CN107129589B - Resin sheet with support - Google Patents

Resin sheet with support Download PDF

Info

Publication number
CN107129589B
CN107129589B CN201710108030.8A CN201710108030A CN107129589B CN 107129589 B CN107129589 B CN 107129589B CN 201710108030 A CN201710108030 A CN 201710108030A CN 107129589 B CN107129589 B CN 107129589B
Authority
CN
China
Prior art keywords
resin
resin composition
mass
support
resin sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710108030.8A
Other languages
Chinese (zh)
Other versions
CN107129589A (en
Inventor
中村茂雄
鸟居恒太
藤原千寻
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ajinomoto Co Inc
Original Assignee
Ajinomoto Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Publication of CN107129589A publication Critical patent/CN107129589A/en
Application granted granted Critical
Publication of CN107129589B publication Critical patent/CN107129589B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0843—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention provides a resin sheet with a support, a method for manufacturing a printed wiring board, and a semiconductor device, wherein the generation of recessed portions generated in the extending direction of the interface of each cured resin composition layer is suppressed. The solution of the present invention is a resin sheet with a support, comprising a support and a resin sheet provided on the support, wherein the resin sheet comprises: a first resin composition layer formed of a first resin composition provided on the support body side, and a second resin composition layer formed of a second resin composition provided on the side opposite to the support body side; the first resin composition contains (a) an inorganic filler, wherein the content of the component (a) is 30% by mass or less; the second resin composition contains (a) an inorganic filler, wherein the content of the component (a) is 60% by mass or more; the difference between the thermal conductivity of the first thermal cured product and the thermal conductivity of the second thermal cured product is 0.4W/mK or less.

Description

Resin sheet with support
Technical Field
The present invention relates to a resin sheet with a support. Also disclosed are a method for producing a printed wiring board, and a semiconductor device.
Background
As a method for manufacturing a printed wiring board (hereinafter, also referred to as "wiring board"), a stacked (build up) method of alternately stacking conductor layers and insulating layers, in which a circuit is formed, is widely used, and it is known that an insulating layer is formed by curing a 2-layer resin composition layer including a side in contact with a conductor layer and a side subjected to plating (for example, see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-17301.
Disclosure of Invention
Problems to be solved by the invention
In recent years, the amount of information communication has increased, and therefore, in the manufacture of printed wiring boards, fine wiring is desired.
In order to achieve fine wiring, the surface of the insulating layer has low roughness, and it is desirable to reduce the content of the inorganic filler in the 2-layer resin composition layer on the side to be subjected to plating (the side in contact with the conductor layer). On the other hand, from the viewpoint of reducing the thermal expansion coefficient, it is desirable to increase the content of the inorganic filler in the other resin composition layer (the side in contact with the substrate).
The present inventors have tried to form a via hole in an insulating layer formed by curing such a 2-layer resin composition layer. As a result, it was found that a recessed portion (No. れ) was generated in the extending direction of the interface between the cured resin composition layers on the side wall of the through-hole (see fig. 1). When such a recessed portion is generated, a void is generated during plating processing, which may hinder fine wiring.
The invention provides a resin sheet with a support, a method for manufacturing a printed wiring board, and a semiconductor device, wherein the generation of recessed portions generated in the extending direction of the interface of each cured resin composition layer is suppressed.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that the length of the recessed portion generated in the extending direction of the interface of the cured resin composition layers can be reduced by reducing the difference in thermal conductivity between the thermally cured products of the first and second resin composition layers. As a result of further intensive studies, the present inventors have found that the difference in thermal conductivity can be reduced by making the content of the inorganic filler in the first resin composition layer on the side on which plating is performed smaller than the content of the inorganic filler in the second resin composition layer, and have completed the present invention.
That is, the present invention includes the following.
[1] A resin sheet with a support, comprising a support and a resin sheet provided on the support,
the resin sheet has:
a first resin composition layer formed of a first resin composition provided on the support body side, and
a second resin composition layer formed of a second resin composition provided on the side opposite to the support body side,
the first resin composition contains (a) an inorganic filler, and the content of the component (a) is 30% by mass or less, based on 100% by mass of nonvolatile components in the first resin composition,
the second resin composition contains (a) an inorganic filler, and the content of the component (a) is 60% by mass or more, based on 100% by mass of nonvolatile components in the second resin composition,
the difference between the thermal conductivity of the first thermal cured product and the thermal conductivity of the second thermal cured product is 0.4W/mK or less,
the first thermosetting resin composition is obtained by thermosetting a first resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes,
the second thermosetting product is obtained by thermally curing the second resin composition at 100 ℃ for 30 minutes, and further at 190 ℃ for 90 minutes.
[2] The resin sheet with a support according to [1], wherein the thickness of the resin sheet is 40 μm or less.
[3] The resin sheet with a support according to any one of [1] and [2], wherein the thickness of the resin sheet is 25 μm or less.
[4] The resin sheet with a support according to any one of [1] to [3], wherein when the average particle diameter of the component (a) in the first resin composition is represented by R1(μm) and the average particle diameter of the component (a) in the second resin composition is represented by R2(μm), the ratio of R1 to R2, that is, R2/R1 is 1 to 15.
[5] The resin sheet with a support according to any one of [1] to [4], wherein the first resin composition comprises (b) an epoxy resin, and the component (b) has a mesogenic skeleton (mesogenic skeleton).
[6] The resin sheet with a support according to [5], wherein the component (b) is at least 1 selected from the group consisting of a biphenol-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a biphenyl-type epoxy resin, and a naphthalene-type epoxy resin.
[7] The resin sheet with a support according to any one of [1] to [6], which is used for forming an insulating layer of a printed wiring board.
[8] A method for manufacturing a printed wiring board, the method comprising the steps of:
a step (I) of laminating the resin sheet with a support according to any one of [1] to [7] on the inner layer substrate so that the second resin composition layer is bonded to the inner layer substrate,
a step (II) of forming an insulating layer by thermally curing the resin sheet with the support, and
and (III) forming a through hole in the insulating layer and removing the support.
[9] The method of manufacturing a printed wiring board according to item [8], wherein in the step (III), the via hole is formed in the insulating layer by laser.
[10] The method of manufacturing a printed wiring board according to item [8] or [9], wherein an opening diameter of the through hole is 40 μm or less.
[11] A printed wiring board comprising an insulating layer formed of the resin sheet with a support according to any one of [1] to [7 ].
[12] A semiconductor device comprising the printed wiring board [11 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a resin sheet with a support, a method for manufacturing a printed wiring board, and a semiconductor device, in which the occurrence of recessed portions generated in the extending direction of the interface of each cured resin composition layer is suppressed.
Drawings
Fig. 1 is a photograph of a cross section of an insulating layer having a recessed portion.
Fig. 2 is a schematic view showing one embodiment of a resin sheet with a support according to the present invention.
Fig. 3 is a photograph of a cross section for explaining the length of the recessed portion.
Detailed Description
The resin sheet with a support, the method for manufacturing a printed wiring board, the printed wiring board, and the semiconductor device of the present invention will be described in detail below.
Before the detailed description of the resin sheet with a support of the present invention, a first resin composition and a second resin composition used for forming a first resin composition layer and a second resin composition layer included in the resin sheet of the present invention will be described.
(first resin composition)
The first resin composition for forming the first resin composition layer contains (a) an inorganic filler, and when the nonvolatile content of the first resin composition is 100 mass%, the content of the component (a) is not particularly limited as long as it is 30 mass% or less, and a cured product thereof has sufficient plating releasability and insulating properties. Examples of the first resin composition include a composition containing a curable resin and a curing agent thereof in addition to an inorganic filler. As the curable resin, conventionally known curable resins that can be used in forming an insulating layer of a printed wiring board can be used, and among them, epoxy resins are preferable. Accordingly, in one embodiment, the first resin composition comprises (b) an epoxy resin, and (c) a curing agent. The first resin composition further contains a thermoplastic resin, a curing accelerator, a flame retardant and an organic filler, as required.
Hereinafter, each component that can be used as a material of the first resin composition will be described in detail.
- (a) inorganic filler materials-
The material of the inorganic filler is not particularly limited, and examples thereof 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 zirconate, barium zirconate, zirconium phosphate, zirconium phosphotungstate phosphate, and silicon carbide. Among these, silicon carbide and silicon dioxide are preferable, and silicon dioxide is particularly preferable. In addition, spherical silica is preferable as silica. The inorganic filler may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The average particle size of the inorganic filler is not particularly limited, but is preferably 2 μm or less, more preferably 1.5 μm or less, and still more preferably 1 μm or less, from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and further preferably 0.3 μm or more. Commercially available products of the inorganic filler having such an average particle diameter include "UFP-30" manufactured by electrochemical industries, Nippon Steel & Sumikin Materials co., Ltd. "SPH 516-05" manufactured by Nippon Steel & Sumikin Materials co., Ltd., "SER-A06" manufactured by concentrated electric gas industries, and the like.
The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is set as an average particle size. For the measurement sample, a product in which an inorganic filler is dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering particle size distribution measuring apparatus, SALD-2200 manufactured by Shimadzu corporation, and the like can be used.
The inorganic filler is preferably surface-treated with at least 1 surface-treating agent selected from a silane coupling agent, an alkoxysilane compound, and an organosilicon azane compound, from the viewpoint of improving moisture resistance and dispersibility. They may be oligomers. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. Examples of commercially available products of the surface treatment agent include "KBM 403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBE 903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 573" (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 can be used alone in 1 kind, also can be combined with more than 2 kinds.
The degree of surface treatment based on the surface treatment agent can be evaluated using the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving the dispersibility of the inorganic filler2Above, more preferably 0.1mg/m2Above, more preferably 0.2mg/m2The above. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1mg/m2The concentration is more preferably 0.8mg/m or less2The concentration is more preferably 0.5mg/m or less2The following.
The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is subjected to a washing treatment with a solvent (for example, Methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent may be added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, the solid component was dried, and then the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, there may be used "EMIA-320V" manufactured by horiba, Ltd.
The content of the inorganic filler in the first resin composition is 30 mass% or less, preferably 25 mass% or less, and more preferably 20 mass% or less, with respect to 100 mass% of nonvolatile components in the first resin composition, from the viewpoint of improving the plating peeling property. The lower limit of the content of the component (c) in the first resin composition is not particularly limited, and may be 0% by mass, and usually may be 5% by mass or more, 10% by mass or more, or the like.
- (b) epoxy resins
Examples of the epoxy resin 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 type epoxy resin (naphthol novolac epoxy resin), a phenol novolac type epoxy resin (phenol novolac 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 glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol formaldehyde (cresolnovolac) 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 having a spiro ring, a cyclohexane dimethanol type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a naphthol novolac type epoxy resin, a naphthol, Naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. The epoxy resin may be used alone in 1 kind, or may be used in combination with 2 or more kinds. The component (b) is preferably an epoxy resin having a mesogenic skeleton, and more preferably 1 or more selected from the group consisting of a biphenol-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a biphenyl-type epoxy resin, and a naphthalene-type epoxy resin, from the viewpoint of improving the thermal conductivity. The mesogenic skeleton is a general term for a group containing a rigid group (aromatic ring) having a rod-like or plate-like shape and exhibiting liquid crystallinity.
The epoxy resin preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. When the nonvolatile content of the epoxy resin is taken as 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having 2 or more epoxy groups in 1 molecule. Among them, an epoxy resin having 2 or more epoxy groups in 1 molecule and being liquid at a temperature of 20 ℃ (hereinafter referred to as "liquid epoxy resin") and an epoxy resin having 3 or more epoxy groups in 1 molecule and being solid at a temperature of 20 ℃ (hereinafter referred to as "solid epoxy resin") are preferably contained. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.
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 dimethanol type epoxy resin, a glycidyl amine type epoxy resin, or an epoxy resin having a butadiene structure, and 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. Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D", "HP 4032 SS" (naphthalene-type epoxy resin), "828 US", "jER 828 EL", "825" (bisphenol a-type epoxy resin), "jER 807", "1750" (bisphenol F-type epoxy resin), "jER 152" (novolac-type epoxy resin), "630", "630 LSD" (glycidyl amine-type epoxy resin), "ZX 1059" (a mixture of bisphenol a-type epoxy resin and bisphenol F-type epoxy resin) manufactured by mitsubishi chemical corporation, "EX-721" (glycidyl ester-type epoxy resin), and "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton), which are manufactured by Nagase ChemteX corporation, "PB-3600" (epoxy resin having a butadiene structure), and "zxide 1658" (ZX 1658 manufactured by mitshi chemical corporation, "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane), "630 LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These can be used alone in 1 kind, also can be combined with more than 2 kinds and use.
The solid epoxy resin is preferably a naphthalene-type 4-functional epoxy resin, a cresol formaldehyde-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, or a tetraphenylethane-type epoxy resin, and more preferably a naphthalene-type 4-functional epoxy resin, a naphthol-type epoxy resin, or a biphenyl-type epoxy resin. Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type 4-functional epoxy resin), "N-690" (cresol-formaldehyde-type epoxy resin), "N-695" (cresol-formaldehyde-type epoxy resin), "HP-7200" (dicyclopentadiene-type epoxy resin), "HP-7200 HH," HP-7200H, "" EXA-7311-G3, "" EXA-7311-G4, "" EXA-7311-G4S, "" HP6000 "(naphthylene ether-type epoxy resin)," EPPN-502H "(trisphenol-type epoxy resin)," NC L "(naphthol-type NC-NC 7000-type epoxy resin)," 3000 NC H, "" 3000, "" 593000, "" NC3100 "(NC-type epoxy resin)," produced by Nippon Kagaku Kogyo, "ESN 475V" (naphthalene type epoxy resin), "ESN 485" (naphthol novolac type epoxy resin), "YX 4000H", "YL 6121" (biphenyl type epoxy resin), "YX 4000 HK" (biphenol type epoxy resin), "YX 8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka gas chemistry (Osaka ガスケミカル), and "YL 7760" (bisphenol AF type epoxy resin), "YL 7800" (fluorene type epoxy resin), "JeR 1010" (solid bisphenol A type epoxy resin), "JeR 1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi chemical corporation. These can be used alone in 1 kind, also can be combined with more than 2 kinds and use.
When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1-1: 15, or more. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in the above range, the following effects can be obtained: i) when used in the form of a resin sheet, the adhesive composition can provide adequate adhesiveness; ii) when used in the form of a resin sheet, sufficient flexibility is obtained and handling properties are improved; and, iii) a cured product having sufficient breaking strength can be obtained; and so on. From the viewpoint of the effects of the above i) to iii), the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: 0.3-1: 10, more preferably 1: 0.6-1: and 8, in the above range.
The content of the epoxy resin in the first resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is obtained, and is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.
In the present invention, the content of each component in the resin composition means a value obtained by setting a nonvolatile component in the resin composition to 100 mass% unless otherwise specified.
The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and further preferably 110 to 1000. By setting the above range, the crosslinking density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent is measured in accordance with JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
- (c) curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include phenol (phenol) curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, cyanate curing agents, and carbodiimide curing agents. The curing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. (c) The component (b) is preferably 1 or more selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, carbodiimide-based curing agents and cyanate ester-based curing agents.
The phenol curing agent and the naphthol curing agent are preferably a phenol curing agent having a phenol resin (novolac) structure or a naphthol curing agent having a phenol resin structure from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol curing agent is preferable, and a phenol curing agent having a triazine skeleton is more preferable. Among them, a novolac resin curing agent containing a triazine skeleton is preferable from the viewpoint of satisfying heat resistance, water resistance, and adhesion to a conductor layer to a high degree.
Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851H", available from Nippon chemical Co., Ltd, "NHN", "CBN", "GPH", available from Nippon chemical Co., Ltd, "SN 170", "SN 180", "SN 190", "SN 475", "SN 485", "SN 495", "SN 375", "SN 395", available from Nippon chemical Co., Ltd, "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P" and "EXB-9500".
From the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, an active ester-based curing agent is also preferable. The active ester curing agent is not particularly limited, and in general, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, can be preferably used. The active ester curing agent is preferably 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 obtainable from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtainable 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, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol on 1 molecule of dicyclopentadiene.
Specifically, preferred are an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a phenol novolac resin, and an active ester compound containing a benzoyl compound of a phenol novolac resin, and among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferred. The "dicyclopentadiene type diphenol structure" means a 2-valent structural unit formed from phenylene-dicyclopentylene (ジシクロペンチレン) -phenylene.
Commercially available products of the active ester-based curing agent include "EXB 9451", "EXB 9460S", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65 TM" (manufactured by DIC Co., Ltd.) as an active ester compound having a dicyclopentadiene structure, "EXB 9416-70 BK" (manufactured by DIC Co., Ltd.) as an active ester compound having a naphthalene structure, "DC 808" (manufactured by Mitsubishi chemical Co., Ltd.) as an active ester compound having an acylate of a novolak resin, "YLH 1026" (manufactured by Mitsubishi chemical Co., Ltd.) as an active ester-based curing agent having an acylate of a novolak resin, and "YLH 1026" (manufactured by Mitsubishi chemical Co., Ltd.) as an active ester-based curing agent having an acylate of a novolak resin, "YLH 1030" (manufactured by Mitsubishi chemical corporation) and "YLH 1048" (manufactured by Mitsubishi chemical corporation) are exemplified.
Specific examples of the benzoxazine-based curing agent include "HFB 2006M" available from Showa Polymer K.K., and "P-d" and "F-a" available from Shikoku chemical industries, Ltd.
Examples of the cyanate ester curing agent include 2-functional 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' -ethylene (ethylidene) diphenyl dicyanate, 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 novolak resins, cresol formaldehyde resins, and the like, prepolymers obtained by partially triazinating these cyanate ester resins, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (both of which are novolak type polyfunctional cyanate ester resins), "BA 230" and "BA 230S 75" (prepolymers in which a part or all of bisphenol a dicyanate is triazinized to form a trimer), which are manufactured by Lonza Japan corporation.
Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.
Regarding the amount ratio of the epoxy resin to the curing agent, in terms of [ the total number of epoxy groups of the epoxy resin ]: [ total number of reactive groups of curing agent ], preferably 1: 0.01-1: 2, more preferably 1: 0.015 to 1: 1.5, more preferably 1: 0.02-1: 1. here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the kind of the curing agent. The total number of epoxy groups of the epoxy resin is a value obtained by calculating the sum of values obtained by dividing the mass of the solid content of each epoxy resin by the epoxy equivalent for all the epoxy resins, and the total number of reactive groups of the curing agent is a value obtained by calculating the sum of values obtained by dividing the mass of the solid content of each curing agent by the equivalent of the reactive groups for all the curing agents. When the amount ratio of the epoxy resin to the curing agent is in the above range, the heat resistance of the cured product of the resin composition is further improved.
In one embodiment, the first resin composition comprises the epoxy resin (b) and the curing agent (c). In the resin composition, it is preferable that the epoxy resin (b) is a mixture of a liquid epoxy resin and a solid epoxy resin (the mass ratio of the liquid epoxy resin to the solid epoxy resin is preferably 1: 0.1 to 1: 15, more preferably 1: 0.3 to 1: 12, and further preferably 1: 0.6 to 1: 10), and the curing agent (c) is 1 or more selected from the group consisting of a phenol curing agent, a naphthol curing agent, an active ester curing agent, a carbodiimide curing agent, and a cyanate curing agent.
The content of the curing agent in the first resin composition is not particularly limited, and is preferably 45% by mass or less, more preferably 43% by mass or less, and further preferably 40% by mass or less. The lower limit is not particularly limited, but is preferably 10% by mass or more, and more preferably 15% by mass or more.
- (d) thermoplastic resins
The first resin composition may contain (d) a thermoplastic resin in addition to the components (a) to (c).
Examples of the thermoplastic resin 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, and phenoxy resins are preferable. The thermoplastic resin can be used alone in 1 kind, or can also be used in combination with more than 2 kinds.
The thermoplastic resin preferably has a weight average molecular weight in terms of polystyrene in the range of 8,000 to 70,000, more preferably 10,000 to 60,000, and still more preferably 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene can be measured by a Gel Permeation Chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured at a column temperature of 40 ℃ using LC-9A/RID-6A manufactured by Shimadzu corporation as a measuring apparatus, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K., chloroform or the like as a mobile phase, and a calibration curve of standard polystyrene was used for calculation.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from the group consisting of a bisphenol a skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol resin 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 such as a phenolic hydroxyl group and an epoxy group. The phenoxy resin may be used alone in 1 kind, or in combination of 2 or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both of which are phenoxy resins having a bisphenol a skeleton), "YX 8100" (phenoxy resins having a bisphenol S skeleton), and "YX 6954" (phenoxy resins having a bisphenol acetophenone skeleton), which are manufactured by mitsubishi chemical corporation, "FX 280" and "FX 293", which is manufactured by mitsubishi chemical corporation, "YX 6954BH 30", "YX 7553BH 30", "YL 7769BH 30", "YL 6794", "YL 7213", "YL 7290", "YL 7891BH 30", and "YL 7482".
Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Denka butyl ral 4000-2", "Denka butyl ral 5000-A", "Denka butyl ral 6000-C", "Denka butyl ral 6000-EP" manufactured by electrochemical chemical Co., Ltd, S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series and the like manufactured by Water chemical Co., Ltd.
Specific examples of the polyimide resin include "RIKACOAT SN 20" and "RIKACOAT PN 20" manufactured by shin-shin chemical co. Specific examples of the polyimide resin include modified polyimides such as linear polyimides obtained by reacting 2-functional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimides described in jp 2006-37083 a), polyimides containing a polysiloxane skeleton (polyimides described in jp 2002-12667 a, jp 2000-319386 a and the like).
Specific examples of the polyamideimide resin include "VYLOMAX HR11 NN" and "VYLOMAX HR16 NN" manufactured by toyoyo gmbh. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS 9100" and "KS 9300" (polyamide-imide having a polysiloxane skeleton) manufactured by hitachi chemical industries, ltd.
Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by sumitomo chemical co.
Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers, inc.
Specific examples of the polyphenylene ether resin include an oligomeric polyphenylene ether-styrene resin "OPE-2 St 1200" manufactured by Mitsubishi gas chemical corporation.
Among them, the thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin. Therefore, in a preferred embodiment, the thermoplastic resin contains 1 or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins.
When the first resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5 to 15% by mass, more preferably 0.6 to 12% by mass, and still more preferably 0.7 to 10% by mass.
- (e) curing accelerators-
The first resin composition may contain (e) a curing accelerator in addition to the components (a) to (c).
Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and an organic peroxide-based curing accelerator, and the phosphorus-based curing accelerator, the amine-based curing accelerator, the imidazole-based curing accelerator, and the metal-based curing accelerator are preferable, and the amine-based curing accelerator, the imidazole-based curing accelerator, and the metal-based curing accelerator are more preferable. The curing accelerator may be used alone in 1 kind, or may be used in combination with 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, butyltriphenylphosphonium thiocyanate, and the like, and 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, and preferably 4-dimethylaminopyridine and 1, 8-diazabicyclo (5,4,0) -undecene.
Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-dodecylimidazole, 2-, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, and mixtures thereof, Imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.
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, 1- (o-tolyl) biguanide and the like, dicyandiamide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferred.
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 organic peroxide-based curing accelerator include dicumyl peroxide, cyclohexanone peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like. As the organic peroxide-based curing accelerator, commercially available products can be used, and examples thereof include "PERCUMYL D" manufactured by Nichiba oil Co.
The content of the curing accelerator in the first resin composition is not particularly limited, and is preferably 0.01 to 3% by mass, based on 100% by mass of nonvolatile components of the epoxy resin and the curing agent.
- (f) flame retardants-
The first resin composition may comprise (f) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, an organic silicon flame retardant, and a metal hydroxide. The flame retardant may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
As the flame retardant, commercially available products can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., and "PX-200" manufactured by Daihachi chemical industries Co., Ltd.
When the first resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 0.5 to 10% by mass.
- (g) organic filling materials-
The resin composition may contain (g) an organic filler, from the viewpoint of improving the elongation. As the organic filler, any organic filler that can be used when forming an insulating layer of a printed wiring board can be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.
As the rubber particles, commercially available products can be used, and examples thereof include "EXL 2655" manufactured by Nippon chemical Co., Ltd and "AC 3816N" manufactured by ガンツ Kabushiki Kaisha.
When the first resin composition contains an organic filler, the content of the organic filler is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, even more preferably 0.3 to 5% by mass, or 0.5 to 3% by mass.
- (h) optional additives
The first resin composition may further contain other additives as needed, and examples of the other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion imparting agents, and colorants.
(second resin composition)
The second resin composition forming the second resin composition layer contains (a) an inorganic filler, and the content of the component (a) is not particularly limited if the nonvolatile content in the second resin composition is 60 mass% or more based on 100 mass%, that is, if the composition is different from that of the first resin composition, and the second resin composition preferably contains an inorganic filler, an epoxy resin, and a curing agent.
Examples of the inorganic filler in the second resin composition include the same inorganic fillers as those described in the section (first resin composition).
The average particle diameter of the inorganic filler in the second resin composition is not particularly limited, but is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.5 μm or less, from the viewpoint of uniformity of the sidewall shape of the through-hole (via). The lower limit of the average particle size is not particularly limited, but is preferably 0.8 μm or more, more preferably 0.9 μm or more, and further preferably 1.0 μm or more. Examples of commercially available products of inorganic fillers having such an average particle size include "SP 60-05" and "SP 507-05" manufactured by Nippon Tekken metals, and "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Admacechs corporation, "UFP-30" manufactured by electrochemical industries, and "シルフィル NSS-3N", "シルフィル NSS-4N", "シルフィル NSS-5N" manufactured by Deshan (トクヤマ) of Kaisho, and "SC 2500 SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Admacechs corporation.
When the average particle diameter of the inorganic filler in the first resin composition is represented by R1(μm) and the average particle diameter of the inorganic filler in the second resin composition is represented by R2(μm), the relationship R1. ltoreq.R 2 is preferably satisfied. The ratio of R1 to R2 (R2/R1) is preferably 1 or more, more preferably 1.1 or more, and still more preferably 1.5 or more, or 2 or more. The upper limit of R2/R1 is not particularly limited, but is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less. For example, when the first resin composition contains a plurality of inorganic fillers, the average value of the average particle diameters of the plurality of inorganic fillers is represented as R1 (the same applies to the second resin composition).
The content of the inorganic filler in the second resin composition is 60 mass% or more, preferably 65 mass% or more, and more preferably 67 mass% or more, with respect to 100 mass% of nonvolatile components in the second resin composition, from the viewpoint of suppressing warpage. The upper limit of the content of the inorganic filler in the second resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.
When the content of the inorganic filler in the first resin composition is denoted as a1 (mass%) and the content of the inorganic filler in the second resin composition is denoted as a2 (mass%), it is preferable that a relationship of a1 < a2 is satisfied. The difference between a1 and a2 (a2-a1) is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit of the difference (A2-A1) is not particularly limited, and may be usually 90 mass% or less, 80 mass% or less, or the like.
In one embodiment, the second resin composition includes an epoxy resin and a curing agent in addition to the inorganic filler. The second resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, as required.
Examples of the epoxy resin, the curing agent and the additive contained in the second resin composition include those similar to the epoxy resin (b), the curing agent (c) and the additive described in the section < first resin composition >.
The content of the epoxy resin in the second resin composition is preferably 0.1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is obtained, and is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 22% by mass or less. Therefore, the content of the epoxy resin (b) in the second resin composition is preferably 0.1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 8 to 22% by mass.
When the content of the epoxy resin in the first resin composition is B1 (mass%), and the content of the epoxy resin in the second resin composition is B2 (mass%), it is preferable that the relationship of B1 > B2 is satisfied. The difference between B1 and B2 (B1-B2) is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more. The upper limit of the difference (B1-B2) is not particularly limited, and may be usually 60 mass% or less, 50 mass% or less, or the like.
When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1-1: 15, or more. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin to the above range, the following effects can be obtained: i) when used in the form of a resin sheet, the adhesive composition can provide adequate adhesiveness; ii) when used in the form of a resin sheet, sufficient flexibility is obtained and handling properties are improved; and, iii) a cured product having sufficient breaking strength can be obtained; and so on. From the viewpoint of the effects of the above i) to iii), the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: 0.3-1: 10, more preferably 1: 0.6-1: and 8, in the above range.
The preferable ranges of the epoxy equivalent of the epoxy resin and the weight average molecular weight of the epoxy resin in the second resin composition are the same as those of the epoxy resin contained in the first resin composition.
The content of the curing agent in the second resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more, from the viewpoint of obtaining an insulating layer having a low dielectric loss tangent. The upper limit of the content of the curing agent is not particularly limited as long as the effect of the present invention is obtained, and is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. Therefore, the content of the curing agent in the second resin composition is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 5 to 12% by mass.
Regarding the amount ratio of the epoxy resin to the curing agent in the second resin composition, in terms of [ the total number of epoxy groups of the epoxy resin ]: [ total number of reactive groups of curing agent ], preferably 1: 0.2-1: 2, more preferably 1: 0.3-1: 1.5, more preferably 1: 0.4-1: 1. when the amount ratio of the epoxy resin to the curing agent is in the above range, the heat resistance of the cured product of the second resin composition is further improved.
The content of the thermoplastic resin in the second resin composition is not particularly limited, but is preferably 0 to 10 mass%, more preferably 0.2 to 8 mass%, and still more preferably 0.5 to 5 mass%.
The content of the curing accelerator in the second resin composition is not particularly limited, and is preferably used in a range of 0.001 to 3% by mass.
The content of the flame retardant in the second resin composition is not particularly limited, but is preferably 0.2 to 20 mass%, more preferably 0.5 to 15 mass%, and still more preferably 0.8 to 10 mass%.
The content of the organic filler in the second resin composition is preferably 0.1 to 20% by mass, and more preferably 0.2 to 10% by mass.
The second resin composition may contain, as required, any additives, for example, organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additives such as organic fillers, thickeners, defoaming agents, leveling agents, adhesion imparting agents, and colorants, as in the case of the first resin composition.
[ resin sheet with support ]
The resin sheet with a support of the present invention is a resin sheet with a support having a support and a resin sheet provided on the support, the resin sheet having: a first resin composition layer formed of a first resin composition provided on the support body side, and a second resin composition layer formed of a second resin composition provided on the side opposite to the support body side; the first resin composition contains (a) an inorganic filler, and when the nonvolatile content of the first resin composition is 100% by mass, the content of the component (a) is 30% by mass or less, the second resin composition contains (a) an inorganic filler, and when the nonvolatile content of the second resin composition is 100% by mass, the content of the component (a) is 60% by mass or more, and the difference between the thermal conductivity of the first thermosetting product obtained by thermally curing the first resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes and the thermal conductivity of the second thermosetting product obtained by thermally curing the second resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes is 0.4W/mK or less.
Fig. 2 shows an example of the resin sheet with a support according to the present invention. In fig. 2, a resin sheet with support 10 includes a support 11 and a resin sheet 12 provided on the support 11. In fig. 2, the resin sheet 12 includes: a first resin composition layer 13 provided on the support body side, and a second resin composition layer 14 provided on the side opposite to the support body side.
The support of the resin sheet with support and the resin sheet of the present invention will be described in detail below.
< support body >
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and preferably a film made of a plastic material and a metal foil.
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 simply referred to as "PET"), polyethylene naphthalate (hereinafter, sometimes simply referred to as "PEN"), acrylics such as polycarbonate (hereinafter, sometimes simply referred to as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.
When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a 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 support may be subjected to a matte treatment or a corona treatment on the surface bonded to the first resin composition layer.
In addition, as the support, a support with a release layer having a release layer on a surface bonded to the first resin composition layer can be used. Examples of the release agent used in the release layer of the support with a release layer include 1 or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available products can be used, and examples thereof include "SK-1", "AL-5" and "AL-7" manufactured by Linekekekco, Inc. as PET films having a release layer containing an alkyd resin-based release agent as a main component.
The thickness of the support is not particularly limited, but is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. When the support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
< resin sheet >
The resin sheet has: the resin composition layer includes a first resin composition layer provided on the support body side, and a second resin composition layer provided on the opposite side of the support body side and formed of a second resin composition having a different composition from the first resin composition forming the first resin composition layer.
In the resin sheet with a support of the present invention, the thickness of the resin sheet is preferably 3 μm or more, and more preferably 5 μm or more. The upper limit of the thickness of the resin sheet is preferably 40 μm or less, more preferably 35 μm or less, and further preferably 30 μm or less, or 25 μm or less, from the viewpoint of setting the thickness of the resin layer on the conductor.
The thickness of the first resin composition layer formed of the first resin composition is preferably 10 μm or less, more preferably 7 μm or less, and further preferably 8 μm or less. The lower limit of the thickness of the first resin composition layer is not particularly limited, and may be usually 0.05 μm or more, 0.1 μm or more, or the like, from the viewpoint of obtaining an insulating layer exhibiting excellent peel strength with respect to the conductor layer after the roughening treatment, and from the viewpoint of ease of manufacturing the resin sheet with a support. By the presence of the first resin composition layer, the plating peelability can be improved.
The thickness of the second resin composition layer formed of the second resin composition is preferably 2.5 μm or more, more preferably 5 μm or more, and further preferably 7 μm or more, 8 μm or more, 9 μm or more, or 10 μm or more. The upper limit of the thickness of the second resin composition layer is preferably 30 μm or less, more preferably 25 μm or less, and still more preferably 20 μm or less. By the presence of the second resin composition layer, warpage can be suppressed.
The resin sheet with support 10 of the present invention may further include a protective film on the surface of the resin sheet 12 that is not joined to the support 11 (i.e., the surface on the side opposite to the support). The protective film helps prevent dust and the like from adhering to the surface of the resin sheet 12 and the like, and prevents the resin sheet 12 from being damaged. As a material of the protective film, the same material as that described with respect to the support 11 can be used. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. The resin sheet with support 10 can be used by peeling off the protective film when manufacturing a printed wiring board.
The thermal conductivity of the first thermosetting product obtained by thermally curing the first resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes is preferably 1W/mK or less, more preferably 0.7W/mK or less, and still more preferably 0.5W/mK or less. The lower limit is not particularly limited, and may be 0.01W/mK or more. The thermal conductivity can be measured according to the procedure of [ measurement of thermal conductivity of cured product ] described later.
The thermal conductivity of the second thermosetting product obtained by thermally curing the second resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes is preferably 1.5W/mK or less, more preferably 1.0W/mK or less, and still more preferably 0.7W/mK or less. The lower limit is not particularly limited, and may be 0.01W/mK or more. The thermal conductivity can be measured according to the procedure of [ measurement of thermal conductivity of cured product ] described later.
In the present invention, the difference in thermal conductivity between the first thermal cured product and the second thermal cured product is 0.4W/mK or less. By setting the difference in thermal conductivity between the first cured product and the second cured product to 0.4W/mK or less as described above, the length of the recessed portion generated in the extending direction of the interface of the cured products can be reduced. Regarding the mechanism, the following mechanism is considered: by reducing the difference in thermal conductivity between the first thermosetting material and the second thermosetting material, the thermal decomposability of the first thermosetting material and the second thermosetting material by the laser beam is made uniform.
In the present invention, the difference in thermal conductivity between the first cured product and the second cured product is 0.4W/mK or less, preferably 0.35W/mK or less, and more preferably 0.3W/mK or less. The lower limit is not particularly limited, and may be 0.01W/mK or more.
The length of the recessed portion in the extending direction of the interface is defined as follows. When the vertical cross section of the through-hole was observed, a straight line extrapolated from the side wall of the through-hole was drawn, and the distance from the straight line to the interface between the first resin composition layer and the second resin composition layer was defined as the length d of the recessed portion. Specifically, as for the length of the recessed portion, a straight line is drawn as in the example shown in fig. 3, and the length of the recessed portion is a distance d from the interface between the first resin composition layer and the second resin composition layer to the straight line.
The length of the recessed portion is preferably 2.0 μm or less, more preferably 1.8 μm or less, and further preferably 1.5 μm or less, or 1.4 μm or less, from the viewpoint of suppressing generation of voids during plating. The lower limit is not particularly limited, but is 0.01 μm or more. The length of the recessed portion can be measured according to the procedure of "confirmation of the shape of the through-hole (evaluation of the length of the recessed portion and laser processability)" described later.
In the resin sheet with a support according to the present invention, since the length of the recessed portion generated in the extending direction of the interface of each cured resin composition layer can be reduced, the following characteristics are exhibited: the laser processability is excellent even if the opening diameter (top diameter) is 40 μm or less. This makes it possible to form fine wiring of the printed wiring board.
[ method for producing resin sheet with support ]
An example of the method for producing the resin sheet with a support according to the present invention will be described below.
First, a first resin composition layer formed of a first resin composition and a second resin composition layer formed of a second resin composition are formed on a support.
As a method for forming the first resin composition layer and the second resin composition layer, for example, a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other is cited. As a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other, for example, the following method can be mentioned: the first resin composition layer is formed by coating a first resin composition on a support and drying the coating film, and then the second resin composition layer is formed by coating a second resin composition on the first resin composition layer and drying the coating film.
In the method, the first resin composition layer may be produced by: a resin varnish in which the first resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to a support by a die coater or the like and dried.
Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The resin varnish may be dried by a known drying method such as heating or blowing hot air. 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 first resin composition layer can be formed on the support by drying at 50 to 150 ℃ for 1 to 10 minutes.
In the above method, the second resin composition layer may be produced by: a resin varnish in which the second resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to the first resin composition layer formed on the support by a die coater or the like, and dried.
As the organic solvent used for the preparation of the resin varnish in which the second resin composition is dissolved, the same organic solvent as that used for the preparation of the resin varnish in which the first resin composition is dissolved can be used, and the resin varnish in which the second resin composition is dissolved can be dried by the same method as that for the drying of the resin varnish in which the first resin composition is dissolved.
In addition to the above coating method, the resin sheet may be formed by a tandem coating method in which 2 kinds of resin varnishes are sequentially coated on 1 coating line. In addition, the resin sheet may be formed by: a method of coating the first resin composition on the second resin composition layer and drying the coating film to form a first resin composition layer; and a method of laminating the first resin composition layer and the second resin composition layer prepared separately so as to be bonded to each other; and so on.
In the present invention, for example, the resin sheet with the support may be produced by sequentially forming the second resin composition layer and the first resin composition layer on the protective film and then laminating the support on the first resin composition layer.
[ printed Wiring Board and method for manufacturing printed Wiring Board ]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin sheet in the resin sheet with a support of the present invention. In addition, the method for manufacturing a printed wiring board of the present invention includes:
a step (I) of laminating the resin sheet with a support of the present invention on the inner layer substrate so that the second resin composition layer is bonded to the inner layer substrate,
a step (II) of forming an insulating layer by thermally curing the resin sheet with the support, and,
and (III) forming a through hole in the insulating layer and removing the support.
The "inner layer substrate" used in the step (I) is mainly a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate, or a circuit substrate having a conductor layer (circuit) patterned on one surface or both surfaces of the substrate. The term "inner layer substrate" as used herein includes an inner layer circuit substrate in which an intermediate product of an insulating layer and/or a conductor layer is to be further formed when a printed wiring board is manufactured. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used (the conductor layer is also referred to as a wiring layer).
The lamination of the inner layer substrate and the resin sheet with a support can be performed, for example, by heat-pressing the resin sheet with a support to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet with a support to the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (such as SUS end plate) and a metal roll (SUS roll). It is preferable that the heating and pressure-bonding member is not directly pressed against the resin sheet with a support, but is pressed through an elastic material such as a heat-resistant rubber so that the resin sheet with a support sufficiently follows the surface irregularities of the inner layer substrate.
The lamination of the inner layer substrate and the resin sheet with a support can be performed by a vacuum lamination method. In the vacuum lamination method, the heating and pressure bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and pressure bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and pressure bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7hPa or less.
The lamination can be carried out using a commercially available vacuum lamination apparatus. Examples of commercially available vacuum laminating apparatuses include a vacuum pressure laminating apparatus manufactured by Nikko-Materials, vacuum applicators (vacuum applicators) manufactured by Nikko-Materials, and the like.
After lamination, the thermocompression bonding member is pressurized at normal pressure (atmospheric pressure), for example, from the support side, whereby the smoothing treatment of the laminated resin sheets can be performed. The pressure condition for the smoothing treatment may be set to the same condition as the above-described heat and pressure bonding condition for the lamination. The smoothing treatment can be carried out by using a commercially available laminating apparatus. The lamination and smoothing processes can be continuously performed using the above-mentioned commercially available vacuum lamination apparatus.
In the step (II), the resin sheet of the resin sheet with a support is thermally cured to form the insulating layer.
The conditions for heat curing of the resin sheet (first and second resin composition layers) are not particularly limited, and conditions generally employed in forming the insulating layer of the printed wiring board can be used.
For example, the heat curing conditions of the resin sheet may be varied depending on the kind of the first and second resin compositions, and the curing temperature may be set to a range of 120 to 240 ℃ (preferably a range of 150 to 220 ℃, and more preferably a range of 170 to 200 ℃), and the curing time may be set to a range of 5 to 120 minutes (preferably 10 to 100 minutes, and more preferably 15 to 90 minutes).
The resin sheet may be preheated at a temperature lower than the curing temperature before the resin sheet is thermally cured. For example, before the resin sheet is thermally cured, the resin sheet is preheated at a temperature of 50 ℃ or higher and lower than 120 ℃ (preferably 60 ℃ or higher and 110 ℃ or lower, and more preferably 70 ℃ or higher and 100 ℃ or lower) for 5 minutes or longer (preferably 5 minutes to 150 minutes, and more preferably 15 minutes to 120 minutes).
In step (III), a through hole is formed in the insulating layer, and the support is removed. The formation of the through hole is not particularly limited, and laser irradiation, etching, mechanical drilling, and the like can be mentioned, and laser irradiation is preferably used. From the viewpoint of further suppressing the occurrence of recessed portions, it is preferable to peel off the support after forming the through holes in the insulating layer, and more specifically, it is preferable to peel off the support after forming the through holes in the insulating layer by laser.
The laser irradiation can be performed by any suitable laser processing machine using a carbon dioxide laser, a YAG laser, an excimer laser, or the like as a light source. Examples of usable laser processing machines include a Vickers (Via Mechanics) CO manufactured by Kabushiki Kaisha2"LC-2 k 212/2C", 605GTWIII (-P) manufactured by Mitsubishi Motor corporation, and laser processing machine manufactured by Panasonic Welding Systems, K.K. システム (Panasonic Welding Systems).
The conditions of laser irradiation are not particularly limited, and laser irradiation may be carried out by any suitable process according to a conventional method corresponding to the selected means.
The shape of the through hole, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, and is usually circular (substantially circular). Hereinafter, when referring to the "diameter (diameter)" of the through-hole, it means the diameter (diameter) of the outline of the opening as viewed in the extending direction. In this specification, the opening diameter (top diameter) refers to the diameter of the outline on the insulating layer (cured product of the first resin composition layer) side of the through hole, and the bottom diameter r2 refers to the diameter of the outline on the wiring layer side of the through hole.
The through-hole is preferably formed so that the opening diameter r1 of the through-hole has the following value: preferably 40 μm or less, more preferably 35 μm or less, and still more preferably 30 μm or less, or 25 μm or less.
The through-hole may be formed in such a manner that the opening diameter r1 is larger than the bottom diameter r2, or may be formed in such a manner that the opening diameter r1 of the through-hole is the same as the bottom diameter r2 of the through-hole. By doing so, the embedding property of the through hole becomes good, and the generation of voids can be suppressed.
In the manufacture of the printed wiring board, the step (IV) of roughening the insulating layer; (V) a step of forming a conductor layer. The steps (IV) to (V) can be carried out by various methods known to those skilled in the art and usable in the production of printed wiring boards.
The step (IV) is a step of roughening the insulating layer. The step and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used for forming an insulating layer of a printed wiring board can be used. For example, the insulating layer may be subjected to a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing solution in this order. The swelling solution is not particularly limited, and an alkali solution and a surfactant solution are exemplified, and an alkali solution is preferable, and a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available Swelling liquids include "spinning Dip securigant P" and "spinning Dip securigant SBU" manufactured by ato ech JAPAN corporation. The swelling treatment with the swelling solution is not particularly limited, and may be performed, for example, by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, the cured product is preferably immersed in a swelling solution at 40 to 80 ℃ for 5 to 15 minutes. The oxidizing agent (roughening solution) is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution can be 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", "Concentrate Compact P" and "Dosing Solution securigant P" manufactured by ato ech JAPAN corporation. The neutralizing Solution is preferably an acidic aqueous Solution, and examples of commercially available products include "Reduction Solution securigant P" manufactured by ato ech JAPAN corporation. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of workability, a method of immersing the object subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes is preferable.
The step (V) is a step of forming a conductor layer.
The conductor material used in the conductor layer is 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 conductor layer may be a single metal layer or an alloy layer, and 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 pattern formation, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.
The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more layers of single metal layers or alloy layers made of different metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.
The thickness of the conductor layer depends on the design of the desired printed wiring board, and is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.
In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. An example of forming a conductor layer by the semi-additive method is described below.
First, a plating seed layer (めっきシード body regions) is formed on the surface of the insulating layer by electroless plating (around dissolution めっき). Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with 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.
[ semiconductor device ]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
Examples of the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, airplanes, and the like).
The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conducting position of a printed wiring board. The "conduction position" refers to a "position of the printed wiring board where an electrical signal is transmitted", and the position may be a surface or a buried position. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
The method of mounting the semiconductor chip in the production of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method based on a Build-Up non-uneven Layer (BBUL), a mounting method based on an Anisotropic Conductive Film (ACF), and a mounting method based on a non-conductive film (NCF). Here, the "mounting method by a base band non-convex layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".
Examples
The present invention will be described in more detail with reference to the following 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.
[ production of resin sheet with support ]
Using the resin varnish (resin composition) prepared by the following procedure, resin sheets with supports of examples and comparative examples were produced.
(preparation of resin varnish 1)
10 parts of a biphenol-type epoxy resin ("YX 4000 HK" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 185), 25 parts of a biphenyl-type epoxy resin ("NC 3000L" manufactured by Nippon Kasei corporation, having an epoxy equivalent of 288), and 20 parts of a phenoxy resin ("YX 7553BH 30" manufactured by Mitsubishi chemical corporation, having a solid content of 30 mass% of cyclohexanone: a 1: 1 solution of Methyl Ethyl Ketone (MEK)) were dissolved in a mixed solvent of 5 parts of solvent naphtha and 5 parts of cyclohexanone while stirring under heating. After cooling to room temperature, 10 parts of a triazine skeleton-containing novolak resin curing agent (hydroxyl equivalent: 125, "LA-7054" available from DIC K., solid: 60% MEK solution) and a diphenol resin curing agent (hydroxyl equivalent: 218, "MEH-7851H" available from Minghua chemical Co., Ltd., solid: MEK) were mixed together60% MEK solution), a polyvinyl butyral resin (glass transition temperature 105 ℃, solid content of "KS-1" manufactured by water-logging chemical industries co., ltd. "1: 1 mixed solution) 10 parts, 1 part of an amine-based curing accelerator (4-Dimethylaminopyridine (DMAP), MEK solution having a solid content of 5 mass%), 2 parts of an imidazole-based curing accelerator (P200-H50, manufactured by mitsubishi chemical corporation, propylene glycol monomethyl ether solution having a solid content of 50 mass%), and spherical silica (SPH 516-05, manufactured by shin-shikaki chemical corporation, average particle diameter of 0.2 μm, carbon amount per unit surface area of 0.43mg/m, and surface-treated with an aminosilicone-based coupling agent (KBM 573, manufactured by shin-shiki chemical corporation)2)22 parts by weight, and uniformly dispersed in a high-speed rotary mixer, and then filtered through a drum filter ("SHP 020" manufactured by ROKITECHNO) to prepare a resin varnish 1.
(preparation of resin varnish 2)
5 parts of bisphenol F type epoxy resin ("1750" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 159), 10 parts of biphenol type epoxy resin ("YX 4000 HK" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 185), 20 parts of biphenyl type epoxy resin ("NC 3000L" manufactured by Nippon chemical corporation, having an epoxy equivalent of 288), 3 parts of naphthalene type epoxy resin ("HP-4710" manufactured by DIC corporation, having an epoxy equivalent of about 170), and 5 parts of phenoxy resin ("YX 7553BH 30" manufactured by Mitsubishi chemical corporation, having a solid content of 30 mass% of 1: 1 solution of cyclohexanone, Methyl Ethyl Ketone (MEK) were heated and dissolved in a mixed solvent of 20 parts of solvent naphtha and 5 parts of cyclohexanone while stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing novolak resin curing agent ("LA-7054" manufactured by DIC K.K., 60% MEK solution) 5 parts of a triazine skeleton-containing cresol formaldehyde resin curing agent ("LA-3018-50P" manufactured by DIC K.K., 50% 2-methoxypropanol solution) 10 parts of a triazine skeleton-containing cresol formaldehyde resin curing agent ("SN 485" manufactured by Nippon Steel chemical Co., Ltd., hydroxyl equivalent 215, 60% MEK solution) 10 parts of an amine curing accelerator (4-Dimethylaminopyridine (DMAP), solid content MEK solution) were mixed therewithA 5 mass% MEK solution) 1 part, a flame retardant ("HCA-HQ" manufactured by Sanko K.K., 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide having an average particle diameter of 1.5 μm)3 parts, and a spherical silica surface-treated with an aminosilane-based coupling agent ("KBM 573" manufactured by shin-Etsu chemical Co., Ltd.) (SP 60-05 "manufactured by Nippon iron-based Material K.K., having an average particle diameter of 1.3 μm, and an amount of carbon per unit surface area of 0.30mg/m2)190 parts by weight, was uniformly dispersed in a high-speed rotary mixer, and then filtered through a drum filter ("SHP 050" manufactured by ROKITECHNO), to prepare a resin varnish 2.
(preparation of resin varnish 3)
5 parts of a naphthalene-type epoxy resin ("HP 4032 SS", manufactured by DIC Co., Ltd.), 5 parts of a biphenyl-type epoxy resin ("NC 3100", manufactured by Nippon Kagaku K.K., having an epoxy equivalent of 258), 20 parts of a naphthylene ether-type epoxy resin ("EXA-7311", manufactured by DIC Co., Ltd., having an epoxy equivalent of 277), and 6 parts of a phenoxy resin ("YX 7553BH 30", manufactured by Mitsubishi chemical Co., Ltd., having a solid content of 30 mass% of cyclohexanone: 1 solution of Methyl Ethyl Ketone (MEK)) were dissolved in a mixed solvent of 5 parts of solvent naphtha and 5 parts of cyclohexanone with stirring under heating. After cooling to room temperature, 5 parts of an active ester compound (a toluene solution having a weight average molecular weight of about 2700 and a nonvolatile content of about 223 in terms of an active group equivalent of about 223 by mass) "HPC-8000-65T", 5 parts of a carbodiimide resin (a toluene solution having a nonvolatile content of 50% by mass "V-03" manufactured by Nisshinbo Chemical Co., Ltd.), 5 parts of a bisphenol A dicyanate prepolymer (a toluene solution having a nonvolatile content of about 232, BA230S75 "manufactured by Lonza Japan K., a cyanate equivalent of about 232), 30 parts of a curing accelerator (4-Dimethylaminopyridine (DMAP) having a solid content of 5% by mass of an MEK solution), 0.1 part of an imidazole curing accelerator (a propylene glycol monomethyl ether solution having a solid content of 50% by mass" P200-H50 "manufactured by Mitsubishi Chemical Co., Ltd.), and 0.1 part of a curing accelerator (Tokyo Chemical Co., Ltd., cobalt (III) acetylacetonate [ Co (III) Ac ] a MEK solution having a solid content of 1% by mass])3 parts of a rubber particle (PARALOID EXL2655, made by Tao chemical Japan K.K.) 2 parts of a phenylaminosilane coupling agent (Xin Ji)Spherical silica surface-treated with "KBM 573" manufactured by Nippon iron-based materials, Inc. (SPH 516-05 manufactured by Nippon iron-based materials Co., Ltd., average particle diameter: 0.2 μm, and carbon amount per unit surface area: 0.43mg/m2)12 parts by weight, and uniformly dispersed in a high-speed rotary mixer, and then filtered through a drum filter ("SHP 020" manufactured by ROKITECHNO) to prepare a resin varnish 3.
(preparation of resin varnish 4)
10 parts of bisphenol A type epoxy resin ("825" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 176), 20 parts of naphthylene ether type epoxy resin ("EXA-7311" manufactured by DIC corporation, having an epoxy equivalent of 277), and 12 parts of phenoxy resin ("YX 7553BH 30" manufactured by Mitsubishi chemical corporation, having a solid content of 30 mass% of 1: 1 solution of cyclohexanone: Methyl Ethyl Ketone (MEK)) were dissolved in a mixed solvent of 12 parts of solvent naphtha and 5 parts of cyclohexanone while stirring under heating. After cooling to room temperature, 30 parts of an active ester compound (a toluene solution having a weight average molecular weight of about 2700 and a nonvolatile content of about 223 in terms of active group equivalent of about 65% by mass) "was mixed with 30 parts of a curing accelerator (4-dimethylaminopyridine, a MEK solution having a solid content of 5% by mass), 0.5 part of an imidazole curing accelerator (1B 2 PZ" 1-benzyl-2-phenylimidazole, a MEK solution having a solid content of 5% by mass ", manufactured by Sikko Kagaku K.), 3 parts of a flame retardant (HCA-HQ, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, having an average particle diameter of 2 μm), and spherical silica (a novel spherical silica) surface-treated with an aminosilicone coupling agent (KBM 573, manufactured by shin Kagaku K Co., Ltd.) "SP 507-05" manufactured by Nippon iron-based alloy Ltd., average particle diameter of 1.0 μm, and carbon amount per unit surface area of 0.35mg/m2)120 parts by weight, and uniformly dispersed by a high-speed rotary mixer, and then filtered by a drum filter ("SHP 050" manufactured by ROKITECHNO) to prepare a resin varnish 4.
(preparation of resin varnish 5)
5 parts of a bisphenol F-type epoxy resin ("1750" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 159), 20 parts of a biphenyl-type epoxy resin ("NC 3000L" manufactured by Nippon Kabushiki Kaisha, having an epoxy equivalent of 288), 3 parts of a biphenyl-type epoxy resin ("NC 3100" manufactured by Nippon Kabushiki Kaisha, having an epoxy equivalent of 258), and 12 parts of a phenoxy resin ("YX 7553BH 30" manufactured by Mitsubishi chemical corporation, having a solid content of 30 mass%, of a 1: 1 solution of cyclohexanone-Methyl Ethyl Ketone (MEK)) were dissolved in a mixed solvent of 5 parts of solvent naphtha and 5 parts of cyclohexanone while stirring with heating. After cooling to room temperature, 5 parts of a curing agent of cresol formaldehyde resin containing a triazine skeleton (hydroxyl equivalent: 151, "LA-3018-50P" manufactured by DIC K.K., a 2-methoxypropanol solution having a solid content of 50%), 15 parts of an active ester compound (a toluene solution having a weight average molecular weight of about 2700 and a nonvolatile content of about 223, a weight average molecular weight of about 65 mass%), 2 parts of an amine curing accelerator (4-Dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5 mass%), 2 parts of an imidazole curing accelerator (1B 2PZ "1-benzyl-2-phenylimidazole manufactured by Sikko chemical Co., Ltd., a MEK solution having a solid content of 5%), 0.1 part of an epoxy silane coupling agent (KBM 403 manufactured by shin-Etsu chemical Co., Ltd.), 0.1 part of a, 5 parts of fine silicon carbide powder ("SER-A06" manufactured by concentrated electric gas Co., Ltd., average particle diameter of 0.6 μm) was uniformly dispersed in a high-speed rotary mixer, and then filtered through a drum filter ("SHP 030" manufactured by ROKITECHNO) to prepare a resin varnish 5.
(preparation of resin varnish 6)
10 parts of a bisphenol A-type epoxy resin ("825" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 176), 25 parts of a xylene-type epoxy resin ("YX 7700" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of 270), and 20 parts of a phenoxy resin ("YX 7553BH 30" manufactured by Mitsubishi chemical corporation, having a solid content of 30 mass% of a 1: 1 solution of cyclohexanone-Methyl Ethyl Ketone (MEK)) were dissolved in a mixed solvent of 5 parts of naphtha and 5 parts of cyclohexanone while stirring under heating. After cooling to room temperature, 10 parts of a triazine skeleton-containing novolak type curing agent ("LA-7054" available from DIC K., solid content: 60% MEK solution) and 10 parts of a naphthol type curing agent ("SN 485" available from Nippon Steel Co., Ltd., hydroxyl equivalent of 215, solid content: phenol resin (R) were mixedMEK solution having a volume content of 60%) 15 parts, a polyvinyl butyral resin (glass transition temperature 105 ℃, KS-1 manufactured by waterlogging chemical corporation) having a solid content of 15% ethanol and toluene 1: 1 mixed solution) 10 parts, 1 part of an amine-based curing accelerator (4-Dimethylaminopyridine (DMAP) with a solid content of a 5 mass% MEK solution), 2 parts of an imidazole-based curing accelerator (product of mitsubishi chemical corporation, "P200-H50", with a solid content of a 50 mass% propylene glycol monomethyl ether solution), and 2 parts of a spherical silica (product of admithsc "SO-C1", with an average particle diameter of 0.4 μm and a carbon amount per unit surface area of 0.35mg/m, surface-treated with an aminosilicone-based coupling agent (product of shin-shi chemical corporation, "KBM 573")2)22 parts by weight, and uniformly dispersed in a high-speed rotary mixer, and then filtered through a drum filter ("SHP 030" manufactured by ROKITECHNO) to prepare a resin varnish 6.
(preparation of resin varnish 7)
5 parts of bisphenol A type epoxy resin ("825" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 176), 10 parts of biphenol type epoxy resin ("YX 4000 HK" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 185), 20 parts of biphenyl type epoxy resin ("NC 3000L" manufactured by Nippon chemical corporation, having an epoxy equivalent of 288), 3 parts of naphthalene type epoxy resin ("HP-4710" manufactured by DIC corporation, having an epoxy equivalent of about 170), and 5 parts of phenoxy resin ("YX 7553BH 30" manufactured by Mitsubishi chemical corporation, having a solid content of 30 mass% of 1: 1 solution of cyclohexanone, Methyl Ethyl Ketone (MEK) were heated and dissolved in a mixed solvent of 10 parts of solvent naphtha and 5 parts of cyclohexanone, while stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing novolak resin curing agent ("LA-7054" manufactured by DIC K.K., 60% MEK solution) 5 parts of a triazine skeleton-containing cresol formaldehyde resin curing agent ("LA 3018-50P" manufactured by DIC K.K., 50% 2-methoxypropanol solution) 10 parts of a naphthol curing agent ("SN 485" manufactured by Nippon Steel chemical Co., Ltd., hydroxyl equivalent 215, 60% MEK solution) 10 parts of an amine curing accelerator (4-Dimethylaminopyridine (DMAP)) were mixed together with a solid content of 60% MEK solution5% MEK solution) 1 part, 3 parts of a flame retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide having an average particle diameter of 1.5 μm), and a ground silica (IMSIL A-8 "manufactured by shin-Etsu chemical Co., Ltd., average particle diameter of 2 μm, carbon amount per unit surface area of 0.21mg/m2)120 parts by weight, and uniformly dispersed by a high-speed rotary mixer, and then filtered by a drum filter ("SHP 050" manufactured by ROKITECHNO) to prepare a resin varnish 7.
Table 1 shows the materials used for preparing each resin varnish and the amounts thereof blended (parts by mass of nonvolatile components).
[ Table 1]
Figure DEST_PATH_IMAGE002
。
< example 1: production of resin sheet with support
As the support, a PET film (manufactured by Tollio Co., Ltd. "Koleylor R80", thickness: 38 μm, softening point: 130 ℃ C., "demolded PET") which had been subjected to a mold release treatment with an alkyd resin-based mold release agent ("AL-5", manufactured by Lindco Co., Ltd.) was prepared.
The resin varnish 1 was uniformly applied to a release PET using a die coater so that the thickness of the dried first resin composition layer became 5 μm, and dried at a temperature of from 80 ℃ to 160 ℃ for 5 minutes, thereby obtaining a first resin composition layer on the release PET. Next, the resin varnish 2 was applied onto the first resin composition layer so that the total thickness of the varnish and the first resin composition layer after drying became 20 μm, and the varnish was dried at 70 to 110 ℃ (average 90 ℃) for 3 minutes to form a 2-layer resin composition layer (resin sheet). Next, a rough surface of a polypropylene film (アルファン MA-411, manufactured by prince エフテックス, thickness 15 μm) as a protective film was laminated on the surface of the resin sheet not bonded to the support (i.e., the surface of the second resin composition layer not bonded to the first resin composition layer) so as to be bonded to the second resin composition layer. Thus, a resin sheet 1 with a support was obtained, which was formed sequentially from the support, the first resin composition layer (derived from the resin varnish 1), the second resin composition layer (derived from the resin varnish 2), and the protective film.
< example 2: production of resin sheet 2 with support
In example 1, a resin sheet 2 with a support was obtained in the same manner as in example 1 except for 1) using a resin varnish 3 instead of the resin varnish 1 and applying the resin varnish so that the thickness of the dried first resin composition layer became 3 μm and 2) using a resin varnish 4 instead of the resin varnish 2.
< example 3: production of resin sheet 3 with support
In example 1, a resin sheet 3 with a support was obtained in the same manner as in example 1 except for 1) using a resin varnish 5 instead of the resin varnish 1 and applying the resin varnish so that the thickness of the dried first resin composition layer became 4 μm and 2) using a resin varnish 4 instead of the resin varnish 2.
< comparative example 1: production of resin sheet 4 with support
A resin sheet 4 with a support was obtained in the same manner as in example 1, except that in example 1, the resin varnish 6 was used in place of the resin varnish 1, and coating was performed so that the thickness of the dried first resin composition layer became 4 μm.
Comparative example 2: production of resin sheet 5 with support
A resin sheet 5 with a support was obtained in the same manner as in example 1, except that the resin varnish 7 was used instead of the resin varnish 2 in example 1.
(preparation of cured products of the respective resin compositions)
The resin varnishes 1 to 7 were uniformly applied to the same release PET film as in examples and comparative examples using a die coater so that the thickness of the dried resin composition layer became 50 μm, and dried at a temperature of from 70 ℃ to 120 ℃ for 5 minutes, thereby obtaining a resin film having the resin composition layer formed on the release PET film.
The release PET film was placed on the double-sided copper-clad glass cloth substrate epoxy resin laminate so that the untreated surface of the release PET film ("501010" manufactured by Leideke corporation, 38 μm thick, 240mm square) was in contact with the double-sided copper-clad glass cloth substrate epoxy resin laminate ("R5715 ES" manufactured by Songtou electric corporation, 0.7mm thick, 255mm square), and the four sides of the release film were fixed with a polyimide adhesive tape (10 mm wide).
For each resin film (167 × 107mm square) having a thickness of 50 μm of the resin composition layer, a batch-type vacuum pressure lamination apparatus (CVP 700, 2-stage stacked lamination apparatus manufactured by Nikko-Materials corporation) was used, and lamination was performed at the center so that the resin composition layer was in contact with the release surface of the release PET film. The lamination process was carried out by the following method: the pressure was reduced to 13hPa or less for 30 seconds, and then pressure-bonded for 30 seconds at 100 ℃ and a pressure of 0.74 MPa.
Next, the support was peeled off, and a resin composition layer of the same resin film was further laminated on the resin composition layer under the same conditions to prepare a resin composition layer having a thickness of 50 μm × 2 — 100 μm, and then the resin composition layer was cured under curing conditions of 100 ℃ for 30 minutes and 190 ℃ for 90 minutes in a state where the support was peeled off.
After thermosetting, the polyimide adhesive tape was peeled off, and the resin composition layer was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled from the resin composition layer to obtain a sheet-like cured product having a thickness of about 100 μm. The sheet-like cured product was referred to as a cured product for evaluation.
[ measurement of thermal conductivity of cured product ]
(1) Determination of thermal diffusivity, alpha
The thermal diffusivity in the thickness direction α (m) of the cured product for evaluation was measured by a temperature wave analysis method using "ai-Phase Mobile 1 u" manufactured by ai-Phase2In s). The same sample was measured 3 times, and the average value was calculated.
(2) Determination of specific Heat Capacity Cp
Specific heat capacity Cp (J/kg. seed. K) of the cured product sample at 20 ℃ was calculated by measuring the temperature at 10 ℃/min from-40 ℃ to 80 ℃ using a differential scanning calorimeter (SII Nano Technology Co., Ltd. "DSC 7020").
(3) Measurement of Density ρ
The density (kg/m) of the cured product for evaluation was measured using an analytical balance XP105 (using a gravimetric kit) manufactured by METTLER TOLEDO3)。
(4) Calculation of thermal conductivity λ
The thermal diffusivity rates α (m) obtained in the above (1) to (3)2(s), specific heat capacity Cp (J/kg. seed. K), and density rho (kg/m)3) The thermal conductivity λ (W/m;,) was calculated by substituting the following formula (I). The results are shown in the following table;
λ＝α×Cp×ρ (I)。
< evaluation of the length of the recessed portion and laser processability >
(preparation of sample)
(1) Base treatment of wiring substrate
Both surfaces of a glass cloth-based epoxy resin laminate (a wiring board having a copper foil thickness of 12 μm, a substrate thickness of 0.3mm, a size of 510mm × 340mm, and a conductor pattern formed using "R-1515A" manufactured by sonko corporation (the copper remaining ratio is about 70%)) having circular conductor patterns (wiring patterns) with a diameter of 150 μm formed on both surfaces thereof were subjected to treatment (i): the surface of the conductor pattern was roughened by etching and removing the conductor pattern to a thickness of about 0.8 μm using "CZ 8101" manufactured by MEC K.K.
(2) Laminating step of resin sheet
The protective films of the resin sheets with supports (size 504mm × 334mm) each having 2 layers of the resin composition prepared in examples and comparative examples were peeled off, and laminated on both surfaces of the wiring substrate so that the second resin composition layer was in contact with the wiring substrate treated in the above (1) using a batch type vacuum pressure lamination apparatus (CVP 700, a 2-stage stacked lamination apparatus manufactured by Nikko-Materials co., ltd.). The lamination step is carried out by the following method: the pressure was reduced to 13hPa or less for 30 seconds, and then pressure-bonded for 30 seconds at 120 ℃ and a pressure of 0.74 MPa. Next, a hot pressing step was performed for 60 seconds at a temperature of 110 ℃ and a pressure of 0.5 MPa.
(3) Curing of resin composition layer
The resin composition layer was thermally cured under curing conditions of 100 ℃ for 30 minutes and then 175 ℃ for 30 minutes on the wiring board on which the resin sheet with a support was laminated to form an insulating layer (about 15 μm thick on the conductor).
(4) Formation of vias
The evaluation substrate was obtained by irradiating the support with laser light from above to form a small-diameter through hole in the insulating layer directly above the circular conductor pattern having a diameter of 150 μm on the inside.
The through-hole formation process was performed under the following conditions.
Using a Mitsubishi Motor Co., Ltd., CO2The laser processing machine "605 GTWIII (-P)" irradiates laser from above the support side to form a through hole having a top diameter (diameter) of 30 μm in the insulating layer. The irradiation conditions of the laser were: the mask diameter was 1mm, the pulse width was 16. mu.s, the energy was 0.20 mJ/gun (shot), the number of guns was 2, and the process was carried out in burst mode (10 kHz).
(evaluation)
(5) Confirmation of the shape of the through-hole (evaluation of the length of the recessed portion and laser processability)
The evaluation substrate obtained in (4) above was peeled off from the support, cut into an appropriate size, and a sample including a through hole was embedded in a cold embedding resin, and a cross section of the central portion of the through hole was formed by a sample polishing apparatus (RotoPol-22, manufactured by Struers corporation) and observed by a scanning electron microscope (S4800, manufactured by hitachi ハイテクノロジーズ). The length (μm) of the dent portion generated in the interface between the first resin composition layer and the second resin composition layer along the extending direction of the interface was measured from the obtained image. Specifically, a straight line extrapolated from the sidewall of the through hole is drawn, and the distance d from the straight line to the interface between the first resin composition layer and the second resin composition layer is measured. The 4 through holes were measured, and the average values were obtained, and evaluated according to the following criteria;
o: the length of the recessed part is less than 3 μm
X: the length of the indentation exceeds 3 μm.
[ Table 2]
Figure DEST_PATH_IMAGE004
。
Description of the symbols
10 resin sheet with support
11 support body
12 resin sheet
13 first resin composition layer
14 a second resin composition layer.

Claims (21)

1. A resin sheet with a support, comprising a support and a resin sheet provided on the support,
the resin sheet has:
a first resin composition layer formed of a first resin composition provided on the support body side, and
a second resin composition layer formed of a second resin composition provided on the side opposite to the support body side,
the first resin composition contains (a) an inorganic filler, and the content of the component (a) is 30% by mass or less, based on 100% by mass of nonvolatile components in the first resin composition,
the second resin composition contains (a) an inorganic filler, and the content of the component (a) is 60% by mass or more, based on 100% by mass of nonvolatile components in the second resin composition,
the difference between the thermal conductivity of the first thermal cured product and the thermal conductivity of the second thermal cured product is 0.35W/mK or less,
the first thermosetting resin composition is obtained by thermosetting a first resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes,
the second thermosetting product is obtained by thermally curing the second resin composition at 100 ℃ for 30 minutes, and further at 190 ℃ for 90 minutes.
2. The resin sheet with a support according to claim 1, wherein the content of the component (a) in the first resin composition is 25% by mass or less, assuming that the nonvolatile content in the first resin composition is 100% by mass.
3. The resin sheet with a support according to claim 1, wherein the content of the component (a) in the first resin composition is 5% by mass or more, assuming that the nonvolatile content in the first resin composition is 100% by mass.
4. The resin sheet with a support according to claim 1, wherein the content of the component (a) in the second resin composition is 65% by mass or more, assuming that the nonvolatile content in the second resin composition is 100% by mass.
5. The resin sheet with a support according to claim 1, wherein the content of the component (a) in the second resin composition is 95% by mass or less, assuming that the nonvolatile content in the second resin composition is 100% by mass.
6. The resin sheet with support according to claim 1, wherein the difference between the thermal conductivity of the first thermal cured product and the thermal conductivity of the second thermal cured product is 0.01W/mK or more,
the first thermosetting product is obtained by thermally curing a first resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes, and the second thermosetting product is obtained by thermally curing a second resin composition at 100 ℃ for 30 minutes and further at 190 ℃ for 90 minutes.
7. The resin sheet with support according to claim 1, wherein the resin sheet has a thickness of 40 μm or less.
8. The resin sheet with support according to claim 1, wherein the resin sheet has a thickness of 25 μm or less.
9. The resin sheet with support according to claim 1, wherein the resin sheet has a thickness of 3 μm or more.
10. The resin sheet with a support according to claim 1, wherein when the average particle diameter of the component (a) in the first resin composition is represented by R1(μm) and the average particle diameter of the component (a) in the second resin composition is represented by R2(μm), the ratio of R1 to R2, that is, R2/R1 is 1 to 15.
11. The resin sheet with a support according to claim 1, wherein when the average particle diameter of the component (a) in the first resin composition is represented by R1(μm) and the average particle diameter of the component (a) in the second resin composition is represented by R2(μm), the ratio of R1 to R2, that is, R2/R1 is 1.1 to 10.
12. The resin sheet with support according to claim 1, wherein the first resin composition comprises (b) an epoxy resin, and the component (b) has a mesogenic skeleton.
13. The resin sheet with a support according to claim 12, wherein the component (b) is 1 or more selected from the group consisting of a biphenol-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a biphenyl-type epoxy resin, and a naphthalene-type epoxy resin.
14. The resin sheet with a support according to claim 1, which is used for forming an insulating layer of a printed wiring board.
15. A method for manufacturing a printed wiring board, comprising the steps of:
a step (I) of laminating the resin sheet with a support according to any one of claims 1 to 14 on an inner layer substrate so that the second resin composition layer is bonded to the inner layer substrate;
a step (II) in which the resin sheet with the support is thermally cured to form an insulating layer; and
and (III) forming a through hole in the insulating layer and removing the support.
16. The method for manufacturing a printed wiring board according to claim 15, wherein in the step (III), the via hole is formed in the insulating layer by laser.
17. The method for manufacturing a printed wiring board according to claim 15, wherein the opening diameter of the through hole is 40 μm or less.
18. The method for manufacturing a printed wiring board according to claim 15, wherein the opening diameter of the through hole is 35 μm or less.
19. The method for manufacturing a printed wiring board according to claim 15, wherein the opening diameter of the through hole is 30 μm or less.
20. A printed wiring board comprising an insulating layer formed of the resin sheet with a support according to any one of claims 1 to 14.
21. A semiconductor device comprising the printed wiring board according to claim 20.
CN201710108030.8A 2016-02-29 2017-02-27 Resin sheet with support Active CN107129589B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016037562A JP6834144B2 (en) 2016-02-29 2016-02-29 Resin sheet with support
JP2016-037562 2016-02-29

Publications (2)

Publication Number Publication Date
CN107129589A CN107129589A (en) 2017-09-05
CN107129589B true CN107129589B (en) 2021-07-16

Family

ID=59721923

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710108030.8A Active CN107129589B (en) 2016-02-29 2017-02-27 Resin sheet with support

Country Status (3)

Country Link
JP (1) JP6834144B2 (en)
CN (1) CN107129589B (en)
TW (1) TWI717464B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7296191B2 (en) * 2018-01-09 2023-06-22 味の素株式会社 Curable resin composition, resin sheet, printed wiring board and semiconductor device
JP7263701B2 (en) * 2018-05-31 2023-04-25 味の素株式会社 Resin sheet with support
WO2019240083A1 (en) * 2018-06-12 2019-12-19 積水化学工業株式会社 Resin material and multilayer printed wiring board
CN109337289B (en) * 2018-09-07 2021-10-19 广东生益科技股份有限公司 Thermosetting resin composition, prepreg, laminate and high-frequency circuit board containing the same
JP7196551B2 (en) * 2018-11-14 2022-12-27 味の素株式会社 RESIN SHEET WITH SUPPORT AND RESIN COMPOSITION LAYER
WO2021010209A1 (en) * 2019-07-12 2021-01-21 日東電工株式会社 Sealing resin sheet
CN112856336B (en) * 2021-01-14 2021-10-29 广东凯晟照明科技有限公司 High-efficient heat dissipation formula high-power LED lamp holder
EP4317237A1 (en) * 2021-03-31 2024-02-07 Sumitomo Bakelite Co.Ltd. Resin composition for encapsulating and electronic device using same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239767A (en) * 2004-02-24 2005-09-08 Matsushita Electric Works Ltd Resin composition, and prepreg and laminate using the same
CN103650649A (en) * 2011-07-07 2014-03-19 日立化成株式会社 Adhesive film, multilayer printed wiring board using adhesive film, and method for manufacturing multilayer printed wiring board
CN104053721A (en) * 2012-01-23 2014-09-17 味之素株式会社 Resin composition
CN104842609A (en) * 2014-02-19 2015-08-19 味之素株式会社 Resin sheet with support

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5869871B2 (en) * 2011-12-22 2016-02-24 太陽インキ製造株式会社 Dry film and printed wiring board using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239767A (en) * 2004-02-24 2005-09-08 Matsushita Electric Works Ltd Resin composition, and prepreg and laminate using the same
CN103650649A (en) * 2011-07-07 2014-03-19 日立化成株式会社 Adhesive film, multilayer printed wiring board using adhesive film, and method for manufacturing multilayer printed wiring board
CN104053721A (en) * 2012-01-23 2014-09-17 味之素株式会社 Resin composition
CN104842609A (en) * 2014-02-19 2015-08-19 味之素株式会社 Resin sheet with support

Also Published As

Publication number Publication date
TWI717464B (en) 2021-02-01
CN107129589A (en) 2017-09-05
KR20170101816A (en) 2017-09-06
TW201800257A (en) 2018-01-01
JP2017157618A (en) 2017-09-07
JP6834144B2 (en) 2021-02-24

Similar Documents

Publication Publication Date Title
TWI701289B (en) Resin composition
CN107129589B (en) Resin sheet with support
CN107236138B (en) Resin sheet
KR102535432B1 (en) Resin composition
CN107118515B (en) Resin sheet with support
JP6866858B2 (en) Resin composition layer
JP6969099B2 (en) Resin sheet manufacturing method
KR102422859B1 (en) Resin sheet
KR102490658B1 (en) Resin composition
JP2017059779A (en) Method for manufacturing printed wiring board
JP2022137095A (en) resin composition
JP6919508B2 (en) Resin composition
CN110016203B (en) Resin composition
CN106470524B (en) Resin sheet with support
CN109423015B (en) Resin composition
KR20150017297A (en) Process for producing component mounting substrate
JP6776874B2 (en) Manufacturing method of printed wiring board
JP7176556B2 (en) Resin sheet with support
JP2021120466A (en) Resin sheet, printed wiring board and semiconductor device
JP7196551B2 (en) RESIN SHEET WITH SUPPORT AND RESIN COMPOSITION LAYER
JP7247471B2 (en) resin composition
JP6911311B2 (en) Resin composition
JP7427455B2 (en) Adhesive films, printed wiring boards and semiconductor devices
JP7452560B2 (en) Manufacturing method of printed wiring board
JP6881552B2 (en) Resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant