CN109666260A - Resin composition layer - Google Patents

Resin composition layer Download PDF

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Publication number
CN109666260A
CN109666260A CN201811183033.9A CN201811183033A CN109666260A CN 109666260 A CN109666260 A CN 109666260A CN 201811183033 A CN201811183033 A CN 201811183033A CN 109666260 A CN109666260 A CN 109666260A
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Prior art keywords
resin
resin composition
composition layer
mass
layer
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Inventor
鹤井彦
鹤井一彦
阪内启之
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides the resin composition layer etc. that can inhibit halo phenomenon thickness is thin.A kind of resin composition layer, it is 15 μm of resin composition layers below of thickness comprising resin combination, wherein, resin combination includes (A) epoxy resin, (B) curing agent, (C) magnesium hydroxide and (D) silica.

Description

Resin composition layer
Technical field
The present invention relates to resin composition layers.The invention further relates to the resin sheet comprising the resin composition layer and Printed wiring board and semiconductor device comprising the insulating layer formed by the solidfied material of resin composition layer.
Background technique
In recent years, in order to realize the miniaturization of electronic equipment, printed wiring board is constantly thinned.Cloth in internal substrate Line circuit is miniaturize therewith.Low medium is coped with comprising supporting mass and resin composition layer for example, describing in patent document 1 The resin sheet (adhesive film) of loss angle tangent.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2014-5464 bulletin.
Summary of the invention
The technical problems to be solved by the invention
The present inventor is in order to realize the further miniaturization of electronic equipment, be thinned, to the resin combination for reducing resin sheet The thickness of nitride layer is studied.Research as a result, the inventors discovered that by thin resin composition layer be suitable for insulation In the case where layer, if forming through-hole on which insulating layer, haloing (haloing) phenomenon is generated.Here, halo phenomenon refers to Around through-hole the phenomenon that the resin discoloration of insulating layer.When such halo phenomenon is typically due to be formed through-hole around through-hole Resin is deteriorated and is generated.
Above-mentioned project (technical problem) be due to reduce the thickness of resin composition layer and generate for the first time it is previous not The new project known.From the viewpoint of the conducting reliability of interlayer for improving printed wiring board, it is desirable to which these projects can be with It is resolved.
The present invention is the invention proposed in view of above-mentioned project, and the purpose is to provide to can inhibit haloing thickness is thin The resin composition layer of phenomenon, the resin sheet comprising the resin composition layer, comprising can inhibit halo phenomenon it is thin absolutely The printed wiring board of edge layer and semiconductor device comprising the printed wiring board.
Technical scheme applied to solve the technical problem
The present inventor is conscientiously studied to solve the project, as a result, it has been found that including (A) asphalt mixtures modified by epoxy resin by combination Rouge, (B) curing agent, (C) magnesium hydroxide and (D) silica resin combination, can solve the project, thus complete At the present invention.
That is, the present invention includes following content；
[1] a kind of resin composition layer, be comprising resin combination and with a thickness of 15 μm of resin composition layers below, In,
Resin combination includes (A) epoxy resin, (B) curing agent, (C) magnesium hydroxide and (D) silica；
[2] resin composition layer according to [1], wherein the average grain diameter of (D) ingredient is 3 μm or less；
[3] resin composition layer according to [1] or [2], wherein the average grain diameter of (D) ingredient is 0.3 μm or less；
[4] resin composition layer according to any one of [1]~[3], wherein by the nonvolatile component in resin combination When being set as 100 mass %, the content of (D) ingredient is 3 mass % or more and 50 mass % or less；
[5] resin composition layer according to any one of [1]~[4], wherein (B) ingredient be selected from phenol curing agent, One or more of active esters curing agent, cyanate curing agent, benzoxazine class curing agent；
[6] resin composition layer according to any one of [1]~[5], wherein by the nonvolatile component in resin combination When being set as 100 mass %, the content of (A) ingredient is 3 mass % or more and 50 mass % or less；
[7] resin composition layer according to any one of [1]~[6], wherein (C) ingredient is carried out with surface treating agent Surface treatment；
[8] resin composition layer according to [7], wherein surface treating agent is alkoxysilane compound containing trialkylsilyl group in molecular structure；
[9] resin composition layer according to [8], wherein alkoxysilane compound containing trialkylsilyl group in molecular structure has amino or vinyl；
[10] resin composition layer according to any one of [7]~[9], wherein the amount of surface treating agent is relative to 100 matter The magnesium hydroxide for measuring part is 5 below the mass；
[11] resin composition layer according to any one of [1]~[10], wherein by resin combination it is non-volatile at When being divided into 100 mass %, the content of (C) ingredient is 2 mass % or more and 40 mass % or less；
[12] resin composition layer according to any one of [1]~[11], wherein the resin composition layer is multi-sheet printed The resin compositions for insulating layer layer of wiring plate；
[13] resin composition layer according to any one of [1]~[12], wherein the resin composition layer is used to form tool Having top diameter is the insulating layer of 35 μm of through-holes below；
[14] a kind of resin sheet is comprising described in any one of supporting mass and [1] that is set on supporting mass~[13] Resin composition layer；
[15] a kind of printed wiring board comprising the resin composition layer as described in any one of [1]~[13] solidfied material The insulating layer of formation；
[16] a kind of semiconductor device is comprising printed wiring board described in [15].
The effect of invention
If using the present invention, it is possible to provide can inhibit the resin composition layer of halo phenomenon thickness is thin, comprising described The resin sheet of resin composition layer, the printed wiring board of thin dielectric layer comprising can inhibit halo phenomenon and comprising described Printed wiring board semiconductor device.
Detailed description of the invention
Fig. 1 is to schematically show obtained by making the solidification of resin composition layer described in first embodiment of the invention absolutely The cross-sectional view of edge layer and internal substrate；
Fig. 2 is to schematically show insulating layer obtained by making the solidification of resin composition layer described in first embodiment of the invention The side opposite with conductor layer face top view；
Fig. 3 is to schematically show roughening obtained by making the solidification of resin composition layer described in first embodiment of the invention The cross-sectional view of treated insulating layer and internal substrate；
Fig. 4 is the schematic cross sectional views of printed wiring board described in second embodiment of the present invention.
Specific embodiment
Hereinafter, showing embodiment and example object, the present invention is described in detail.But the present invention is not limited to Under the embodiment enumerated and example object, can be any in the range of not departing from claims of the present invention and its equivalency range Implement change.
In the following description, " resin component " of resin combination refers to be removed in nonvolatile component contained by resin combination (C) ingredient and the ingredient other than (D) ingredient.
[resin composition layer]
Resin composition layer of the invention is the thin resin composition layer with specified value thickness below.In addition, of the invention Resin combination contained by resin composition layer includes (A) epoxy resin, (B) curing agent, (C) magnesium hydroxide and (D) titanium dioxide Silicon.
By using such resin composition layer, the thin dielectric layer of specified value thickness below can get.And it is possible to It is desired to obtain the present invention as the halo phenomenon that can inhibit when implementing roughening treatment to the insulating layer for being formed with through-hole Effect.
Resin combination can also be added arbitrarily comprising (E) thermoplastic resin, (F) curing accelerator and (G) as needed Agent.Hereinafter, each ingredient contained by resin combination is described in detail.
< (A) epoxy resin >
As the epoxy resin of (A) ingredient, it can be mentioned, for example union II cresols (bixylenol) type epoxy resin, bisphenol type epoxy Resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, three Phenol-type epoxy resin, naphthol novolac (naphthol novolac) type epoxy resin, phenol novolac (phenol novolac) type Epoxy resin, tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, shrink Glyceramine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac (cresol novolac) type epoxy resin, biphenyl Type epoxy resin, linear aliphatic epoxy resin, the epoxy resin with butadiene structure, cycloaliphatic epoxy resin, heterocyclic type Epoxy resin, the epoxy resin containing loop coil, hexamethylene type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type Epoxy resin, trihydroxy methyl type epoxy resin, tetraphenyl ethane type epoxy resin etc..Epoxy resin can be used alone a kind, can also Two or more is applied in combination.
Resin combination is preferably as (A) epoxy resin comprising having the asphalt mixtures modified by epoxy resin of 2 or more epoxy groups in 1 molecule Rouge.100 matter of nonvolatile component from the viewpoint of significantly obtaining the desired effect of the present invention, relative to (A) epoxy resin % is measured, the ratio of the epoxy resin with 2 or more epoxy groups is preferably 50 mass % or more in 1 molecule, more preferably 60 mass % More than, particularly preferably 70 mass % or more.
The epoxy resin (below also referred to as " liquid-state epoxy resin ") and temperature being in a liquid state when including 20 DEG C of temperature in epoxy resin In solid epoxy resin (below also referred to as " solid epoxy resin ") when spending 20 DEG C.(A) epoxy resin is used as in resin combination It can only include liquid-state epoxy resin, can also only include solid epoxy resin, preferably combination includes liquid-state epoxy resin and solid-state Epoxy resin.As (A) epoxy resin, by the way that liquid-state epoxy resin and solid epoxy resin is applied in combination, resin combination can be made The flexible of nitride layer is improved, or improves the breaking strength of the solidfied material of resin composition layer.
As liquid-state epoxy resin, there is the liquid-state epoxy resin of 2 or more epoxy groups in preferably 1 molecule.
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 hexamethylene type epoxy resin.
As the specific example of liquid-state epoxy resin, can enumerate " HP4032 " of Dainippon Ink Chemicals, " HP4032D ", " HP4032SS " (naphthalene type epoxy resin), " 828US " of Mitsubishi chemical Co., Ltd, " jER828EL ", " 825 ", " EPIKOTE 828EL " (bisphenol A type epoxy resin), " jER807 ", " 1750 " (bisphenol-f type of Mitsubishi chemical Co., Ltd Epoxy resin), " jER152 " (phenol novolak type epoxy) of Mitsubishi chemical Co., Ltd, Mitsubishi chemical Co., Ltd's system " 630 ", " 630LSD " (glycidyl amine type epoxy resin), " ZX1059 " of Nippon Steel & Sumitomo Metal Corporation be (double The melange of phenol A type epoxy resin and bisphenol f type epoxy resin), " EX-721 " (contracting of Nagase ChemteX Co. Ltd. system Water glycerol ester type epoxy resin), " CELLOXIDE 2021P " (aliphatic ring with ester skeleton of Daicel Co. Ltd. system Oxygen resin), " PB-3600 " (epoxy resin with butadiene structure) of Daicel Co. Ltd. system, aurification is lived by Nippon Steel " ZX1658 " of Co. Ltd. system, " ZX1658GS " (liquid 1,4- glycidol butylcyclohexane type ring oxygen resin) etc..These liquid State epoxy resin can be used alone a kind, can also two or more be applied in combination.
As solid epoxy resin, there is the solid epoxy resin of 3 or more epoxy groups, more preferably in preferably 1 molecule It is the solid epoxy resin of the aromatic species in 1 molecule with 3 or more epoxy groups.
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, naphthylene ether type epoxy, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type asphalt mixtures modified by epoxy resin Rouge, tetraphenyl ethane type epoxy resin, more preferably union II first phenol-type epoxy resin, naphthalene type epoxy resin and bisphenol AF type asphalt mixtures modified by epoxy resin Rouge.
As the specific example of solid epoxy resin, " HP4032H " (naphthalene type asphalt mixtures modified by epoxy resin of Dainippon Ink Chemicals can be enumerated Rouge), " HP-4700 ", " HP-4710 " (naphthalene type tetrafunctional epoxy resin) of Dainippon Ink Chemicals, " the N- of Dainippon Ink Chemicals 690 " (cresol novolak type epoxy resins), " N-695 " (the cresol novolak type epoxy resin) of Dainippon Ink Chemicals, DIC plants of formula meetings " HP-7200 " (dicyclopentadiene-type epoxy resin) of society, " HP-7200HH " of Dainippon Ink Chemicals, " HP-7200H ", " EXA-7311 ", " EXA-7311-G3 ", " EXA-7311-G4 ", " EXA-7311-G4S ", " HP6000 " (naphthylene ether type epoxy Resin), " EPPN-502H " (tris phenol type epoxy) of Nippon Kayaku K. K, Nippon Kayaku K. K " NC7000L " (naphthol novolac type epoxy resin), " NC3000H " of Nippon Kayaku K. K, " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), " ESN475V " (naphthalene type ring of Nippon Steel & Sumitomo Metal Corporation Oxygen resin), " ESN485 " (the naphthol novolac type epoxy resin) of Nippon Steel & Sumitomo Metal Corporation, Mitsubishi Chemical's strain formula meeting " YX4000H ", " YX4000 ", " YL6121 " (biphenyl type epoxy resin) of society, Mitsubishi chemical Co., Ltd " YX4000HK " (union II first phenol-type epoxy resin), " YX8800 " (anthracene type epoxy resin) of Mitsubishi chemical Co., Ltd, greatly " PG-100 ", " CG-500 " of slope combustion gas chemistry Co. Ltd. system, " YL7760 " (bisphenol AF type of Mitsubishi chemical Co., Ltd Epoxy resin), " YL7800 " (the fluorenes type epoxy resin) of Mitsubishi chemical Co., Ltd, Mitsubishi chemical Co., Ltd " jER1010 " (solid-state bisphenol A type epoxy resin resin), " jER1031S " (tetraphenyl ethane type ring of Mitsubishi chemical Co., Ltd Oxygen resin) etc..These solid epoxy resins can be used alone a kind, can also two or more be applied in combination.
As (A) epoxy resin, in the case where liquid-state epoxy resin and solid epoxy resin is applied in combination, their amount ratio (liquid-state epoxy resin: solid epoxy resin) by quality ratio be preferably 1:1~1:40, more preferably 1:3~1:30, particularly preferably 1:5~1:20.By making the amount of liquid-state epoxy resin and solid epoxy resin than can significantly obtain this hair in the range Bright desired effect.In addition, in general, bringing appropriate adhesiveness in the form of resin sheet in the case where use.In addition, In general, can obtain enough flexibility in the form of resin sheet in the case where use, operability is improved.In addition, usually can get Solidfied material with enough breaking strengths.
(A) epoxide equivalent of epoxy resin 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 crosslinking of the solidfied material of resin composition layer is close Degree becomes sufficiently, the insulating layer that surface roughness can be brought small.Epoxide equivalent is the matter of the resin of the epoxy group comprising 1 equivalent Amount.The epoxide equivalent can be measured according to JIS K7236.
From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of (A) epoxy resin compared with It is well 100~5000, more preferably 250~3000, further more preferably 400~1500.
The weight average molecular weight of resin can be surveyed by gel permeation chromatography (GPC) method, the value as polystyrene conversion It is fixed.
It, will be in resin combination from the viewpoint of the insulating layer for obtaining the good mechanical strength of display, insulating reliability Nonvolatile component when being set as 100 mass %, the amount of (A) epoxy resin in resin combination is preferably 3 mass % or more, more preferably It is 10 mass % or more, further more preferably 20 mass % or more, 30 mass % or more.The desired effect of the present invention is obtained from significant From the viewpoint of fruit, the upper limit of the content of epoxy resin is preferably 50 mass % hereinafter, more preferably 45 mass % are hereinafter, particularly preferably 40 mass % or less.
< (B) curing agent >
It include curing agent as (B) ingredient in resin combination.(B) curing agent, which usually has, reacts with (A) epoxy resin and is made The cured function of resin combination.
As (B) curing agent, can be used has the function of making the curing agent of (A) epoxy resin cure.Solidify as (B) Agent, it can be mentioned, for example active esters curing agent, phenol curing agent, aphthols curing agent, benzoxazine class curing agent, cyanate Class curing agent and carbodiimide class curing agent etc..In addition, curing agent can be used alone a kind, can also two or more be used in combination.
As active esters curing agent, the compound in 1 molecule with 1 or more active ester groups can be used.Wherein, make For active esters curing agent, preferably 1 point of phenolic ester class, thiophenol esters, N- hydroxylamine esters, esters of heterocycle hydroxyl compound etc. The compound for the ester group for having 2 or more reactivities high in son.The activity esters curing agent is preferably by carboxylic acid chemical combination The compound that the condensation reaction of object and/or thiocarboxylic acid compound and hydroxy compounds and/or mercaptan compound obtains.Especially From the viewpoint of heat resistance raising, the active esters curing agent preferably obtained by carboxylic acid compound and hydroxy compounds, more It is the active esters curing agent obtained by carboxylic acid compound and oxybenzene compound and/or naphthol compound well.
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, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, Phenolphthalin, methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, Alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benzophenone, trihydroxy hexichol Ketone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type bisphenol compounds, phenol novolacs (phenol Novolac) etc..Here, " dicyclopentadiene-type bisphenol compounds " refer to 1 molecule bicyclopentadiene be condensed 2 molecule phenol and The bisphenol compounds obtained.
As the preferred specific example of active esters curing agent, the preferably work of the structure of biphenol containing dicyclopentadiene-type Property ester compounds, the active ester compound containing naphthalene structure, the acetyl group compound containing phenol novolacs active ester compound, contain The active ester compound of the benzoyl compound of phenol novolacs.Wherein, the active ester compound more preferably containing naphthalene structure, contain The active ester compound of dicyclopentadiene-type biphenol structure." dicyclopentadiene-type biphenol structure " is indicated by phenylene-Asia The divalent structural unit that bicyclopentyl-phenylene is formed.
As the commercially available product of active esters curing agent, the active ester compound of the structure of biphenol containing dicyclopentadiene-type can be arranged Lift " 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 esters curing agent of the acetyl group compound as phenol novolacs " DC808 " (Mitsubishi chemical Co., Ltd's system) etc., the active esters of the benzoyl compound as phenol novolacs can be enumerated Curing 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..
Preferably have from the viewpoint of heat resistance and water resistance as phenol curing agent and aphthols curing agent The curing agent of phenolic structure.In addition, from the viewpoint of the adaptation with conductor layer, preferably nitrogenous phenol curing agent, The more preferably 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 ", " TD-2090 ", " LA-7052 ", " LA-7054 ", " LA-1356 ", " LA- of Dainippon Ink Chemicals 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 formd 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..
From the viewpoint of significantly obtaining the desired effect of the present invention, relative to the resin component in resin combination The amount of 100 mass %, (B) curing agent in resin combination are preferably 5 mass % or more, more preferably 8 mass % or more, further More preferably 10 mass % or more, preferably 30 mass % hereinafter, more preferably 25 mass % hereinafter, further more preferably 20 mass % with Under.
Among the above, it is preferably selected from the viewpoint of significantly obtaining the desired effect of the present invention as (B) curing agent From one or more of phenol curing agent, active esters curing agent, cyanate curing agent, benzoxazine class curing agent, more preferably It is active esters curing agent.
(B) in the case that curing agent includes active esters curing agent, relative to 100 matter of resin component in resin combination % is measured, the containing ratio of active esters curing agent is preferably 3 mass % or more, more preferably 5 mass % or more, further more preferably 8 matter Measure % or more, preferably 20 mass % hereinafter, more preferably 15 mass % hereinafter, further more preferably 10 mass % or less.
In the case that the epoxy radix of (A) epoxy resin is set as 1, the active group number of (B) curing agent be preferably 0.1 with On, more preferably 0.2 or more, further more preferably 0.24 or more, preferably 2 hereinafter, more preferably 1.5 hereinafter, further more preferably 1 Hereinafter, particularly preferably 0.5 or less.Here, " the epoxy radix of (A) epoxy resin " refers to for will be present in resin combination (A) epoxy resin nonvolatile component quality divided by the whole values that are added up to of value obtained by epoxide equivalent.In addition, " the active group number of (B) curing agent " refers to the nonvolatile component for (B) curing agent that will be present in resin combination The value that quality is all added up to divided by value obtained by active group equivalent.By making the epoxy group of (A) epoxy resin The active group number of (B) curing agent in the case where being set as 1 is counted in the range, can significantly obtain the desired effect of the present invention Fruit, and the heat resistance of the solidfied material of usually resin composition layer further increases.
< (C) magnesium hydroxide >
It include magnesium hydroxide as (C) ingredient in resin combination.By making resin combination include (C) ingredient, energy can get The insulating layer for inhibiting halo phenomenon, can also be such that the anti-flammability of the solidfied material of resin composition layer improves.
As the magnesium hydroxide for being used as (C) ingredient, it can be any one of synthetic, natural goods.(C) ingredient can be independent Using a kind, can also two or more be applied in combination.
As the commercially available product of magnesium hydroxide, it can be mentioned, for example " EP-4A ", " EP- of Konoshima Chemical Co., Ltd. 2E ", " EP-2A ", " EP-1SII ", " ECOMAG Z-10 ", " the ECOMAG PZ-1 " of Tateho chemical industry Co. Ltd. system, " MGZ-1 ", " MGZ-3 " of Sakai Chemical Industry Co., Ltd., " the KISUMA 5E " of Kyowa Chemical Industry Co., Ltd, " KISUMA 8SN ", " KISUMA 5A ", " KISUMA 5L " etc..
In general, magnesium hydroxide is contained in resin combination with the state of particle.Come from the viewpoint for effectively inhibiting halo phenomenon It sees, the average grain diameter of magnesium hydroxide is preferably 0.5 μm or more, and more preferably 0.8 μm or more, further more preferably 1 μm or more, preferably Be 3 μm hereinafter, more preferably 2 μm hereinafter, further more preferably 1.5 μm or less.
As long as the shape particle shape of magnesium hydroxide, is not particularly limited, from the viewpoint for effectively inhibiting halo phenomenon From the point of view of, it can be ellipticity (sheet).In this case, as aspect ratio, preferably 1 or more, more preferably 1.2 or more, further More preferably 1.4 or more, preferably 10 hereinafter, more preferably 9 hereinafter, further more preferably 8 or less.Aspect ratio refers to the length of particle The value that the length of axis (length of the longest part of partial size) is acquired divided by the length of short axle (length of the vertical direction of major diameter).
The average grain diameter of magnesium hydroxide can be surveyed by the laser diffraction scattering method based on Michaelis (Mie) scattering theory It is fixed.Specifically, the partial size of magnesium hydroxide can be made with volume reference by laser diffraction and scattering formula particle size distribution analyzer Distribution, its median particle diameter is measured as average grain diameter.Measurement sample preferably makes hydroxide using by ultrasonic wave Sample obtained by magnesium is scattered in methyl ethyl ketone.As laser diffraction and scattering formula particle size distribution analyzer, strain formula can be used Commercial firm's hole field makes made " LA-500 ", Shimadzu Scisakusho Ltd's system " SALD-2200 " etc..
From the viewpoint of further suppressing halo phenomenon, magnesium hydroxide has carried out at surface better with surface treating agent Reason.As surface treating agent, alkoxysilane compound containing trialkylsilyl group in molecular structure, organic silazane hydride compounds, titante coupling agent etc. can be enumerated, it is special It is not the preferably alkoxysilane compound containing trialkylsilyl group in molecular structure from the viewpoint of inhibiting halo phenomenon.
Alkoxysilane compound containing trialkylsilyl group in molecular structure preferably has " X-Si (OR1)a(R2)3-a" structure.In formula, R1Indicate carbon atom number The aryl of 1~3 alkyl, the alkoxyalkyl of carbon atom number 2~8 or carbon atom number 6~10, R2Indicate hydrogen atom, hydroxyl, halogen Plain atom or alkyl.A indicates 1~3 integer.When a is 2 or 3, multiple R1Can be identical, it can also be different.In addition, when a is 1, it is multiple R2Can be identical, it can also be different.X indicate amino, epoxy group, sulfydryl, vinyl, isocyanate group, methylacryloyl, urea groups, Phenyl, the alkyl of carbon atom number 1~3 and by group obtained by 2 combination of the above in these groups.
X as alkoxysilane compound containing trialkylsilyl group in molecular structure, from the viewpoint of effectively inhibiting halo phenomenon, in preferably above-mentioned formula Expression includes the group of amino, vinyl, aminophenyl.That is, alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably the alkoxy with amino Silane compound or alkoxysilane compound containing trialkylsilyl group in molecular structure with vinyl.
As the commercially available product of alkoxysilane compound containing trialkylsilyl group in molecular structure, it can be mentioned, for example Shin-Etsu Chemial Co., Ltd's system " KBM573 " (N- phenyl -3- TSL 8330), Shin-Etsu Chemial Co., Ltd's system " KBM1003 " (vinyl trimethoxy Base silane), Shin-Etsu Chemial Co., Ltd's system " KBM403 " (3- glycidoxypropyltrime,hoxysilane), SHIN-ETSU HANTOTAI chemistry Industrial Co., Ltd's system " KBM803 " (3-mercaptopropyi trimethoxy silane), Shin-Etsu Chemial Co., Ltd's system " KBE903 " (3-aminopropyltriethoxysilane), Shin-Etsu Chemial Co., Ltd's system " KBM5783 " (N- phenyl -3- aminoheptyl three Methoxy silane), Shin-Etsu Chemial Co., Ltd's system " KBM103 " (phenyltrimethoxysila,e), SHIN-ETSU HANTOTAI's chemical industry strain formula Commercial firm's system " KBM-4803 " (long-chain epoxy type silane coupling agent) etc..Alkoxysilane compound containing trialkylsilyl group in molecular structure can be used alone a kind, can also 2 Kind combination of the above uses.
From the viewpoint of effectively inhibiting halo phenomenon, hydroxide of the amount of surface treating agent relative to 100 mass parts Magnesium, preferably 5 below the mass, and more preferably 4.5 below the mass, and further more preferably 4 below the mass, preferably 0.5 matter Part or more is measured, more than more preferably 0.6 mass parts, further more preferably more than 0.7 mass parts.
The degree of the surface treatment carried out by surface treating agent can by the carbon amounts of the per surface area of magnesium hydroxide into Row evaluation.From the viewpoint of the dispersibility raising of magnesium hydroxide, the carbon amounts of the per surface area of magnesium hydroxide is preferably 0.02mg/m2More than, more preferably 0.1mg/m2More than, further more preferably 0.2mg/m2More than.On the other hand, from inhibition resin From the viewpoint of the rising of the melt viscosity and the melt viscosity under sheet form of varnish, preferably 1mg/m2Hereinafter, more preferably 0.8mg/m2Hereinafter, further more preferably 0.5mg/m2Below.
The carbon amounts of the per surface area of magnesium hydroxide can be in the hydroxide after being surface-treated with surface treating agent Magnesium is measured after being started the cleaning processing using solvent (such as methyl ethyl ketone (MEK)).Specifically, to surface treating agent Enough MEK are added in the magnesium hydroxide being surface-treated as solvent, 25 DEG C ultrasonic cleaning 5 minutes.In removing After keeping solid component dry, the carbon amounts of the per surface area of carbon analyzer measurement magnesium hydroxide is can be used in clear liquid.It is analyzed as carbon Horiba Ltd's system " EMIA-320V " etc. can be used in instrument.
From the viewpoint of effectively inhibiting halo phenomenon, the nonvolatile component in resin combination is set as 100 mass % When, the content of (C) ingredient is preferably 2 mass % or more, more preferably 5 mass % or more, further more preferably 10 mass % or more.From From the viewpoint of keeping the shape of through-hole good, the upper limit is preferably 40 mass % hereinafter, more preferably 38 mass % are hereinafter, further more preferable It is 35 mass % or less.
< (D) silica >
It include silica as (D) ingredient in resin combination.By the way that (D) silica is used for resin combination, can subtract The thermal expansion coefficient of the solidfied material of small resin combination, also reduces dielectric loss angle tangent.
As (D) silica, amorphous silica, fused silica, crystalline silica, synthesis two can be enumerated Silica, hollow silica etc., preferably spherical silicon dioxide.(D) silica can be used alone a kind, can also two or more It is applied in combination.
As the commercially available product of (D) silica, it can be mentioned, for example " KE-P30 " of Nippon Shokubai Co., Ltd, Nippon Steel Firmly " SP60-05 ", " SP507-05 " of golden material Co. Ltd. system, " YC100C " of Admatechs Co. Ltd. system, " YA050C ", " YA050C-MJE ", " YA010C ", " UFP-30 " of Denka Co. Ltd. system, Tokuyama Corp (Tokuyama) make " Silfil (シ Le Off ィ Le) NSS-3N ", " Silfil NSS-4N ", " Silfil NSS-5N ", " SC2500SQ " of Admatechs Co. Ltd. system, " SO-C4 ", " SO-C2 ", " SO-C1 " etc..
In general, (D) silica is contained in resin combination with the state of particle.(D) average grain diameter of silica is preferable 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 3 μm hereinafter, more preferably 2 μm hereinafter, Further more preferably 1.5 μm or less, 1.0 μm or less, 0.5 μm or less, 0.3 μm or less.By the average grain for making (D) silica Diameter is in the range, even the insulating layer of film, also becomes that insulating reliability is good, can inhibit the recess of through-hole wall surface The generation in portion's (picking out the portion れ).In addition, the circuit imbedibility of resin composition layer can usually improved, or reduce the surface of insulating layer Roughness.(D) average grain diameter of silica can be measured by method same as the average grain diameter of (C) magnesium hydroxide.
From the viewpoint of making the control of shape of through holes be easy and realize good shape, the specific surface of (D) silica Product is preferably 15m2/ g or more, more preferably 20m2/ g or more, particularly preferably 30m2/ g or more.It is without particular limitation to the upper limit, preferably It is 60m2/ g or less, 50m2/ g or less or 40m2/ g or less.The specific surface area of silica is measured by BET method.
From the viewpoint of improving moisture-proof and dispersibility, (D) silica can carry out surface by surface treating agent Processing.As surface treating agent, surface treating agent same as the surface treating agent in (C) magnesium hydroxide can be used.Pass through table The case where degree for the surface treatment that surface treatment agent carries out can be with (C) magnesium hydroxide is identical.
From the viewpoint of obtaining desired effect, the nonvolatile component in resin combination is set as 100 mass % When, the content of (D) silica is preferably 3 mass % or more, more preferably 10 mass % or more, further more preferably 20 mass % with Upper, 25 mass % or more.The upper limit be preferably 60 mass % hereinafter, more preferably 55 mass % hereinafter, further more preferably 50 mass % with Under.
From the viewpoint of more effectively inhibiting halo phenomenon, the nonvolatile component in resin combination is set as 100 matter When measuring %, the total content of (D) silica and (C) magnesium hydroxide is preferably 30 mass % or more, more preferably 40 mass % or more, into One step more preferably 50 mass % or more.The upper limit is preferably 80 mass % hereinafter, more preferably 70 mass % are hereinafter, further more preferably 60 Quality % or less.
< (E) thermoplastic resin >
In addition to above-mentioned ingredient, resin combination also can further include (E) thermoplastic resin as arbitrary ingredient.
As the thermoplastic resin of (E) ingredient, it can be mentioned, for example phenoxy resin, polyvinyl acetal resin, polyolefin trees Rouge, polybutadiene, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyether sulfone Resin, polyphenylene oxide resin, polycarbonate resin, polyether-ether-ketone resin, polyester resin etc..Wherein, from significantly obtaining institute of the present invention The viewpoint of desired effect and the viewpoint for obtaining the small and particularly preferred insulating layer of adaptation with conductor layer of surface roughness are come It sees, preferably phenoxy resin.In addition, thermoplastic resin can be used alone a kind, can also two or more be applied in combination.
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..
As the specific example of phenoxy resin, " 1256 " and " 4250 " that can enumerate Mitsubishi chemical Co., Ltd (are Phenoxy resin containing bisphenol A skeleton), " YX8100 " (phenoxy resin of the skeleton containing bisphenol S) of Mitsubishi chemical Co., Ltd, three " YX6954 " (phenoxy resin of the benzene skeleton of acetyl containing bis-phenol) of water chestnut Chemical Co., Ltd., Nippon Steel & Sumitomo Metal Corporation " FX280 " and " FX293 " of system, " YL7500BH30 " of Mitsubishi chemical Co., Ltd, " 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, electrochemically industrial strain can be enumerated " the electrochemical butyral 4000-2 " of formula commercial firm, " electrochemical butyral 5000-A ", " electrochemical butyral 6000-C ", " electrochemical contracting fourth Aldehyde 6000-EP ", the S-LEC BH series of Sekisui Chemical Co., Ltd, BX serial (such as BX-5Z), KS series (such as KS-1), BL series, BM series etc..
The specific example of polyimide resin, can enumerate New Japan Chem Co., Ltd " RIKACOAT SN20 " and "RIKACOAT PN20".As the specific example of polyimide resin, can also enumerate makes two functional hydroxyl groups end polybutadienes Linear polyimide obtained by alkene, diisocyanate cpd and quaternary anhydride reaction (Japanese Patent Laid-Open 2006-37083 Bulletin record polyimides), polyimides (Japanese Patent Laid-Open 2002-12667 bulletin and day containing silicone matrix The polyimides recorded in this patent special 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, oligomeric phenylate-benzene second of Mitsubishi Gas Chemical Co., Ltd can be enumerated Olefine resin " OPE-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..
From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of (E) thermoplastic resin Preferably 8000 or more, more preferably 10000 or more, particularly preferably 20000 or more, preferably 70000 hereinafter, more preferably 60000 Hereinafter, particularly preferably 50000 or less.
In the case where using (E) thermoplastic resin, from the viewpoint of significantly obtaining the desired effect of the present invention, relatively The amount of 100 mass % of resin component in resin combination, (E) thermoplastic resin in resin combination are preferably 0.1 matter % or more, more preferably 0.5 mass % or more are measured, further more preferably 1 mass % or more, preferably 15 mass % are hereinafter, more preferably 12 Quality % is hereinafter, further more preferably 10 mass % or less.
< (F) curing accelerator >
In addition to above-mentioned ingredient, resin combination also can further include (F) curing accelerator as arbitrary ingredient.
As curing accelerator, it can be mentioned, for example Phosphorus curing accelerator, amine-type cure accelerator, imidazoles solidifications to promote Agent, guanidine curing accelerator, metal class curing accelerator etc..Wherein, preferably Phosphorus curing accelerator, amine-type cure promote Agent, imidazoles curing accelerator, metal class curing accelerator, more preferably amine-type cure accelerator, imidazoles curing accelerator, gold Belong to class curing 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 triphenyl phasphine, Phosphonium borate compounds, tetraphenylphosphoniphenolate tetraphenylboronic acid Salt, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyl) triphenyl phosphonium rhodanate, tetraphenylphosphoniphenolate Rhodanate, Ding base triphenyl phosphonium rhodanate etc., preferably triphenyl phasphine, 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 '-methylimidazolyls-(1 ')]-ethyl s-triazine, 2,4- diamino -6- [2 '-undecyl imidazole bases - (1 ')]-ethyl s-triazine, 2,4- diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl s-triazine, 2,4- bis- Amino -6- [2 '-methylimidazolyls-(1 ')]-ethyl s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid addition Object, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole, 2,3- dihydro -1H- pyrroles [1, 2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2- benzylimidazoline etc. The adduct of imidazolium compounds and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- benzyl -2- benzene Base imidazoles.
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 It is organic to close organic copper complex, the acetyl acetone zinc (II) such as organic cobalt complex, acetyl acetone copper (II) such as cobalt (III) etc. The organonickel complexes, acetyl such as organic iron complexes such as Zn complex, acetyl acetone iron (III), nickel acetylacetonate (II) Acetone 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, Cobalt naphthenate, stearic acid tin, zinc stearate etc..
In the case where using (F) curing accelerator, from the viewpoint of significantly obtaining the desired effect of the present invention, relatively The amount of 100 mass % of resin component in resin combination, (F) curing accelerator in resin combination are preferably 0.01 matter % or more, more preferably 0.05 mass % or more are measured, further more preferably 0.1 mass % or more, preferably 1.5 mass % are hereinafter, more preferable It is 1 mass % hereinafter, further more preferably 0.5 mass % or less.
The arbitrary additive > of < (G)
In addition to above-mentioned ingredient, resin combination also can further include arbitrary additive as arbitrary ingredient.As Such additive, it can be mentioned, for example organic filler material, the resins such as thickener, defoaming agent, flat agent, adaptation imparting agent add Add agent etc..These additives can be used alone a kind, can also two or more be applied in combination.
The thickness G T.GT.GT of < resin composition layer
Resin composition layer is the layer formed by above-mentioned resin combination, has specified value thickness below.Resin combination Layer specific thickness be usually 15 μm hereinafter, preferably 14 μm hereinafter, more preferably 12 μm or less.In the past, printed wiring board The thickness of the resin composition layer of insulating layer formation is usually thicker than above-mentioned thickness.For this point, the present inventor makes usually After the resin composition layer of composition is thinning as described above, find that it is existing generation haloing occur in such thin resin composition layer The project being not aware that in the past as this.Come from the viewpoint for solving such new issue and facilitating the filming of printed wiring board It sees, resin composition layer of the invention is designed relatively thin as described above.The lower limit of the thickness of resin composition layer is any, such as can It is set as 1 μm or more, 3 μm or more.
The characteristic > of < resin composition layer
By solidifying resin composition layer of the invention, the thin insulating formed by the solidfied material of resin composition layer can get Layer.In the case where forming through-hole on which insulating layer, the halo phenomenon of the resin discoloration of the insulating layer around through-hole can inhibit.With Under, these effects are illustrated referring to attached drawing.
Fig. 1 is to schematically show obtained by making the solidification of resin composition layer described in first embodiment of the invention absolutely The cross-sectional view of edge layer 100 and internal substrate 200.Indicated in the Fig. 1 the center 120C by the bottom 120 of through-hole 110 and with Section (section) obtained by the parallel plane truncation insulating layer 100 of the thickness direction of insulating layer 100.
As shown in Figure 1, insulating layer 100 described in first embodiment of the invention is to make to be formed in comprising conductor layer 210 Internal substrate 200 on resin composition layer solidification obtained by layer, formed by the solidfied material of the resin composition layer.This Outside, through-hole 110 is formed in insulating layer 100.Through-hole 110 is generally in along cone-shaped (Shun テ ー パ shape) formed, that is, closer to Then diameter is bigger by the face 100U of the insulating layer 100 of the opposite side of conductor layer 210, and closer to conductor layer 210, then diameter is smaller, reason What is thought is in the thickness direction in insulating layer 100 there is the column of constant diameter to be formed.The through-hole 110 usually by with conductor The face 100U of the insulating layer 100 of 210 opposite side of layer irradiates laser and removes a part of insulating layer 100 to be formed.
The bottom of 210 side of conductor layer of the through-hole 110 is properly termed as " via bottoms ", is indicated with label 120.Separately Outside, the diameter of the via bottoms 120 is known as base diameter Lb.In addition, by the side opposite with conductor layer 210 of through-hole 110 It is formed by opening and is properly termed as " via top ", indicated with label 130.In addition, the diameter of the via top 130 is known as pushing up Portion diameter Lt.For via bottoms 120 and via top 130, observed from the thickness direction of insulating layer 100 Flat shape is formed as circle but it is also possible to be ellipse.The flat shape of via bottoms 120 and via top 130 is ellipse In the case where shape, base diameter Lb and top diameter Lt respectively indicate the oval major diameter.
At this moment, base diameter Lb is more connect divided by taper ratio obtained by top diameter Lt (テ ー パ ー rate) Lb/Lt (%) Nearly 100%, then the shape of the through-hole 110 is better.If can easily control through-hole using resin composition layer of the invention 110 shape, so through-hole 110 of the taper ratio Lb/Lt close to 100% can be realized.The taper ratio of through-hole refers to the bottom of through-hole Ratio of portion's diameter relative to top diameter.
For example, consolidating it for heating resin composition layer 30 minutes at 100 DEG C, then heating 30 minutes at 180 DEG C Insulating layer 100 obtained by change, with mask diameters 1mm, 16 μ s of pulse width, energy 0.2mJ/ irradiation (shot), irradiation number 2, at The condition of group mode (burst mode) (10kHz) irradiates CO2Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm In the case where, can make the taper ratio Lb/Lt of the through-hole 110 is preferably 75%~100%, more preferably 80%~100%, especially It is well 85%~100%.
The taper ratio Lb/Lt of through-hole 110 can be calculated according to the base diameter Lb and top diameter Lt of through-hole 110.In addition, The base diameter Lb and top diameter Lt of through-hole 110 can be measured by following methods: use FIB (focused ion beam) cutting insulation Layer 100, after so that it is shown the section of center 120C that is parallel with the thickness direction of the insulating layer 100 and passing through via bottoms 120, With the electron microscope observation section.
Fig. 2 is to schematically show obtained by making the solidification of resin composition layer described in first embodiment of the invention absolutely The top view of the face 100U of the side opposite with conductor layer 210 (in Fig. 2 not shown) of edge layer 100.
As shown in Fig. 2, if the insulating layer 100 that observation is formed with through-hole 110 may be in the through-hole due to halo phenomenon Discoloration portion 140 made of the discoloration of insulating layer 100 is observed around 110.When the discoloration portion 140 is due to forming through-hole 110 Resin is deteriorated and is formed, and is usually formed continuously from through-hole 110.In addition, in most cases, discoloration portion 140 is in albefaction part.
Fig. 3 is to schematically show obtained by making the solidification of resin composition layer described in first embodiment of the invention slightly The cross-sectional view of roughening treated insulating layer 100 and internal substrate 200.It indicates in the Fig. 3 in the via bottoms for passing through through-hole 110 120 center 120C and the plane parallel with the thickness direction of insulating layer 100 truncation insulating layer 100 obtained by section.
As shown in figure 3, if to be formed with through-hole 110 insulating layer 100 implement roughening treatment, discoloration portion 140 it is exhausted Edge layer 100 may be removed from conductor layer 210, be formed from the continuous clearance portion 160 in the edge of via bottoms 120 150.The gap The usually discoloration portion 140 in roughening treatment, portion 160 is etched and is formed.
By using resin composition layer of the invention, above-mentioned halo phenomenon can inhibit.Therefore, discoloration portion can be reduced 140 size.Therefore, it can inhibit the removing of insulating layer 100 from conductor layer 210, so the size of clearance portion 160 can be reduced.
As shown in figure 3, the size in discoloration portion 140 can be reduced by using resin composition layer of the invention, it is generally desirable to Discoloration portion 140 can be eliminated.The size in discoloration portion 140 can pass through the dizzy from the edge of via top 130 180 of through-hole 110 Circle remote is evaluated from Wt.
The edge 180 of via top 130 is equivalent to the edge part of the inner circumferential side in discoloration portion 140.From the side of via top 130 Haloing distance Wt that edge 180 rises indicates the edge part 190 from the edge of via top 130 180 to the peripheral side in discoloration portion 140 Distance.Haloing distance Wt from the edge of via top 130 180 is smaller, then can be evaluated more to restrained effectively discoloration portion 140 formation.
For example, consolidating it for heating resin composition layer 30 minutes at 100 DEG C, then heating 30 minutes at 180 DEG C Insulating layer 100 obtained by change, with mask diameters 1mm, 16 μ s of pulse width, energy 0.2mJ/ irradiation, irradiation number 2, burst mode The condition of (10kHz) irradiates CO2Laser is formed in the case that top diameter Lt is 30 μm ± 2 μm of through-hole 110, can make from The haloing distance Wt that the edge 180 of via top 130 rises is preferably 6 μm hereinafter, more preferably 5 μm or less.
Haloing distance Wt from the edge of via top 130 180 can be surveyed by using the observation of optical microscopy It is fixed.
In addition, according to the present invention the research of people and distinguish usually there is the more big then discoloration portion 140 of diameter of through-hole 110 The tendency that size more tends to get bigger.Therefore, it can be commented by the size in discoloration portion 140 relative to the ratio of the diameter of through-hole 110 The inhibition level of the formation in valence discoloration portion 140.For example, the haloing for top radius Lt/2 of through-hole 110 can be passed through It is evaluated than Ht.Here, the top radius Lt/2 of through-hole 110 refers to the radius of the via top 130 of through-hole 110.In addition, logical The haloing ratio Ht for top radius Lt/2 in hole 110 refer to by the haloing from the edge of via top 130 180 away from From ratio obtained by top radius Lt/2 of the Wt divided by through-hole 110.The haloing for top radius Lt/2 of through-hole 110 It is more smaller than Ht, then it represents that more to restrained effectively the formation in discoloration portion 140.
For example, consolidating it for heating resin composition layer 30 minutes at 100 DEG C, then heating 30 minutes at 180 DEG C Insulating layer 100 obtained by change, with mask diameters 1mm, 16 μ s of pulse width, energy 0.2mJ/ irradiation, irradiation number 2, burst mode The condition of (10kHz) irradiates CO2Laser can make to lead in the case where forming the through-hole 110 that top diameter Lt is 30 μm ± 2 μm The haloing ratio Ht for top radius Lt/2 in hole 110 is for preferably 45% hereinafter, more preferably 40% hereinafter, further more It is well 35% or less.
The haloing ratio Ht for top radius Lt/2 of through-hole 110 can according to the top diameter Lt of through-hole 110 and The haloing distance Wt from the edge of via top 130 180 of through-hole 110 is calculated.
The edge 150 of via bottoms 120 is equivalent to the edge part of the inner circumferential side of clearance portion 160.Therefore, from via bottoms 120 edge 150 to clearance portion 160 peripheral part end (that is, the farther away side 120C away from the center of via bottoms 120 End) 170 distance Wb is equivalent to the size in direction in the face of clearance portion 160.Here, direction refers to and insulating layer 100 in face The vertical direction of thickness direction.In addition, the distance Wb to be known as to the slave through-hole of through-hole 110 sometimes in the following description The haloing distance Wb that the edge 150 of bottom 120 rises.It can be commented by the haloing distance Wb the edge 150 from via bottoms 120 The inhibition level of valence halo phenomenon.Specifically, the haloing distance Wb from the edge of via bottoms 120 150 is smaller, then can comment Valence is that more restrained effectively halo phenomenon.
For example, consolidating it for heating resin composition layer 30 minutes at 100 DEG C, then heating 30 minutes at 180 DEG C Insulating layer 100 obtained by change, with mask diameters 1mm, 16 μ s of pulse width, energy 0.2mJ/ irradiation, irradiation number 2, burst mode The condition of (10kHz) irradiates CO2Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm.Then, in swelling liquid in 60 DEG C impregnate 10 minutes, then impregnate 20 minutes in oxidizing agent solution in 80 DEG C, then impregnate 5 points in 40 DEG C in neutralizer Zhong Hou is 15 minutes dry in 80 DEG C.If the insulating layer 100 obtained in this way can be made using resin composition layer of the invention Through-hole 110 the haloing distance Wb from the edge of via bottoms 120 150 be preferably 10 μm hereinafter, more preferably 5 μm with Under, further more preferably 4 μm hereinafter, particularly preferably 3 μm or less.
Haloing distance Wb from the edge of via bottoms 120 150 can be measured by following methods: using FIB (focus from Beamlet) cutting insulating layer 100, so that it is shown center that is parallel with the thickness direction of the insulating layer 100 and passing through via bottoms 120 After the section of 120C, with the electron microscope observation section.
In addition, then can easily control the insulating layer before roughening treatment by using resin composition layer of the invention The shape of 100 through-hole 110, even so insulating layer 100 usually after roughening treatment, can also easily control through-hole 110 shape.Therefore, and same before roughening treatment even if after roughening treatment, the shape of through-hole 110 can also be made good. Therefore, if using resin composition layer of the invention, for the insulating layer after roughening treatment, it can be achieved that taper ratio Through-hole 110 of the Lb/Lt close to 100%.
For example, consolidating it for heating resin composition layer 30 minutes at 100 DEG C, then heating 30 minutes at 180 DEG C Insulating layer 100 obtained by change, with mask diameters 1mm, 16 μ s of pulse width, energy 0.2mJ/ irradiation, irradiation number 2, burst mode The condition of (10kHz) irradiates CO2Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm.Then, in swelling liquid in 60 DEG C impregnate 10 minutes, then impregnate 20 minutes in oxidizing agent solution in 80 DEG C, then impregnate 5 points in 40 DEG C in neutralizer Zhong Hou is 15 minutes dry in 80 DEG C.If the insulating layer 100 obtained in this way can be made using resin composition layer of the invention On to be formed by the taper ratio Lb/Lt of through-hole 110 be preferably 76%~100%, more preferably 80%~100%, particularly preferably 85% ~100%.
The taper ratio Lb/Lt of through-hole 110 can be calculated according to the base diameter Lb and top diameter Lt of through-hole 110.In addition, The base diameter Lb and top diameter Lt of through-hole 110 can be measured by following methods: use FIB (focused ion beam) cutting insulation Layer 100, after so that it is shown the section of center 120C that is parallel with the thickness direction of the insulating layer 100 and passing through via bottoms 120, With the electron microscope observation section.
In addition, according to the present invention the research of people and distinguish usually there is the more big then discoloration portion 140 of diameter of through-hole 110 Size more tends to get bigger, so the tendency that the size of clearance portion 160 also more tends to get bigger.It therefore, can be opposite by clearance portion 160 The inhibition level of halo phenomenon is evaluated in the ratio of the diameter of through-hole 110.For example, can be by through-hole 110 relative to bottom Haloing ratio Hb for radius Lb/2 is evaluated.Here, the bottom radius Lb/2 of through-hole 110 refers to the through-hole bottom of through-hole 110 The radius in portion 120.In addition, refer to will be from via bottoms 120 by the haloing ratio Hb for bottom radius Lb/2 of through-hole 110 Bottom radius Lb/2 of the haloing distance Wb that rises of edge 150 divided by through-hole 110 obtained by ratio.Through-hole 110 the bottom of relative to Haloing ratio Hb for portion radius Lb/2 is smaller, then it represents that more restrained effectively halo phenomenon.
For example, consolidating it for heating resin composition layer 30 minutes at 100 DEG C, then heating 30 minutes at 180 DEG C Insulating layer 100 obtained by change, with mask diameters 1mm, 16 μ s of pulse width, energy 0.2mJ/ irradiation, irradiation number 2, burst mode The condition of (10kHz) irradiates CO2Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm.Then, in swelling liquid in 60 DEG C impregnate 10 minutes, then impregnate 20 minutes in oxidizing agent solution in 80 DEG C, then impregnate 5 points in 40 DEG C in neutralizer Zhong Hou is 15 minutes dry in 80 DEG C.If the insulating layer 100 obtained in this way can be made using resin composition layer of the invention On to be formed by the haloing ratio Hb for bottom radius Lb/2 of through-hole 110 be preferably 50% hereinafter, more preferably 40% Hereinafter, further more preferably 30% or less.
The haloing ratio Hb for bottom radius Lb/2 of through-hole 110 can according to the base diameter Lb of through-hole 110 and The haloing distance Wb from the edge of via bottoms 120 150 of through-hole 110 is calculated.
In the manufacturing process of printed wiring board, through-hole 110 is usually in the insulating layer of the side opposite with conductor layer 210 The state of other not set conductor layers (not shown) of 100 face 100U is formed.Therefore, if it is known that the manufacture of printed wiring board Journey, can clearly distinguish has via bottoms 120 in 210 side of conductor layer and has through-hole in a side opening opposite with conductor layer 210 The structure at top 130.But in the printed wiring board of completion, conductor layer may be equipped in the two sides of insulating layer 100.The feelings Under condition, according to the positional relationship with conductor layer, via bottoms 120 and via top 130 may be difficult to differentiate between.But usually The top diameter Lt of via top 130 is the size of the base diameter Lb or more of via bottoms 120.Therefore, in situation above-mentioned, Via bottoms 120 and via top 130 can be distinguished according to the size of diameter.
The purposes > of < resin composition layer
Resin composition layer of the invention can well as the insulating layer for being used to form printed wiring board resin composition layer (resin composition layer of the insulating layer formation of printed wiring board) is used to form " for forming conductor layer (including wiring layer again) The resin composition layer of the insulating layer of (conductor layer is formed on insulating layer) " is (for forming the insulating layer formation of conductor layer Resin composition layer) use, in turn, resin combination that can preferably as the interlayer insulating film for being used to form printed wiring board Nitride layer (resin composition layer of the interlayer insulating film formation of printed wiring board) uses.
In addition, in the case where for example manufacturing semiconductor chip packaging by (1) below~(6) process, tree of the invention Oil/fat composition layer can also be used as well: as the resin combination for being routed forming layer again for forming again the insulating layer of wiring layer Nitride layer (being routed the resin composition layer of forming layer formation again) and the resin combination for being sealed to semiconductor chip Nitride layer (resin composition layer of semiconductor chip sealing) uses.It, can be enterprising in sealant when manufacturing semiconductor chip packaging One step forms wiring layer again.
(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 in the face of semiconductor chip removed substrate and be fixed temporarily film cambial as being routed again for insulating layer Process；And
(6) it is being routed the process that the wiring layer again as conductor layer is formed on forming layer again.
Especially from the viewpoint of it can inhibit halo phenomenon, the resin composition layer is suitable as being used to form tool There is the resin composition layer (resin composition layer of the insulating layer formation with through-hole) of the insulating layer of through-hole, wherein especially good It is the resin composition layer as the insulating layer formation with 35 μm of through-holes below of top diameter.
[resin sheet]
Resin sheet of the invention includes supporting mass and the resin composition layer of the invention being set on the supporting mass.
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 "), The acrylic polymers such as polycarbonate (below also referred to as " PC "), polymethyl methacrylate (below also referred to as " PMMA "), Cyclic polyolefin, triacetyl cellulose (below also referred to as " TAC "), polyether sulfides (below also referred to as " PES "), polyether-ketone, Polyimides etc..Wherein, preferably polyethylene terephthalate, polyethylene naphthalate are 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, delustring processing, sided corona treatment, antistatic can be implemented to the face engaged with resin composition layer The processing such as processing.
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 have with the PET film of alkyd resin class release agent release layer as main component, i.e. Lindeke Co., Ltd's system " SK-1 ", " AL-5 ", " AL-7 ", " the LUMIRROR T60 " of Dongli Ltd., Teijin Ltd " Purex ", " Unipeel " of UNITIKA Co. Ltd. system etc..
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 addition, resin sheet can include the arbitrary layer in addition to supporting mass and resin composition layer as needed.As The arbitrary layer, it can be mentioned, for example be set to the face of resin composition layer not engaged with supporting mass (that is, with supporting mass phase The face of anti-side) the protective film etc. selected according to supporting mass.The thickness of protective film is not particularly limited, for example, 1 μm~40 μ m.Using protective film, it can inhibit surface attachment rubbish of resin composition layer etc. or form damage.
Resin sheet can for example manufacture as follows: preparation includes the resin varnish of organic solvent and resin combination, uses mouth mold The resin varnish is coated on supporting mass by the apparatus for coating such as formula coating machine (die coater), re-dry and form resin combination Nitride layer.
As organic solvent, it can be mentioned, for example the ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone；Ethyl acetate, acetic acid The acetate solvents such as butyl ester, cellosolve acetate, propylene glycol methyl ether acetate and carbitol acetate；Cellosolve and butyl card must The carbitols solvent such as alcohol；The aromatic solvents such as toluene and dimethylbenzene；Dimethylformamide, dimethyl acetamide (DMAc) and N- methyl Amide solvents such as pyrrolidones etc..Organic solvent can be used alone a kind, can also two or more be applied in combination.
Drying the methods of can be brushed by heating, hot wind to be implemented.Drying condition is not particularly limited, in resin composition layer Organic solvent content be usually 10 mass % or less, preferably 5 mass % conditions below be dried.According to resin varnish In the boiling point of organic solvent and it is different, such as using the organic solvent containing 30 mass of mass %~60 % resin varnish the case where Under, 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.In the case that resin sheet has protective film, it can usually be protected by removing Film come using.
[printed wiring board]
Printed wiring board of the invention includes the insulating layer formed as described above by the solidfied material of thin resin composition layer.This Outside, which can inhibit halo phenomenon.Therefore, by using resin composition layer of the invention, halo phenomenon can inhibited While, realize the slimming of printed wiring board.
Through-hole is arranged typically to the conductor layer for the two sides for being set to the insulating layer with the through-hole is connected.Cause This, printed wiring board of the invention generally comprises the first conductor layer, the second conductor layer and is formed in the first conductor layer and second Insulating layer between conductor layer.Also, through-hole has been formed on the insulating layer, by the through-hole, the first conductor layer and the second conductor Layer can be connected.
It can inhibit halo phenomenon by flexibly utilization and resin composition layer as the through-hole of excellent in shape can be formed Advantage is, it can be achieved that the specific printed wiring board being difficult to realize in the past.The specific printed wiring board is comprising the first conductor layer, second The printed wiring board of conductor layer and the insulating layer being formed between the first conductor layer and the second conductor layer meets following wholes Important document (i)~(iv):
(i) insulating layer with a thickness of 15 μm or less；
(ii) insulating layer has 35 μm of through-holes below of top diameter；
(ii) the haloing distance from the edge of via top of the through-hole is 5 μm or less；
(iv) the haloing ratio for top radius of the through-hole is 35% or less.
Hereinafter, showing attached drawing, specific printed wiring board is illustrated.Fig. 4 is described in second embodiment of the present invention Printed wiring board 300 schematic cross sectional views.This is represented in Fig. 4 the center 120C in the via bottoms 120 by through-hole 110 And section obtained by the plane truncation printed wiring board 300 parallel with the thickness direction of insulating layer 100.In addition, in Fig. 4, with Fig. 1 The corresponding position of documented element in~Fig. 3, using with similarly label indicates used in FIG. 1 to FIG. 3.
As shown in figure 4, specific printed wiring board 300 described in second embodiment of the present invention includes the first conductor layer 210, the second conductor layer 220 and the insulating layer 100 being formed between the first conductor layer 210 and the second conductor layer 220.Insulation Through-hole 110 is formed on layer 100.In addition, usual second conductor layer 220 is arranged after forming through-hole 110.Therefore, the second conductor Layer 220 is usually not only formed on the face 100U of insulating layer 100, but also is also formed in through-hole 110, by the through-hole 110, the One conductor layer 210 and the second conductor layer 220 are connected.
The thickness T for the insulating layer 100 that specific printed wiring board 300 includes be usually 15 μm hereinafter, preferably 12 μm hereinafter, More preferably 10 μm hereinafter, particularly preferably 5 μm or less.Specific printed wiring board 300 has insulating layer 100 thin in this way, so can Realize the slimming of specific printed wiring board 300 itself.From the viewpoint of the insulation performance for improving insulating layer 100, insulating layer The lower limit of 100 thickness T is preferably 1 μm or more, and more preferably 2 μm or more, particularly preferably 3 μm or more.Here, insulating layer 100 Thickness T indicates the size of the insulating layer 100 between the first conductor layer 210 and the second conductor layer 220, is not representing there is no the The size of insulating layer 100 at the position of one conductor layer 210 or the second conductor layer 220.The thickness T of insulating layer 100 usually with every Between the interarea 210U of the first opposite conductor layer 210 of the insulating layer 100 and the interarea 220D of the second conductor layer 220 away from It is also consistent with the depth of through-hole 110 from consistent.
The top diameter Lt of through-hole 110 possessed by the insulating layer 100 that specific printed wiring board 300 includes is usually 35 μm Hereinafter, preferably 33 μm hereinafter, particularly preferably 32 μm or less.Specific printed wiring board 300 includes having above-mentioned top diameter Lt The insulating layer 100 of small through-hole 110, so can promote the fine of the wiring comprising the first conductor layer 210 and the second conductor layer 220 Change.From the viewpoint of the easy formation for carrying out through-hole 110, the lower limit of the top diameter Lt of through-hole 110 is preferably 3 μm or more, More preferably 10 μm or more, particularly preferably 15 μm or more.
The edge of the slave via top 130 of through-hole 110 possessed by the insulating layer 100 that specific printed wiring board 300 includes 180 haloing distance Wt are usually 5 μm hereinafter, preferably 4 μm or less.For specific printed wiring board 300, from through-hole The haloing distance Wt that the edge 180 at top 130 rises is such as above-mentioned smaller value.Therefore, specific printed wiring board 300 can usually mention The reliability of conducting between high first conductor layer 210 and the second conductor layer 220.
Through-hole 110 possessed by the insulating layer 100 that specific printed wiring board 300 includes relative to top radius Lt/2 and The haloing ratio Ht of speech is usually 35% hereinafter, preferably 30% hereinafter, more preferably 25% or less.For specific printed wiring board 300 Speech, haloing ratio Ht for top radius Lt/2 are such as above-mentioned smaller value, thus insulating layer 100 is from the first conductor layer 210 removing is less.Specific printed wiring board 300 comprising such as lesser insulating layer 100 of above-mentioned haloing ratio Ht usually can be improved The reliability of conducting between first conductor layer 210 and the second conductor layer 220.Haloing ratio for top radius Lt/2 The lower limit of Ht preferably zero, but usually 5% or more.
The edge of the slave via bottoms 120 of through-hole 110 possessed by the insulating layer 100 that specific printed wiring board 300 includes 150 haloing distance Wb be usually 5 μm hereinafter, preferably 4 μm hereinafter, more preferably 3 μm or less.For specific printed wiring board For 300, the haloing distance Wb from the edge of via bottoms 120 150 is such as above-mentioned smaller value, thus insulating layer 100 is certainly The removing of first conductor layer 210 is less.Therefore, specific printed wiring board 300 usually can be improved the first conductor layer 210 and lead with second The reliability of conducting between body layer 220.
Through-hole 110 possessed by the insulating layer 100 that specific printed wiring board 300 includes relative to bottom radius Lb/2 and The haloing ratio Hb of speech is usually 35% hereinafter, preferably 30% hereinafter, more preferably 25% or less.For specific printed wiring board 300 Speech, haloing ratio Hb for bottom radius Lb/2 are such as above-mentioned smaller value, thus insulating layer 100 is from the first conductor layer 210 removing is less.Specific printed wiring board 300 comprising such as lesser insulating layer 100 of above-mentioned haloing ratio Hb usually can be improved The reliability of conducting between first conductor layer 210 and the second conductor layer 220.Haloing ratio for bottom radius Lb/2 The lower limit of Hb preferably zero, but usually 5% or more.
The taper ratio Lb/Lt (%) of through-hole 110 possessed by the insulating layer 100 that specific printed wiring board 300 includes is usual It is 80%~100%.Specific printed wiring board 300 includes with the through-hole such as the higher excellent in shape of above-mentioned taper ratio rate Lb/Lt 110 insulating layer 100.Therefore, specific printed wiring board 300 usually can be improved the first conductor layer 210 and the second conductor layer 220 it Between conducting reliability.
The number of through-hole 110 possessed by the insulating layer 100 that specific printed wiring board 300 includes can be 1, can also be with It is 2 or more.Insulating layer 100 in the case where 2 or more through-holes 110, can be met with part of it important document (i)~ (iv), but preferably its whole meets important document (i)~(iv).In addition, preferably for example from insulating layer 100 randomly selected 5 Through-hole 110 meet important document (i)~(iv) in terms of averagely.
Above-mentioned specific printed wiring board 300 can form insulating layer by the solidfied material by resin composition layer of the invention 100 and realize.At this moment, the via bottoms 120 of through-hole 110 and the flat shape of via top 130 are formed by insulating layer 100 It is arbitrary, it is generally circular or oval, it is preferably round.
The printed wiring boards such as specific printed wiring board for example can be used resin sheet by implementing including following processes (I) The manufacturing method of~process (IV) manufactures:
(I) process being laminated in resin sheet in such a way that resin composition layer is engaged with internal substrate on internal substrate；
(II) process that resin composition layer heat cure is formed into insulating layer；
(III) process of through-hole is formed on the insulating layer；
(IV) implement the process of roughening treatment to insulating layer.
" internal substrate " used in process (I) is the component of the substrate as printed wiring board.It, can as internal substrate It is poly- to enumerate such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type Phenylate substrate etc..Usually as internal substrate, it may be used at the substrate that its one or both sides has conductor layer.Then, it leads at this Insulating layer is formed on body layer.The conductor layer can carry out pattern processing to for example play the role of circuit.The one of substrate The internal substrate that face or two sides are formed with the conductor layer as circuit is also referred to as " internal layer circuit substrate ".In addition, manufacture printing cloth The intermediate manufacture object that insulating layer and/or conductor layer need to be further formed when line plate is also contained in " internal substrate ".Printed wiring In the case that 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 and resin composition layer is fitted in into internal substrate to carry out.As the structure that resin sheet heating is crimped on to internal substrate Part (following also referred to as " heating crimping component "), it can be mentioned, for example the metal plates (SUS panelling etc.) or metallic roll (SUS roller) after heating Deng.It should be noted that preferably heating crimping component is not pressed on resin sheet directly, but across heat resistant rubber elastomeric material It is suppressed, so that resin sheet sufficiently complies with the concave-convex surface of internal substrate.
The stacking of internal substrate and resin sheet can for example be implemented by vacuum lamination method.In vacuum lamination method, heating pressure Preferably in the range of 60 DEG C~160 DEG C, more preferably 80 DEG C~140 DEG C, heating crimping pressure preferably exists jointing temp In the range of 0.098MPa~1.77MPa, more preferably 0.29MPa~1.47MPa, heating crimping the time preferably 20 seconds~ In the range of 400 seconds, more preferably 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 compacting of crimping component self-supporting side will be heated to carry out The smoothing techniques of the resin sheet of stacking.The pressing conditions of smoothing techniques, which can be used, crimps condition with the heating of above-mentioned stacking Same condition.Smoothing techniques can be carried out by commercially available laminator.It should be noted that stacking and smoothing techniques can be used The commercially available vacuum laminator stated is carried out continuously.
In process (II), resin composition layer heat cure is formed into insulating layer.The heat cure condition of resin composition layer Be not particularly limited, can arbitrarily using the insulating layer for forming printed wiring board when used condition.
For example, the heat cure condition of resin composition layer is different according to type of resin combination etc., it can be as divided into It is fixed: solidification temperature usually in the range of 120 DEG C~240 DEG C (in the range of preferably 150 DEG C~220 DEG C, more preferably 170 DEG C In the range of~200 DEG C), curing time usually in the range of 5 minutes~120 minutes (preferably 10 minutes~100 minutes In range, in the range of more preferably 15 minutes~90 minutes).
Resin composition layer can be carried out at a temperature of lower than solidification temperature before making resin composition layer heat cure Preheating.For example, can be before making resin composition layer heat cure, usually at 50 DEG C more than or lower than 120 DEG C (preferably 60 DEG C Above and 115 DEG C hereinafter, more preferably 70 DEG C or more and 110 DEG C or less) at a temperature of, resin composition layer is preheated usual 5 Minute or more (preferably 5 minutes~150 minutes, more preferably 15 minutes~120 minutes, further more preferably 15 minutes~100 points Clock).
In process (III), through-hole is formed on the insulating layer.As the forming method of through-hole, laser irradiation, erosion can be enumerated Quarter, mechanical drilling etc..Wherein, because being generally not likely to produce halo phenomenon, from effectively apply flexibly inhibit halo phenomenon this From the viewpoint of effect, preferably laser irradiation.
The laser irradiation, which for example can be used, has the laser lights such as carbon dioxide laser, YAG laser, excimer laser Source is carried out as the laser machine of light source.As workable laser machine, it can be mentioned, for example Via Mechanics Ltd. CO processed2Laser machine " LC-2k212/2C ", the 605GTWIII (- P) of Mitsubishi Electric Corporation, Panasonic's welding system strain The laser machine etc. of formula commercial firm.
The irradiation condition of the laser such as wavelength, umber of pulse, pulse width, the power of laser is not particularly limited, can be according to laser The type of light source sets condition appropriate.
In process (IV), roughening treatment is implemented to insulating layer.The step of roughening treatment and condition are not particularly limited, can Used any step and condition when using the insulating layer for forming printed wiring board.For example, successively implementing to use swelling liquid Swelling process, the roughening treatment using oxidant and the neutralisation treatment using neutralizer insulating layer is carried out at roughening Reason.
It as swelling liquid, is not particularly limited, it can be mentioned, for example aqueous slkali, surfactant solutions etc., preferably aqueous slkali. As the aqueous slkali, more preferably sodium hydroxide solution and potassium hydroxide solution.As commercially available swelling liquid, it can be mentioned, for example peace beauty Special Japan's (ATOTECH JAPAN) Co. Ltd. system " Swelling Dip Securiganth P ", " Swelling Dip Securiganth SBU " etc..In addition, swelling liquid can be used alone a kind, can also two or more used with arbitrary ratio combine. It is not particularly limited using the swelling process of swelling liquid, such as can be by the way that insulating layer is impregnated 1 in 30 DEG C~90 DEG C of swelling liquid Minute~carry out within 20 minutes.It controls from the viewpoint of proper level, preferably makes absolutely from by the swelling of the resin of insulating layer Edge layer impregnates 5 minutes~15 minutes in 40 DEG C~80 DEG C of swelling liquid.
It as oxidant, is not particularly limited, 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.In addition, oxidant can be used alone a kind, can also two or more with arbitrary ratio group It closes and uses.Preferably insulating layer is made to be heated to 60 DEG C~80 DEG C using the roughening treatment of the oxidants such as alkaline permanganic acid solution Oxidizing agent solution in impregnate 10 minutes~30 minutes to carry out.In addition, the concentration of the permanganate in alkaline permanganic acid solution Preferably 5 mass of mass %~10 %.As commercially available oxidant, it can be mentioned, for example Atotech Amada Co., Ltd. systems The alkalinity permanganic acid solution such as " Concentrate Compact CP ", " Dosing solution Securiganth P ".
As neutralizer, preferably acid aqueous solution, as commercially available product, it can be mentioned, for example Atotech Amada Co., Ltd.s " the Reduction solution Securiganth P " of system.In addition, neutralizer can be used alone a kind, can also two or more with Arbitrary ratio combine uses.It can be by making to have carried out the processing of the roughening treatment using oxidant using the processing of neutralizer Face impregnates 5 minutes~30 minutes in 30 DEG C~80 DEG C of neutralizer to carry out.It, preferably will be into from the perspective of operability It has gone and 5 minutes~20 minutes sides is impregnated in 40 DEG C~70 DEG C of neutralizer using the object of the roughening treatment of oxidant Method.
In addition, supporting mass can remove between process (I) and process (II), it can be between process (II) and process (III) It removes, can be removed between process (III) and process (IV), can also be removed after process (IV).
The manufacturing method of printed wiring board may also include the process that (V) forms conductor layer.The process (V) can be according to printing cloth Various methods used in the manufacture of line plate are implemented.
Process (V) is the process to form conductor layer.Conductor material for conductor layer is not particularly limited.Preferred embodiment party In formula, conductor layer includes selected from one or more of gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Metal.Conductor layer can be individual metal layer, be also possible to alloy-layer.As alloy-layer, it can be mentioned, for example by selected from above-mentioned The layer that the alloy (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) of metal of more than two kinds in metal is formed.Wherein, From the point of view of the viewpoints such as difficulty that versatility, cost, pattern that conductor layer is formed are formed, preferably chromium, nickel, titanium, aluminium, zinc, gold, Palladium, the individual metal layer or nickel-chromium alloy of silver or copper, copper-nickel alloy, copper-titanium alloy alloy-layer.More preferably chromium, Nickel, titanium, aluminium, zinc, gold, palladium, the individual metal layer of silver or copper or nickel-chromium alloy alloy-layer, particularly preferably copper is independent Metal layer.
Conductor layer can be single layer structure, be also possible to be formed comprising 2 layers or more by different types of metal or alloy The multilayered structure of individual metal layer or alloy-layer.In the case that conductor layer is multilayered structure, the layer that connects with insulating layer compared with It is the individual metal layer of chromium, zinc or titanium or the alloy-layer of nickel-chromium alloy well.
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.
Conductor layer is formed by plating.For example, can by the technologies such as semi-additive process, fully-additive process the surface of insulating layer into Row plating forms the conductor layer with desired wiring pattern.Wherein, from the viewpoint of the simplicity of manufacture, preferably It is formed by semi-additive process.
Hereinafter, showing the example for forming conductor layer by semi-additive process.Firstly, the surface in insulating layer passes through electroless plating It covers to form plating seed layer.Then, desired wiring pattern formation is corresponded on the plating seed layer of formation makes plating seed crystal The mask pattern that a part of layer is exposed.After forming metal layer by electrolytic coating on the plating seed layer of exposing, removing is covered Mould pattern.Then, unwanted plating seed layer is removed by etching etc., so as to be formed with desired wiring pattern Conductor layer.
In addition, the formation of insulating layer and conductor layer based on process (I)~process (V) can be implemented repeatedly as needed and made Make multilayer printed-wiring board.
[semiconductor device]
Semiconductor device of the invention includes the printed wiring board.Printed wiring board manufacture can be used in the semiconductor device.
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..
Semiconductor device can for example be made by the way that component (semiconductor chip) is installed on the conduction position of printed wiring board It makes." conduction position " refers to " position that electric signal is conducted in printed wiring board ", and position can be also possible to be wrapped on surface The position buried.In addition, semiconductor chip can arbitrarily use the electrical circuit components using semiconductor as material.
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.As the example of installation method, wire bonding installation method can be enumerated, flip-chip installation method, used The installation method of solderless buildup layer (BBUL), using the installation method of anisotropic conductive film (ACF), using non-conductive film (NCF) installation method etc..Here, referring to " using the installation method of solderless buildup layer (BBUL) " " semiconductor chip is direct It is embedded to the recess portion of printed wiring board, makes the installation method of the wiring connection on semiconductor chip and printed wiring board ".
Embodiment
The present invention is specifically described hereinafter, showing embodiment.But the present invention is not limited to implementations below Example.In the following description, as long as no separately expressing, " part " and " % " of expression amount respectively indicates " mass parts " and " quality % ". In addition, operation described below carries out in the environment of normal temperature and pressure as long as no separately expressing.
The magnesium hydroxide > that < is used
Magnesium hydroxide 1: relative to 100 parts of magnesium hydroxides (Konoshima Chemical Co., Ltd.'s system " EP-4A ", average grain diameter 1.1 μm (having carried out inorganic matter processing)) with 3 parts of Shin-Etsu Chemial Co., Ltd's systems " KBM573 " (N- phenyl -3- aminopropyl Trimethoxy silane) material that is surface-treated；
Magnesium hydroxide 2: relative to 100 parts of magnesium hydroxides (Konoshima Chemical Co., Ltd.'s system " EP-4A ", average grain diameter 1.1 μm (having carried out inorganic matter processing)) with 3 parts Shin-Etsu Chemial Co., Ltd's system " KBM1003 " (vinyl trimethoxy silicon Alkane) material that is surface-treated.
The silica > that < is used
Silica 1: relative to 100 parts of spherical silicon dioxides (Deuki Kagaku Kogyo Co., Ltd's system " UFP-30 ", average grain 0.1 μm of diameter, specific surface area 30.7m2/ g) with 2 parts of Shin-Etsu Chemial Co., Ltd's systems " KBM573 " (N- phenyl -3- amino Propyl trimethoxy silicane) material that is surface-treated；
Silica 2: relative to 100 parts of spherical silicon dioxides (Deuki Kagaku Kogyo Co., Ltd's system " UFP-30 ", average grain 0.1 μm of diameter, specific surface area 30.7m2/ g) with 2 parts Shin-Etsu Chemial Co., Ltd's system " KBM1003 " (vinyl trimethoxies Base silane) material that is surface-treated；
Silica 3: relative to 100 parts of spherical silicon dioxides (Nippon Shokubai Co., Ltd's system " KE-P30 ", average grain diameter 0.3 μm, specific surface area 35m2/ g) with 2 parts of Shin-Etsu Chemial Co., Ltd's systems " KBM573 " (N- phenyl -3- aminopropyl Trimethoxy silane) material that is surface-treated；
Silica 4: relative to 100 parts of spherical silicon dioxides (Nippon Shokubai Co., Ltd's system " KE-P30 ", average grain diameter 0.3 μm, specific surface area 35m2/ g) with 2 parts Shin-Etsu Chemial Co., Ltd's system " KBM1003 " (vinyl trimethoxy silicon Alkane) material that is surface-treated.
1 > of < embodiment
Make 6 parts of union II first phenol-type epoxy resins (Mitsubishi chemical Co., Ltd's system " YX4000HK ", epoxide equivalents while stirring About 185), 5 parts of naphthalene type epoxy resins (Nippon Steel & Sumitomo Metal Corporation's system " ESN475V ", epoxide equivalent about 332), 15 parts Bisphenol AF type epoxy resin (Mitsubishi chemical Co., Ltd's system " YL7760 ", epoxide equivalent about 238), 2 parts of hexamethylene type asphalt mixtures modified by epoxy resin Rouge (Mitsubishi chemical Co., Ltd's system " ZX1658GS ", epoxide equivalent about 135), 2 parts of phenoxy resin (Mitsubishi chemical Co., Ltd's systems " YL7500BH30 ", the cyclohexanone of 30 mass % of solid component: the 1:1 solution of methyl ethyl ketone (MEK), Mw=44000) heating it is molten Solution is in the in the mixed solvent of 20 parts of solvent naphthas and 10 parts of cyclohexanone.After being cooled to room temperature, 6 parts of active esters are mixed thereto Curing agent (Dainippon Ink Chemicals's system " EXB-8000L-65TM ", active group equivalent about 220, the first of 65 mass % of nonvolatile component Benzene: the 1:1 solution of MEK), the cresol novolac class curing agent of 4 parts of skeletons containing triazine (Dainippon Ink Chemicals's system " LA-3018-50P ", Hydroxyl equivalent about 151, the 2- methoxy propyl alcoholic solution of solid component 50%), 15 parts of magnesium hydroxides 1,35 part of silica 1,0.05 Part amine-type cure accelerator (4-dimethylaminopyridine (DMAP)), after being uniformly dispersed with high speed rotation mixing machine, passes through cylinder Formula filter (ROKITECHNO Co. Ltd. system " SHP020 ") filtering, is made resin combination 1.
2 > of < embodiment
In the preparation of resin combination 1, the amount of magnesium hydroxide 1 is changed to 25 parts from 15 parts, the amount of silica 1 is changed from 35 parts It is 25 parts.Resin combination 2 is made in the same manner as the preparation of resin combination 1 in addition to above item.
3 > of < embodiment
In the preparation of resin combination 1,15 parts of magnesium hydroxide 1 is changed to 15 parts of magnesium hydroxide 2.In addition to above item Resin combination 3 is made in the same manner as the preparation of resin combination 1.
4 > of < embodiment
In the preparation of resin combination 1,35 parts of silica 1 is changed to 35 parts of silica 2.In addition to above item Resin combination 4 is made in the same manner as the preparation of resin combination 1.
5 > of < embodiment
In the preparation of resin combination 1,35 parts of silica 1 is changed to 35 parts of silica 3.In addition to above item Resin combination 5 is made in the same manner as the preparation of resin combination 1.
6 > of < embodiment
In the preparation of resin combination 1,35 parts of silica 1 is changed to 35 parts of silica 4.In addition to above item Resin combination 6 is made in the same manner as the preparation of resin combination 1.
1 > of < comparative example
In the preparation of resin combination 1, magnesium hydroxide 1 is free of, the amount of silica 1 is changed to 50 parts from 35 parts.Except above Resin combination 7 is made other than item in the same manner as the preparation of resin combination 1.
2 > of < comparative example
In the preparation of resin combination 7,50 parts of silica 1 is changed to 50 parts of silica 2.In addition to above item Resin combination 8 is made in the same manner as the preparation of resin combination 7.
3 > of < comparative example
In the preparation of resin combination 7,50 parts of silica 1 is changed to 50 parts of silica 3.In addition to above item Resin combination 9 is made in the same manner as the preparation of resin combination 7.
4 > of < comparative example
In the preparation of resin combination 7,50 parts of silica 1 is changed to 50 parts of silica 4.In addition to above item Resin combination 10 is made in the same manner as the preparation of resin combination 7.
Ingredient used in the preparation of resin combination 1~10 and its blended amount are shown in following table.It should be noted that in following table Term etc. is as follows；
Total content (resin component conversion): in nonvolatile component contained by resin combination in addition to (C) ingredient and (D) ingredient Amount
(B) total content of ingredient: the total content of (B) ingredient when resin component in resin combination to be set as to 100 mass %
The content of active esters curing agent: the resin component in resin combination is set as to active esters solidification when 100 mass % The content of agent
(C) total content of ingredient and (D) ingredient: (C) when the nonvolatile component in resin combination to be set as to 100 mass % at Divide the total content with (D) ingredient
(C) content of ingredient: the content of (C) ingredient when nonvolatile component in resin combination to be set as to 100 mass %.
[table 1]
。
The production > of < resin sheet
As supporting mass, prepare to have carried out demoulding processing using alkyd resin class release agent (Lindeke Co., Ltd's system " AL-5 ") PET film (Dongli Ltd.'s system " LUMIRROR R80 ", 38 μm of thickness, 130 DEG C of softening point, " demoulding PET ").
Each resin combination is reached 10 μm according to the thickness of the resin composition layer after drying using die coater Condition be equably coated on demoulding PET on, 70 DEG C~95 DEG C drying 2 minutes, thus demould PET on obtain resin combination Nitride layer.Then, it is laminated in a manner of being engaged with resin composition layer in the face of resin sheet not engaged with supporting mass as guarantor The rough surface of the polypropylene screen (Oji F-Tex Co. Ltd. system " ALPHAN MA-411 ", 15 μm of thickness) of cuticula.It obtains as a result, The resin sheet A sequentially formed by demoulding PET (supporting mass), resin composition layer and protective film.
The measurement > of the thickness of < resin composition layer etc.
Thickness is measured using contact film thickness gauge (Mitutoyo Corp (Mitutoyo) makes, MCD-25MJ).
The evaluation > of haloing after the processing of < laser via
Evaluate the production-of substrate A
(1) copper-clad laminated board
As copper-clad laminated board, prepare to be laminated with the glass cloth base material epoxy resin two sides copper-clad laminated board of copper foil layer on two sides (3 μm of copper thickness, substrate thickness 0.15mm, Mitsubishi chemical Co., Ltd's system " HL832NSF LCA ", 255 × 340mm of size).
(2) resin sheet is laminated
From each resin sheet A removing protective film made of resin combination 1~10 is used, with batch-type vacuum pressed laminator (Nikko-Materials Co. Ltd. system, 2 stage lamination laminators, CVP700) are with resin composition layer and copper-clad laminated board The mode to connect is laminated at the two sides of copper-clad laminated board.It is laminated to be implemented as follows: decompression so that air pressure is reached 13hPa within 30 seconds hereinafter, with 130 DEG C, pressure 0.74MPa crimping 45 seconds.Then, hot pressing in 75 seconds is carried out with 120 DEG C, pressure 0.5MPa.
(3) heat cure of resin composition layer
The copper-clad laminated board of laminated resin sheet is put into after 100 DEG C of baking oven heat cure 30 minutes, is then moving to 180 DEG C Baking oven after heat cure 30 minutes, formed insulating layer, removing demoulding PET.As solidification substrate A.
(4) laser via is processed
Use Mitsubishi Electric Corporation CO2Laser machine " 605GTWIII (- P) ", irradiates laser from insulating layer, Insulating layer forms 30 μm of top diameter of through-hole.The irradiation condition of laser is mask diameters 1mm, 16 μ s of pulse width, energy 0.2mJ/ irradiation, irradiation number 2, burst mode (10kHz).Substrate A is processed as through-hole.
(5) process being roughened
Through-hole processing substrate A handle as the desmearing (desmear) of roughening treatment.It should be noted that as going Dirty processing is bored, following wet process desmearing processing is implemented.
The processing of wet process desmearing:
In swelling liquid, (Atotech Amada Co., Ltd. system " Swelling Dip Securiganth P " contains diethylene glycol mono butyl The aqueous solution of ether and sodium hydroxide) in 60 DEG C impregnate 10 minutes, then in oxidizing agent solution (Atotech Amada Co., Ltd. system " Concentrate Compact CP ", the aqueous solution of potassium permanganate concentration about 6%, naoh concentration about 4%) in 80 DEG C soak Stain 20 minutes, finally neutralizer (Atotech Amada Co., Ltd. system " Reduction solution Securiganth P ", Aqueous sulfuric acid) in 40 DEG C of dippings after five minutes, it is 15 minutes dry in 80 DEG C.As roughening substrate A.
The measurement > of < desmearing treated through-hole diameter
Section is carried out with FIB-SEM set composite (SII Nanoentech Co., Ltd. system " SMI3050SE ") to roughening substrate A Observation.Specifically, the section that the vertical direction of laser via is cut out by FIB (focused ion beam), according to cross-section SEM image Measure desmearing treated laser via diameter.For each sample, according to the cross-section SEM image at 5 randomly selected, measurement Desmearing treated via top diameter is shown in following table using their average value as via top diameter Lt (μm).
The measurement > of haloing distance after < roughening treatment
Pass through optical microscopy (great view (Hirox) system " KH8700 " of Co., Ltd.) observation roughening substrate A.Specifically, make With insulating layer of the optical microscopy (CCD) from the top of roughening substrate A around through-hole.The observation is by by optical microphotograph The focus alignment via top of mirror carries out.Observation as a result, observing around through-hole from the via top of the through-hole Continuous edge, insulating layer discoloration are white cricoid haloing portion.Then, the image arrived according to the observation measures the through-hole of through-hole The peripheral radius r2 of radius (the inner circumferential radius for the being equivalent to haloing portion) r1 and haloing portion at top, by these radiuses r1 and radius r2 Poor r2-r1 as this locate from the edge of via top haloing distance calculate.
Measurement through-hole at 5 randomly selected carries out.Then, using the haloing distance of through-hole at 5 measured Measured value haloing distance Wt from the edge of via top of the average value as the sample.
In following table, haloing ratio Ht indicate the haloing distance Wt from the edge of via top after roughening treatment with it is coarse Change the ratio between the radius (Lt/2) of via top of treated through-hole (" Wt/ (Lt/2) ").If haloing ratio Ht be 35% with Under, then it is determined as "○", if haloing ratio Ht is greater than 35%, is determined as "×".
[table 2]
。
Even if forming insulating layer, haloing using with a thickness of 10 μm thin in this way of resin composition layer known in Examples 1 to 6 It is also smaller than Ht.It can be confirmed according to the result, resin composition layer through the invention thickness is thin, it can be achieved that be able to suppress The insulating layer of halo phenomenon.In addition, anti-flammability might as well in confirmation Examples 1 to 6.
Confirm in Examples 1 to 6, even if in the case where being free of (E) ingredient~(F) ingredient, although in the presence of poor in degree It is different, but also it is attributed to result same as above-described embodiment.
The explanation of label
100 insulating layers
The face of the insulating layer of side 100U opposite with conductor layer
110 through-holes
120 via bottoms
The center of 120C via bottoms
130 via tops
140 discoloration portions
The edge of the via bottoms of 150 through-holes
160 clearance portions
The end of the peripheral part of 170 clearance portions
The edge of the via top of 180 through-holes
The edge part of the peripheral part in 190 discoloration portions
200 internal substrates
210 conductor layers (the first conductor layer)
The interarea of the first conductor layer of 210U
220 second conductor layers
The interarea of the second conductor layer of 220D
300 printed wiring boards
The base diameter of Lb through-hole
The top diameter of Lt through-hole
The thickness of T insulating layer
Haloing distance of the Wt from the edge of via top
Haloing distance of the Wb from the edge of via bottoms.

Claims (16)

1. a kind of resin composition layer is comprising resin combination and with a thickness of 15 μm of resin composition layers below, wherein
Resin combination includes (A) epoxy resin, (B) curing agent, (C) magnesium hydroxide and (D) silica.
2. resin composition layer according to claim 1, wherein the average grain diameter of (D) ingredient is 3 μm or less.
3. resin composition layer according to claim 1, wherein the average grain diameter of (D) ingredient is 0.3 μm or less.
4. resin composition layer according to claim 1, wherein the nonvolatile component in resin combination is set as 100 When quality %, the content of (D) ingredient is 3 mass % or more and 50 mass % or less.
5. resin composition layer according to claim 1, wherein (B) ingredient is selected from phenol curing agent, active esters One or more of curing agent, cyanate curing agent, benzoxazine class curing agent.
6. resin composition layer according to claim 1, wherein the nonvolatile component in resin combination is set as 100 When quality %, the content of (A) ingredient is 3 mass % or more and 50 mass % or less.
7. resin composition layer according to claim 1, wherein (C) ingredient is surface-treated with surface treating agent.
8. resin composition layer according to claim 7, wherein surface treating agent is alkoxysilane compound containing trialkylsilyl group in molecular structure.
9. resin composition layer according to claim 8, wherein alkoxysilane compound containing trialkylsilyl group in molecular structure has amino or vinyl.
10. resin composition layer according to claim 7, wherein hydrogen of the amount of surface treating agent relative to 100 mass parts Magnesia is 5 below the mass.
11. resin composition layer according to claim 1, wherein the nonvolatile component in resin combination is set as 100 When quality %, the content of (C) ingredient is 2 mass % or more and 40 mass % or less.
12. resin composition layer according to claim 1, wherein the resin composition layer is multilayer printed-wiring board Resin compositions for insulating layer layer.
13. resin composition layer according to claim 1, wherein the resin composition layer is used to form straight with top Diameter is the insulating layer of 35 μm of through-holes below.
14. a kind of resin sheet is comprising supporting mass and any one of the claim 1~13 being set on supporting mass The resin composition layer.
15. a kind of printed wiring board is comprising the resin composition layer as described in any one of claim 1~13 is consolidated The insulating layer that compound is formed.
16. a kind of semiconductor device is comprising printed wiring board described in claim 15.
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