CN109423011B - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN109423011B
CN109423011B CN201810940295.9A CN201810940295A CN109423011B CN 109423011 B CN109423011 B CN 109423011B CN 201810940295 A CN201810940295 A CN 201810940295A CN 109423011 B CN109423011 B CN 109423011B
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resin composition
mass
component
resin
amount
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CN109423011A (en
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渡边真俊
长嶋将毅
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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

Abstract

The invention provides a resin composition which can obtain an insulating layer with low dielectric constant and high adhesion to a conductor layer after HAST test and further can inhibit resin flow. The resin composition comprises (A) an epoxy resin, (B) a curing agent, (C) rubber particles and (D) a fluorine-based filler, wherein the amount of the component (C) is 0.1 to 3% by mass based on 100% by mass of nonvolatile components in the resin composition.

Description

Resin composition
Technical Field
The invention relates to a resin composition, an adhesive film, a circuit board and a semiconductor device.
Background
As a manufacturing technique of a circuit board, a manufacturing method based on a build-up (build) method is known in which insulating layers and conductor layers are alternately stacked on an inner layer substrate. The insulating layer may be formed generally by: the resin composition layer is obtained as a coating film of a resin varnish comprising a resin composition, and the resin composition layer is cured. For example, patent document 1 describes a resin composition containing an epoxy resin, a curing agent, and a fluororesin filler, wherein the content of the fluororesin filler is 50 to 85 mass% based on the solid content of the resin composition.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2016-166347.
Disclosure of Invention
Problems to be solved by the invention
The resin composition for forming the insulating layer generally contains a large amount of a thermosetting resin from the viewpoint of achieving high insulating performance. As the thermosetting resin, an epoxy resin and a curing agent thereof are generally used. In addition, it is also known to use an inorganic filler as a filler to reduce the thermal expansion coefficient of a cured product of a resin composition. In contrast, the present inventors have studied the use of a fluorine-based filler as a filler in order to develop an insulating layer having a low dielectric constant.
However, an insulating layer formed from a cured product of a resin composition containing a fluorine-based filler tends to have low adhesion to a conductive layer formed on the insulating layer. Among them, after being subjected to a high accelerated high temperature and high humidity life test (HAST test), the adhesion of the insulating layer is particularly reduced. In order to improve the insulation reliability over a long period of time, it is desired that the insulating layer exhibit high adhesion to the conductor layer even after the HAST test.
In addition, when an adhesive film is produced using a resin composition containing a fluorine-based filler, resin flow (resin molding resin 1250112525125404. The term "resin flow" as used herein refers to a phenomenon in which, when the adhesive film is laminated with the inner layer substrate, the resin composition flows out from a portion between the support of the adhesive film and the inner layer substrate. When the resin flow occurs, the resin composition layer generally overflows (bulges) to the outside of the edge portion of the support body of the adhesive film. Further, when resin flow occurs, there is a tendency that: at the end of the adhesive film, the thickness of the resin composition layer is thinned by an amount corresponding to the amount of the resin composition flowing out. Therefore, if a large resin flow occurs, the thickness of the resin composition layer becomes uneven, and thickness control becomes difficult.
The present invention has been made in view of the above problems, and an object of the present invention is to provide: a resin composition which can provide an insulating layer having a low dielectric constant and high adhesion to a conductor layer after a HAST test and can suppress the flow of a resin; an adhesive film having a layer comprising the aforementioned resin composition; a circuit board and a semiconductor device each comprising an insulating layer formed from a cured product of the resin composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by combining (a) an epoxy resin, (B) a curing agent, (C) a predetermined amount of rubber particles, and (D) a fluorine-based filler, and have completed the present invention.
That is, the present invention includes the following aspects;
[1] a resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) rubber particles and (D) a fluorine-based filler,
the amount of the component (C) is 0.1 to 3% by mass based on 100% by mass of the nonvolatile component in the resin composition;
[2] the resin composition according to [1], wherein the component (D) is a fluorine-based polymer particle;
[3] the resin composition according to [2], wherein the component (D) is polytetrafluoroethylene particles;
[4] the resin composition according to any one of [1] to [3], which comprises (E) an inorganic filler;
[5] the resin composition according to [4], wherein the component (E) is silica;
[6] the resin composition according to [4] or [5], wherein the amount of the component (E) is 5 to 70% by mass based on 100% by mass of nonvolatile components in the resin composition;
[7] the resin composition according to any one of [1] to [6], wherein the amount of the component (D) is 10 to 80% by mass based on 100% by mass of nonvolatile components in the resin composition;
[8] the resin composition according to any one of [1] to [7], wherein the component (A) is at least 1 epoxy resin selected from bisphenol A type epoxy resins, bixylenol (bixylenol) type epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, naphthalene type tetrafunctional epoxy resins, and naphthol type epoxy resins;
[9] the resin composition according to any one of [1] to [8], which is used for forming an insulating layer of a circuit board;
[10] an adhesive film comprising a support and, provided on the support, a resin composition layer comprising the resin composition according to any one of [1] to [9 ];
[11] a circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [9 ];
[12] a semiconductor device comprising the circuit board according to [11 ].
ADVANTAGEOUS EFFECTS OF INVENTION
By the present invention, there can be provided: a resin composition which can provide an insulating layer having a low dielectric constant and high adhesion to a conductor layer after a HAST test and can suppress the flow of a resin; an adhesive film having a layer comprising the aforementioned resin composition; a circuit board and a semiconductor device each comprising an insulating layer formed from a cured product of the resin composition.
Drawings
Fig. 1 is a plan view schematically showing the periphery (periphery) of an end portion of an adhesive film laminated on an inner layer substrate in an embodiment.
Detailed Description
The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be implemented by being arbitrarily changed within the scope not departing from the claims and the equivalent scope thereof.
In the following description, unless otherwise specified, the amounts of the respective components in the resin composition are values of 100 mass% relative to nonvolatile components in the resin composition.
In the following description, the term "dielectric constant" means a relative dielectric constant unless otherwise specified.
[1. Summary of resin composition ]
The resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) rubber particles, and (D) a fluorine-based filler. The term "fluorine-based" as used herein means containing a fluorine atom. The term "fluorine-based filler" refers to a filler containing "a compound containing a fluorine atom" as a material. The amount of the rubber particles (C) in the resin composition is within a predetermined range.
The resin composition can provide the following effects expected by the present invention: an insulating layer having a low dielectric constant and high adhesion to a conductor layer after HAST test can be obtained, and resin flow can be suppressed.
[2. (A) epoxy resin ]
Examples of the epoxy resin of the component (a) include a bisxylenol type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac (naphthol novolac) 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 biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, an epoxy resin containing a spiro ring, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. The epoxy resin may be used alone in 1 kind, or in combination of 2 or more kinds.
As the epoxy resin (a), an aromatic epoxy resin is preferable from the viewpoint of reducing the average linear thermal expansion coefficient of the insulating layer. The aromatic epoxy resin as used herein means an epoxy resin having an aromatic skeleton in its molecule. The aromatic skeleton generally refers to a chemical structure defined as aromatic, and includes not only a single-ring structure such as a benzene ring but also a polycyclic aromatic structure such as a naphthalene ring and an aromatic heterocyclic structure. Among them, from the viewpoint of remarkably obtaining the desired effects of the present invention, the (a) epoxy resin is preferably 1 or more epoxy resins selected from bisphenol a type epoxy resins, biphenol type epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, naphthalene type tetrafunctional epoxy resins, and naphthol type epoxy resins, and particularly preferably a bisphenol a type epoxy resin, a biphenol type epoxy resin, and a naphthol type epoxy resin.
As the (a) epoxy resin, the resin composition preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, 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, and particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the epoxy resin (a).
The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (sometimes referred to as "solid epoxy resin"). As the (a) epoxy resin, the resin composition may contain only a liquid epoxy resin or only a solid epoxy resin, but preferably contains a liquid epoxy resin and a solid epoxy resin in combination. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin (a), the flexibility of the resin composition layer can be improved, or the breaking strength of a cured product of the resin composition can be improved.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule, and more preferably an aromatic liquid epoxy resin having 2 or more epoxy groups in 1 molecule.
The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, or an epoxy resin having a butadiene structure, more preferably a glycidyl amine type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, or a naphthalene type epoxy resin, and particularly preferably a bisphenol a type epoxy resin.
Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC corporation; "828US", "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER152" (phenol novolac epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nissian Ciki Kaisha; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by DAICEL corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by DAICEL corporation; "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) available from Nippon iron and Tanjin chemical Co., ltd; and so on. These epoxy resins may be used alone in 1 kind, or in combination of 2 or more kinds.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
As the solid epoxy resin, a bisxylenol type epoxy resin, a biphenylaralkyl type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol 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 tetraphenylethane type epoxy resin are preferable, and a bisxylenol type epoxy resin, a biphenylaralkyl type epoxy resin, a naphthylene ether type epoxy resin, a naphthalene type tetrafunctional epoxy resin, and a naphthol type epoxy resin are more preferable.
Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC corporation; "N-690" (cresol novolac epoxy resin) manufactured by DIC; "N-695" (cresol novolac epoxy resin) manufactured by DIC corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; "HP-7200HH", "HP-7200H", "EXA-7311-G3", "EXA-7311-G4S" and "HP6000" (naphthylene ether type epoxy resins) manufactured by DIC; EPPN-502H (a triphenol-type epoxy resin) manufactured by Nippon chemical company; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Chemicals); "NC3000H", "NC3000L" and "NC3100" (biphenyl aralkyl type epoxy resins) manufactured by Nippon Chemicals; ESN475V (naphthol type epoxy resin) manufactured by Nissian iron and gold chemical Co., ltd; ESN485 (naphthol novolac epoxy resin) manufactured by Nissian iron-on-gold chemical company; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX4000HK" (dicresol-type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; PG-100 and CG-500 (bisphenol AF epoxy resin) manufactured by Osaka gas chemical Co., ltd; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation. These epoxy resins may be used alone in 1 kind, or in combination of 2 or more kinds.
As the (a) epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:15, more preferably 1:0.5 to 1:10, particularly preferably 1:1 to 1:8. when the mass ratio of the liquid epoxy resin to the solid epoxy resin is within the above range, a desired adhesive property can be obtained when the adhesive film is used. In addition, when used in the form of an adhesive film, sufficient flexibility can be obtained, and handling properties can be improved. In addition, the breaking strength of the cured product of the resin composition can be effectively improved.
(A) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and particularly preferably 110 to 1000. When the epoxy equivalent of the epoxy resin (a) is in the above range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent is the mass of a resin containing 1 equivalent of epoxy group, and can be measured according to JIS K7236.
The weight average molecular weight of the epoxy resin (a) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of a resin such as an epoxy resin is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).
From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the amount of the epoxy resin (a) in the resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, particularly preferably 10% by mass or more, preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less, relative to 100% by mass of the nonvolatile component in the resin composition.
[3. (B) curing agent ]
The curing agent as the component (B) generally has a function of curing the resin composition by reacting with the epoxy resin (a). Examples of the curing agent (B) include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate curing agent, and a carbodiimide curing agent. Further, 1 kind of curing agent may be used alone, or 2 or more kinds may be used in combination.
As the active ester curing agent, a compound having 1 or more active ester groups in 1 molecule can be used. Among them, as the active ester curing agent, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters (phenoenolesters), thiophenol esters (thiophenol esters), N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, are preferable. The active ester-based curing agent is preferably an active ester-based curing agent obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac (phenol novolac), and the like. The "dicyclopentadiene type diphenol compound" as used herein refers to a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene with 2 molecules of phenol.
Preferred examples of the active ester-based curing agent include active ester compounds having a dicyclopentadiene type diphenol structure, active ester compounds having a naphthalene structure, active ester compounds having an acetyl compound of a phenol-novolac resin, and active ester compounds having a benzoyl compound of a phenol-novolac resin. Among them, an active ester compound having a naphthalene structure and an active ester compound having a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" refers to a 2-valent structural unit formed from phenylene-dicyclopentylene-phenylene.
Examples of commercially available products of the active ester-based curing agent include "EXB9451", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC) which are active ester compounds having a dicyclopentadiene type diphenol structure; "EXB9416-70BK" (product of DIC corporation) as an active ester compound containing a naphthalene structure; "DC808" (manufactured by mitsubishi chemical corporation) which is an active ester compound containing an acetylate of a phenol novolac resin; "YLH1026" (manufactured by mitsubishi chemical corporation) which is an active ester compound including a benzoyl compound of a phenol novolac resin; "DC808" (manufactured by mitsubishi chemical corporation) which is an active ester-based curing agent that is an acetylate of a phenol novolac resin; "YLH1026" (manufactured by mitsubishi chemical corporation), "YLH1030" (manufactured by mitsubishi chemical corporation), and "YLH1048" (manufactured by mitsubishi chemical corporation), which are active ester-based curing agents for benzoylates of phenol-novolac resins; and so on.
The phenol curing agent and the naphthol curing agent preferably have a phenolic structure from the viewpoint of heat resistance and water resistance. In view of adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenol curing agent is preferable, and a phenol curing agent having a triazine skeleton is more preferable.
Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Minghe chemical Co., ltd; "NHN", "CBN" and "GPH" manufactured by Nippon chemical Co., ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Xinri Cingjin chemical company; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P" and "EXB-9500" manufactured by DIC corporation; and so on.
Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., ltd, "P-d" and "F-a" manufactured by Shikoku Industrial Co., ltd.
Examples of the cyanate ester curing agent include bifunctional cyanate ester resins such as bisphenol a dicyanate, polyphenol cyanate ester, oligo (3-methylene-1, 5-phenylene cyanate ester), 4 '-methylenebis (2, 6-dimethylphenylcyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-1- (methylethylidene)) benzene, bis (4-cyanate ester phenyl) sulfide, and bis (4-cyanate ester phenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac resins, cresol novolac resins, and the like; prepolymers obtained by partially triazinating these cyanate ester resins; and so on. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymer in which a part or all of bisphenol a dicyanate ester is triazinized to form a trimer), which are manufactured by Lonza Japan.
Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical company.
Among the above, from the viewpoint of remarkably obtaining the desired effect of the present invention, 1 or more curing agents selected from the group consisting of an active ester curing agent, a phenol curing agent and a naphthol curing agent are preferable as the curing agent (B). In addition, from the viewpoint of effectively reducing the dielectric constant of a cured product of the resin composition, an active ester-based curing agent is particularly preferable. Therefore, the curing agent (B) used in the resin composition preferably contains an active ester curing agent.
When the active ester-based curing agent is used, the amount of the active ester-based curing agent is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less, relative to 100% by mass of the (B) curing agent. When the amount of the active ester-based curing agent is in the above range, the desired effect of the present invention can be obtained remarkably, and particularly, the dielectric constant of a cured product of the resin composition can be effectively reduced.
From the viewpoint of remarkably obtaining the desired effect of the present invention, the amount of the (B) curing agent in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, relative to 100% by mass of the nonvolatile component in the resin composition.
When the number of epoxy groups of the epoxy resin (a) is 1, the number of active groups of the curing agent (B) is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, preferably 1.5 or less, more preferably 1.2 or less, further preferably 1 or less, and particularly preferably 0.8 or less. The term "(number of epoxy groups of the epoxy resin (a)") as used herein means a value obtained by adding all values obtained by dividing the mass of nonvolatile components of the epoxy resin (a) present in the resin composition by the epoxy equivalent. The term "(number of active groups of the (B) curing agent") means a value obtained by adding all values obtained by dividing the mass of nonvolatile components of the (B) curing agent present in the resin composition by the equivalent weight of the active groups. When the number of epoxy groups of the epoxy resin (a) is 1, the number of active groups of the curing agent (B) is in the above range, whereby the desired effects of the present invention can be remarkably obtained, and the heat resistance of the cured product of the resin composition is generally further improved.
[4. (C) rubber particles ]
The rubber particles as the component (C) are particles containing rubber, and generally function as an organic filler having rubber elasticity. By including the rubber particles (C) in a predetermined amount, it is possible to suppress the resin flow of the resin composition and to improve the adhesion of the cured product of the resin composition to the conductor layer after the HAST test. The amount of the rubber particles (C) in the resin composition is usually 0.1% by mass or more, preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more, and usually 3% by mass or less, preferably 2.6% by mass or less, and particularly preferably 2.2% by mass or less, relative to 100% by mass of the nonvolatile matter in the resin composition.
As the rubber particles (C), for example, rubber particles which are insoluble in an organic solvent described later and incompatible with the epoxy resin (a) and the curing agent (B) can be used. The rubber particles (C) can be present in the resin varnish and in the resin composition in a dispersed state.
Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. Among them, core-shell type rubber particles are preferable from the viewpoint of remarkably obtaining the effect desired by the present invention.
The core-shell type rubber particle is a rubber particle including a shell layer located on the surface of the particle and a core layer located inside the shell layer. There can be mentioned, for example, a core-shell type rubber particle comprising a shell layer formed of a polymer having a relatively high glass transition temperature and a core layer formed of a polymer having a relatively low glass transition temperature. Among them, preferred is a core-shell type rubber particle in which the shell layer is made of a glassy polymer and the core layer is made of a rubbery polymer. Such core-shell rubber particles can exhibit excellent rubber elasticity due to the core layer, while suppressing aggregation of the rubber particles or improving dispersibility of the rubber particles in resin components such as (a) an epoxy resin and (B) a curing agent, due to the shell layer.
The core-shell rubber particle may have a 2-layer structure including only a shell layer and a core layer, or may have a 3-or more-layer structure further including any layer. For example, the core-shell type rubber particle may include an arbitrary layer between the shell layer and the core layer, or may include an arbitrary layer inside the core layer. Specifically, the core-shell type rubber particle may have a 3-layer structure including a shell layer made of a glassy polymer, a core layer made of a rubbery polymer, and an arbitrary layer made of a glassy polymer located inside the core layer.
Among the core-shell rubber particles, examples of the glassy polymer include acrylic polymers such as polymethyl methacrylate; styrene polymers such as polystyrene and styrene-divinylbenzene copolymers; and so on. Among them, acrylic polymers are preferable, and polymethyl methacrylate is particularly preferable. On the other hand, examples of the rubbery polymer include acrylic rubbers such as homopolymers and copolymers of acrylic monomers such as butyl acrylate; butadiene rubbers such as polybutadiene; an isoprene rubber; butyl rubber; and so on. Among them, acrylic rubber and butadiene rubber are preferable, and acrylic rubber is particularly preferable. Herein, the aforementioned term "acrylic monomer" includes acrylates, methacrylates, and combinations thereof.
Specific examples of the core-shell rubber particles include StaphyLOID "AC3832", "AC3816N", "IM 401-modified 7-17" manufactured by AICA industries, inc.; "METABLEN KW-4426" manufactured by Mitsubishi chemical corporation; PARALOID "EXL-2655" manufactured by the Dow chemical Japan K.K.
Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include "XER-91" (average particle diameter of 0.5 μm) manufactured by JSR Corp; and so on.
Specific examples of the crosslinked Styrene Butadiene Rubber (SBR) particles include "XSK-500" (average particle diameter of 0.5 μm) manufactured by JSR corporation; and so on.
Specific examples of the acrylic rubber particles include METABLEN "W300A" (average particle diameter of 0.1 μm) and "W450A" (average particle diameter of 0.2 μm), manufactured by Mitsubishi chemical corporation; and so on.
(C) The rubber particles may be used alone in 1 kind, or in combination of 2 or more kinds.
(C) The rubber particles generally have an effect of improving the toughness of a cured product of the resin composition. Therefore, the insulating layer formed from the cured product of the resin composition containing the rubber particles (C) has excellent mechanical strength. In addition, (C) the rubber particles generally have a stress relaxation effect. Therefore, in the insulating layer formed of a cured product of the resin composition containing the rubber particles (C), the internal stress generated when the insulating layer is formed can be relaxed by the rubber particles (C). Therefore, the residual stress of the insulating layer can be reduced, and thus the mechanical strength of the insulating layer can also be improved.
(C) The rubber particles can be produced, for example, by: the molecular weight of the rubber component is increased to a level at which the rubber component is insoluble in the organic solvent and the resin component, and the rubber component is formed into particles. In addition, in particular, the core-shell type rubber particles can be produced, for example, by: the 1 or 2 or more kinds of monomers corresponding to each layer are seed-polymerized in a plurality of stages.
(C) The average particle diameter of the rubber particles is preferably 0.005 μm or more, more preferably 0.2 μm or more, preferably 1 μm or less, and more preferably 0.6 μm or less. (C) The average particle diameter of the rubber particles can be measured by a dynamic light scattering method. Specifically, the rubber particles can be uniformly dispersed in an appropriate organic solvent by means of ultrasonic waves or the like, a particle size distribution of the rubber particles can be prepared on a mass basis by using a dense particle size analyzer ("FPAR-1000" manufactured by Otsuka electronics), and the median particle size can be measured as an average particle size.
[5. (D) fluorine-based filler ]
The fluorine-based filler as the component (D) is a filler containing "a compound containing a fluorine atom" as a material. The fluorine-based filler is usually in the form of particles. Therefore, as the fluorine-based filler (D), particles containing "a compound containing a fluorine atom" as a material are generally used.
The material of the fluorine-based filler (D) is preferably a fluorine-based polymer in view of reducing the dielectric constant of the insulating layer. Therefore, the fluorine-based filler (D) is preferably a fluorine-based polymer particle.
Examples of the fluorine-based polymer include Polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene-propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE/PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). These fluorine-based polymers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among these, polytetrafluoroethylene is preferred as the fluorine-based polymer from the viewpoint of particularly lowering the dielectric constant of the insulating layer. Therefore, as the fluorine-based filler (D), polytetrafluoroethylene particles, which are particles containing polytetrafluoroethylene, are preferable.
From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight of the fluorine-based polymer is preferably 5000000 or less, more preferably 4000000 or less, and particularly preferably 3000000 or less.
(D) The average particle diameter of the fluorine-based filler is preferably 0.05 μm or more, more preferably 0.08 μm or more, particularly preferably 0.10 μm or more, preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 4 μm or less. When the average particle diameter of the fluorine-based filler (D) is within the above range, the desired effect of the present invention can be remarkably obtained, and the dispersibility of the fluorine-based filler (D) in the resin composition can be generally improved.
(D) The average particle diameter of particles such as fluorine-based fillers can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the particles can be measured on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the average particle size can be obtained from the particle size distribution as a median size. For the measurement sample, a product in which particles are dispersed in a solvent by ultrasonic waves can be preferably used. As the laser diffraction/scattering type particle size distribution measuring apparatus, "LA-500" manufactured by horiba Ltd.
Examples of commercially available fluorine-based fillers (D) include "LUBRON L-2", "LUBRON L-5F", manufactured by Daikin industries, inc.; "Fluon PTFE L-170JE", "Fluon PTFEL-172JE" and "Fluon PTFE L-173JE" manufactured by Asahi glass company; KTL-500F, KTL-2N, and KTL-1N available from XDUOMUN; "TLP10F-1" manufactured by DuPont-Mitsui Fluorochemicals Co., ltd; and so on.
The fluorine-based filler (D) may be surface-treated. For example, the fluorine-based filler (D) may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants, and anionic surfactants; inorganic fine particles; and so on. From the viewpoint of affinity, a fluorine-based surfactant is preferably used as the surface treatment agent. As the fluorine-based surfactant, a suitable non-particulate fluorine-based polymer or fluorine-based oligomer can be used. Specific examples of the fluorine-based surfactant include "Surflon S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Clarithromium Chemicals; MEGAFACE F-251, MEGAFACE F-477, MEGAFACE F-553, MEGAFACE R-40, MEGAFACE R-43, and MEGAFACE R-94 manufactured by DIC; "FTX-218" and "Ftergent 610FM" manufactured by NEOS corporation.
The amount of the fluorine-based filler (D) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less, relative to 100% by mass of nonvolatile components in the resin composition. When the amount of the fluorine-based filler (D) is within the above range, the desired effect of the present invention can be obtained remarkably, and in particular, the dielectric constant of a cured product of the resin composition can be effectively reduced.
In particular, when the resin composition contains the (E) inorganic filler, the amount of the (D) fluorine-based filler in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 35% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less, relative to 100% by mass of the total of the (D) fluorine-based filler and the (E) inorganic filler. When the amount of the fluorine-based filler (D) is within the above range, the desired effect of the present invention can be obtained remarkably, and in particular, the dielectric constant of a cured product of the resin composition can be effectively reduced.
[6. (E) inorganic Filler ]
The resin composition may contain (E) an inorganic filler as an optional component in addition to the above components. Examples of the material of the inorganic filler as the component (E) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the effect desired by the present invention. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Among them, spherical silica is preferable. (E) The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Usually, (E) the inorganic filler is contained in the resin composition in a state of particles. From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle diameter of the (E) inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5.0 μm or less, more preferably 2.0 μm or less, and further preferably 1.0 μm or less. In addition, when the average particle diameter of the inorganic filler (E) is in the above range, the circuit embeddability of the resin composition layer can be generally improved, or the surface roughness of the insulating layer can be reduced.
Examples of commercially available products of the inorganic filler (E) include "SP60-05" and "SP507-05" manufactured by Nissian iron-base alloy materials Ltd; "YC100C", "YA050C-MJE", and "YA010C" manufactured by Admatechs corporation; "UFP-30" manufactured by Denka corporation; "Silfil (1247112523125011245112523manufactured by Deshan (Tokuyama) Inc.", "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs corporation; and so on. (E) The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory, in the same manner as the fluorine-based filler (D).
The specific surface area of the (E) inorganic filler is preferably 1m from the viewpoint of remarkably obtaining the desired effect of the present invention 2 A value of at least g, more preferably 2m 2 A total of 3m or more, particularly 3m 2 More than g. The upper limit is not particularly limited, but is preferably 60m 2 Less than g, 50m 2 Less than g or 40m 2 The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained by: according to the BET method, a specific surface area measuring apparatus (Macsorb HM-1210, mountech) was used to adsorb nitrogen gas to the surface of the sampleThe BET multipoint method calculates the specific surface area.
The inorganic filler (E) may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include coupling agents such as an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, and a titanate-based coupling agent; an alkoxysilane compound; an organic silazane compound; and so on. The moisture resistance and dispersibility of the inorganic filler (E) can be improved by surface treatment with these surface-treating agents.
Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., ltd, "KBM803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., ltd, "KBE903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., ltd, "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) available from shin-Etsu chemical Co., ltd, "SZ-31" (hexamethyldisilazane) available from shin-Etsu chemical Co., ltd, "KBM-103" (phenyltrimethoxysilane) available from shin-Etsu chemical Co., ltd, "KBM-4803" (long-chain epoxy-type silane coupling agent) available from shin-Etsu chemical Co., ltd. The surface treatment agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The degree of surface treatment with the surface treatment agent can be evaluated by (E) the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the (E) inorganic filler is preferably 0.02mg/m from the viewpoint of improving the dispersibility of the (E) inorganic filler 2 Above, more preferably 0.1mg/m 2 Above, 0.2mg/m is particularly preferable 2 As described above. On the other hand, the amount of carbon is preferably 1mg/m from the viewpoint of suppressing an increase in melt viscosity of the resin varnish and in the form of a sheet 2 The concentration is more preferably 0.8mg/m or less 2 The concentration is preferably 0.5mg/m 2 The following.
(E) The amount of carbon per unit surface area of the inorganic filler can be measured after (E) the inorganic filler after the surface treatment is subjected to a washing treatment with a solvent (for example, methyl ethyl ketone (hereinafter, sometimes abbreviated as "MEK"). Specifically, (E) an inorganic filler surface-treated with a surface treatment agent and a sufficient amount of MEK were mixed, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. Next, the supernatant liquid was removed, the nonvolatile matter was dried, and then the amount of carbon per unit surface area of the inorganic filler (E) was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, ltd.
The amount of the inorganic filler (E) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less, relative to 100% by mass of the nonvolatile component in the resin composition. When the amount of the inorganic filler (E) is not less than the lower limit of the above range, the thermal expansion coefficient of the cured product of the resin composition can be reduced, and thus warpage of the insulating layer can be suppressed. Further, when the amount of the inorganic filler (E) is not more than the upper limit of the above range, the mechanical strength of a cured product of the resin composition, particularly the resistance to elongation, can be improved.
[7. (F) thermoplastic resin ]
The resin composition may contain (F) a thermoplastic resin as an optional component in addition to the above components. Examples of the thermoplastic resin as the component (F) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. Among them, phenoxy resins are preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. The thermoplastic resin may be used alone in 1 kind, or in combination of 2 or more kinds.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from a bisphenol a skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The end of the phenoxy resin may be any functional group of a phenolic hydroxyl group, an epoxy group, or the like.
Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resins containing a bisphenol a skeleton, manufactured by mitsubishi chemical corporation); "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi chemical company; "FX280" and "FX293" manufactured by Nissin iron-on-Steel chemical Co., ltd; "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482" manufactured by Mitsubishi chemical corporation.
From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight of the thermoplastic resin (F) in terms of polystyrene is preferably 8000 or more, more preferably 10000 or more, particularly preferably 20000 or more, preferably 70000 or less, more preferably 60000 or less, and particularly preferably 50000 or less. (F) The weight average molecular weight of the thermoplastic resin in terms of polystyrene can be measured by Gel Permeation Chromatography (GPC).
When the thermoplastic resin (F) is used, the amount of the thermoplastic resin (F) in the resin composition is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, further preferably 0.7% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 10% by mass or less, relative to 100% by mass of nonvolatile components in the resin composition.
[8. (G) curing accelerators ]
The resin composition may contain (G) a curing accelerator as an optional component in addition to the above components. By using the curing accelerator (G), curing can be accelerated when curing the resin composition.
Examples of the curing accelerator (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators and peroxide-based curing accelerators. Among them, preferred are a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator, more preferred are an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator, and particularly preferred is an amine-based curing accelerator. (G) The curing accelerator may be used alone in 1 kind, or in combination of 2 or more kinds.
Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.
Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5, 4, 0) -undecene. Among them, preferred are 4-dimethylaminopyridine and 1, 8-diazabicyclo (5, 4, 0) -undecene.
As an imidazole-based curing accelerator, there can be mentioned, examples thereof 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' -ethylimido-6- [2' -ethylimido- (1 ') ] -methyl-s-triazine, 2' -ethylimido-6- [2' -ethylimido-methyl ] -methyl-4 ' -methyl-s-triazine, 2' -ethylimido-6- [2' -methyl ] -methyl-4 ' -methyl-s-methyl-4 ' -isocyanurate, imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline; and adducts of imidazole compounds with epoxy resins. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.
As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.
Examples of the guanidine-based 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, and 1- (o-tolyl) biguanide. Among them, dicyandiamide and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferable.
Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and 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 octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
Examples of the peroxide-based curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, dicumyl hydroperoxide, cumyl hydroperoxide, and tert-butylhydroperoxide.
As the peroxide-based curing accelerator, a commercially available product can be used, and for example, "PERCUMYL D" manufactured by Nichiba oil Co.
When the curing accelerator (G) is used, the amount of the curing accelerator (G) in the resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, particularly preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less, relative to 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention.
[9 (H) fluorine-based Polymer or fluorine-based oligomer ]
The resin composition may contain, as an optional component, a non-particulate (H) fluorine-based polymer or fluorine-based oligomer in addition to the above components. The fluorine-based polymer and the fluorine-based oligomer as the component (H) may be used alone or in combination. The component (H) is a component which can be in a non-particulate state in the resin composition, and generally has excellent compatibility with the resin component (a) such as an epoxy resin. Since the component (H) contains fluorine atoms in its molecule, it has high affinity for the fluorine-based filler (D). Therefore, the component (H) functions as a surfactant at the interface between the fluorine-based filler (D) and the resin component, and the dispersibility of the fluorine-based filler (D) can be improved. Further, by improving the dispersibility of the fluorine-based filler (D) as described above, the surface roughness of the insulating layer after the roughening treatment can be reduced. Further, the use of the component (H) generally lowers the dielectric constant of the cured product of the resin composition.
Examples of the fluorine-based polymer include "LE-605" manufactured by Kyoeisha chemical Co. Examples of the fluorine-based oligomer include MEGAFACE "F-556", "F-558", "F-561", "F-563", "F-569", "DS-21", "R-40" and "R-41" manufactured by DIC corporation. The component (H) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When the component (H) is used, the amount of the component (H) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less, relative to 100% by mass of the nonvolatile components in the resin composition. When the amount of the component (H) is in the above range, the surface roughness of the insulating layer after the roughening treatment can be reduced, or the dielectric constant of the cured product of the resin composition can be effectively reduced.
[10. (I) coupling agent ]
The resin composition may contain (I) a coupling agent as an optional component in addition to the above components. By using the coupling agent (I), the dispersibility of the inorganic filler (E) can be improved, and therefore the surface roughness of the insulating layer after the roughening treatment can be reduced.
Examples of the coupling agent (I) include the same coupling agents as those listed as the surface treatment agent for the inorganic filler (E). The coupling agent (I) may be used alone in 1 kind or in combination of 2 or more kinds.
When the coupling agent (I) is used, the amount of the coupling agent (I) in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less, relative to 100% by mass of nonvolatile components in the resin composition. By making the amount of the (I) coupling agent within the foregoing range, the surface roughness of the insulating layer after the roughening treatment can be reduced.
[11. (J) additive ]
The resin composition may contain an additive as an optional component in addition to the above components. Examples of such additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; a thickener; defoaming agent; leveling agent; an adhesion imparting agent; a colorant; a flame retardant; and so on. Further, 1 kind of the additive may be used alone, or 2 or more kinds may be used in any combination.
[12. Method for producing resin composition ]
The resin composition can be produced, for example, by a method of mixing the compounding ingredients with a solvent used as needed, and stirring the mixture using a stirring device such as a rotary mixer. In particular, when the component (H) is used, it is preferable to mix the fluorine-based filler (D) and the component (H) with the other components, respectively, rather than mixing the fluorine-based filler (D) and the component (H) with the other components after mixing them. This can particularly effectively suppress the resin flow of the resin composition.
[13. Characteristics of the resin composition ]
The cured product of the resin composition can have a reduced dielectric constant. Therefore, an insulating layer having a low dielectric constant can be obtained by using a cured product of the resin composition. For example, when a cured product is obtained by curing the resin composition by the method described in examples, the dielectric constant of the cured product can be preferably 3.00 or less, more preferably 2.98 or less, and particularly preferably 2.97 or less. The dielectric constant of the cured product can be measured by the method described in examples.
The above resin composition can reduce resin flow. Therefore, when the adhesive film produced using the resin composition is laminated with the inner layer substrate, the resin composition can be inhibited from flowing out from the end of the adhesive film, and the undesirable change in the thickness of the resin composition layer can be inhibited. For example, when an adhesive film including a resin composition layer having a thickness of 50 μm formed from a resin composition is laminated on an inner substrate by the method described in examples, the amount of resin flow is preferably 3mm or less. Further, by using such a resin composition, the thickness of the insulating layer can be easily controlled.
When the conductive layer is formed on the layer of the cured product of the resin composition, the adhesion between the layer of the cured product and the conductive layer can be improved even after the HAST test. Therefore, an insulating layer having high adhesion to the conductor layer after the HAST test can be obtained by curing the resin composition. For example, an insulating layer is formed from a cured product of the resin composition by the method described in examples, and a conductor layer is formed on the insulating layer by plating. In this case, the peel strength after the HAST test under the conditions described in the examples can be increased. Specifically, the peel strength after the HAST test can be set to 0.3kgf/cm or more. The peel strength can be measured by the method described in examples. In addition, the insulating layer can improve the adhesion between the insulating layer and the conductor layer over a long period of time.
The present inventors speculate that the mechanism by which the above-described effects can be obtained by the above-described resin composition is as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
(D) The fluorine-based filler has an effect of lowering the dielectric constant of a cured product of the resin composition when combined with (a) the epoxy resin and (B) the curing agent.
However, the fluorine-based filler (D) generally has low affinity with the resin component (a) such as an epoxy resin. Therefore, when the resin composition contains the fluorine-based filler (D) in combination with the resin component, the interaction between the fluorine-based filler and the resin component is small, and thus the fluidity of the resin composition is high. Therefore, when the fluorine-based filler (D) is used, the resin flow of the resin composition becomes large. In contrast, when the resin composition contains the rubber particles (C), the thixotropy of the resin composition can be improved because the rubber particles (C) have high affinity for the resin component. This can suppress the fluidity of the resin composition at the time of lamination, and can suppress the resin flow.
In addition, the fluorine-based filler (D) generally expands and contracts greatly due to a temperature change. Therefore, in the HAST test, (D) the fluorine-based filler expands and then contracts when cooled. As a result, stress is generated in the cured product of the resin composition due to expansion and contraction of the fluorine-based filler (D). In addition, in general, since the affinity of the fluorine-based filler (D) with the resin component is low, the interface between the fluorine-based filler (D) and the resin component lacks adhesiveness. Therefore, when stress is applied to the cured product of the resin composition, the interface between the (D) fluorine-based filler and the resin component is likely to be peeled off, and the fluorine-based filler is likely to serve as a starting point of a crack. Therefore, there is a tendency that: after the HAST test, peeling occurs at the interface between the (D) fluorine-based filler and the resin component, or a fine crack starting from the interface between the (D) fluorine-based filler and the resin component occurs, so that the mechanical strength of the insulating layer is reduced, and peeling of the conductor layer is likely to occur with breakage in the vicinity of the surface of the insulating layer. On the other hand, when the rubber particles (C) are used, the rubber particles (C) can absorb the stress caused by the expansion and contraction of the fluorine-based filler (D) accompanying the temperature change. Therefore, the decrease in the mechanical strength of the insulating layer due to the HAST test can be suppressed. The rubber particles (C) have an effect of improving the toughness of the cured product of the resin composition. Therefore, even if the mechanical strength of the insulating layer is decreased by the HAST test, the decrease can be compensated by the toughness-improving effect of the (C) rubber particles. Therefore, when the cured product of the resin composition is used, an insulating layer having high adhesion to the conductor layer after the HAST test can be obtained.
[14. Use of resin composition ]
The resin composition of the present invention can be used as a resin composition for forming an insulating layer of a circuit board such as a printed circuit board. The insulating layer includes an insulating layer for forming a conductor layer (including a rewiring layer) on the insulating layer. Therefore, the resin composition can also be used as a resin composition for forming an insulating layer for forming a conductor layer. Among these, the resin composition is preferably used as a resin composition for forming a stacked insulating layer for forming an insulating layer in the production of a circuit board by a stacked system.
In particular, the resin composition can be suitably used as a resin composition for forming an insulating layer of a high-frequency circuit board (resin composition for forming an insulating layer of a high-frequency circuit board), taking advantage of the advantage that an insulating layer having a low dielectric constant can be obtained. Among these, the resin composition can be more suitably used as a resin composition for forming an interlayer insulating layer of a high-frequency circuit board (resin composition for forming an interlayer insulating layer of a high-frequency circuit board). The term "high-frequency circuit board" as used herein refers to a circuit board which can operate even with an electric signal of a high-frequency band. The term "high frequency band" generally means a frequency band of 1GHz or more, and the above resin composition is effective particularly in a frequency band of 28GHz to 80 GHz.
Further, the insulating layer having a low dielectric constant contributes to a reduction in height of the circuit board (reduction in height), and is therefore suitable for applications requiring a thin circuit board. Further, an insulating layer having a low dielectric constant is preferable because it facilitates impedance control of the circuit board, and thus increases the degree of freedom in designing the circuit board. From such a viewpoint, preferable applications of the resin composition include, for example, circuit boards such as mother boards (motherboards) used in portable devices, IC package boards, camera module boards, and fingerprint sensor boards. As a specific example, a fingerprint sensor may include an insulating layer included in a circuit board, a plurality of electrodes formed on the insulating layer, and an insulating film in this order. This fingerprint recognition sensor recognizes a fingerprint by using the principle that the capacitance values of a finger placed on an insulating film, electrodes, and a capacitor formed by the insulating film are different between a concave portion and a convex portion of the fingerprint. In such a fingerprint sensor, if the insulating layer is made thin, the sensor itself can be miniaturized.
The resin composition of the present invention can be used in a wide range of applications where resin compositions can be used, such as adhesive films, sheet-like laminate materials such as prepregs, solder resists, underfill materials, die-bonding materials, semiconductor sealing materials, filling resins (cavity filling resin (12417resin), component embedding resins, and the like.
[15. Adhesive film ]
The resin composition can be applied in a varnish state to form an insulating layer. However, industrially, it is preferable to use an adhesive film having a resin composition layer containing the resin composition for forming an insulating layer. The adhesive film includes a support and a resin composition layer provided on the support. The resin composition layer is a layer formed of the above resin composition, and is sometimes referred to as an "adhesive layer".
From the viewpoint of reduction in thickness, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and particularly preferably 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 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. As the support, a film or a metal foil made of a plastic material is preferable.
When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, sometimes referred to as "PET"), polyethylene naphthalate (hereinafter, sometimes referred to as "PEN"), and the like; polycarbonate (hereinafter, sometimes referred to as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter, may be referred to as "PMMA"); a cyclic polyolefin; triacetyl cellulose (hereinafter sometimes referred to as "TAC"); polyether sulfide (hereinafter sometimes referred to as "PES"); a polyether ketone; and (3) polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and easily available.
When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil. Among them, copper foil is preferable. As the copper foil, a foil formed of metal copper alone may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.
The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, an antistatic treatment, or the like.
In addition, as the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. Examples of the release agent that can be used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available release agents include, for example, "SK-1", "AL-5" and "AL-7" manufactured by Linekco, which are alkyd resin-based release agents. Examples of the support having a release layer include "lumiror T60" manufactured by dongli corporation; "Purex" manufactured by Imperial corporation; unipel manufactured by UNITIKA corporation; and so on.
The thickness of the support is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
The adhesive film can be produced, for example, by: a resin varnish containing an organic solvent and a resin composition is prepared, and the resin varnish is applied to a support using an application device such as a die coater, and is dried to form a resin composition layer.
Examples of the organic solvent include ketone solvents such as acetone, methyl Ethyl Ketone (MEK), and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolve and carbitol solvents such as butyl carbitol; aromatic solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are set so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although the boiling point of the organic solvent in the resin varnish varies, for example, when a resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin varnish may be dried at 50 to 150 ℃ for 3 to 10 minutes to form a resin composition layer. In general, the resin composition layer can be obtained as a film obtained by semi-curing a coating film of a resin varnish.
The adhesive film may include any layer other than the support and the resin composition layer, as necessary. For example, in the adhesive film, a protective film may be provided on the support on the side of the resin composition layer not bonded to the support (i.e., on the side opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust or the like from adhering to or being damaged on the surface of the resin composition layer. When the adhesive film has a protective film, the adhesive film can be used by peeling off the protective film. The adhesive film may be wound into a roll and stored.
[16. Prepreg ]
The insulating layer may be formed by using a prepreg instead of the adhesive film. The prepreg can be formed by impregnating a sheet-like fibrous base material with a resin composition.
The sheet-like fibrous base material used in the prepreg is not particularly limited. As the sheet-like fibrous base material, any fibrous base material that can be used as a base material for a prepreg, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, and the like, can be used. From the viewpoint of reduction in thickness, the thickness of the fibrous base material in sheet form is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and particularly preferably 600 μm or less. From the viewpoint of suppressing the depth of penetration (12418\1236826) of plating involved in the formation of the conductor layer to a low value, the thickness of the sheet-like fiber base material is preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is usually 1 μm or more, and may be 1.5 μm or more or 2 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 adhesive film.
[17. Circuit Board ]
The circuit board of the present invention comprises an insulating layer formed of a cured product of the above resin composition. In one embodiment, a circuit board includes an inner layer substrate and an insulating layer provided on the inner layer substrate.
The "inner layer substrate" refers to a member serving as a base material of the circuit board. Examples of the inner layer substrate include substrates including a core substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In general, the inner layer substrate includes a conductor layer formed directly or indirectly on one or both surfaces of the core base material. In order to make the conductor layer function as, for example, an electric circuit, the conductor layer may be subjected to patterning. An inner layer substrate in which a conductor layer is formed as a circuit on one surface or both surfaces of a core substrate is sometimes referred to as an "inner layer circuit substrate". In addition, an intermediate manufactured article in which at least either one of an insulating layer and a conductor layer is to be further formed in order to manufacture a circuit substrate is also included in the term "inner layer substrate". When the circuit board incorporates components, an inner layer board incorporating the components may be used.
The thickness of the inner layer substrate is usually 50 μm to 4000 μm, and is preferably 200 μm to 3200 μm from the viewpoint of improving the mechanical strength of the circuit substrate and reducing the height (reducing the thickness).
In order to electrically connect the conductor layers on both sides of the inner layer substrate to each other, the inner layer substrate may be provided with 1 or more through holes from one surface to the other surface. The inner layer substrate may include further components such as a passive element.
The insulating layer is a layer of a cured product of the resin composition. The insulating layer formed from the cured product is suitably applicable to insulating layers for circuit boards, such as circuit boards for a build-up system, high-frequency circuit boards, and mother cards for use in portable devices, IC package boards, camera module boards, and fingerprint sensor boards.
The circuit board may have only 1 insulating layer, or may have 2 or more insulating layers. When the circuit board has 2 or more insulating layers, the circuit board can be provided as a stacked layer in which a conductor layer and an insulating layer are alternately stacked.
The thickness of the insulating layer is usually 20 μm to 200 μm, and is preferably 50 μm to 150 μm from the viewpoint of improving electrical characteristics and reducing the height of the circuit board.
The insulating layer may be provided with 1 or more through holes for electrically connecting the conductor layers of the circuit board to each other.
The insulating layer is a layer formed from a cured product of the resin composition, and therefore can exhibit excellent characteristics of a cured product of the resin composition. Therefore, it is preferable that the insulating layer of the circuit board has properties such as a dielectric constant of the insulating layer and a peeling strength between the insulating layer and the conductive layer after the HAST test, which are adjusted to the same ranges as those described in the section of the properties of the resin composition. These properties can be measured by the methods described in examples.
The circuit board can be manufactured by a manufacturing method including the following steps (I) and (II) using an adhesive film,
(I) Laminating the adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate;
(II) a step of forming an insulating layer by thermally curing the resin composition layer.
The lamination of the inner substrate and the adhesive film can be performed, for example, by a heat-pressure bonding step of heating the adhesive film while pressing the adhesive film against the inner substrate from the support side. Examples of the member used in the heat and pressure bonding step (also referred to as "heat and pressure bonding member") include a heated metal plate (e.g., SUS end plate) and a metal roll (e.g., SUS roll). In order to make the adhesive film sufficiently follow the irregularities on the surface of the inner layer substrate, it is preferable that the pressure-bonding member is pressed through an elastic material such as a heat-resistant rubber, instead of being pressed by directly contacting the pressure-bonding member with the support of the adhesive film.
The lamination of the inner substrate and the adhesive film can be performed by, for example, a vacuum lamination method. In the vacuum lamination method, the temperature for heating and pressure bonding is preferably 60 to 160 ℃, and more preferably 80 to 140 ℃. The pressure for the thermal compression bonding is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa. The time for the heat-pressure bonding is preferably 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7hPa or less.
Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Nikko-Materials, vacuum applicators (vacuum applicators), batch vacuum pressure laminators, and the like.
After lamination, the resin composition layer of the laminate is subjected to a smoothing treatment by pressing from the support side with a heat-pressure bonding member under normal pressure (atmospheric pressure), for example. The pressing conditions for the smoothing treatment may be set to the same conditions as those for the above-described heat and pressure bonding of the laminate. The smoothing treatment can be performed using a commercially available laminator. The lamination and smoothing treatment can be continuously performed using a commercially available vacuum laminator as described above.
The support may be removed between the steps (I) and (II), or may be removed after the step (II).
In the step (II), the resin composition layer is thermally cured to form the insulating layer. The conditions for heat curing of the resin composition layer are not particularly limited, and conditions that can be employed in forming the insulating layer of the circuit substrate can be arbitrarily employed.
The heat curing conditions of the resin composition layer vary depending on, for example, the kind of the resin composition. The curing temperature of the resin composition layer is usually in the range of 120 to 240 ℃ (preferably in the range of 150 to 220 ℃, and more preferably in the range of 170 to 200 ℃). The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).
The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is subjected to thermal curing. For example, the resin composition layer may be preheated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) at a temperature of usually 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 110 ℃ or less, more preferably 70 ℃ or more and 100 ℃ or less) before the resin composition layer is thermally cured.
The method for manufacturing a circuit board may further include (III) a step of forming a hole in the insulating layer, (IV) a step of performing roughening treatment on the insulating layer, and (V) a step of forming a conductor layer. The steps (III) to (V) can be carried out by an appropriate method used for manufacturing a circuit board. When the support is removed after the step (II), the removal of the support may be performed at any time point between the steps (II), (III), (IV), or (V).
The step (III) is a step of forming a hole in the insulating layer. By forming the hole, a hole such as a through hole or a through hole can be formed in the insulating layer. The step (III) can be performed by, for example, a drilling method, a laser method, a plasma method, or the like, depending on the composition of the resin composition for forming the insulating layer. The size and shape of the hole may be determined as appropriate according to the design of the circuit substrate.
The step (IV) is a step of roughening the insulating layer. The step and conditions of the roughening treatment are not particularly limited, and any step and conditions that can be used for forming an insulating layer of a circuit board can be used. For example, the insulating layer may be subjected to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.
Examples of the swelling solution include an alkali solution and a surfactant solution, and preferably an alkali solution. The alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available Swelling liquids include "spinning Dip securigrant P" and "spinning Dip securigrant SBU" manufactured by ato ech JAPAN. The swelling solution may be used alone in 1 kind, or in combination of 2 or more kinds. The swelling treatment with the swelling liquid is not particularly limited. The swelling treatment can be performed, for example, by immersing the insulating layer in a swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, the insulating layer is preferably immersed in a swelling solution at 40 to 80 ℃ for 5 to 15 minutes.
Examples of the oxidizing agent include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidizing agent may be used alone in 1 kind, or in combination of 2 or more kinds. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution securigant P" manufactured by ATOTECH JAPAN.
As the neutralizing solution, an acidic aqueous solution is preferable. Examples of commercially available products of the neutralization Solution include "Reduction Solution securigant P" manufactured by ATOTECH JAPAN company. The neutralizing solution may be used alone in 1 kind, or in combination of 2 or more kinds. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer on which the roughening treatment with the oxidizing agent is performed in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of workability, the insulating layer subjected to the roughening treatment with the oxidizing agent is preferably immersed in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.
The step (V) is a step of forming a conductor layer. Materials that can be used for the conductor layer are not particularly limited. In a preferred embodiment, the conductor layer contains 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 conductive layer may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed of an alloy of 2 or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferable; or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy. Further, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is more preferable; or an alloy layer of a nickel-chromium alloy; a single metal layer of copper is further preferred.
The conductor layer may have a single-layer structure or a multi-layer structure including 2 or more single metal layers or alloy layers formed of different kinds of metals or alloys. 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 a nickel-chromium alloy.
The thickness of the conductor layer is usually 3 μm to 200. Mu.m, preferably 10 μm to 100. Mu.m.
The conductor layer can be formed by directly patterning a metal foil used as a support of the adhesive film, for example. The conductor layer may be formed by plating, for example. As a formation method by plating, for example, plating can be performed on the surface of the insulating layer by a method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Among them, from the viewpoint of ease of production, the formation by the semi-addition method is preferable.
An example of forming the conductor layer by the semi-additive method will be described below. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating (electroless plating). Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer so as to correspond to a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.
The conductor layer can be formed using, for example, a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the steps (I) and (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. The lamination of the resin composition layer and the metal foil may be performed using a vacuum lamination method. The lamination conditions may be the same as those of the lamination of the inner layer substrate and the adhesive film in the step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a subtractive method, a modified semi-additive method, or the like using the metal foil on the insulating layer. The metal foil can be produced by, for example, an electrolytic method, a rolling method, or the like. As commercially available products of metal foils, there are mentioned, for example, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil, etc. manufactured by JX Metal Co.
When the circuit board includes 2 or more insulating layers and conductor layers (stacked layers), the step of forming the insulating layer and the step of forming the conductor layer are repeated 1 or more times, whereby a circuit board having a multilayer wiring structure that can function as a circuit can be manufactured.
In other embodiments, the circuit substrate may be manufactured by using a prepreg instead of the adhesive film. The manufacturing method using the prepreg is basically the same as the case of using the adhesive film.
[18. Semiconductor device ]
The semiconductor device includes the circuit board. The semiconductor device can be manufactured using a circuit substrate.
Examples of the semiconductor device include various semiconductor devices which can be used for electric products (for example, a computer, a mobile phone, a digital camera, a television, and the like) and vehicles (for example, a motorcycle, an automobile, a train, a ship, an airplane, and the like).
The semiconductor device can be manufactured by, for example, mounting a component (semiconductor chip) at a conducting position of a circuit board. The "conduction position" refers to a "position in the circuit board where an electrical signal can be transmitted", and the position may be a surface of the circuit board or a position embedded in the circuit board. In addition, the semiconductor chip may be an electric circuit element using a semiconductor as a material.
As for the method of mounting the semiconductor chip in the manufacture of the semiconductor device, any method that allows the semiconductor chip to function effectively can be employed. Examples of the method of mounting the semiconductor chip include a wire bonding mounting method, a flip chip mounting method, a mounting method using a solderless Build-Up Layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), and a mounting method using a nonconductive film (NCF). The "mounting method by a build-up solderless layer (BBUL)" as used herein means a "mounting method in which a semiconductor chip is directly embedded in a circuit board and the semiconductor chip is connected to wiring of the circuit board".
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise explicitly stated.
[ example 1]
A resin solution was obtained by heating and dissolving 20 parts of a liquid bisphenol A-type epoxy resin (epoxy equivalent 187, product of Mitsubishi chemical corporation "JeR828 US"), 10 parts of a bicresol-type epoxy resin (epoxy equivalent 190, product of Mitsubishi chemical corporation "YX4000 HK"), 30 parts of a biphenyl aralkyl-type epoxy resin (epoxy equivalent 276, product of Nippon chemical corporation "NC 3000"), 10 parts of a naphthol-type epoxy resin (epoxy equivalent 332, product of Nippon Tekken chemical corporation "ESN 475V"), and 20 parts of a phenoxy resin (a solid content of 30 mass% methyl ethyl ketone/cyclohexanone =1/1 solution, product of Mitsubishi chemical corporation "YL7553BH 30") in 60 parts of methyl ethyl ketone and 20 parts of cyclohexanone with stirring.
To this resin solution were mixed 15 parts of an active ester curing agent ("HPC 8000-65T" manufactured by DIC corporation) 15 parts of a cresol novolak-type curing agent having a triazine skeleton ("phenol equivalent) 151 (" phenol equivalent "50% by solid 2-methoxypropanol solution" manufactured by DIC corporation), 25 parts of a curing accelerator ("LA 3018-50P" manufactured by DIC corporation), 4 parts of a curing accelerator ("4-dimethylaminopyridine" (DMAP) and a methyl ethyl ketone solution (5% by solid) 4 parts of a spherical silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM 573" manufactured by Smartech corporation) (SO-C2 "manufactured by Admatechs corporation, average particle diameter 0.5 μm, specific surface area 5.9m 2 Per g) 100 parts of polytetrafluoroethylene particles ("LUBRON L-2" manufactured by Daikin industries, inc., having an average particle diameter of 3 μm) 80 parts, 2 parts of core-shell rubber particles ("AC 3816N" manufactured by AICA industries, inc.), and 4 parts of non-particulate fluoropolymer ("LE-605" manufactured by Kyoho chemical Co., ltd.) were uniformly dispersed in a high-speed rotary mixer to obtain a resin varnish.
A polyethylene terephthalate film (38 μm thick, "AL5" manufactured by Linekeko) having an alkyd resin-based release layer on the surface thereof was prepared as a support. The aforementioned resin varnish was uniformly coated on the support using a metal die coater. The coated resin varnish was dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes to form a resin composition layer, and an adhesive film having a support and the resin composition layer was obtained. The thickness of the resin composition layer was 50 μm, and the amount of the residual solvent in the resin composition was about 2 mass%.
Then, a polypropylene film having a thickness of 15 μm was laminated on the surface of the resin composition layer, and the adhesive film was wound in a roll form. The wound adhesive film was cut into a width of 507mm to obtain a sheet-like adhesive film having dimensions of 507mm × 336 mm.
[ example 2]
The amount of the core-shell rubber particles (manufactured by AICA industries, inc. 'AC 3816N') was changed from 2 parts to 6 parts. Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
[ example 3]
80 parts of polytetrafluoroethylene particles ("LUBRON L-2" manufactured by Daikin industries, ltd.) and 4 parts of a fluoropolymer ("LE-605" manufactured by Kyoho chemical Co., ltd.) were mixed in advance, and then mixed into a resin solution. Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
[ example 4]
30 parts of a biphenylaralkyl type epoxy resin ("NC 3000" manufactured by Nippon chemical Co., ltd.) was changed to 27 parts of a naphthylene ether type epoxy resin ("HP 6000" manufactured by DIC Co., ltd.);
further, 2 parts of core-shell rubber particles ("AC 3816N" manufactured by AICA industries) were changed to 2 parts of core-shell rubber particles ("IM 401-to 7-17" manufactured by AICA industries, wherein the core was polybutadiene and the shell was a styrene-divinylbenzene copolymer). Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
[ example 5]
30 parts of a biphenyl aralkyl type epoxy resin ("NC 3000" manufactured by Nippon chemical Co., ltd.) were changed to 20 parts of a naphthylene ether type epoxy resin ("epoxy equivalent 260", "HP6000" manufactured by DIC Co., ltd.) and 5 parts of a naphthalene type tetrafunctional epoxy resin ("HP 4700" manufactured by DIC Co., ltd.). Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
[ example 6]
15 parts of an active ester curing agent (a toluene solution containing 65 mass% of a nonvolatile component, "HPC8000-65T" manufactured by DIC) and 25 parts of a cresol novolak-type curing agent having a triazine skeleton (a 2-methoxypropanol solution containing 50 mass% of a solid component, "LA3018-50P" manufactured by DIC) were changed to 15 parts of a naphthol-type curing agent (hydroxyl equivalent 215, "SN485" manufactured by Nippon iron King chemical Co., ltd.) and 12 parts of a triazine-containing phenol novolak resin (hydroxyl equivalent 125, a methyl ethyl ketone solution containing 60% of a solid component, "LA7054" manufactured by DIC Co., ltd.). Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
[ example 7]
2 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM 573" by shin-Etsu chemical Co., ltd.) was further added to the resin varnish. Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
Comparative example 1
The amount of the core-shell rubber particles (manufactured by AICA industries, inc. 'AC 3816N') was changed from 2 parts to 0 part. Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
Comparative example 2
2 parts of core-shell rubber particles ("AC 3816N" manufactured by AICA industries) were changed to 2.5 parts of an epoxy resin having a polybutadiene structure (epoxy equivalent 190, a methyl ethyl ketone solution having a solid content of 80% by weight, manufactured by DAICEL Chemicals) which functions as a non-particulate rubber. Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
Comparative example 3
The amount of the core-shell rubber particles (manufactured by AICA industries, inc. 'AC 3816N') was changed from 2 parts to 12 parts. Except for the above, a resin varnish and an adhesive film were produced in the same manner as in example 1.
[ measurement of dielectric constant ]
A polyethylene terephthalate film (manufactured by Lindelco corporation, "PET 501010") whose surface was subjected to a mold release treatment was prepared. The resin varnishes obtained in examples and comparative examples were uniformly applied to the polyethylene terephthalate film using a die coater so that the thickness of the dried resin composition layer became 50 μm. The coated resin varnish was dried at 80 to 110 ℃ (average 95 ℃) for 6 minutes to obtain a resin composition layer. Then, the resin composition layer was subjected to a heat treatment at 200 ℃ for 90 minutes to be cured, and the support was peeled off, thereby obtaining a cured product film formed of a cured product of the resin composition. The cured film was cut into a size of 80mm in length and 2mm in width to obtain an evaluation sample.
The dielectric constant of the cured product of the resin composition was measured using an analyzer ("HP 8362B" manufactured by Agilent Technologies) at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ by a resonance cavity perturbation method. The average value of the measurements of 2 test pieces was calculated.
[ measurement of the amount of resin flow ]
An inner layer substrate (glass cloth substrate epoxy resin double-sided copper-clad laminate, copper foil 18 μm thick, substrate 0.8mm thick, "R5715ES" manufactured by Sonar electric corporation) was prepared. The adhesive films produced in examples and comparative examples were laminated on both sides of the inner layer substrate using a batch type vacuum pressure Laminator (2-Stage build up Laminator (CVP 700), manufactured by Nikko Materials), so that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by: the pressure was reduced to 13hPa or less for 30 seconds, and then the sheet was pressure-bonded at 100 ℃ for 30 seconds under a pressure of 0.74 MPa. Next, hot pressing was performed at 100 ℃ for 60 seconds under a pressure of 0.5 MPa.
Then, the end of the adhesive film laminated on the inner layer substrate was observed. Fig. 1 is a plan view schematically showing the periphery of an end portion of an adhesive film 100 laminated on an inner layer substrate 200 in the embodiment. As a result of the above observation, as shown in fig. 1, the resin composition layer 110 of the adhesive film 100 was observed to protrude outside the edge 120E of the support 120 of the adhesive film 100. The overflow of the resin composition layer 110 is formed by flowing out the resin composition layer 110 that has become fluid at the time of lamination in the in-plane direction parallel to the surface 200U of the inner layer substrate 200. Therefore, the distance W from the edge 120E of the support 120 of the adhesive film 100 to the tip 110T of the resin composition layer 110 that has overflowed is measured, and the distance W is obtained as the amount of resin flow. The flow rate of the resin was determined to be "good" when the flow rate was 3mm or less, and determined to be "poor" when the flow rate was greater than 3 mm.
[ measurement of peeling Strength ]
(1) Base treatment of the inner layer substrate:
a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.8mm thick, "R5715ES" from Suzu Denko K.K.) on which an inner layer circuit was formed was prepared as an inner layer substrate. Both surfaces of the inner layer substrate were etched with an etchant (CZ 8100, MEC) for 1 μm, and the copper surfaces on both sides of the inner layer substrate were roughened.
(2) Lamination of adhesive film:
the adhesive films produced in examples and comparative examples were laminated on both sides of the inner substrate using a batch type vacuum pressure laminator (2-stage stack laminator "CVP700" manufactured by Nikko Materials) in such a manner that the resin composition layer was in contact with the inner substrate. The lamination was carried out by: the pressure was reduced to 13hPa or less for 30 seconds, and then the sheet was pressure-bonded at 100 ℃ and a pressure of 0.74MPa for 30 seconds. Next, hot pressing was performed at 100 ℃ for 60 seconds under a pressure of 0.5 MPa.
(3) Curing of the resin composition:
the adhesive film laminated on the inner substrate is heated under curing conditions of 100 ℃ for 30 minutes and further 180 ℃ for 30 minutes to thermally cure the resin composition layer, thereby forming an insulating layer. Then, the polyethylene terephthalate film as the support was peeled off. Thus, a sample substrate having the insulating layer, the inner layer substrate, and the insulating layer in this order was obtained.
(4) Roughening treatment:
the sample substrate was immersed in a Swelling solution ("spinning Dip securigant P" manufactured by ato ech JAPAN, inc., containing diethylene glycol monobutyl ether) at 60 ℃ for 10 minutes. Next, the sample substrate was immersed in a roughening solution ("Concentrate Compact P" KMnO manufactured by ATOTECH JAPAN) at 80 ℃ 4 :60g/L, naOH:40g/L aqueous solution) for 20 minutes. Next, the sample substrate was immersed in a neutralization solution ("Reduction solution securiganteh P" manufactured by ATOTECH JAPAN) at 40 ℃ for 5 minutes. Then, the sample substrate was dried at 80 ℃ for 30 minutes to obtain a roughened substrate.
(5) Plating by semi-addition:
immersing the roughened substrate in a solution containing PdCl at 40 deg.C 2 The electroless copper plating solution of (1) was immersed in an electroless copper plating solution at 25 ℃ for 20 minutes after 5 minutes. Then, the roughened substrate was subjected to an annealing treatment by heating at 150 ℃ for 30 minutes. An etching resist (etching resist) is formed on the roughened substrate after the annealing treatment, and patterning is performed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer on the surface of the insulating layer in a thickness of 25 μm. Then, annealing treatment was performed by heating at 180 ℃ for 30 minutes to obtain a circuit board having a conductor layer on an insulating layer.
(6) Measurement of tear strength (peel strength) of plated conductor layer:
a cut was made in the conductor layer of the circuit board so as to surround a rectangular portion having a width of 10mm and a length of 100 mm. One end of the rectangular portion in the longitudinal direction was peeled off and held by a jig (AUTO COM model testing machine "AC-50CSL" manufactured by t.s.e.). Then, a peel test was performed at room temperature by tearing the conductive layer at a speed of 50 mm/min in a direction perpendicular to the surface of the circuit board, and the load (kgf/cm) when the conductive layer was torn at a length of 35mm was measured as the peel strength. The peel strength was judged to be "good" when it was 0.3kgf/cm or more. In addition, the case where the peel strength was less than 0.3kgf/cm and the case where the swelling occurred were determined to be "poor".
[ measurement of peeling Strength after HAST test ]
An accelerated environment test, which is a HAST test in which the circuit board was exposed to an environment of 130 ℃ and 85% rh for 100 hours using a high accelerated life test apparatus ("PM 422" manufactured by nanba ltd). Then, the peel strength when the conductor layer of the circuit board was peeled off was measured by the same operation as "measurement of the peel strength (peel strength) of the plated conductor layer" in the step (6) "measurement of peel strength".
The peel strength after the accelerated environmental test was 0.3kgf/cm or more was judged as "good", and the peel strength after the accelerated environmental test was less than 0.3kgf/cm was judged as "poor".
[ results ]
The results of the above examples and comparative examples are shown in the following tables. In the following tables, the amounts of the respective components represent parts by mass of nonvolatile components.
[ Table 1]
[ Table 1. Results of examples and comparative examples ]
Figure DEST_PATH_IMAGE001
。
[ examination ]
As is clear from Table 1, low dielectric constants were obtained in the examples. In addition, in the examples, the amount of resin flow was small, and the peel strength after HAST test was large. Therefore, it was confirmed from the above results that the present invention can provide a resin composition which can provide an insulating layer having a low dielectric constant and high adhesion to a conductor layer after a HAST test and which can suppress resin flow.
Further, from the results of comparative example 1 containing the rubber particles (C) and comparative example 3 in which the amount of the rubber particles is excessive, it is understood that the amount of the rubber particles (C) should be controlled within a predetermined range in order to obtain the desired effects of the present invention. In particular, in comparative example 3, it is considered that the mechanical strength of the resin composition is decreased due to the excessive amount of the (C) rubber particles, the peel strength before the HAST test is decreased, and the influence of the swelling of the (C) rubber particles is increased, and the peel strength after the HAST test is decreased.
Further, from the results of comparative example 2 using an epoxy resin ("PB-3600M" manufactured by DAICEL corporation) capable of functioning as a liquid rubber in place of (C) the rubber particles, it was found that particles should be used as a rubber component in order to obtain the desired effects of the present invention. It is considered that in comparative example 2, since a non-particulate rubber component was used, the effect of improving the thixotropy could not be obtained, and the amount of resin flow became large. In comparative example 2, it is considered that the peel strength after the HAST test is decreased because the non-particulate rubber component cannot sufficiently absorb the stress generated by the temperature change at the time of the HAST test.
In addition, comparing example 1 with example 3, the amount of resin flow of example 1 was small. Therefore, in order to effectively suppress the resin flow, as described in example 1, it is preferable to mix the (D) fluorine-based filler and the (H) fluorine-based polymer with the components other than them, as compared with mixing the (D) fluorine-based filler and the (H) fluorine-based polymer with the components other than them.
In the above examples, it was confirmed that even when the components (E) to (I) were not used, the results were similar to those in the above examples, although the degrees of the differences were different.
Description of the reference numerals
100. Adhesive film
110. Layer of resin composition
120. Support body
200. An inner layer substrate.

Claims (26)

1. A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) rubber particles and (D) a fluorine-based filler,
(D) The component (A) is a fluorine-based polymer particle,
the amount of the component (C) is 0.1 to 3% by mass based on 100% by mass of nonvolatile components in the resin composition,
the amount of the component (D) is 10 to 80% by mass based on 100% by mass of nonvolatile components in the resin composition,
(B) The components comprise: a compound having 1 or more active ester groups in 1 molecule, or a phenol-based curing agent having a triazine skeleton.
2. A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) rubber particles and (D) a fluorine-based filler,
(D) The component (A) is a fluorine-based polymer particle,
the amount of the component (C) is 0.1 to 3% by mass based on 100% by mass of the nonvolatile component in the resin composition,
the amount of the component (D) is 20 to 80% by mass based on 100% by mass of nonvolatile components in the resin composition.
3. The resin composition according to claim 1 or 2, wherein the amount of the component (C) is 0.5% by mass or more based on 100% by mass of nonvolatile components in the resin composition.
4. The resin composition according to claim 1 or 2, wherein the amount of the component (C) is 2.2% by mass or less based on 100% by mass of nonvolatile components in the resin composition.
5. The resin composition according to claim 1 or 2, wherein the component (D) is polytetrafluoroethylene particles.
6. The resin composition according to claim 1 or 2, wherein (E) an inorganic filler is contained.
7. The resin composition according to claim 6, wherein the component (E) is silica.
8. The resin composition according to claim 6, wherein the amount of the component (E) is 5 to 70% by mass based on 100% by mass of nonvolatile components in the resin composition.
9. The resin composition according to claim 6, wherein the amount of the component (E) is 20% by mass or more based on 100% by mass of nonvolatile components in the resin composition.
10. The resin composition according to claim 6, wherein the amount of the component (E) is 40% by mass or less based on 100% by mass of nonvolatile components in the resin composition.
11. The resin composition according to claim 6, wherein the amount of the component (D) is 20 to 90% by mass based on 100% by mass of the total of the components (D) and (E).
12. The resin composition according to claim 6, wherein the amount of the component (D) is 35% by mass or more based on 100% by mass of the total of the components (D) and (E).
13. The resin composition according to claim 6, wherein the amount of the component (D) is 50% by mass or less based on 100% by mass of the total of the components (D) and (E).
14. The resin composition according to claim 1, wherein the amount of the component (D) is 20% by mass or more based on 100% by mass of nonvolatile components in the resin composition.
15. The resin composition according to claim 1 or 2, wherein the amount of the component (D) is 40% by mass or less based on 100% by mass of nonvolatile components in the resin composition.
16. The resin composition according to claim 1 or 2, wherein the component (A) is at least 1 epoxy resin selected from the group consisting of bisphenol A type epoxy resins, biphenol type epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, naphthalene type tetrafunctional epoxy resins, and naphthol type epoxy resins.
17. The resin composition according to claim 1 or 2, wherein the amount of the component (A) is 5% by mass or more and 70% by mass or less with respect to 100% by mass of nonvolatile components in the resin composition.
18. The resin composition according to claim 1 or 2, wherein the amount of the component (A) is 10% by mass or more based on 100% by mass of nonvolatile components in the resin composition.
19. The resin composition according to claim 1 or 2, wherein the amount of the component (A) is 30% by mass or less based on 100% by mass of nonvolatile components in the resin composition.
20. The resin composition according to claim 1 or 2, wherein the amount of the component (B) is 0.1% by mass or more and 40% by mass or less based on 100% by mass of nonvolatile components in the resin composition.
21. The resin composition according to claim 1 or 2, wherein the amount of the component (B) is 1% by mass or more based on 100% by mass of nonvolatile components in the resin composition.
22. The resin composition according to claim 1 or 2, wherein the amount of the component (B) is 20% by mass or less based on 100% by mass of nonvolatile components in the resin composition.
23. The resin composition according to claim 1 or 2, which is used for forming an insulating layer of a circuit substrate.
24. An adhesive film comprising a support and, provided on the support, a resin composition layer comprising the resin composition according to any one of claims 1 to 23.
25. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 23.
26. A semiconductor device comprising the circuit board according to claim 25.
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