polysulfone resin, a polyether sulfone resin, a polyphenylene ether resin, a polycarbonate resin, a polyether ether ketone, a polyester resin and the like, radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators, organic fillers such as rubber particles, organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds, colorants such as phthalocyanine blue, phthalocyanine green, olive green, diazo yellow, crystal violet, titanium oxide, and carbon black, polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and thenazine, silicone leveling agents, acrylic polymer leveling agents, leveling agents such as bentonite, and montmorillonite, and other thickening agents, silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers, benzotriazole ultraviolet absorbers, and other ultraviolet absorbers, urea silane and other adhesion improving agents, triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, an adhesion-imparting agent such as a triazine-based adhesion-imparting agent, an antioxidant such as a hindered phenol-based antioxidant, a fluorescent whitening agent such as a stilbene derivative, a surfactant such as a fluorine-based surfactant or an organosilicon-based surfactant, a flame retardant such as a phosphorus-based flame retardant (for example, a phosphate compound, a phosphazene compound, a phosphinic acid compound or red phosphorus), a nitrogen-based flame retardant (for example, melamine sulfate), a halogen-based flame retardant or an inorganic flame retardant (antimony trioxide), a phosphate-based dispersant, a polyoxyalkylene-based dispersant, an acetylene-based dispersant, an organosilicon-based dispersant, an anionic dispersant, a cationic dispersant or the like, a borate-based stabilizer, a titanate-based stabilizer, an aluminate-based stabilizer, a zirconate-based stabilizer, an isocyanate-based stabilizer, a carboxylic acid-based stabilizer or a carboxylic acid anhydride-based stabilizer, or the like. (E) The other additives may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds. The content of the other additives (E) can be appropriately set if it is a person skilled in the art.
Organic solvent (F)
The resin composition of the present invention may further contain an optional organic solvent. As the organic solvent (F), a known organic solvent can be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (F) include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, and the like; 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, carbitol acetate (ethyl diglycol acetate), γ -butyrolactone, methyl methoxypropionate, and the like; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane and methylcyclohexane; aromatic solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (F) The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds in an arbitrary ratio.
The content of the organic solvent (F) in the varnish-like resin composition before drying is not particularly limited, but is, for example, 40 mass% or less, 30 mass% or less, preferably 20 mass% or less, more preferably 10 mass% or less, still more preferably 8 mass% or less, and particularly preferably 6 mass% or less, based on 100 mass% of the total components in the resin composition. The content of the organic solvent (F) in the resin composition forming the dried resin composition layer in the resin sheet is not particularly limited, but is preferably 5 mass% or less, more preferably 3 mass% or less, still more preferably 2 mass% or less, particularly preferably 1 mass% or less, based on 100 mass% of the total components in the resin composition.
Method for producing resin composition
The resin composition of the present invention can be produced, for example, as follows: to an arbitrary preparation vessel, (A) an epoxy resin, (B) an active ester curing agent, (C) an inorganic filler, (D) a curing accelerator, if necessary, (E) other additives, and (F) an organic solvent, if necessary, are added in an arbitrary order and/or partially or all at the same time and mixed. In addition, the temperature may be set appropriately during the addition and mixing of the components, and heating and/or cooling may be performed for a part of the time or at all times. Further, the resin composition may be uniformly dispersed by stirring or shaking with a stirring device such as a mixer or a shaking device during or after the addition and mixing. In addition, the defoaming may be performed under low pressure conditions such as vacuum while stirring or shaking.
< Properties of resin composition >
The resin composition of the present invention comprises (A) an epoxy resin, (B) an active ester-based curing agent, and (C) an inorganic filler, wherein the content of the component (C) is 60 mass% or more, and the component (B) comprises (B1) a terminal sterically hindered active ester-based curing agent, assuming that the nonvolatile component in the resin composition is 100 mass%. By using such a resin composition, a cured product having excellent crack resistance can be obtained.
The cured product of the resin composition of the present invention may have a feature of being able to suppress the occurrence of cracks after the desmutting treatment (roughening treatment). Therefore, in one embodiment, after the circuit board is manufactured and desmear treated as in test example 3 below, when 100 copper pad portions of the circuit board are observed, the number of cracks may be preferably 10 or less (10% or less).
In one embodiment, the cured product of the resin composition of the present invention may have a characteristic that the dielectric loss tangent (Df) is suppressed to a low value. Accordingly, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8GHz and 23 ℃ as in test example 1 below may be preferably 0.010 or less, more preferably 0.008 or less, still more preferably 0.007 or less, still more preferably 0.005 or less, or 0.003 or less, particularly preferably 0.0025 or less, or 0.002 or less.
In one embodiment, the cured product of the resin composition of the present invention may have a characteristic of high glass transition temperature (Tg). Accordingly, in one embodiment, the glass transition temperature (Tg) when measured as in test example 2 below may be preferably 100℃or higher, more preferably 120℃or higher, still more preferably 130℃or higher, still more preferably 140℃or higher, particularly preferably 150℃or higher.
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) for forming the conductor layer (the conductor layer includes a rewiring layer) is provided. In addition, in a printed wiring board described later, it can be suitably used as: a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can be widely used in applications requiring a resin composition, such as a sheet-like laminate material such as a resin sheet or a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin, and a component embedding resin.
In addition, for example, in the case of manufacturing a semiconductor chip package 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 forming (a resin composition for a re-wiring layer forming) as an insulating layer for forming a re-wiring layer, and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). In manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer;
(1) A step of laminating a temporary fixing film on the base material,
(2) A step of temporarily fixing the semiconductor chip on the temporary fixing film,
(3) A step of forming a sealing layer on the semiconductor chip,
(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,
(5) A step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and
(6) And forming a rewiring layer as a conductor layer on the rewiring layer.
Further, the resin composition of the present invention can form an insulating layer having excellent embedding properties for a component, and therefore can be suitably applied to a case where a printed wiring board is a circuit board with a built-in component.
< sheet laminate >)
The resin composition of the present invention may be applied in the form of a varnish, but is generally preferably used in the form of a sheet laminate containing the resin composition in industry.
As the sheet-like laminate, a resin sheet or a prepreg shown below is preferable.
In one embodiment, a resin sheet includes a support, and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.
The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoints of thinning of the printed wiring board and providing a cured product of the resin composition which is excellent in insulation even if it 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 a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
When a film formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter, sometimes abbreviated as "PEN"), polycarbonates (hereinafter, sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfides (PES), polyether ketones, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and low-cost polyethylene terephthalate is particularly preferable.
In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
The surface of the support to be bonded to the resin composition layer may be subjected to a matting treatment, a corona treatment, or an antistatic treatment.
Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer can be used. As the release agent for the release layer of the support with a release layer, for example, 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins are exemplified. As the support having a release layer, commercially available ones can be used, and examples thereof include "SK-1", "AL-5", "AL-7", made by Wallike corporation, "LUMIRROR T60", made by Toli corporation, "Purex", made by Di people corporation, "Unipel" made by You Niji, and the like, which are PET films having a release layer composed mainly of an alkyd-based release agent.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In the case of using the support with a release layer, the thickness of the entire support with a release layer is preferably within the above range.
In one embodiment, the resin sheet may further include an optional layer as needed. Examples of the optional layer include a protective film selected for the support and provided on a surface of the resin composition layer that is not joined to the support (i.e., a surface opposite to 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, the surface of the resin composition layer can be prevented from being damaged by adhesion of refuse or the like.
The resin sheet can be produced, for example, by: the resin composition layer is formed by directly applying a liquid (varnish-like) resin composition to a support using a die coater or the like, or by dissolving a resin composition in an organic solvent to prepare a liquid (varnish-like) resin composition, applying the liquid (varnish-like) resin composition to a support using a die coater or the like, and drying the same.
The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of 1 or more than 2.
Drying can be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, and the drying is performed under such conditions that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. For example, when a resin composition containing 30 to 60 mass% of an organic solvent is used, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes, depending on the boiling point of the organic solvent in the resin composition.
The resin sheet may be wound into a roll and stored. In the case where the resin sheet has a protective film, the protective film can be peeled off for use.
In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous base material with the resin composition of the present invention.
The sheet-like fibrous base material used for the prepreg is not particularly limited, and a base material commonly used as a base material for the prepreg, such as a glass cloth, an aramid nonwoven fabric, and a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, 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 more 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 by a method including the following steps (I) and (II), for example, using the resin sheet described above;
and (I) laminating a resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate, and (II) curing (e.g., thermally curing) the resin composition layer to form an insulating layer.
The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, an intermediate product to be further formed into an insulating layer and/or a conductor layer at the time of manufacturing a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.
Lamination of the inner substrate and the resin sheet can be performed by, for example, thermally pressing the resin sheet against the inner substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the heat and pressure bonding member is not directly pressed against the resin sheet but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.
Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heat press-bonding temperature is preferably in the range of 60℃to 160℃and more preferably 80℃to 140℃and the heat press-bonding pressure is preferably in the range of 0.098MPa to 1.77MPa and more preferably 0.29MPa to 1.47MPa, and the heat press-bonding time is preferably in the range of 20 seconds to 400 seconds and more preferably 30 seconds to 300 seconds. The lamination is preferably 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 pressurized laminators manufactured by the company name machine, vacuum applicators (vacuum applicator) manufactured by Nikko-Materials, and batch vacuum pressurized laminators.
After lamination, the heat and pressure bonding member is pressed from the support body side at normal pressure (atmospheric pressure), for example, whereby the laminated resin sheets can be smoothed. The pressing conditions for the smoothing treatment may be set to the same conditions as those for the above-described lamination of the heat press-bonding. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator described above.
The support may be removed between the step (I) and the step (II), or may be removed after the step (II).
In the step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and those generally employed in forming an insulating layer of a printed wiring board can be used.
For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition, etc., and in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, still more preferably 170 to 210 ℃. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.
The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer 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℃and preferably 60℃to 115℃and 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. The steps (III) to (V) may be performed according to various methods known to those skilled in the art for producing 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). The insulating layer and the conductor layer in the steps (II) to (V) may be formed repeatedly as necessary, thereby forming a multilayer wiring board.
In other embodiments, the printed wiring board of the present invention may be manufactured using the prepreg described above. The production method is basically the same as in the case of using a resin sheet.
The step (III) is a step of forming a hole in the insulating layer, whereby a through hole, a through hole (through hole), or the like can be formed in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.
The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), the removal of the contamination is also performed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions generally used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid.
The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and as the alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Anmeite Japan Co., ltd. The swelling treatment with the swelling liquid is not particularly limited, and for example, the insulating layer may be immersed in the swelling liquid at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of controlling the swelling of the resin of the insulating layer to an appropriate level, it is preferable to impregnate the insulating layer with a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.
The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Anmei Japanese Kogyo Co., ltd.
The neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction solution Securiganth P" manufactured by ameter japan.
The treatment with the neutralizing solution may be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of handling, etc., a method of immersing the object subjected to roughening treatment with an oxidizing agent in a neutralizing liquid at 40 to 70 ℃ for 5 to 20 minutes is preferable.
In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, but 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 roughened insulating layer surface 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 arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.
The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 1 or more metals selected from 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 above metals (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, more preferably a single metal layer of copper, is preferable from the viewpoints of versatility of conductor layer formation, cost, ease of pattern formation, and the like.
The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more layers of 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 to be connected to the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel-chromium alloy.
The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the desired printed wiring board.
In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer may be plated by a conventionally known technique such as a half-addition method or a full-addition method to form a conductor layer having a desired wiring pattern, and it is preferably formed by a half-addition method from the viewpoint of ease of production. Hereinafter, an example of forming a conductor layer by a half-additive method is shown.
First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer so as to expose a part of the plating seed layer in accordance with the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.
In other embodiments, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed 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 for step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method using a metal foil on the insulating layer.
The metal foil can be produced by a known method such as electrolysis or rolling. Examples of the commercial products of the metal foil include HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil, etc. manufactured by JX Nitshi metal Co., ltd.
Semiconductor device
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, two-wheeled motor vehicles, automobiles, electric trains, ships, aircraft, and the like).
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. In the following, unless otherwise indicated, "part" and "%" indicating amounts refer to "part by mass" and "% by mass", respectively. The temperature condition in the case where the temperature is not specified is room temperature (23 ℃), and the pressure condition in the case where the pressure is not specified is atmospheric pressure (1 atm).
Synthesis example 1: preparation of active ester A (terminal sterically hindered ester curing agent)
To a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 492 parts by mass of p-tert-amylphenol, 200 parts by mass of toluene, 130 parts by mass of divinylbenzene (purity of divinylbenzene: 81%, containing 19% of ethyl styrene), and 1 part by mass of p-toluenesulfonic acid monohydrate were charged. The contents of the flask were heated to 120℃with stirring, and stirred at 120℃for 1 hour to react. After the completion of the reaction, 1 part by mass of a 49% aqueous sodium hydroxide solution was added to neutralize the reaction mixture, 400 parts by mass of toluene was added thereto, and the mixture was washed 3 times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure to obtain 601 parts by mass of a mixture (1) comprising unreacted p-tert-amylphenol and a phenolic hydroxyl group-containing resin (A-1).
To a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 152 parts by mass of isophthaloyl dichloride and 1000 parts by mass of toluene were charged, and the inside of the system was dissolved while being subjected to a nitrogen substitution under reduced pressure. Then, 297 parts by mass of the mixture (1) obtained above was added, and the inside of the system was dissolved while being subjected to nitrogen substitution under reduced pressure. 0.4g of tetrabutylammonium bromide was added thereto, and the reaction system was controlled to 60℃or lower while purging with nitrogen gas, and 300 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued in this state for 1 hour to allow the reaction. After the completion of the reaction, the reaction mixture was allowed to stand for separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and after stirring and mixing for about 15 minutes, the mixture was left to stand for separation, and the aqueous layer was removed. After this operation was repeated until the pH of the aqueous layer became 7, toluene and the like were distilled off under heating and reduced pressure to obtain 409 parts by mass of active ester A. The active ester equivalent of the active ester A obtained was 271. The active ester A was prepared as a solution of 70 mass% of a nonvolatile component with toluene, and used for the preparation of the resin composition of examples.
(gel permeation chromatography (GPC) of active ester A)
GPC chart of the active ester A is shown in FIG. 1.
The measurement conditions were as follows.
Measurement device: HLC-8420GPC manufactured by Tosoh Co., ltd "
Column: the protective column "HXL-L" manufactured by Tosoh corporation+TSK-GEL SuperHZ2000 "manufactured by Tosoh corporation+TSK-GEL SuperHZ3000" manufactured by Tosoh corporation+TSK-GEL SuperHZ4000 "manufactured by Tosoh corporation"
A detector: RI (differential refractometer)
And (3) data processing: "GPC WorkStation EcoSEC-workbench" manufactured by Tosoh Co., ltd "
Column temperature: 40 DEG C
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35 ml/min
Standard: the following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of "GPC station EcoSEC-workbench".
Sample and assay: the sample was diluted with a tetrahydrofuran solution under conditions such that the resin solid content was 0.2 mass%, and 10. Mu.L of the sample was filtered with a microfilter.
(Infrared spectroscopic analysis (IR) of active ester A)
The IR diagram of the active ester a is shown in figure 2.
The measurement conditions were as follows.
Measurement device: FT/IR-4600 manufactured by Kaiki Kaisha
The measuring method comprises the following steps: KBr plate method, transmission measurement
Sample and assay: the sample was prepared by diluting with a tetrahydrofuran solution under the condition of 10 mass% in terms of the resin solid content. The sample was dropped onto KBr plate at 0.1ml and THF and H were allowed to dry in an oven at 100deg.C 2 After drying for 10 minutes, transmission measurements were performed.
< synthetic example 2: synthesis of active ester B (terminal o-cresol type ester curing agent)
320g (2.0 mol) of 2, 7-dihydroxynaphthalene, 184g (1.7 mol) of benzyl alcohol, and 5.0g of p-toluenesulfonic acid monohydrate were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, and stirred while blowing nitrogen gas at room temperature. Then, the temperature was raised to 150℃and the water thus produced was distilled off to the outside 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 to neutralize the mixture, and then the aqueous layer was removed by separation, and the mixture was washed with 280g of water 3 times, and methyl isobutyl ketone was removed under reduced pressure to obtain 460g of benzyl-modified naphthalene compound (A-1). The obtained benzyl-modified naphthalene compound (A-1) was a black solid, and the hydroxyl equivalent was 180 g/equivalent.
To a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 203.0g (mole number of acyl chloride groups: 2.0 mole) of isophthaloyl chloride and 1400g of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Next, 72.4g (0.67 mol) of o-cresol and 240g (number of moles of phenolic hydroxyl groups: 1.33 mol) of benzyl-modified naphthalene compound (A-1) were added, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve the same. Then, 0.70g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60℃or lower while 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. Further, 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 became 7. Then, the water was removed by decantation and dehydration, whereby active ester B was obtained in the form of a toluene solution having a nonvolatile content of 61.5 mass%. The active ester equivalent of the active ester B obtained was 206g/eq.
< synthesis example 3: synthesis of active ester C (terminal o-phenylphenol ester curing agent)
To a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 203.0g (mole number of acyl chloride groups: 2.0 mole) of isophthaloyl chloride and 1400g of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Then, 113.9g (0.67 mol) of o-phenylphenol and 240g (number of moles of phenolic hydroxyl groups: 1.33 mol) of benzyl-modified naphthalene compound (A-1) were added, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve the same. Then, 0.70g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60℃or lower while 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. Further, 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 became 7. Then, the water was removed by decantation and dehydration, whereby active ester C was obtained in the form of a toluene solution containing 65 mass% of nonvolatile components. The active ester equivalent of the active ester C obtained was 238g/eq.
< synthetic example 4: synthesis of active ester D (terminal styrenated phenol type ester curing agent)
To a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 203.0g (mole number of acyl chloride groups: 2.0 mole) of isophthaloyl chloride and 1400g of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Next, 132.7g (0.67 mol) of styrenated phenol (styrene addition reaction product of phenol, "SP" manufactured by Sanguang Co., ltd.) and 240g (mol of phenolic hydroxyl group: 1.33 mol) of benzyl-modified naphthalene compound (A-1) were added, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.70g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60℃or lower while 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. Further, 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 became 7. Then, the water was removed by decantation and dehydration, whereby active ester D was obtained in the form of a toluene solution containing 65 mass% of nonvolatile components. The active ester equivalent of the active ester D obtained was 259g/eq.
Example 1 >
6 parts of epoxy resin "ESN475V" (manufactured by Nitro chemical materials Co., ltd., epoxy equivalent: about 330 g/eq.) and 4 parts of epoxy resin "HP-4032-SS" (manufactured by DIC Co., ltd., epoxy equivalent: about 144 g/eq.) were dissolved in 10 parts of Methyl Ethyl Ketone (MEK) to obtain an epoxy resin solution.
To the obtained epoxy resin solution were added 11 parts of the active ester A (a sterically hindered ester curing agent at the end, a toluene solution containing 70 mass% of nonvolatile components), 11 parts of a naphthol-terminated active ester curing agent at the end (HPC-8150-62T, manufactured by DIC Co., ltd., active ester equivalent 229, a toluene solution containing 61.5 mass% of nonvolatile components), 65 parts of spherical silica surface-treated with an amine alkoxysilane compound (KBM 573, manufactured by Xinyue chemical Co., ltd.) (SO-C2, manufactured by Sangya Co., ltd., average particle diameter: 0.77 μm) and 0.2 part of an imidazole curing accelerator (manufactured by Sikukukukukuku Kao Co., ltd. "1B2 PZ"), and the mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish-like resin composition.
Example 2 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 11 parts of a terminal naphthol-type active ester curing agent (HPC-8000-65T, manufactured by DIC Co., ltd.) was used instead of 11 parts of a terminal naphthol-type active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.) and that the active ester equivalent weight was 223 and the nonvolatile content was 65% by mass.
Example 3 >
A varnish-like resin composition was produced in the same manner as in example 1, except that the amount of spherical silica (SO-C2, manufactured by yaku ma, ltd.) was changed from 65 parts to 70 parts, the amount of imidazole-based curing accelerator (1B 2PZ, manufactured by siku ma, ltd.) was changed from 0.2 parts to 0.02 parts, and 2 parts of phenol-based curing agent (LA-3018-50P, manufactured by DIC, ltd.) and 1 part of carbodiimide-based curing agent (V-03, manufactured by riqing spinning chemical, ltd.) were further added, respectively.
Example 4 >
A varnish-like resin composition was produced in the same manner as in example 2, except that the amount of spherical silica (SO-C2, manufactured by yaku ma, ltd.) was changed from 65 parts to 70 parts, the amount of imidazole-based curing accelerator (1B 2PZ, manufactured by daku ma, ltd.) was changed from 0.2 parts to 0.02 parts, and 2 parts of phenol-based curing agent (LA-3018-50P, manufactured by DIC, ltd.) and 1 part of carbodiimide-based curing agent (V-03, manufactured by riken, ltd.) were further added, the phenol equivalent 151, and the nonvolatile content was 50 mass% of 1-methoxy-2-propanol solution.
Example 5 >
A varnish-like resin composition was prepared in the same manner as in example 3 except that the amount of spherical silica (SO-C2, manufactured by yaku ma, ltd.) was changed from 70 parts to 35 parts, and 35 parts of hollow silica (BA-S, manufactured by yaku catalyst chemical Co., ltd., average particle diameter 2.6 μm, and porosity 25 vol%) surface-treated with an amine alkoxysilane compound (KBM 573, singe chemical industry Co., ltd.) was further added.
Example 6 >
A varnish-like resin composition was prepared in the same manner as in example 5, except that the amount of active ester A (terminal sterically hindered ester curing agent) obtained in Synthesis example 1 was changed from 11 parts to 22 parts without using the terminal naphthol-type active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.).
Example 7 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 11 parts of the active ester B (terminal o-cresol type active ester curing agent, toluene solution containing 65% by mass of nonvolatile components) obtained in Synthesis example 2 was used instead of 11 parts of the terminal naphthol type active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.).
Example 8 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 11 parts of the active ester C (terminal o-phenylphenol-type active ester curing agent, toluene solution containing 65% by mass of nonvolatile components) obtained in Synthesis example 3 was used instead of 11 parts of the terminal naphthol-type active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.).
Example 9 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 11 parts of the active ester D (a terminal styrenated phenol type active ester curing agent, a toluene solution containing 65 mass% of nonvolatile components) obtained in Synthesis example 4 was used instead of 11 parts of the terminal naphthol type active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.).
Comparative example 1 >
A varnish-like resin composition was prepared in the same manner as in example 1, except that the active ester A (terminal sterically hindered ester curing agent) obtained in Synthesis example 1 was not used and the amount of the terminal naphthol-type active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.) used was changed from 11 parts to 22 parts.
Comparative example 2 >
A varnish-like resin composition was prepared in the same manner as in example 2, except that the active ester A (terminal sterically hindered ester curing agent) obtained in Synthesis example 1 was not used and the amount of the terminal naphthol-type active ester curing agent (HPC-8000-65T, manufactured by DIC Co., ltd.) used was changed from 11 parts to 22 parts.
Comparative example 3 >
A varnish-like resin composition was prepared in the same manner as in example 3, except that the active ester A (terminal sterically hindered ester curing agent) obtained in Synthesis example 1 was not used and the amount of the terminal naphthol-type active ester curing agent (HPC-8150-62T, manufactured by DIC Co., ltd.) used was changed from 11 parts to 22 parts.
Comparative example 4 >
A varnish-like resin composition was prepared in the same manner as in example 4, except that the active ester A (terminal sterically hindered ester curing agent) obtained in Synthesis example 1 was not used and the amount of the terminal naphthol-type active ester curing agent (HPC-8000-65T, manufactured by DIC Co., ltd.) used was changed from 11 parts to 22 parts.
Preparation example 1: resin sheet having a thickness of 40 μm of the resin composition layer
As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindeke Co., ltd., thickness: 38 μm) having a release layer was prepared. The resin compositions obtained in examples and comparative examples were uniformly applied onto the release layer of the support under such conditions that the thickness of the dried resin composition layer became 40. Mu.m. Then, the resin composition was dried at 80 to 100 ℃ (average 90 ℃) for 4 minutes to obtain a resin sheet comprising a support and a resin composition layer.
Preparation example 2: resin sheet having a thickness of 25 μm of the resin composition layer
The resin compositions obtained in examples and comparative examples were uniformly applied under the condition that the thickness of the dried resin composition layer became 25. Mu.m, and dried at 70℃to 80℃for 2.5 minutes, to obtain a resin sheet comprising a support and a resin composition layer, in the same manner as in production example 1.
Test example 1: determination of dielectric loss tangent (Df) and dielectric constant (Dk)
The resin sheet having a thickness of 40 μm produced in production example 1 was heated at 190℃for 90 minutes, and the resin composition layer was thermally cured. Then, the support is peeled off to obtain a cured product of the resin composition. The cured product was cut into test pieces having a width of 2mm and a length of 80 mm. For this test piece, dielectric loss tangent (Df) and dielectric constant (Dk) were measured by a cavity perturbation method using "HP8362B" manufactured by Agilent technologies Co., ltd. Under conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃. The average value of the 3 test pieces measured is shown in table 1 below.
Test example 2: determination of glass transition temperature (Tg)
The cured product prepared in test example 1 was cut out to have a length of 20mm and a width of 6mm as evaluation samples. For each evaluation sample, the glass transition temperature (Tg) was measured by heating from 25 ℃ to 250 ℃ at a heating rate of 5 ℃/min using a TMA device manufactured by the company corporation. For the same test piece, 2 determinations were performed, and the value of the 2 nd time was recorded.
Test example 3: evaluation of crack resistance after desmear treatment
The resin sheet having a thickness of 25 μm produced in production example 2 was laminated on both surfaces of the inner substrate by bonding the resin composition layer to the inner substrate using a batch vacuum press laminator (grade 2 stack laminator "CVP700" manufactured by Nikko Materials Co., ltd.) to form round copper pads (copper thickness 35 μm) having a diameter of 350 μm into a lattice shape at 400 μm intervals so that the copper residue ratio became 60% (E705 GR manufactured by Hitachi chemical industries Co., ltd., thickness 400 μm). The lamination is carried out by: after the pressure was reduced to 13hPa or less for 30 seconds, the pressure was applied at 100℃under a pressure of 0.74MPa for 30 seconds. It was put into an oven at 130 ℃ for 30 minutes heating, and then transferred into an oven at 170 ℃ for 30 minutes heating. The support layer was further peeled off, and the obtained circuit board was immersed in Swelling Dip Securiganth P of Anmei Japanese Co., ltd., as a swelling liquid, at 60℃for 10 minutes. Next, the mixture was subjected to a roughening treatment in an aqueous solution of Concentrate Compact P (KMnO 4 :60g/L, naOH:40g/L in water) was immersed in the solution at 80℃for 30 minutes. Finally, the resultant solution was immersed in Reduction solution Securiganth P made by Anmei Japanese Co., ltd. As a neutralizing solution at 40℃for 5 minutes. The copper pad portions of the circuit board after 100 roughening treatments were observed to confirm the presence or absence of cracks in the resin composition layer. If the number of cracks is 10 or less, it is determined as good, and if it is more than 10, it is determined as x.
The amounts of raw materials used, and the measurement results and evaluation results of the test examples, which are contained in the resin compositions of the examples and comparative examples, are summarized in table 1 below.
TABLE 1
From the results shown in Table 1, it was found that when a resin composition containing the (B1) terminal sterically hindered active ester curing agent was used, a cured product having excellent crack resistance was obtained as compared with a resin composition containing no (B1) terminal sterically hindered active ester curing agent. In addition, when a resin composition containing (B1) a terminal sterically hindered active ester type curing agent and further containing (B2) another active ester type curing agent is used, a cured product excellent in glass transition temperature can be obtained. Examples 5 and 6 using hollow silica as the component (C) have lower dielectric constants than examples 3 and 4, and are more preferable.
The present application is based on Japanese patent application No. 2021-138354 (application day: month 8, 26 of 2021), filed by the Japanese patent office, which is incorporated herein in its entirety.

Claims (20)

1. A resin composition comprising (A) an epoxy resin, (B) an active ester-based curing agent, and (C) an inorganic filler, wherein,
when the nonvolatile content in the resin composition is set to 100 mass%, the content of the component (C) is 60 mass% or more,
(B) The components comprise: (B1) An active ester curing agent having a structure represented by the formula (B1-1),
in the method, in the process of the invention,
R 1a r is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents;
R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 2 each independently represents a substituent;
a represents 0, 1 or 2;
* Indicating the binding site.
2. The resin composition according to claim 1, wherein the component (B1) comprises an active ester curing agent having a structure represented by the formula (B1-2B) in addition to the structure represented by the formula (B1-1),
In the method, in the process of the invention,
R 1a r is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents;
R 1c represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 2 each independently represents a substituent;
R 3 each independently represents a hydrogen atom or a methyl group;
ring X 1 Represents an aromatic carbocyclic ring optionally having a substituent;
a represents 0, 1 or 2;
* Indicating the binding site.
3. The resin composition according to claim 1, wherein the component (B1) comprises a resin represented by the formula (B1 c),
in the method, in the process of the invention,
R 1a r is R 1b Each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, or R 1a R is R 1b Taken together to form a non-aromatic carbocyclic ring optionally having substituents;
R 1c each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 2 each independently represents a substituent;
R 3 each independently represents a hydrogen atom or a methyl group;
ring X 1 Ring Y 1 Each independently represents an aromatic carbocyclic ring optionally having a substituent;
a each independently represents 0, 1 or 2;
b represents an integer of 0 or 1 or more.
4. The resin composition according to claim 1, wherein the content of the component (B1) is 3 to 20% by mass based on 100% by mass of the nonvolatile component in the resin composition.
5. The resin composition according to claim 1, wherein component (B) further comprises: (B2) An active ester curing agent having a structure represented by the formula (B2-1),
in the method, in the process of the invention,
with respect to R 4 、R 5 R is R 6 ，(1)R 4 Represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-, and R 5 R is R 6 Each independently represents a hydrogen atom or a substituent, (2) R 4 R is R 5 Taken together to form an optionally substituted aromatic carbocyclic ring, and R 6 Represents a hydrogen atom or a substituent, or (3) R 5 R is R 6 Taken together to form an optionally substituted aromatic carbocyclic ring, and R 4 Represents a hydrogen atom, a halogen atom, a methyl group, or R 41 -A-；
R 7 R is R 8 Each independently represents a hydrogen atom or a substituent;
R 41 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
a represents-CH 2 -、-CH(CH 3 ) -, -CO-, or-O-;
* Indicating the binding site.
6. The resin composition according to claim 1, wherein the content of the component (A) is 1 to 20% by mass based on 100% by mass of the nonvolatile component in the resin composition.
7. The resin composition according to claim 1, wherein the content of the component (B) is 12% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition.
8. The resin composition according to claim 1, wherein the component (C) is silica.
9. The resin composition according to claim 1, wherein the content of the component (C) is 70% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
10. The resin composition according to claim 1, further comprising (D) a curing accelerator.
11. The resin composition according to claim 1, further comprising a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
12. The resin composition according to claim 1, wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.003 or less when measured at 5.8GHz and 23 ℃.
13. The resin composition according to claim 1, wherein a glass transition temperature (Tg) of a cured product of the resin composition is 140℃or higher.
14. The resin composition according to claim 1, which is used for forming an insulating layer for forming a conductor layer.
15. The resin composition according to claim 1, which is used for forming an insulating layer of a printed wiring board.
16. A cured product of the resin composition according to any one of claims 1 to 15.
17. A sheet laminate comprising the resin composition according to any one of claims 1 to 15.
18. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 15 provided on the support.
19. A printed wiring board comprising an insulating layer formed of the cured product of the resin composition according to any one of claims 1 to 15.
20. A semiconductor device comprising the printed wiring board according to claim 19.
CN202280057106.8A 2021-08-26 2022-08-25 Resin composition Pending CN117881715A (en)

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FR2865734B1 (en) 2004-02-03 2006-05-19 Servier Lab NOVEL BENZO [b] CHROMENO-NAPHTHYRIDIN-7-ONE AND PYRANO [2'3 ': 7,8] QUINO [2,3-b] QUINOXALIN-7-ONE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND PHARMACEUTICAL COMPOSITIONS WHICH CONTAIN THEM
TWI751266B (en) * 2017-03-24 2022-01-01 日商迪愛生股份有限公司 Active ester composition
JP7222320B2 (en) * 2019-06-25 2023-02-15 味の素株式会社 resin composition
JP2021014545A (en) 2019-07-12 2021-02-12 味の素株式会社 Resin composition
JP2020023714A (en) 2019-10-24 2020-02-13 積水化学工業株式会社 Resin material and multilayer printed board
JP7351201B2 (en) * 2019-11-29 2023-09-27 味の素株式会社 resin composition
JP7402681B2 (en) * 2019-12-27 2023-12-21 太陽ホールディングス株式会社 Curable resin compositions, dry films, copper foils with resin, cured products, and electronic components

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