CN116987364A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN116987364A
CN116987364A CN202310489251.XA CN202310489251A CN116987364A CN 116987364 A CN116987364 A CN 116987364A CN 202310489251 A CN202310489251 A CN 202310489251A CN 116987364 A CN116987364 A CN 116987364A
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China
Prior art keywords
resin composition
mass
resin
curing agent
less
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CN202310489251.XA
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Chinese (zh)
Inventor
中村洋介
渡边真俊
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN116987364A publication Critical patent/CN116987364A/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894—Materials of the insulating layers or coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/5329—Insulating materials
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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

Abstract

The invention aims to provide a resin composition capable of obtaining low minimum melt viscosity. The solution of the present invention is a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with a carbodiimide compound.

Description

Resin composition
Technical Field
The present invention relates to a resin composition and a method for producing the same. The present invention also relates to a cured product, a sheet-like laminate, a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device using the aforementioned resin composition.
Background
Insulating layers are generally provided in circuit substrates and semiconductor chip packages. For example, in a printed circuit board which is one type of a circuit board, an interlayer insulating layer may be provided as an insulating layer. In addition, for example, in a semiconductor chip package, a rewiring forming layer may be provided as an insulating layer. These insulating layers can be formed by a cured product obtained by curing a resin composition (patent documents 1 and 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2020-136542
Patent document 2: japanese patent laid-open No. 2020-63392
Disclosure of Invention
Problems to be solved by the invention
In recent years, the density of wiring of circuit boards and semiconductor chip packages has been increased. Therefore, from the viewpoint of embedding a fine wiring resin composition without any gap and achieving high performance and high reliability of a semiconductor device, it is required to develop a technique capable of reducing the minimum melt viscosity of the resin composition.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin composition capable of obtaining a low minimum melt viscosity and a method for producing the same; a cured product of the resin composition; a sheet-like laminate and a resin sheet each comprising the resin composition; a circuit board, a semiconductor chip package and a semiconductor device comprising a cured product of the resin composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-described problems. As a result, the present inventors have found that the above-described problems can be solved by combining a resin composition comprising an epoxy resin, a curing agent, and an inorganic filler subjected to a specific surface treatment, and have completed the present invention.
Namely, the present invention includes the following.
[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with a carbodiimide compound.
[2] The resin composition according to [1], wherein the carbodiimide compound contains a structural unit represented by the following formula (C-1),
[ chemical 1]
(in the formula (C-1), Y represents a 2-valent hydrocarbon group optionally having a substituent).
[3] The resin composition according to [1] or [2], wherein the carbodiimide compound contains an ethylenically unsaturated bond.
[4] The resin composition according to any one of [1] to [3], wherein the amount of the component (C) is 50% by mass or more relative to 100% by mass of the nonvolatile component of the resin composition.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) contains 1 or more selected from the group consisting of an active ester-based curing agent, a phenol-based curing agent and a cyanate-based curing agent.
[6] The resin composition according to any one of [1] to [5], which comprises (D) a curing accelerator.
[7] The resin composition according to any one of [1] to [6], which comprises (E) a thermoplastic resin.
[8] The resin composition according to any one of [1] to [7], which has a minimum melt viscosity of less than 2000 poise.
[9] The resin composition according to any one of [1] to [8], wherein when the resin composition is heated at 200℃for 90 minutes to obtain a cured product, the cured product has a breaking point elongation of 1% or more.
[10] The resin composition according to any one of [1] to [9], wherein when the resin composition is heated at 170℃for 30 minutes to obtain a cured product, and the cured product is subjected to roughening treatment, the cured product has an arithmetic average roughness Ra of less than 300 nm.
[11] The resin composition according to any one of [1] to [10], which is used for forming an insulating layer.
[12] The cured product of the resin composition according to any one of [1] to [11 ].
[13] A sheet laminate comprising the resin composition according to any one of [1] to [11 ].
[14] A resin sheet having a support and a resin composition layer formed on the support,
the resin composition layer comprising the resin composition of any one of [1] to [11 ].
[15] A circuit board comprising a cured product of the resin composition according to any one of [1] to [11 ].
[16] A semiconductor chip package comprising a cured product of the resin composition according to any one of [1] to [11 ].
[17] A semiconductor device having the circuit board according to [15 ].
[18] A semiconductor device having the semiconductor chip package of [16 ].
[19] A method for producing a resin composition, comprising:
a first step of mixing a carbodiimide compound with an inorganic filler to obtain (C) an inorganic filler surface-treated with a carbodiimide compound; and
A second step of mixing (C) an inorganic filler surface-treated with a carbodiimide compound, (A) an epoxy resin, and (B) a curing agent.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resin composition capable of obtaining a low minimum melt viscosity and a method for producing the same can be provided; a cured product of the resin composition; a sheet-like laminate and a resin sheet each comprising the resin composition; a circuit board, a semiconductor chip package and a semiconductor device comprising a cured product of the resin composition.
Drawings
Fig. 1 is a cross-sectional view schematically showing a Fan-out WLP as an example of a semiconductor chip package according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments and examples of the present invention will be described. However, the present invention is not limited to the embodiments and examples described below, and may be modified and implemented arbitrarily without departing from the scope of the claims and their equivalents.
In the following description, the term "optionally substituted" as used with respect to a compound or group refers to both the case where a hydrogen atom of the compound or group is unsubstituted and the case where a part or all of hydrogen atoms of the compound or group are substituted with substituents.
In the following description, the term "(meth) acrylic" includes acrylic acid, methacrylic acid, and combinations thereof. Furthermore, the term "(meth) acrylate" includes acrylates, methacrylates, and combinations thereof.
In the following description, the term "dielectric constant" means a relative dielectric constant unless otherwise specified.
[ overview of resin composition ]
The resin composition according to one embodiment of the present invention comprises (a) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with a carbodiimide compound. "(C) inorganic filler surface-treated with carbodiimide Compound" hereinafter sometimes referred to as "(C) treated filler".
The resin composition according to one embodiment of the present invention may have a low minimum melt viscosity. Further, according to the resin composition according to one embodiment of the present invention, a cured product having excellent mechanical strength, for example, a cured product having a large elongation at break point can be obtained. Further, according to the resin composition according to one embodiment of the present invention, a cured product that can reduce the surface roughness after the roughening treatment can be generally obtained. Further, the cured product of the resin composition according to one embodiment of the present invention can generally reduce dielectric characteristics such as the relative permittivity and the dielectric loss tangent.
The present inventors speculate that the resin composition according to one embodiment of the present invention provides the excellent effects as described above. However, the scope of the present invention is not limited to the mechanism described below.
By performing the surface treatment with the carbodiimide compound, the filler (C) can have high miscibility with the resin components such as (a) the epoxy resin and (B) the curing agent. The carbodiimide compound can be reacted with (a) an epoxy resin, and further, can be reacted with (B) a curing agent or the like which can react with (a) an epoxy resin. Therefore, the filler (C) surface-treated with the carbodiimide compound can undergo a large interaction with a large number of components in the resin composition containing the epoxy resin (A) and the curing agent (B). Therefore, the resin composition can have high uniformity, and thus can exhibit high fluidity in a molten state, and thus can reduce the minimum melt viscosity. Further, the resin composition has high uniformity, and thus can suppress local formation of portions different in composition. Therefore, since the fracture starting from the portion can be suppressed when stress is applied, mechanical strength such as elongation at break point can be improved. Further, as described above, since the formation of the portions having different compositions can be suppressed locally, roughening can be performed uniformly at a high level during the roughening treatment. Therefore, in the roughening treatment, the removal or the residue of large blocks is generally suppressed, and thus the surface roughness can be reduced.
[ (A) epoxy resin ]
The resin composition according to one embodiment of the present invention contains (a) an epoxy resin as the component (a). (A) The epoxy resin may be a curable resin having an epoxy group.
Examples of the epoxy resin (a) include a bixylenol 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-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidol amine type epoxy resin, a glycidyl ester 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 type epoxy resin, and the like. (A) The epoxy resin may be used alone or in combination of 1 or more than 2.
(A) The epoxy resin preferably contains an epoxy resin having an aromatic structure from the viewpoint of obtaining a cured product excellent in heat resistance. The aromatic structure refers to a chemical structure generally defined as aromatic, and also includes polycyclic aromatic and aromatic heterocyclic rings. Examples of the epoxy resin having an aromatic structure include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, xylenol type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, glycidylester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic type epoxy resin, spiro ring-containing epoxy resin having an aromatic structure, cyclohexane dimethanol type epoxy resin having an aromatic structure, naphthalene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, tetraphenyl ethane type epoxy resin having an aromatic structure, and the like.
The resin composition preferably contains, as the (a) epoxy resin, an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, based on 100% by mass of the nonvolatile component of the (a) epoxy resin.
Among the epoxy resins, there are epoxy resins that are liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resins"). The resin composition may contain, as the epoxy resin, 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.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.
The liquid epoxy resin is preferably bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, or epoxy resin having a butadiene structure.
Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC corporation; "828US", "828EL", "jER828EL", "825", "EPIKOTE 828EL" manufactured by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ED-523T" (glycerol type epoxy resin) manufactured by ADEKA Co; "EP3950L" and "EP3980S" manufactured by ADEKA corporation (glycidylamine type epoxy resins); "EP4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co., ltd; the "ZX1059" manufactured by solar iron chemical company (a mixture of bisphenol a type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel corporation; "PB-3600" by Daicel corporation, and "JP-100" and "JP-200" by Nippon Caesada corporation (epoxy resin having butadiene structure); and "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) produced by solar chemical. The number of these may be 1 alone or 2 or more.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
The solid epoxy resin is preferably a xylenol-type epoxy resin, a naphthalene-type 4-functional epoxy resin, a naphthol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a 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, or a phenol benzopyrrolone-type epoxy resin.
Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700", "HP-4710" manufactured by DIC corporation (naphthalene type 4-functional epoxy resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" manufactured by DIC Co., ltd. (cresol novolak type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Co; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" manufactured by DIC; "EPPN-502H" (triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical pharmaceutical company; an ESN475V (naphthol type epoxy resin) manufactured by Equial company "ESN4100V" (naphthalene type epoxy); an "ESN485" (naphthol type epoxy resin) manufactured by solar iron chemical company; a solar chemical, ESN375 (dihydroxynaphthalene type epoxy resin) manufactured by the company of a large scale; "YX4000H", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "YX7700" manufactured by Mitsubishi chemical corporation (phenol aralkyl type epoxy resin); "PG-100", "CG-500" manufactured by Osaka gas chemistry Co., ltd; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Japanese chemical Co., ltd. The number of these may be 1 alone or 2 or more.
When the liquid epoxy resin and the solid epoxy resin are used in combination, the mass ratio of them (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 7:1 to 1:7.
(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 60g/eq to 3,000g/eq, still more preferably 80g/eq to 2,000g/eq, particularly preferably 110g/eq to 1,000 g/eq. The epoxy equivalent represents the mass of the resin of an average of 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.
(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
The amount of the epoxy resin (a) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less, relative to 100% by mass of the nonvolatile component in the resin composition. (A) When the amount of the epoxy resin is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the epoxy resin (a) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less, relative to 100% by mass of the resin component in the resin composition. The resin component of the resin composition means a component other than the inorganic filler such as the (C) treatment filler among the nonvolatile components of the resin composition. (A) When the amount of the epoxy resin is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
(A) The mass ratio of the epoxy resin to the filler (C) (i.e., the (a) epoxy resin/(C) filler) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.5 or less, and particularly preferably 0.2 or less. When the mass ratio ((a) epoxy resin/(C) treatment filler) is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
[ (B) curing agent ]
The resin composition according to one embodiment of the present invention contains a (B) curing agent as a (B) component. (B) The curing agent may have a function of reacting with the (a) epoxy resin to cure the resin composition. (B) Unless otherwise specified, the curing agent does not include any substance belonging to the component (A). (B) The curing agent may be used alone or in combination of 1 or more than 2.
Preferable examples of the curing agent (B) include an active ester curing agent, a cyanate curing agent, a phenol curing agent, a carbodiimide curing agent, an acid anhydride curing agent, an amine curing agent, a benzoxazine curing agent, and a thiol curing agent. Among them, the curing agent (B) particularly preferably contains 1 or more selected from the group consisting of an active ester curing agent, a phenolic curing agent and a cyanate curing agent.
As the active ester-based curing agent, generally, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, the active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and the active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or the naphthol 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, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, calcite, dicyclopentadiene type diphenol compound, phenol novolac, and the like. The "dicyclopentadiene type diphenol compound" herein means a diphenol compound obtained by condensing phenol 2 molecules on dicyclopentadiene 1 molecules.
Specifically, the active ester-based curing agent is preferably at least 1 selected from dicyclopentadiene-based active ester-based curing agents, naphthalene-based active ester-based curing agents containing naphthalene structures, active ester-based curing agents containing an acetyl compound of phenol novolac, and active ester-based curing agents containing a benzoyl compound of phenol novolac, and more preferably dicyclopentadiene-based active ester-based curing agents and naphthalene-based active ester-based curing agents. The dicyclopentadiene type active ester-based curing agent is preferably an active ester-based curing agent containing a dicyclopentadiene type diphenol structure.
Examples of the commercially available active ester curing agents include "EXB9451", "EXB9460S", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC); examples of the active ester-based curing agent having a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Co.); examples of the phosphorus-containing active ester curing agent include "EXB9401" (manufactured by DIC Co., ltd.); examples of the active ester-based curing agent of the acetyl compound of the phenol novolac include "DC808" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent of the benzoyl compound of the phenol novolac include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent containing a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by one company).
(A) When the number of epoxy groups of the epoxy resin is 1, the number of active ester groups of the active ester-based curing agent is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.2 or more, particularly preferably 0.5 or more, preferably 10 or less, more preferably 5 or less, still more preferably 2 or less. The "(a) epoxy resin epoxy number" means the total of the values obtained by dividing the mass of the nonvolatile components of the (a) epoxy resin present in the resin composition by the epoxy equivalent weight. The "number of active esters of the active ester-based curing agent" refers to the total of the mass of the nonvolatile components of the active ester-based curing agent present in the resin composition divided by the equivalent number of active ester groups. When the number of active esters of the active ester-based curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the active ester-based curing agent in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, particularly preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, relative to 100% by mass of the nonvolatile component of the resin composition. When the amount of the active ester-based curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the active ester-based curing agent in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, relative to 100% by mass of the resin component of the resin composition. When the amount of the active ester-based curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The mass ratio of the active ester-based curing agent to the filler (C) (active ester-based curing agent/(C) treated filler) is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.05 or more, particularly preferably 0.1 or more, preferably 0.5 or less, more preferably 0.4 or less, and further preferably 0.3 or less. When the mass ratio (active ester-based curing agent/(C) treatment filler) falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative permittivity and dielectric loss tangent can be generally made particularly good.
As the cyanate-based curing agent, a compound having 1 or more cyanate groups, preferably 2 or more cyanate groups, in 1 molecule can be used. Examples of the cyanate-based curing agent include bisphenol a dicyanate, polyphenylenecyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylidenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate-based) phenylpropane, 1-bis (4-cyanate-based) phenylmethane, bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate-phenyl) sulfide, bis (4-cyanate-phenyl) ether, and other 2-functional cyanate-based curing agents derived from phenol novolac and cresol novolac, and prepolymers obtained by partially triazinizing these cyanate-based curing agents. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" manufactured by the company of eun, both of which are phenol novolac type polyfunctional cyanate ester curing agents, "BA230" and "BA230S75" (prepolymer for forming a trimer obtained by triazinizing a part or the whole of bisphenol a dicyanate).
(A) When the number of epoxy groups of the epoxy resin is 1, the cyanate group number of the cyanate-based curing agent is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.2 or more, preferably 5 or less, more preferably 3 or less, still more preferably 1 or less. The "cyanate number of the cyanate ester-based curing agent" means a total of the mass of the nonvolatile components of the cyanate ester-based curing agent present in the resin composition divided by the cyanate ester equivalent weight. When the number of cyanate groups of the cyanate ester-based curing agent falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the cyanate ester-based curing agent in the resin composition is preferably 0.1 mass% or more, more preferably 1 mass% or more, still more preferably 5 mass% or more, preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less, based on 100 mass% of the nonvolatile component of the resin composition. When the amount of the cyanate ester-based curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the cyanate-based curing agent in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, relative to 100% by mass of the resin component of the resin composition. When the amount of the cyanate ester-based curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The mass ratio of the cyanate-based curing agent to the filler (C) (cyanate-based curing agent/(C) -based filler) is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.05 or more, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less. When the mass ratio (cyanate ester-based curing agent/(C-treated filler) falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative permittivity and dielectric loss tangent can be generally made particularly good.
(A) When the number of epoxy groups of the epoxy resin is 1, the total of the number of active esters of the active ester-based curing agent and the number of cyanate esters of the cyanate ester-based curing agent is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.5 or more, particularly preferably 1 or more, preferably 10 or less, still more preferably 5 or less, still more preferably 2 or less. When the total number of active esters of the active ester-based curing agent and the number of cyanate esters of the cyanate ester-based curing agent falls within the above-described range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, the mechanical strength such as the elongation at break point of the cured product of the resin composition, the surface roughness after the roughening treatment, and the dielectric characteristics such as the relative dielectric constant and the dielectric loss tangent can be made particularly good.
The total amount of the active ester curing agent and the cyanate curing agent in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, particularly preferably 15% by mass or more, preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, relative to 100% by mass of the nonvolatile component of the resin composition. When the total amount of the active ester-based curing agent and the cyanate-based curing agent falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, the mechanical strength such as the elongation at break point of the cured product of the resin composition, the surface roughness after the roughening treatment, and the dielectric properties such as the relative dielectric constant and the dielectric loss tangent can be generally made particularly good.
The total amount of the active ester-based curing agent and the cyanate-based curing agent in the resin composition is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more, particularly preferably 40 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, further preferably 60 mass% or less, based on 100 mass% of the resin component of the resin composition. When the total amount of the active ester-based curing agent and the cyanate-based curing agent falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, the mechanical strength such as the elongation at break point of the cured product of the resin composition, the surface roughness after the roughening treatment, and the dielectric properties such as the relative dielectric constant and the dielectric loss tangent can be generally made particularly good.
The mass ratio of the total amount of the active ester-based curing agent and the cyanate-based curing agent to the (C) -treated filler ("total amount of the active ester-based curing agent and the cyanate-based curing agent"/(C) -treated filler) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, particularly preferably 0.21 or more, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less. When the mass ratio ("total of active ester-based curing agent and cyanate ester-based curing agent"/(C) treatment filler) falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of the cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
As the phenolic curing agent, a compound having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in 1 molecule can be used. From the viewpoints of heat resistance and water resistance, a phenol-based curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, a phenol novolac-type curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851", NHN "," CBN "," GPH ", nippon chemical company," SN-170"," SN-180"," SN-190"," SN-475"," SN-485"," SN-495"," SN-375"," SN-395", and" LA-7052"," LA-7054"," LA-3018-50P "," LA-1356"," TD2090"," TD-2090-60M ", which are manufactured by Ming He Cheng Co.
(A) When the number of epoxy groups of the epoxy resin is 1, the phenolic hydroxyl group number of the phenolic curing agent is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less. "phenolic hydroxyl" refers to a hydroxyl group bonded to an aromatic ring. The term "phenolic hydroxyl group number of the phenolic curing agent" means a value obtained by dividing the mass of the non-volatile component of the phenolic curing agent present in the resin composition by the phenolic hydroxyl equivalent weight, and the total value is the total. When the phenolic hydroxyl number of the phenolic curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative permittivity and dielectric loss tangent can be made particularly good.
The amount of the phenolic curing agent in the resin composition is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, still more preferably 0.5 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 2 mass% or less, based on 100 mass% of the nonvolatile component of the resin composition. When the amount of the phenolic curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the phenolic curing agent in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, based on 100% by mass of the resin component of the resin composition. When the amount of the phenolic curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The mass ratio of the phenolic curing agent to the filler (C) (phenolic curing agent/(C) filler) is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less. When the mass ratio (phenolic curing agent/(C) treatment filler) falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be generally made particularly good.
(A) When the number of epoxy groups of the epoxy resin is 1, the total of the number of active esters of the active ester-based curing agent and the number of phenolic hydroxyl groups of the phenolic curing agent is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.2 or more, particularly preferably 1 or more, preferably 10 or less, still more preferably 5 or less, still more preferably 2 or less. When the total of the number of active esters of the active ester-based curing agent and the number of phenolic hydroxyl groups of the phenolic curing agent falls within the above-described range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, the mechanical strength such as the elongation at break point of the cured product of the resin composition, the surface roughness after the roughening treatment, and the dielectric properties such as the relative dielectric constant and the dielectric loss tangent can be made particularly good.
The total amount of the active ester-based curing agent and the phenolic curing agent in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, particularly preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, relative to 100% by mass of the nonvolatile component of the resin composition. When the total amount of the active ester-based curing agent and the phenolic curing agent falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be generally made particularly good.
The total amount of the active ester-based curing agent and the phenolic curing agent in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 65% by mass or less, relative to 100% by mass of the resin component of the resin composition. When the total amount of the active ester-based curing agent and the phenolic curing agent falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be generally made particularly good.
The mass ratio of the total amount of the active ester-based curing agent and the phenolic curing agent to the (C) -treated filler ("total amount of the active ester-based curing agent and the phenolic curing agent"/(C) -treated filler) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, particularly preferably 0.2 or more, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less. When the mass ratio ("total of active ester-based curing agent and phenolic curing agent"/(C) treatment filler) falls within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of the cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
As the carbodiimide-based curing agent, a compound having 1 or more carbodiimide groups in 1 molecule, preferably 2 or more carbodiimide groups can be used. Specific examples of the carbodiimide-based curing agent include aliphatic biscarbodiimides such as tetramethylene-bis (t-butylcarbodiimide) and cyclohexanedis (methylene-t-butylcarbodiimide); an aromatic dicarboximide such as phenylene-bis (xylyl carbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexyl carbodiimide), and poly (isophorone carbodiimide); and aromatic polycarbodiimides such as poly (phenylene carbodiimide), poly (naphthalene carbodiimide), poly (toluene carbodiimide), poly (methyl diisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylene carbodiimide), poly (tetramethylxylylene carbodiimide), poly (methylenediphenylene carbodiimide), poly [ methylenebis (methylphenyl) carbodiimide ], and the like. Examples of the commercial products of the carbodiimide-based curing agent include "chemical V-02B", "chemical V-03", "chemical V-04K", "chemical V-07" and "chemical V-09" manufactured by chemical company; the "oven" by the company "oven P", "oven P400", "oven 510", and the like.
As the acid anhydride-based curing agent, a compound having 1 or more acid anhydride groups in 1 molecule, preferably 2 or more acid anhydride groups, may be used. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic 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 (dehydrated trimellitate), styrene and maleic acid-copolymerized polymer-based maleic acid anhydride and the like. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by New Japan physical and chemical Co., ltd; "YH-306", "YH-307" manufactured by Mitsubishi chemical corporation; "HN-2200", "H-5500" manufactured by Hitachi chemical Co., ltd; "EF-30", "EF-40", "EF-60", "EF-80", etc. manufactured by the company UK.
As the amine-based curing agent, a compound having 1 or more, preferably 2 or more amino groups in 1 molecule can be used. Examples of the amine-based curing agent include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, and among these, aromatic amines are preferable. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. 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. Examples of the commercial products of the amine-based curing agent include SeikACURE-S manufactured by SeikACURE corporation; "KAYABOND C-200S", "KAYABOND C-100", "A-A", "a-B", "a-S" manufactured by japan chemical pharmaceutical company; "d" by Mitsubishi chemical corporation; "DTDA" manufactured by Sumitomo refinement Co., ltd.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE chemical company; "HFB2006M" manufactured by Showa Polymer Co., ltd; "P-d", "F-a", etc. manufactured by the chemical industry Co., ltd.
Examples of the thiol curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.
(B) The reactive group equivalent of the curing agent 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. Reactive group equivalent means the mass of the resin on average of 1 equivalent of reactive group.
(A) When the number of epoxy groups of the epoxy resin is 1, the number of active groups of the curing agent (B) is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.5 or more, particularly preferably 1 or more, preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. The "(number of reactive groups of (B) curing agent" means a value obtained by dividing the mass of the nonvolatile component of (B) curing agent present in the resin composition by the equivalent of reactive groups, and totaling all the values. (B) When the number of active groups of the curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the curing agent (B) in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, particularly preferably 15% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, relative to 100% by mass of the nonvolatile component of the resin composition. (B) When the amount of the curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount of the curing agent (B) in the resin composition is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, particularly preferably 50 mass% or more, preferably 90 mass% or less, more preferably 80 mass% or less, still more preferably 70 mass% or less, based on 100 mass% of the resin component of the resin composition. (B) When the amount of the curing agent is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
(B) The mass ratio of the curing agent to the (C) -treated filler ((B) curing agent/(C) -treated filler) is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.18 or more, particularly preferably 0.22, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less. When the mass ratio ((B) curing agent/(C) treatment filler) is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
[ (C) inorganic filler (treated filler) surface-treated with carbodiimide Compound ]
The resin composition according to one embodiment of the present invention contains a (C) -treated filler as the (C) component. (C) The treated filler is an inorganic filler surface-treated with a carbodiimide compound. (C) The treatment filler is generally contained in the resin composition in the form of particles.
(C) The treatment filler generally contains an inorganic filler as particles of an inorganic compound, and the surface of the inorganic filler may have a carbodiimide compound thereon. The carbodiimide compound may be bonded to the inorganic filler by chemical bond such as covalent bond or ionic bond, or may be attached to the inorganic filler by physical adsorption. The carbodiimide compound may be directly bonded or attached to the surface of the inorganic filler, or may be indirectly bonded or attached via other components such as an optional surface treatment agent. Here, the "direct" bonding or attachment of the carbodiimide compound to the surface of the inorganic filler means that no other component is present between the surface of the inorganic filler and the carbodiimide compound. In addition, the "indirect" bonding or attachment of the carbodiimide compound on the surface of the inorganic filler means that there are other components between the surface of the inorganic filler and the carbodiimide compound.
As the material of the inorganic filler contained in the filler (C), an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among these, silica and alumina are preferable, and 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. The inorganic filler may be used alone or in combination of 1 or more than 2.
The inorganic filler can be classified into a hollow inorganic filler having pores inside and a solid inorganic filler having no pores inside. As the inorganic filler, only a hollow inorganic filler, only a solid inorganic filler, or a combination of a hollow inorganic filler and a solid inorganic filler may be used. When a hollow inorganic filler is used, the relative dielectric constant of the cured product of the resin composition can be reduced in general.
Hollow inorganic filler materials have porosity and therefore typically have a porosity of greater than 0% by volume. From the viewpoint of reducing the relative dielectric constant of the cured product of the resin composition, the porosity of the hollow inorganic filler is preferably 5% by volume or more, more preferably 10% by volume or more, and particularly preferably 15% by volume or more. In addition, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the hollow inorganic filler is preferably 95% by volume or less, more preferably 90% by volume or less, and particularly preferably 85% by volume or less.
The porosity P (volume%) of a particle is defined as the volume basis ratio of the total volume of 1 or 2 or more pores (total volume of pores/volume of particle) existing inside the particle with respect to the volume of the whole particle based on the outer surface of the particle. The porosity P may be measured using the actual density of the particles D M (g/cm 3 ) And theoretical value D of the mass density of the particle-forming material T (g/cm 3 ) Calculated by the following formula (M1).
[ number 1]
The hollow inorganic filler can be produced by, for example, the methods described in japanese patent No. 5940188 and japanese patent No. 5864299, or a method based on the methods.
Examples of the commercial products of the inorganic filler (D) include "SP60-05", "SP507-05" manufactured by the company "delta; "YC100C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by admatechs; "UFP-30", "DAW-03", "FB-105FD" manufactured by Duhong; the frames include "wire NSS-3N", "wire NSS-4N", "wire NSS-5N" manufactured by the company of the end; the solar volatile catalyst is "Efstef-1", "BA-S" manufactured by Nissy catalyst formation Co; and "MG-005" and "organic film" manufactured by pacific camera company.
The average particle diameter of the inorganic filler 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, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, from the viewpoint of significantly obtaining the desired effect of the present invention.
The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie (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 diameter is recorded 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 in a vial and dispersing the mixture by ultrasonic waves for 10 minutes was used. The measurement sample was measured for volume-based particle size distribution of the inorganic filler by a flow cell method using a laser diffraction type particle size distribution measuring apparatus with the wavelength of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median diameter. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba corporation.
The specific surface area of the inorganic filler is preferably 0.1m from the viewpoint of significantly obtaining the desired effect of the present invention 2 Preferably at least/g, more preferably 0.5m 2 Preferably 1m or more, more preferably per gram 2 Preferably 3m or more per gram 2 Preferably 100m or more per gram 2 Less than/g, more preferably 70m 2 Preferably less than/g, more preferably 50m 2 Preferably less than/g, particularly preferably 40m 2 And/g or less. The specific surface area of the inorganic filler was obtained by adsorbing nitrogen gas onto the sample surface by a BET method using a specific surface area measuring device (Macsorb HM-1210 manufactured by the company of mek), and calculating the specific surface area by a BET multipoint method.
The inorganic filler may be used alone or in combination of at least 2 kinds.
The carbodiimide compound means a compound having 1 or more carbodiimide groups (-n=c=n-) in 1 molecule. The number of carbodiimide groups in 1 molecule of the carbodiimide compound is preferably 2 or more. The carbodiimide compound may be used alone or in combination of 1 or more than 2.
The carbodiimide compound preferably contains a structural unit represented by the following formula (C-1).
[ chemical 2]
In the formula (C-1), Y represents a 2-valent hydrocarbon group optionally having a substituent. The number of carbon atoms of the 2-valent hydrocarbon group in Y is usually 1 or more, preferably 2 or more, and usually 30 or less. The 2-valent hydrocarbon group may be a 2-valent saturated hydrocarbon group or a 2-valent unsaturated hydrocarbon group. The 2-valent unsaturated hydrocarbon group means a hydrocarbon group having at least 1 carbon-carbon double bond, carbon-carbon triple bond or aromatic hydrocarbon ring, and includes straight-chain, branched-chain and cyclic ones unless otherwise specified.
Examples of the preferable 2-valent hydrocarbon group in Y include alkylene groups, cycloalkylene groups, arylene groups, and a combination thereof.
The number of carbon atoms of the alkylene group in Y is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of the alkylene group include methylene, ethylene, propylene and butylene.
The number of carbon atoms of the cycloalkylene group in Y is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
The arylene group in Y represents a group obtained by removing 2 hydrogen atoms on the aromatic ring from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of arylene groups include phenylene, naphthylene and anthracenylene.
The substituent in Y is not particularly limited, and examples thereof include a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy 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 the like. Among them, the 2-valent hydrocarbon group in Y preferably has no substituent.
More preferably, Y represents a 2-valent saturated hydrocarbon group having 2 to 30 carbon atoms which may be substituted, or a 2-valent unsaturated hydrocarbon group having 2 to 30 carbon atoms which may be substituted. Further preferably, Y represents a 2-valent saturated hydrocarbon group having 2 to 30 carbon atoms which optionally has a substituent and having a ring structure (e.g., a ring structure selected from the group consisting of a cycloalkane ring, a benzene ring and a naphthalene ring), or a 2-valent unsaturated hydrocarbon group having 2 to 30 carbon atoms which optionally has a substituent and having a ring structure (e.g., a ring structure selected from the group consisting of a cycloalkane ring, a benzene ring and a naphthalene ring).
Y particularly preferably represents a 2-valent group represented by the following formula (C-2).
[ chemical 3]
(in the formula (C-2),
Y a 、Y b and Y c Each independently represents a single bond or C (R) y ) 2 ；
R y Each independently represents a hydrogen atom or a methyl group;
ring Y 1 And ring Y 2 Each independently represents a cycloalkane ring having 4 to 10 carbon atoms optionally having a substituent, a benzene ring optionally having a substituent, or a naphthalene ring optionally having a substituent;
n y Represents 0 or 1;
* Indicating the bonding site).
In the formula (C-2), Y a 、Y b And Y c Each independently represents a single bond or C (R) y ) 2 . Preferably Y a And Y c Is a single bond, and Y b Represents C (R) y ) 2 。R y Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In the formula (C-2), the ring Y 1 And ring Y 2 Each independently represents an optionally substituted cycloalkane ring having 4 to 10 carbon atoms, an optionally substituted benzene ring, or an optionally substituted naphthaleneA ring. Preferably ring Y 1 And ring Y 2 Each independently represents a cycloalkane ring having 4 to 10 carbon atoms and optionally having a substituent. Examples of the cycloalkane ring having 4 to 10 carbon atoms include monocyclic saturated hydrocarbon rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring and cyclodecane ring; 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 [3.3.0]Octane ring, bicyclo [3.3.1]Saturated hydrocarbon rings of a bicyclic system such as a nonane ring; tricyclo [5.2.1.0 2，6 ]Decane ring (tetrahydrodicyclopentadiene ring), tricyclo [3.3.1.1 3， 7]And a saturated hydrocarbon ring having a tricyclic ring system such as decane ring (adamantane ring). More preferably ring Y 1 And ring Y 2 Each independently represents a cyclohexane ring optionally having a substituent. Examples of the substituent in the cycloalkane ring, benzene ring and naphthalene ring include, but are not particularly limited to, a halogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), an alkyl-aryl group (an aryl group substituted with an alkyl group), an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy 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 and an aryl-carbonyl-oxy group. Wherein ring Y 1 And ring Y 2 Unsubstituted cyclohexane rings are particularly preferred.
Specific examples of Y include 2-valent groups represented by the formulae (Y1) to (Y14), and particularly preferably 2-valent groups represented by the formula (Y1).
[ chemical 4]
(in the formulae (Y1) to (Y14)), the bonding site is represented.
In a preferred example, the proportion of the structural unit represented by the formula (C-1) contained in the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and may be 90% by mass or more, based on 100% by mass of the entire molecule of the carbodiimide compound. The carbodiimide compound may be substantially composed of a structural unit represented by the formula (C-1) in addition to the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group, which may have a substituent.
The carbodiimide compound may or may not contain an ethylenically unsaturated bond. When the carbodiimide compound having an ethylenically unsaturated bond is used, mechanical strength such as elongation at break point of a cured product of the resin composition can be effectively improved. In addition, when a carbodiimide compound containing no ethylenically unsaturated bond is used, the minimum melt viscosity of the resin composition can be effectively reduced.
The carbodiimide compound having an ethylenically unsaturated bond may have a radical polymerizable group having an ethylenically unsaturated bond. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α, β -unsaturated carbonyl groups such as acryl, methacryl, maleimide group (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl), and the like. The carbodiimide compound may have 1 radical polymerizable group or may have 2 or more groups.
The carbodiimide compound may contain a urethane bond (-O-CO-NH-). The number of urethane bonds contained in 1 molecule of the carbodiimide compound may be 1 or 2 or more.
As a preferable example of the carbodiimide compound having an ethylenically unsaturated bond, a compound represented by the following formula (C-3) can be given.
[ chemical 5]
(in the formula (C-3),
each R independently represents a hydrogen atom or a methyl group;
X 1 each independently represents a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group;
X 2 each independently represents a 2-valent saturated hydrocarbon group having 2 to 4 carbon atoms;
each Z independently represents a 2-valent saturated hydrocarbon group having 2 to 300 carbon atoms which may be substituted, or a 2-valent unsaturated hydrocarbon group having 2 to 300 carbon atoms which may be substituted;
a each independently represents 0 or an integer of 1 or more;
b each independently represents an integer of 1 or more;
c each independently represents an integer of 1 or more;
d represents an integer of 0 or 1 or more;
y each independently represents the above-described group. The a unit, b unit, c unit and d unit may be the same or different for each unit).
In the formula (C-3), R each independently represents a hydrogen atom or a methyl group.
In the formula (C-3), X 1 Each independently represents a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (the bonding direction is not particularly limited, and the phenylene side is preferably bonded to C in "R-C"). Preferably X 1 Each independently represents a methylene group or a carbonyl group. Phenylene-methylene includes 1, 2-phenylene-methylene, 1, 3-phenylene-methylene and 1, 4-phenylene-methylene.
In the formula (C-3), X 2 Each independently represents a 2-valent saturated hydrocarbon group having 2 to 4 carbon atoms. The 2-valent saturated hydrocarbon group may be linear, branched, or cyclic. Specific examples of the 2-valent saturated hydrocarbon group having 2 to 4 carbon atoms include a linear alkylene group having 2 to 4 carbon atoms such as an ethylene group, a trimethylene group, and a tetramethylene group; branched alkylene groups having 2 to 4 carbon atoms such as ethylidene, propylidene, isopropylidene and ethylmethyl methylene. X is X 2 In one embodiment, each independently preferably represents a 2-valent saturated hydrocarbon group having 2 or 3 carbon atoms, more preferably represents an ethylene group (-CH) 2 -CH 2 -)。
In the formula (C-3), each Z independently represents a 2-valent saturated hydrocarbon group having 2 to 300 carbon atoms which may be substituted, or a 2-valent unsaturated hydrocarbon group having 2 to 300 carbon atoms which may be substituted. Preferably, each Z independently represents a 2-valent saturated hydrocarbon group having 2 to 300 carbon atoms or a 2-valent unsaturated hydrocarbon group having 2 to 300 carbon atoms. More preferably, each Z independently represents a 2-valent hydrocarbon group having 300 or less carbon atoms and having a structural unit selected from the following formulae (Z1) to (Z8). Further preferably, each Z independently represents a 2-valent hydrocarbon group having 300 or less carbon atoms composed of a structural unit selected from the formulae (Z1) to (Z8).
[ chemical 6]
Z further preferably each independently represents a 2-valent hydrocarbon group having 300 or less carbon atoms having a structural unit represented by the formula (Z1); further preferably, the structural unit is a 2-valent hydrocarbon group having at least 300 carbon atoms and comprising structural units represented by the formula (Z1) and structural units selected from the formulae (Z1) to (Z8). Among them, Z particularly preferably represents a 2-valent hydrocarbon group having 300 or less carbon atoms represented by the following formula (Z1').
[ chemical 7]
(in the formula (Z1'), n z An integer of 1 or more; * Indicating the bonding site).
In the formula (C-3), a independently represents an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 10, and more preferably 0 or 1.
In the formula (C-3), b each independently represents an integer of 1 or more, preferably an integer of 1 to 100, and more preferably an integer of 1 to 10.
In the formula (C-3), C independently represents an integer of 1 or more, preferably an integer of 1 to 100, more preferably an integer of 1 to 10, and still more preferably 1.
In the formula (C-3), d each independently represents an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 100, and more preferably an integer of 0 or 1 to 10.
Carbodiimide compounds sometimes contain isocyanate groups (-n=c=o) in the molecule, derived from the process for their preparation. The content of the isocyanate group (also referred to as "NCO content") in the carbodiimide compound is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, further more preferably 2% by mass or less, particularly preferably 1% by mass or less, or 0.5% by mass or less.
The weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, further preferably 700 or more, further preferably 800 or more, further preferably 900 or more, further preferably 1000 or more, preferably 10,000 or less, more preferably 8,000 or less, further preferably 7,000 or less, further preferably 6,000 or less. The weight average molecular weight of the carbodiimide compound can be measured by Gel Permeation Chromatography (GPC) (polystyrene conversion).
The carbodiimide compound may be commercially available. Examples of the commercially available carbodiimide compounds include, for example, solar textile chemical, registered trademark V-02B, V-03, V-04K, V-07 and V-09; the laver oven P, P, manufactured by the company laver, and the harbour oven 510. Furthermore, the carbodiimide compound preferably contains no silicon.
The degree of the surface treatment of the filler with the carbodiimide compound (C) is preferably within a specific range from the viewpoint of significantly obtaining the effect of the present invention. Specifically, the amount of the carbodiimide compound to be surface-treated is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, relative to 100% by mass of the inorganic filler before the surface treatment.
(C) The treated filler may be combined with a carbodiimide compound and surface treated with any surface treating agent. For example, the filler (C) may be surface-treated with an optional surface-treating agent after the inorganic filler is surface-treated with the carbodiimide compound. The filler (C) may be surface-treated with a carbodiimide compound after the inorganic filler is surface-treated with an optional surface-treating agent. Further, the filler (C) may be subjected to surface treatment with a carbodiimide compound and an optional surface treatment agent simultaneously with the inorganic filler. From the viewpoint of remarkably obtaining the effect of the present invention, it is preferable that (C) the filler be surface-treated with an optional surface-treating agent and then surface-treated with a carbodiimide compound.
As the optional surface treatment agent, a surface treatment agent other than a carbodiimide compound may be used, and examples thereof include silane-based coupling agents such as a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxy silane-based coupling agent, a mercapto silane-based coupling agent, and a silane-based coupling agent; an alkoxysilane; an organosilane-nitrogen compound; titanate coupling agents, and the like.
Examples of the commercial products of the surface treatment agent include "KBM403" manufactured by Xinshi chemical industry Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" manufactured by Xinshi chemical industry Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" manufactured by Xinshi chemical industry Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" manufactured by Xinshi chemical industry Co., ltd. (N-phenyl-3-aminopropyl trimethoxysilane), "SZ-31" manufactured by Xinshi chemical industry Co., ltd. (hexamethyldisilazane), "KBM103" manufactured by Xinshi chemical industry Co., ltd. (phenyl trimethoxysilane), "KBM-4803" manufactured by Xinshi chemical industry Co., ltd. (long-chain epoxy silane coupling agent), and "KBM-7103" manufactured by Xinshi chemical industry Co., ltd. (3, 3-trifluoropropyl trimethoxysilane). Any one of the surface treating agents may be used alone or in combination of at least 2. Among the optional surface treating agents, a silicon-containing surface treating agent is preferable, and a silane-based coupling agent is more preferable.
The degree of the surface treatment of the filler with (C) an optional surface treatment agent preferably falls within a specific range from the viewpoint of significantly obtaining the effect of the present invention. Specifically, the amount of any surface treatment agent that surface-treats the inorganic filler is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, still more preferably 0.05 mass% or more, preferably 5 mass% or less, more preferably 1 mass% or less, still more preferably 0.5 mass% or less, based on 100 mass% of the inorganic filler before surface treatment.
When the carbodiimide compound and the optional surface treatment agent are used in combination for the surface treatment, the mass ratio of the carbodiimide compound to the optional surface treatment agent (optional surface treatment agent/carbodiimide compound) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, particularly preferably 1 or more, preferably 20 or less, still more preferably 10 or less, still more preferably 5 or less, from the viewpoint of significantly obtaining the effect of the present invention.
The degree of surface treatment with a carbodiimide compound and an optional surface treatment agent such as a surface treatment agent can be evaluated by (C) treating the carbon amount per unit surface area of the filler. (C) The carbon amount per unit surface area of the filler is preferably 0.02mg/m from the viewpoint of significantly obtaining the effect of the present invention 2 The above, more preferably 0.05mg/m 2 The above, more preferably 0.1mg/m 2 The above is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The following is more preferably 0.5mg/m 2 The following is given.
(C) The carbon amount per unit surface area of the treated filler material can be determined by subjecting the (C) treated filler material to a wash treatment with a solvent such as Methyl Ethyl Ketone (MEK). In detail, a sufficient amount of MEK was added as a solvent to the (C) treated filler material, and ultrasonic washing was performed 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, for example, "EMIA-320V" manufactured by horiba, inc. can be used. Specific operations may employ, for example, the method described in < measurement of carbon amount of cell area > of examples described later.
The amount (mass%) of the filler (C) to be treated in the resin composition is preferably 50 mass% or more, more preferably 55 mass% or more, still more preferably 60 mass% or more, preferably 90 mass% or less, more preferably 85 mass% or less, still more preferably 80 mass% or less, based on 100 mass% of the nonvolatile component of the resin composition. (C) When the amount of the filler is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
The amount (vol%) of the filler (C) in the resin composition is preferably 30 vol% or more, more preferably 40 vol% or more, still more preferably 50 vol% or more, preferably 80 vol% or less, more preferably 70 vol% or less, still more preferably 60 vol% or less, based on 100 vol% of the nonvolatile component of the resin composition. (C) When the amount of the filler is within the above range, the lowest melt viscosity of the resin composition can be effectively reduced, and further, mechanical strength such as elongation at break point of a cured product of the resin composition, surface roughness after roughening treatment, and dielectric characteristics such as relative dielectric constant and dielectric loss tangent can be made particularly good.
[ (D) curing accelerator ]
The resin composition according to one embodiment of the present invention may further contain (D) a curing accelerator as an optional component. The curing accelerator (D) as the component (D) does not include any components belonging to the above-mentioned components (A) to (C). (D) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (B) 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, and amine-based curing accelerators. Among them, imidazole-based curing accelerators are preferable. (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-methylbenzophenolate and di-t-butyldimethylphosphinium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphine tetraphenylborate, tris (3-methylphenyl) ethylphosphine tetraphenylborate, tris (2-methoxyphenyl) ethylphosphine tetraphenylborate, (4-methylphenyl) triphenylphosphine thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenyl) 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-based 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-methylphenyl) bis (N, N-4-methylphenyl) bis (3, N ' -phenylene), and aromatic dimethylurea such as N' -dimethylurea) [ toluene dimethylurea ].
Examples of the guanidine-based 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-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazole- (1 ') ] -ethyl-s triazine, 2, 4-diamino-6- [2' -undecylimidazole ] -ethyl-s triazine, and 2, 4-diamino-6- [2' -methyl ] -4' -imidazolyl-s triazine 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct, 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-phenylmethylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and the like imidazole compounds and adducts of imidazole compounds with epoxy resins. Examples of the commercially available imidazole-based curing accelerator include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK-PW", "2PHZ-PW", "Cl1Z-CN", "Cl1Z-CNS", and "Cl1Z-A", which are manufactured by the four kingdoms chemical industry company; "P200-H50" manufactured by Mitsubishi chemical corporation, etc.
Examples of the metal curing accelerator include metal, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include cobalt (II) acetylacetonate, cobalt (III) acetylacetonate and other organic cobalt complexes, copper (II) acetylacetonate and other organic copper complexes, zinc (II) acetylacetonate and other organic zinc complexes, iron (III) acetylacetonate and other organic iron complexes, nickel (II) acetylacetonate and other organic nickel complexes, manganese (II) acetylacetonate and other organic manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5, 4, 0) -undecene. Examples of the amine-based curing accelerator include commercially available products such as "MY-25" manufactured by tique corporation.
The amount of the curing accelerator (D) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.02 mass% or more, still more preferably 0.03 mass% or more, preferably 2 mass% or less, more preferably 1 mass% or less, still more preferably 0.5 mass% or less, relative to 100 mass% of the nonvolatile component of the resin composition.
The amount of the curing accelerator (D) in the resin composition may be 0% by mass or more than 0% by mass, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, relative to 100% by mass of the resin component of the resin composition.
[ (E) thermoplastic resin ]
The resin composition according to one embodiment of the present invention may further contain (E) a thermoplastic resin as an optional component. The thermoplastic resin (E) as the component (E) does not include any components belonging to the above-mentioned components (A) to (D).
Examples of the thermoplastic resin (E) include phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. (E) The thermoplastic resin may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from bisphenol a skeletons, bisphenol F skeletons, bisphenol S skeletons, bisphenol acetophenone skeletons, novolak skeletons, biphenyl skeletons, fluorene skeletons, dicyclopentadiene skeletons, norbornene skeletons, naphthalene skeletons, anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" manufactured by mitsubishi chemical company (both of which are phenoxy resins having bisphenol a skeleton); "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX6954" manufactured by Mitsubishi chemical corporation (phenoxy resin containing bisphenol acetophenone skeleton); the "FX280" and "FX293" manufactured by solar chemical company; "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi chemical corporation, and the like.
Specific examples of the polyimide resin include "SLK-6100" manufactured by the chemical industry company, and "sheath コ -SN 20" and "sheath コ -PN 20" manufactured by new japan physicochemical company.
Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "electrochemical drive 4000-2", "electrochemical drive 5000-a", "electrochemical drive 6000-C", "electrochemical drive 6000-EP" manufactured by the electric chemical industry company; the inox series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, etc. manufactured by the Water chemical industry Co.
Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.
Examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl-containing polybutadiene resin, a phenolic hydroxyl-containing polybutadiene resin, a carboxyl-containing polybutadiene resin, an anhydride-containing polybutadiene resin, an epoxy-containing polybutadiene resin, an isocyanate-containing polybutadiene resin, a urethane-containing polybutadiene resin, and a polyphenylene ether-polybutadiene resin.
Specific examples of the polyamide imide resin include "heart HR11NN" and "heart HR16NN" manufactured by eastern spinning corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by hitachi chemical industry, inc.
Specific examples of the polyethersulfone resin include "PES5003P" manufactured by sumitomo chemical company.
As a specific example of the polysulfone resin, a polysulfone resin, as the solver, there may be mentioned a polysulfone "P1700" or a polysulfone "P3500" manufactured by the company of the multi-layer company.
Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "clo tecar" manufactured by GE corporation.
Examples of the polycarbonate resin include a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi gas chemical corporation, "T6002" and "T6001" (polycarbonate diol) manufactured by Xudio chemical corporation, and "C-1090" and "C-2090" and "C-3090" (polycarbonate diol) manufactured by Mitsubishi gas chemical corporation. Specific examples of the polyether-ether-ketone resin include "su-i K" manufactured by sumitomo chemical company.
Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.
(E) The weight average molecular weight (Mw) of the thermoplastic resin is preferably more than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less. The weight average molecular weight can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
The amount of the thermoplastic resin (E) in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, relative to 100% by mass of the nonvolatile component of the resin composition.
The amount of the thermoplastic resin (E) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, still more preferably 1 mass% or more, preferably 20 mass% or less, still more preferably 10 mass% or less, still more preferably 5 mass% or less, relative to 100 mass% of the resin component of the resin composition.
[ (F) radical polymerizable Compound ]
The resin composition according to one embodiment of the present invention may further contain (F) an optional radical polymerizable compound as an optional component. The radical polymerizable compound (F) as the component (F) does not include any of the components (A) to (E). (F) The radical polymerizable compound may be used alone or in combination of 1 or more than 2.
(F) The radical polymerizable compound may contain an ethylenically unsaturated bond. Accordingly, the (F) radical polymerizable compound may have a radical polymerizable group containing an ethylenically unsaturated bond. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α, β -unsaturated carbonyl groups such as acryl, methacryl, maleimide group (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl), and the like. (F) The radical polymerizable compound preferably has 2 or more radical polymerizable groups.
Examples of the radical polymerizable compound (F) include (meth) acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds, and the like.
The (meth) acrylic acid-based radical polymerizable compound is a compound having, for example, 1 or more, preferably 2 or more acryl groups and/or methacryl groups. Examples of the (meth) acrylic acid-based radical polymerizable compound include aliphatic (meth) acrylate compounds having a low molecular weight (molecular weight of less than 1000) such as cyclohexane-1, 4-dimethanol di (meth) acrylate, cyclohexane-1, 3-dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like; ether-containing (meth) acrylate compounds having a low molecular weight (molecular weight of less than 1000) such as dioxane glycol (tall コ) di (meth) acrylate, 3, 6-dioxa-1, 8-octanediol di (meth) acrylate, 3,6, 9-trioxaundecane-1, 11-diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, ethoxylated bisphenol a di (meth) acrylate, propoxylated bisphenol a di (meth) acrylate, and the like; isocyanurate group-containing (meth) acrylate compounds having a low molecular weight (molecular weight of less than 1000), such as tris (3-hydroxypropyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and ethoxylated isocyanurate tri (meth) acrylate; and high molecular weight (molecular weight 1000 or more) acrylate compounds such as (meth) acrylic acid-modified polyphenylene ether resins. Examples of the commercially available (meth) acrylic acid-based radical polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) manufactured by Xinzhou chemical industry Co., ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate), "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate), and "SA9000" or "SA9000-111" (methacrylic acid modified polyphenylene ether) manufactured by SABIC company.
The styrene-based radical polymerizable compound is, for example, a compound having 1 or more, preferably 2 or more vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene-based radical polymerizable compound include low molecular weight (molecular weight lower than 1000) styrene-based compounds such as divinylbenzene, 2, 4-divinylbenzene, 2, 6-divinylnaphthalene, 1, 4-divinylnaphthalene, 4' -divinylbiphenyl, 1, 2-bis (4-vinylphenyl) ethane, 2-bis (4-vinylphenyl) propane, and bis (4-vinylphenyl) ether; and high molecular weight (molecular weight 1000 or more) styrene compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercial products of the styrene-based radical polymerizable compound include "ODV-XET (X03)", "ODV-XET (X04)", "ODV-XET (X05)" (styrene-divinylbenzene copolymer), and "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether resin) by Mitsubishi gas chemical company.
The allyl radical polymerizable compound is, for example, a compound having 1 or more, preferably 2 or more allyl groups. Examples of the allyl radical polymerizable compound include aromatic carboxylic acid allyl ester compounds such as diallyl phthalate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2, 6-naphthalate, and diallyl 2, 3-naphthalate; allyl isocyanurate compounds such as 1,3, 5-triallyl isocyanurate and 1, 3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2, 2-bis [ 3-allyl-4- (glycidoxy) phenyl ] propane; benzoxazine-containing aromatic allyl compounds such as bis [ 3-allyl-4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane; ether-containing aromatic allyl compounds such as 1,3, 5-triallyl ether benzene; allylsilane compounds such as diallyldiphenylsilane, and the like. Examples of the commercial products of the allyl radical polymerizable compound include "TAIC" (1, 3, 5-triallyl isocyanurate) manufactured by Japanese chemical industry Co., ltd., japanese touch-Teflon-made "DAD" (diallyl phthalate) manufactured by Japanese chemical industry Co., ltd., and "TRIAM-705" (triallyl trimellitate) manufactured by photo-pure chemical industry Co., ltd., trade name "DAND" (diallyl 2, 3-naphthoate) manufactured by Japanese distillation industry Co., ltd., and "ALP-d" (bis [ 3-allyl-4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane) manufactured by Japanese chemical industry Co., ltd., RE-NM "(2, 2-bis [ 3-allyl-4- (glycidyloxy) phenyl ] propane) manufactured by Japanese chemical industry Co., ltd., and" DA-IC "(1, 3-diallyl-5-glycidylisocyanurate) manufactured by Japanese chemical industry Co., ltd.
The maleimide-based radically polymerizable compound is, for example, a compound having 1 or more maleimide groups, preferably 2 or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound having an aliphatic amine skeleton or an aromatic maleimide compound having an aromatic amine skeleton. As a commercially available product of the maleimide-based radical polymerizable compound, examples thereof include "SLK-2600" manufactured by the Santa Classification chemical industry Co., ltd., dupont "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure), and the like the term "BMI-6100" (aromatic maleimide compound) of the company of UK, the term "MIR-5000-60T" (biphenyl aralkyl maleimide compound) of the company of Japan chemical industry, the term "BMI-70" (biphenyl aralkyl maleimide compound) of the company of UK chemical industry, the term "BMI-80" of the company of UK chemical industry, the term "BMI-2300" of the company of UK chemical industry, the term "BMI-TMH" of the company of UK chemical industry, and the like. Further, as the maleimide-based radical polymerizable compound, a maleimide resin (a maleimide compound having an indane ring skeleton) disclosed in technical publication No. 2020-500211 of the institute of Electrical and electronics Endoconcha may be used.
(F) The ethylenically unsaturated bond equivalent weight of the radical polymerizable compound is preferably 20g/eq to 3,000g/eq, more preferably 50g/eq to 2,500g/eq, still more preferably 70g/eq to 2,000g/eq, and particularly preferably 90g/eq to 1,500g/eq. The ethylenically unsaturated bond equivalent means the mass of the radical polymerizable compound having an average of 1 equivalent of ethylenically unsaturated bonds.
(F) The weight average molecular weight (Mw) of the radical polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more. The weight average molecular weight can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
The amount of the radical polymerizable compound (F) in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, relative to 100% by mass of the nonvolatile component in the resin composition.
The amount of the radical polymerizable compound (F) in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less, relative to 100% by mass of the resin component in the resin composition.
[ (G) optional additives ]
The resin composition according to one embodiment of the present invention further comprises (G) an optional additive as an optional ingredient. Examples of the optional additive (G) include an organic filler such as rubber particles; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acryl polymer leveling agents; thickeners such as BENTONE and montmorillonite; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as ureidosilane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants; fluorescent whitening agents such as stilbene derivatives; a surfactant such as a fluorine-based surfactant and an organosilicon-based surfactant; flame retardants such as phosphorus flame retardants (for example, phosphate compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen flame retardants (for example, melamine sulfate), halogen flame retardants, and inorganic flame retardants (for example, antimony trioxide); a dispersant such as a phosphate dispersant, a polyoxyalkylene dispersant, an acetylene dispersant, a silicone dispersant, an anionic dispersant, and a cationic dispersant; boric acid ester stabilizer, titanate stabilizer, aluminate stabilizer, zirconate stabilizer, isocyanate stabilizer, carboxylic acid stabilizer, carboxylic anhydride stabilizer, and the like. (G) The optional additives may be used alone or in combination of 1 or more than 2.
[ (H) solvent ]
The resin composition according to one embodiment of the present invention may further contain (H) a solvent as an optional volatile component in combination with the nonvolatile components such as the above-mentioned components (a) to (G). As the (H) solvent, an organic solvent is generally used. Examples of the organic solvent 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, ethyl diethylene glycol acetate, コ megaly, 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 hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) The solvent may be used alone or in combination of 1 or more than 2.
(H) The amount of the solvent is not particularly limited, and may be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, or the like, based on 100 mass% of the total components of the resin composition.
[ method for producing resin composition ]
The resin composition according to one embodiment of the present invention can be produced by a production method including the steps of:
a first step of mixing a carbodiimide compound with an inorganic filler to obtain (C) a treated filler; and
a second step of mixing (C) the treated filler, (A) the epoxy resin and (B) the curing agent.
The first step includes mixing a carbodiimide compound and an inorganic filler material. By mixing the carbodiimide compound with the inorganic filler, the inorganic filler is surface-treated with the carbodiimide compound, and thus (C) -treated filler can be obtained.
The inorganic filler before being mixed with the carbodiimide compound may be subjected to surface treatment with no surface treatment agent or may be subjected to surface treatment with a surface treatment agent. Thus, the first step may include mixing the inorganic filler material with any surface treatment agent prior to mixing the carbodiimide compound with the inorganic filler material. Further, the first step may include mixing the inorganic filler with an optional surface treating agent after mixing the carbodiimide compound and the inorganic filler. Further, the first step may include simultaneously mixing the carbodiimide compound, the inorganic filler material, and any surface treatment agent.
The mixing of the carbodiimide compound and the inorganic filler may be performed by a dry method or a wet method. The dry method means a method of mixing a carbodiimide compound and an inorganic filler in a system containing no solvent. In addition, the wet method means a method of mixing a carbodiimide compound and an inorganic filler in a system containing a solvent. As the solvent, a substance capable of dissolving the carbodiimide compound may be selected from those exemplified as the (H) solvent, for example, and used. In the case of the wet method, the carbodiimide compound and the solvent may be mixed, and then the inorganic filler may be further mixed. In addition, the carbodiimide compound may be further mixed after the inorganic filler and the solvent are mixed.
For example, the carbodiimide compound and the inorganic filler may be mixed by spraying the carbodiimide compound on the inorganic filler while stirring the inorganic filler, to obtain (C) -treated filler. The mixing may be carried out, for example, at a temperature of 0℃to 50 ℃.
After the filler (C) is obtained, a second step of mixing the filler (C), the epoxy resin (A) and the curing agent (B) is performed to obtain a resin composition. In the case of producing a resin composition containing optional components such as components (D) to (H), the optional components may be mixed in combination with (a) an epoxy resin, (B) a curing agent, and (C) a treatment filler. The mixing may be performed by mixing a part or all of them simultaneously or sequentially. In the process of mixing the components, heating and/or cooling may be performed temporarily or constantly in order to set the temperature to be appropriate. Further, stirring or shaking may be performed during the mixing of the components.
[ physical Properties of resin composition ]
The resin composition according to one embodiment of the present invention may have a low minimum melt viscosity. For example, in the temperature range of 60 ℃ to 200 ℃, the minimum melt viscosity is preferably less than 2,000 poise, more preferably 1,900 poise, still more preferably 1,800 poise, particularly preferably 1,700 poise or less when measured under the measurement conditions of a temperature rising rate of 5 ℃/min, a measurement temperature interval of 2.5 ℃ and a vibration frequency of 1 Hz. The lower limit may be, for example, 100 poise or more, 200 poise or more from the viewpoint of smoothly forming a thick insulating layer. Specifically, the lowest melt viscosity of the resin composition may be < test example 1: determination of minimum melt viscosity > methods described in.
The resin composition according to one embodiment of the present invention is cured to obtain a cured product. In the curing, heat is generally applied to the resin composition. Therefore, among the components contained in the resin composition, the volatile components such as the (H) solvent may volatilize by heat at the time of curing, but the nonvolatile components such as the components (a) to (G) may not volatilize by heat at the time of curing. Accordingly, the cured product of the resin composition may contain a nonvolatile component of the resin composition or a reaction product thereof.
According to the resin composition of one embodiment of the present invention, a cured product having excellent mechanical strength, for example, a cured product having a large elongation at break point can be obtained. In a specific example, when the cured product is subjected to a tensile test in accordance with JIS K7127 of the japanese industrial standard at 25 ℃ under atmospheric pressure, the elongation at break point of the cured product measured in the tensile test is preferably 1.0% or more, more preferably 1.1% or more. The more the upper limit, the more preferable, usually 5% or less. In one example, the breaking point elongation may be obtained by heating the resin composition at 200 ℃ for 90 minutes to obtain a cured product, and < test example 4: evaluation of elongation at Break Point > the method described in the following.
According to the resin composition of one embodiment of the present invention, a cured product having a reduced surface roughness after roughening treatment can be obtained. In the specific example, the cured product is immersed in an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide for 10 minutes, followed by immersing in a solution containing KMnO 4 In the case of roughening treatment of immersing in aqueous solutions of 60g/L and 40g/L NaOH at 80℃for 20 minutes and immersing in aqueous sulfuric acid solution at 40℃for 5 minutes, the cured product may have an arithmetic average roughness Ra in a specific range. The aforementioned range of the arithmetic average roughness Ra is preferably less than 300nm, more preferably less than 290nm, further preferably less than 280nm, particularly preferably less than 250nm. The lower limit is not particularly limited, and may be, for example, 10nm or more, 30nm or more, 50nm or more, or the like. For example, the arithmetic average roughness Ra of the cured product may be obtained by heating the resin composition at 170℃for 30 minutes, which is described in the following examples <Test example 2: determination of arithmetic average roughness (Ra)>The method described in (a) was used for measurement.
The cured product of the resin composition according to one embodiment of the present invention may generally have excellent dielectric characteristics. For example, the relative dielectric constant of the cured product is preferably 4.0 or less, more preferably 3.6 or less, and particularly preferably 3.4 or less. The lower limit of the relative dielectric constant is not particularly limited, and may be, for example, 1.5 or more, 2.0 or more, or the like. For example, the dielectric loss tangent of the cured product is preferably 0.0100 or less, more preferably 0.0090 or less, still more preferably 0.0080 or less, and particularly preferably 0.0070 or less. The lower limit of the dielectric loss tangent is not particularly limited, and may be, for example, 0.0010 or more. As an example, the above-mentioned cured product may have a relative dielectric constant and dielectric loss tangent obtained by heating the resin composition at 200 ℃ for 90 minutes, and the following < test example 3: measurement of relative permittivity (Dk) and dielectric loss tangent (Df) by the method described in the above.
[ use of resin composition ]
The resin composition according to one embodiment of the present invention can be used as a resin composition for insulation, and is particularly suitable as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer). For example, the resin composition according to the present embodiment can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), and a resin composition for forming an insulating layer of a circuit board (including a printed circuit board) (a resin composition for an insulating layer of a circuit board). In particular, the resin composition is suitable for forming an interlayer insulating layer provided between the conductor layer and the conductor layer.
Examples of the semiconductor chip package include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and Fan-in type PLP.
The resin composition can be used as an underfill material, and can be used as a material of MUF (Molding Under Filling) used after a semiconductor chip is connected to a substrate, for example.
The resin composition can be used in a wide range of applications using a resin composition such as a resin sheet, a sheet laminate such as a prepreg, a solder resist, a die bonding material, a semiconductor sealing material, a hole-filling resin, and a component embedding resin.
[ sheet laminate ]
The resin composition can be applied in the form of a varnish, and is industrially suitably used as a sheet laminate containing the resin composition.
The sheet-like laminate is preferably a resin sheet or prepreg as shown below.
In one embodiment, a resin sheet includes a support and a resin composition layer formed on the support. The resin composition layer is formed from the above resin composition. Therefore, the resin composition layer generally contains a resin composition, preferably contains only a resin composition.
The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning and from the viewpoint of providing a cured product excellent in insulation properties even when the resin composition is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be 5 μm or more, 10 μm or more, or the like.
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET"), polyethylene naphthalate (hereinafter, abbreviated as "PEN"), polycarbonates (hereinafter, abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper 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 support may be subjected to a matte treatment, a corona treatment, or an antistatic treatment on the surface to be joined to the resin composition layer.
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. The release agent used in the release layer of the support with a release layer may be, for example, 1 or more types of release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins. Examples of the support having a release layer include a PET film having a release layer containing an alkyd-based release agent as a main component, that is, "SK-1", "AL-5", "AL-7" made by LINTEC, ". 1 st 60" made by toli, ". 1 st 60" made by teh, and "one st" made by uni tika.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In the case of using the support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.
In one embodiment, the resin sheet further may include an optional layer as desired. Examples of the optional layer include a protective film with a support as a standard, which is provided on a surface not bonded to the support of the resin composition layer (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, adhesion of dirt to the surface of the resin composition layer and damage can be suppressed.
The resin sheet can be produced, for example, by dissolving a liquid (varnish-like) resin composition directly or in a solvent to prepare a liquid (varnish-like) resin composition, applying the liquid (varnish-like) resin composition onto a support by using an applicator such as a die coater, and further drying the coated support to form a resin composition layer.
The solvent may be the same as the solvent (H) described as a component of the resin composition. The solvent may be used alone or in combination of 1 or more than 2.
Drying may be performed by a drying method such as heating or hot air blowing. The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the solvent in the resin composition layer is usually 10 mass% or less, preferably 5 mass% or less. Depending on the boiling point of the solvent in the resin composition, for example, in the case of using a resin composition containing 30 to 60 mass% of the solvent, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.
The resin sheet may be stored in a roll form. In the case where the resin sheet has a protective film, the protective film can be generally peeled off for use.
In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous base material with the resin composition.
As the sheet-like fibrous base material used for the prepreg, for example, glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, or the like, which is commonly used as a base material for the prepreg, can be used. From the viewpoint of thickness reduction, the thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, and is usually 10 μm or more.
The prepreg can be produced by a hot-melt method, a solvent method, or the like.
The thickness of the prepreg may be in the same range as the resin composition layer in the above resin sheet.
The sheet-like laminate material can be suitably used for forming an insulating layer (insulating resin sheet for semiconductor chip package) in the manufacture of semiconductor chip package, for example. Examples of the applicable semiconductor chip package include a Fan-out type WLP, a Fan-in type WLP, a Fan-out type PLP, and a Fan-in type PLP. Further, the sheet-like laminated material can be used for, for example, forming an insulating layer of a circuit board (resin sheet for insulating layer of circuit board). Further, a sheet-like laminated material may be used as a material of the MUF used after the semiconductor chip is connected to the substrate. In particular, the sheet-like laminated material is suitable for forming an interlayer insulating layer.
[ Circuit Board ]
The circuit board according to one embodiment of the present invention includes a cured product of the resin composition. In general, a circuit board has an insulating layer formed of a cured product of a resin composition. The insulating layer preferably contains only a cured product of the resin composition. The circuit board can be manufactured by a manufacturing method including, for example, the following steps (I) and (II).
(I) And forming a resin composition layer on the inner layer substrate.
(II) a step of curing the resin composition layer to form an insulating layer.
The "inner layer substrate" used in the step (I) is a member forming a base material of a circuit substrate, 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 subjected to patterning. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, intermediate products, in which an insulating layer and/or a conductor layer should be further formed when manufacturing the circuit substrate, are also included in the aforementioned "inner layer substrate". When the circuit board is a component-built-in circuit board, an inner layer board having a component built therein may be used.
The resin composition has a low minimum melt viscosity and thus excellent wiring embedding properties, and when the conductor layer of the inner layer substrate is patterned, the resin composition exhibits excellent embedding properties even when the minimum line width/pitch ratio of the conductor layer is small. "linewidth" refers to the circuit width of the conductor layer, and "pitch" refers to the spacing between circuits. The range of the minimum line width/pitch ratio is preferably 20/20 μm or less (i.e., pitch is 40 μm or less), more preferably 15/15 μm or less, still more preferably 10/10 μm or less. The lower limit may be, for example, 0.5/0.5 μm or more. The pitch may or may not be uniform throughout the transconductor layer. The minimum pitch of the conductor layers may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.
The formation of the resin composition layer on the inner layer substrate may be performed by, for example, laminating the inner layer substrate and a resin sheet. Lamination of the inner layer substrate and the resin sheet can be performed by, for example, thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS mirror plate or the like) or a metal roller (SUS roller or the like) may be mentioned. 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 thermocompression bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the thermocompression bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the thermocompression bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably 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 Ming machine Co, vacuum applicators manufactured by Xuey コ, intermittent vacuum pressurized laminators, and the like.
After lamination, the laminated resin sheets may be smoothed by pressing the thermocompression bonding member from the support body side at normal pressure (atmospheric pressure), for example. The pressing conditions for the smoothing treatment may be the same as the above-described lamination thermocompression bonding conditions. 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 step (I) and step (II), or may be removed after step (II).
In the step (II), the resin composition layer is cured to form an insulating layer containing a cured product of the resin composition. The curing of the resin composition layer is generally performed by thermal curing. The specific curing conditions of the resin composition layer may be different depending on the kind of the resin composition. In one example, the curing temperature is preferably 120℃to 240℃and more preferably 150℃to 220℃and even 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 method for producing a circuit board preferably includes preheating the resin composition layer at a temperature lower than the curing temperature before thermally curing the resin composition layer. For example, the resin composition layer may be preheated for usually 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, usually at a temperature of 50 ℃ to 150 ℃, preferably 60 ℃ to 140 ℃, more preferably 70 ℃ to 130 ℃ before the resin composition layer is thermally cured.
In the case of manufacturing the circuit board, (III) a step of forming a hole in the insulating layer, (IV) a step of removing the adhesive residue from the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art used in the manufacture of circuit boards. In the case where the support is removed after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, the insulating layer and the conductor layer are formed repeatedly in the steps (I) to (V) as necessary, whereby a circuit board having a multilayer structure such as a multilayer printed circuit board can be manufactured.
In other embodiments, the circuit substrate may be manufactured using the above prepreg. The manufacturing method may be substantially the same as in the case of using a resin sheet.
The step (III) is a step of forming a hole such as a via hole or a through hole in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used in forming the insulating layer, or the like. The size and shape of the holes may be appropriately determined according to the design of the circuit substrate.
Step (IV) is a step of roughening the insulating layer. In this step (IV), usually, the removal of the gum residue is also performed. Therefore, the aforementioned roughening treatment is sometimes also referred to as "desmear treatment". The flow and conditions of the roughening treatment are not particularly limited, and known flow and conditions generally used in forming an insulating layer of a circuit 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.
Examples of the swelling liquid used for the roughening treatment include an alkali solution and a surfactant solution, and alkali solutions are preferable. The alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. As a commercially available swelling liquid, a water-soluble swelling liquid, examples thereof include a station from a station to a station, and a station from station to station. And (c) wielding (P), and wielding (P). And d, i.e. d the part of the setawaking, the part of the setawaking. The swelling treatment with the swelling liquid may be performed by, for example, immersing the insulating layer in the swelling liquid at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to a proper level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.
Examples of the oxidizing agent used in the roughening treatment 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%. As the oxidizing agent to be used in the market, examples of the alkaline permanganate solution include "コ parts by gamma, コ parts by gamma", and "parts by gamma, P, etc.
The neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and is commercially available, examples thereof include "gamma" manufactured by gamma corporation; the method includes the steps of (a) preparing a solution of a raxacum, (b) preparing a solution of a raxacum, and (c) preparing a solution of a raxacum. 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 workability and the like, 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.
Step (V) is a step of forming a conductor layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises 1 or more metals selected from 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 (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, and the like of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is more preferable, and a single metal layer of nickel-chromium alloy is further preferable.
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 composed of a different metal or alloy are stacked. In the case where the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.
The thickness of the conductor layer varies depending on the design of the desired circuit board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.
In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a half-addition method or a full-addition method. From the viewpoint of ease of production, the semi-additive method is preferable. Hereinafter, an example of forming a conductor layer by a half-additive method is shown.
First, a plating seed layer is formed by electroless plating on the surface of an insulating layer. Next, a mask pattern is formed on the formed plating seed layer, wherein a part of the plating seed layer is exposed corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer 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. In the case of forming the conductor layer using a metal foil, step (V) is suitably performed between step (I) and 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. Thereafter, a conductor layer having a desired wiring pattern can be formed by conventional techniques such as a subtractive process and a modified semi-additive process using a metal foil on an insulating layer.
The metal foil can be produced by a known method such as electrolysis or rolling. Examples of the commercial products of the metal foil include HLP foil manufactured by JX Nitshi metal Co., ltd., JXUT-III foil, 3EC-III foil manufactured by Mitsui metal mine Co., ltd., TP-III foil, and the like.
[ semiconductor chip Package ]
The semiconductor chip package according to one embodiment of the present invention includes a cured product of a resin composition. Generally, a semiconductor chip package includes an insulating layer formed of a cured product of a resin composition. The insulating layer preferably contains only a cured product of the resin composition. Examples of the semiconductor chip package include the following.
The semiconductor chip package according to the first example includes the circuit board and a semiconductor chip mounted on the circuit board. The semiconductor chip package may be manufactured by bonding a semiconductor chip on a circuit substrate.
The bonding conditions between the circuit board and the semiconductor chip may be any conditions that can connect the terminal electrode of the semiconductor chip to the circuit wiring of the circuit board in a conductive manner. For example, conditions used in flip-chip mounting of a semiconductor chip may be employed. For example, the semiconductor chip and the circuit board may be bonded to each other with an insulating adhesive interposed therebetween.
As an example of the bonding method, a method of crimping a semiconductor chip to a circuit board is given. The pressure conditions are such that the pressure temperature is usually in the range of 120 to 240 ℃ (preferably 130 to 200 ℃, more preferably 140 to 180 ℃), and the pressure time is usually in the range of 1 to 60 seconds (preferably 5 to 30 seconds).
Further, as another example of the bonding method, a method of bonding a semiconductor chip by reflow on a circuit board is given. The reflow conditions may be set in the range of 120℃to 300 ℃.
The semiconductor chip may be filled with a molding underfill material after bonding the semiconductor chip to the circuit substrate. As the molding underfill material, the above-mentioned resin composition can be used.
The semiconductor chip package according to the second example includes a semiconductor chip and an insulating layer formed of a cured product of a resin composition. The semiconductor chip package according to the second example includes, for example, a Fan-out WLP and a Fan-out PLP.
Fig. 1 is a cross-sectional view schematically showing a Fan-out WLP as an example of a semiconductor chip package according to an embodiment of the present invention. As shown in fig. 1, for example, a semiconductor chip package 100 as a Fan-out WLP includes a semiconductor chip 110; a sealing layer 120 formed to cover the periphery of the semiconductor chip 110; a rewiring forming layer 130 as an insulating layer provided on a surface of the semiconductor chip 110 opposite to the sealing layer 120; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and bumps 160.
The method for manufacturing the semiconductor chip package comprises the following steps:
(i) A step of laminating a temporary fixing film on a base material;
(ii) A step of temporarily fixing the semiconductor chip on the temporary fixing film;
(iii) A step of forming a sealing layer on the semiconductor chip;
(iv) A step of peeling the base material and the temporary fixing film from the semiconductor chip;
(v) A step of forming a rewiring forming layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled off;
(vi) A step of forming a rewiring layer as a conductor layer on the rewiring layer; and
(vii) And forming a solder resist layer on the rewiring layer.
In addition, the aforementioned method of manufacturing a semiconductor chip package may include:
(viii) And cutting the plurality of semiconductor chip packages into individual semiconductor chip packages, and performing singulation.
(step (i))
Step (i) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporary fixing film may be the same as those of the inner layer substrate and the resin sheet in the method of manufacturing a circuit substrate.
Examples of the substrate include a silicon wafer; a glass wafer; a glass substrate; metal substrates such as copper, titanium, stainless steel, and cold rolled steel Sheet (SPCC); a substrate such as an FR-4 substrate in which glass fibers are impregnated with an epoxy resin or the like and thermally cured; a substrate made of bismaleimide triazine resin such as BT resin, and the like.
The temporary fixing film may be made of any material that can be peeled off from the semiconductor chip and temporarily fix the semiconductor chip. Examples of the commercial products include "cartridge ヴ a" manufactured by the eastern electrician company.
(step (ii))
Step (ii) is a step of temporarily fixing the semiconductor chip on the temporary fixing film; temporary fixing of the semiconductor chip may be performed using a device such as a flip chip bonder, a die bonder, or the like. The layout and the number of the arrangement of the semiconductor chips may be appropriately set according to the shape, size, number of production of the target semiconductor chip package, and the like of the temporary fixing film. For example, the semiconductor chips may be arranged in an array of a plurality of rows and a plurality of columns, and temporarily fixed.
(step (iii))
Step (iii) is a step of forming a sealing layer on the semiconductor chip. The sealing layer may be formed of, for example, a photosensitive resin composition or a thermosetting resin composition. The sealing layer may be formed of a cured product of the resin composition according to the above embodiment. The sealing layer may be generally formed by a method including a step of forming a resin composition layer on the semiconductor chip, and a step of forming the sealing layer by curing the resin composition layer.
(step (iv))
Step (iv) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. The peeling method is preferably an appropriate method corresponding to the material of the temporary fixing film. Examples of the peeling method include a method of peeling a temporary fixing film by heating, foaming, or swelling. Further, as a peeling method, for example, a method of irradiating ultraviolet rays to the temporary fixing film through the base material to lower the adhesive force of the temporary fixing film and peel it off is mentioned.
As described above, if the base material and the temporary fixing film are peeled off from the semiconductor chip, the surface of the sealing layer is exposed. The method of manufacturing the semiconductor chip package may include polishing a surface of the exposed sealing layer. By grinding, the smoothness of the surface of the sealing layer can be improved.
(step (v))
Step (v) is 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 off. Generally, the redistribution layer is formed on the semiconductor chip and the encapsulation layer. The redistribution layer may be formed from a cured product of the resin composition according to the above embodiment. The rewiring-forming layer may be formed by a method including a step of forming a resin composition layer on a semiconductor chip, and a step of forming the rewiring-forming layer by curing the resin composition layer. The formation of the resin composition layer on the semiconductor chip may be performed by, for example, the same method as the method of forming the resin composition layer on the inner layer substrate described in the foregoing method of manufacturing the circuit substrate, except that the semiconductor chip is used instead of the inner layer substrate.
After forming a resin composition layer on a semiconductor chip, the resin composition layer is cured to obtain a rerouting layer as an insulating layer containing a cured product of the resin composition. The curing conditions of the resin composition layer may be the same as those of the resin composition layer in the method for producing a circuit board. In the case of thermally curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature before thermally curing the resin composition layer. The pretreatment conditions for the preheating treatment may be the same as those for the preheating treatment in the method for producing a circuit board. In general, after forming the redistribution layer, holes are formed in the redistribution layer in order to connect the semiconductor chip and the redistribution layer.
(step (vi))
Step (vi) is a step of forming a rewiring layer as a conductor layer on the rewiring-forming layer. The method of forming the rewiring layer on the rewiring layer may be the same as the method of forming the conductor layer on the insulating layer in the manufacturing method of the circuit substrate. Further, step (v) and step (vi) may be repeated, and the rewiring layer and the rewiring-forming layer may be alternately laminated (stacked).
(step (vii))
Step (vii) is a step of forming a solder resist layer on the rewiring layer. As a material of the solder resist layer, any material having insulating properties can be used. Among them, a photosensitive resin composition and a thermosetting resin composition are preferable from the viewpoint of ease of manufacturing the semiconductor chip package. The solder resist layer may be formed from a cured product of the resin composition according to the above embodiment.
In step (vii), a bump forming process for forming bumps may be performed, if necessary. The bump forming process may be performed by a method such as bead welding or plating. The formation of the via hole in the bump forming process may be performed in the same manner as in step (v).
(step (viii))
The method for manufacturing the semiconductor chip package may include step (viii) in addition to steps (i) to (vii). Step (viii) is a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and performing singulation. The method of dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.
[ semiconductor device ]
The semiconductor device has the above-described circuit substrate or semiconductor chip package. Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, smartphones, tablet personal computers, wearable devices, digital cameras, medical devices, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, and the like).
Examples
The present invention will be specifically described below by way of examples. However, the present invention is not limited to the following examples. In the following description, "part" and "%" representing amounts represent "part by mass" and "% by mass", respectively, unless otherwise explicitly stated. In particular, the temperature conditions and the pressure conditions in the absence of the specified temperature are room temperature (25 ℃) and atmospheric pressure (1 atm).
Synthesis example 1: synthesis of polycarbodiimide Compound 1
[ chemical 8]
100 parts by mass of dicyclohexylmethane-4, 4' -diisocyanate (HMDI) and 0.5 part by mass of 3-methyl-1-phenyl-2-phosphole-1-oxide as a carbodiimidization catalyst were charged into a reaction vessel equipped with a reflux tube and a stirrer. Stirring under nitrogen flow at 185 deg.C for 24 hr to obtain the final productThe isocyanate-terminated polycarbodiimide shown in (S1). As a result of IR spectrum measurement of the obtained isocyanate-terminated polycarbodiimide, it was confirmed that the wavelength was 2150cm -1 Absorption peaks based on carbodiimide groups at the front and back. The terminal NCO content was 8.19% by mass, and the average polymerization degree of carbodiimide groups obtained by the above-described measurement method was 3.5.
[ chemical 9]
To the isocyanate-terminated polycarbodiimide obtained in the above manner, 8.8 parts by mass of ethylene glycol monoacrylate and 4 parts by mass of both terminal hydroxyl polybutadiene (G-1000, manufactured by Seto Co., ltd., number average molecular weight 1400, 1, 2-addition structural unit 85% or more and trans-1, 4-addition structural unit 15% or less) were added, and the mixture was heated to 180℃and stirred for 2 hours to effect a reaction. By IR spectrometry, it was confirmed that the wavelength was 2200cm -1 ～2300cm -1 The absorption peak of the isocyanate group disappears. Thereafter, the reaction product was taken out of the reaction vessel and cooled to room temperature, whereby a pale yellow transparent solid polycarbodiimide compound 1 (a compound having a carbodiimide structure and containing a radical polymerizable group) was obtained. The main component of the obtained polycarbodiimide compound 1 is the compound of the above formula (S2). In the formula (S2), b' means the average polymerization degree of carbodiimide groups. d' refers to the average degree of polymerization of the combined units of polybutadiene and polycarbodiimide. e' means the average degree of polymerization of butadiene units corresponding to the number average molecular weight described above. As e' units, only 1, 2-addition structural units are indicated, but 1, 4-addition structural units (cis, trans) are also included.
< measurement of carbon content per unit area >
3g of the surface-treated inorganic filler was used as a sample. The sample and 30g of MEK (methyl ethyl ketone) were placed in a centrifuge tube of a centrifuge, and stirred to suspend the solid content, and 500W of ultrasonic waves were applied for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugal separation, and the supernatant was taken out. Further, 30g of MEK was added thereto, and the mixture was stirred to suspend the solid content, and 500W of ultrasonic waves were applied thereto for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugal separation, and the supernatant was taken out. The solid component was dried at 150℃for 30 minutes. The dried sample (0.3 g) was accurately weighed into a measuring crucible, and a combustion improver (tungsten 3.0g, tin 0.3 g) was further added to the measuring crucible. The measuring crucible was attached to a carbon analyzer, and the amount of carbon was measured. The carbon analyzer used was EMIA-320V manufactured by horiba, ltd. The measured carbon amount was divided by the specific surface area of the inorganic filler to obtain a carbon amount per unit area.
< production example 1: production of surface-treated spherical silica 1
Spherical silica (SO-C2, manufactured by admatechs Co., ltd., average particle diameter of 0.5 μm, specific surface area of 5.8 m) 2 100 parts by mass of (g)) was charged into a Henschel mixer, and 0.3 part by mass of a silane coupling agent (KBM-573, manufactured by Xinyue chemical industries Co., ltd.) was sprayed and, at the same time, spherical silica was stirred for 10 minutes. Thereafter, 0.3 parts by mass of a carbodiimide-based curing agent (toluene solution having an active group equivalent of about 216g/eq. And a nonvolatile content of 50%) was sprayed (Niqing textile chemical company, "V-03"), and the spherical silica was stirred for 10 minutes to prepare treated silica 1 (carbon content per unit area: 0.20 mg/m) 2 )。
< production example 2: production of surface-treated spherical silica 2-
Spherical silica (SO-C2, manufactured by admatechs Co., ltd., average particle diameter of 0.5 μm, specific surface area of 5.8 m) 2 100 parts by mass of (g)) was charged into a Henschel mixer, and 0.3 part by mass of a silane coupling agent (KBM-573, manufactured by Xinyue chemical industries Co., ltd.) was sprayed and, at the same time, spherical silica was stirred for 10 minutes. Thereafter, 0.3 part by mass of the "polycarbodiimide compound 1" obtained in Synthesis example 1 was sprayed, and the spherical silica was stirred for 10 minutes to prepare treated silica 2 (carbon content per unit area: 0.18 mg/m) 2 )。
< manufacturing example 3: production of surface-treated hollow aluminosilicate 3
Hollow aluminosilicate particles (too100 parts by mass of MG-005, hollow inorganic filler, average particle diameter 1.6 μm and porosity 80 vol% manufactured by Seaman, pacific, were put into a Henschel mixer, and 0.5 part by mass of silane coupling agent (KBM-573, manufactured by Xinyue chemical industry Co., ltd.) was sprayed and the hollow aluminosilicate particles were stirred for 10 minutes. Thereafter, 0.5 parts by mass of a carbodiimide-based curing agent (toluene solution having an active group equivalent of about 216g/eq., nonvolatile content of 50%) was sprayed (Niqing textile chemical company, "V-03"), and the hollow aluminosilicate particles were stirred for 10 minutes to prepare treated aluminosilicate 3 (carbon amount per unit area: 0.22 mg/m) 2 )。
< production example 4: production of surface-treated hollow aluminosilicate 4
100 parts by mass of hollow aluminosilicate particles (MG-005, hollow inorganic filler, average particle diameter 1.6 μm, porosity 80 vol%) were charged into a Henschel mixer, and 0.5 part by mass of silane coupling agent (KBM-573, xinyue chemical Co., ltd.) was sprayed, while stirring the hollow aluminosilicate particles for 10 minutes. Thereafter, 0.5 parts by mass of the "polycarbodiimide compound 1" obtained in Synthesis example 1 was sprayed, and the hollow aluminosilicate particles were stirred for 10 minutes, whereby treated aluminosilicate 4 (carbon amount per unit area: 0.21 mg/m) was produced 2 )。
< production example 5: production of surface-treated spherical silica 5-
In production example 1, the amount of the silane coupling agent (KBM-573, made by Xinyue chemical industries Co., ltd.) was changed from 0.3 to 0.4 parts by mass based on 100 parts by mass of the spherical silica. The amount of the carbodiimide-based curing agent (V-03, manufactured by riqing chemical company, active group equivalent of about 216g/eq., 50% nonvolatile matter content toluene solution) was changed from 0.3 to 0.2 parts by mass based on 100 parts by mass of the spherical silica. Except for the above, a treated silica 5 (carbon amount per unit area: 0.21 mg/m) was produced in the same manner as in production example 1 2 )。
< production example 6: production of surface-treated spherical silica 6-
In production example 1, the amount of the silane coupling agent (KBM-573, made by Xinyue chemical industries Co., ltd.) was changed from 0.3 parts by mass to 0.1 parts by mass based on 100 parts by mass of the spherical silica. The amount of the carbodiimide-based curing agent (V-03, manufactured by riqing chemical company, active group equivalent of about 216g/eq., 50% nonvolatile matter content toluene solution) was changed from 0.3 parts by mass to 0.5 parts by mass based on 100 parts by mass of the spherical silica. Except for the above, a treated silica 6 (carbon amount per unit area: 0.17 mg/m) was produced in the same manner as in production example 1 2 )。
< production example 7: production of surface-treated spherical silica 7
In production example 1, the order of treatment of the spherical silica with a silane coupling agent (KBM-573, made by Xinyue chemical industry Co., ltd.) and treatment with a carbodiimide-based curing agent (toluene solution having an active group equivalent of about 216g/eq., nonvolatile matter content of 50%) was changed. That is, the spherical silica is sprayed with the carbodiimide-based curing agent while stirring, and then further sprayed with the silane coupling agent while stirring. Except for the above, a treated silica 7 (carbon amount per unit area: 0.19 mg/m) was produced in the same manner as in production example 1 2 )。
Example 1 ]
5 parts of biphenyl type epoxy resin (NC 3000L, manufactured by Japan chemical Co., ltd., epoxy equivalent of about 269 g/eq.) and 5 parts of naphthalene type epoxy resin (HP-4032-SS, manufactured by DIC Co., ltd., 1, 6-bis (glycidyloxy) naphthalene, epoxy equivalent of about 145 g/eq.) were dissolved in 20 parts of solvent naphtha by heating while stirring, to obtain a solution. The solution was cooled to room temperature to prepare a dissolved composition of epoxy resin.
To the epoxy resin-dissolved composition, 80 parts of the "treated silica 1" obtained in production example 1, 5 parts of an active ester-based curing agent (toluene solution having an active ester group equivalent of about 220g/eq., 62 mass% of non-volatile matter content, manufactured by DIC corporation), 0.1 part of a triazine skeleton-containing phenol-based curing agent (LA-3018-50P, manufactured by DIC corporation, an active group equivalent of about 151g/eq., a non-volatile matter content 50% 2-methoxypropanol solution), 2 parts of a carbodiimide-based curing agent (toluene solution having an active group equivalent of about 216g/eq., 50% of non-volatile matter content, manufactured by daily-life chemical corporation), 5 parts of an imidazole-based curing accelerator (toluene solution having an active group equivalent of about 216g/eq., 1B2PZ, 1-benzyl-2-phenylimidazole, manufactured by the national chemical corporation), and 5 parts of a phenoxy resin (MEK 1, 30 mass% of non-volatile matter content, and 1 part of cyclohexanone were mixed uniformly, and a high-speed dispersion resin was prepared.
Example 2 ]
In example 1, the amount of "treated silica 1" was changed from 80 parts to 60 parts. Further, 3"5 parts of the" treated aluminosilicate "obtained in production example 3 was added to the resin composition. Further, the amount of the phenoxy resin (YX 7553BH30, manufactured by Mitsubishi chemical corporation, a 1:1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass) was changed from 5 parts to 2 parts. Except for the above matters, a resin composition was prepared in the same manner as in example 1.
Example 3 ]
In example 1, 5 parts of naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC Co., ltd., 1, 6-bis (glycidoxy) naphthalene, and an epoxy equivalent of about 145 g/eq.) was changed to 5 parts of bisphenol A type epoxy resin (828 EL "manufactured by Mitsubishi chemical corporation, and an epoxy equivalent of about 180 g/eq.). Further, 80 parts of the "treated silica 1" was changed to 60 parts of the "treated silica 2" obtained in production example 2 and 4"5 parts of the" treated aluminosilicate obtained in production example 4. Further, the amount of the phenoxy resin (YX 7553BH30, manufactured by Mitsubishi chemical corporation, a 1:1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass) was changed from 5 parts to 2 parts. Further, 3 parts of biphenyl aralkyl novolak type maleimide (MIR-3000-70 MT, manufactured by Japanese chemical Co., ltd., MEK/toluene mixed solution having a nonvolatile content of 70%) was added to the resin composition. Except for the above matters, a resin composition was prepared in the same manner as in example 1.
Example 4 ]
In example 3, the amount of "treated silica 2" was changed from 60 parts to 80 parts, and 16 parts of "treated aluminosilicate 4" was not used. Further, 3 parts of biphenyl aralkyl novolak type maleimide (MIR-3000-70 MT, manufactured by Japanese chemical Co., ltd., MEK/toluene mixed solution having a nonvolatile content of 70%) was changed to 3 parts of vinylbenzyl-modified polyphenylene ether (OPE-2 St 2200, manufactured by Mitsubishi gas chemical Co., ltd., toluene solution having a nonvolatile content of 65%). Further, 5 parts of a carbodiimide-based curing agent (toluene solution having an active group equivalent of about 216g/eq and a nonvolatile matter content of 50%) was not used (V-03, manufactured by Niqing textile chemical Co., ltd.). A resin composition was prepared in the same manner as in example 3, except for the above matters.
Example 5 ]
10 parts of naphthalene type epoxy resin (HP-4032-SS, 1, 6-bis (glycidoxy) naphthalene, about 145g/eq. In terms of epoxy equivalent), 10 parts of bisphenol A type epoxy resin (828 EL, about 180g/eq. In terms of epoxy equivalent, manufactured by Mitsubishi chemical corporation) and 15 parts of naphthalene ether type epoxy resin (HP-6000, 250g/eq. In terms of epoxy equivalent, manufactured by DIC corporation) were dissolved in 50 parts of solvent naphtha by heating while stirring, to obtain a solution. The solution was cooled to room temperature to prepare a dissolved composition of epoxy resin.
To this epoxy resin dissolved composition, 120 parts of the "treated silica 1" obtained in production example 1, 20 parts of an active ester curing agent (HPC-8150-62T, manufactured by DIC corporation, a toluene solution having an active ester equivalent of about 220g/eq., a nonvolatile content of 62 mass%) 15 parts of a bisphenol a dicyanate prepolymer (lyn) manufactured by zepan, b.p. "Primaset BA230S75", a MEK solution having a cyanate equivalent of about 232g/eq., a nonvolatile content of 75 mass%), 0.2 part of a curing accelerator (4-Dimethylaminopyridine (DMAP)), 0.01 part of cobalt (III) acetylacetonate (manufactured by tokyo, co (III) AcAc), 8 parts of a phenoxy resin (yo 7553BH30, a 1:1 solution of MEK and cyclohexanone, manufactured by mitsubishi chemical corporation) were mixed, and uniformly dispersed by a high-speed rotary mixer.
Example 6 ]
A resin composition was prepared in the same manner as in example 1, except that 80 parts of "treated silica 1" in example 1 was changed to 80 parts of "treated silica 5" obtained in production example 5.
Example 7 ]
A resin composition was prepared in the same manner as in example 1, except that 80 parts of "treated silica 1" in example 1 was changed to 80 parts of "treated silica 6" obtained in production example 6.
Example 8 ]
A resin composition was prepared in the same manner as in example 1, except that 80 parts of "treated silica 1" in example 1 was changed to 80 parts of "treated silica 7" obtained in production example 7.
Comparative example 1 ]
In example 1, 80 parts of "treated silica 1" was changed to untreated spherical silica (SO-C2, manufactured by admatechs Co., ltd.), an average particle diameter of 0.5 μm, and a specific surface area of 5.8m 2 A resin composition was prepared in the same manner as in example 1 except that 80 parts per gram) of the resin composition was used.
< production of resin sheet >
As a support, a polyethylene terephthalate film (AL 5, manufactured by LINTEC Co., ltd., thickness: 38 μm) having a release layer was prepared. The resin compositions obtained in the examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 40. Mu.m. Thereafter, the resin composition was dried at 80℃to 100℃for 4 minutes (average 90 ℃) to obtain a resin sheet comprising a support and a resin composition layer.
< test example 1: determination of minimum melt viscosity-
The resin composition layers of the resin sheets were stacked by 25 sheets to obtain 1mm thick resin composition layers. The resin composition layer was punched out to have a diameter of 20mm to prepare a measurement sample. The lowest melt viscosity (poise) was determined by measuring the dynamic viscoelasticity (measured as the viscoelasticity of the small) of the prepared measurement sample using a dynamic viscoelasticity measuring apparatus (Rheogel-G3000, manufactured by UBM Co.) under the measurement conditions of a start temperature of 60 to 200 ℃, a temperature rise rate of 5 ℃/min, a measurement temperature interval of 2.5 ℃ and a vibration frequency of 1 Hz.
< test example 2: determination of arithmetic average roughness (Ra)
(1) Base treatment of the built-in substrate:
as the inner layer substrate, a glass cloth base epoxy resin double-sided copper-clad laminate having copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8mm, panasonic corporation "R1515A") was prepared. The copper foil on the surface of the inner layer substrate was roughened by etching with a copper etching amount of 1 μm using a micro etcher ("CZ 8101" manufactured by tikun corporation). Thereafter, drying was performed at 190℃for 30 minutes.
(2) Lamination and curing of resin sheets:
the resin sheet was laminated on both surfaces of the inner substrate using a batch vacuum laminator ("CVP 700") so that the resin composition layer was bonded to the inner substrate. The lamination was performed by reducing the pressure to 13hPa or less for 30 seconds and then pressing at a temperature of 100℃and a pressure of 0.74MPa for 30 seconds.
Next, the laminated resin sheet was subjected to hot pressing at 100℃under a pressure of 0.5MPa for 60 seconds under atmospheric pressure, and was smoothed. Further, it was put into an oven at 130℃for 30 minutes, and then transferred into an oven at 170℃for 30 minutes. The insulating layer is formed by curing the aforementioned heated resin composition layer.
(3) Formation of a via:
CO manufactured by Fangyi corporation is used 2 A laser processing machine (LK-2K 212/2C) processes the insulating layer at a frequency of 2000Hz and a pulse width of 3 μsec, an output power of 0.95W, and an irradiation number of 3, thereby forming a via hole. The opening diameter (top diameter, diameter) of the via hole in the surface of the insulating layer was 50 μm, and the diameter of the via hole in the bottom surface of the insulating layer was 40 μm. Thereafter, the polyethylene terephthalate film as a support was peeled off to obtain a sample substrate having a layer structure of an insulating layer/an inner layer substrate/an insulating layer.
(4) Roughening treatment
The sample substrate was immersed in a solution of doctor blade P (an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) as a swelling solution at 60 ℃ for 10 minutes. Next, the sample substrate was set to コ by seta, コ by the company seta as a roughening liquid (KMnO 4 :60g/L, naOH:40g/L in water) was immersed in the solution at 80℃for 20 minutes. Finally, the step of obtaining the product, sample substrates were used in a reader device manufactured by the company of the field as a neutralization solution immersing in the solution of part P of part (sulfuric acid aqueous solution) at 40 ℃ for 5 minutes, the evaluation substrate a was obtained as a sample substrate after the roughening treatment.
(5) Determination of arithmetic average roughness (Ra):
the arithmetic average roughness Ra of the surface of the insulating layer of the obtained evaluation substrate a was measured by a VSI mode and a 50-fold lens under a measurement condition of a measurement range of 121 μm×92 μm using a non-contact surface roughness meter (WYKO NT3300, fluxwell corporation). For each evaluation substrate a, the arithmetic average roughness Ra at 10 points selected at random was measured, and the average value was obtained.
< test example 3: determination of relative permittivity (Dk) and dielectric loss tangent (Df)
The resin sheet was heated at 200℃for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off, whereby a cured product film formed from the cured product of the resin composition was obtained. The cured film was cut into a width of 2mm and a length of 80mm to obtain a cured product A for evaluation.
The obtained cured product a for evaluation was subjected to cavity resonance perturbation method to measure the relative dielectric constant (Dk value) and dielectric loss tangent (Df value) at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using "HP8362B" manufactured by Agilent Technologies corporation. The measurement was performed on 3 test pieces, and an average value was calculated.
< test example 4: evaluation of elongation at break point ]
The cured film obtained in test example 3 was subjected to a tensile test by a tentilon universal tester ("RTC-1250A" manufactured by tentilon corporation) in accordance with JIS K7127, and the breaking point elongation [% ] was measured.
< results >
The results of the above examples and comparative examples are shown in the table below. In the tables below, the meanings for short are as follows.
Ra: arithmetic average roughness of the surface of the cured product.
TABLE 1
TABLE 1 results of examples 1-5 and comparative example 1
TABLE 2
TABLE 2 results for examples 1 and 6-8
Treated silica 1: spherical silica treated in the order KBM-573 (0.3%) and V-03 (0.3%).
Treated silica 2: spherical silica treated in the order KBM-573 (0.3%) and polycarbodiimide compound 1 (0.3%).
Treated aluminosilicate 3: hollow aluminosilicate particles treated in the order KBM-573 (0.5%) and V-03 (0.5%).
Treated aluminosilicate 4: hollow aluminosilicate particles treated in the order KBM-573 (0.5%) and polycarbodiimide compound 1 (0.5%).
Treated silica 5: spherical silica treated in the order KBM-573 (0.4%) and V-03 (0.2%).
Treated silica 6: spherical silica treated in the order KBM-573 (0.1%) and V-03 (0.5%).
Treated silica 7: spherical silica treated in the order of V-03 (0.3%) and KBM-573 (0.3%).
Description of the reference numerals
100. Semiconductor chip package
110. Semiconductor chip
120. Sealing layer
130. Rerouting layer formation
140. Rewiring layer
150. Solder resist layer
160. Bump

Claims (19)

1. A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with a carbodiimide compound.
2. The resin composition according to claim 1, wherein the carbodiimide compound contains a structural unit represented by the following formula (C-1),
in the formula (C-1), Y represents a 2-valent hydrocarbon group optionally having a substituent.
3. The resin composition according to claim 1, wherein the carbodiimide compound contains an ethylenically unsaturated bond.
4. The resin composition according to claim 1, wherein the amount of the component (C) is 50% by mass or more relative to 100% by mass of the nonvolatile component of the resin composition.
5. The resin composition according to claim 1, wherein the component (B) contains 1 or more selected from the group consisting of an active ester-based curing agent, a phenol-based curing agent and a cyanate-based curing agent.
6. The resin composition according to claim 1, which comprises (D) a curing accelerator.
7. The resin composition of claim 1, comprising (E) a thermoplastic resin.
8. The resin composition of claim 1 having a minimum melt viscosity of less than 2000 poise.
9. The resin composition according to claim 1, wherein when the resin composition is heated at 200℃for 90 minutes to obtain a cured product, the cured product has a breaking point elongation of 1% or more.
10. The resin composition according to claim 1, wherein the cured product has an arithmetic average roughness Ra of less than 300nm when the cured product is roughened by heating the resin composition at 170 ℃ for 30 minutes.
11. The resin composition according to claim 1, which is used for forming an insulating layer.
12. A cured product of the resin composition according to any one of claims 1 to 11.
13. A sheet-like laminate comprising the resin composition according to any one of claims 1 to 11.
14. A resin sheet having a support and a resin composition layer formed on the support,
the resin composition layer comprises the resin composition according to any one of claims 1 to 11.
15. A circuit board comprising a cured product of the resin composition according to any one of claims 1 to 11.
16. A semiconductor chip package comprising a cured product of the resin composition according to any one of claims 1 to 11.
17. A semiconductor device having the circuit board according to claim 15.
18. A semiconductor device having the semiconductor chip package of claim 16.
19. A method for producing a resin composition, comprising:
a first step of mixing a carbodiimide compound with an inorganic filler to obtain (C) an inorganic filler surface-treated with a carbodiimide compound, and
a second step of mixing (C) an inorganic filler surface-treated with a carbodiimide compound, (A) an epoxy resin, and (B) a curing agent.
CN202310489251.XA 2022-05-02 2023-04-28 Resin composition Pending CN116987364A (en)

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