CN113462276A - Resin composition, cured product of resin composition, resin sheet, printed wiring board, semiconductor chip package, and semiconductor device - Google Patents

Resin composition, cured product of resin composition, resin sheet, printed wiring board, semiconductor chip package, and semiconductor device Download PDF

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Publication number
CN113462276A
CN113462276A CN202110339761.XA CN202110339761A CN113462276A CN 113462276 A CN113462276 A CN 113462276A CN 202110339761 A CN202110339761 A CN 202110339761A CN 113462276 A CN113462276 A CN 113462276A
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resin composition
resin
cured product
group
mass
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CN113462276B (en
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池平秀
阪内启之
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67121—Apparatus for making assemblies not otherwise provided for, e.g. package constructions
    • 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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
    • H05K2201/09872—Insulating conformal coating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The invention provides a resin composition which can obtain a cured product with excellent long-term reliability and restrained warping; and the resin compositionA cured product of the above, a resin sheet, a printed wiring board, a semiconductor chip package and a semiconductor device. The solution of the present invention is that a resin composition comprises (A) an epoxy resin and (B) a curing agent, and the value Z obtained by dividing the average linear thermal expansion coefficient alpha of a cured product by the crosslinking density n of the cured productf(ppm・cm3Seed and seed K) satisfying 145 < Zf＜1300。

Description

Resin composition, cured product of resin composition, resin sheet, printed wiring board, semiconductor chip package, and semiconductor device
Technical Field
The present invention relates to a resin composition. Further relates to a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.
Background
A printed wiring board for a semiconductor device generally includes an insulating layer. As an insulating material constituting the insulating layer, a resin composition is used. Patent document 1 discloses an insulating material containing a thermosetting compound and a curing agent (see claim 1). Such a resin composition is sometimes used for sealing a semiconductor chip.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-188667.
Disclosure of Invention
Problems to be solved by the invention
When a semiconductor chip is sealed (particularly, when one surface of the semiconductor chip is sealed), warpage may occur due to stress bias. Therefore, suppression of warpage is required.
However, a thermoplastic resin is sometimes contained in the resin composition. Further, since the resin composition contains the thermoplastic resin, the elastic modulus of a cured product of the resin composition is lowered, and as a result, it is expected that warpage generated in the semiconductor chip is suppressed. However, the results of the studies by the present inventors have shown that if a resin composition containing a thermoplastic resin is used, long-term reliability is sometimes poor. Here, the long-term reliability can be confirmed by, for example, comparing physical properties before and after an HTS test (High Thermal Storage test) performed on a test piece and making a change degree small. That is, it has been found that it is not sufficient to adjust the elastic modulus of a cured product of the resin composition only in order to suppress warpage and to obtain excellent long-term reliability. Therefore, if adjustment items other than the elastic modulus are obtained, it is expected that a resin composition which can provide a cured product having excellent long-term reliability with suppressed warpage can be provided regardless of the presence or absence of the thermoplastic resin or the content of the thermoplastic resin.
The invention provides a resin composition which can obtain a cured product with excellent long-term reliability and suppressed warpage; and a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.
Means for solving the problems
The present inventors have conducted extensive studies on a resin composition comprising (a) an epoxy resin and (B) a curing agent, and as a result, have found that a value Z obtained by dividing an average linear thermal expansion coefficient α by a crosslink density n of a cured product of the resin composition using the average linear thermal expansion coefficient α of the cured product and the crosslink density n of the cured product as parametersf(ppm・cm3Seed and seed K) satisfying 145 < Zf< 1300, the above problems can be solved, and the present invention has been completed.
That is, the present invention includes the following.
[1] A resin composition comprising (A) an epoxy resin and (B) a curing agent,
the average linear thermal expansion coefficient alpha (ppm/K) of a cured product obtained by curing the resin composition at 180 ℃ for 90 minutes is divided by the crosslinking density n (mol/cm) of the cured product3) And the value Z obtainedf(ppm・cm3Seed/mol) satisfies the following formula:
145＜Zf＜1300。
[2] the resin composition according to [1], further comprising (C) an inorganic filler.
[3] The resin composition according to item [2], wherein the content of the component (C) is 70% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
[4] The resin composition according to [2] or [3], wherein the average particle diameter of the component (C) is 10 μm or less.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) comprises a maleimide compound having in the molecule at least one hydrocarbon chain of an alkyl group having 5 or more carbon atoms which may have a substituent, and an alkylene group having 5 or more carbon atoms which may have a substituent.
[6] The resin composition according to any one of [1] to [5], wherein the content of the component (B) is 0.5% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass.
[7] The resin composition according to any one of [1] to [6], further comprising (D) a thermoplastic resin.
[8] The resin composition according to [7], wherein the content of the component (D) is 25% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
[9] The resin composition according to any one of [1] to [8], wherein a glass transition temperature Tg of the cured product is in a range of 150 to 240 ℃.
[10] The resin composition according to any one of [1] to [9], wherein the average linear thermal expansion coefficient α of the cured product is 25ppm/K or less.
[11]According to [1]~[10]The resin composition as described in any one of the above, wherein the storage modulus E' at a predetermined temperature T (K) of the cured product is less than 1.50X 109Pa, the predetermined temperature T (K) is a temperature which represents the sum of the glass transition temperature Tg (. degree.C.) of the cured product and 353 (K).
[12]According to [1]~[11]The resin composition as described in any one of the above, wherein the crosslinked density n of the cured product is 0.15mol/cm3The following.
[13]According to [1]~[12]The resin composition as described in any one of the above, wherein the aforementioned value ZfSatisfies the following formula:
150≤Zf≤1000。
[14] the resin composition according to any one of [1] to [13], which is used for forming an insulating layer.
[15] The resin composition according to any one of [1] to [14], which is used for forming a solder resist layer.
[16] A cured product of the resin composition according to any one of [1] to [15 ].
[17] A resin sheet comprising a support and, provided on the support, a resin composition layer comprising the resin composition according to any one of [1] to [15 ].
[18] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [15] or the cured product according to [16 ].
[19] A semiconductor chip package comprising the printed wiring board according to [18] and a semiconductor chip mounted on the printed wiring board.
[20] A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of [1] to [15] or the cured product according to [16] sealing the semiconductor chip.
[21] A semiconductor device comprising the printed wiring board according to [18] or the semiconductor chip package according to [19] or [20 ].
Effects of the invention
According to the present invention, a resin composition capable of providing a cured product with suppressed warpage and excellent long-term reliability; and a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.
Detailed Description
The resin composition of the present invention, a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device will be described in detail below.
[ resin composition ]
The resin composition of the present invention is a resin composition comprising (A) an epoxy resin and (B) a curing agent, and the resin composition is cured at 180 ℃ for 90 minutes to obtain a cured product, wherein the average linear thermal expansion coefficient alpha of the cured product is divided by the crosslink density n of the cured product to obtain a value Zf(ppm・cm3seed/K) falls within the numerical range specified below. According to the resin composition, a cured product with excellent long-term reliability can be obtained, and warpage is suppressed. By using such a resin composition, a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device can be provided.
The resin composition of the present invention may further contain optional components in combination with the component (a) and the component (B). Examples of the optional components include (C) an inorganic filler, (D) a thermoplastic resin, (E) a curing accelerator, and (F) other additives (except for the components (a) to (E)). Hereinafter, each component contained in the resin composition will be described in detail. In the present invention, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100 mass%, unless otherwise explicitly indicated.
(A) epoxy resin
The resin composition contains (A) an epoxy resin. The epoxy resin is a resin having 1 or more epoxy groups in a molecule. The resin composition contains (a) an epoxy resin, and thus a cured product having a crosslinked structure can be obtained.
Examples of the epoxy resin include a bixylenol type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac type epoxy resin, a phenol novolac type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthalene ether type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a bisphenol F 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 novolac type epoxy resin, a novolac type epoxy resin, a thermosetting, 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 in 2 or more kinds.
The epoxy resin preferably contains an epoxy resin having 2 or more epoxy groups in the molecule. When the nonvolatile content of the epoxy resin is 100% by mass, it is preferable that 50% by mass or more of the epoxy resin is an epoxy resin having 2 or more epoxy groups in a molecule.
The epoxy resin may be (A-1) a liquid epoxy resin or (A-2) a solid epoxy resin. The resin composition may contain (A-1) a liquid epoxy resin and (A-2) a solid epoxy resin in combination.
((A-1) liquid epoxy resin)
The liquid epoxy resin (A-1) is an epoxy resin which is liquid at a temperature of 20 ℃. The resin composition preferably contains (A-1) a liquid epoxy resin. Here, the liquid epoxy resin is one of the components which tend to lower the glass transition temperature of a cured product of the resin composition, but according to the present invention, even if the resin composition contains the above components, a cured product having a sufficiently low average linear thermal expansion coefficient and excellent heat resistance can be obtained.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in the molecule, and more preferably an aromatic liquid epoxy resin having 2 or more epoxy groups in the molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.
The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, and an epoxy resin having a butadiene structure, and more preferably a bisphenol a type epoxy resin.
Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D" and "HP-4032-SS" (naphthalene type epoxy resin) manufactured by DIC; 828US, jER828EL, 825 and 828EL (bisphenol A epoxy resin) manufactured by Mitsubishi chemical company; "YX 7400" (flexible epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX 1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nissian Ciki Kaisha; "EX-721" (glycidyl ester type epoxy resin) manufactured by ナガセケムテックス Co; "セロキサイド 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by bare chip セル; "PB-3600" (epoxy resin having a butadiene structure) manufactured by bare chip セル; "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron Japan chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
The content of the component (a-1) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 2% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of obtaining the effect of including the component (a-1) (for example, improvement in handling properties and improvement in compatibility of the resin varnish). The upper limit of the content of the component (A-1) is not particularly limited as long as the effect of the present invention is not excessively impaired, and may be 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less.
((A-2) solid epoxy resin)
The solid epoxy resin is an epoxy resin that is solid at a temperature of 20 ℃. The resin composition contains, as the component (A), only the solid epoxy resin (A-2), and preferably contains the solid epoxy resin (A-2) in combination with the liquid epoxy resin (A-1) from the viewpoint of lowering the average linear thermal expansion coefficient or increasing the crosslinking density. The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in the molecule.
The solid epoxy resin is preferably a bixylenol-type epoxy resin, a naphthalene-type 4-functional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthalene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, or a tetraphenylethane-type epoxy resin, and more preferably a naphthol-type epoxy resin, a bisphenol AF-type epoxy resin, a naphthalene-type epoxy resin, or a biphenyl-type epoxy resin.
Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200L", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP 6000" and "HP 6000L" manufactured by DIC corporation (naphthalene ether type epoxy resins); EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; ESN475V (naphthol type epoxy resin) manufactured by Nippon iron and gold Chemicals; ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon iron and gold Chemicals, Ltd; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "157S 70" (bisphenol A novolac type epoxy resin) manufactured by Mitsubishi chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-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.
The content of the component (a-2) in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of obtaining the effect of utilizing the inclusion of the component (a-2) (for example, reduction in the average linear thermal expansion coefficient, improvement in heat resistance, or good crosslinking density). The upper limit of the content of the component (a-2) is not particularly limited as long as the effect of the present invention is not excessively impaired, and may be 10 mass% or less, 8 mass% or less, 5 mass% or less, or 3 mass% or less from the viewpoint of appropriately suppressing the crosslinking density.
When the liquid epoxy resin (a-1) and the solid epoxy resin (a-2) are used in combination as the component (a), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.01-1: 20, or more. By setting the amount ratio of the liquid epoxy resin (A-1) to the solid epoxy resin (A-2) to the above range, the following effects can be obtained: i) has appropriate adhesiveness when used in the form of a resin sheet, ii) obtains sufficient flexibility and improved handleability when used in the form of a resin sheet, and iii) enables to obtain a cured product having sufficient breaking strength. From the viewpoint of obtaining the effects of the above i) to iii) and from the viewpoint of appropriately suppressing the crosslinking density, the amount ratio of (a-1) the liquid epoxy resin to (a-2) the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: 0.01-1: 10, more preferably 1: 0.01-1: and 8, in the above range.
The content of the component (a) in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more, when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of achieving the desired effect of the present invention. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is achieved, and may be 70% by mass or less, 60% by mass or less, 50% by mass or 35% by mass or less.
(A) The epoxy equivalent of the component is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, further preferably 70g/eq to 2000g/eq, and further more preferably 70g/eq to 1000g/eq. By setting the amount to the above range, a cured product having sufficient crosslinking density and excellent strength and heat resistance can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
(A) The weight average molecular weight of the component (A) 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.
(B) curing agent
The resin composition contains (B) a curing agent. As the component (B), a component having a function of curing the component (A) can be used. The resin composition contains (B) a curing agent together with (A) an epoxy resin, and thus a cured product having excellent heat resistance can be obtained.
Examples of the curing agent (B) include (B-1) maleimide curing agents and (B-2) curing agents other than maleimide curing agents. Examples of the curing agent (B-2) other than the maleimide curing agent include 1 or more curing agents selected from the group consisting of an active ester curing agent, a phenol curing agent, a naphthol curing agent, a carbodiimide curing agent, a benzoxazine curing agent, an acid anhydride curing agent, an amine curing agent, and a cyanate curing agent (except for a curing agent containing a maleimide group). The curing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among them, the component (B) preferably contains (B-1) a maleimide-based curing agent from the viewpoint of achieving the desired effect of the present invention. The component (B) preferably contains (B-1) a maleimide-based curing agent and 1 or more curing agents selected from (B-2) curing agents other than the maleimide-based curing agent. More preferably, the component (B) contains (B-1) a maleimide curing agent and 1 or more curing agents selected from the group consisting of an active ester curing agent and a phenol curing agent as the component (B-2).
((B-1) Maleimide-based curing agent)
Examples of the maleimide curing agent include (B-1a) maleimide compounds having in the molecule at least one hydrocarbon chain selected from an optionally substituted alkyl group having 5 or more carbon atoms and an optionally substituted alkylene group having 5 or more carbon atoms. The maleimide-based curing agent may be (B-1B) other than the component (B-1 a). The maleimide curing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The maleimide-based curing agent preferably contains the component (B-1a), and may further contain the component (B-1B) in combination.
The component (B-1) is a compound containing at least 1 maleimide group represented by the following formula in the molecule, and preferably a maleimide compound containing an aliphatic structure. In the structure represented by the following formula, 1 bonding site that is not bonded to other atoms among 3 bonding sites of a nitrogen atom means a single bond.
[ CHEM 1]
Figure DEST_PATH_IMAGE002
The number of maleimide groups of 1 molecule on average in the component (B-1) is preferably 2 or more, more preferably 3 or more, from the viewpoint of enhancing the desired effect of the present invention, and the upper limit is not particularly limited, and may be 10 or less, 6 or less, 4 or less, or 3 or less.
The alkyl group having 5 or more carbon atoms in the maleimide compound having an aliphatic structure preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, preferably 50 or less, more preferably 45 or less, and still more preferably 40 or less carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear. Examples of such an alkyl group include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group having 5 or more carbon atoms may be a substituent of an alkylene group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or a part of an alkenyl group (the number of double bonds is preferably 2).
The alkylene group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, and preferably 50 or less, more preferably 45 or less, and still more preferably 40 or less carbon atoms. The alkylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkylene group is a concept including a case where the cyclic alkylene group is composed only of the cyclic alkylene group and a case where both of the linear alkylene group and the cyclic alkylene group are included. Examples of such alkylene groups include pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, trihexadecylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like. The alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a part of an alkenylene group (the number of double bonds is preferably 2).
The aliphatic structure-containing maleimide compound is (B-1a) a maleimide compound having in the molecule at least one hydrocarbon chain of an alkyl group having 5 or more carbon atoms which may have a substituent and an alkylene group having 5 or more carbon atoms which may have a substituent, and is preferably a maleimide compound having both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms, from the viewpoint of improving the desired effect of the present invention.
The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may be linear, or at least a part of carbon atoms may be bonded to each other to form a ring, and the ring structure further includes a spiro ring and a condensed ring. Examples of the ring to be bonded to each other include a cyclohexane ring and the like.
The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may have no substituent or a substituent. Examples of the substituent include a halogen atom, -OH, -O-C1-10Alkyl, -N (C)1-10Alkyl radical)2、C1-10Alkyl radical, C6-10Aryl, -NH2、-CN、-C(O)O-C1-10Alkyl, -COOH, -C (O) H, -NO2And the like. Here, "C" isx-yThe term "(x and y are positive integers, and x < y) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, "C1-10The expression "alkyl" denotes an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to formThe ring structure also includes spiro and fused rings. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms. The substituent may further have a substituent (hereinafter, sometimes referred to as "secondary substituent"). As the secondary substituent, the same groups as those described above may be used unless otherwise specified.
In the maleimide compound having an aliphatic structure, an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms are preferably directly bonded to a nitrogen atom of the maleimide group.
The number of maleimide groups of 1 molecule on average in the maleimide compound having an aliphatic structure may be 1, preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. The maleimide compound having an aliphatic structure has 2 or more maleimide groups in an average of 1 molecule, and thus the desired effect of the present invention can be enhanced.
The maleimide compound having an aliphatic structure is preferably a maleimide compound represented by the following general formula (B1).
[ CHEM 2]
Figure DEST_PATH_IMAGE004
In the general formula (B1), M represents an optionally substituted 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, and L represents a single bond or a 2-valent linking group.
M represents an optionally substituted 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms. Preferably, M represents an alkylene group, alkenylene group, or alkenylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2) which may have a substituent. The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms. Examples of the substituent for M include a halogen atom, -OH, -O-C1-10Alkyl, -N (C)1-10Alkyl radical)2、C1-10Alkyl radical, C6-10Aryl, -NH2、-CN、-C(O)O-C1-10Alkyl, -COOH, -C (O) H, -NO2And the like. Here, "C" isx-yThe term "(x and y are positive integers, and x < y) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, "C1-10The expression "alkyl" denotes an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. The substituent may further have a substituent (hereinafter, sometimes referred to as "secondary substituent"). As the secondary substituent, the same groups as those described above may be used unless otherwise specified. The substituent of M is preferably an alkyl group having 5 or more carbon atoms. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkylene group having 5 or more carbon atoms.
L represents a single bond or a 2-valent linking group. Examples of the 2-valent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C (= O) -O-, -NR0-(R0Hydrogen atom, alkyl group having 1 to 3 carbon atoms), oxygen atom, sulfur atom, C (= O) NR0A 2-valent group derived from phthalimide, a 2-valent group derived from pyromellitic diimide, a group containing a combination of 2 or more of them, and the like. The alkylene group, the alkenylene group, the alkynylene group, the arylene group, the 2-valent group derived from phthalimide, the 2-valent group derived from pyromellitic diimide, and a group containing a combination of 2 or more of the 2-valent groups may have an alkyl group having a carbon number of 5 or more as a substituent.
The term "2-valent group derived from phthalimide" means a group having a valence of 2 derived from phthalimide, and specifically a group represented by the following general formula. In the formula, "", indicates a bonding site.
[ CHEM 3]
Figure DEST_PATH_IMAGE006
The 2-valent group derived from pyromellitic diimide means a 2-valent group derived from pyromellitic diimide, specifically a group represented by the following general formula. In the formula, "", indicates a bonding site.
[ CHEM 4]
Figure DEST_PATH_IMAGE008
The alkylene group as the 2-valent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be linear, branched or cyclic. Examples of such alkylene groups include methylethylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexadecylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.
The alkenylene group as the 2-valent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. The alkenylene group may be linear, branched or cyclic. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, and octenylene.
The alkynyl group as a 2-valent linking group in L is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 15 carbon atoms, and particularly preferably an alkynyl group having 2 to 10 carbon atoms. The alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include methylacetylene, cyclohexylene, pentylene, hexylene, heptylene, and octylene.
The arylene group as the 2-valent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms, and yet more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.
The alkylene group, alkenylene group, alkynylene group, and arylene group as the 2-valent linking group in L may have a substituent. As the substituent, an alkyl group having 5 or more carbon atoms is preferable, similarly to the substituent of M in the general formula (B1).
Examples of the group containing a combination of 2 or more kinds of 2-valent groups in L include, for example, a 2-valent group containing a combination of an alkylene group, a 2-valent group derived from phthalimide, and an oxygen atom; a 2-valent group comprising a combination of a 2-valent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a 2-valent group comprising a combination of an alkylene group and a 2-valent group derived from pyromellitic diimide, and the like. Groups containing a combination of 2 or more 2-valent groups may form a ring such as a condensed ring by the combination of the respective groups. Further, the group containing a combination of 2 or more kinds of 2-valent groups may be a repeating unit having a repeating unit number of 1 to 10.
Among them, L in the general formula (B1) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may be substituted, an alkylene group having 1 to 50 carbon atoms which may be substituted, an alkyl group having 5 or more carbon atoms, a 2-valent group derived from phthalimide, a 2-valent group derived from pyromellitic diimide, or a 2-valent group containing a combination of 2 or more of these groups. Among them, as L, an alkylene group is more preferable; a 2-valent group having a structure of alkylene-a 2-valent group derived from phthalimide-an oxygen atom-a 2-valent group derived from phthalimide; a 2-valent group having a structure of alkylene-a 2-valent group derived from phthalimide-an oxygen atom-arylene-alkylene-arylene-an oxygen atom-a 2-valent group derived from phthalimide; a 2-valent group having the structure of an alkylene-2-valent group derived from pyromellitic diimide.
The maleimide compound having an aliphatic structure is preferably a maleimide compound represented by the following general formula (B2).
[ CHEM 5]
Figure DEST_PATH_IMAGE010
In the general formula (B2), M1Each independently represents a 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and each A independently represents a 2-valent group having an alkylene group having 5 or more carbon atoms which may have a substituent or an aromatic ring which may have a substituent. t represents an integer of 1 to 10.
M1Each independently represents an optionally substituted 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms. Preferably, M1Each independently represents an alkylene group, an alkenylene group or an alkenylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2) which may have a substituent. M1More preferably, it is the same as M in the general formula (B1).
Each A independently represents a 2-valent group having an optionally substituted alkylene group having 5 or more carbon atoms or an optionally substituted aromatic ring. The alkylene group in a may be any of a chain, a branched chain and a cyclic group, and among them, a cyclic alkylene group having 5 or more carbon atoms, which may have a substituent, is preferable. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. Examples of the alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.
Examples of the aromatic ring in the 2-valent group having an aromatic ring represented by a include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic diimide ring, an aromatic heterocycle, and the like, and a benzene ring, a phthalimide ring, and a pyromellitic diimide ring are preferable. That is, as the 2-valent group having an aromatic ring, a 2-valent group having a benzene ring optionally having a substituent, a 2-valent group having a phthalimide ring optionally having a substituent, and a 2-valent group having a pyromellitic diimide ring optionally having a substituent are preferable. Examples of the 2-valent group having an aromatic ring include a group containing a combination of a 2-valent group derived from phthalimide and an oxygen atom; a group comprising a combination of a 2-valent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group comprising a combination of an alkylene group and a 2-valent group derived from pyromellitic diimide; comprises a 2-valent group derived from pyromellitic diimide; groups derived from combinations of phthalimide-2-valent groups and alkylene groups, and the like. The arylene group and the alkylene group are the same as those in the 2-valent linking group represented by L in the general formula (B1).
The alkylene group represented by a and the 2-valent group having an aromatic ring may have a substituent. The substituent is the same as the substituent represented by the substituent of M in the general formula (B1).
Specific examples of the group represented by a include the following groups. In the formula, "", indicates a bonding site.
[ CHEM 6]
Figure DEST_PATH_IMAGE012
[ CHEM 7]
Figure DEST_PATH_IMAGE014
The maleimide compound represented by the general formula (B2) is preferably either a maleimide compound represented by the following general formula (B2-1) or a maleimide compound represented by the following general formula (B2-2).
[ CHEM 8]
Figure DEST_PATH_IMAGE016
In the general formula (B2-1), M2And M3Each independently represents an optionally substituted 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, R30Each independently represents an oxygen atom, an arylene group, an alkylene group, or a compound containing the same2-valent groups of combinations of 2 or more of these groups. t1 represents an integer of 1 to 10.
[ CHEM 9]
Figure DEST_PATH_IMAGE018
In the general formula (B2-2), M4、M6And M7Each independently represents an optionally substituted 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, M5Each independently represents a 2-valent group having an aromatic ring optionally having a substituent, R31And R32Each independently represents an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.
M2And M3Each independently represents an optionally substituted 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms. Preferably, M2And M3Each independently represents an alkylene group, an alkenylene group or an alkenylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2) which may have a substituent. M2And M3More preferably, the alkylene group having 5 or more carbon atoms represented by M in the general formula (B1) is the same as, and is preferably a tridecylene group.
R30Each independently represents an oxygen atom, an arylene group, an alkylene group, or a group containing a combination of 2-valent groups of 2 or more of these. The arylene group and the alkylene group are the same as those in the 2-valent linking group represented by L in the general formula (B1). As R30Preferably a group containing a combination of 2 or more 2-valent groups or an oxygen atom.
As R30The group containing a combination of 2 or more kinds of 2-valent groups in (b) includes a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group containing a combination of 2 or more 2-valent groups include the following groups. In the formula, "", indicates a bonding site.
[ CHEM 10]
Figure DEST_PATH_IMAGE020
M4、M6And M7Each independently represents an optionally substituted 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms. Preferably, M4、M6And M7Each independently represents an alkylene group, an alkenylene group or an alkenylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2) which may have a substituent. M4、M6And M7The alkylene group having 5 or more carbon atoms, which is optionally substituted with a substituent, is preferably a hexylene group, heptylene group, octylene group, nonylene group, or decylene group, and more preferably an octylene group, as in the case of the alkylene group having 5 or more carbon atoms represented by M in the general formula (B1).
M5Each independently represents a 2-valent group having an aromatic ring which may have a substituent. M5The same 2-valent group having an aromatic ring optionally having a substituent as represented by a in the general formula (B2), is preferably a group comprising a combination of an alkylene group and a 2-valent group derived from pyromellitic diimide; a group comprising a combination of a 2-valent group derived from phthalimide and an alkylene group, more preferably a group comprising a combination of an alkylene group and a 2-valent group derived from pyromellitic diimide.
As M5Specific examples of the group include the following groups. In the formula, "", indicates a bonding site.
[ CHEM 11 ]
Figure DEST_PATH_IMAGE022
R31And R32Each independently represents an alkyl group having 5 or more carbon atoms. R31And R32The alkyl group having 5 or more carbon atoms is preferably a hexyl group, heptyl group, octyl group, nonyl group, or decyl group, and more preferably a hexyl group or octyl group.
u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.
Specific examples of the maleimide compound having an aliphatic structure include the following compounds (b1), (b2), (b3), (b4), (b5) and (b 6). However, the maleimide compound containing an aliphatic structure is not limited to these specific examples. In formulae (b1), (b2), (b3), (b5) and (b6), n9, n10, n11, n12 and n13 represent integers of 1 to 10.
[ CHEM 12 ]
Figure DEST_PATH_IMAGE024
[ CHEM 13]
Figure DEST_PATH_IMAGE026
[ CHEM 14]
Figure DEST_PATH_IMAGE028
[ CHEM 15]
Figure DEST_PATH_IMAGE030
[ CHEM 16]
Figure DEST_PATH_IMAGE032
[ CHEM 17]
Figure DEST_PATH_IMAGE034
Specific examples of the maleimide compound having an aliphatic structure (component (B-1)) include "BMI-1500" (compound of formula (B1), compound of formula (B5), "BMI-1700" (compound of formula (B2), compound of formula (B6)), and "BMI-3000J" (compound of formula (B3)) and "BMI-689" (compound of formula (B4)) manufactured by デザイナーモレキュールズ.
The maleimide group equivalent of the component (B-1) is preferably 50g/eq to 2000g/eq, more preferably 100g/eq to 1000g/eq, and still more preferably 150g/eq to 500g/eq, from the viewpoint of obtaining the desired effect of the present invention remarkably. The maleimide group equivalent is the mass of the maleimide compound containing 1 equivalent of maleimide group.
The content of the component (B-1) is 0.2% by mass or more, 0.5% by mass or more, 1.0% by mass or more, or 2.0% by mass or more, from the viewpoint of improving the desired effect of the present invention, although it depends on the content of components other than the components (A) and (B-1) when the nonvolatile component of the resin composition is 100% by mass. From the viewpoint of improving the desired effect of the present invention, the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and still more preferably 10% by mass or less. The proportion of the component (B-1) in the component (B) is preferably 30% by mass or more, 40% by mass or more, or 50% by mass or more, and the upper limit is 100% by mass, from the viewpoint of improving the desired effect of the present invention.
(B-2) curing agent other than maleimide-based curing agent)
The active ester curing agent is not particularly limited, and in general, a compound having 2 or more ester groups with high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, is preferably used. The active ester-based 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 obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenol benzopyrrolidone, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing a phenol 2 molecule on a dicyclopentadiene 1 molecule.
Specifically, preferred are an active ester compound having a dicyclopentadiene structure, an active ester compound having a naphthalene structure, an active ester compound having an acetyl compound of phenol novolac, and an active ester compound having a benzoyl compound of phenol novolac, and more preferred are an active ester compound having a naphthalene structure and an active ester compound having a dicyclopentadiene structure. The "dicyclopentadiene type diphenol structure" means a 2-valent structural unit comprising phenylene-dicyclopentylene-phenylene.
Commercially available active ester curing agents include "EXB-9451", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65 TM", "HPC-8000L-65 TM" (manufactured by DIC), examples of active ester compounds having a naphthalene structure include "EXB-9416-70 BK", "EXB-8100L-65T", "EXB-8150L-65T", "HPC-8150-60T", "HPC-8150-62T", "HP-B-8151-62T" (manufactured by DIC), examples of active ester compounds having an acetyl compound of phenol novolak include "DC 808" (manufactured by Mitsubishi chemical), examples of the active ester compound containing a benzoylate of a phenol novolak include "YLH 1026" (manufactured by mitsubishi chemical corporation), examples of the active ester-based curing agent of an acetylate of a phenol novolak include "DC 808" (manufactured by mitsubishi chemical corporation), examples of the active ester-based curing agent of a benzoylate of a phenol novolak include "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation), and examples of the active ester compound containing a styryl group include "PC 1300-02-65 MA" (manufactured by エア. multidot. ウォーター).
The phenol curing agent (excluding the active ester compound) and the naphthol curing agent (excluding the active ester compound) are preferably a phenol curing agent having a novolac structure or a cresol novolac structure or a naphthol curing agent having a novolac structure from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a phenol-based curing agent having a triazine skeleton is more preferable.
Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Kagaku corporation, "NHN", "CBN", "GPH" manufactured by Nippon chemical company, "SN 170", "SN 180", "SN 190", "SN 475", "SN 485", "SN 495", "SN-495V", "SN 375", "SN 395", and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and "KA-1160" manufactured by DIC corporation.
Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", "V-07", "V-09", and "Elastostab H01" manufactured by Nisshinbo chemical Co., Ltd.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP 100D" manufactured by JFE chemical company, "ODA-BOZ", "HFB 2006M" manufactured by Showa Polymer company, "P-d" and "F-a" manufactured by four national chemical industries. The benzoxazine-based curing agent is a compound having a benzoxazine structure. The benzoxazine structure refers to a substituted or unsubstituted benzoxazine ring (e.g., 1, 2-benzoxazine ring, 1, 3-benzoxazine ring), or a benzoxazine ring in which a part of the double bond is hydrogenated (e.g., 3, 4-dihydro-2H-1, 3-benzoxazine ring).
Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (anhydrous trimellitic acid ester), and polymer type acid anhydrides such as styrene resin obtained by copolymerizing styrene with maleic acid. Examples of commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Nippon chemical Co., Ltd "," YH-306 "," YH-307 "manufactured by Mitsubishi chemical Co., Ltd", "HN-2200" and "HN-5500" manufactured by Hitachi chemical Co., Ltd.
The amine-based curing agent includes a curing agent having 1 or more, preferably 2 or more amino groups in 1 molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4' -methylenebis (2, 6-dimethylaniline), diphenyldiaminosulfone, 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, 3' -dimethyl-4, 4-diphenylmethanediamine, and the like, 2, 2-bis (4-aminophenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. As the amine-based curing agent, commercially available ones can be used, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "カヤハード A-A", "カヤハード A-B", "カヤハード A-S" manufactured by Nippon chemical company, and "エピキュア W" manufactured by Mitsubishi chemical company.
Examples of the cyanate ester-based curing agent include 2-functional cyanate ester resins such as bisphenol A dicyanate, polyphenolic cyanate ester, oligo (3-methylene-1, 5-phenylene cyanate ester), 4 '-methylenebis (2, 6-dimethylphenylcyanate), 4' -ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanatophenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) ether, Polyfunctional cyanate ester resins derived from phenol novolak, cresol novolak 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" (phenol novolac-type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA 230" and "BA 230S 75" (prepolymer in which a part or all of bisphenol a dicyanate is triazinated to form a trimer) manufactured by ロンザジャパン.
(A) The amount ratio of the epoxy resin to the (B) curing agent is in [ total count of epoxy groups of the epoxy resin ]: [ total number of reactive groups of curing agent ] is preferably 1: 0.01-1: 2, more preferably 1: 0.05-1: 3. more preferably 1: 0.1-1: 1.5. the reactive group of the (B) curing agent means an active ester group, an active hydroxyl group, and the like, and varies depending on the type of the (B) curing agent. The total count of the epoxy groups of the (a) epoxy resin is a value obtained by dividing the mass of each nonvolatile component of the (a) epoxy resin by the epoxy equivalent for the total of all the epoxy resins, and the total count of the reactive groups of the (B) curing agent is a value obtained by dividing the mass of each nonvolatile component of the (B) curing agent by the equivalent of the reactive groups for the total of all the curing agents. By setting the amount ratio of the (a) epoxy resin to the (B) curing agent to the above range, the desired effects of the present invention can be improved.
(B) The content of the component (B) is preferably determined so as to satisfy the range of the amount ratio of the epoxy resin (a) to the curing agent (B). From the viewpoint of improving the desired effect of the present invention, the content of the component (B) may be 0.5 mass% or more, 1 mass% or more, 2 mass% or more, or 3 mass% or more, 50 mass% or less, 40 mass% or less, 30 mass% or less, or 25 mass% or less, when the nonvolatile content in the resin composition is 100 mass%.
(C) inorganic filler
The resin composition may contain (C) an inorganic filler. The resin composition preferably contains an inorganic filler from the viewpoint of reducing the average linear thermal expansion coefficient of a cured product of the resin composition.
The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, 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, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Further, the silica is preferably spherical silica. The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Commercially available products of silica include "SO-C2" manufactured by アドマテックス, and "SO-C1", and "UFP-30" and "UFP-40" manufactured by デンカ.
The average particle size of the inorganic filler is usually 20 μm or less, and from the viewpoint of enhancing the desired effect of the present invention, it is preferably 10 μm or less, more preferably 5.0 μm or less, still more preferably 2.5 μm or less, and still more preferably 2.0 μm or less. The lower limit of the average particle diameter is not particularly limited, and may be 1nm (0.001 μm) or more, 5nm or more, 10nm or more, or the like.
The average particle size of the inorganic filler can be determined by laser diffraction/seed scattering based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured by preparing the particle size distribution on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus and setting the median diameter as the average particle size. The measurement sample may preferably use a substance obtained by dispersing an inorganic filler material in methyl ethyl ketone by ultrasound. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by horiba, Inc., SALD-2200 manufactured by Shimadzu, Inc., and the like can be used.
The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving the embedding property, more preferably with 1 or more surface treatment agents selected from fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilicon nitrogen compounds, titanate coupling agents, and the like, and still more preferably with an aminosilane coupling agent. The surface treatment agent preferably has another component, for example, a functional group that reacts with the resin, for example, an epoxy group, an amino group, or a mercapto group, and more preferably the functional group is bonded to a terminal group. Examples of commercially available surface-treating agents include silane-based coupling agent "KBM 403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., silane-based coupling agent "KBM 803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., silane-based coupling agent "KBE 903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., Ltd., silane-based coupling agent "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., silane-based coupling agent "SZ-31" (hexamethyldisilazane) available from shin-Etsu chemical Co., Ltd., alkoxysilane compound "KBM 103" (phenyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., silane-based coupling agent "KBM-4803" (long-chain epoxy-based silane coupling agent) available from shin-Etsu chemical Co., Ltd, Silane coupling agent "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd.
The degree of surface treatment with the surface treatment agent is preferably 0.2 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and even more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the component (C), from the viewpoint of improving embeddability.
The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving the embedding property2Above, more preferably 0.1mg/m2Above, more preferably 0.2mg/m2The above. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, 1mg/m is preferable2Less than, more preferably 0.8mg/m2The concentration is preferably 0.5mg/m or less2The following.
The amount of carbon per surface area of the inorganic filler can be measured after the inorganic filler after surface treatment is subjected to a washing treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, as a solvent, a sufficient amount of MEK was added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the nonvolatile components, the amount of carbon per surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd.
The specific surface area of the component (C) is preferably 1m2A ratio of 2m or more, more preferably 2m2A specific ratio of 3m or more in terms of/g2More than g. The upper limit is not particularly limited, but is preferably 60m2Less than g, 50m2Less than or equal to 40 m/g2The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area was obtained by adsorbing nitrogen gas on the surface of the sample according to the BET method using a BET full-automatic specific surface area measuring apparatus ("Macsorb HM-1210" manufactured by マウンテック Co., Ltd.) and calculating the specific surface area by the BET multipoint method.
(C) The content of the component (b) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, or 71% by mass or more, when the nonvolatile fraction in the resin composition is 100% by mass, from the viewpoint of reducing the average linear thermal expansion coefficient of a cured product of the resin composition. The upper limit is not particularly limited, but is usually 95% by mass or less, and may be 94% by mass or less or 93% by mass or less. In the present invention, as exemplified in examples, when the nonvolatile content of the resin composition is 100 mass%, even if the content of the component (C) is 70 mass% or more, it is confirmed that a cured product having excellent long-term reliability and suppressed warpage is obtained.
< (D) thermoplastic resin
The resin composition may contain (D) a thermoplastic resin as an optional component. When the resin composition is treated in the form of a resin sheet or film, the resin composition preferably contains the component (D). However, the value Z is only required to be described laterfIf the content is within the predetermined range, the resin composition may contain no component (D).
(D) The weight average molecular weight (Mw) of the component (a) in terms of polystyrene is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more, 3000 or more. The upper limit is preferably 1000000 or less, more preferably 900000 or less. (D) The number average molecular weight (Mn) of the component (a) in terms of polystyrene is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more, and 3000 or more. The upper limit is preferably 1000000 or less, more preferably 900000 or less. (D) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the component (d) in terms of polystyrene were measured by a Gel Permeation Chromatography (GPC) method. Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (D) in terms of polystyrene can be measured 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., Shodex K-800P/K-804L/K-804L as a column, chloroform or the like as a mobile phase, with the column temperature being 40 ℃ and calculated using a standard curve of standard polystyrene.
Examples of the thermoplastic resin (D) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins, and phenoxy resins are preferred. The thermoplastic resin can be used alone in 1 kind, or can also be combined with more than 2 kinds.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from a bisphenol a skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac 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 or an epoxy group. The phenoxy resin may be used alone in 1 kind, or in combination with 2 or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resins having a bisphenol a skeleton), and "YX 8100" (phenoxy resin having a bisphenol S skeleton), and "YX 6954" (phenoxy resin having a bisphenol acetophenone skeleton), which are manufactured by mitsubishi chemical corporation, "FX 280" and "FX 293", which are manufactured by mitsubishi chemical & マテリアル corporation, "YX 7200B 35", "YL 7500BH 30", "YX 6954BH 30", "YX 7553BH 30", "YL 7769BH 30", "YL 6794", "YL 7213", "YL 7290", and "YL 7482".
Examples of the polyvinyl acetal resin include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include "electrochemical ブチラール 4000-2", "electrochemical ブチラール 5000-A", "electrochemical ブチラール 6000-C", "electrochemical ブチラール 6000-EP" manufactured by the chemical industries, エスレック BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series and the like manufactured by the chemical industries.
Specific examples of the polyimide resin include "リカコート SN 20" and "リカコート PN 20" manufactured by nippon chemical and physical corporation.
Specific examples of the polyamideimide resin include "バイロマックス HR11 NN" and "バイロマックス HR16 NN" manufactured by Toyobo Co. 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.
Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by sumitomo chemical corporation. Specific examples of polyphenylene ether resins include oligophenylene ether/seed/styrene resin "OPE-2 St 1200" manufactured by Mitsubishi gas chemical corporation. Specific examples of the polyether ether ketone resin include "スミプロイ K" manufactured by sumitomo chemical corporation. Specific examples of the polyetherimide resin include "ウルテム" manufactured by GE corporation.
Specific examples of polysulfone resins include polysulfone "P1700" and polysulfone "P3500" manufactured by ソルベイアドバンストポリマーズ corporation.
Examples of the polyolefin resin include vinyl copolymer resins such as low density polyethylene, ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin elastomers such as polypropylene and ethylene-propylene block copolymers.
Examples of the polyester resin include polyethylene terephthalate resins, polyethylene naphthalate resins, polybutylene terephthalate resins, polybutylene naphthalate resins, polytrimethylene terephthalate resins, polytrimethylene naphthalate resins, polycyclohexane dimethylterephthalate resins, and the like.
The component (D) is preferably a resin having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, more preferably a resin having 1 or 2 or more structures selected from a polybutadiene structure, a poly (meth) acrylate structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure, and still more preferably a resin having 1 or more structures selected from a polybutadiene structure and a polycarbonate structure. It should be noted that "(meth) acrylate" means a term including methacrylate and acrylate and a combination thereof. These structures may be contained in the main chain or in the side chain.
(D) Component (B) is preferably incorporated in the crosslinked structure composed of component (a) and component (B) by having a reactive functional group (hereinafter also referred to as a "reactive functional group"). The reactive functional group may be a substance that exhibits reactivity by heating or light irradiation.
Examples of the reactive group contained in the component (D) include a hydroxyl group, a carboxyl group, an amino group, a vinyl group, an acryloyl group, and a methacryloyl group. Instead of the vinyl group, a group having a double bond between carbon and carbon may be used. The hydroxyl group is preferably a phenolic hydroxyl group from the viewpoint of improving the heat resistance of the crosslinked structure.
(D) One suitable embodiment of the component is a resin containing a polybutadiene structure, which may be contained in the main chain or in the side chain. It should be noted that the polybutadiene structure may be partially or entirely hydrogenated. A resin containing a polybutadiene structure is called a polybutadiene resin.
Specific examples of the polybutadiene resin include "Ricon 130MA 8", "Ricon 130MA 13", "Ricon 130MA 20", "Ricon 131MA 5", "Ricon 131MA 10", "Ricon 131MA 17", "Ricon 131MA 20", "Ricon 184MA 6" (polybutadiene containing an acid anhydride group), "GQ-1000" (hydroxyl-and carboxyl-introduced polybutadiene), manufactured by Nippon Cauda "," G-1000 "," G-2000 "," G-3000 "(hydroxyl-terminated polybutadiene),", "GI-1000", "GI-2000", "GI-3000" (hydroxyl-terminated hydrogenated polybutadiene), and "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), manufactured by ナガセケムテックス. Further, as the polybutadiene resin, the thermoplastic resin a having a reactive functional group contained in the thermoplastic resin solution a prepared in < preparation of thermoplastic resin solution a > described later, or a modified product thereof may be used. As the polybutadiene resin, a resin having a residue obtained by removing the hydroxyl group of 2-functional hydroxyl-terminated polybutadiene disclosed in japanese patent application laid-open No. 2006-037083 or a modified product thereof can be used, and among these, from the viewpoint of obtaining a cured product excellent in flexibility, a resin having a residue obtained by removing the hydroxyl group of 2-functional hydroxyl-terminated polybutadiene having an average molecular weight of 800 to 1000 or a modified product thereof, or a resin having a polybutadiene structure content of 45 mass% or more or a modified product thereof is preferably used. As the polybutadiene resin, a resin having a polybutadiene structure or a modified product thereof can be used which uses as a raw material a polybutadiene polyol compound having 2 or more alcoholic hydroxyl groups in 1 molecule as disclosed in international publication No. 2008/153208, and among them, a resin having a polybutadiene structure or a modified product thereof which uses as a raw material a polybutadiene polyol compound having a number average molecular weight of 300 to 5000 is preferable from the viewpoint of obtaining a cured product excellent in flexibility. The content of the butadiene structure in the polybutadiene resin is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more, and the upper limit of the content of the butadiene structure is roughly determined depending on other structural sites in the molecule.
(D) One suitable embodiment of component (b) is a resin containing a poly (meth) acrylate structure. A resin containing a poly (meth) acrylate structure is called a poly (meth) acrylic resin. Examples of the poly (meth) acrylic resin include テイサン resin manufactured by ナガセケムテックス Co., Ltd., "ME-2000", "W-116.3", "W-197C", "KG-25" and "KG-3000" manufactured by Korea Co., Ltd.
(D) A suitable embodiment of component (B) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin. As the polycarbonate resin, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals ズ, and "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by クラレ can be used. In addition, as the polycarbonate resin, the thermoplastic resin B having a reactive functional group or a modified product thereof contained in the thermoplastic resin solution B prepared in < preparation of thermoplastic resin solution B > described later can be used. The polycarbonate resin may be a resin having a residue obtained by removing a hydroxyl group of a polycarbonate diol as disclosed in international publication No. 2016/129541 or a modified product thereof, and among them, a resin having a residue obtained by removing a hydroxyl group of a polycarbonate diol having a hydroxyl equivalent weight of 250 to 1250 or a modified product thereof is preferably used from the viewpoint of obtaining a cured product excellent in flexibility and chemical resistance. Further, as the polycarbonate resin, a resin having a residue obtained by removing a hydroxyl group of a polycarbonate polyol, or a modified product thereof can be used. The content of the carbonate structure in the polycarbonate resin is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 75% by mass or more, and the upper limit of the content of the carbonate structure is roughly determined depending on other structural sites in the molecule.
Another embodiment of the component (D) is a resin having a siloxane structure. Resins containing siloxane structures are referred to as siloxane resins. Examples of the silicone resin include "SMP-2006", "SMP-2003 PGMEA", "SMP-5005 PGMEA", and linear polyimide in which an amino-terminal polysiloxane and a tetrabasic acid anhydride are used as raw materials (International publication No. 2010/053185, Japanese patent application laid-open Nos. 2002-012667 and 2000-319386, etc.), which are manufactured by shin-Etsu Silicone Co., Ltd.
Another embodiment of the component (D) is a resin having an alkylene structure or an alkyleneoxy structure. The resin containing an alkylene structure is referred to as an alkylene resin, and the resin containing an alkyleneoxy structure is referred to as an alkyleneoxy resin. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and still more preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of the alkylene resin and the alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei せ Ph い Co.
Another embodiment of the component (D) is a resin having an isoprene structure. The resin containing an isoprene structure is referred to as an isoprene resin. Specific examples of the isoprene resin include "KL-610" and "KL 613" manufactured by クラレ.
Another embodiment of the component (D) is a resin having an isobutylene structure. The resin having an isobutylene structure is called an isobutylene resin. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by カネカ.
(D) The content of the component (b) may be 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more, when the resin component in the resin composition is 100 mass%. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more, from the viewpoint of achieving the desired effect of containing the component (D). The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less, from the viewpoint of obtaining a cured product excellent in long-term reliability. The resin component is a component excluding (C) the inorganic filler and (F) other additives from all components contained in the resin composition.
(D) The content of the component (b) may be 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, from the viewpoint of achieving the desired effect of containing the component (D). The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less, from the viewpoint of obtaining a cured product excellent in long-term reliability.
(E) curing Accelerator
The resin composition may contain (E) a curing accelerator. 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, and a metal-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 is more preferable. The curing accelerator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium caprate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, and triphenylphosphine and tetrabutylphosphonium caprate are preferable.
Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-Dimethylaminopyridine (DMAP), 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-cyanoethyl-2-methylimidazole, 2-decylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-methylimidazole, 2-decylimidazole, 2-iodonium, 2-methylimidazole, and the like, 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, and mixtures thereof, Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline and adducts of imidazole compounds with epoxy resins, 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 imidazole compound "1B 2 PZ" manufactured by Sizhou chemical Co., Ltd., P200-H50 "manufactured by Mitsubishi chemical Co., Ltd.
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, dicyanodiamine and 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.
When the resin composition contains the component (E), the content of the component (E) is usually 0.001 mass% or more, preferably 0.01 mass% or more, and more preferably 0.02 mass% or more, assuming that the nonvolatile fraction in the resin composition is 100 mass%. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. This can reliably accelerate the curing of the resin composition.
< (F) optional additives
In one embodiment, the resin composition may further contain (F) other additives (except the components (a) to (E)) as required, and examples of the other additives include organic fillers, 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 coloring agents.
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, silicone particles, and the like. Examples of the rubber particles include "EXL 2655" manufactured by ダウ & seeded chemical japan, and "AC 3401N" and "AC 3816N" manufactured by アイカ industrial corporation.
(F) The content of the component (b) is arbitrary as long as the desired effect of the present invention is not excessively impaired, and may be, for example, 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more, for example, 15 mass% or less, 13 mass% or less, or 10 mass% or less, when the nonvolatile component in the resin composition is 100 mass%.
< Property of resin composition >
(value Z)f)
The resin composition of the present invention satisfies a value Z obtained by dividing an average linear thermal expansion coefficient alpha by a crosslinking density n for a cured product obtained by curing at 180 ℃ for 90 minutesf(ppm・cm3Seed with/mol K) of 145 < Zf< 1300, preferably 150. ltoreq. Zf. ltoreq.1000. Thus, as demonstrated by way of example in the column of examples, the resin composition of the present invention can provide a cured product which is suppressed in warpage and has excellent long-term reliability as compared with comparative examples. Preferably, in this case, ZfCan be expressed as < value ZfGet > get. ZfUsually greater than 145(ppm, seed and cm)3seed/K), preferably 150(ppm seed/cm)3Seed/seed K) or more, preferably 155(ppm seed/cm) from the viewpoint of improving the desired effects (suppression of warpage and long-term reliability) of the present invention3Seed (seed/seed) or more, more preferably 160(ppm seed/cm)3More than/mol, typically less than 1300(ppm, seed, cm)3seed/K), preferably 1000(ppm seed/cm)3seed/K) or less, preferably 700 (ppm/seed/cm) from the viewpoint of enhancing the desired effect of the present invention3Seed or seed of/mol, more preferably 500(ppm, seed or seed cm)3Seed and seed of/mol K) or less. Here, the value ZfThe amount of the component (B) may be adjusted by the kind and amount of the component (a) and the component (B) contained in the resin composition. Value ZfThe parameter represented by the relational expression between the average linear thermal expansion coefficient α and the crosslink density n is a parameter relating to suppression of warpage and long-term reliability, and therefore can be understood as one of indexes that reflect parameters relating to: (i) generally speaking, the presence or absence of a component that lowers the average linear thermal expansion coefficient α, that is, the content of the component (C); (ii) the presence or absence of a component or a site (for example, the component (C) and the component (D)) capable of suppressing the formation of a crosslinked structure formed by an epoxy resin and a curing agent or suppressing the increase in crosslinking density, and the content thereof; and (iii) the presence or absence of a component capable of promoting the formation of the aforementioned crosslinked structure (e.g., component (E)) and the content thereof.
(glass transition temperature Tg)
The glass transition temperature Tg (DEG C) of a cured product obtained by curing the resin composition of the present invention at 180 ℃ for 90 minutes is preferably in the range of 150 to 240 ℃ from the viewpoint of obtaining a cured product having excellent heat resistance. The glass transition temperature Tg (. degree.C.) can be obtained at < measurement of dynamic elastic modulus > described later. The glass transition temperature Tg (. degree.C.) is usually 150 ℃ or higher, and is preferably higher than 165 ℃ and more preferably 176 ℃ or higher from the viewpoint of obtaining a cured product excellent in heat resistance. The upper limit of the glass transition temperature Tg (. degree.C.) is usually 240 ℃ or lower, and may be 210 ℃ or lower, 209 ℃ or lower, or 205 ℃ or lower, for example, from the viewpoint of obtaining a cured product having excellent handling properties.
(average linear thermal expansion coefficient. alpha.)
In the resin composition of the present invention, from the viewpoint of enhancing the desired effect of the present invention, the average linear thermal expansion coefficient α of a cured product obtained by curing at 180 ℃ for 90 minutes is preferably small. Here, the value of the average linear thermal expansion coefficient α can be adjusted to be decreased by, for example, the type and amount of the components such as the component (a) and the component (B) contained in the resin composition. The average linear thermal expansion coefficient α can be measured in terms of < determination of average linear thermal expansion Coefficient (CTE) α > described later. The average linear thermal expansion coefficient α of the cured product is usually less than 30ppm/K, preferably 25ppm/K or less, more preferably 20ppm/K or less, and the lower limit is not particularly limited, and may be, for example, 1ppm/K or more or 2ppm/K or more. The average linear thermal expansion coefficient alpha of the cured product is from the value ZfFrom the viewpoint of satisfying the above numerical range, it is, for example, 5ppm/K or more or 7ppm/K or more.
(storage modulus at a prescribed temperature T (K))
The resin composition of the present invention has a storage modulus E' of usually 2.00X 10 at a predetermined temperature T (K) for a cured product obtained by curing at 180 ℃ for 90 minutes9Pa or less. The predetermined temperature T (K) is a temperature which represents the sum of the glass transition temperature Tg (. degree.C.) and 353(K) of the cured product (i.e., 273K and 80K should be added in terms of K). Here, the value of the storage modulus E' at the predetermined temperature t (k) can be adjusted by, for example, the kinds and amounts of the components such as the component (a) and the component (B) included in the resin composition. From the viewpoint of improving the desired effect of the present invention, the storage modulus E' is preferably less than 1.50 × 109Pa, more preferably 1.40X 109Pa or less, more preferably 1.30X 109Pa or less or 1.20X 109Pa or less, usually 0.10X 109Pa is atFrom the viewpoint of enhancing the desired effect of the present invention, it is preferably more than 0.30 × 109Pa, more preferably 0.35X 109Pa or more, and more preferably 0.40X 109Pa or above. The cured product has a value Z offFrom the viewpoint of satisfying the above numerical range and improving the desired effect of the present invention, it is preferable that the average linear thermal expansion coefficient α is 25ppm/K or less and the storage modulus E' at a predetermined temperature T (K) is less than 1.50X 109Pa, or preferably an average linear thermal expansion coefficient alpha of 25ppm/K or less, and a storage modulus E' at a predetermined temperature T (K) of more than 0.30X 109Pa. The prescribed temperature T (K) is, for example, within the range of 473K-673K.
(crosslink Density n)
In the resin composition of the present invention, from the viewpoint of enhancing the desired effect of the present invention, the crosslinking density n of a cured product obtained by curing at 180 ℃ for 90 minutes is preferably 0.15mol/cm3The following. Here, the value of the crosslinking density n can be adjusted by, for example, the kind and amount of the components such as the component (a) and the component (B) contained in the resin composition. The crosslinking density n can be obtained by using the measurement result in < measurement of dynamic elastic modulus > described later. From the viewpoint of enhancing the desired effect of the present invention, the crosslinking density n is preferably 0.15mol/cm3Less than, more preferably 0.07mol/cm3The concentration is preferably 0.05mol/cm or less3Less than or 0.04mol/cm3Below, it is usually 0.01mol/cm3As described above, from the viewpoint of enhancing the desired effect of the present invention, it is preferably 0.02mol/cm3Above, more preferably 0.03mol/cm3The above.
The resin composition of the present invention can provide an insulating layer formed from a cured product which is suppressed in warpage and has excellent long-term reliability. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board). Further, the resin composition of the present invention has an insulating layer formed of a cured product with suppressed warpage and excellent long-term reliability, and therefore can be suitably used also in the case where a printed wiring board is a component-embedded circuit board. Further, the resin composition of the present invention has an insulating layer formed from a cured product with suppressed warpage and excellent long-term reliability, and therefore can be used more suitably as a resin composition for forming a solder resist layer (a solder resist layer-forming resin composition for a printed wiring board). The resin composition of the present invention has an insulating layer formed of a cured product with suppressed warpage, and therefore can be suitably used as a resin composition for forming a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation (a resin composition for forming a sealing layer for semiconductor chip encapsulation). Further, the resin composition of the present invention can be suitably used as a resin composition for forming a rewiring-forming layer of a semiconductor chip package (resin composition for forming a rewiring-forming layer for semiconductor chip package).
The semiconductor chip package including the rewiring formation layer is manufactured, for example, by the following steps (1) to (6).
(1) A step of laminating a pre-fixing film on a base material,
(2) a step of pre-fixing the semiconductor chip on the pre-fixing film,
(3) a step of forming a sealing layer on the semiconductor chip,
(4) a step of peeling the substrate and the pre-fixing film from the semiconductor chip,
(5) a step of forming a rewiring formation layer as an insulating layer on a surface from which the base material of the semiconductor chip and the pre-fixing film are peeled off, and
(6) a step of forming a rewiring layer as a conductor layer on the rewiring-forming layer
Further, in manufacturing a semiconductor chip package including a sealing layer, a rewiring layer may be further formed on the sealing layer.
< method for producing resin composition >
The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing the compounding ingredients with a solvent and the like as needed, and dispersing the mixture using a rotary mixer or the like. In the production of the resin composition of the present inventionIn the case of the above-mentioned compound, the value Z can be adjusted by selecting the component (A) and the component (B) and adjusting the content of the component (A) and the content of the component (B)fFalling within the above range.
The resin composition can be made into a resin varnish by containing, for example, a solvent. In addition, from the viewpoint of achieving the desired effect of the present invention, it is preferable to dry the resin varnish and use the resin composition in a B-stage state or in a film shape.
< Properties and applications of cured product of resin composition >
(Long term reliability)
A cured product obtained by thermally curing the resin composition of the present invention is generally excellent in long-term reliability. The long-term reliability can be evaluated according to the following description of < evaluation of long-term reliability >. For example, a cured product obtained by thermally curing the resin composition at 180 ℃ for 90 minutes preferably has a small absolute value of the change degree of the tensile breaking point strength before and after the HTS test (for example, less than 20% or 10% or less).
(suppression of warpage)
When a cured product obtained by thermally curing the resin composition of the present invention is formed on a substrate, warpage of the substrate is generally suppressed. The warpage can be evaluated according to the following description of < evaluation of warpage >. For example, the maximum warpage amount that can be generated in a substrate having a cured product with a thickness of 300 μm formed thereon, which is obtained by thermally curing the resin composition at 180 ℃ for 90 minutes, may be 2000 μm or less.
(drug resistance)
A cured product obtained by thermally curing the resin composition of the present invention generally exhibits excellent chemical resistance. The chemical resistance can be evaluated according to the following description < evaluation of chemical resistance >. For example, a cured product having a thickness of 100 μm obtained by thermally curing the resin composition at 180 ℃ for 90 minutes may have a mass reduction rate of 1 mass% or less before and after the cured product is immersed in a strong alkaline aqueous solution (for example, an aqueous potassium hydroxide solution, a tetramethylammonium hydroxide solution, an aqueous sodium hydroxide solution, or an aqueous sodium carbonate solution).
(glass transition temperature Tg)
The glass transition temperature Tg (c) of a cured product obtained by thermally curing the resin composition of the present invention is preferably in the range of 150 to 240 ℃. More preferable ranges and the like are as described above for the resin composition.
(average linear thermal expansion coefficient. alpha.)
The cured product obtained by thermally curing the resin composition of the present invention preferably has a small average linear thermal expansion coefficient α in order to improve the desired effect of the present invention. More preferable ranges and the like are as described above for the resin composition.
(storage modulus at a prescribed temperature T (K))
The storage modulus E' at a predetermined temperature T (K) of a cured product obtained by thermally curing the resin composition of the present invention is usually 2.00X 109Pa or less. The preferred ranges and the like are as described above for the resin composition.
(crosslink Density n)
The cured product obtained by thermally curing the resin composition of the present invention preferably has a crosslinking density n of 0.15mol/cm from the viewpoint of improving the desired effect of the present invention3The following. More preferable ranges and the like are as described above for the resin composition.
(value Z)f)
The cured product obtained by thermally curing the resin composition of the present invention preferably satisfies a value Z obtained by dividing the average linear thermal expansion coefficient α by the crosslinking density nf(ppm・cm3Seed with/mol K) of 145 < Zf< 1300, more preferably 150. ltoreq. Zf. ltoreq.1000. As demonstrated exemplarily in the column of examples, such a cured product is suppressed in warpage and excellent in long-term reliability. More preferable ranges and the like are as described above for the resin composition.
The resin composition of the present invention has excellent long-term reliability, while suppressing warpage of a cured product thereof. Therefore, the cured product of the resin composition of the present invention can be suitably used as an insulating layer of a printed wiring board, and can be more suitably used as an interlayer insulating layer of a printed wiring board. Further, the cured product of the resin composition of the present invention has an insulating layer with suppressed warpage and excellent long-term reliability, and therefore, can be suitably used also in the case where a printed wiring board is a component-embedded circuit board. Further, the cured product of the resin composition of the present invention has an insulating layer formed from a cured product with suppressed warpage and excellent long-term reliability, and therefore can be used more suitably as a solder resist layer. Further, the cured product of the resin composition of the present invention has an insulating layer formed of a cured product with suppressed warpage, and therefore can be suitably used as a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation. The cured product of the resin composition of the present invention can be suitably used as a rewiring-forming layer (insulating layer) for forming a rewiring layer in semiconductor chip packaging.
[ resin sheet ]
The resin sheet of the present invention comprises a support and a resin composition layer comprising the resin composition of the present invention provided on the support. The resin composition layer may be in a B-stage state.
The thickness of the resin composition layer of the resin sheet is usually 150 μm or less, preferably 110 μm or less, and may be 50 μm or less or 40 μm or less from the viewpoint of thinning of the printed wiring board. The thickness can be further reduced. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and 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 abbreviated as "PET") and polyethylene naphthalate (hereinafter, sometimes abbreviated as "PEN"), polycarbonates (hereinafter, sometimes abbreviated as "PC"), acrylates such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. 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 single metal foil containing copper may be used, and a foil containing 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 matte treatment, corona treatment, or antistatic treatment on the surface bonded to the resin composition layer.
In addition, as the support, a support with a release layer having a release layer on a surface bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a releasing layer, commercially available products can be used, and examples thereof include "SK-1", "AL-5" and "AL-7" manufactured by リンテック, a "ルミラー T60" manufactured by east レ, a "ピューレックス" manufactured by imperial corporation, a "ユニピール" manufactured by ユニチカ, and the like, which are PET films having a releasing layer containing an alkyd resin-based releasing agent as a main component.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In the case of using the support with the release layer, the thickness of the entire support with the release layer is preferably in the above range.
In one embodiment, the resin sheet may further include other layers as necessary. Examples of the other layer include a protective film for the support provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support), and the like. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dirt or the like to the surface of the resin composition layer and scratches can be suppressed.
The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in a solvent, applying the resin varnish onto a support using a die coater or the like, and further drying the resin varnish to form a resin composition layer.
Examples of the organic solvent include ketones such as acetone, Methyl Ethyl Ketone (MEK), 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; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the organic solvent in the resin composition layer is dried so that the content thereof is 10 mass% or less, preferably 5 mass% or less. When a resin varnish containing 30 to 60 mass% of an organic solvent is used, for example, the resin varnish can be dried at 50 to 150 ℃ for 3 to 10 minutes to form a resin composition layer, depending on the boiling point of the organic solvent in the resin varnish.
The resin sheet can be wound into a roll and stored. In the case where the resin sheet has a protective film, the protective film may be peeled off for use.
The resin sheet of the present invention has an insulating layer formed of a cured product which is suppressed in warpage and has excellent long-term reliability. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a printed wiring board (resin sheet for forming an insulating layer of a printed wiring board), and can be more suitably used as a resin sheet for forming an interlayer insulating layer of a printed wiring board (resin sheet for an interlayer insulating layer of a printed wiring board). The resin sheet of the present invention can be suitably used as a resin sheet for forming a solder resist layer of a printed wiring board (a solder resist layer-forming resin sheet for a printed wiring board). The resin sheet of the present invention has an insulating layer formed of a cured product with suppressed warpage, and therefore can be suitably used as a resin composition for forming a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation (a resin sheet for forming a sealing layer for semiconductor chip encapsulation). Further, the resin sheet of the present invention can be suitably used as a resin sheet for forming a rewiring-forming layer (insulating layer) of a semiconductor chip package (rewiring-forming resin sheet for semiconductor chip package).
< printed wiring board >
The printed wiring board of the present invention comprises an insulating layer formed from a cured product of the resin composition of the present invention. The printed wiring board can be manufactured by a manufacturing method including, for example, the following steps (1) and (2).
(1) A step of forming a resin composition layer containing the resin composition on a substrate using the resin composition of the present invention.
(2) And a step of forming an insulating layer by thermally curing the resin composition layer.
In step (1), a substrate is prepared. Examples of the base material include substrates such as a glass epoxy substrate, a metal substrate (stainless steel, cold-rolled steel Sheet (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a metal layer such as a copper foil on the surface as a part of the substrate. For example, a substrate having a peelable first metal layer and a peelable second metal layer on both surfaces may be used. When such a substrate is used, a conductor layer, which is a wiring layer capable of functioning as a circuit wiring, is usually formed on the surface of the second metal layer opposite to the first metal layer. Examples of the substrate having such a metal layer include an extra Thin copper foil "Micro Thin" with a carrier copper foil manufactured by mitsui metal mining.
Further, on one or both surfaces of the substrate, a conductor layer may be formed. In the following description, a member including a base material and a conductor layer formed on a surface of the base material is sometimes referred to as a "base material with a wiring layer" as appropriate. Examples of the conductor material included in the conductor layer include materials containing 1 or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductor material, a single metal or an alloy may be used. Examples of the alloy include alloys of 2 or more metals selected from the above-mentioned group (for example, nickel, copper, and/or chromium alloys, copper, and/or a seed, and/or copper, and/or a copper, and/. Among them, from the viewpoint of versatility of conductor layer formation, cost, and easiness of pattern formation, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal is preferable; and alloys of nickel, seeds, and seeds as alloys. Among them, a monometal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is more preferable; and, nickel-seeded chromium alloys, with copper being particularly preferred as the monometallic metal.
The conductor layer may be patterned to function as a wiring layer, for example. In this case, the ratio of the line (circuit width)/pitch (width between circuits) of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (i.e., pitch of 40 μm or less), more preferably 10/10 μm or less, further preferably 5/5 μm or less, further preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The pitch need not be the same across the entirety of the conductor layers. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.
The thickness of the conductor layer varies depending on the design of the printed wiring board, and is preferably 3 to 35 μm, more preferably 5 to 30 μm, still more preferably 10 to 20 μm, and particularly preferably 15 to 20 μm.
The conductor layer may be formed, for example, by a method including: a step of laminating a dry film (photosensitive resist film) on a substrate; a step of exposing and developing the dry film under a predetermined condition using a photomask to form a pattern, thereby obtaining a dry film pattern; forming a conductor layer by a plating method such as an electrolytic plating method using the developed pattern dry film as a plating mask; and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film containing a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The conditions for laminating the base material and the dry film may be the same as those for laminating the base material and the resin sheet described later. The dry film can be peeled off using an alkaline peeling solution such as a sodium hydroxide solution.
After preparing the base material, a resin composition layer is formed on the base material. In the case where the conductor layer is formed on the surface of the base material, the resin composition layer is preferably formed so that the conductor layer is embedded in the resin composition layer.
The resin composition layer is formed by, for example, laminating a resin sheet and a base material. The lamination can be performed, for example, by thermally pressing a resin sheet on a base material from the support side to bond a resin composition layer on the base material. Examples of the member for thermally and pressure-bonding the resin sheet to the base material (hereinafter, sometimes referred to as "thermally and pressure-bonding member") include a heated metal plate (e.g., SUS mirror plate) and a metal roll (e.g., SUS roll). It is preferable that the heating and pressure-bonding member is not directly pressed on the resin sheet, and is pressed through an elastic material such as a heat-resistant rubber so as to sufficiently follow the uneven surface of the base material.
The lamination of the substrate and the resin sheet may be performed, for example, by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably 60-160 ℃, and more preferably 80-140 ℃. The pressure of the heat-pressure bonding is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47 MPa. The heating and pressure bonding time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 13hPa or less.
After lamination, the smoothing treatment of the laminated resin sheets may be performed by, for example, pressing the heat and pressure bonding member from the support body side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment may be the same as the above-described conditions for the heat and pressure bonding of the laminate. The lamination and smoothing treatment may be continuously performed using a vacuum laminator.
Further, the formation of the resin composition layer may be performed by, for example, a compression molding method. The molding conditions may be the same as the method of forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package described later.
After the resin composition layer is formed on the base material, the resin composition layer is thermally cured to form the insulating layer. The thermosetting condition of the resin composition layer is different according to the kind of the resin composition, the curing temperature is generally in the range of 120 ℃ to 240 ℃ (preferably in the range of 150 ℃ to 220 ℃, and more preferably in the range of 170 ℃ to 200 ℃), and the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, and more preferably in the range of 15 minutes to 90 minutes).
Before the resin composition layer is thermally cured, a preliminary heat treatment of heating at a lower temperature than the curing temperature may be performed on the resin composition layer. For example, the resin composition layer may be preheated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) at a temperature of usually 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 110 ℃ or less, more preferably 70 ℃ or more and 100 ℃ or less) before the resin composition layer is thermally cured.
In the above manner, a printed wiring board having an insulating layer can be manufactured. The method for manufacturing a printed wiring board may further include any steps.
For example, in the case of manufacturing a printed wiring board using a resin sheet, the method for manufacturing a printed wiring board may include a step of peeling off a support of the resin sheet. The support may be peeled off before the thermosetting of the resin composition layer, or may be peeled off after the thermosetting of the resin composition layer.
The method for manufacturing a printed wiring board may include, for example, a step of polishing the surface of the insulating layer after the insulating layer is formed. The polishing method is not particularly limited. For example, the surface of the insulating layer may be ground using a flat grinding disk.
The method for manufacturing a printed wiring board may include, for example, the step (3) of interlayer-connecting conductor layers, and the step of opening a hole in an insulating layer, for example. This makes it possible to form a via hole, a through hole, or the like in the insulating layer. Examples of the method for forming the via hole include laser irradiation, etching, and mechanical drilling. The size and shape of the via hole may be appropriately determined according to the design of the printed wiring board. In step (3), the interlayer connection may be performed by polishing or grinding the insulating layer.
After the formation of the via hole, it is preferable to perform a step of removing the smear in the via hole. This step is sometimes referred to as a desmear step. For example, when the conductor layer is formed on the insulating layer by a plating step, wet desmearing treatment may be performed on the via hole. Further, in the case where the formation of the conductor layer on the insulating layer is performed by a sputtering step, a dry desmearing step such as a plasma treatment step may be performed. Further, by the desmear step, the insulating layer may be subjected to roughening treatment.
Further, before forming the conductor layer on the insulating layer, roughening treatment may be performed on the insulating layer. According to the roughening treatment, the surface of the insulating layer including the via hole is usually roughened. As the roughening treatment, any of dry and wet roughening treatments may be performed. Examples of the dry roughening treatment include plasma treatment. In addition, as an example of the wet roughening treatment, there is a method in which swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralizing treatment with a neutralizing liquid are sequentially performed.
After the via hole is formed, a conductor layer may be formed on the insulating layer. By forming a conductor layer at the position where the via hole is formed, the newly formed conductor layer is conducted to the conductor layer on the surface of the base material, and interlayer connection is performed. Examples of the method for forming the conductor layer include plating, sputtering, and vapor deposition, and among them, plating is preferred. In a preferred embodiment, a conductor layer having a desired wiring pattern is formed by plating on the surface of the insulating layer by an appropriate method such as a semi-additive method or a full-additive method. In the case where the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. The conductor layer may have a single-layer structure or a multilayer structure including 2 or more layers of different materials.
Here, an example of an embodiment in which a conductor layer is formed over an insulating layer will be described in detail. On the surface of the insulating layer, a plating seed layer is formed by electroless plating. 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. An electroplating layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed. The dry film used for forming the mask pattern when forming the conductor layer is the same as the dry film described above.
The method for manufacturing a printed wiring board may include the step (4) of removing the base material. The base material is removed to obtain a printed wiring board having an insulating layer and a conductor layer embedded in the insulating layer. This step (4) can be performed, for example, when a substrate having a peelable metal layer is used.
< semiconductor chip Package >
A semiconductor chip package according to a first embodiment of the present invention includes the printed wiring board and a semiconductor chip mounted on the printed wiring board. The semiconductor chip package can be manufactured by bonding a semiconductor chip on a printed wiring board.
The conditions for bonding the printed wiring board and the semiconductor chip may be any conditions that can connect the terminal electrodes of the semiconductor chip to the circuit wiring conductors of the printed wiring board. For example, conditions used in flip-chip mounting of a semiconductor chip may be employed. Further, for example, the semiconductor chip and the printed wiring board may be bonded to each other via an insulating adhesive.
As an example of the bonding method, a method of pressure-bonding a semiconductor chip to a printed wiring board is given. The pressure bonding temperature is usually 120 to 240 ℃ (preferably 130 to 200 ℃, and more preferably 140 to 180 ℃), and the pressure bonding time is usually 1 to 60 seconds (preferably 5 to 30 seconds), as the pressure bonding conditions.
As another example of the bonding method, a method of bonding a semiconductor chip by reflowing the semiconductor chip on a printed wiring board is given. The reflux condition can be set to be in the range of 120-300 ℃.
After the semiconductor chip is bonded on the printed wiring board, the semiconductor chip may be filled with a mold underfill material. The resin composition may be used as the mold underfill material, and the resin sheet may be used.
A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition sealing the semiconductor chip. In such a semiconductor chip package, a cured product of the resin composition generally functions as an encapsulating layer. An example of the semiconductor chip package according to the second embodiment is a Fan-out (Fan-out) WLP.
The method of manufacturing such a semiconductor chip package may include:
(A) a step of laminating a pre-fixing film on a base material;
(B) a step of pre-fixing the semiconductor chip on the pre-fixing film;
(C) a step of forming a sealing layer on the semiconductor chip;
(D) a step of peeling the substrate and the pre-fixing film from the semiconductor chip;
(E) a step of forming a rewiring formation layer as an insulating layer on a surface from which the base material of the semiconductor chip and the pre-fixing film are peeled;
(F) a step of forming a rewiring layer as a conductor layer on the rewiring-forming layer; and
(G) and forming a solder resist layer on the rewiring layer.
In addition, the aforementioned method of manufacturing a semiconductor chip package may include:
(H) and a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and singulating the individual semiconductor chip packages.
(step (A))
The step (a) is a step of laminating a pre-fixing film on a base material. The lamination conditions of the base material and the pre-fixing film may be the same as those of the base material and the resin sheet in the manufacturing method of the printed wiring board.
Examples of the substrate include silicon wafers; a glass wafer; a glass substrate; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel Sheet (SPCC); substrates such as FR-4 substrates, which are heat cured by impregnating glass fibers with epoxy resin or the like; and substrates comprising bismaleimide triazine resins such as BT resins.
The pre-fixing film can be made of any material that can be peeled off from the semiconductor chip and can pre-fix the semiconductor chip. Examples of commercially available products include "リヴァ α" manufactured by Nindon electric engineering Co.
(step (B))
The step (B) is a step of pre-fixing the semiconductor chip on the pre-fixing film. The pre-fixing of the semiconductor chip may be performed using a device such as a flip chip bonder, a die bonder or the like. The layout and the number of arrangements of the semiconductor chips may be appropriately set according to the shape and size of the pre-fixing film, the number of productions of the target semiconductor chip package, and the like. For example, the semiconductor chips may be arranged in a matrix of a plurality of rows and a plurality of columns and may be pre-fixed.
(step (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed by curing the resin composition. The sealing layer is typically formed by: the step of forming a resin composition layer on a semiconductor chip, and the step of forming a sealing layer by thermally curing the resin composition layer.
The formation of the resin composition layer is preferably performed by compression molding. In the compression molding method, the semiconductor chip and the resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor chip.
The specific operation of the compression molding method can be performed, for example, as follows. An upper mold and a lower mold were prepared as a mold for compression molding. Further, as described above, the resin composition is applied to the semiconductor chip preliminarily fixed on the preliminary fixing film. The semiconductor chip coated with the resin composition is mounted in a lower mold together with a base material and a pre-fixing film. Thereafter, the upper mold and the lower mold are closed, and heat and pressure are applied to the resin composition to perform compression molding.
Further, the specific operation of the compression molding method can be performed, for example, as follows. An upper mold and a lower mold were prepared as a mold for compression molding. The resin composition is placed in a lower mold. Further, the semiconductor chip is mounted together with the base material and the pre-fixing film in the upper mold. Thereafter, the upper mold and the lower mold are closed so that the resin composition placed on the lower mold comes into contact with the semiconductor chip mounted on the upper mold, and heat and pressure are applied to the mold to perform compression molding.
The molding conditions vary depending on the composition of the resin composition, and appropriate conditions may be adopted so as to achieve good sealing. For example, the temperature of the mold at the time of molding is preferably 70 ℃ or higher, more preferably 80 ℃ or higher, particularly preferably 90 ℃ or higher, preferably 200 ℃ or lower, more preferably 170 ℃ or lower, and particularly preferably 150 ℃ or lower. The pressure applied during molding is preferably 1MPa or more, more preferably 3MPa or more, particularly preferably 5MPa or more, preferably 50MPa or less, more preferably 30MPa or less, and particularly preferably 20MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. Generally, after the formation of the resin composition layer, the mold is disassembled. The detachment of the mold may be performed before or after the thermosetting of the resin composition layer.
The resin composition layer may be formed by laminating a resin sheet and a semiconductor chip. For example, the resin composition layer of the resin sheet can be formed on the semiconductor chip by thermally and pressure-bonding the resin composition layer to the semiconductor chip. The lamination of the resin sheet and the semiconductor chip is usually performed in the same manner as the lamination of the resin sheet and the base material in the method for manufacturing the printed wiring board, by using the semiconductor chip instead of the base material.
After a resin composition layer is formed on a semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thus, the semiconductor chip is sealed with the cured product of the resin composition. The conditions for the thermal curing of the resin composition layer may be the same as those for the thermal curing of the resin composition layer in the method for producing a printed wiring board. Further, before the resin composition layer is thermally cured, a preliminary heat treatment of heating at a temperature lower than the curing temperature may be performed on the resin composition layer. The process conditions for this preliminary heating process may be the same as those for the preliminary heating process in the manufacturing method of the printed wiring board.
(step (D))
The step (D) is a step of peeling the substrate and the pre-fixing film from the semiconductor chip. The peeling method is preferably an appropriate method depending on the material of the pre-fixing film. Examples of the peeling method include a method in which the pre-fixing film is peeled off by heating, foaming, or expanding. In addition, as a peeling method, for example, a method of irradiating ultraviolet rays to a pre-fixed film through a base material to reduce the adhesive force of the pre-fixed film and peeling off may be mentioned.
In the method of peeling the pre-fixed film by heating, foaming or expanding, the heating condition is usually 1 second to 90 seconds or 5 minutes to 15 minutes at 100 ℃ to 250 ℃. In the method of peeling the pre-fixing film by reducing the adhesive force of the pre-fixing film by irradiating with ultraviolet light, the irradiation amount of ultraviolet light is usually 10mJ/cm2~1000mJ/cm2。
(step (E))
The step (E) is a step of forming a rewiring formation layer as an insulating layer on a surface of the semiconductor chip from which the base material and the pre-fixing film are peeled.
Any insulating material may be used as the material of the rewiring layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Further, as the thermosetting resin, the resin composition of the present invention can be used.
After the rewiring layer is formed, a via hole may be formed in the rewiring layer in order to connect the semiconductor chip and the rewiring layer between layers.
In the method of forming a via hole in the case where the material of the rewiring formation layer is a photosensitive resin, the rewiring formation layer of the irradiation portion is usually photo-cured by irradiating the surface of the rewiring formation layer with an active energy ray through a mask pattern. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The irradiation amount and the irradiation time of the ultraviolet ray can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern and the rewiring line forming layer are exposed to light in close contact, and a non-contact exposure method in which the mask pattern and the rewiring line forming layer are exposed to light using parallel light without being in close contact.
After the rewiring formation layer is photocured, the rewiring formation layer is developed, and the unexposed portions are removed to form the via hole. The development may be either wet development or dry development. Examples of the developing method include a dipping method, a paddle method, a spraying method, a brushing method, and a wiping method, and the paddle method is suitable from the viewpoint of resolution.
Examples of a method for forming a via hole in the case where the rewiring formation layer is made of a thermosetting resin include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferable. The laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, a UV-YAG laser, or an excimer laser.
The shape of the via hole is not particularly limited, and is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole at the surface of the rewiring formation layer.
(step (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring-forming layer. The method of forming the rewiring layer on the rewiring-forming layer may be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing the printed wiring board. Further, the step (E) and the step (F) may be repeated to alternately stack the rewiring layer and the rewiring-forming layer (build-up layer).
(step (G))
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any material having insulating properties can be used as the material of the solder resist layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Further, as the thermosetting resin, the resin composition of the present invention can be used.
In step (G), a bump process for forming a bump may be performed as necessary. The bumping process may be performed by a method of solder ball, solder plating, or the like. The formation of the via hole in the bump processing may be performed in the same manner as in step (E).
(step (H))
The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (a) to (G). The step (H) is a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and singulating the individual semiconductor chip packages. The method of cutting the semiconductor chip package into individual semiconductor chip packages is not particularly limited.
< semiconductor device >
The semiconductor device has a semiconductor chip package. Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, smartphones, tablet computers, wearable devices, digital cameras, medical devices, televisions, and the like) and passenger tools (for example, motorcycles, automobiles, trains, ships, airplanes, and the like).
Examples
The present invention will be specifically explained below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "part" and "%" representing amounts mean "part by mass" and "% by mass", respectively, unless otherwise explicitly stated. The operations described below are performed under an ambient temperature and pressure environment, unless otherwise explicitly described.
< preparation of thermoplastic resin solution A >
In a reaction vessel, 69G of 2-functional hydroxyl-terminated polybutadiene ("G-3000" manufactured by Nippon Caoda corporation, number-average molecular weight: 3000, hydroxyl equivalent: 1800G/eq.), 40G of an aromatic hydrocarbon-based mixed solvent ("イプゾール 150" manufactured by Takara Shuzo chemical corporation), and 0.005G of dibutyltin laurate were charged and mixed and dissolved uniformly. Thus, a solution was obtained. The solution was heated to 60 ℃ and 8g of isophorone diisocyanate (IPDI, manufactured by エボニックデグサジャパン Co., Ltd.; isocyanate group equivalent: 113g/eq.) was added while stirring, and the reaction was carried out for about 3 hours. Thus, a1 st reaction solution was obtained.
Then, 23g of cresol novolak resin ("KA-1160" manufactured by DIC corporation and having a hydroxyl equivalent of 117g/eq.) and 60g of ethyl diglycol acetate (manufactured by ダ イ セル corporation) were added to the first reaction solution 1, and the mixture was heated to 150 ℃ while stirring, and the reaction was carried out for about 10 hours. Thus, a2 nd reaction solution was obtained. 2250cm by FT-IR-1The disappearance of NCO peak (2) was confirmed. The reaction solution 2 was cooled to room temperature, taking the disappearance of the NCO peak as the end point of the reaction. Then, the 2 nd reaction solution was filtered through a 100 mesh filter cloth. Thus, as the filtrate, a solution containing the thermoplastic resin a having a reactive functional group (phenolic hydroxyl group-containing polybutadiene resin) as a nonvolatile component (nonvolatile component 50 mass%; hereinafter referred to as "thermoplastic resin solution a") was obtained. The number average molecular weight of the thermoplastic resin A was 5900, and the glass transition temperature was-7 ℃.
< preparation of thermoplastic resin solution B >
In a flask equipped with a stirrer, a thermometer and a capacitor, 368.41g of ethyl diglycol acetate and 368.41g of "ソルベッソ 150 (registered trademark)" (aromatic solvent) manufactured by エクソンモービル were charged as solvents. Further, 100.1g (0.4 mol) of diphenylmethane diisocyanate and 400g (0.2 mol) of polycarbonate diol (C-2015N manufactured by クラレ, number average molecular weight: about 2000, hydroxyl equivalent: 1000g/eq., nonvolatile matter: 100 mass%) were charged into the flask, and the reaction was carried out at 70 ℃ for 4 hours. Thus, a1 st reaction solution was obtained.
Next, 195.9g (0.2 mol) of nonylphenol novolak resin (hydroxyl equivalent: 229.4g/eq, average 4.27 functions, average calculated molecular weight: 979.5 g/mol) andethylene glycol bis (anhydrous trimellitate) 41.0g (0.1 mol) took 2 hours, and the reaction was carried out at 150 ℃ for 12 hours. Thus, a2 nd reaction solution was obtained. 2250cm by FT-IR-1The disappearance of NCO peak (2) was confirmed. Upon confirmation of disappearance of NCO peak, the reaction solution of the 2 nd reaction was cooled to room temperature as the end point of the reaction. Then, the 2 nd reaction solution was filtered through a 100 mesh filter cloth. Thus, a solution containing the thermoplastic resin B having a reactive functional group (a polycarbonate resin containing a phenolic hydroxyl group) as a nonvolatile component (nonvolatile component 50 mass%; hereinafter referred to as "thermoplastic resin solution B") was obtained as a filtrate. The number average molecular weight of the thermoplastic resin B was 6100, and the glass transition temperature was 5 ℃.
[ example 1]
< preparation of resin varnish A >
3 parts of bisphenol A epoxy resin ("JeR 828 EL" manufactured by Mitsubishi chemical corporation), epoxy equivalent: 184-194 g/eq.) as a component (A), 1 part of biphenyl type epoxy resin ("NC 3000L" manufactured by Nippon chemical corporation, epoxy equivalent: 276g/eq.) as a component (A), 2 parts of glycidyl amine type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq.) as a component (A), 2 parts of cresol novolac resin ("KA-1160" manufactured by DIC corporation, phenolic hydroxyl equivalent: 117g/eq.) as a component (B-2), 1.54 parts of active ester resin ("HPC-8000-65T" manufactured by DIC corporation, active group equivalent: about 223, toluene solution of 65 mass% of nonvolatile component) as a component (B-2), and "I-eq" manufactured by デザイナーモレキュールズ "manufactured by BMI-1" as a component (B-1) 689 "), 4 parts of an inorganic filler a70 part as the component (C), a thermoplastic resin solution a (nonvolatile content: 50%), 0.05 part of a curing accelerator (product of national chemical industry Co., Ltd., "1B 2 PZ") as the component (E) and 15 parts of methyl ethyl ketone as the solvent were mixed and uniformly dispersed in a high-speed rotary mixer. In this manner, a resin varnish was prepared. Hereinafter, the resin varnishes prepared as described below are also collectively referred to as "resin varnish a".
Here, the inorganic filler A is an amino silane coupling agent (KBM 573, manufactured by shin-Etsu chemical Co., Ltd.)") surface-treated spherical silica (" SO-C2 "manufactured by アドマテックス Co.), the average particle diameter thereof was measured to be 0.5 μm, and the specific surface area thereof was measured to be 5.8m2/g。
< production of resin sheet B >
As the support, a PET film (ルミラー R80, manufactured by east レ, thickness: 38 μm, softening point: 130 ℃ C., and hereinafter sometimes referred to as "release PET") whose one main surface was subjected to a release treatment with an alkyd resin-based release agent ("AL-5", manufactured by リンテック) was prepared.
The resin varnish A was uniformly applied to the release-treated surface of the release PET by the film coater so that the thickness of the dried resin composition layer became 100. mu.m. Thereafter, the resin varnish A was dried at 80 ℃ to 120 ℃ (average 100 ℃) for 6 minutes. Thus, a resin sheet comprising a support and a resin composition layer comprising a resin composition provided on the support was obtained. Hereinafter, the resin sheet produced in this manner is also referred to as "resin sheet B".
< preparation of cured product C for evaluation >
A part of the resin sheet B was cut out, and heated at 180 ℃ for 90 minutes to thermally cure the resin composition layer. Thereafter, the support was peeled off to obtain a cured product for evaluation. Hereinafter, the cured product for evaluation produced in this manner is also referred to as "cured product for evaluation C".
< acquisition and evaluation of various parameters of cured product of resin composition >
The resin composition layer of the resin sheet B or the cured product C for evaluation was evaluated by the evaluation method described later from the viewpoint of warpage and long-term reliability while obtaining various parameters for the cured product of the resin composition. Further, the cured product C for evaluation was evaluated by the evaluation method described below from the viewpoint of chemical resistance.
[ example 2]
In example 1, 70 parts of the inorganic filler a as the component (a) was changed to 115 parts of the inorganic filler B. Here, the inorganic filler B is made by shin-Etsu chemical industries, LtdSpherical alumina treated with "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) was used with a maximum cleavage diameter of 5 μm. As a result of the measurement, the inorganic filler B had an average particle diameter of 1.5 μm and a specific surface area of 2.0m2/g。
In the same manner as in example 1 except for the above matters, resin varnish a containing a resin composition was prepared. Then, using the resin varnish a, a resin sheet B and a cured product C for evaluation were obtained in the same manner as in example 1, and using the resin composition layer of the resin sheet B and the cured product C for evaluation, a cured product of the resin composition was evaluated in the same manner as in example 1.
[ example 3]
In example 1,3 parts of bisphenol A epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation), 1 part of biphenyl type epoxy resin ("NC 3000L" manufactured by Nippon chemical corporation), 2 parts of glycidyl amine type epoxy resin ("630" manufactured by Mitsubishi chemical corporation), 2 parts of bisphenol A type epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 184 to 194g/eq.)2 parts of naphthalene type epoxy resin ("HP 4032" manufactured by DIC corporation, epoxy equivalent: 135 to 165g/eq.) and 2 parts of biphenyl type epoxy resin ("YX 4000" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq.) were changed as the component (A).
Further, in example 1,2 parts of cresol novolak resin ("KA-1160" from DIC) as the component (B-2), 1.54 parts of active ester resin ("HPC-8000-65T" from DIC) as the component (B-2), 4 parts of maleimide compound ("BMI-689" from デザイナーモレキュールズ) as the component (B-1), 1 part of cresol novolak resin ("KA-1160" from DIC) as the component (B-2), and 4 parts of maleimide compound ("BMI-689" from デザイナーモレキュールズ) as the component (B-1) were changed.
Further, in example 1, 20 parts of the thermoplastic resin solution A (nonvolatile content: 50%) as the component (D), 12 parts of the thermoplastic resin solution A (nonvolatile content: 50%) as the component (D), and 12 parts of the thermoplastic resin solution B (nonvolatile content: 50%) as the component (D) were changed. In example 1, the curing accelerator (product of chemical industries of four nations, "1B 2 PZ") was changed to 0.05 part as the component (E) and 0.05 part as the curing accelerator (4-Dimethylaminopyridine (DMAP)) was changed to the component (E).
In the same manner as in example 1 except for the above matters, resin varnish a containing a resin composition was prepared. Then, using the resin varnish a, a resin sheet B and a cured product C for evaluation were obtained in the same manner as in example 1, and using the resin composition layer of the resin sheet B and the cured product C for evaluation, a cured product of the resin composition was evaluated in the same manner as in example 1.
Comparative example 1
In example 1, the components (A) were changed to 3 parts of bisphenol A epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation), 1 part of biphenyl epoxy resin ("NC 3000L" manufactured by Mitsubishi chemical corporation) and 2 parts of glycidyl amine epoxy resin ("630" manufactured by Mitsubishi chemical corporation), 1 part of bisphenol A epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation and having an epoxy equivalent of 184 to 194g/eq.), 6 parts of naphthalene epoxy resin ("HP 4032" manufactured by DIC and having an epoxy equivalent of 135 to 165g/eq.), and 1 part of biphenyl epoxy resin ("NC 3000L" manufactured by Mitsubishi chemical corporation and having an epoxy equivalent of 276 g/eq.).
Further, in example 1,2 parts of cresol novolak resin ("KA-1160" from DIC) as the component (B-2), 1.54 parts of active ester resin ("HPC-8000-65T" from DIC ") as the component (B-2), 4 parts of maleimide compound (" BMI-689 "from デザイナーモレキュールズ) as the component (B-1), and 4.62 parts of active ester resin (" HPC-8000-65T "from DIC) as the component (B-2) were changed. The component (B-1) is not used.
In example 1, the components (C) were changed to 70 parts of the inorganic filler a and 60 parts of the inorganic filler a. Further, in example 1, the components (D) were changed to 20 parts of the thermoplastic resin solution A (nonvolatile component: 50%) and 16 parts of the thermoplastic resin solution B (nonvolatile component: 50%). In example 1, the components (E) were changed to 0.05 parts of a curing accelerator (product of Sizhou chemical industry Co., Ltd. "1B 2 PZ") and 0.10 parts of a curing accelerator (product of Sizhou chemical industry Co., Ltd. "1B 2 PZ").
In the same manner as in example 1 except for the above matters, resin varnish a containing a resin composition was prepared. Then, using the resin varnish a, a resin sheet B and a cured product C for evaluation were obtained in the same manner as in example 1, and using the resin composition layer of the resin sheet B and the cured product C for evaluation, a cured product of the resin composition was evaluated in the same manner as in example 1.
Comparative example 2
In example 1, the components (A) were changed to 3 parts of bisphenol A epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation), 1 part of biphenyl epoxy resin ("NC 3000L" manufactured by Nippon chemical corporation) and 2 parts of glycidyl amine epoxy resin ("630" manufactured by Mitsubishi chemical corporation), 1 part of bisphenol A epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 184-194 g/eq.), 4 parts of biphenyl epoxy resin ("NC 3000L" manufactured by Nippon chemical corporation, epoxy equivalent: 276g/eq.), and 2 parts of biphenyl epoxy resin ("YX 4000" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185 g/eq.).
Further, in example 1,2 parts of a cresol novolak resin (KA-1160, phenolic hydroxyl equivalent: 117g/eq.) as the component (B-2), 1.54 parts of an active ester resin (HPC-8000-65T, manufactured by DIC) as the component (B-2), 4 parts of a maleimide compound (BMI-689, manufactured by デザイナーモレキュールズ) as the component (B-1), 2 parts of a cresol novolak resin (KA-1160, phenolic hydroxyl equivalent: 117g/eq.) as the component (B-2), and 6.16 parts of an active ester resin (HPC-8000-65T, manufactured by DIC) as the component (B-2) were changed. The component (B-1) is not used.
In example 1, the components (C) were changed to 70 parts of the inorganic filler a and 50 parts of the inorganic filler a. Further, in example 1, 5.71 parts of an epoxy group-containing phenoxy resin ("YX 7200B 35", manufactured by Mitsubishi chemical corporation, epoxy equivalent: 3000 to 16000g/eq., nonvolatile: 35%) was used in place of 20 parts of the thermoplastic resin solution A (nonvolatile: 50%) as the component (D). In example 1, the components (E) were changed to 0.05 parts of a curing accelerator (product of Sizhou chemical industry Co., Ltd., "1B 2 PZ") and 0.10 parts of a curing accelerator (product of Sizhou chemical industry Co., Ltd., "1B 2 PZ").
In the same manner as in example 1 except for the above matters, resin varnish a containing a resin composition was prepared. Then, using the resin varnish a, a resin sheet B and a cured product C for evaluation were obtained in the same manner as in example 1, and using the resin composition layer of the resin sheet B and the cured product C for evaluation, a cured product of the resin composition was evaluated in the same manner as in example 1.
Comparative example 3
In example 1,3 parts of bisphenol A epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation), 1 part of biphenyl type epoxy resin ("NC 3000L" manufactured by Mitsubishi chemical corporation), 2 parts of glycidyl amine type epoxy resin ("jER 630" manufactured by Mitsubishi chemical corporation), 2 parts of bisphenol A type epoxy resin ("jER 828 EL" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 184-194 g/eq.)2 parts of biphenyl type epoxy resin ("NC 3000L" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 276g/eq.)1 part of glycidyl amine type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq.) were changed as the component (A).
Further, in example 1,2 parts of a cresol novolak resin (KA-1160, manufactured by DIC Co.) as the component (B-2), 1.54 parts of an active ester resin (manufactured by DIC Co., HPC-8000-65T) as the component (B-2), 4 parts of a maleimide compound (BMI-689, manufactured by デザイナーモレキュールズ Co., Ltd.) as the component (B-1), 2 parts of a cresol novolak resin (KA-1160, manufactured by DIC Co., phenolic hydroxyl equivalent: 117g/eq.) as the component (B-2), and 1.54 parts of an active ester resin (manufactured by DIC Co., Ltd., "HPC-8000-65T") as the component (B-2) were changed. The component (B-1) is not used.
In example 1, the components (C) were changed to 70 parts of the inorganic filler a and 40 parts of the inorganic filler a. In example 1, the amounts of the thermoplastic resin solution A (nonvolatile content: 50%) and the thermoplastic resin solution A (nonvolatile content: 50%) were changed to 20 parts and 32 parts, respectively, as the component (D).
In the same manner as in example 1 except for the above matters, resin varnish a containing a resin composition was prepared. Then, using the resin varnish a, a resin sheet B and a cured product C for evaluation were obtained in the same manner as in example 1, and using the resin composition layer of the resin sheet B and the cured product C for evaluation, a cured product of the resin composition was evaluated in the same manner as in example 1.
[ evaluation method ]
The resin composition layer of the resin sheet B and the cured product C for evaluation obtained in the examples and comparative examples were evaluated by the following methods from the viewpoint of heat resistance, warpage, and long-term reliability, while obtaining various parameters for the cured product of the resin composition. Further, the cured product C for evaluation was evaluated by the following method from the viewpoint of chemical resistance. In table 1, parameters used for evaluation are described in the parameters obtained. The evaluation results are shown in table 1.
< acquisition of various parameters >
(measurement of average coefficient of Linear thermal expansion (CTE) α)
The cured product C for evaluation was cut into a width of about 5mm and a length of about 15mm to obtain a test piece D. The test piece D was subjected to thermomechanical analysis by a tensile and weight method using a thermomechanical analyzer ("Thermo Plus TMA 8310" manufactured by リガク). Specifically, after the test piece D was mounted on the thermomechanical analyzer, the thermal expansion coefficient was measured 2 times continuously under the measurement conditions of a load of 1g and a temperature rise rate of 5 ℃/min. And based on the 2 nd measurement results, the average linear thermal expansion coefficient α (ppm/K) in the range from 25 ℃ (298K) to 150 ℃ (423K) was calculated.
(measurement of dynamic elastic modulus; acquisition of glass transition temperature Tg, storage modulus E' and crosslink density n)
The cured product C for evaluation was cut into a width of 5mm and a length of 15mm to obtain a test piece E. The test piece E was subjected to thermomechanical analysis by the tensile-weight method using a viscoelasticity measuring apparatus ("DMA 7100" manufactured by hitachi ハイテクサイエンス). Specifically, the test piece E was mounted on the thermomechanical analyzer, and then the storage modulus and the loss modulus were measured under the measurement conditions of a load of 200mN and a temperature rise rate of 5 ℃/min.
First, the glass transition temperature Tg (deg.c) is obtained from the peak position of tan δ (temperature-dependent curve of the ratio of storage modulus to loss modulus) obtained as a measurement result.
Subsequently, a predetermined temperature t (k) is determined. Specifically, the predetermined temperature t (K) is determined by adding 273K to convert the acquired glass transition temperature Tg (c) to the unit K and adding 80K. Since the value of the storage modulus tends not to greatly vary in a temperature region around the predetermined temperature t (k), the predetermined temperature t (k) is allowed to be within a range of-5 ℃ to +5 ℃. Then, a measured value E' (unit: GPa, that is, 10) of the storage modulus at a predetermined temperature T (K) is obtained9Pa)。
Next, the obtained E' (Pa) of the storage modulus was substituted into the following formula to calculate the crosslinking density n (mol/cm)3). Here, the crosslinking density n can be considered as an index indicating the number of crosslinking molecules present per unit volume.
n=E'/3RT
(in the above formula, T is a predetermined temperature T (K), E' is a measured value (Pa) of storage modulus at the predetermined temperature T (K), and R is 8310000 (Pa. seed/cm) as a gas constant3And/mol seed and seed K). As E '/3, the measured value (10) of the shear elastic modulus G' at a predetermined temperature T (K) can be used9Pa))。
(value Z)fGet of (1)
Value ZfIs defined as the average linear thermal expansion coefficient alpha (ppm/K) of the cured product divided by the crosslinking density n (mol/cm) of the cured product3) And obtaining the value Zf(ppm・cm3/mol @) as a parameter of a cured product of the resin composition. The obtained value ZfIn comparison with the evaluation results of the respective evaluations described later, the scope in which the problems of the present invention can be solved was examined.
< evaluation of Long-term reliability >
Evaluation of long-term reliability the HTS test was performed on the cured product of the resin composition, and the breaking point strength was measured before and after the HTS test, and the degree of change (%) in the breaking point strength was calculated.
(HTS test)
Evaluation cured product C was subjected to an HTS test (High Thermal Storage test). In the HTS test, the cured product C for evaluation was held at 150 ℃ for 1000 hours. Thus, a cured product C' for evaluation after HTS test was obtained.
(determination of breaking Point Strength before and after HTS test)
The cured product C for evaluation was cut into a dumbbell shape in top view, i.e., shape No. 1, to obtain 5 test pieces F. Similarly, the cured product C 'for evaluation was cut into a dumbbell shape in top view No. 1, thereby obtaining 5 test pieces F'. Tensile test was carried out on each test piece F, F' under the measurement conditions of 23 ℃ and a test speed of 5mm/min using a tensile tester "RTC-1250A" manufactured by オリエンテック company, and the tensile breaking point strength (hereinafter also referred to simply as "breaking point strength") was determined from the stress-strain curve. Measurement was carried out according to JIS K7127: 1999. The average of the breaking point strengths of 5 test pieces F divided by the tensile breaking point strength σ before HTS test0. The average of the breaking point strengths of 5 test pieces F' divided by the tensile breaking point strength σ after HTS test1。
(calculation of degree of Change (%))
Next, the degree of change (%) in tensile breaking point strength before and after the HTS test was calculated based on the following formula.
Degree of change (%) = { (σ)1-σ0)/σ0}×100
(evaluation)
The degree of change (%) obtained as described above was evaluated according to the following criteria.
". o": when the degree of change (%) is within the range of-10% to +10%, the degree of change is small and the long-term reliability is excellent
"×": the degree of change (%) is not in the range of-10% to +10%, the degree of change is large, and the long-term reliability is poor
Further, if the test piece F' of comparative example 3 evaluated as poor long-term reliability was observed, deterioration by oxidation was confirmed.
< evaluation of warpage >
(preparation of silicon wafer with insulating layer for warp measurement)
The resin sheet B was laminated by using a batch vacuum pressure laminator (ニッコー seed & マテリアル ズ,2 nd build-up laminator "CVP 700") so as to bond a resin composition layer to the entire surface of one side of a 12-inch disk-shaped silicon wafer (thickness 775 μm), and thereafter, the support was peeled off. The lamination of the resin sheets and the peeling of the support by the same flow can be further repeated 2 times on the resin composition layer laminated on the silicon wafer. Thus, a laminate of 300 μm thick resin composition layers including 3 resin composition layers in total was formed on the silicon wafer. The silicon wafer of the laminate with the obtained resin composition layer was subjected to heat treatment in an oven at 180 ℃ for 90 minutes. Thus, a silicon wafer with a cured resin composition layer (i.e., a silicon wafer with an insulating layer) was obtained.
(measurement of warpage)
The distance in the vertical direction between the lower surface of the end portion of the silicon wafer with an insulating layer and the upper surface of the stage was measured as a warpage amount in a state where one end of the obtained silicon wafer with an insulating layer was pressed against a flat stage, and the end portion showing the maximum warpage amount (μm) was determined.
(evaluation)
As described above, the specified maximum warpage amount (μm) was evaluated according to the following criteria.
". o": when the maximum warpage amount is in the range of 0 μm to 2000 μm, warpage is small and warpage is sufficiently suppressed.
"×": when the maximum warpage amount is more than 2000 μm, the warpage is large and sufficient warpage is difficult.
< evaluation of chemical resistance >
(test for drug impregnation)
The cured product C for evaluation was cut into a square of 1 side and 5cm to obtain a plurality of test pieces G. The test piece G was immersed in a strong alkali aqueous solution at 70 ℃ for 1 hour. As the strong alkali aqueous solution, a1 mass% potassium hydroxide aqueous solution was used. Thereafter, the test piece G was taken out, washed with distilled water, and dried in an oven at 130 ℃ for 1 hour. Thus, a test piece G' after the drug immersion test was obtained.
(measurement of Mass before and after the drug immersion test and calculation of the Mass reduction Rate)
The mass of the test piece G was measured and recorded as mass M before the drug immersion test0. The mass of the test piece G' was measured and recorded as mass M before the drug immersion test1。
Next, the mass reduction rate (%) before and after the drug immersion test was calculated based on the following formula.
Mass reduction rate (%) = { (M)0-M1)/M0}×100
(evaluation)
The mass reduction (%) obtained as described above was evaluated according to the following criteria.
". o": when the mass reduction rate (%) is less than 1% by mass, the amount of the dissolved drug is sufficiently small, and the drug resistance is excellent
"×": when the mass reduction rate (%) is 1 mass% or more, the amount of the dissolved drug is large, and the drug resistance is poor.
[ results ]
The results of the above examples and comparative examples are shown in table 1 below. In table 1 below, the amount of each component is expressed in terms of nonvolatile content. The "inorganic filler content ratio" shown in table 1 represents the content of the component (C) when the resin component in the resin composition is 100 mass%. In addition, α represents the average linear thermal expansion coefficient, T represents a predetermined temperature, E' represents the storage modulus at the predetermined temperature T, n represents the crosslinking density, ZfThe average linear thermal expansion coefficient α is divided by the storage modulus E' at a predetermined temperature T, and Tg is the glass transition temperature.
[ TABLE 1]
Figure DEST_PATH_IMAGE036
。
< study >
As is clear from Table 1, in the examples, the average linear thermal expansion coefficient α (ppm/K) of the cured product was divided by the crosslinking density n (mol/cm) of the cured product in the resin composition containing the component (A) and the component (B) by comparing the examples with the comparative examples3) And the value Z obtainedf(ppm・cm3Seed/mol) satisfies the following formula:
145＜Zf＜1300
therefore, there is a tendency that a resin composition capable of providing a cured product which is suppressed in warpage and has excellent long-term reliability can be provided.
Further, the value ZfSatisfying the above formula also provides a resin composition capable of providing a cured product having excellent chemical resistance. Further, it is also found that a cured product of the resin composition according to the example, a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device can be provided.
In examples 1 to 3, even when the components (C) to (E) were not contained, the results were found to be similar to those in the above examples, although the degrees of difference were different. In examples 1 to 3, it was also confirmed that the same results as in the above examples were obtained by using any of a tetramethylammonium hydroxide solution, a sodium hydroxide aqueous solution and a sodium carbonate aqueous solution instead of the potassium hydroxide aqueous solution used for the evaluation of the chemical resistance.

Claims (21)

1. A resin composition comprising (A) an epoxy resin and (B) a curing agent,
the average linear thermal expansion coefficient alpha (ppm/K) of a cured product obtained by curing the resin composition at 180 ℃ for 90 minutes is divided by the crosslinking density n (mol/cm) of the cured product3) And the value Z obtainedf(ppm・cm3Seed/mol) satisfies the following formula:
145＜Zf＜1300。
2. the resin composition according to claim 1, further comprising (C) an inorganic filler.
3. The resin composition according to claim 2, wherein the content of the component (C) is 70% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
4. The resin composition according to claim 2, wherein the average particle diameter of the component (C) is 10 μm or less.
5. The resin composition according to any one of claims 1 to 4, wherein the component (B) comprises a maleimide compound having in the molecule at least one hydrocarbon chain selected from an alkyl group having 5 or more carbon atoms which may have a substituent and an alkylene group having 5 or more carbon atoms which may have a substituent.
6. The resin composition according to claim 1, wherein the content of the component (B) is 0.5% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
7. The resin composition according to claim 1, further comprising (D) a thermoplastic resin.
8. The resin composition according to claim 7, wherein the content of the component (D) is 25% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass.
9. The resin composition according to claim 1, wherein the glass transition temperature Tg (DEG C) of the cured product is in the range of 150 to 240 ℃.
10. The resin composition according to any one of claims 1 to 9, wherein the average linear thermal expansion coefficient α of the cured product is 25ppm/K or less.
11. The resin composition according to claim 1, wherein the storage modulus E' at a predetermined temperature T (K) of the cured product is less than 1.50X 109Pa, the predetermined temperature T (K) is a temperature which represents the sum of the glass transition temperature Tg (. degree.C.) of the cured product and 353 (K).
12. The resin composition according to claim 1, wherein the cured product has a crosslinking density n of 0.15mol/cm3The following.
13. The resin composition according to claim 1, wherein the aforementioned value ZfSatisfies the following formula:
150≤Zf≤1000。
14. the resin composition according to claim 1, which is used for forming an insulating layer.
15. The resin composition according to claim 1, which is used for forming a solder resist layer.
16. A cured product of the resin composition according to any one of claims 1 to 15.
17. A resin sheet comprising a support and, provided on the support, a resin composition layer comprising the resin composition according to any one of claims 1 to 15.
18. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 15 or the cured product according to claim 16.
19. A semiconductor chip package comprising the printed wiring board according to claim 18 and a semiconductor chip mounted on the printed wiring board.
20. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 15 or the cured product according to claim 16, which encapsulates the semiconductor chip.
21. A semiconductor device comprising the printed wiring board according to claim 18 or the semiconductor chip package according to claim 19 or 20.
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