CN109456672A - Resin combination - Google Patents

Resin combination Download PDF

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Publication number
CN109456672A
CN109456672A CN201811031213.5A CN201811031213A CN109456672A CN 109456672 A CN109456672 A CN 109456672A CN 201811031213 A CN201811031213 A CN 201811031213A CN 109456672 A CN109456672 A CN 109456672A
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resin
resin combination
carbon atom
group
atom number
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CN201811031213.5A
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CN109456672B (en
Inventor
川合贤司
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention, which provides, can get the insulating layer and the low resin combination of melt viscosity, the resin sheet comprising the resin combination, the printed wiring board and semiconductor device for having the insulating layer formed with the resin combination after HAST test to conductor layer with high adhesion.A kind of resin combination, it is the resin combination comprising (A) epoxy resin and (B) maleimide compound, wherein, (B) ingredient includes at least any one in the alkyl that carbon atom number is 5 or more and the alkylidene that carbon atom number is 5 or more.

Description

Resin combination
Technical field
The present invention relates to resin combinations.The invention further relates to the resin sheets for using the resin combination to obtain, printing Wiring plate and semiconductor device.
Background technique
Manufacturing technology as printed wiring board, it is known that using the stacking of alternately stacked insulating layer and conductor layer (buildup) manufacturing method of mode.
There is one kind as disclosing in the insulating materials of printed wiring board used in such insulating layer, such as patent document 1 Compositions of thermosetting resin comprising fusing point be 40 DEG C of maleimide compounds (A) below, epoxide (B), Cyanate esters (C) and inorganic filling material (D).
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2016-010964 bulletin.
Summary of the invention
The technical problems to be solved by the invention
From the viewpoint for the wiring that can form fine pattern, the viewpoint of the installation reliability of raising printed wiring board and improve printing cloth From the viewpoint of the connection reliability of line plate, it is generally desirable to which insulating layer is high for the adaptation of conductor layer.Therefore, in recent years, make For the performance of insulating layer, it is desirable that there is high adhesion to conductor layer.In addition, in order to improve the long-term reliability of printed wiring board, Preferably in super acceleration high temperature and humidity life test (HAST test), insulating layer is also high for the adaptation of conductor layer afterwards.This Outside, it also requires to keep low melt viscosity, keeps wiring imbedibility good.
As described above, disclosing the resin combination packet for being used in the insulation layer use of printed wiring board in patent document 1 Containing maleimide.But for the adaptation after HAST test and imbedibility is routed without any discussion in patent document 1.This Inventor has found that conductor can also be maintained after HAST test by the way that defined maleimide compound is used for resin combination Adaptation between layer and insulating layer.Moreover, it has been found that by the way that defined maleimide compound is used for resin combination, It is also good to be routed imbedibility.It can for being obtained and making resin combination include defined maleimide compound like this The technical ideas such as the insulating layer of high adhesion after maintaining HAST test, with regard to known to the present inventor, it may be said that previous not any Motion.
The issue of the present invention is to provide can get HAST test after to conductor layer have high adhesion insulating layer and The low resin combination of melt viscosity, the resin sheet comprising the resin combination, have with the resin combination formed it is exhausted The printed wiring board and semiconductor device of edge layer.
Technical scheme applied to solve the technical problem
In order to solve the problem of the present invention, after the present inventor conscientiously studies, as a result, it has been found that by the inclusion of defined maleimide Compound can also maintain the adaptation between conductor layer and insulating layer after HAST test.Moreover, it has been found that except above-mentioned closely sealed Except property, glue residue (smear) removability is also good, and the melt viscosity of resin combination is low, so as to complete the present invention.
That is, the present invention includes content below,
[1] a kind of resin combination, it is the resin combination comprising (A) epoxy resin and (B) maleimide compound, Wherein,
(B) ingredient includes at least any one in the alkyl that carbon atom number is 5 or more and the alkylidene that carbon atom number is 5 or more；
[2] resin combination according to [1], wherein (B) ingredient is indicated by the following general formula (B-1)；
[chemical formula 1]
In general formula (B-1), R each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more, and L indicates single Key or divalent linking group；
[3] resin combination according to [1] or [2], wherein the nonvolatile component in resin combination is set as 100 matter When measuring %, the content of (B) ingredient is 0.1 mass % or more and 10 mass % or less；
[4] resin combination according to any one of [1]~[3], wherein also include (C) active ester compound；
[5] resin combination according to [4], wherein when the nonvolatile component in resin combination is set as 100 mass %, (C) content of ingredient is 5 mass % or more；
[6] resin combination according to any one of [1]~[5], wherein also include (D) inorganic filling material；
[7] resin combination according to [6], wherein the content of (D) ingredient is 50 mass % or more；
[8] resin combination according to any one of [1]~[7], wherein in general formula (B-1), L is oxygen atom, can have The arlydene of the carbon atom number 6~24 of substituted base can have alkylidene, carbon atom that the carbon atom number of substituent group is 1~50 Alkyl, divalent group from phthalimide, divalent base from Pyromellitic Acid imidodicarbonic diamide of the number for 5 or more Group or the divalent group as made of 2 combination of the above in these groups；
[9] resin combination according to any one of [1]~[8], wherein (B) ingredient is by the following general formula (B-2) table Show；
[chemical formula 2]
In general formula (B-2), R' each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more, and A is respectively only On the spot indicate can there is the alkylidene or the divalent base with aromatic ring that there can be substituent group that the carbon atom number of substituent group is 5 or more Group, n indicate 1~10 integer；
[10] resin combination according to [9], wherein in general formula (B-2), A, which is each independently represented, can have substituent group Carbon atom number be 5 or more cyclic alkylidene, can have substituent group the divalent group with phenyl ring, can have substituent group Divalent group with phthalimide ring or the divalent base with Pyromellitic Acid imidodicarbonic diamide ring that can have substituent group Group；
[11] resin combination according to any one of [1]~[10], wherein the resin combination is used to form printing The insulating layer of wiring plate；
[12] resin combination according to any one of [1]~[11], wherein the resin combination is used to form printing The interlayer insulating film of wiring plate；
[13] a kind of resin sheet comprising supporting mass and on the supporting mass by any one of [1]~[12] The resin composition layer that the resin combination is formed；
[14] resin sheet according to [13], wherein resin composition layer with a thickness of 25 μm or less；
[15] a kind of printed wiring board, it is comprising the first conductor layer, the second conductor layer and to be formed in the first conductor layer and the The printed wiring board of insulating layer between two conductor layers, wherein
The insulating layer is the solidfied material of resin combination described in any one of [1]~[12]；
[16] a kind of semiconductor device is comprising printed wiring board described in [15].
The effect of invention
If according to the present invention, it is possible to provide: can get HAST test after to conductor layer have high adhesion insulating layer and The low resin combination of melt viscosity, the resin sheet comprising the resin combination, have with the resin combination formed it is exhausted The printed wiring board and semiconductor device of edge layer.
Detailed description of the invention
Fig. 1 is the partial sectional view for schematically showing an example of printed wiring board.
Specific embodiment
Hereinafter, being carried out specifically to resin combination of the invention, resin sheet, printed wiring board and semiconductor device It is bright.
[resin combination]
Resin combination of the invention includes (A) epoxy resin and (B) maleimide compound, and (B) ingredient includes carbon atom Count at least any one in the alkylidene for being 5 or more for 5 or more alkyl and carbon atom number.
By make comprising 5 or more carbon atom number alkyl and carbon atom number be 5 or more alkylidene in it is at least any Kind maleimide compound be contained in resin combination, can obtain HAST test after can also maintain with conductor layer it Between adaptation, and glue residue removability also good solidfied material.In addition, by making the maleimide compound include In resin combination, the low resin combination of melt viscosity can be obtained.Also, it usually like this can also after HAST test High adhesion can be played for a long time by maintaining the solidfied material of high adhesion.
In addition to (A)~(B) ingredient, resin combination can also include (C) active ester compound, (D) inorganic as needed Packing material, (E) curing agent, (F) curing accelerator, (G) thermoplastic resin and (H) arbitrary additive.Hereinafter, to the present invention Resin combination contained by each ingredient be described in detail.
< (A) epoxy resin >
Resin combination includes (A) epoxy resin.As (A) epoxy resin, it can be mentioned, for example union II cresols (bixylenol) types Epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, two Cyclopeutadiene type epoxy resin, tris phenol type epoxy, naphthol novolac (naphthol novolac) type epoxy resin, phenol phenol Aldehyde (phenol novolac) type epoxy resin, tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type asphalt mixtures modified by epoxy resin Rouge, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac (cresol Novolac) type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, the asphalt mixtures modified by epoxy resin with butadiene structure Rouge, cycloaliphatic epoxy resin, heterocyclic-type epoxy resin, the epoxy resin containing loop coil, hexamethylene type epoxy resin, hexamethylene diformazan Alcohol type epoxy resin, naphthalene ether type epoxy, trihydroxy methyl type epoxy resin, tetraphenyl ethane type epoxy resin etc..Asphalt mixtures modified by epoxy resin Rouge can be used alone a kind, can also two or more be applied in combination.
(A) epoxy resin is preferably the epoxy group in 1 molecule with 2 or more.The nonvolatile component of epoxy resin is set In the case where for 100 mass %, the above are the asphalt mixtures modified by epoxy resin of the epoxy group in 1 molecule with 2 or more by preferably at least 50 mass % Rouge.Wherein, resin combination is preferably that the epoxy resin being in a liquid state when combining comprising 20 DEG C of temperature (is also referred to as " liquid epoxy below Resin ") and at 20 DEG C of temperature in solid epoxy resin (below also referred to as " solid epoxy resin ").As liquid-state epoxy resin, There is the liquid-state epoxy resin of 2 or more epoxy groups in preferably 1 molecule, there is 2 or more epoxies in more preferably 1 molecule The aromatic species liquid-state epoxy resin of base.There is consolidating for 3 or more epoxy groups as solid epoxy resin, in preferably 1 molecule State epoxy resin, with the aromatic species solid epoxy resin of 3 or more epoxy groups in more preferably 1 molecule.In the present invention, aromatics Based epoxy resin refers to that its intramolecular has the epoxy resin of aromatic ring.
As liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type asphalt mixtures modified by epoxy resin Rouge, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy, Cycloaliphatic epoxy resin, hexamethylene type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine with ester skeleton Type epoxy resin and epoxy resin with butadiene structure, more preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin. As the specific example of liquid-state epoxy resin, " HP4032 ", " HP4032D ", " HP4032SS " of Dainippon Ink Chemicals can be enumerated (naphthalene type epoxy resin), " 828US ", " jER828EL ", " 825 ", " the EPIKOTE 828EL " of Mitsubishi chemical Co., Ltd (bisphenol A type epoxy resin), " jER807 ", " 1750 " (bisphenol f type epoxy resin), " jER152 " (phenol novolak type asphalt mixtures modified by epoxy resin Rouge), " 630 ", " 630LSD " (glycidyl amine type epoxy resin), " ZX1059 " of Nippon Steel & Sumitomo Metal Corporation (melange of bisphenol A type epoxy resin and bisphenol f type epoxy resin), " EX-721 " of Nagase ChemteX Co. Ltd. system " the CELLOXIDE 2021P " of (glycidyl ester type epoxy resin), Daicel Co. Ltd. system is (alicyclic with ester skeleton Epoxy resin), " PB-3600 " (with butadiene structure epoxy resin), Nippon Steel & Sumitomo Metal Corporation " ZX1658 ", " ZX1658GS " (liquid Isosorbide-5-Nitrae-glycidol butylcyclohexane type ring oxygen resin), Mitsubishi chemical Co., Ltd " 630LSD " (glycidyl amine type epoxy resin) etc..These liquid-state epoxy resins can be used alone a kind, can also two or more group It closes and uses.
As solid epoxy resin, preferably union II first phenol-type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy Resin, cresol novolak type epoxy resin, dicyclopentadiene-type epoxy resin, tris phenol type epoxy, naphthol type epoxy resin, connection Benzene-type epoxy resin, naphthalene ether type epoxy, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, four Diphenylphosphino ethane type epoxy resin, more preferably naphthalene type epoxy resin.As the specific example of solid epoxy resin, DIC plants can be enumerated " HP4032H " (naphthalene type epoxy resin) of formula commercial firm, " HP-4700 ", " HP-4710 " (naphthalene type tetrafunctional epoxy resin), " N- 690 " (cresol novolak type epoxy resins), " N-695 " (cresol novolak type epoxy resin), " HP-7200 " (bicyclopentadiene type ring Oxygen resin), " HP-7200HH ", " HP-7200H ", " EXA-7311 ", " EXA-7311-G3 ", " EXA-7311-G4 ", " EXA- 7311-G4S ", " HP6000 " (naphthalene ether type epoxy), " EPPN-502H " (triphenol type ring oxygen of Nippon Kayaku K. K Resin), " NC7000L " (naphthol novolac type epoxy resin), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (connection Benzene-type epoxy resin), " ESN475V " (naphthalene type epoxy resin), " ESN485 " (naphthols of Nippon Steel & Sumitomo Metal Corporation Phenol aldehyde type epoxy resin), " YX4000H " of Mitsubishi chemical Co., Ltd, " YX4000 ", " YL6121 " (biphenyl type epoxy tree Rouge), " YX4000HK " (union II first phenol-type epoxy resin), " YX8800 " (anthracene type epoxy resin), Osaka combustion gas chemistry strain formula meeting " PG-100 " of society, " CG-500 ", Mitsubishi chemical Co., Ltd " YL7760 " (bisphenol AF type epoxy resin), " jER1010 " (the solid-state bisphenol A type epoxy resin resin) of " YL7800 " (fluorenes type epoxy resin), Mitsubishi chemical Co., Ltd, " jER1031S " (tetraphenyl ethane type epoxy resin) etc..They can be used alone a kind, can also two or more be applied in combination.
As (A) ingredient, and in the case where liquid-state epoxy resin and solid epoxy resin, their amount ratio (liquid ring Oxygen resin: solid epoxy resin) it is by quality ratio preferably in the range of 1:1~1:20.By make liquid-state epoxy resin with The amount of solid epoxy resin than in such range, can get i) in the form of resin sheet using when bring appropriate adherency Property, ii) can be obtained when use in the form of resin sheet it is enough flexible and operability improves and iii) can obtain that there is foot Enough solidfied materials of breaking strength and other effects.From it is above-mentioned i)~iii) effect from the viewpoint of, liquid-state epoxy resin and solid-state The amount ratio (liquid-state epoxy resin: solid epoxy resin) of epoxy resin by quality ratio more preferably in the range of 1:1~1:15, Further more preferably in the range of 1:1~1:10.
When nonvolatile component in resin combination is set as 100 mass %, from obtaining the good mechanical strength of display, absolutely From the viewpoint of the insulating layer of edge reliability, the content of (A) ingredient in resin combination is preferably 5 mass % or more, more preferably 10 mass % or more, further more preferably 15 mass % or more.As long as playing effect of the invention, the upper limit of the content of epoxy resin Be not particularly limited, but preferably 30 mass % hereinafter, more preferably 25 mass % hereinafter, further more preferably 20 mass % or less.
It should be noted that, as long as no separately expressing, the content of each ingredient in resin combination is by resin in the present invention Nonvolatile component in composition is set as value when 100 mass %.
(A) epoxide equivalent of ingredient is preferably 50~5000, and more preferably 50~3000, further more preferably 80~2000, Further more preferably 110~1000.By making it in the range, the crosslink density of solidfied material is abundant, and surface can be brought thick The small insulating layer of rugosity.It should be noted that epoxide equivalent can be measured according to JIS K7236, it is the epoxy group comprising 1 equivalent The quality of resin.
(A) weight average molecular weight of ingredient is preferably 100~5000, and more preferably 250~3000, further more preferably 400~ 1500.Here, the weight average molecular weight of epoxy resin is the weight of the polystyrene conversion measured by gel permeation chromatography (GPC) Average molecular weight.
< (B) maleimide compound >
Resin combination includes maleimide compound, and the maleimide compound includes that carbon atom number is 5 or more Alkyl and carbon atom number are at least any one in 5 or more alkylidene.(B) maleimide compound be molecule in containing with The compound for the dimaleoyl imino that following formula (1) indicates.
[chemical formula 3]
。
(B) maleimide compound includes the alkyl that carbon atom number is 5 or more and the alkylidene that carbon atom number is 5 or more In at least any one.In addition, comprising carbon atom number be 5 or more alkyl and carbon atom number be 5 or more alkylidene in extremely Effect of few any maleimide compound due to its Long carbon chain, molecular structure softness.Therefore, and in main composition Maleimide compound containing arlydene is compared, it can be achieved that lower minimum melt viscosity.In addition, dimaleoyl imino is easy It is dissolved in aqueous slkali, so the usually available good solidfied material of glue residue removability.The alkyl and carbon that carbon atom number is 5 or more are former The alkylidene that subnumber is 5 or more shows hydrophobicity due to carbon chain length.Therefore, (B) maleimide compound is in high temperature and humidity It is not easily deteriorated under environment, also can inhibit the splitting of the destruction with insulating layer after HAST test.As a result, can get There is after HAST test to conductor layer the insulating layer of high adhesion.
The carbon atom number of alkyl that carbon atom number is 5 or more is preferably 6 or more, more preferably 8 or more, preferably 50 hereinafter, More preferably 45 hereinafter, further more preferably 40 or less.The alkyl can be any one of straight-chain, branched, ring-type, wherein Preferably straight-chain.As such alkyl, it can be mentioned, for example amyl, hexyl, heptyl, octyl, nonyl, decyls etc..Carbon atom Number can be used as the substituent group for the alkylidene that carbon atom number is 5 or more and have for 5 or more alkyl.
The carbon atom number of alkylidene that carbon atom number is 5 or more is preferably 6 or more, more preferably 8 or more, preferably 50 with Under, more preferably 45 hereinafter, further more preferably 40 or less.The alkylidene can be straight-chain, branched, ring-type in any Kind, wherein preferably straight-chain.Include the case where only being formed by cricoid alkylidene and same here, cricoid alkylidene refers to When the case where including the alkylidene and cricoid alkylidene of straight-chain concept.As such alkylidene, it can be mentioned, for example Asias Amyl, hexylidene, heptamethylene, octamethylene, nonylene, decylene, alkylene undecyl, sub-dodecyl, sub- tridecyl, Asia ten Seven alkyl, sub- hexatriacontane base (hexatriacontylene), with octamethylene-cyclohexylene structure group, have it is sub- pungent Base-cyclohexylidene-octamethylene structure group, with propylidene-cyclohexylidene-octamethylene structure group etc..
(B) in maleimide compound, alkylidene that the alkyl and carbon atom number that carbon atom number is 5 or more are 5 or more Preferably with the nitrogen-atoms Direct Bonding of dimaleoyl imino.Here, " direct " refer to nitrogen-atoms in dimaleoyl imino with There is no other groups between alkyl or alkylidene.Adaptation and minimum melt viscosity after HAST can as a result, tested is especially good It is good.
From the viewpoint of the insulating layer after obtaining HAST test to conductor layer with high adhesion, (B) maleimide Compound is preferably while including the alkyl that carbon atom number is 5 or more and the alkylidene that carbon atom number is 5 or more.
The alkylidene that the alkyl and carbon atom number that carbon atom number is 5 or more are 5 or more can be combined with each other and form ring, ring knot Structure also includes loop coil or condensed ring.As the ring for be combineding with each other and being formed, it can be mentioned, for example cyclohexane rings etc..
The alkylidene that the alkyl and carbon atom number that carbon atom number is 5 or more are 5 or more does not preferably have substituent group, but can With substituent group.It as substituent group, is not particularly limited, it can be mentioned, for example halogen atom ,-OH ,-O-C1-6Alkyl ,-N (C1-10Alkane Base)2、C1-10Alkyl, C6-10Aryl ,-NH2、-CN、-C(O)O-C1-10Alkyl ,-COOH ,-C (O) H ,-NO2Deng.Here, term “Cp-q" (p and q are positive integer, meet p < q) indicate that the carbon atom number for the organic group recorded after the immediately term is p~q.Example Such as, " C1-10The alkyl of this statement of alkyl " expression carbon atom number 1~10.These substituent groups can be combined with each other and form ring, ring Structure also includes loop coil or condensed ring.
Above-mentioned substituent group can further have substituent group (below also referred to as " second level substituent group ").As second level substituent group, It is recorded as long as no special, group identical with above-mentioned substituent group can be used.
(B) quantity of the dimaleoyl imino of average 1 molecule of maleimide compound can be 1, preferably 2 More than, preferably 10 hereinafter, more preferably 6 hereinafter, particularly preferably 3 or less.By using average 1 molecule have 2 with On dimaleoyl imino (B) maleimide compound, can get HAST test after to conductor layer have more Gao Mihe The insulating layer of property.
(B) maleimide compound can be used alone a kind, can also two or more be applied in combination.
(B) if maleimide compound comprising carbon atom number be 5 or more alkyl and carbon atom number be 5 or more Asia At least any one in alkyl, but from obtaining the sight after HAST test to conductor layer with the insulating layer of more high adhesion From the point of view of point, preferably by the maleimide compound of the following general formula (B-1) expression；
[chemical formula 4]
In general formula (B-1), R each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more, and L indicates single Key or divalent linking group.
R each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more.R and above-mentioned carbon atom Number is identical for 5 or more alkylidene meaning, and preferred range is also identical.
L indicates singly-bound or divalent linking group.As divalent linking group, alkylidene, alkenylene, alkynylene, Asia can be enumerated Aryl ,-C (=O)-,-C (=O)-O- ,-NR0-(R0For hydrogen atom, the alkyl of carbon atom number 1~3), oxygen atom, sulphur atom, C (= O)NR0, the divalent group from phthalimide, the divalent group from Pyromellitic Acid imidodicarbonic diamide and by this Divalent group made of 2 combination of the above in a little groups etc..Divalent group from phthalimide is indicated by adjacent benzene Divalent group derived from dicarboximide, the group specially indicated with general formula (2).From the 2 of Pyromellitic Acid imidodicarbonic diamide Valence group indicates the divalent group as derived from Pyromellitic Acid imidodicarbonic diamide, the group specially indicated with general formula (3).In formula, " * " indicates chemical bond；
[chemical formula 5]
。
It is special as alkylidene, the preferably alkylidene of carbon atom number 1~50, the more preferably alkylidene of carbon atom number 1~45 Not it is good be carbon atom number 1~40 alkylidene.The alkylidene can be any one of straight-chain, branched, ring-type.As this The alkylidene of sample can enumerate methyl ethylidene, cyclohexylidene, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene, the sub- last of the ten Heavenly stems Base, sub-dodecyl, sub- tridecyl, sub- heptadecyl, sub- hexatriacontane base, has octamethylene-Asia hexamethylene at alkylene undecyl The group of based structures, with octamethylene-cyclohexylidene-octamethylene structure group, have propylidene-cyclohexylidene-octamethylene The group etc. of structure.
It is special as alkenylene, the preferably alkenylene of carbon atom number 2~20, the more preferably alkenylene of carbon atom number 2~15 Not it is good be carbon atom number 2~10 alkenylene.The alkenylene can be any one of straight-chain, branched, ring-type.As this The alkenylene of sample, it can be mentioned, for example methyl ethenylidene, cyclohexadienylidene, inferior pentenyl, sub- hexenyls, heptene base, Ya Xin Alkenyl etc..
It is special as alkynylene, the preferably alkynylene of carbon atom number 2~20, the more preferably alkynylene of carbon atom number 2~15 Not it is good be carbon atom number 2~10 alkynylene.The alkynylene can be any one of straight-chain, branched, ring-type.As this The alkynylene of sample, it can be mentioned, for example methyl ethynylene, sub- hexamethylene alkynyl, sub- pentynyl, sub- hexin base, sub- heptynyls, Ya Xin Alkynyl etc..
As arlydene, the preferably arlydene of carbon atom number 6~24, the more preferably arlydene of carbon atom number 6~18, into The arlydene of one step more preferably carbon atom number 6~14, the further more preferably arlydene of carbon atom number 6~10.As sub- virtue Base, it can be mentioned, for example phenylene, naphthylene, anthrylene etc..
There can be substituent group as the alkylidene of divalent linking group, alkenylene, alkynylene and arlydene.As substituent group, The substituent group that the alkyl that carbon atom number with the R expression in general formula (B-1) is 5 or more can have is identical, preferably carbon atom number For 5 or more alkyl.
As the divalent group as made of 2 combination of the above in these groups, it can be mentioned, for example by alkylidene, derive from The divalent group that the divalent group and oxygen atom of phthalimide are composed, origin are derived from the divalent of phthalimide The divalent group that group, oxygen atom, arlydene and alkylidene are composed, by alkylidene and from two acyl of Pyromellitic Acid Asia Divalent group made of the divalent moiety combinations of amine etc..The divalent group as made of 2 combination of the above in these groups can be by each The combination of group forms the rings such as condensed ring.In addition, the divalent group as made of 2 combination of the above in these groups can be repetition The repetitive unit that unit number is 1~10.
Wherein, as the L in general formula (B-1), preferably oxygen atom, can have substituent group carbon atom number 6~24 Asia Alkyl that aryl, the alkylidene that the carbon atom number that can have substituent group is 1~50, carbon atom number are 5 or more, from adjacent benzene two The divalent group of carboximide, from the divalent group of Pyromellitic Acid imidodicarbonic diamide or by 2 or more in these groups The divalent group being composed.Wherein, as L, more preferably alkylidene, with alkylidene-derive from the 2 of phthalimide Valence group-oxygen atom-is derived from from the divalent group of the structure of the divalent group of phthalimide, with alkylidene- Divalent group-oxygen atom-arylene-alkylene-arlydene-oxygen atom-of phthalimide is sub- from phthalyl The divalent group of the structure of the divalent group of amine, with alkylidene-from Pyromellitic Acid imidodicarbonic diamide divalent group structure Divalent group.
The maleimide compound indicated with general formula (B-1) is preferably indicated with general formula (B-2)；
[chemical formula 6]
In general formula (B-2), R' each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more, and A is respectively only On the spot indicate can there is the alkylidene or the divalent base with aromatic ring that there can be substituent group that the carbon atom number of substituent group is 5 or more Group.N indicates 1~10 integer.
R' each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more.In R' and general formula (B-1) R it is identical.
A each independently represents the alkylidene or can have substituent group that can have that the carbon atom number of substituent group is 5 or more Divalent group with aromatic ring.But when A expression alkylidene, do not include the case where being only made of the alkylidene of straight-chain.A is indicated In the case where alkylidene, any one of branched, ring-type can be, wherein preferably ring-type, there can be the carbon of substituent group The cyclic alkylidene that atomicity is 5 or more.Its carbon atom number is preferably 6 or more, and more preferably 8 or more, preferably 50 hereinafter, more preferable It is 45 hereinafter, further more preferably 40 or less.As such alkylidene, it can be mentioned, for example with octamethylene-cyclohexylidene knot The group of structure, with octamethylene-cyclohexylidene-octamethylene structure group, have propylidene-cyclohexylidene-octamethylene structure Group etc..
As the aromatic ring in the divalent group with aromatic ring that can have substituent group, it can be mentioned, for example phenyl ring, naphthalene nucleus, anthracene nucleus, Phthalimide ring, Pyromellitic Acid imidodicarbonic diamide ring, aromatic heterocycle etc., preferably phenyl ring, phthalimide ring, Pyromellitic Acid imidodicarbonic diamide ring.That is, can preferably have 2 with phenyl ring of substituent group as the divalent group with aromatic ring Valence group, the divalent group with phthalimide ring that can have substituent group, can have substituent group have equal benzene tetramethyl The divalent group of pyromellitic imide ring.As the divalent group with aromatic ring, it can be mentioned, for example origin to be derived from phthalimide Divalent group and the group that is composed of oxygen atom, origin is derived from divalent group, oxygen atom, the arlydene of phthalimide And the group that alkylidene is composed, made of the divalent moiety combinations as alkylidene and from Pyromellitic Acid imidodicarbonic diamide Group, from the divalent group of Pyromellitic Acid imidodicarbonic diamide, origin is derived from the divalent group and alkylene of phthalimide The group etc. that base is composed.The Asia in divalent linking group that L in above-mentioned arlydene and alkylidene and general formula (B-1) is indicated Aryl is identical with alkylidene, and preferred range is also identical.
The alkylidene that A is indicated and the divalent group with aromatic ring can have substituent group.As in substituent group, with general formula (B-1) The carbon atom number that indicates of R be 5 or more the substituent group that can have of alkyl it is identical.
As the specific example of the A group indicated, group below can be enumerated.In formula, " * " indicates chemical bond；
[chemical formula 7]
[chemical formula 8]
。
The maleimide compound indicated with general formula (B-1) is preferably the maleimation indicated with general formula (B-3) Any one of the maleimide compound for closing object and being indicated with general formula (B-4)；
[chemical formula 9]
In general formula (B-3), R1Each independently represent the alkylidene that can have that the carbon atom number of substituent group is 5 or more, R2Respectively Independently indicate oxygen atom, arlydene, alkylidene or the divalent group as made of 2 combination of the above in these groups.N1 is indicated 1~15 integer；
In general formula (B-4), R3Each independently represent the alkylidene that can have that the carbon atom number of substituent group is 5 or more, R4Respectively Independently indicate the divalent group with aromatic ring that there can be substituent group, R5Each independently represent the alkane that carbon atom number is 5 or more Base.N2 indicates that 0~10 integer, m each independently represent 0~4 integer.
R1Each independently represent the alkylidene that can have that the carbon atom number of substituent group is 5 or more.R1In general formula (B-1) The carbon atom number that indicates of R be 5 or more alkylidene it is identical, preferably sub- hexatriacontane base.
R2Each independently represent oxygen atom, arlydene, alkylidene or as made of 2 combination of the above in these groups Divalent group.Arlydene, alkylidene in general formula (B-1) L indicate divalent linking group in arlydene and alkylidene it is identical, Preferred range is also identical.As R2, preferably divalent group or oxygen atom as made of 2 combination of the above in these groups.
As the divalent group as made of 2 combination of the above in these groups, oxygen atom, arlydene and alkylene can be enumerated The combination of base.As the specific example of the divalent group as made of 2 combination of the above in these groups, base below can be enumerated Group.In formula, " * " indicates chemical bond；
[chemical formula 10]
。
R3Each independently represent the alkylidene that can have that the carbon atom number of substituent group is 5 or more.R3In general formula (B-1) The carbon atom number that indicates of R be 5 or more alkylidene it is identical, preferably hexylidene, heptamethylene, octamethylene, nonylene, the sub- last of the ten Heavenly stems Base, more preferably octamethylene.
R4Each independently represent the divalent group with aromatic ring that there can be substituent group.R4It is indicated with the A in general formula (B-2) The divalent group with aromatic ring it is identical, preferably by alkylidene and from the divalent moiety combinations of Pyromellitic Acid imidodicarbonic diamide Made of group, origin derived from phthalimide divalent group and the group that is composed of alkylidene, more preferably by alkylene Group made of base and divalent moiety combinations from Pyromellitic Acid imidodicarbonic diamide.Above-mentioned arlydene and alkylidene and general formula (B-1) arlydene in divalent linking group that the L in is indicated is identical with alkylidene, and preferred range is also identical.
As R4The specific example of the group of expression, it can be mentioned, for example groups below.In formula, " * " indicates chemical bond；
[chemical formula 11]
。
R5Each independently represent the alkyl that carbon atom number is 5 or more.R5The alkyl for being 5 or more with above-mentioned carbon atom number It is identical, preferably hexyl, heptyl, octyl, nonyl, decyl, more preferably hexyl, octyl.
M indicates 0~4 integer, preferably 1~3 integer, more preferably 2.
As the specific example of (B) maleimide compound, the compound of (4) below~(7) can be enumerated.But (B) maleimide compound is not limited to these specific examples.In formula, n indicates 1~10 integer；
[chemical formula 12]
[chemical formula 13]
。
As the specific example of (B) maleimide compound, artificial molecule company (Designer can be enumerated Molecules, Inc.) system " BMI1500 " (compound of formula (4)), " BMI1700 " (compound of formula (5)), " BMI3000J " (compound of formula (6)), " BMI689 " (compound of formula (7)) etc..
The adaptation raising with conductor layer as the molecular weight of (B) maleimide compound, after testing HAST From the viewpoint of, preferably 200 or more, more preferably 300 or more, further more preferably 400 or more, preferably 100000 hereinafter, More preferably 80000 hereinafter, further more preferably 60000 or less.
When nonvolatile component in resin combination is set as 100 mass %, the content of (B) maleimide compound compared with It is 0.1 mass % or more well, more preferably 0.5 mass % or more, further more preferably 1 mass % or more.The upper limit is preferably 10 mass % Hereinafter, more preferably 8 mass % are hereinafter, further more preferably 5 mass % or less or 3 mass % or less.By the content for making (B) ingredient In the range, the rising of the minimum melt viscosity of resin combination can be further suppressed, and is obtained exhausted after HAST test The adaptation and the better solidfied material of glue residue removability of edge layer and conductor layer.
< (C) active ester compound >
In one embodiment, resin combination may include (C) active ester compound.If known using active ester compound, Usual glue residue removability is deteriorated.But resin combination of the invention includes (B) maleimide compound, so the resin The glue residue removability of the solidfied material of composition is good.Even if glue residue removability will not be deteriorated therefore using active ester compound.
As active ester compound, be not particularly limited, it is generally preferable to using phenolic ester class, thiophenol esters, N- hydroxylamine esters, The compound for the ester group for having 2 or more reactivities high in 1 molecule such as esters of heterocycle hydroxyl compound.This is active esterifying Object is closed preferably by the condensation of carboxylic acid compound and/or thiocarboxylic acid compound and hydroxy compounds and/or mercaptan compound React the compound obtained.Especially from the viewpoint of heat resistance raising, preferably by carboxylic acid compound and hydroxy compounds The active ester compound of acquisition, the active ester more preferably obtained by carboxylic acid compound and oxybenzene compound and/or naphthol compound Compound.As carboxylic acid compound, it can be mentioned, for example benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), pyromellitic acid etc..As oxybenzene compound or naphthol compound, it can be mentioned, for example quinhydrones, Benzenediol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, adjacent first Phenol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, Dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type biphenol chemical combination Object, phenol novolacs etc..Here, " dicyclopentadiene-type bisphenol compounds " refer to that 1 molecule bicyclopentadiene is condensed 2 molecules Bisphenol compounds obtained by phenol.
Specifically, the preferably active ester compound of the structure of biphenol containing dicyclopentadiene-type, the activity containing naphthalene structure Active ester compound, the benzoyl containing phenol novolacs of ester compounds, acetyl group compound containing phenol novolacs The active ester compound of object, wherein the more preferably active ester compound containing naphthalene structure, biphenol containing dicyclopentadiene-type structure Active ester compound." dicyclopentadiene-type biphenol structure " indicates the divalent formed by phenylene-Asia bicyclopentyl-phenylene Structural unit.
As the commercially available product of active ester compound, the active ester compound of the structure of biphenol containing dicyclopentadiene-type can be enumerated “EXB9451”、“EXB9460”、“EXB9460S”、“HPC-8000-65T”、“HPC-8000H-65TM”、“EXB-8000L- 65TM ", " EXB-8150-65T " (Dainippon Ink Chemicals's system) etc., the active ester compound containing naphthalene structure can enumerate " EXB9416- 70BK " (Dainippon Ink Chemicals's system) etc., the active ester compound of the acetyl group compound containing phenol novolacs can enumerate " DC808 " The active ester compound of (Mitsubishi chemical Co., Ltd's system) etc., the benzoyl compound containing phenol novolacs can be enumerated " YLH1026 " (Mitsubishi chemical Co., Ltd's system) etc., the active ester compound of the acetyl group compound as phenol novolacs can It enumerates " DC808 " (Mitsubishi chemical Co., Ltd's system) etc., the active esters of the benzoyl compound as phenol novolacs are solid Agent can enumerate " YLH1026 " (Mitsubishi chemical Co., Ltd's system), " YLH1030 " (Mitsubishi chemical Co., Ltd's system), " YLH1048 " (Mitsubishi chemical Co., Ltd's system) etc..
In the case that resin combination includes (C) active ester compound, the amount ratio of epoxy resin and active ester compound with [sum of the epoxy group of epoxy resin]: the ratio meter of [sum of the reactive group of active ester compound] is preferably in 1:0.01 In the range of~1:5, more preferably in the range of 1:0.05~1:3, further more preferably in the range of 1:0.1~1:1.5. Here, the reactive group of active ester compound refers to active ester groups.In addition, the sum of the epoxy group of epoxy resin refers to for institute The value that some epoxy resin is added up to the solid component quality of each epoxy resin divided by value obtained by epoxide equivalent, it is living The sum of the reactive group of property ester compounds refer to for all active ester compounds by the solid of each active ester compound at The value that sub-prime amount is added up to divided by value obtained by reactive group equivalent.By making epoxy resin and active ester compound Amount is than in such range, the heat resistance of the solidfied material of resin combination is further increased.
When resin combination includes (C) active ester compound, the nonvolatile component in resin combination is set as 100 matter When measuring %, the content of (C) ingredient is preferably 1 mass % or more, more preferably 3 mass % or more, further more preferably 5 mass % or more. In addition, the upper limit is preferably 30 mass % hereinafter, more preferably 20 mass % are hereinafter, further more preferably 15 mass % or less.By making (C) content of ingredient can be such that the peel strength of HAST test front and back improves in the range.
< (D) inorganic filling material >
In one embodiment, resin combination may include (D) inorganic filling material.(D) as long as the material of inorganic filling material It is inorganic compound, is not particularly limited, it can be mentioned, for example silica, aluminium oxide, glass, cordierite, Si oxide, sulphur Sour barium, barium carbonate, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, carbon Sour magnesium, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, oxygen Change titanium, zirconium oxide, barium titanate, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc..Wherein, especially excellent Select silica.As silica, amorphous silica, fused silica, crystalline silica, synthesis two can be enumerated Silica, hollow silica etc..In addition, as silica, preferably spherical silicon dioxide.Inorganic filling material can be independent Using a kind, can also two or more be applied in combination.
As the commercially available product of (D) inorganic filling material, it can be mentioned, for example Nippon Steel to live golden material Co. Ltd. system " SP60-05 ", " SP507-05 ", " YC100C ", " YA050C ", " YA050C- of refined all Mas (Admatechs) system of Co., Ltd. MJE ", " YA010C ", " UFP-30 " of electrochemical (Denka) Co. Ltd. system, Tokuyama Corp (Tokuyama) system " Silfil (シ Le Off ィ Le) NSS-3N ", " Silfil NSS-4N ", " Silfil NSS-5N ", the refined all Mas of Co., Ltd. " SC2500SQ ", " SO-C4 ", " SO-C2 ", " SO-C1 " etc..
In general, (D) inorganic filling material is contained in resin combination with the state of particle.From significantly obtaining desired by the present invention Effect from the viewpoint of, the average grain diameter of (D) inorganic filling material is preferably 0.01 μm or more, more preferably 0.05 μm or more, Particularly preferably 0.1 μm or more, preferably 5.0 μm hereinafter, more preferably 2.0 μm hereinafter, further more preferably 1.0 μm or less.In addition, By making the average grain diameter of (D) inorganic filling material in the range, the circuit of resin composition layer can usually be embedded to Property improve, or reduce insulating layer surface roughness.
(D) average grain diameter of inorganic filling material can pass through the laser diffraction scattering method based on Michaelis (Mie) scattering theory It is measured.Specifically, it is inorganic that (D) can be made with volume reference by laser diffraction and scattering formula particle size distribution analyzer Its median particle diameter is measured by the particle diameter distribution of packing material as average grain diameter.Measurement sample is preferably using passing through Sample obtained by ultrasonic wave is scattered in (D) inorganic filling material in methyl ethyl ketone.As laser diffraction and scattering formula partial size point Horiba Ltd's system " LA-500 ", Shimadzu Scisakusho Ltd's system " SALD-2200 " can be used in cloth measurement device Deng.
From the viewpoint of significantly obtaining desired effect of the invention, the specific surface area of (D) inorganic filling material compared with It is well 1m2/ g or more, more preferably 3m2/ g or more, further more preferably 5m2/ g or more.It is without particular limitation to the upper limit, preferably 30m2/ g is hereinafter, more preferably 20m2/ g is hereinafter, further more preferably 10m2/ g or less.
Specific surface area can use specific area measuring device (Mountech Co. Ltd. system Macsorb HM- according to BET method 1210) make nitrogen adsorption in specimen surface, calculate specific surface area with BET multipoint method to obtain.
From the viewpoint of improving moisture-proof and dispersibility, (D) inorganic filling material can be carried out by surface treating agent Surface treatment.As surface treating agent, it can be mentioned, for example amino silicone alkanes coupling agents, epoxy radicals silicone hydride class coupling agent, sulfydryl silicon Alkanes coupling agent, silane coupling agent, alkoxy silane, organic silazane hydride compounds, titante coupling agent etc..As surface The commercially available product of inorganic agent, it can be mentioned, for example Shin-Etsu Chemial Co., Ltd's system " KBM403 " (3- glycidoxypropyl group front threes Oxysilane), Shin-Etsu Chemial Co., Ltd's system " KBM803 " (3-mercaptopropyi trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry Co. Ltd. system " KBE903 " (3-aminopropyltriethoxysilane), Shin-Etsu Chemial Co., Ltd's system " KBM573 " (N- Phenyl -3- TSL 8330), Shin-Etsu Chemial Co., Ltd's system " SZ-31 " (hexamethyldisilazane), letter More chemical industry Co. Ltd. system " KBM103 " (phenyltrimethoxysila,e), Shin-Etsu Chemial Co., Ltd system " KBM- 4803 " (long-chain epoxy type silane coupling agents), Shin-Etsu Chemial Co., Ltd's system " KBM-7103 " (3,3,3- trifluoro propyl three Methoxy silane) etc..Surface treating agent can be used alone a kind, can also two or more be applied in combination.
The degree of the surface treatment carried out by surface treating agent can pass through the per surface area of (D) inorganic filling material Carbon amounts is evaluated.From the viewpoint of the dispersibility raising of (D) inorganic filling material, the unit table of (D) inorganic filling material The carbon amounts of area is preferably 0.02mg/m2More than, more preferably 0.1mg/m2More than, further more preferably 0.2mg/m2More than.It is another Aspect, from the viewpoint of the rising of the melt viscosity under the melt viscosity and sheet form for inhibiting resin varnish, preferably 1mg/m2Hereinafter, more preferably 0.8mg/m2Hereinafter, further more preferably 0.5mg/m2Below.
(D) carbon amounts of the per surface area of inorganic filling material can be logical in (D) inorganic filling material after being surface-treated It crosses after solvent (such as methyl ethyl ketone (MEK)) starts the cleaning processing and is measured.Specifically, to by surface treating agent into Gone surface treatment (D) inorganic filling material in enough MEK are added as solvent, 25 DEG C ultrasonic cleaning 5 minutes.It removes Supernatant is removed, after keeping solid component dry, the carbon of the per surface area of carbon analyzer measurement (D) inorganic filling material can be used Amount.As carbon analyzer, Horiba Ltd's system " EMIA-320V " etc. can be used.
From the viewpoint of reducing thermal expansion coefficient, when the nonvolatile component in resin combination is set as 100 mass %, (D) content of inorganic filling material is preferably 50 mass % or more, more preferably 55 mass % or more, further more preferably 60 mass % Above or 65 mass % or more.The upper limit is preferably 85 mass % hereinafter, more preferably 80 mass % are hereinafter, further more preferably 75 mass % Below.If known mix a large amount of inorganic filling materials, closing force decline, even if but being mixed in the present invention largely (D) inorganic Packing material can also effectively inhibit the decline of closing force.
< (E) curing agent >
In one embodiment, resin combination may include (E) curing agent.But in (E) curing agent do not include (C) active ester Compound.As (E) curing agent, as long as having makes the cured function of (A) ingredient, it is not particularly limited, it can be mentioned, for example benzene Phenols curing agent, aphthols curing agent, benzoxazine class curing agent, cyanate curing agent and carbodiimide class curing agent etc.. Wherein, from the viewpoint of making insulating reliability raising, (E) curing agent is preferably phenol curing agent, aphthols curing agent, cyanogen Wantonly a kind or more in esters of gallic acid curing agent and carbodiimide class curing agent, more preferably include phenol curing agent.Curing agent can be single Solely use a kind, can also two or more be used in combination.
Preferably have from the viewpoint of heat resistance and water resistance as phenol curing agent and aphthols curing agent The phenol curing agent of phenolic structure or aphthols curing agent with phenolic structure.In addition, from the adaptation with conductor layer From the viewpoint of, preferably nitrogenous phenol curing agent, more preferably the phenol curing agent of the skeleton containing triazine.
As phenol curing agent and the specific example of aphthols curing agent, it can be mentioned, for example bright and chemical conversion Co. Ltd. systems " MEH-7700 ", " MEH-7810 ", " MEH-7851 ", " NHN ", " CBN ", " GPH " of Nippon Kayaku K. K, new day Iron live " SN170 " of aurification Co. Ltd. system, " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495 ", " SN495V ", " SN375 ", " SN395 ", " TD-2090 ", " LA-7052 ", " LA-7054 ", " LA- of Dainippon Ink Chemicals 1356 ", " LA-3018-50P ", " EXB-9500 " etc..
As the specific example of benzoxazine class curing agent, Showa Highpolymer Co., Ltd can be enumerated " P-d ", " F-a " of " HFB2006M ", Shikoku Chem.
As cyanate curing agent, it can be mentioned, for example bisphenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene- 1,5- phenylenecyanate), 4,4' methylene bis (2,6- 3,5-dimethylphenyl cyanate), two cyanic acid of 4,4'- ethylene phenyl It is bis- (the 4- cyanic acid ester group) phenyl-propanes of ester, hexafluoro bisphenol-a dicyanate, 2,2-, 1,1- bis- (4- cyanatephenyl methane), double (4- cyanic acid ester group -3,5- 3,5-dimethylphenyl) methane, 1,3- bis- (4- cyanatephenyl -1- (methyl ethylidene)) benzene, bis- (4- Cyanatephenyl) the two function cyanate ester resins such as thioether and bis- (4- cyanatephenyl) ethers, by phenol novolacs and first Multifunctional cyanate ester resin derived from phenol phenolic resin etc., prepolymer obtained by these cyanate ester resin part triazines etc.. As the specific example of cyanate curing agent, " PT30 " and " PT60 " (phenol of Lonza Japan Co. Ltd. system can be enumerated Phenol aldehyde type multifunctional cyanate ester resin), " ULL-950S " (multifunctional cyanate ester resin), " BA230 ", " BA230S75 " (bisphenol-A Part or all of dicyanate is formed the prepolymer of tripolymer by triazine) etc..
As the specific example of carbodiimide class curing agent, Nisshinbo Chemical Co., Ltd. system " V-03 ", " V- can be enumerated 07 " etc..
In the case that resin combination includes (E) curing agent, the amount ratio of epoxy resin and curing agent is with [the ring of epoxy resin The sum of oxygroup]: the ratio meter of [sum of the reactive group of curing agent] is preferably in the range of 1:0.01~1:2, more preferably It is in the range of 1:0.01~1:3, further more preferably in the range of 1:0.01~1:1.5.Here, the reaction of curing agent Group refers to activity hydroxy etc., different according to the type of curing agent.In addition, the sum of the epoxy group of epoxy resin refer to for The value that all epoxy resin is added up to the solid component quality of each epoxy resin divided by value obtained by epoxide equivalent, The sum of the reactive group of curing agent refers to the solid component quality of each curing agent for all curing agent divided by reactive group The value that value obtained by group's equivalent is added up to.By making the amount of epoxy resin and curing agent than setting in such range The heat resistance of the solidfied material of oil/fat composition further increases.
In the case that resin combination includes (C) active ester compound and (E) curing agent, epoxy resin and active ester chemical combination The amount of object is than with [sum of the epoxy group of epoxy resin]: it is good that the ratio of [sum of the reactive group of (C) and (E) ingredient] is haggled over It is in the range of 1:0.01~1:5, more preferably in the range of 1:0.01~1:3, further more preferably in 1:0.01~1: In the range of 1.5.By making the amount of epoxy resin and (C) ingredient and (E) ingredient than in such range, resin combination The heat resistance of solidfied material further increases.
When resin combination includes (E) curing agent, when the nonvolatile component in resin combination is set as 100 mass %, (E) content of curing agent is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further more preferably 0.5 mass % with On.The upper limit is preferably 5 mass % hereinafter, more preferably 3 mass % are hereinafter, further more preferably 1 mass % or less.By solidifying (E) Adaptation raising with conductor layer of the content of agent in the range, after HAST can be made to test.
< (F) curing accelerator >
In one embodiment, resin combination may include (F) curing accelerator.As curing accelerator, it can be mentioned, for example phosphorus Class curing accelerator, amine-type cure accelerator, imidazoles curing accelerator, guanidine curing accelerator, metal class curing accelerator Deng, preferably Phosphorus curing accelerator, amine-type cure accelerator, imidazoles curing accelerator, metal class curing accelerator, more preferably It is amine-type cure accelerator.Curing accelerator can be used alone a kind, can also two or more be applied in combination.
As Phosphorus curing accelerator, it can be mentioned, for example triphenylphosphine, Phosphonium borate compounds, tetraphenylphosphoniphenolate tetraphenyl boron Hydrochlorate, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyl) triphenyl phosphonium rhodanate, tetraphenyl Phosphonium rhodanate, Ding base triphenyl phosphonium rhodanate etc., preferably triphenylphosphine, 4-butyl-phosphonium caprate.
As amine-type cure accelerator, it can be mentioned, for example the trialkylamines such as triethylamine, tri-n-butylamine, 4- dimethylamino pyrrole Pyridine, benzyl dimethylamine, 2,4,6- tri- (dimethylaminomethyl) phenol, 1,8- diazabicyclo [5.4.0] hendecene etc., preferably It is 4-dimethylaminopyridine, 1,8- diazabicyclo [5.4.0] hendecene.
As imidazoles curing accelerator, it can be mentioned, for example 2-methylimidazole, 2- undecyl imidazole, 2- heptadecyl miaows Azoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl miaow Azoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2- methyl miaow Azoles, 1- cyano ethyl -2- undecyl imidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenyl miaow Azoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acid salt, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt, 2, 4- diamino -6- [2'- methylimidazolyl-is (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- undecyl imidazole base - (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- ethyl -4'- methylimidazolyl-is (1')]-ethyl-s-triazine, 2,4- Diamino -6- [2'- methylimidazolyl-is (1')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid add At object, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole, 2,3- dihydro -1H- pyrroles And [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2- phenyl miaow The adduct of the glyoxaline compounds such as oxazoline and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- benzyl -2- phenylimidazole.
As imidazoles curing accelerator, commercially available product can be used, it can be mentioned, for example Mitsubishi chemical Co., Ltd " P200-H50 " etc..
As guanidine curing accelerator, it can be mentioned, for example dicyandiamide, 1- methylguanidine, 1- ethyl guanidine, 1- cyclohexyl guanidines, 1- benzene Base guanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethylguanidine, pentamethyl guanidine, tri- azepine of 1,5,7- Bicyclic [4.4.0] decene -5,7- methyl-1, tri- azabicyclo of 5,7- [4.4.0] decene -5,1- methyl biguanides, 1- ethyl biguanides, 1- normal-butyl biguanides, 1- n-octadecane base biguanides, 1,1- dimethylbiguanide, 1,1- diethyl biguanides, 1- cyclohexyl biguanides, 1- alkene Propyl biguanides, 1- phenyl biguanide, 1- (o-tolyl) biguanides etc., preferably dicyandiamide, 1,5,7- tri- azabicyclo [4.4.0] last of the ten Heavenly stems Alkene -5.
As metal class curing accelerator, it can be mentioned, for example the organometallic ligands of the metals such as cobalt, copper, zinc, iron, nickel, manganese, tin Close object or organic metal salt.As the specific example of organometallic complex, acetyl acetone cobalt (II), acetylacetone,2,4-pentanedione can be enumerated Close the organic zincs such as organic cobalt complex, the organic copper complex of acetyl acetone copper (II), acetyl acetone zinc (II) such as cobalt (III) The organonickel complexes, levulinic such as organic iron complexes such as complex, acetyl acetone iron (III), nickel acetylacetonate (II) Ketone closes organic manganese complexes such as manganese (II) etc..As organic metal salt, it can be mentioned, for example zinc octoate, tin octoate, zinc naphthenate, rings Alkanoic acid cobalt, stearic acid tin, zinc stearate etc..
When resin combination includes (F) curing accelerator, the nonvolatile component in resin combination is set as 100 mass % When, the content of (F) curing accelerator is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and further more preferably 0.1 Quality % or more.The upper limit is preferably 3 mass % hereinafter, more preferably 2 mass % are hereinafter, further more preferably 1 mass % or less.By making (F) content of curing accelerator is in the range, even if the inorganic filling material small using average grain diameter, also can get HAST The good solidfied material of closing force after test.
< (G) thermoplastic resin >
In one embodiment, resin combination may include (G) thermoplastic resin.As (G) thermoplastic resin, it can be mentioned, for example Phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene, polyimide resin, polyamidoimide tree Rouge, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyether-ether-ketone resin, gathers polyetherimide resin Ester resin etc., preferably phenoxy resin.Thermoplastic resin can be used alone a kind, can also two or more be applied in combination.
(G) thermoplastic resin polystyrene conversion weight average molecular weight be preferably 38000 or more, more preferably 40000 with On, further more preferably 42000 or more.The upper limit is preferably 100000 hereinafter, more preferably 70000 hereinafter, further more preferably 60000 or less.(G) weight average molecular weight of the polystyrene conversion of thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, Shimadzu Scisakusho Ltd LC- can be used in the weight average molecular weight of the polystyrene conversion of (G) thermoplastic resin 9A/RID-6A as measurement device, use Showa Denko K. K Shodex K-800P/K-804L/K-804L as Column uses chloroform etc. as mobile phase, makes 40 DEG C of column temperature to be measured, and is calculated using the calibration curve of standard polystyren.
As phenoxy resin, it can be mentioned, for example have to be selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol acetyl Benzene skeleton, phenolic aldehyde skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, enb skeleton, naphthalene skeleton, anthracene skeleton, gold The phenoxy resin of the skeleton of one or more of rigid alkane skeleton, terpenes skeleton and trimethyl-cyclohexane skeleton.The end of phenoxy resin It can be any functional group in phenolic hydroxyl, epoxy group etc..Phenoxy resin can be used alone a kind, can also two or more combination It uses.As the specific example of phenoxy resin, " 1256 " and " 4250 " that can enumerate Mitsubishi chemical Co., Ltd (are containing double The phenoxy resin of phenol A skeleton), " YX8100 " (phenoxy resin of the skeleton containing bisphenol S) and " YX6954 " (benzene skeleton of acetyl containing bis-phenol Phenoxy resin) and Nippon Steel & Sumitomo Metal Corporation " FX280 " and " FX293 ", Mitsubishi chemical Co., Ltd's system " YX7500BH30 ", " YX6954BH30 ", " YX7553 ", " YX7553BH30 ", " YL7769BH30 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc..
As polyvinyl acetal resin, it can be mentioned, for example vinyl-formal resin, polyvinyl butyral resin, Preferably polyvinyl butyral resin.As the specific example of polyvinyl acetal resin, it can be mentioned, for example electrochemically works " the electrochemical butyral 4000-2 " of industry Co. Ltd. system, " electrochemical butyral 5000-A ", " electrochemical butyral 6000-C ", " electrification Butyral 6000-EP ", S-LEC BH series, BX serial (such as BX-5Z), the KS series of Sekisui Chemical Co., Ltd (such as KS-1), BL series, BM series etc..
As the specific example of polyimide resin, " the RIKACOAT of New Japan Chem Co., Ltd can be enumerated SN20 " and " RIKACOAT PN20 ".As the specific example of polyimide resin, can also enumerate makes two functional hydroxyl groups ends Linear polyimide (Japanese Patent Laid-Open 2006- obtained by polybutadiene, diisocyanate cpd and quaternary anhydride reaction No. 37083 bulletins record polyimides), polyimides (Japanese Patent Laid-Open 2002-12667 containing silicone matrix The polyimides recorded in bulletin and Japanese Patent Laid-Open 2000-319386 bulletin etc.) etc. modified polyimides.
As the specific example of polyamide-imide resin, " the VYLOMAX that Co. Ltd. system is spun by Japan can be also enumerated HR11NN " and " VYLOMAX HR16NN ".As the specific example of polyamide-imide resin, Hitachi's chemical conversion strain formula can be also enumerated The modified polyamide imides such as " KS9100 " of commercial firm, " KS9300 " (polyamidoimide containing silicone matrix).
As the specific example of polyethersulfone resin, " PES5003P " of Sumitomo Chemical Co etc. can be enumerated.As The specific example of polyphenylene oxide resin can enumerate oligomeric phenylate-styrene resin " OPE- of Mitsubishi Gas Chemical Co., Ltd 2St 1200 " etc..
As the specific example of polysulfone resin, the polysulfones of Solvay Advanced Polymers Co. Ltd. system can be enumerated " P1700 ", " P3500 " etc..
Wherein, as (G) thermoplastic resin, preferably phenoxy resin, polyvinyl acetal resin.Accordingly, it is preferred that one In a embodiment, thermoplastic resin includes to be selected from one or more of phenoxy resin and polyvinyl acetal resin.Wherein, make For thermoplastic resin, preferably phenoxy resin, the phenoxy resin that particularly preferably weight average molecular weight is 40000 or more.
In the case that resin combination includes (G) thermoplastic resin, the nonvolatile component in resin combination is set as 100 When quality %, the content of (G) thermoplastic resin is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, further more preferably 0.3 mass % or more.The upper limit is preferably 5 mass % hereinafter, more preferably 3 mass % are hereinafter, further more preferably 1 mass % or less.It is logical Crossing makes the content of (G) thermoplastic resin in the range, even if the inorganic filling material small using average grain diameter, also can get The good solidfied material of closing force after HAST test.
The arbitrary additive > of < (H)
In one embodiment, resin combination can also include other additives as needed, as other such additives, It can be mentioned, for example organic gold such as fire retardant, organic filler material, organocopper compound, organic zinc compound and organic cobalt compounds Belong to resin additives such as compound and thickener, defoaming agent, flat agent, adaptation imparting agent and colorant etc..
As fire retardant, it can be mentioned, for example the nitrogenous phosphorus compound of phosphazene compound, organic phosphates fire retardant, organic, Nitrogen compound, silicone based flame retardant, metal hydroxides etc..As the specific example of phosphazene compound, it can be mentioned, for example big " SPH-100 ", " SPS-100 ", " SPB-100 ", " SPE-100 ", Fushimi Pharmaceutical Company, Limited of tomb Chemical Co., Ltd. " FP-100 ", " FP-110 ", " FP-300 ", " FP-400 " etc. of system can be used as the fire retardant in addition to phosphazene compound Commercially available product, it can be mentioned, for example " HCA-HQ " of Sanko Co., Ltd., " PX-200 " of Daihachi Chemical Industry Co., Ltd. etc..
As organic filler material, the arbitrary organic filling that can be used when forming the insulating layer of printed wiring board can be used Material, it can be mentioned, for example rubber particles, polyamide particles, organic silicon particles etc..As rubber particles, commercially available product can be used, it can Enumerate " EXL2655 " of such as DOW Chemical Amada Co., Ltd., " AC3401N " of Eike Kogyo K.K., " AC3816N " etc..
The physical property of < resin combination, purposes >
Make resin combination 100 DEG C of heat cures 30 minutes, 170 DEG C after heat cure 30 minutes, 200 DEG C heat cure 90 minutes Obtained by solidfied material usually show HAST test before copper foil peel strength (peel strength) good characteristic.That is, bringing HAST The good insulating layer of adaptation before test.Peel strength before being tested as HAST, preferably 0.4kgf/cm or more, more preferably It is 0.5kgf/cm or more, further more preferably 0.6kgf/cm or more.The upper limit is not particularly limited, but can be set as 10kgf/cm or less Deng.Copper foil peel strength before HAST test can be measured by the method recorded in aftermentioned embodiment.
Make resin combination 100 DEG C of heat cures 30 minutes, at 170 DEG C after heat cure 30 minutes, in 200 DEG C of heat cures 90 Solidfied material obtained by minute usually shows copper foil peel strength (peel strength) good characteristic after HAST test.That is, bringing Adaptation after HAST test is good, can play the insulating layer of high adhesion for a long time.Peel strength after being tested as HAST, compared with It is well 0.15kgf/cm or more, more preferably 0.2kgf/cm or more, further more preferably 0.3kgf/cm or more.The upper limit is without special limit It is fixed, but it is such as the following to be set as 10kgf/cm.Peel strength after HAST test can method by recording in aftermentioned embodiment It is measured.
Make resin combination at 100 DEG C after heat cure 30 minutes, is usual in 170 DEG C of solidfied materials obtained by heat cure 30 minutes Show the good characteristic of glue residue removability.That is, bringing even if forming through-hole, the maximum glue of via bottoms on the solidfied material Slag length is also 5 μm of insulating layers below.Glue residue removability can be measured by the method recorded in aftermentioned embodiment.
The low characteristic of minimum melt viscosity when resin combination of the invention shows 60~200 DEG C.That is, wiring is brought to bury The good resin combination of entering property.Minimum melt viscosity at 60~200 DEG C of resin combination is preferably 5000 pools hereinafter, more It is 4500 pools well hereinafter, further more preferably 4000 pools are following.From the relatively thin sight for stablizing maintenance thickness of resin composition layer From the point of view of point, the lower limit of the minimum melt viscosity is preferably 100 pools or more, more than more preferably 1000 pools.Minimum melt viscosity can lead to It crosses dynamic viscoelastic method to be measured, such as can be measured according to the method recorded in aftermentioned embodiment.
Resin combination of the invention can bring film-insulated property good and can maintain between conductor layer after HAST test Adaptation insulating layer.Therefore, resin combination of the invention is preferably used as the resin combination of insulation applications.It is specific next It says, is preferably used as: being used to form the insulating layer " for forming the conductor layer being formed on the insulating layer (comprising wiring layer again) " Resin combination (for forming the insulating layer formation resin combination of conductor layer), be used to form the insulating layer of printed wiring board Resin combination (resin compositions for insulating layer of printed wiring board)；It can more preferably be used as: be used to form printed wiring board Interlayer insulating film resin combination (the interlayer insulating film resin combination of printed wiring board).In addition, for the present invention Resin combination for, due to bringing the good insulating layer of component imbedibility, printed wiring board be built-in with component Circuit board when, it also may be preferable for use.
In addition, in the case where for example manufacturing semiconductor chip packaging by (1) below~(6) process, it is of the invention Resin combination is also preferably used as: the resin combination for being routed forming layer again as the insulating layer for being used to form again wiring layer Object (being routed the resin combination of forming layer formation again) and the resin combination for being sealed to semiconductor chip (are partly led The resin combination of body chip sealing).When manufacturing semiconductor chip packaging, it can be further formed on sealant and be routed again Layer,
(1) process for being fixed temporarily film is laminated on substrate；
(2) semiconductor chip is temporarily fixed on to the process being fixed temporarily on film；
(3) process of sealant is formed on a semiconductor die；
(4) by substrate and it is fixed temporarily the process that film removes from semiconductor chip；
(5) it is formed on the face of semiconductor chip removed substrate and be fixed temporarily film as insulating layer and is routed forming layer again Process；And
(6) it is being routed the process that the wiring layer again as conductor layer is formed on forming layer again.
[resin sheet]
Resin sheet of the invention includes supporting mass and being formed on the supporting mass with resin combination of the invention Resin composition layer.
Even from the slimming of printed wiring board and can provide film also from the viewpoint of the good solidfied material of insulating properties, The thickness of resin composition layer be preferably 25 μm hereinafter, more preferably 20 μm hereinafter, further more preferably 15 μm or less or 10 μm with Under.The lower limit of the thickness of resin composition layer is not particularly limited, and can usually be set as 1 μm or more, 1.5 μm or more, 2 μm with first-class.
As supporting mass, it can be mentioned, for example the film being molded of plastic material, metal foil, processing release papers, preferably by plastics material Expect the film formed, metal foil.
Use the film that is molded of plastic material as in the case where supporting mass, as plastic material, it can be mentioned, for example poly- pair The polyester such as ethylene terephthalate (below also referred to as " PET "), polyethylene naphthalate (below also referred to as " PEN "), Acrylic polymers, cyclic polyolefin, three such as polycarbonate (below also referred to as " PC "), polymethyl methacrylate (PMMA) Acetylcellulose (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferably poly terephthalic acid second two Alcohol ester, polyethylene naphthalate, particularly preferably cheap polyethylene terephthalate.
Use metal foil as in the case where supporting mass, as metal foil, it can be mentioned, for example copper foil, aluminium foils etc., preferably Copper foil.As copper foil, the foil formed by the single metal of copper can be used, it is possible to use by copper and other metals (such as tin, chromium, Silver, magnesium, nickel, zirconium, silicon, titanium etc.) alloy formed foil.
For supporting mass, can the face engaged with resin composition layer implement matte management, Corona discharge Treatment, Antistatic process.
In addition, as supporting mass, may be used at the face that is engaged with resin composition layer have release layer with release layer Supporting mass.As the release agent of the release layer for the supporting mass with release layer, it can be mentioned, for example be selected from alkyd resin, polyolefin The release agent of one or more of resin, polyurethane resin and organic siliconresin.Commercially available product can be used in supporting mass with release layer, It can be mentioned, for example as with the Lindeke Co., Ltd of the PET film of alkyd resin class release agent release layer as main component " SK-1 " of system, " AL-5 ", " AL-7 ", " the LUMIRROR T60 " of Dongli Ltd., Teijin Ltd " Unipeel " etc. of " Purex ", UNITIKA Co. Ltd. system.
As the thickness of supporting mass, be not particularly limited, preferably in the range of 5 μm~75 μm, more preferably 10 μm~ In the range of 60 μm.It should be noted that the supporting mass preferably with release layer is whole in the case where using the supporting mass with release layer Thickness within the above range.
In one embodiment, resin sheet can be as needed also comprising other layers.It, can as other layers Enumerate the basis for example set on the face (that is, face of the side opposite with supporting mass) of resin composition layer not engaged with supporting mass The protective film etc. that supporting mass is selected.The thickness of protective film is not particularly limited, and for example, 1 μm~40 μm.It, can by the way that protective film is laminated Inhibit in the surface of resin composition layer attachment rubbish etc. or forms damage.
Resin sheet can for example manufacture as follows: resin varnish obtained by dissolving resin composition in organic solvent is prepared, The resin varnish is coated on supporting mass with chill coating machine (die coater) etc., re-dry and form resin combination Layer.
As organic solvent, it can be mentioned, for example the ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, second The acetate esters such as acid butyl ester, cellosolve acetate, propylene glycol methyl ether acetate and carbitol acetate, cellosolve and butyl card must The carbitols class such as alcohol, the aromatic hydrocarbons such as toluene and dimethylbenzene, dimethylformamide, dimethyl acetamide (DMAc) and N- methylpyrrole Amide solvents such as alkanone etc..Organic solvent can be used alone a kind, can also two or more be applied in combination.
Drying can be brushed etc. by heating, hot wind well known to method implement.Drying condition is not particularly limited, with resin combination The content of organic solvent in nitride layer reaches 10 mass % or less, preferably 5 mass % conditions below are dried.According to resin The boiling point of organic solvent in varnish and it is different, such as use the resin varnish of the organic solvent containing 30 mass of mass %~60 % In the case of, it can be by forming resin composition layer in 50 DEG C~150 DEG C dryings 3 minutes~10 minutes.
Resin sheet can be rolled into a roll to save.Resin sheet have protective film in the case where, can by removing protective film come It uses.
[printed wiring board]
Printed wiring board of the invention include by resin combination of the invention solidfied material formed insulating layer, the first conductor layer With the second conductor layer.Insulating layer is set between the first conductor layer and the second conductor layer, and the first conductor layer and the second conductor layer is exhausted Edge (conductor layer is also referred to as wiring layer).
Insulating layer is formed by the solidfied material of resin combination of the invention.The insulation of first conductor layer and the second conductor interlayer Layer thickness be preferably 6 μm hereinafter, more preferably 5.5 μm hereinafter, further more preferably 5 μm or less.Lower limit is not particularly limited, 0.1 μm can be set as with first-class.An example as shown in Figure 1, the first conductor layer and the second conductor layer interval (the first conductor layer and The thickness of the insulating layer of second conductor interlayer) refer to it is exhausted between the interarea 11 of the first conductor layer 1 and the interarea 21 of the second conductor layer 2 The thickness t1 of edge layer 3.First conductor layer and the second conductor layer are the conductor layers adjacent with insulating layer that be situated between, and interarea 11 and interarea 21 are mutual It is opposite.
It should be noted that the thickness t2 of insulating layer entirety be preferably 15 μm hereinafter, more preferably 13 μm hereinafter, further more preferably 10 μm or less.Lower limit is not particularly limited, can usually be set as 1 μm or more, 1.5 μm or more, 2 μm with first-class.
Above-mentioned resin sheet can be used to manufacture by the inclusion of the method for the process of following (I) and (II) for printed wiring board,
(I) process being laminated in such a way that the resin composition layer of resin sheet is engaged with internal substrate on internal substrate；
(II) process that resin composition layer heat cure is formed into insulating layer.
" internal substrate " used in process (I) refers to the component of the substrate as printed wiring board, and it can be mentioned, for example glass Glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate etc..This Outside, which can have conductor layer in its one or both sides, which can process by pattern.In the one or both sides of substrate The internal substrate for being formed with conductor layer (circuit) is also referred to as " internal layer circuit substrate ".In addition, need to be into one when manufacture printed wiring board Step forms insulating layer and/or the intermediate manufacture object of conductor layer is also included in the present invention in described " internal substrate ".Print cloth In the case that line plate is component internal circuit board, the internal substrate for being built-in with component can be used.
Resin sheet heating for example can be crimped on internal layer by self-supporting side by the stacking of internal substrate and resin sheet Substrate carries out.It, can as the component (following also referred to as " heating crimping component ") that resin sheet heating is crimped on to internal substrate Enumerate metal plate (SUS panelling) or metallic roll (SUS roller) after heating etc..It should be noted that heating is not pressed preferably Connection member is directly pressed on resin sheet, but is suppressed across heat resistant rubber elastomeric material, so that resin sheet is sufficiently suitable Answer the concave-convex surface of internal substrate.
The stacking of internal substrate and resin sheet can be implemented by vacuum lamination method.In vacuum lamination method, heating crimping temperature Degree is preferably in the range of 60 DEG C~160 DEG C, more preferably 80 DEG C~140 DEG C, and heating crimping pressure is preferably in 0.098MPa In the range of~1.77MPa, more preferably 0.29MPa~1.47MPa, the heating crimping time preferably 20 seconds~400 seconds, it is more preferable It is in the range of 30 seconds~300 seconds.Stacking is preferably implemented under pressure 26.7hPa reduced pressure below.
Stacking can be carried out by commercially available vacuum laminator.As commercially available vacuum laminator, it can be mentioned, for example strain formula meetings Society's name mechanism makees made vacuum pressure type laminator, the vacuum pack system device of Nikko-Materials Co. Ltd. system, batch-type Vacuum pressed laminator etc..
Can be after stacking, under normal pressure (under atmospheric pressure), such as the pressurization of crimping component self-supporting side will be heated to carry out layer The smoothing techniques of folded resin sheet.The pressing conditions of smoothing techniques can be used that crimp condition with the heating of above-mentioned stacking same The condition of sample.Smoothing techniques can be carried out by commercially available laminator.It should be noted that stacking and smoothing techniques can be used it is above-mentioned Commercially available vacuum laminator be carried out continuously.
Supporting mass can remove between process (I) and process (II), can also remove after process (II).
In process (II), resin composition layer heat cure is formed into insulating layer.
The heat cure condition of resin composition layer is not particularly limited, can be used formed it is usual when the insulating layer of printed wiring board Used condition.
For example, the heat cure condition of resin composition layer is different according to type of resin combination etc., solidification temperature compared with It is 120 DEG C~240 DEG C, more preferably 150 DEG C~220 DEG C, further more preferably 170 DEG C~200 DEG C well.Curing time is preferably 5 Minute~120 minutes, more preferably 10 minutes~100 minutes, further more preferably 15 minutes~90 minutes.
Resin composition layer can be carried out in advance in the temperature lower than solidification temperature before making resin composition layer heat cure Heating.For example, can before making resin composition layer heat cure, 50 DEG C more than or lower than 120 DEG C (preferably 60 DEG C or more and 115 DEG C hereinafter, more preferably 70 DEG C or more and 110 DEG C or less) at a temperature of, by resin composition layer preheat 5 minutes or more (compared with It is 5 minutes~150 minutes, more preferably 15 minutes~120 minutes, further more preferably 15 minutes~100 minutes well).
When manufacturing printed wiring board, also implementable (III) carries out insulating layer in the process of insulating layer perforating, (IV) coarse Change the process of processing, the process that (V) forms conductor layer.These processes (III)~process (V) can be according to the manufacture of printed wiring board Various methods well known to those skilled in the art used are implemented.It should be noted that removing supporting mass after process (II) In the case of, the removing of the supporting mass can between process (II) and process (III), between process (III) and process (IV) or Implement between process (IV) and process (V).In addition, can implement repeatedly as needed process (II)~process (V) insulating layer and The formation of conductor layer forms multiwiring board.In this case, the thickness (t1 of Fig. 1) of the insulating layer of preferably each conductor interlayer Respectively within the above range.
Process (III) is the process in insulating layer perforating, can take this to form the holes such as through-hole, via hole in insulating layer.Process It (III) can be according to composition of the resin combination of the formation for insulating layer etc. using such as drill bit, laser, plasma Implement.The size and shape in hole can be suitably determined according to the design of printed wiring board.
Process (IV) is the process being roughened to insulating layer.The step of roughening treatment, condition are without special limit It is fixed, commonly used known step, condition when the insulating layer to form printed wiring board can be used.For example, successively implementing to adopt Insulating layer is carried out with the swelling treatment of swelling solution, the roughening treatment using oxidant, the neutralisation treatment using neutralizer Roughening treatment.It as swelling solution used in roughening treatment, is not particularly limited, it is molten that aqueous slkali, surfactant can be enumerated Liquid etc., preferably aqueous slkali, as the aqueous slkali, more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling Liquid, it can be mentioned, for example ATOTECH JAPAN Co. Ltd. systems " Swelling Dip Securiganth P ", " Swelling Dip Securiganth SBU " etc..Be not particularly limited using the swelling treatment of swelling solution, for example, can by by insulating layer 30 DEG C~90 DEG C of swelling solution in impregnate 1 minute~20 minutes to carry out.It controls from by the swelling of the resin of insulating layer in appropriate water From the viewpoint of flat, impregnate insulating layer 5 minutes~15 minutes in 40 DEG C~80 DEG C of swelling solution.As roughening Oxidant used in processing, is not particularly limited, and it can be mentioned, for example potassium permanganate or height are dissolved in the aqueous solution of sodium hydroxide Alkalinity permanganic acid solution obtained by sodium manganate.Roughening treatment using oxidants such as alkaline permanganic acid solutions is preferably to make to insulate Layer impregnates 10 minutes~30 minutes in the oxidizing agent solution for being heated to 60 DEG C~80 DEG C to carry out.In addition, alkaline permanganic acid is molten The concentration of permanganate in liquid is preferably 5 mass of mass %~10 %.As commercially available oxidant, it can be mentioned, for example ATOTECH The alkalinity such as JAPAN Co. Ltd. system " Concentrate Compact CP ", " Dosing solution Securiganth P " Permanganic acid solution.In addition, preferably acid aqueous solution can as commercially available product as neutralizer used in roughening treatment It enumerates such as " the Reduction solution Securiganth P " of ATOTECH JAPAN Co. Ltd. system.In Processing with liquid can be by making to have carried out the process face using the roughening treatment of oxidant in 30 DEG C~80 DEG C of neutralizer 5 minutes~30 minutes are impregnated to carry out.From the perspective of operability, will preferably it carry out at the roughening using oxidant The method that the object of reason impregnates 5 minutes~20 minutes in 40 DEG C~70 DEG C of neutralizer.
In one embodiment, the arithmetic average roughness (Ra) of the surface of insulating layer after roughening treatment is preferably 400nm hereinafter, more preferably 350nm hereinafter, further more preferably 300nm or less.Lower limit is not particularly limited, preferably 0.5nm or more, more preferably 1nm is with first-class.In addition, the r.m.s. roughness (Rq) of the surface of insulating layer after roughening treatment is preferable It is 400nm hereinafter, more preferably 350nm is hereinafter, further more preferably 300nm or less.Lower limit is not particularly limited, can be set as compared with It is well 0.5nm or more, more preferably 1nm is with first-class.The arithmetic average roughness (Ra) and r.m.s. roughness of surface of insulating layer (Rq) non-contact type surface roughness meter can be used to be measured.
Process (V) is the process to form conductor layer.In internal substrate in the case where not formed conductor layer, process (V) is shape At the process of the first conductor layer, in the case where being formed with conductor layer in internal substrate, which is the first conductor layer, process (V) process to form the second conductor layer.
Conductor material for conductor layer is not particularly limited.In preferred embodiment, conductor layer include selected from gold, platinum, The metal of one or more of palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor layer can be single metal layer Or alloy-layer, as alloy-layer, it can be mentioned, for example alloy (such as the nickel-chromes by the metal of more than two kinds in above-mentioned metal Alloy, copper-nickel alloy and copper-titanium alloy) formed layer.Wherein, it is formed from the versatility, cost, pattern of conductor layer formation From the point of view of the viewpoints such as difficulty, the preferably single metal layer of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper or nickel-chromium alloy, copper- Nickel alloy, copper-titanium alloy alloy-layer, the more preferably single metal layer or nickel-chrome of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper The alloy-layer of alloy, the more preferably single metal layer of copper.
Conductor layer can be single layer structure, be also possible to the single metal layer formed by different types of metal or alloy or Multilayered structure obtained by 2 layers of alloy layer stackup or more.In the case that conductor layer is multilayered structure, the layer to connect with insulating layer is preferable It is the single metal layer of chromium, zinc or titanium or the alloy-layer of nickel-chromium alloy.
The thickness of conductor layer as expected the design of printed wiring board and it is different, but generally 3 μm~35 μm, preferably It is 5 μm~30 μm.
In one embodiment, conductor layer is formed by plating.For example, can be previous by semi-additive process, fully-additive process etc. Well known technology carries out plating on the surface of insulating layer, the conductor layer with desired wiring pattern is formed, from the letter of manufacture Just it from the viewpoint of property, is formed preferably by semi-additive process.Hereinafter, showing the example for forming conductor layer by semi-additive process.
Firstly, forming plating seed layer by electroless plating on the surface of insulating layer.Then, in the plating seed crystal of formation Desired wiring pattern is corresponded on layer forms the mask pattern for exposing a part of plating seed layer.In the plating seed of exposing After forming metal layer by electrolytic coating on crystal layer, mask pattern is removed.Then, unwanted plating seed is removed by etching etc. Crystal layer, so as to form the conductor layer with desired wiring pattern.
Because component imbedibility also good insulating layer can be brought, therefore resin sheet of the invention can also be used to print well The case where brush wiring plate is component internal circuit board.Component internal circuit board can be made by well known manufacturing method.
The printed wiring board for using resin sheet of the invention to manufacture can be the resin combination having as resin sheet The insulating layer of the solidfied material of nitride layer and embedment to insulating layer buried wiring layer form.
[semiconductor device]
Semiconductor device of the invention includes printed wiring board of the invention.Semiconductor device of the invention can be used of the invention Printed wiring board manufacture.
As semiconductor device, can enumerate for electric product (such as computer, mobile phone, digital camera and television set etc.) and The various semiconductor devices of the vehicles (such as autobicycle, automobile, electric car, ship and aircraft etc.) etc..
Component (semiconductor chip) can be by being installed on the conduction position of printed wiring board by semiconductor device of the invention To manufacture." conduction position " refers to " position that electric signal is conducted in printed wiring board ", and position can be also possible on surface The position being embedded.In addition, as long as semiconductor chip using semiconductor as the electrical circuit components of material, is limited without special It is fixed.
As long as the installation method semiconductor chip of semiconductor chip when manufacturing semiconductor device effectively plays a role i.e. Can, it is not particularly limited, specific enumerable wire bonding installation method, flip-chip installation method, using solderless buildup layer (BBUL) installation method, using the installation method of anisotropic conductive film (ACF), using the installation of non-conductive film (NCF) Method etc..Here, " installation method for using solderless buildup layer (BBUL) ", which refers to, " is directly embedded to printed wiring for semiconductor chip The recess portion of plate makes the installation method of the wiring connection on semiconductor chip and printed wiring board ".
Embodiment
Hereinafter, the present invention is specifically described by embodiment.The invention is not limited to these embodiments.It should say It is bright, hereinafter, " part " and " % " of expression amount respectively indicates " mass parts " and " quality % " as long as no separately expressing.
[embodiment 1]
Make 10 parts of bisphenol-type epoxy resins (Nippon Steel & Sumitomo Metal Corporation's system " ZX1059 ", bisphenol A-type while stirring With the 1:1 melange of bisphenol-f type, epoxide equivalent 169) and 50 parts of naphthol type epoxy resin (Nippon Steel & Sumitomo Metal Corporation It makes " ESN475V ", 330) epoxide equivalent is about dissolved by heating in 40 parts of solvent naphthas.It is cooled to room temperature, (A) epoxy is made The dissolved composition of resin.
5 parts of phenoxy resin (Mitsubishi chemical Co., Ltd's systems are mixed into the dissolved composition of (A) epoxy resin " YX7553BH30 ", the MEK of 30 mass % of solid component and the 1:1 solution of cyclohexanone), 5 parts have triazine skeleton and phenolic structure Phenol curing agent (Dainippon Ink Chemicals's system " LA-3018-50P ", active group equivalent about 151, the 2- first of solid component 50% Oxygroup propanol solution), (Dainippon Ink Chemicals's system " HPC-8000-65T ", active group equivalent is about for 50 parts of active esters curing agent 223, the toluene solution of 65 mass % of solid component), 5 parts of curing accelerators (1- benzyl -2- phenylimidazole (1B2PZ), solid at The MEK solution of point 10 mass %), 250 parts pass through amine alkoxysilane compound containing trialkylsilyl group in molecular structure (Shin-Etsu Chemial Co., Ltd's system " KBM573 ") be surface-treated spherical silicon dioxide (0.77 μm of average grain diameter, specific surface area 5.9m2/ g, Co., Ltd. Refined all Ma systems " SO-C2 ") and maleimide compound (artificial molecule corporation " BMI3000J ") 40 mass % toluene solutions It 25 parts, is uniformly dispersed with high speed rotation mixing machine, resin varnish is made.
As supporting mass, prepare polyethylene terephthalate film (the Lindeke Co., Ltd's system for having release layer " AL5 ", 38 μm thick).Reach with the thickness of the resin composition layer after drying 25 μm of condition on the release layer of the supporting mass Equably it is coated with the resin varnish.Then, resin varnish is 4 minutes dry at 80 DEG C~120 DEG C (100 DEG C average), it obtains Obtain the resin sheet comprising supporting mass and resin composition layer.
[embodiment 2]
In embodiment 1, by 40 mass % toluene solutions 25 of maleimide compound (artificial molecule corporation " BMI3000J ") Part is changed to 40 25 parts of mass % toluene solutions of maleimide compound (artificial molecule corporation " BMI1700 ").Except above It other than item, is operated similarly to Example 1, resin varnish, resin sheet is made.
[embodiment 3]
In embodiment 1, by 40 mass % toluene solutions 25 of maleimide compound (artificial molecule corporation " BMI3000J ") Part is changed to 40 25 parts of mass % toluene solutions of maleimide compound (artificial molecule corporation " BMI1500 ").Except above It other than item, is operated similarly to Example 1, resin varnish, resin sheet is made.
[embodiment 4]
In embodiment 1, by 40 mass % toluene solutions 25 of maleimide compound (artificial molecule corporation " BMI3000J ") Part is changed to 40 25 parts of mass % toluene solutions of maleimide compound (artificial molecule corporation " BMI689 ").Except above It other than item, is operated similarly to Example 1, resin varnish, resin sheet is made.
[comparative example 1]
In embodiment 1, by 40 mass % toluene solutions 25 of maleimide compound (artificial molecule corporation " BMI3000J ") Part is changed to 40 mass %MEK of the maleimide compound (KI is melted into Co. Ltd. system " BMI70 ") indicated with following structural formula 25 parts of solution.It in addition to above item, is operated similarly to Example 1, resin varnish, resin sheet is made；
[chemical formula 14]
In formula, Me indicates that methyl, Et indicate ethyl.
[comparative example 2]
In embodiment 2, it will be carried out by amine alkoxysilane compound containing trialkylsilyl group in molecular structure (Shin-Etsu Chemial Co., Ltd's system " KBM573 ") The amount of the spherical silicon dioxide (0.77 μm of average grain diameter, the refined all Ma systems " SO-C2 " of Co., Ltd.) of surface treatment becomes from 250 parts It is 240 parts, does not use maleimide compound (artificial molecule corporation " BMI3000J ").In addition to above item, with Embodiment 2 is carried out similarly operation, and resin varnish, resin sheet is made.
[evaluation method]
Resin sheet obtained in the above embodiments and comparative example is evaluated by following methods.
[measuring method of peel strength]
The < closely sealed evaluation production > of substrate
(1) base treatment of internal substrate:
As internal substrate, the glass cloth base material epoxy resin two sides copper-clad laminated board (copper foil that there is copper foil on surface is prepared 18 μm of thickness, substrate thickness 0.8mm, Panasonic's Co. Ltd. system " R1515A ").The copper foil on the surface of the internal substrate is all lost It carves and removes.Then, 30 minutes dry at 190 DEG C.
(2) stacking of resin sheet:
By the batch-type vacuum pressed laminator (Nikko- of resin sheet obtained in the above embodiments and comparative example Materials Co. Ltd. system, 2 stages stack laminator " CVP700 ") it is connect with resin composition layer and the internal substrate The mode of conjunction is laminated at the two sides of internal substrate.This is laminated to be implemented as follows: after decompression makes air pressure reach 13hPa or less in 30 seconds, with 100 DEG C of temperature, pressure 0.74MPa are crimped 30 seconds.
Then, resin sheet after will be laminated under atmospheric pressure with 100 DEG C, pressure 0.5MPa carry out 60 seconds hot pressing and into Row smoothing.Then, remove supporting mass, obtain successively comprising resin composition layer, internal substrate and resin composition layer " in Between layered body I ".
On the other hand, prepare the copper foil (35 μm of thickness, Mitsui Metal Co., Ltd.'s Co. Ltd. system " 3EC-III ") with glassy surface. The glassy surface of the copper foil is lost with micro-etching agent (Mitsuku K.K.'s system " CZ8101 ") with 1 μm of copper etch quantity of condition It carves, is roughened.The copper foil obtained in this way is known as " roughening copper foil ".
By the roughening copper foil with the resin in the face for implementing roughening treatment of the roughening copper foil and intermediate multilayer body I The mode of composition layer engagement is laminated at the two sides of intermediate multilayer body I.This it is laminated with the above-mentioned inside laminar substrate of resin sheet Laminated same condition carry out.It obtains as a result, successively comprising roughening copper foil, resin composition layer, internal substrate, resin group It closes nitride layer and is roughened " the intermediate multilayer body II " of copper foil.
The intermediate multilayer body II baking oven for putting into 100 DEG C is heated 30 minutes, 170 DEG C of baking oven is then moved to and heats 30 points Clock.Then, after intermediate multilayer body II being taken out from baking oven to room temperature atmosphere, then 200 DEG C of additional 90 points of the heating of baking oven is put into Clock.The heat cure for carrying out resin composition layer as a result, obtains successively comprising roughening copper foil, consolidating as resin composition layer The insulating layer of compound, internal substrate, as resin composition layer solidfied material insulating layer and roughening copper foil " evaluation base Plate A ".In evaluation substrate A, roughening copper foil is equivalent to conductor layer.
The measurement > of peel strength before < HAST test
Using above-mentioned evaluation substrate A, the measurement of the peel strength of roughening copper foil and insulating layer has been carried out.The peel strength Measurement is carried out according to JIS C6481.Specifically, the measurement of peel strength has been carried out by following operations.
It is formed and is cut in a manner of surrounding the rectangle part of width 10mm, long 100mm on the roughening copper foil of evaluation substrate A Mouthful.One end of the rectangle part is removed, with fixture (Co., Ltd.'s T.S.E system, AUTO COM type testing machine " AC-50C-SL ") It clamps.The range of the length 35mm of the rectangle part is vertically removed, the load (kgf/cm) when by the removing is made It is determined for peel strength.The removing is carried out at room temperature with 50mm/ minutes speed.
The measurement > of peel strength after < HAST test
Then, to evaluation substrate A carried out 130 DEG C of temperature, humidity 85%RH environment in places 100 hours HAST test. After HAST test, by same method before testing with HAST, the roughening copper foil and insulating layer of evaluation substrate A have been carried out The measurement of peel strength.
[evaluation of glue residue removability]
(1) base treatment of internal substrate:
As internal substrate, the glass cloth base material epoxy resin two sides copper-clad laminated board (copper foil that there is copper foil on surface is prepared 18 μm of thickness, substrate thickness 0.8mm, Panasonic's Co. Ltd. system " R1515A ").By the copper foil microetch on the internal substrate surface Agent (Mitsuku K.K.'s system " CZ8101 ") is etched with 1 μm of copper etch quantity of condition, is roughened.Then, exist 190 DEG C drying 30 minutes.
(2) stacking, solidification of resin sheet:
By the batch-type vacuum pressed laminator (Nikko- of resin sheet obtained in the above embodiments and comparative example Materials Co. Ltd. system, 2 stages stack laminator " CVP700 ") it is connect with resin composition layer and the internal substrate The mode of conjunction is laminated at the two sides of internal substrate.This is laminated to be implemented as follows: after decompression makes air pressure reach 13hPa or less in 30 seconds, with 100 DEG C of temperature, pressure 0.74MPa are crimped 30 seconds.
Then, resin sheet after will be laminated under atmospheric pressure with 100 DEG C, pressure 0.5MPa carry out 60 seconds hot pressing and into Row smoothing.Then, it is put into 100 DEG C of baking oven to heat 30 minutes, then moves to 170 DEG C of baking oven and heat 30 minutes.
(3) formation of through-hole:
Use sub- machinery (VIA MECH) the Co. Ltd. system CO of dimension2Laser machine (LK-2K212/2C), under frequency 2000Hz Pulse width 3 is delicate, power 0.95W, the condition for irradiating number 3 process insulating layer, and the top diameter for foring surface of insulating layer is 50 μm, the through-hole that the diameter of insulating layer bottom surface is 50 μm.Then, it removes supporting mass and has obtained circuit substrate.
(4) roughening treatment
The surface of insulating layer of circuit substrate is used as to the Swelling Dip of the ATOTECH JAPAN Co. Ltd. system of swelling solution Securiganth P impregnates 10 minutes in 60 DEG C.Then, by the surface of insulating layer of circuit substrate as roughening liquid The Concentrate Compact P (KMnO of ATOTECH JAPAN Co. Ltd. system4: 60g/L, NaOH:40g/L's is water-soluble Liquid) in 80 DEG C impregnate 25 minutes.Finally, by the surface of insulating layer of circuit substrate in the ATOTECH JAPAN as neutralizer It is impregnated 5 minutes in the Reduction solution Securiganth P of Co. Ltd. system in 40 DEG C.
(5) the residue evaluation of via bottoms
Observed around via bottoms by scanning electron microscope (SEM), according to resulting determining image via bottoms from The maximum glue residue length of wall surface, is evaluated according to benchmark below；
〇: maximum glue residue length is less than 5 μm
×: maximum glue residue length is 5 μm or more.
[measurement of minimum melt viscosity]
For the melt viscosity of the resin composition layer of the resin sheet made in embodiment and comparative example, dynamic viscoelastic is used Measurement device (Co., Ltd.'s UBM system " Rheosol-G3000 ") is determined.The measurement from resin composition layer for acquiring 1g sample using diameter 18mm parallel-plate carry out.Determination condition is used from 60 DEG C to 200 DEG C of start temperature, heating rate 5 DEG C/min, 2.5 DEG C of measuring temperature interval, vibration 1Hz/deg.Minimum melt is found out according to the measured value of resulting melt viscosity Viscosity.
[result]
The result of the above embodiments and comparative example is shown in following tables.In following tables, the amount expression of each ingredient is not waved Send out ingredient conversion amount.
[table 1]
。
Confirm in Examples 1 to 4, even if in the case where being free of (C)~(G) ingredient, although there are difference in degree, Also it is attributed to result same as above-described embodiment.
The explanation of symbol
1 first conductor layer
The interarea of 11 first conductor layers
2 second conductor layers
The interarea of 21 second conductor layers
3 insulating layers
Interval (the thickness of the insulating layer of the first conductor layer and the second conductor interlayer of the first conductor layer of t1 and the second conductor layer Degree)
The thickness of t2 insulating layer entirety.

Claims (16)

1. a kind of resin combination, it is the resin combination comprising (A) epoxy resin and (B) maleimide compound, In,
(B) ingredient includes at least any one in the alkyl that carbon atom number is 5 or more and the alkylidene that carbon atom number is 5 or more.
2. resin combination according to claim 1, wherein (B) ingredient is indicated by the following general formula (B-1)；
In general formula (B-1), R each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more, and L indicates single Key or divalent linking group.
3. resin combination according to claim 1, wherein the nonvolatile component in resin combination is set as 100 matter When measuring %, the content of (B) ingredient is 0.1 mass % or more and 10 mass % or less.
4. resin combination according to claim 1, wherein also include (C) active ester compound.
5. resin combination according to claim 4, wherein the nonvolatile component in resin combination is set as 100 matter When measuring %, the content of (C) ingredient is 5 mass % or more.
6. resin combination according to claim 1, wherein also include (D) inorganic filling material.
7. resin combination according to claim 6, wherein the content of (D) ingredient is 50 mass % or more.
8. resin combination according to claim 1, wherein in general formula (B-1), L is oxygen atom, can have substituent group Arlydene that carbon atom number is 6~24, can to have alkylidene, carbon atom number that the carbon atom number of substituent group is 1~50 be 5 or more Alkyl, the divalent group from phthalimide, the divalent group from Pyromellitic Acid imidodicarbonic diamide or by Divalent group made of 2 combination of the above in these groups.
9. resin combination according to claim 1, wherein (B) ingredient is indicated by the following general formula (B-2)；
In general formula (B-2), R' each independently represents the alkylidene that can have that the carbon atom number of substituent group is 5 or more, and A is respectively only On the spot indicate can there is the alkylidene or the divalent base with aromatic ring that there can be substituent group that the carbon atom number of substituent group is 5 or more Group, n indicate 1~10 integer.
10. resin combination according to claim 9, wherein in general formula (B-2), A is each independently represented to have and be taken The carbon atom number of Dai Ji be 5 or more cyclic alkylidene, can have substituent group the divalent group with phenyl ring, can have substitution The divalent group with phthalimide ring of base or 2 with Pyromellitic Acid imidodicarbonic diamide ring that can have substituent group Valence group.
11. resin combination according to claim 1, wherein the resin combination is used to form the exhausted of printed wiring board Edge layer.
12. resin combination according to claim 1, wherein the resin combination is used to form the layer of printed wiring board Between insulating layer.
13. a kind of resin sheet, it includes supporting mass and on the supporting mass by any one of claim 1~12 institute The resin composition layer that the resin combination stated is formed.
14. resin sheet according to claim 13, wherein resin composition layer with a thickness of 25 μm or less.
15. a kind of printed wiring board, it is comprising the first conductor layer, the second conductor layer and to be formed in the first conductor layer and second The printed wiring board of insulating layer between conductor layer, wherein
The insulating layer is the solidfied material of resin combination described in any one of claim 1~12.
16. a kind of semiconductor device, it includes the printed wiring boards described in claim 15.
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