CN116082792A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN116082792A
CN116082792A CN202211375909.6A CN202211375909A CN116082792A CN 116082792 A CN116082792 A CN 116082792A CN 202211375909 A CN202211375909 A CN 202211375909A CN 116082792 A CN116082792 A CN 116082792A
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Prior art keywords
resin composition
mass
resin
epoxy resin
manufactured
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Inventor
中村洋介
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Epoxy Resins (AREA)

Abstract

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a (meth) acrylate having a biphenyl skeleton, wherein the content of the (B) active ester compound is 10% by mass or more when the nonvolatile content in the resin composition is 100% by mass, and the content of the (C) inorganic filler is 60% by mass or more when the nonvolatile content in the resin composition is 100% by mass.

Description

Resin composition
Technical Field
The present invention relates to a resin composition.
Background
As a technique for manufacturing a printed wiring board, a manufacturing method using a stacked (build-up) method of alternately stacking insulating layers and conductor layers is known. In the manufacturing method using the stacking method, generally, an insulating layer is formed by curing a resin composition to obtain a cured product (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2020-23714.
Disclosure of Invention
Technical problem to be solved by the invention
The cured product contained in the insulating layer is required to have a low dielectric loss tangent. One of the methods for obtaining a cured product having a low dielectric loss tangent is to blend an active ester compound and an inorganic filler in a resin composition at a high concentration. However, when a resin composition containing an active ester compound and an inorganic filler in high concentrations is used, the stain removability, the plating adhesion and the metal foil adhesion tend to be lowered.
Specifically, when an insulating layer is formed from a cured product of a resin composition, holes such as a via hole and a via hole may be formed in the insulating layer. In the case where such holes are formed in the insulating layer, contamination as resin residues may be formed in the holes. Generally, it is desirable to remove the stain. The removal of stains is mostly carried out using pharmaceutical agents. However, when a resin composition containing an active ester compound and an inorganic filler at a high concentration is used, the stain removal property tends to be low.
In the case of forming a conductor layer on an insulating layer, the conductor layer may be formed by plating. However, when a resin composition containing an active ester compound and an inorganic filler at a high concentration is used, adhesion between the insulating layer and the conductor layer formed by plating tends to be lowered.
In addition, in the process of manufacturing a printed wiring board, an insulating layer may be formed with a resin composition on a conductor layer as a base. The conductor layer as a substrate is usually a metal foil when forming the insulating layer. Therefore, the insulating layer is required to have good adhesion to the metal foil as a base. However, when a resin composition containing an active ester compound and an inorganic filler at a high concentration is used, the adhesion between the insulating layer and the metal foil as a base tends to be lowered.
The present invention has been made in view of the above problems, and an object thereof is to provide: a resin composition which can obtain a cured product excellent in stain removability, plating adhesion and metal foil adhesion; a cured product of the resin composition; a sheet laminate containing the resin composition; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; a semiconductor device provided with the printed wiring board.
Technical proposal adopted for solving the technical problems
The present inventors have made intensive studies to solve the above-described problems. As a result, the present inventors have found that the above-mentioned problems can be solved by combining a resin composition comprising (a) an epoxy resin, a specific range of amount of (B) an active ester compound, a specific range of amount of (C) an inorganic filler, and (D) a (meth) acrylate having a biphenyl skeleton, and have completed the present invention. Namely, the present invention includes the following.
[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a (meth) acrylate having a biphenyl skeleton, wherein,
When the nonvolatile content in the resin composition is set to 100 mass%, the content of the (B) active ester compound is 10 mass% or more,
when the nonvolatile content in the resin composition is set to 100 mass%, the content of the inorganic filler (C) is 60 mass% or more;
[2] the resin composition according to [1], wherein the (D) acrylate (meth) having a biphenyl skeleton comprises: a compound containing an ether structure;
[3] the resin composition according to [1] or [2], wherein the (D) acrylic acid ester having a biphenyl skeleton comprises a compound represented by the following formula (D1),
[ chemical formula 1]
Figure BDA0003926640920000021
In the formula (D1), the amino acid sequence of the formula (D),
R 11 each independently represents a hydrogen atom or a methyl group,
R 12 each independently represents a divalent aliphatic hydrocarbon group,
m1 represents an integer of 0 to 5,
n1 represents an integer of 0 to 6,
R 21 each independently represents a hydrogen atom or a methyl group,
R 22 each independently represents a divalent aliphatic hydrocarbon group,
m2 represents an integer of 0 to 5,
n2 represents an integer of 0 to 6,
wherein m1+m2 is 1 or more;
[4] the resin composition according to any one of [1] to [3], wherein the content of (D) the (meth) acrylate having a biphenyl skeleton is 0.5 mass% or more and 25 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition;
[5] The resin composition according to any one of [1] to [4], wherein the resin composition comprises 1 or more (E) curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents;
[6] the resin composition according to any one of [1] to [5], wherein (F) a curing accelerator is contained;
[7] the resin composition according to any one of [1] to [6], wherein (G) a thermoplastic resin is contained;
[8] the resin composition according to any one of [1] to [7], wherein the resin composition is used for forming an insulating layer;
[9] a cured product of the resin composition according to any one of [1] to [8 ];
[10] a sheet laminate comprising the resin composition according to any one of [1] to [8 ];
[11] a resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [8] provided on the support;
[12] a printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [8 ];
[13] a semiconductor device comprising the printed wiring board according to [12 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a resin composition which can provide a cured product excellent in stain removability, plating adhesion and metal foil adhesion; a cured product of the resin composition; a sheet laminate containing the resin composition; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; a semiconductor device provided with the printed wiring board.
Detailed Description
Hereinafter, the present invention will be described with reference to the embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be modified in any manner without departing from the scope of the claims and their equivalents.
In the following description, unless otherwise specified, the term "(meth) acrylate" includes acrylates, methacrylates, and combinations thereof. In the following description, unless otherwise specified, the term "(meth) acryl" includes acryl, methacryl, and combinations thereof. In the following description, unless otherwise specified, the term "(meth) acryloyloxy" includes acryloyloxy, methacryloyloxy and combinations thereof. In addition, in the following description, unless otherwise specified, the term … ester of (meth) acrylic acid includes … ester of acrylic acid, … ester of methacrylic acid, and combinations thereof.
[1. Outline of resin composition ]
The resin composition according to one embodiment of the present invention comprises (a) an epoxy resin, (B) an active ester compound in an amount within a specific range, (C) an inorganic filler in an amount within a specific range, and (D) a (meth) acrylate having a biphenyl skeleton. When the resin composition is used, a cured product excellent in stain removability, plating adhesion and metal foil adhesion can be obtained. In addition, the cured product may generally have a low dielectric loss tangent. In addition, the cured product generally has a small surface roughness after the roughening treatment. The cured product can be suitably used as a material for an insulating layer of a printed wiring board, for example.
The present inventors speculate that the cured product of the resin composition according to the present embodiment can obtain excellent advantages as described above, based on the following principle. However, the technical scope of the present invention is not limited by the principle described below.
The cured product of a conventional resin composition containing an epoxy resin, a predetermined amount or more of an active ester compound, and a predetermined amount or more of an inorganic filler may generally have a low dielectric loss tangent. However, the cured product of the resin composition generally tends to be poor in stain removability, plating adhesion and metal foil adhesion.
In contrast, the resin composition according to the present embodiment contains (a) an epoxy resin, (B) an active ester compound in an amount within a specific range, (C) an inorganic filler in an amount within a specific range, and (D) a (meth) acrylate having a biphenyl skeleton. Hereinafter, the (meth) acrylate having a biphenyl skeleton as the component (D) may be referred to as "specific (meth) acrylate". (D) The carbon-carbon unsaturated bond (ethylenic unsaturated bond) of the (meth) acryl contained in the specific (meth) acrylate may undergo radical polymerization reaction when the resin composition is cured, so that the specific (meth) acrylates in the cured product may be bonded to each other. The bond between the (D) specific (meth) acrylic acid esters contained in the cured product can be easily oxidized and cut off by the oxidizing agent for removing stains. Therefore, removal of the cured product by the oxidizing agent can be promoted, so that stain removal performance is improved.
Further, since the biphenyl skeleton contained in the specific (meth) acrylate (D) has high rigidity, the mechanical strength of the cured product of the resin composition can be improved by the action of the specific (meth) acrylate (D) containing the biphenyl skeleton. Thus, the resistance of the cured product to stress can be improved. Therefore, peeling (interlayer peeling) accompanying breakage of the cured product can be suppressed, so that the plating adhesion and the metal foil adhesion can be improved.
Further, polar groups such as hydroxyl groups are not generally generated by radical polymerization of (D) a specific (meth) acrylate. Thus, even if (D) a specific (meth) acrylate is contained, the polarity of the cured product can be low. Therefore, the cured product of the resin composition may generally have a low dielectric loss tangent.
Further, the (D) specific (meth) acrylate having a biphenyl skeleton can realize excellent affinity with (a) the epoxy resin and (B) the active ester compound. Thus, phase separation of the resin components such as component (A), component (B) and component (D) in the resin composition is suppressed. If a large amount of phase separation occurs in the resin component, large domains (phase domains) are formed in the cured product, and the domains are separated during roughening treatment, and the surface roughness may be increased. However, in the resin composition according to the present embodiment, since phase separation of the resin component is suppressed, formation of a large domain is suppressed. Therefore, it is usual to have a smaller surface roughness after the roughening treatment.
[2. (A) epoxy resin ]
The resin composition according to the present embodiment 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 bisxylenol (biscatechol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol novolac (naphthalene type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a alicyclic epoxy resin, a heterocyclic type epoxy resin, a spiro-ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenyl ethane type epoxy resin, an isocyanatone type epoxy resin, and an phthalone type epoxy resin. (A) The epoxy resin may be used alone or in combination of two or more.
From the viewpoint of obtaining a cured product excellent in heat resistance, the (a) epoxy resin preferably contains an epoxy resin containing an aromatic structure. Aromatic structures are chemical structures that are generally defined as aromatic, and also include 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, glycidyl amine type epoxy resin having an aromatic structure, glycidyl ester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure, alicyclic epoxy resin having an aromatic structure, heterocyclic type epoxy resin having an aromatic structure, spiro ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, tetraphenyl ethane type epoxy resin having an aromatic structure, and the like.
In the resin composition, the epoxy resin (a) preferably contains 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.
The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). In the resin composition, the epoxy resin may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination.
As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferable.
Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", 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" (glycidyl amine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ED-523T" (GLYCIROL epoxy resin) manufactured by ADEKA Co; "EP-3950L", "EP-3980S" (glycidyl amine type epoxy resins) manufactured by ADEKA Co; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co., ltd; "ZX1059" manufactured by Nissan chemical materials chemical Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "Celloxide2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daxil corporation; "PB-3600" by Daxillon corporation, and "JP-100" and "JP-200" by Japan, respectively (epoxy resin having butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nissan chemical materials Co., ltd. These may be used singly or in combination of two or more.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
As the solid epoxy resin, there are preferable a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene-ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenylethane-type epoxy resin, and 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 tetrafunctional epoxy resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" manufactured by DIC Co., ltd. (cresol novolak type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Co; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Co., ltd; "EPPN-502H" (triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical pharmaceutical company; "ESN475V" and "ESN4100V" manufactured by Nissan chemical materials Co., ltd. (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nissan chemical materials Co., ltd; "ESN375" manufactured by Nissan chemical materials Co., ltd. (dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000HK", "YL7890" (Bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "YX7700" manufactured by Mitsubishi chemical corporation (phenol aralkyl type epoxy resin); "PG-100", "CG-500" manufactured by Osaka gas chemical Co., ltd; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Japanese chemical Co., ltd. These may be used singly or in combination of two or more.
When the liquid epoxy resin is used in combination with the solid epoxy resin as the epoxy resin (a), the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, particularly preferably 7:1 to 1:7.
(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5000g/eq, more preferably 60g/eq to 3000g/eq, still more preferably 80g/eq to 2000g/eq, particularly preferably 110g/eq to 1000g/eq. The epoxy equivalent represents the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.
(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500. The weight average molecular weight of the resin can be measured by Gel Permeation Chromatography (GPC) as a value converted to polystyrene.
When the nonvolatile content in the resin composition is set to 100% by mass, the content of the (a) epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 4% by mass or more, more preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less. (A) When the amount of the epoxy resin is within the above range, the stain removability, the plating adhesion, the metal foil adhesion, the dielectric loss tangent and the surface roughness after the roughening treatment can be particularly good.
The content of the epoxy resin (a) in the resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, particularly preferably 20 mass% or more, still more preferably 70 mass% or less, still more preferably 50 mass% or less, particularly preferably 30 mass% or less, based on 100 mass% of the resin component in the resin composition. The resin component of the resin composition means a component other than the inorganic filler (C) in the nonvolatile component of the resin composition. (A) When the amount of the epoxy resin is within the above range, the stain removability, the plating adhesion, the metal foil adhesion, the dielectric loss tangent and the surface roughness after the roughening treatment can be particularly good.
[3. (B) active ester Compound ]
The resin composition according to the present embodiment contains the (B) active ester compound as the (B) component in a content within a specific range. (B) The active ester compound may have a function as an epoxy resin curing agent that reacts with the (a) epoxy resin to cure the resin composition. (B) The active ester compound may be used singly or in combination of two or more.
As the active ester compound (B), a compound 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, etc., is generally preferably used. The active ester compound is preferably a compound obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound 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, trihydroxybenzone, tetrahydroxybenzophenone, phloroglucinol, and novolac (phenol novolac). The "dicyclopentadiene type phenol compound" refers to a phenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.
Specifically, as the (B) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a novolac resin, and an active ester compound containing a benzoyl compound of a novolac resin are preferable, and at least one selected from the dicyclopentadiene type active ester compound and the naphthalene type active ester compound is more preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.
As the commercial product of the active ester compound (B), for example, the active ester compounds containing dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC); examples of the active ester compound having a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Co.); examples of the phosphorus-containing active ester compound include "EXB9401" (manufactured by DIC Co., ltd.); examples of the active ester compound of the acetyl compound of the novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester compound of the benzoyl compound of the novolac resin include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation); examples of the active ester compound having a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by AIRWATER Co., ltd.).
(B) The active ester group equivalent of the active ester compound is preferably 50g/eq to 500g/eq, more preferably 50g/eq to 400g/eq, still more preferably 100g/eq to 300g/eq. Active ester group equivalent means the mass of active ester compound per 1 equivalent of active ester group.
When the number of epoxy groups of the epoxy resin (a) is 1, the number of active ester groups of the active ester compound (B) is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, still more preferably 5.0 or less, still more preferably 4.0 or less, and particularly preferably 3.0 or less. The "(a) epoxy resin epoxy number" means a value 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 "(active ester number of (B) active ester compound" means a value obtained by summing up all the values obtained by dividing the mass of the nonvolatile components of (B) active ester compound present in the resin composition by the equivalent of active ester groups.
The content of the active ester compound (B) in the resin composition is usually 10 mass% or more, preferably 11 mass% or more, more preferably 12 mass% or more, further preferably 13 mass% or more, particularly preferably 14 mass% or more, more preferably 35 mass% or less, more preferably 30 mass% or less, further more preferably 25 mass% or less, particularly preferably 20 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. (B) When the amount of the active ester compound is within the above range, stain removability, plating adhesion, metal foil adhesion, dielectric loss tangent and surface roughness after roughening treatment can be particularly good.
The content of the active ester compound (B) in the resin composition is preferably 25 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, particularly preferably 50 mass% or more, more preferably 90 mass% or less, more preferably 80 mass% or less, further preferably 70 mass% or less, particularly preferably 60 mass% or less, based on 100 mass% of the resin component in the resin composition. (B) When the amount of the active ester compound is within the above range, stain removability, plating adhesion, metal foil adhesion, dielectric loss tangent and surface roughness after roughening treatment can be particularly good.
[4 ] (C) inorganic filler ]
The resin composition according to the present embodiment contains (C) an inorganic filler in a content within a specific range. (C) The inorganic filler is generally contained in the resin composition in the form of particles.
As the material of the inorganic filler (C), an inorganic compound can be used. Examples of the material of the inorganic filler (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among them, silica 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. (C) The inorganic filler may be used alone or in combination of two or more.
Examples of the commercial products of the inorganic filler (C) include "UFP-30" manufactured by electric chemical industry Co., ltd., SP60-05"," SP507-05 "manufactured by Nippon Kagaku Co., ltd., YC100C", "YA050C-MJE", "YA010C" manufactured by Admatechs, DENKA Co., ltd., UFP-30 "manufactured by Tokuyama Co., ltd., SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" manufactured by Ma Co., ltd., SC2500SQ "," SO-C4"," SO-C2"," SO-C1", and" DAW-03"," FB-105FD "manufactured by DENKA Co., ltd.
From the viewpoint of significantly obtaining the desired effect of the present invention, (C) 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, still more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less.
(C) The average particle size of the inorganic filler material can be determined by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced by a laser diffraction scattering type particle size distribution measuring apparatus on a volume basis, and the median particle size can be measured as the average particle size. As a measurement sample, a sample obtained by weighing 100mg of an inorganic filler and 10g of methyl ethyl ketone into a vial and dispersing by ultrasonic waves for 10 minutes was used. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus was used, blue and red were used as light source wavelengths, the volume-based particle size distribution of the inorganic filler was measured by a flow cell (flow cell), and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
From the viewpoint of significantly obtaining the desired effect of the present invention, (C) the specific surface area of the inorganic filler is preferably 0.1m 2 Preferably at least 0.5m 2 Preferably at least/g, more preferably at least 1m 2 Preferably at least 3m 2 Preferably at least 100m 2 Preferably less than or equal to/g, more preferably 70m 2 Preferably less than or equal to/g, more preferably 50m 2 Preferably less than/g, particularly preferably 40m 2 And/g or less. The specific surface area of the inorganic filler can be measured by adsorbing nitrogen gas onto the surface of a sample by a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech corporation) according to the BET method, and calculating the specific surface area by the BET multipoint method.
From the viewpoint of improving moisture resistance and dispersibility, (C) the inorganic filler is preferably treated with a surface treating agent. Examples of the surface treating agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of 2 or more kinds.
Examples of the commercial products of the surface treatment agent include "KBM403" (3-glycidoxypropyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., "KBM803" (3-mercaptopropyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., KBE903 "(3-aminopropyl triethoxysilane) manufactured by Shimadzu chemical Co., ltd., KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., SZ-31 "(hexamethyldisilazane) manufactured by Shimadzu chemical Co., ltd., KBM103" (phenyl trimethoxysilane) manufactured by Shimadzu chemical Co., ltd., KBM-4803 "(long chain epoxy silane coupling agent) manufactured by Shimadzu chemical Co., ltd., KBM-7103" (3, 3-trifluoropropyl trimethoxysilane) and the like.
The degree of the surface treatment with the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, it is preferable that 100 mass% of the inorganic filler is surface-treated with 0.2 mass% to 5 mass% of the surface treating agent, it is preferable that 100 mass% of the inorganic filler is surface-treated with 0.2 mass% to 3 mass% of the surface treating agent, and it is further preferable that 100 mass% of the inorganic filler is surface-treated with 0.3 mass% to 2 mass% of the surface treating agent.
The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m 2 The above is more preferably 0.1mg/m 2 The above is more preferably 0.2mg/m 2 The above. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin composition, it is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The following is more preferable to be 0.5mg/m 2 The following is given.
(C) The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is subjected to a washing treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with the surface treating agent, and the mixture was ultrasonically cleaned at 25 ℃ for 5 minutes. After the supernatant is removed and the solid component is dried, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.
When the nonvolatile content in the resin composition is set to 100% by mass, the content of the inorganic filler (C) in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, particularly preferably 70% by mass or more, preferably 86% by mass or less, more preferably 82% by mass or less, particularly preferably 78% by mass or less. (C) When the amount of the inorganic filler is within the above range, the stain removability, the plating adhesion, the metal foil adhesion, the dielectric loss tangent and the surface roughness after the roughening treatment can be particularly good.
[5. (D) a (meth) acrylate having a biphenyl skeleton ]
The resin composition according to the present embodiment contains (D) a (meth) acrylate having a biphenyl skeleton as the (D) component (i.e., (D) a specific (meth) acrylate).
(D) The specific (meth) acrylate contains a (meth) acryloyloxy group in its molecule. The carbon-carbon unsaturated bond (ethylenic unsaturated bond) contained in the (meth) acryloyloxy group may generally undergo radical polymerization when the resin composition is cured. (D) The number of (meth) acryloyloxy groups contained in the molecule of the specific (meth) acrylate may be 1 or 2 or more. (D) The specific number of (meth) acryloyloxy groups contained in the molecule of the specific (meth) acrylate is preferably 1 or more, more preferably 6 or less, still more preferably 4 or less, still more preferably 3 or less, particularly preferably 2 or less.
(D) The specific (meth) acrylate has a biphenyl skeleton in its molecule. (D) The number of biphenyl skeletons contained in the molecule of the specific (meth) acrylate may be 2 or more, but is usually 1. The (meth) acryloyloxy group may be directly bonded to a benzene ring of the biphenyl skeleton or indirectly bonded thereto via a linking group. (D) When the specific (meth) acrylate has 2 or more (meth) acryloyloxy groups, the (meth) acryloyloxy groups may be bonded to only one of the 2 benzene rings of the biphenyl skeleton, but it is preferable that the (meth) acryloyloxy groups are bonded to the 2 benzene rings of the biphenyl skeleton.
(D) In the specific (meth) acrylic acid ester, it is preferable that the (meth) acryloyloxy group and the biphenyl skeleton are combined, and the ether structure is further contained. Accordingly, (D) the specific (meth) acrylate preferably comprises: a compound containing an ether structure. The ether structure does not include an ether structure contained in the (meth) acryloyloxy group. The number of ether structures contained in the molecule of the (D) specific (meth) acrylate containing an ether structure may be 1 or 2 or more. The ether structure is preferably contained in a linking group linking the (meth) acryloyloxy group to the benzene ring of the biphenyl skeleton. Further, it is preferable that at least one oxygen atom contained in the ether structure is directly bonded to the benzene ring.
Further, the linking group linking the (meth) acryloyloxy group to the benzene ring of the biphenyl skeleton preferably contains a divalent aliphatic hydrocarbon group. Thus, (D) the specific (meth) acrylate preferably comprises: a compound containing a "linking group comprising a divalent aliphatic hydrocarbon group". The divalent aliphatic hydrocarbon group is preferably a chain aliphatic hydrocarbon group, and may be linear or branched. The divalent aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. The number of carbon atoms of the divalent aliphatic hydrocarbon group is usually 1 or more, preferably 12 or less, more preferably 6 or less, further preferably 4 or less, particularly preferably 2 or less. Examples of the preferable divalent aliphatic hydrocarbon group include methylene, ethylene, propylene, butylene, pentylene, and hexylene.
The specific (meth) acrylate (D) is particularly preferably a compound represented by the following formula (D1). Accordingly, the specific (meth) acrylate preferably contains a compound represented by the following formula (D1), more preferably contains only a compound represented by the following formula (D1).
[ chemical formula 2]
Figure BDA0003926640920000131
In the formula (D1), R 11 Each independently represents a hydrogen atom or a methyl group. In the formula (D1), R is 21 Each independently represents a hydrogen atom or a methyl group.
In the formula (D1), R 12 Each independently represents a divalent aliphatic hydrocarbon group. In the formula (D1), R is 22 Each independently represents a divalent aliphatic hydrocarbon group. As the divalent aliphatic hydrocarbon group, the groups in the ranges described above as the divalent aliphatic hydrocarbon group that may contain a linking group that links the (meth) acryloyloxy group to the benzene ring of the biphenyl skeleton can be used.
In the formula (D1), m1 represents an integer of 0 to 5, preferably 0 or 1, particularly preferably 1. In the formula (D1), m2 represents an integer of 0 to 5, preferably 0 or 1, particularly preferably 1. Wherein m1+m2 is 1 or more.
In the formula (D1), n1 independently represents an integer of 0 to 6. In the formula (D1), n2 independently represents an integer of 0 to 6. Specifically, n1 and n2 are usually 0 or more, preferably 1 or more, usually 6 or less, preferably 4 or less, more preferably 3 or less, particularly preferably 2 or less. n1 and n2 may be the same or different.
Specific examples of the specific (meth) acrylate (D) include compounds represented by the following formulas (D1) to (D4). In the following formula, n represents an integer of 1 or more, preferably 1 to 2, more preferably 1.
[ chemical formula 3]
Figure BDA0003926640920000141
Examples of the commercial products of the specific (meth) acrylate (D) include "A-LEN-10" (a compound represented by formula (D1) manufactured by Xinzhou chemical industry Co., ltd.), and "A-BP-2EO" (a compound represented by formula (D3)) manufactured by Benzhou chemical industry Co., ltd.
(D) The specific (meth) acrylic acid esters may be used singly or in combination of two or more.
Mass W of (D) a specific (meth) acrylate in the resin composition D Mass W of epoxy resin (A) A Mass ratio W of (2) D /W A Preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, particularly preferably 0.7 or more, preferably 10 or less, still more preferably 5.0 or less, still more preferably 2.0 or less, particularly preferably 1.0 or less. Mass ratio W D /W A When the amount is within the above range, the plating adhesion and the metal foil adhesion can be effectively improved, and the dielectric loss tangent can be effectively reduced.
Mass W of (D) a specific (meth) acrylate in the resin composition D Mass W of active ester compound (B) B Mass ratio W of (2) D /W B The content is preferably at least 0.01, more preferably at least 0.05, even more preferably at least 0.10, particularly preferably at least 0.15, even more preferably at most 2.0, even more preferably at most 1.5, even more preferably at most 1.0, and particularly preferably at most 0.5. Mass ratio W D /W B When the amount is within the above range, the plating adhesion and the metal foil adhesion can be effectively improved, and the dielectric loss tangent can be effectively reduced.
Mass W of (D) a specific (meth) acrylate in the resin composition D Total mass W of the epoxy resin (A) and the active ester compound (B) A +W B Mass ratio W of (2) D /(W A +W B ) It is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, particularly preferably 0.20 or more, still more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.0 or less, particularly preferably 0.5 or less. Mass ratio W D /(W A +W B ) When the amount is within the above range, the plating adhesion and the metal foil adhesion can be effectively improved, and the dielectric loss tangent can be effectively reduced.
Mass W of (D) a specific (meth) acrylate in the resin composition D And (C) mass W of inorganic filler C Mass ratio W of (2) D /W C Preferably 0.001The content is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.03 or more, more preferably 0.4 or less, more preferably 0.3 or less, still more preferably 0.2 or less, particularly preferably 0.1 or less. Mass ratio W D /W C When the amount is within the above range, the plating adhesion and the metal foil adhesion can be effectively improved, and the dielectric loss tangent can be effectively reduced.
The content of the specific (meth) acrylate (D) in the resin composition is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, particularly preferably 2.0 mass% or more, more preferably 25 mass% or less, more preferably 20 mass% or less, particularly preferably 10 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. (D) When the amount of the specific (meth) acrylate is within the above range, stain removability, plating adhesion, metal foil adhesion, dielectric loss tangent and surface roughness after roughening treatment can be particularly good.
The content of the specific (meth) acrylate (D) in the resin composition is preferably 2 mass% or more, more preferably 5 mass% or more, particularly preferably 10 mass% or more, still more preferably 70 mass% or less, still more preferably 40 mass% or less, particularly preferably 20 mass% or less, based on 100 mass% of the resin component in the resin composition. (D) When the amount of the specific (meth) acrylate is within the above range, stain removability, plating adhesion, metal foil adhesion, dielectric loss tangent and surface roughness after roughening treatment can be particularly good.
[ 6.(E) any curing agent ]
The resin composition according to the present embodiment may further contain (E) an optional curing agent as an optional component in combination with the above-described components (a) to (D). Any curing agent of the component (E) does not include curing agents belonging to the components (A) to (D). (E) Any curing agent may function as an epoxy resin curing agent for curing the resin composition by reacting with the epoxy resin (a) in the same manner as the active ester compound (B). (E) Any one of the curing agents may be used alone, or two or more of the curing agents may be used in combination.
Examples of the optional curing agent (E) include phenol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate curing agents, and thiol curing agents. Among them, it is preferable to use 1 or more curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
As the phenolic curing agent, a curing agent having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in 1 molecule can be used. From the viewpoints of heat resistance and water resistance, a phenolic curing agent having a phenolic structure (novolac structure) is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. Among them, a novolac resin (phenol novolac resin) containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He Chemicals, japan chemical Co., ltd., "NHN", "CBN", "GPH", and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by DIC, and "LA-7052", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by Nissan chemical Co., ltd.
As the carbodiimide-based curing agent, a curing agent having 1 or more, preferably 2 or more carbodiimide structures in 1 molecule can be used. Specific examples of the carbodiimide-based curing agent include: aliphatic dicarboximides such as tetramethylene-bis (t-butylcarbodiimide), and cyclohexanedis (methylene-t-butylcarbodiimide); aromatic dicarboximides such as phenylene-bis (xylyl carbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexyl carbodiimide) and poly (isophorone carbodiimide); and aromatic polycarbodiimides such as poly (phenylene carbodiimide), poly (naphthylene carbodiimide), poly (tolylene carbodiimide), poly (methyldiisopropylphenylene 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 commercially available carbodiimide curing agents include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nigrossedente chemical Co., ltd., "Stabaxol P", "Stabaxol P400" and "Hycasyl 510".
The acid anhydride-based curing agent may be a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -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-furanyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (dehydrated trimellitate), styrene-maleic anhydride copolymerized from styrene and maleic acid, and the like. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", mitsubishi chemical corporation, "YH306", "YH307", hitachi chemical corporation, "HN-2200", "HN-5500", and "EF-30", "EF-40", "EF-60" and "EF-80" of the company Lei Weili (CRAY VALLEY).
As the amine curing agent, a curing agent having 1 or more, preferably 2 or more amino groups in 1 molecule can be used. Examples of the amine curing agent include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, and among these, aromatic amines are preferable. The amine curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. As a specific example of the amine-based curing agent, examples thereof include 4,4' -methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine 4,4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Examples of commercial products of the amine curing agent include "SEIKACURE-S" manufactured by KayaBOND C-200S, kayaBOND C-100, KAYAHARD A-A, KAYAHARD A-B, KAYAHARD A-S, and "EPICURE W" manufactured by Mitsubishi chemical corporation, sumitomo refining Co., ltd. "(Seika Corporation), and" DTDA "manufactured by Sumitomo refining Co., ltd.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" made by JFE chemical Co., ltd. "ODA-BOZ", made by Showa Polymer Co., ltd. "HFB2006M" and "P-D" made by four-country chemical industry Co., ltd. "F-a".
Examples of the cyanate-based curing agent include difunctional cyanate resins such as bisphenol a dicyanate, polyphenol cyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate-phenyl methane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylene)) benzene, bis (4-cyanate-phenyl) sulfide, and bis (4-cyanate-phenyl) ether; a polyfunctional cyanate resin derived from a phenol novolac resin, a cresol novolac resin, or the like; prepolymers obtained by partially triazining these cyanate resins. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" manufactured by Lonza japan corporation (each of which is a phenol novolac type polyfunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol a dicyanate is triazinized to form a trimer).
Examples of the thiol curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.
(E) The reactive group equivalent of any 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 curing agent per 1 equivalent of reactive group.
When the nonvolatile content in the resin composition is 100% by mass, the content of any curing agent (E) 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, particularly preferably 1.0% by mass or more, more preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less.
The content of any curing agent (E) in the resin composition may be 0% by mass or more, preferably 0.1% by mass or more, more preferably 1.0% by mass or more, particularly preferably 5.0% by mass or more, more preferably 50% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass, based on 100% by mass of the resin component in the resin composition.
[7. (F) curing accelerator ]
The resin composition according to the present embodiment may further contain (F) a curing accelerator as an optional component in combination with the above-described components (a) to (E). The curing accelerator (F) as the component (F) does not include the components (A) to (E) described above. (F) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (a) epoxy resin.
Examples of the curing accelerator (F) 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. (F) The curing accelerator may be used singly or in combination of two or more.
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-methylphenoxy salt, and di-t-butyldimethyl phosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium bromide, propyltriphenyl phosphonium bromide, butyltriphenyl phosphonium bromide, benzyltriphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyltrimethyl phosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetra-p-tolylborate, triphenylethyl phosphonium tetraphenyl borate, tris (3-methylphenyl) ethyl phosphonium tetraphenyl borate, tris (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenyl phosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridyl phosphine, 1, 2-bis (diphenyl) ethane, 1, 3-bis (diphenyl) phosphine, 1,2 '-diphenyl) phosphine, bis (diphenyl) propane, bis (2, 2' -diphenyl) phosphine, etc.
Examples of urea curing accelerators include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; aromatic ureas such as 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 3- (3, 4-dimethylphenyl) -1, 1-dimethylurea, 3- (4-isopropylphenyl) -1, 1-dimethylurea, 3- (4-methoxyphenyl) -1, 1-dimethylurea, 3- (4-nitrophenyl) -1, 1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl ] -1, 1-dimethylurea, 3- [4- (4-chlorophenoxy) phenyl ] -1, 1-dimethylurea, N- (1, 4-phenylene) bis (N ', N ' -dimethylurea, N- (4-dimethylphenyl) bis (N, N ' -dimethylurea, etc.
Examples of the guanidine curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like.
Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate adduct, and process for preparing the same, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Examples of the commercially available imidazole curing accelerator include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK-PW", "2PHZ-PW", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A", which are manufactured by Kabushiki Kaisha; "P200-H50" manufactured by Mitsubishi chemical corporation, etc.
Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include cobalt (II) acetylacetonate, organic cobalt complexes such as cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5, 4, 0) -undecene. As the amine curing accelerator, commercially available ones can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., ltd.
The content of the (F) curing accelerator in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, more preferably 1.0% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.
The content of the (F) curing accelerator 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, particularly preferably 0.1% by mass or more, more preferably 2.0% by mass or less, more preferably 1.5% by mass or less, particularly preferably 1.0% by mass or less, based on 100% by mass of the resin component in the resin composition.
[8. (G) thermoplastic resin ]
The resin composition according to the present embodiment may further contain (G) a thermoplastic resin as an optional component in combination with the above-mentioned components (a) to (F). The thermoplastic resin (G) as the component (G) does not include any of the components (A) to (F).
Examples of the thermoplastic resin (G) include phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. (G) The thermoplastic resin may be used alone or in combination of two or more.
Examples of the phenoxy resin include phenoxy resins having at least one skeleton selected from the group consisting of bisphenol a skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenol skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. 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 resins include "1256" and "4250" manufactured by Mitsubishi chemical corporation (both are phenoxy resins containing bisphenol A skeleton), "YX8100" manufactured by Mitsubishi chemical corporation (phenoxy resins containing bisphenol S skeleton), "YX6954" manufactured by Mitsubishi chemical corporation (phenoxy resins containing bisphenol acetophenone skeleton), "FX280" and "FX293" manufactured by Mitsubishi chemical corporation, and "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7891BH30" manufactured by Mitsubishi chemical corporation.
Specific examples of the polyimide resin include "SLK-6100" manufactured by Kagaku chemical Co., ltd., and "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon chemical Co., ltd.
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 "electric Butyral (Denka butyl) 4000-2", "electric Butyral 5000-A", "electric Butyral 6000-C", "electric Butyral 6000-EP", S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, etc. manufactured by electric chemical industries, inc.
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.
The polybutadiene resin includes, for example: hydrogenated polybutadiene skeleton-containing resins, hydroxyl-containing polybutadiene resins, phenolic hydroxyl-containing polybutadiene resins, carboxyl-containing polybutadiene resins, anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, and the like.
Specific examples of the polyamide-imide resin include "VYLOMAX HR11NN" and "VYLOMAX 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 company.
Specific examples of the polyethersulfone resin include "PES5003P" manufactured by sumitomo chemical corporation.
Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Su Weigao performance polymer (Solvay Advanced Polymers) Co.
Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by Sabert Innovative plastics Co., ltd (SABIC). Specific examples of the polyetherimide resin include "ULTEM" 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 Asahi Kagaku chemical corporation, "C-1090" and "C-2090" manufactured by Kagaku Kogyo Co., ltd., and the like. Specific examples of the polyether-ether-ketone resin include "SUMIPLOYK" manufactured by Sumitomo chemical Co., ltd.
Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.
(G) The weight average molecular weight (Mw) of the thermoplastic resin is preferably more than 5000, more preferably more than 8000, still more preferably more than 10000, particularly preferably more than 20000, still more preferably less than 100000, still more preferably less than 70000, still more preferably less than 60000, particularly preferably less than 50000.
The content of the thermoplastic resin (G) in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.20% by mass or more, more preferably 5.0% by mass or less, more preferably 2.0% by mass or less, particularly preferably 1.0% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.
The content of the (G) thermoplastic resin in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.50% by mass or more, more preferably 10% by mass or less, more preferably 5.0% by mass or less, particularly preferably 3.0% by mass or less, based on 100% by mass of the resin component in the resin composition.
[9. (H) radical polymerizable Compound ]
The resin composition according to the present embodiment may further contain (H) an optional radical polymerizable compound as an optional component in combination with the above-described components (a) to (G). The radical polymerizable compound (H) as the component (H) does not include the components (A) to (G). (H) The radical polymerizable compound may be used singly or in combination of two or more.
(H) The radical polymerizable compound may have an ethylenically unsaturated bond. The radical polymerizable compound (H) may include, for example: unsaturated hydrocarbon groups such as allyl, 3-cyclohexenyl, 3-cyclopentenyl, p-vinylphenyl, m-vinylphenyl, and o-vinylphenyl; and radical polymerizable groups such as α, β -unsaturated carbonyl groups such as acryl, methacryl, and maleimide groups (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl). (H) The radical polymerizable compound preferably has 2 or more radical polymerizable groups.
Examples of the (H) radical polymerizable compound include (meth) acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds, and the like.
The (meth) acrylic radical polymerizable compound is, for example, a compound having 1 or more, preferably 2 or more, acryl groups and/or methacryl groups. Examples of the (meth) acrylic radical polymerizable compound include: low molecular weight (molecular weight less than 1000) aliphatic (meth) acrylate compounds 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-nonanedioldi (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 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; isocyanurate-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 of 1000 or more) acrylate compounds such as (meth) acrylic acid-modified polyphenylene ether resins. Examples of the commercially available (meth) acrylic radical polymerizable compound include: "A-DOG" (dioxane glycol diacrylate) manufactured by Sanremo chemical Co., ltd., and "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kayanad R-684 "(tricyclodecane dimethanol diacrylate)," KAYARAD R-604 "(dioxane glycol diacrylate), and" SA9000 "and" SA9000-111 "(methacrylic acid modified polyphenylene ether) manufactured by Saint Innovative plastics (SABIC Innovative Plastics) manufactured by Sanremo chemical Co., ltd.
The styrene-based radically 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 less than 1000) styrenes 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 of 1000 or more) styrenes such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Examples of the commercial products of the styrene-based radical polymerizable compounds 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) manufactured by Mitsubishi gas chemical Co., ltd.
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 (Diallyl Diphenate), triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2, 6-naphthalate, diallyl 2, 3-naphthalate, and the like; allyl isocyanurate compounds such as 1,3, 5-triallyl isocyanurate and 1, 3-diallyl-5-glycidyl isocyanurate; epoxy group-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-triallylether 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 Co., ltd., "DAD" (diallyl phthalate) manufactured by Nitro-Tech, japan chemical Co., ltd., and "TRIAM-705" (triallyl trimellitate) manufactured by Wako pure chemical industries, ltd., trade name "DAND" (2, 3-diallyl naphthoate) manufactured by Japanese distillation Co., ltd., and "ALP-d" (bis [ 3-allyl-4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane) manufactured by Japanese chemical Co., ltd., and "RE-810" (2, 2-bis [ 3-allyl-4- (glycidox) phenyl ] propane) manufactured by Japanese chemical Co., ltd., and "DA-IC" (1, 3-diallyl) isocyanurate) manufactured by Japanese chemical 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. Examples of the commercial products of maleimide-based radical polymerizable compounds include "SLK-2600" manufactured by Xinyue chemical Co., ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure), "BMI-6100" manufactured by Designer Molecules company (aromatic maleimide compound), "MIR-5000-60T" manufactured by Japanese chemical Co., ltd., "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound), and "BMI-70" manufactured by KI chemical Co., ltd., "BMI-2300", "BMI-TMH" manufactured by Dai chemical Co., ltd., large-size, and the like. Further, as the maleimide-based radical polymerizable compound, maleimide resins (maleimide compounds having an indane ring skeleton) disclosed in Japanese patent application laid-open No. 2020-500211 are used.
(H) The ethylenically unsaturated bond equivalent of the radical polymerizable compound is preferably 20g/eq to 3000g/eq, more preferably 50g/eq to 2500g/eq, still more preferably 70g/eq to 2000g/eq, particularly preferably 90g/eq to 1500g/eq. The ethylenically unsaturated bond equivalent means the mass of the radical polymerizable compound corresponding to each 1 equivalent of the ethylenically unsaturated bond.
(H) The weight average molecular weight (Mw) of the radical polymerizable compound is preferably 40000 or less, more preferably 10000 or less, still more preferably 5000 or less, particularly preferably 3000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more.
The content of the (H) radical polymerizable compound 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, particularly preferably 1.0% by mass or more, more preferably 16% by mass or less, more preferably 12% by mass or less, particularly preferably 8.0% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.
The content of the (H) radical polymerizable compound in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 1.0% by mass or more, more preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less, based on 100% by mass of the resin component in the resin composition.
[ 10..any additive of (I) ]
The resin composition according to the present embodiment may further contain (I) any additive as any nonvolatile component in combination with the above-described components (a) to (H). Examples of the optional additive (I) include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermosetting resins other than epoxy resins, such as epoxy acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organocopper compounds, organozinc compounds, organocobalt compounds, and the like; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; an adhesion improving agent 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 (e.g., phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g., antimony trioxide), and the like; dispersants such as phosphate dispersants, polyoxyalkylene dispersants, alkyne dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; boric acid ester stabilizer, titanate stabilizer, aluminate stabilizer, zirconate stabilizer, isocyanate stabilizer, carboxylic acid stabilizer, carboxylic anhydride stabilizer, and the like. (I) Any additive may be used alone or in combination of two or more.
[ 11.(J) solvent ]
The resin composition according to the present embodiment may further contain a solvent (J) as an optional volatile component in combination with the above-described nonvolatile components such as the components (a) to (I). As the solvent (J), 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 diglycol acetate), γ -butyrolactone, methyl methoxypropionate, and the like; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane and methylcyclohexane; aromatic solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (J) The solvent may be used alone or in combination of two or more.
(J) The content 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, and may be 0 mass% or less, when the total content of the components in the resin composition is 100 mass%.
[12. Process for producing resin composition ]
The resin composition according to the present embodiment can be produced by mixing the above-described components, for example. The above components may be mixed partially or completely at the same time or sequentially. The temperature may be set appropriately during the mixing of the components, and thus heating and/or cooling may be performed temporarily or permanently. In addition, stirring or shaking may be performed during mixing of the components.
[13 physical Properties of the resin composition ]
The resin composition according to the present embodiment can provide a cured product having excellent stain removal properties. For example, in the case of performing the evaluation of the stain-removing property according to the conditions described in the item [ the stain-removing property and the evaluation method of arithmetic average roughness (Ra) ] of the example described later, the maximum stain length of the stain extending from the wall surface of the via hole bottom can be made lower than 5 μm. In general, the shorter the maximum stain length, the more excellent the stain removability.
The resin composition according to the present embodiment can provide a cured product excellent in coating adhesion. That is, when a conductor layer is formed on a cured product of the resin composition by plating, high adhesion between the conductor layer and the cured product can be obtained. For example, when the plating peel strength is measured under the conditions described in the item [ plating adhesion (plating peel strength measurement method) ] of the example described later, the plating peel strength can be increased. The above-mentioned peel strength of the plating layer means the amount of force required to peel the conductor layer formed by plating on the cured product of the resin composition, and the greater the peel strength of the plating layer, the more excellent the adhesion of the plating layer. The peel strength of the plating layer is preferably 0.45kgf/cm or more, more preferably 0.50kgf/cm or more, particularly preferably 0.53kgf/cm or more.
The resin composition according to the present embodiment can provide a cured product excellent in adhesion of a metal foil. That is, when a resin composition is laminated on a metal foil and cured to form a cured product, high adhesion between the metal foil and the cured product can be obtained. For example, when the peel strength of the copper foil is measured under the conditions described in the item [ method for evaluating adhesion of a metal foil ] of the embodiment described below, the peel strength of the copper foil can be increased. The peel strength of the copper foil means the amount of force required to peel the copper foil, which is a metal foil, from the cured product of the resin composition, and the greater the peel strength of the copper foil, the more excellent the adhesion of the metal foil. The peel strength of the copper foil is preferably 0.50kgf/cm or more, more preferably 0.60kgf/cm or more, particularly preferably 0.70kgf/cm or more.
The resin composition according to the present embodiment can generally obtain a cured product having a low dielectric loss tangent. For example, when the dielectric loss tangent of a cured product is measured under the conditions described in the item [ method for measuring dielectric loss tangent ] of examples described below, a low dielectric loss tangent can be obtained. The dielectric loss tangent of the cured product is preferably 0.0040 or less, more preferably 0.0035 or less, particularly preferably 0.0030 or less.
The cured product of the resin composition according to the present embodiment may generally have a small surface roughness when subjected to roughening treatment. For example, in the case of measuring the arithmetic average roughness Ra of the cured product after the roughening treatment under the conditions described in the item [ stain removability and evaluation method of arithmetic average roughness (Ra) ] of the example described later, a smaller arithmetic average roughness Ra can be obtained. The arithmetic average roughness Ra is preferably 120nm or less, more preferably 110nm or less, particularly preferably 100nm or less. The lower limit is not particularly limited, and may be 30nm or more, 40nm or more, or the like.
[14 use of resin composition ]
The resin composition according to the present embodiment is useful as a resin composition for insulation, and in particular, can be suitably used 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 used as a resin composition for forming an insulating layer of a printed wiring board, and can be suitably used as a resin composition for forming an interlayer insulating layer (a resin composition for interlayer insulation).
The resin composition according to the present embodiment can be used as a resin composition for forming a rewiring forming layer (a resin composition for forming a rewiring forming layer). The rewiring-forming layer represents an insulating layer for forming a rewiring layer. Further, the rewiring layer represents a conductor layer formed on the rewiring forming layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment can be used as a resin composition for forming a rewiring forming layer. In addition, when the semiconductor chip package is manufactured by the following steps (1) to (6), a rewiring layer may be further formed on the sealing layer,
(1) Laminating a temporary fixing film on a substrate;
(2) A step of temporarily fixing the semiconductor chip on the temporary fixing film;
(3) Forming a sealing layer on the semiconductor chip;
(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip;
(5) A step of forming a rewiring 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; and
(6) And forming a rewiring layer as a conductor layer on the rewiring layer.
The resin composition according to the present embodiment is widely used in applications where a resin composition is used, such as a sheet-like laminate material such as a resin sheet or a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, or a part-filling resin.
[15 ] sheet laminate
The resin composition according to the present embodiment may be applied in the form of a varnish, but is industrially preferably used in the form of 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 provided on the support. The resin composition layer is formed of the resin composition according to the present embodiment. 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 viewpoints of thinning of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a film. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be 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.
In the case of using a film formed of a plastic material as a support, examples of the plastic material include: polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET"), polyethylene naphthalate (hereinafter, abbreviated as "PEN") and acrylic polymers such as polycarbonate (hereinafter, abbreviated as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly inexpensive polyethylene terephthalate is preferable.
In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
The 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. As the release agent for the release layer of the support with a release layer, for example, 1 or more release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins are exemplified. Examples of the support having a release layer include "SK-1", "AL-5", "AL-7" made by Wallichi Corp, LUMIRROR T60 made by Toli Corp, purex made by Di Corp, and "Unipel" made by UNITKA Corp.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In the case of using the support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.
In one embodiment, the resin sheet may further contain an optional layer as needed. Examples of the optional layer include a protective film selected for the support and provided on a surface of the resin composition layer not joined to the support (i.e., a surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of refuse to the surface of the resin composition layer or the formation of damage can be suppressed.
The resin sheet can be produced, for example, by: the resin composition layer is formed by directly applying a liquid (varnish-like) resin composition to a support using a die coater or the like, or by preparing a liquid (varnish-like) resin composition obtained by dissolving a resin composition in a solvent, applying the liquid (varnish-like) resin composition to a support using a die coater or the like, and drying the same.
The solvent may be the same as the solvent described as a component of the resin composition. The solvent may be used alone or in combination of two or more.
Drying may be performed by heating, hot air blowing, or the like. The drying conditions are not particularly limited, and the resin composition layer is dried so that the solvent content is usually 10 mass% or less, preferably 5 mass% or less. For example, when a resin composition containing 30 to 60 mass% of a solvent is used, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes, depending on the boiling point of the solvent in the resin composition.
The resin sheet may be stored in a roll form. In the case where the resin sheet has a protective film, the protective film is usually peeled off for use.
In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous base material with the resin composition according to the present embodiment.
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 reducing the thickness of the printed wiring board, the thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. Typically 10 μm or more.
The prepreg can be produced by a 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-described resin sheet.
The sheet-like laminate material can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).
[16. Printed wiring board ]
The printed wiring board according to one embodiment of the present invention includes an insulating layer containing a cured product obtained by curing the resin composition according to the present embodiment. The printed wiring board can be manufactured, for example, by a method including the steps of (I) and (II) below using the resin sheet described above:
(I) A step of laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate, and a step of curing the resin composition layer to form an insulating layer.
The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene oxide substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, intermediate products to be further formed into insulating layers and/or conductor layers at the time of manufacturing the printed wiring board are also included in the aforementioned "inner layer substrate". When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.
Lamination of the inner 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 heat-press bonding the resin sheet to the inner layer substrate (hereinafter, also referred to as "heat-press bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the heat pressure bonding member is not directly pressed against the resin sheet but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.
Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heat press-bonding temperature is preferably 60℃to 160℃and more preferably 80℃to 140℃and the heat press-bonding pressure is preferably 0.098MPa to 1.77MPa and more preferably 0.29MPa to 1.47MPa, and the heat press-bonding time is preferably 20 seconds to 400 seconds and more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7hPa or less.
Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators manufactured by the company name machine, vacuum applicators (vacuum applicator) manufactured by Nikko-Materials, and batch vacuum pressurized laminators.
After lamination, the laminated resin sheet can 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 set to the same conditions as those for the thermocompression bonding of the laminate. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator described above.
The support may be removed between the step (I) and the step (II), or may be removed after the step (II).
In the step (II), the resin composition layer is cured to form an insulating layer formed of a cured product of the resin composition. The curing of the resin composition layer is generally performed by thermal curing. Specific curing conditions of the resin composition layer may be those generally employed in forming an insulating layer of a printed wiring board.
For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition, but in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, still more preferably 170 to 210 ℃. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.
The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer is preheated at a temperature of 50 to 150 ℃, preferably 60 to 140 ℃, more preferably 70 to 130 ℃ for at least 5 minutes, preferably 5 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 15 to 100 minutes, before the resin composition layer is thermally cured.
In the case of manufacturing a printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art, which can be used for manufacturing a printed wiring board. When the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V). The insulating layer and the conductor layer may be formed repeatedly in the steps (I) to (V) as needed, to form a multilayer wiring board.
In other embodiments, the printed wiring board may be manufactured using the prepreg described above. The production method can be basically the same as in the case of using a resin sheet.
The step (III) is a step of forming holes such as through holes and through holes in the insulating layer by forming holes in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the holes may be appropriately determined according to the design of the printed wiring board.
The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), the removal of the contamination is also performed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions generally used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.
Examples of the swelling liquid used in the roughening treatment include an alkali solution, a surfactant solution, and the like, and an alkali solution is preferable, and a sodium hydroxide solution and a potassium hydroxide solution are more preferable as the alkali solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH Japan Co., ltd. The swelling treatment with the swelling solution may be performed by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes, for example. 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%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Anmeite Japan Co., ltd.
The neutralization solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by Anmei Japanese Co., ltd. The neutralization solution-based treatment may be performed by immersing the treated surface, on which the roughening treatment by the oxidizing agent is completed, in the neutralization solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to impregnate the object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.
In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 500nm or less, more preferably 400nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The root mean square roughness (Rq) of the roughened insulating layer surface is preferably 500nm or less, more preferably 400nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a noncontact surface roughness meter.
The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises 1 or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include a layer formed of an alloy of 2 or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a 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, or copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is still more 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 made of a different metal or alloy are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel-chromium alloy.
The thickness of the conductor layer varies depending on the design of the desired printed wiring board, but 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 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 on the surface of an insulating layer by electroless plating. Next, a mask pattern exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.
In other embodiments, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by vacuum lamination. The conditions for lamination may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method using a metal foil on 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.
[17 ] semiconductor device ]
A semiconductor device according to an embodiment of the present invention includes the above-described printed wiring board. Semiconductor devices may be fabricated using printed wiring boards.
Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, and aircraft, and the like).
Examples
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. In the following description, unless otherwise indicated, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively. Further, the temperature conditions and the pressure conditions in the case where the temperature is not specified are room temperature (25 ℃) and atmospheric pressure (1 atm).
Example 1
8 parts of biphenyl epoxy resin (NC 3000L, manufactured by Nippon Kagaku Co., ltd., epoxy equivalent of about 269 g/eq.) and 2 parts of naphthalene epoxy resin (HP-4032-SS, manufactured by DIC Co., ltd., 1, 6-bis (glycidoxy) naphthalene, epoxy equivalent of about 145 g/eq.) were dissolved in 15 parts of naphtha by heating while stirring. It was cooled to room temperature to prepare a dissolved composition of epoxy resin.
To the direction of theTo the epoxy resin dissolved composition, 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., toluene solution having an active ester group equivalent of about 223g/eq and a nonvolatile content of 65%) and 120 parts of spherical silica surface-treated with a silane coupling agent (KBM-573, available from Xinyue chemical Co., ltd.) (SO-C2, available from Santa Clay Co., ltd., average particle diameter of 0.5 μm, specific surface area of 5.8 μm) were mixed 2 Each of the above-mentioned components was mixed with a resin composition comprising (i) 4 parts of a biphenyl skeleton-containing acrylic ester (A-LEN-10; from Xinzhou Chemicals Co., ltd., (meth) acryl equivalent of about 268 g/eq.), (ii) 2 parts of a triazine skeleton-containing phenol curing agent (LA-3018-50P; from DIC Co., ltd., "active group equivalent of about 151g/eq.," 2-methoxypropanol solution having a nonvolatile content of 50%), 5 parts of a carbodiimide curing agent (V-03; from Nitsche Chemie Co., ltd., "active group equivalent of about 216g/eq.," toluene solution having a nonvolatile content of 50%), 0.1 part of an imidazole curing accelerator (1B 2 PZ; 1-benzyl-2-phenylimidazole; from Katsumaki Co., ltd., "YX7553BH 30; from Mitsujitsujitsujitsu chemical Co., ltd.," 1:1 solution having a nonvolatile content of 30 mass% of MEK and cyclohexanone) and uniformly dispersed by a high-speed rotary mixer.
Example 2
40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). In addition, 4 parts of an acrylic acid ester having a biphenyl skeleton (A-BP-2 EO, manufactured by Benzhou chemical Co., ltd.) was used instead of 4 parts of an acrylic acid ester having a biphenyl skeleton (A-LEN-10, manufactured by Xinzhou chemical Co., ltd., (meth) acryl equivalent of about 268 g/eq.). Except for the above, a resin composition was produced in the same manner as in example 1.
Example 3
The amount of biphenyl type epoxy resin (NC 3000L, manufactured by Nippon chemical Co., ltd., epoxy equivalent weight: about 269 g/eq.) was changed from 8 parts to 10 parts. In addition, naphthalene type epoxy resin ("HP-4032-SS", manufactured by DIC Co., ltd.), 1, 6-bis (glycidoxy) naphthalene, having an epoxy equivalent of about 145g/eq, was not used. Further, 40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). The amount of the biphenyl skeleton-containing acrylic acid ester (A-LEN-10, new Zhongcun chemical industry Co., ltd., (meth) acryl equivalent of about 268 g/eq.) was changed from 4 parts to 8 parts. Except for the above, a resin composition was produced in the same manner as in example 1.
Example 4
A biphenyl type epoxy resin (NC 3000L, manufactured by Japanese chemical Co., ltd.) was not used, and the epoxy equivalent was about 269g/eq. The amount of naphthalene type epoxy resin ("HP-4032-SS", manufactured by DIC Co., ltd., 1, 6-bis (glycidoxy) naphthalene, having an epoxy equivalent of about 145 g/eq.) was changed from 2 parts to 10 parts. Further, 40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). The amount of the biphenyl skeleton-containing acrylic acid ester (A-LEN-10, new Zhongcun chemical industry Co., ltd., (meth) acryl equivalent of about 268 g/eq.) was changed from 4 parts to 2 parts. Except for the above, a resin composition was produced in the same manner as in example 1.
Example 5
40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). Further, 4 parts of a biphenyl aralkyl phenol type maleimide compound (MIR-3000-70 MT, manufactured by Nippon Kagaku Co., ltd., MEK/toluene mixed solution having a nonvolatile content of 70%) was added to the resin composition. Except for the above, a resin composition was produced in the same manner as in example 1.
Example 6
40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). In addition, 4 parts of a methacryloyl modified polyphenylene ether (SA 9000-111, manufactured by Saint Ind. Of the general Ind. Of the root of Saint Co., ltd.) was added to the resin composition. Except for the above, a resin composition was produced in the same manner as in example 1.
Example 7
40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). Further, 4 parts of a vinylbenzyl-modified polyphenylene ether (OPE-2 St 2200, mitsubishi gas chemical Co., ltd.) was added to the resin composition, and a toluene solution having a nonvolatile content of 65% was used. Except for the above, a resin composition was produced in the same manner as in example 1.
Comparative example 1
A biphenyl type epoxy resin (NC 3000L, manufactured by Japanese chemical Co., ltd.) was not used, and the epoxy equivalent was about 269g/eq. The amount of naphthalene type epoxy resin ("HP-4032-SS", manufactured by DIC Co., ltd., 1, 6-bis (glycidoxy) naphthalene, having an epoxy equivalent of about 145 g/eq.) was changed from 2 parts to 10 parts. Further, instead of 4 parts of the biphenyl skeleton-containing acrylic acid ester (New Yoghurt chemical Co., ltd. "A-LEN-10", (meth) acryl equivalent of about 268 g/eq.) 10 parts of acrylic acid ester (New Yoghurt chemical Co., ltd., (meth) acryl equivalent of about 156 g/eq.) were used. Except for the above, a resin composition was produced in the same manner as in example 1.
Comparative example 2
The amount of biphenyl type epoxy resin (NC 3000L, manufactured by Nippon chemical Co., ltd., epoxy equivalent weight: about 269 g/eq.) was changed from 8 parts to 10 parts. In addition, naphthalene type epoxy resin ("HP-4032-SS", manufactured by DIC Co., ltd.), 1, 6-bis (glycidoxy) naphthalene, having an epoxy equivalent of about 145g/eq, was not used. Further, 40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). In addition, instead of 4 parts of the biphenyl skeleton-containing acrylic acid ester (A-LEN-10, manufactured by Xinzhou Chemie Co., ltd., (meth) acryl equivalent of about 268 g/eq.) 5 parts of acrylic acid ester (DCP-A, manufactured by Zoo Chemie Co., ltd., (meth) acryl equivalent of about 152 g/eq.) were used. Further, 4 parts of a biphenyl aralkyl phenol type maleimide compound (MIR-3000-70 MT, manufactured by Nippon Kagaku Co., ltd., MEK/toluene mixed solution having a nonvolatile content of 70%) was added to the resin composition. Except for the above, a resin composition was produced in the same manner as in example 1.
Comparative example 3
The amount of biphenyl type epoxy resin (NC 3000L, manufactured by Nippon chemical Co., ltd., epoxy equivalent weight: about 269 g/eq.) was changed from 8 parts to 10 parts. In addition, naphthalene type epoxy resin ("HP-4032-SS", manufactured by DIC Co., ltd.), 1, 6-bis (glycidoxy) naphthalene, having an epoxy equivalent of about 145g/eq, was not used. Further, 40 parts of an active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active ester group equivalent of about 220g/eq., a toluene solution having a nonvolatile content of 62% by mass) was used instead of 40 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active ester group equivalent of about 223g/eq., a toluene solution having a nonvolatile content of 65% by mass). Furthermore, an acrylic acid ester having a biphenyl skeleton (A-LEN-10, manufactured by Xinzhou chemical industry Co., ltd., (meth) acryl equivalent of about 268 g/eq.) was not used. Except for the above, a resin composition was produced in the same manner as in example 1.
[ production of resin sheet ]
As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindeke Co., ltd., thickness: 38 μm) having a release layer was prepared. The resin compositions obtained in examples and comparative examples were uniformly applied onto the release layer of the support under the condition that the thickness of the dried resin composition layer reached 40. Mu.m. Then, the resin composition was dried at 80 to 100 ℃ (average 90 ℃) for 4 minutes to obtain a resin sheet comprising a support and a resin composition layer. The resin sheet thus obtained was used for evaluation by the following method.
[ evaluation method of stain removing Property and arithmetic average roughness (Ra) ]
< fabrication of evaluation substrate A >)
(1) And (3) base treatment of the inner layer substrate:
as an inner layer substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness: 18 μm, substrate thickness: 0.8mm, manufactured by Songshi Co., ltd. "R1515A") was prepared. The copper foil on the surface of the inner layer substrate was etched with a microetching agent (CZ 8101, manufactured by MEC corporation) at a copper etching amount of 1 μm, and roughened. Then, it was dried at 190℃for 30 minutes.
(2) Lamination and curing of resin sheets:
the resin sheets obtained in the examples and comparative examples were laminated on both sides of the inner substrate using a batch vacuum press laminator (CVP 700, manufactured by Nikko-Materials Co., ltd., 2-stage lamination laminator) so that the resin composition layer was bonded to the inner substrate. The lamination is carried out as follows: after the pressure was reduced to 13hPa or less for 30 seconds, the mixture was pressure-bonded at 100℃under a pressure of 0.74MPa for 30 seconds.
Subsequently, the laminated resin sheet was smoothed by hot pressing at 100℃under a pressure of 0.5MPa for 60 seconds under atmospheric pressure. Further, it was put into an oven at 130℃for 30 minutes, and then moved to an oven at 170℃for 30 minutes. By these heating, the resin composition layer is thermally cured, and an insulating layer is obtained as a cured product layer formed from a cured product of the resin composition.
(3) Formation of the through hole:
using CO 2 A laser processing machine (LK-2K 212/2C manufactured by Weiya machinery Co., ltd.) processes the insulating layer at a pulse width of 3 microseconds at a frequency of 2000Hz, an output power of 0.95W, and a shot number of 3 to form a via hole penetrating the insulating layer. The top diameter of the through hole in the surface of the insulating layer was 50 μm and the diameter of the through hole in the bottom surface of the insulating layer was 40 μm. Then, the support was peeled off to obtain an intermediate substrate composed of layers of insulating layer/inner substrate/insulating layer.
(4) Roughening treatment:
the intermediate substrate was immersed in Swelling Dip Securiganth P of Anmei Japanese Co., ltd. As a swelling liquid at 60℃for 10 minutes. Next, the mixture was subjected to a roughening treatment in an aqueous solution of Concentrate Compact P (KMnO 4 60g/L, naOH:40 g/L) was immersed in an aqueous solution at 80℃for 20 minutes. Finally, the resultant solution was immersed in Reduction solution Securiganth P made by Anmei Japanese Co., ltd. As a neutralizing solution at 40℃for 5 minutes. The obtained substrate was used as the evaluation substrate a.
< evaluation of stain removal Property >)
The periphery of the bottom of the through hole of the substrate a was evaluated by Scanning Electron Microscope (SEM) observation. The maximum contamination length of the contamination extending from the wall surface of the bottom of the through-hole was measured from the image obtained by observation, and evaluated according to the following criteria:
' good: the maximum stain length is less than 5 μm;
"×": the maximum stain length is more than 5 mu m.
< determination of arithmetic average roughness (Ra) >)
The arithmetic average roughness Ra of the insulating layer surface of the evaluation substrate a was measured using a noncontact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments corporation) using a VSI mode and a 50-fold lens, and setting the measurement range to 121 μm×92 μm. The measurement was performed at 10 points selected at random, and the average value thereof was calculated and shown in the table described later.
[ method for measuring coating adhesion (coating peel Strength) ]
< fabrication of evaluation substrate B >
The evaluation substrate A was subjected to a treatment containing PdCl 2 Is immersed in the electroless plating solution at 40 ℃ for 5 minutes, followed by immersion in the electroless copper plating solution at 25 ℃ for 20 minutes. After heating at 150℃for 30 minutes to perform annealing treatment, a resist layer was formed, and after patterning by etching, copper sulfate electrolytic plating was performed to form a plated conductor layer having a thickness of 30. Mu.m. Subsequently, an annealing treatment was performed at 200℃for 60 minutes, and the substrate thus obtained was used as an evaluation substrate B.
< determination of peel Strength (peel Strength) of plated conductor layer >
A scribe line was formed on the plated conductor layer of the evaluation substrate B so as to surround a portion having a width of 10mm and a length of 150 mm. One end of the portion was peeled off and clamped by a clamp of a tensile tester (model AUTO COM tester "AC-50C-SL", manufactured by TSE Co., ltd.). The resultant was stretched in the vertical direction at a speed of 50 mm/min at room temperature (25 ℃) and the load [ kgf/cm ] at 100mm peeling was measured as the peel strength of the plating layer.
[ method for measuring dielectric loss tangent ]
The resin sheets obtained in each example and each comparative example were thermally cured at 190℃for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product was cut to obtain test pieces having a width of 2mm and a length of 80 mm. For this test piece, a dielectric loss tangent (tan δ) was measured by a cavity perturbation method at a measurement frequency of 5.8GHz using a cavity perturbation method dielectric constant measuring device "CP521" manufactured by the Kabushiki Kaisha application electronics development and a Network Analyzer "E8362B" manufactured by agilent technologies, inc. The average value was calculated by measuring 2 test pieces.
[ method for evaluating adhesion of Metal foil ]
The adhesion of the metal foil was evaluated by measuring the peel strength of the copper foil according to the following procedure.
< fabrication of evaluation substrate >
(1) And (3) substrate treatment of copper foil:
the glossy surface of the electrolytic copper foil (3 EC-III, manufactured by Mitsui Metal mine Co., ltd., thickness of 35 μm) was roughened by etching 1 μm with a microetching agent (CZ 8101, manufactured by Meige Co., ltd.), followed by an anti-rust treatment (CL 8300). Hereinafter, the copper foil having the surface etched by the microetching agent is also referred to as "CZ copper foil". Further, this copper foil was subjected to a heat treatment in an oven at 130 ℃ for 30 minutes to obtain a copper foil I having a roughened treated surface.
(2) Preparation of an inner layer substrate:
a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4mm, manufactured by Songshi Co., ltd. "R1515A") having copper foil on the surface and forming an inner layer circuit was prepared. The copper foil surface was roughened by etching both surfaces of the glass cloth base epoxy resin-coated copper laminate with a microetching agent (CZ 8101, megaku Co., ltd.) by 1 μm. Thus, an inner layer substrate having a CZ copper foil with a treated surface on the surface thereof was obtained.
(3) Lamination of resin composition layers:
the resin sheets produced in examples and comparative examples were laminated on both sides of the inner layer substrate. The lamination was performed using a batch vacuum press laminator (CVP 700, manufactured by Nikko-Materials, 2-stage lamination laminator) so that the resin composition layer was in contact with the inner substrate. In addition, the lamination is carried out as follows: the pressure was reduced for 30 seconds to 13hPa or less, and then the mixture was subjected to pressure-bonding at 120℃under a pressure of 0.74MPa for 30 seconds. Subsequently, the laminated resin sheet was subjected to hot pressing at 100℃under a pressure of 0.5MPa for 60 seconds. Then, the support is peeled off to expose the resin composition layer.
(4) Lamination of copper foil and curing of resin composition layer:
The treated surface of the copper foil I was laminated on the exposed resin composition layer under the same conditions as those of the laminate of the resin composition layer (3) above. Next, the resin composition layer was cured under curing conditions of 200 ℃ for 90 minutes to form an insulating layer containing a cured product of the resin composition. By the above-described operations, an evaluation substrate C in which CZ copper foil was laminated on both sides of the insulating layer was obtained. The evaluation substrate C had a layer structure of copper foil I/insulating layer/inner layer substrate/insulating layer/copper foil I.
< determination of copper foil peel Strength >)
The evaluation substrate C was cut into 150mm by 30mm pieces. A dicing mark surrounding a portion having a width of 10mm and a length of 100mm was cut out on the small piece of copper foil I by a cutter. One end of the portion was peeled off and clamped by a clamp of a tensile tester (AUTO COM universal tester "AC-50C-SL", manufactured by TSE Co., ltd.). The copper foil was subjected to a vertical stretching at a speed of 50 mm/min at room temperature (25 ℃) and a load [ kgf/cm ] at the time of peeling off 35mm was measured as peel strength. The measurement was performed in accordance with Japanese Industrial Standard JIS C6481.
Results (results)
The results of the above examples and comparative examples are shown in the following table.
TABLE 1
TABLE 1 results for the examples
Figure BDA0003926640920000401
TABLE 2
TABLE 2 results of comparative examples
Figure BDA0003926640920000411
In the examples, it was confirmed that the same results as in the examples described above were obtained, although the degree of the difference was somewhat different even when the (E) component to the (H) component were not contained.

Claims (13)

1. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a (meth) acrylate having a biphenyl skeleton, wherein,
when the nonvolatile content in the resin composition is set to 100 mass%, the content of the (B) active ester compound is 10 mass% or more,
when the nonvolatile content in the resin composition is set to 100 mass%, the content of the inorganic filler (C) is 60 mass% or more.
2. The resin composition according to claim 1, wherein (D) the (meth) acrylate having a biphenyl skeleton comprises: a compound containing an ether structure.
3. The resin composition according to claim 1, wherein the (D) acrylic acid ester having a biphenyl skeleton comprises a compound represented by the following formula (D1),
Figure FDA0003926640910000011
in the formula (D1), the amino acid sequence of the formula (D),
R 11 each independently represents a hydrogen atom or a methyl group,
R 12 each independently represents a divalent aliphatic hydrocarbon group,
m1 represents an integer of 0 to 5,
n1 represents an integer of 0 to 6,
R 21 Each independently represents a hydrogen atom or a methyl group,
R 22 each independently represents a divalent aliphatic hydrocarbon group,
m2 represents an integer of 0 to 5,
n2 represents an integer of 0 to 6,
wherein m1+m2 is 1 or more.
4. The resin composition according to claim 1, wherein the content of (D) the (meth) acrylate having a biphenyl skeleton is 0.5 mass% or more and 25 mass% or less, based on 100 mass% of the nonvolatile components in the resin composition.
5. The resin composition according to claim 1, wherein the resin composition comprises 1 or more (E) curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
6. The resin composition according to claim 1, wherein (F) a curing accelerator is contained.
7. The resin composition according to claim 1, wherein (G) a thermoplastic resin is contained.
8. The resin composition according to claim 1, which is used for forming an insulating layer.
9. A cured product of the resin composition according to any one of claims 1 to 8.
10. A sheet laminate comprising the resin composition according to any one of claims 1 to 8.
11. A resin sheet, comprising:
support body
A resin composition layer comprising the resin composition according to any one of claims 1 to 8, which is provided on the support.
12. A printed wiring board is provided with an insulating layer,
the insulating layer comprises a cured product of the resin composition according to any one of claims 1 to 8.
13. A semiconductor device comprising the printed wiring board according to claim 12.
CN202211375909.6A 2021-11-08 2022-11-04 Resin composition Pending CN116082792A (en)

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