CN105017721B

CN105017721B - Resin composition for insulating layer of printed wiring board

Info

Publication number: CN105017721B
Application number: CN201510182552.3A
Authority: CN
Inventors: 渡边真俊; 中村茂雄
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2014-04-24
Filing date: 2015-04-17
Publication date: 2018-12-11
Anticipated expiration: 2035-04-17
Also published as: TW201542710A; KR102293385B1; JP6269294B2; KR20150123179A; CN105017721A; TWI666268B; JP2015211086A

Abstract

The invention provides a resin composition for an insulating layer of a printed wiring board, which exhibits good dispersion stability and appropriate melt viscosity, and can suppress warpage in a component mounting process. A resin composition for an insulating layer of a printed wiring board, wherein the content of an inorganic filler is 40 to 75% by volume based on 100% by volume of nonvolatile components in the resin composition, and the resin composition is represented by the formula: a ═ SR ρ/6[ in the formula, S represents the specific surface area of the inorganic filler (m)²(g), R represents the average particle diameter (. mu.m) of the inorganic filler, and ρ represents the density (g/cm) of the inorganic filler³)]The geometric parameter A of the represented inorganic filler material satisfies 20 < 6A < 40.

Description

The resin compositions for insulating layer of printed wiring board

Technical field

The present invention relates to the resin compositions for insulating layer of printed wiring board.

Background technique

Manufacturing technology as printed wiring board, it is known that submit using in internal substrate for lapped insulation layer and conductor layer The manufacturing method of stack manner.In the manufacturing method using stack manner, insulation layers are such as by using containing resin combination Resin composition layer is stacked on internal substrate and makes resin composition layer solidification to be formed by adhesive film of nitride layer etc..Exhausted Resin combination used in the formation of edge layer, from reduce the thermal expansion coefficient of resulting insulating layer, prevent by insulating layer with Crackle caused by the difference of the thermal expansion of conductor layer, circuit modifications generation from the point of view of, typically contain inorganic filling material. As the inorganic filling material, it is suitble to use spherical inorganic filling material (patent document 1).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2010-238667 bulletin.

Summary of the invention

With the soft solder reflux in recent years from leaded soft solder to the replacement of lead-free solder, in the installation procedure of component (reflow) temperature is welded to increase.In addition in recent years, in order to realize the miniaturization of electronic equipment, carried out printed wiring board into one Step slimming.

With the propulsion of the slimming of printed wiring board, printed wiring board is generated sometimes in the installation procedure of component The problems such as poor contact of warpage, circuit modifications or component.The inventors of the present invention have found the inorganic fill material by using broken shape Material replaces spherical inorganic filling material, can be with the warpage in the installation procedure of suppression component.But contain the inorganic of broken shape Dispersion stabilization is poor sometimes for the resin combination of packing material, while being easy to return to high melt viscosity, causes lamination bad.

The subject of the invention is to provide show good dispersion stabilization and suitable melt viscosity, can inhibit component simultaneously Installation procedure in warpage, the resin compositions for insulating layer of printed wiring board.

The inventors of the present invention have carried out the above subject to make great efforts research, as a result, it has been found that specific by using having for specified amount The inorganic filling material of shape can solve the above subject, so as to complete the present invention.

That is, the present invention contains content below,

[1] resin combination is the resin compositions for insulating layer of printed wiring board, wherein

When nonvolatile component in resin combination is set as 100 volume %, the content of inorganic filling material is 40~75 bodies Product %,

By formula: [in formula, S indicates the specific surface area (m of inorganic filling material for ρ/6 A=SR²/ g), R indicates inorganic fill material The average grain diameter (μm) of material, ρ indicate the density (g/cm of inorganic filling material³)] indicate inorganic filling material geometry Parameter A meets 20≤6A≤40；

[2] resin combination is the resin compositions for insulating layer of printed wiring board, wherein

By formula: B=Lc/L [in formula, L indicate as defined in inorganic filling material in section perimeter (μm), Lc indicate with The sectional area of inorganic filling material in above-mentioned section is the perimeter (μm) of the positive round of homalographic] inorganic filling material that indicates The average value of geometric shape parameters B is 0.8 or more and 0.9 or less；

[3] resin combination according to [1] or [2], wherein the Average crystallite diameter of inorganic filling material is 1800 Angstrom or less；

[4] resin combination according to any one of [1]~[3], wherein the specific surface area of inorganic filling material is 3~10m²/g；

[5] resin combination according to any one of [1]~[4], wherein the average grain diameter of inorganic filling material is 4 μm or less；

[6] resin combination according to any one of [1]~[5], wherein the average grain diameter of inorganic filling material is 3 μm or less；

[7] resin combination according to any one of [1]~[6], wherein inorganic filling material is to make Average crystallite Diameter is obtained by the tufted agglutinator dispersion of 1800 angstroms of crystallite particles below, and the maximum particle diameter of the tufted agglutinator is 20 μm Below；

[8] resin combination according to any one of [1]~[7], wherein inorganic filling material contain crystallinity without Machine packing material, when whole inorganic filling materials are set as 100 mass %, the content of the crystallinity inorganic filling material is 50 matter Measure % or more；

[9] resin combination according to [8], wherein crystallinity inorganic filling material is crystalline silica；

[10] resin combination according to any one of [1]~[9], wherein further containing epoxy resin and admittedly Agent；

[11] resin combination according to any one of [1]~[10], is interlayer insulating film resin combination；

[12] sheet laminated material contains the resin that the resin combination as described in any one of [1]~[11] is formed Composition layer；

[13] printed wiring board contains the solidfied material shape of resin combination described in any one of utilization [1]~[11] At insulating layer；

[14] semiconductor device contains printed wiring board described in [13].

The effect of invention

According to the present invention it is possible to provide the resin compositions for insulating layer of printed wiring board, good point can be shown Stability and suitable melt viscosity are dissipated, while can inhibit the warpage in the installation procedure of component.

Specific embodiment

[resin compositions for insulating layer of printed wiring board]

Resin compositions for insulating layer (hereinafter also referred to as " the resin combination of the invention of printed wiring board of the invention Object ") it is characterized in that, having containing specified amount is filled out with currently known spherical inorganic filling material, broken the inorganic of shape Filling material is inorganic filling material of different shapes.

Inorganic filling material used in the present invention is different from spherical inorganic filling material, has angular shape.At this Aspect, the inorganic filling material for being crushed shape have sharp angular shape, and inorganic filling material used in the present invention is slightly With it is round on this point, have and the inorganic filling material of broken shape also different shape.

When being compared for projection of shape in the plane, with the spherical inorganic fill material that cannot clearly identify corner angle Material is different, and inorganic filling material used in the present invention can positively identify corner angle.Wherein, " for projection in the plane Shape can identify corner angle " refer to for projection of shape in the plane, it can recognize certain straight line or substantially straight line and straight with this Line or substantially straight line have certain angle, θ (angle on the inside of projection of shape) and the straight line that connects or substantially straight line.About this Inorganic filling material used in invention, the average value of the angle, θ are bigger compared with the inorganic filling material of broken shape.For example, For inorganic filling material used in the present invention compared with the inorganic filling material of broken shape, the average value of the angle, θ is preferably 5 ° big, It is more preferably 7.5 ° big, and then preferably big 10 °, 12.5 °, 15 °, 17.5 ° or 20 °.

Hereinafter, being joined using 2 geometric shape parameters (shape パラメータ), i.e. geometric shape parameters A and geometry B is counted to illustrate the shape of inorganic filling material used in the present invention.It should be noted that geometric shape parameters A and geometry ginseng Several B presence are the differences of the parameter as derived from three-dimensional method or the parameter as derived from two-dimensional method, but both right In the parameter for the degree that the shape of inorganic filling material, expression deform compared with ball.

< geometric shape parameters A >

Geometric shape parameters A is indicated by following formula (1).

Formula (1): ρ/6 A=SR

[in formula,

Specific surface area (the m of S expression inorganic filling material²/ g),

R indicates the average grain diameter (μm) of inorganic filling material,

Density (the g/cm of ρ expression inorganic filling material³)]。

Consider that there are the system of multiple balls (hereinafter also referred to " ball model systems ").The average grain diameter of these balls When (diameter) is R, the average surface area of existing multiple balls is by π R in ball model system²It indicates, average external volume is by π R³/ 6 indicate.In addition, the average quality of existing multiple balls is by π ρ R in ball model system when the density of ball is ρ³/ 6 tables Show.

Then, consider the system of the inorganic filling material with ball model system average external volume and equal density.If There is the smallest surface area the fact based on object, the ball for same volume, then in the inorganic filling material The average surface area of the inorganic filling material of volume present in system can use A π R²It indicates.Wherein, A is inorganic filling material Geometric shape parameters, lower limit is 1 (the case where inorganic filling material is ball).In addition, if being based on and ball model Be the condition of average external volume and equal density, then in the system of inorganic filling material existing volume inorganic filling material Average quality can be by π ρ R³/ 6 indicate.Then, in the system of inorganic filling material, the specific surface area of inorganic filling material S can use [in the system of inorganic filling material average surface area (the A π R of the inorganic filling material of existing volume²)]/[ Average quality (the π ρ R of the inorganic filling material of existing volume in the system of inorganic filling material³/ 6) it] indicates, is 6A/ (R ρ).That is, the relational expression of S=6A/ (R ρ) is set up, when the formula is deformed for geometric shape parameters A, can be obtained above-mentioned formula (1)。

Inorganic filling material used in the present invention is characterized in that the geometric shape parameters A indicated by above-mentioned formula (1) is full Foot 20≤6A≤40.For the suitable range of geometric shape parameters A, it is described below.

The specific surface area S of the inorganic filling material needed when obtaining geometric shape parameters A can use BET method measurement. Specifically, make to adsorb molecule known to occupied area liquid nitrogen at a temperature of be adsorbed on inorganic filling material sample, can be by Its adsorbance acquires the specific surface area of inorganic filling material sample.As absorption occupied area known to molecule, be suitble to using nitrogen, The inert gases such as helium.The specific surface area S of inorganic filling material can be used automatic specific area measuring device and be measured, as The automatic specific area measuring device can enumerate such as (strain) マウ Application テッ Network system " Macsorb HM-1210 ".

In addition, the average grain diameter R of inorganic filling material can be dissipated by the laser diffraction-based on Michaelis (Mie) scattering theory Method is penetrated to measure.Specifically, being made inorganic fill material using laser diffraction formula particle size distribution device with volume reference The size distribution of material measures its median particle diameter as average grain diameter.Measurement sample preferably makes nothing using using ultrasonic wave Sample made of machine packing material is dispersed in water.As laser diffraction formula particle size distribution device, can enumerate for example (strain) Shimadzu Seisakusho Ltd. system " SALD2200 ", (strain) hole field make made " LA-500 ", " LA-750 ", " LA-950 ".

< geometric shape parameters B >

Geometric shape parameters B is indicated by following formula (2).

Formula (2): B=Lc/L

[in formula,

L indicates the perimeter (μm) of the inorganic filling material in defined section,

Lc indicates the perimeter (μm) with the positive round that the sectional area of the inorganic filling material in above-mentioned section is homalographic.].

Geometric shape parameters B is to be based on the positive round in figure of the same area to have the smallest perimeter the fact and lead Parameter out is limited to 1 in the case where (in defined section, the cross sectional shape of inorganic filling material is positive round) thereon.

Geometric shape parameters B is the parameter set up for each particle of inorganic filling material, by inorganic for constituting The sufficient amount of particle of packing material acquires geometric shape parameters B, can grasp related with the shape of inorganic filling material whole The characteristic of body.In an embodiment of the invention, it for the sufficient amount of particle of composition inorganic filling material, acquires several What form parameter B assigns characteristic to the shape of inorganic filling material according to its average value.In said embodiment, of the invention Used in inorganic filling material be characterized in that, by above-mentioned formula (2) indicate geometric shape parameters B average value be 0.8 with It is upper and 0.9 or less.For the OK range of the average value of geometric shape parameters B, it is described below.

Alternatively, in addition the sufficient amount of particle of composition inorganic filling material is acquired geometric shape parameters B, is based on The value of resulting geometric shape parameters B can also grasp the distribution of shapes for constituting the particle of inorganic filling material.It is used in the present invention Inorganic filling material in, the content of particle of the value less than 0.8 of the geometric shape parameters B indicated by above-mentioned formula (2) is usually 50 several % or less.In addition, in inorganic filling material used in the present invention, by the geometric shape parameters B of above-mentioned formula (2) expression The content of particle of the value greater than 0.9 be usually 30 several % or less.For the OK range of these contents, it is described below.

In the perimeter L and the section of inorganic filling material being needed when obtaining geometric shape parameters B, in regulation section Inorganic filling material sectional area, can by layer for using resin combination of the invention to be formed, carry out section sight It examines to measure.In cross-section observation, it is suitble to use FIB-SEM set composite.It can be used by resulting FIB-SEM image The image processing softwares such as (strain) Leica system " QWin V3 ", acquire the perimeter and area of the inorganic filling material being present in layer (sectional area).As FIB-SEM set composite, such as SII Na ノテ Network ノロジー (strain) system can be enumerated “SMI3050SE”。

For Lc, as long as calculating the perimeter (circumference) with the positive round that the sectional area of resulting inorganic filling material is homalographic ?.

In one embodiment, resin combination of the invention is characterized in that, by resin combination it is non-volatile at When being divided into 100 volume %, the content of inorganic filling material is 40~75 volume %, the inorganic fill material indicated by above-mentioned formula (1) The geometric shape parameters A of material meets 20≤6A≤40 (hereinafter also referred to " resin combination of the 1st embodiment ").

It is important from the point of view of the resin combination for obtaining showing good dispersion stabilization and suitable melt viscosity Be above-mentioned 6A value be 40 or less.In turn from the resin combination for obtaining showing good dispersion stabilization and melt viscosity Angle considers that the value of above-mentioned 6A is preferably 39.8 or less, 39.6 or less, 39.4 or less, 39.2 or less, 39 or less, 38 or less, 37 Below, 36 or less, 35 or less, 34 or less, 33 or less, 32 or less, 31 or less or 30 or less.From the peace for being adequately suppressed component From the point of view of warpage in dress process, it is important that the lower limit of above-mentioned 6A is 20 or more.From the peace that can further suppress component From the point of view of filling the warpage in process, the lower limit value of above-mentioned 6A is preferably 21 or more, 22 or more or 23 or more.

In other embodiments, resin combination of the invention is characterized in that, by not waving in resin combination It sends out into when being divided into 100 volume %, the content of inorganic filling material is 40~75 volume %, inorganic being filled out by what above-mentioned formula (2) indicated The average value for filling the geometric shape parameters B of material is 0.8 or more the and 0.9 or less (hereinafter also referred to " resin of the 2nd embodiment Composition ").

It is important from the point of view of the resin combination for obtaining showing good dispersion stabilization and suitable melt viscosity Be geometric shape parameters B average value be 0.8 or more.And then from obtaining showing good dispersion stabilization and melt viscosity From the point of view of resin combination, the average value of geometric shape parameters B is preferably 0.81 or more or 0.82 or more.From fully From the point of view of warpage in the installation procedure of suppression component, it is important that the upper limit of the average value of geometric shape parameters B is 0.9 Below.From the point of view of the warpage in the installation procedure that can further suppress component, the average value of geometric shape parameters B it is upper Limit preferably 0.89 or less, 0.88 or less, 0.87 or less, 0.86 or less or 0.85 or less.

No matter the difference of the 1st embodiment and the 2nd embodiment, from the warpage in the installation procedure of abundant suppression component Angle, from the point of view of reducing the thermal expansion coefficient of resulting insulating layer sufficiently, by resin combination it is non-volatile at When being divided into 100 volume %, the content of inorganic filling material is 40 volume % or more, preferably 42 volume % or more, more preferably 44 Volume % or more, and then preferably 46 volume % or more, so more preferably 48 volume % or more, particularly preferably 50 volume % with Upper, 52 volume % or more, 54 volume % or more, 56 volume % or more, 58 volume % or more or 60 volume % or more.Use broken shape When inorganic filling material, as the content of the inorganic filling material is got higher, there is the excessively raised tendency of melt viscosity.Relative to This, used in the present invention, meets the inorganic filling material of specific geometric shape parameters condition, may be implemented good Melt viscosity can improve content in turn simultaneously.Such as in resin combination of the invention, the content of the inorganic filling material It can be improved to 62 volume % or more, 64 volume % or more, 66 volume % or more or 68 volume % or more.It is suitable molten from display is obtained The angle of the resin combination of melt-viscosity, to obtain the small and dhering strength (peel strength) with conductor layer of surface roughness excellent From the point of view of insulating layer, the upper limit of the content of the inorganic filling material is 75 volume % hereinafter, preferably 74 volume % are hereinafter, more Preferably 73 volume % hereinafter, be preferably 72 volume % hereinafter, being more preferably 71 volume % in turn hereinafter, particularly preferably 70 in turn Volume % or less.Particularly, implement resin composition layer and internal layer base using vacuum layer platen press in the manufacture of printed wiring board In the case where the lamination of plate, the upper limit of the content of the inorganic filling material is suitably for 70 volume % or less.Inorganic filling material contains Measure (volume %) can inorganic filling material used in the preparation based on resin combination quality and density and in resin group Quality and the density of the nonvolatile component other than inorganic filling material used in the preparation of object are closed to calculate.

No matter the difference of the 1st embodiment and the 2nd embodiment, from obtaining showing that good dispersion stabilization and melting are viscous From the point of view of the resin combination of degree, it is preferred that geometry in inorganic filling material, being indicated by above-mentioned formula (2) The value of parameter B is lower less than the content of 0.8 particle.It is in inorganic filling material, by upper in resin combination of the invention The content for stating particle of the value less than 0.8 of the geometric shape parameters B of formula (2) expression is usually 50 several % hereinafter, preferably 48 Number % hereinafter, more preferably 46 severals % hereinafter, in turn be preferably 44 several % hereinafter, in turn more preferably 42 several % or less or 40 several % or less.Particularly, the value of geometric shape parameters B be 0.75 particle below content be preferably 20 several % or less, 18 number % or less or 16 several % or less.

No matter the difference of the 1st embodiment and the 2nd embodiment, from the warpage in the installation procedure of abundant suppression component Angle considers, it is preferred that the value of geometric shape parameters B in inorganic filling material, being indicated by above-mentioned formula (2) is greater than 0.9 Particle content it is lower.In resin combination of the invention, it is in inorganic filling material, by above-mentioned formula (2) indicate it is several The content of particle of the value of what form parameter B greater than 0.9 is usually 30 severals % hereinafter, preferably 28 several % are hereinafter, more preferable For 26 several % hereinafter, being in turn preferably 24 several % hereinafter, being more preferably 22 number % or less or 20 several % or less in turn.It is special Not, the content for the particle that the value of geometric shape parameters B is 0.94 or more is preferably 6 several % or less, 4 several % or less, 2 Number % or less, 1 several % or less, 0.8 several % or less, 0.6 several % or less, 0.4 several % or less, 0.2 several % or less.

In resin combination of the invention, the material of inorganic filling material is not particularly limited, and can be enumerated for example Silica, aluminium oxide, glass, cordierite, Si oxide, barium sulfate, barium carbonate, talcum, clay, mica powder, zinc oxide, water Talcum, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, boric acid Aluminium, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, zirconium oxide, barium titanate, metatitanic acid barium zirconate, barium zirconate, Calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc., silica is particularly suitable.Inorganic filling material can be used alone 1 Kind, two or more can also be applied in combination.When inorganic filling material of more than two kinds is applied in combination, as obtaining geometric form Average grain diameter (R), specific surface area (S) and the density (ρ) needed when shape parameter A, it is mixed using resulting inorganic filling material respectively Close average grain diameter, specific surface area and the density of object.

The average grain diameter (R) of inorganic filling material, from the point of view of the miniaturization of circuit layout, preferably 4 μm hereinafter, More preferably 3.5 μm hereinafter, be preferably 3 μm or less in turn.The lower limit of the average grain diameter of inorganic filling material, from using resin group It closes from the point of view of obtaining having suitable viscosity, operability good resin varnish when object forms resin varnish, preferably 0.01 μm or more, more preferably 0.03 μm or more, and then preferably 0.05 μm or more, and then more preferably 0.07 μm or more, it is special It You Xuanwei not be 0.1 μm or more.

The specific surface area (S) of inorganic filling material is in terms of with the relationship of average grain diameter (R) and density (ρ), as long as meeting Above-mentioned geometric shape parameters condition, is just not particularly limited.The specific surface area of inorganic filling material for example can for 3~ 10m²The range of/g, preferably 3~8m²The range of/g.

It can be amorphism, crystalline any as long as inorganic filling material meets above-mentioned geometric shape parameters condition Person.In one embodiment, resin combination of the invention contains crystallinity inorganic filling material.In inorganic filling material The content of crystallinity inorganic filling material, when whole inorganic filling materials are set as 100 mass %, preferably 50 mass % with On, more preferably 60 mass % or more, and then preferably 70 mass % or more, and then more preferably 80 mass % or more, particularly preferably For 90 mass % or more, 92 mass % or more, 94 mass % or more, 96 mass % or more, 98 mass % or more or 99 mass % or more. Inorganic filling material, which can be, to be removed the impurity unavoidably contained, is substantially made of crystallinity inorganic filling material.Institute State in embodiment, the Average crystallite diameter of inorganic filling material be preferably 1800 angstroms () hereinafter, more preferably 1600 with Under, and then preferably 1400 or less.The lower limit of the Average crystallite diameter is not particularly limited, typically 100 or more, 200 with first-class.The crystallite diameter of inorganic filling material can be used X-ray diffraction (XRD) device and be measured.As XRD Device can enumerate such as (strain) リガ Network system " Multi FLEX ".

Wherein, as crystallinity inorganic filling material, it is preferable to use crystalline silica.

Meet the inorganic filling material of above-mentioned geometric shape parameters condition, such as can there will be sharp rib by utilization Method that the surface of the inorganic filling material of the broken shape of angular shape is physically and/or chemically ground is heat-treated Method etc., so that it is had circle slightly to prepare.Physical grinding and the method chemically ground are not particularly limited, and can make With currently known any means.As the commercially available product of broken silica, for example imperial gloomy (strain) system " VX-SR " can be enumerated Deng.

In addition, there is the nothing for suitably meeting above-mentioned geometric shape parameters condition in the inorganic oxide of natural output Machine oxide.For example, natural two as the tufted agglutinator output that Average crystallite diameter is 1800 crystallite particles below Silica (especially the maximum particle diameter of tufted agglutinator is 20 μm or less of situation), when preparing resin combination by dispersion Operation, thus tufted agglutinator is unlocked, and meets above-mentioned geometric shape parameters condition.Therefore, in one embodiment, of the invention Resin combination in the inorganic filling material that contains be characterized in that, make the micromeritics below of Average crystallite diameter 1800 The tufted agglutinator of son disperses and obtains, and the maximum particle diameter of the tufted agglutinator is 20 μm or less.As the native silicon dioxide Commercially available product, such as Unimin society system " IMSIL A-8 ", " IMSIL A-10 ", " IMSIL A-15 ", " IMSIL can be enumerated A-25 " etc..

Inorganic filling material used in resin combination of the invention is examined from the angle for improving dispersibility, moisture-proof Consider, is preferably surface-treated with surface treating agent.As surface treating agent, can enumerate such as amino silicone methane series coupling agent, Epoxy silane system coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, organic silazane hydride compounds, the coupling of titanate esters system Agent.Surface treating agent can be used alone, two or more can also be applied in combination.As the commercially available product of surface treating agent, Such as SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 " (3- glycidoxypropyltrime,hoxysilane), SHIN-ETSU HANTOTAI's chemistry can be enumerated Industrial (strain) system " KBM803 " (3-mercaptopropyi trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) make " KBE903 " (3- amino Propyl-triethoxysilicane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 " (N- phenyl -3- TSL 8330), SHIN-ETSU HANTOTAI's chemical industry (strain) makes " SZ-31 " (hexamethyldisilazane) etc..

After the surface treatment for carrying out inorganic filling material, the per unit surface that is combined on the surface of inorganic filling material Long-pending carbon amounts is preferably 0.05mg/m²More than, more preferably 0.08mg/m²More than, and then preferably 0.11mg/m²More than, in turn More preferably 0.14mg/m²More than, particularly preferably 0.17mg/m²Above, 0.20mg/m²Above, 0.23mg/m²Above or 0.26mg/m²More than.The upper limit of the carbon amounts is preferably 1.00mg/m²Hereinafter, more preferably 0.75mg/m²Hereinafter, being preferably in turn 0.70mg/m²Hereinafter, being more preferably 0.65mg/m in turn²Below, 0.60mg/m²Below, 0.55mg/m²Below, 0.50mg/m²With Under.

The carbon amounts of the per unit area combined on the surface of inorganic filling material can be calculated with following step.In table An adequate amount of methyl ethyl ketone (MEK) as solvent is added in inorganic filling material after surface treatment, carries out ultrasonic washing. Supernatant is removed, after keeping solid state component dry, the carbon amounts combined on the surface of inorganic filling material is measured using carbon analysis meter. By the specific surface area with resulting carbon amounts divided by inorganic filling material, the per unit table combined in inorganic filling material is calculated The carbon amounts of area.As carbon analysis meter, such as (strain) hole field can be enumerated and make made " EMIA-320V " etc..

Resin combination of the invention preferably contains thermosetting resin and curing agent in turn.As thermosetting resin, preferably It is epoxy resin.Therefore in one embodiment, resin combination of the invention contains inorganic filling material, but also contains Epoxy resin and curing agent.

Epoxy resin-

As epoxy resin, such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy can be enumerated Resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, tris phenol type epoxy, naphthol novolac type (Na Off トー Le ノボラッ Network type) epoxy resin, novolac type (Off ェノー Le ノボラッ Network type) epoxy resin, tert-butyl-catechu Phenol-type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl group amine type epoxy resin, Glycidyl esters type epoxy resin, Cresol formaldehyde type (Network レゾー Le ノボラッ Network type) epoxy resin, biphenyl type epoxy tree Rouge, linear aliphatic epoxy resin, the epoxy resin with butadiene structure, alicyclic epoxy resin, hetero ring type epoxy resin, Containing whorled epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy, trihydroxy methyl type asphalt mixtures modified by epoxy resin Rouge, tetraphenyl ethane type epoxy resin etc..Epoxy resin can be used alone, two or more can also be applied in combination.

Epoxy resin preferably comprises the epoxy resin in 1 molecule with 2 or more epoxy groups.Not by epoxy resin When volatile ingredient is set as 100 mass %, preferably at least 50 mass % or more are the rings in 1 molecule with 2 or more epoxy groups Oxygen resin.Wherein, the epoxy group in 1 molecule with 2 or more is preferably comprised and in the epoxy resin that 20 DEG C of temperature are liquid (hereinafter referred to as " liquid-state epoxy resin ") and there is 3 or more epoxy groups in 1 molecule and be solid ring at 20 DEG C of temperature Oxygen resin (hereinafter referred to as " solid epoxy resin ").As epoxy resin, by by liquid-state epoxy resin and solid epoxy resin It is used in combination, it is available with excellent flexible resin combination.In addition, the breaking strength of the solidfied material of resin combination also mentions It is high.

As liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, naphthalene type epoxy resin, Glycidyl esters type epoxy resin, novolac type epoxy resin and the epoxy resin with butadiene structure, more preferably Bisphenol A type epoxy resin, bisphenol f type epoxy resin and naphthalene type epoxy resin.It, can as the specific example of liquid-state epoxy resin To enumerate " HP4032 ", " HP4032H ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin), Mitsubishi of DIC (strain) system Learn " jER828EL " (bisphenol A type epoxy resin), " jER807 " (bisphenol f type epoxy resin), " jER152 " (line style of (strain) system Phenol aldehyde type epoxy resin), Nippon Steel live aurification (strain) system " ZX1059 " (bisphenol A type epoxy resin and bisphenol F type epoxy tree The melange of rouge), Na ガセケ system テッ Network ス (strain) system " EX-721 " (glycidyl esters type epoxy resin), ダイセ " PB-3600 " (epoxy resin with butadiene structure) of Le chemical industry (strain) system.They can be used alone, Two or more can be applied in combination.

As solid epoxy resin, preferably 4 function naphthalene type epoxy resins, Cresol formaldehyde type epoxy resin, two rings penta 2 Ene-type epoxy resin, tris phenol type epoxy, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy, Anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenyl ethane type epoxy resin, more preferably 4 function naphthalene type epoxy resins, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy, bisphenol A type epoxy resin, tetraphenyl ethane type Epoxy resin.As the specific example of solid epoxy resin, " HP-4700 ", " HP-4710 " (4 of DIC (strain) system can be enumerated Function naphthalene type epoxy resin), " N-690 " (Cresol formaldehyde type epoxy resin), " N-695 " (Cresol formaldehyde type epoxy resin), " HP-7200 " (dicyclopentadiene-type epoxy resin), " EXA7311 ", " EXA7311-G3 ", " EXA7311-G4 ", " EXA7311- " EPPN-502H " (triphenol type asphalt mixtures modified by epoxy resin that G4S ", " HP6000 " (naphthylene ether type epoxy), Japanese chemical drug (strain) are made Rouge), " NC7000L " (naphthol novolac type epoxy resin), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl Type epoxy resin), Nippon Steel live aurification (strain) system " ESN475V " (naphthol type epoxy resin), " ESN485 " (naphthol novolac Type epoxy resin), Mitsubishi Chemical's (strain) system " YX4000H ", " YL6121 " (biphenyl type epoxy resin), " YX4000HK " (connection Diformazan phenolic (ビキシレノー Le type) epoxy resin), " YX8800 " (anthracene type epoxy resin), Osaka ガスケミカ Le " YL7800 " (fluorenes type epoxy resin), the Mitsubishi Chemical's (strain) that " PG-100 " of (strain) system, " CG-500 ", Mitsubishi Chemical's (strain) make " jER1010 " (solid-state bisphenol A type epoxy resin resin), " jER1031S " (the tetraphenyl ethane type epoxy resin) etc. of system.

As epoxy resin, by liquid-state epoxy resin and solid epoxy resin and used time, preferably their usage ratio (liquid State epoxy resin: solid epoxy resin) it is by quality ratio the range of 1:0.1~1:4.By making liquid-state epoxy resin and solid-state The usage ratio of epoxy resin is the range, available following effects: band when i) being used in the form of sheet laminated material Carry out suitable cementability；Ii) in the form of sheet laminated material using when sufficient flexible, operability can be obtained improve；And Iii the solidfied material etc. with sufficient breaking strength can) be obtained.From it is above-mentioned i)~iii) effect from the point of view of, liquid ring The usage ratio (liquid-state epoxy resin: solid epoxy resin) of oxygen resin and solid epoxy resin is more preferably 1 by quality ratio: The range of 0.3~1:3.5, the further preferably range of 1:0.6~1:3.

Nonvolatile component in resin combination is being set as 100 mass % by the content of the epoxy resin in resin combination When, the preferably 3 mass % of mass %~40, the more preferably 5 mass % of mass %~35, and then preferably 10 mass of mass %~30 %.

The epoxide equivalent of epoxy resin is preferably 50~5000, and more preferably 50~3000, and then preferably 80~2000, And then more preferably 110~1000.By becoming sufficiently, rough surface can be formed for the crosslink density of the range, solidfied material Spend small insulating layer.It should be noted that epoxide equivalent can be measured according to JIS K7236, it is the tree containing 1 equivalent epoxy group The quality of rouge.The weight average molecular weight of epoxy resin is preferably 100~5000, and more preferably 250~3000, further preferably 400~1500.Wherein, the weight average molecular weight of epoxy resin is changed using the polystyrene of gel permeation chromatography (GPC) method measurement The weight average molecular weight of calculation.

Curing agent-

As curing agent, as long as having the function of epoxy resin cure, there is no particular limitation, such as benzene can be enumerated Phenol (phenol) is that curing agent, naphthols system curing agent, active ester system curing agent, benzoxazine system curing agent and cyanate system are solid Agent.Curing agent can be used alone, two or more can also be applied in combination.

Preferably have from the point of view of heat resistance and water resistance as phenol system curing agent and naphthols system curing agent The phenol system curing agent of novolac structure (novolac structure) or with novolac structure naphthols system solidification Agent.In addition, from the point of view of the dhering strength with conductor layer, preferably nitrogenous phenol system curing agent or nitrogenous naphthols system The naphthols system curing agent of curing agent, more preferably the phenol system curing agent of the skeleton containing triazine or the skeleton containing triazine.Wherein, from height Meet heat resistance, water resistance and with from the point of view of the dhering strength of conductor layer, the preferably line style phenolic aldehyde tree of the skeleton containing triazine Rouge.They can be used alone, two or more can also be applied in combination.

As the specific example of phenol system curing agent and naphthols system curing agent, can enumerate for example bright and chemical conversion (strain) system Gold is lived by " MEH-7700 ", " MEH-7810 ", " MEH-7851 ", " NHN " of Japanese chemical drug (strain) system, " CBN ", " GPH ", Nippon Steel " SN-170 " of chemical (strain) system, " SN-180 ", " SN-190 ", " SN-475 ", " SN-485 ", " SN-495 ", " SN-375 ", " LA-7052 ", " LA-7054 ", " LA-3018 ", " LA-1356 ", " TD2090 " etc. of " SN-395 ", DIC (strain) system.

Active ester system curing agent is not particularly limited, it is usually preferred to use phenolic ester class (phenol esters), benzenethiol Ester (thiophenol esters) class, N- hydroxylamine esters, esters of heterocycle hydroxyl compound etc. in 1 molecule have 2 with The compound of the high ester group of upper reactivity.The active ester system curing agent preferably passes through carboxylic acid compound and/or thiocarboxylic It closes the condensation reaction of object and hydroxy compounds and/or mercaptan compound and obtains.It is excellent especially from the point of view of improving heat resistance The active ester system curing agent that choosing is obtained by carboxylic acid compound and hydroxy compounds.More preferably by carboxylic acid compound and oxybenzene compound And/or the active ester system curing agent that naphthol compound obtains.As carboxylic acid compound, it can be mentioned, for example: benzoic acid, acetic acid, amber Amber acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc..As phenol chemical combination Object or naphthol compound, it can be mentioned, for example: quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, methylation bisphenol-A, Methylate Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- bis- Hydroxyl naphthalene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxy hexichol first Ketone, phloroglucin, benzenetriol (benzenetriol), dicyclopentadiene-type bisphenol compounds, linear phenol-aldehyde resin (phenol Novolac) etc..Wherein, " dicyclopentadiene-type bisphenol compounds " refer to that 2 molecule phenol and 1 molecule bicyclopentadiene are condensed Obtained by bisphenol compounds.

As active ester system curing agent, active ester compound preferably containing dicyclopentadiene-type biphenol structure contains There are the active ester compound of naphthalene structure, the active ester compound of acetylate containing linear phenol-aldehyde resin, containing novolak The active ester compound of the benzoylate of resin, wherein the active ester compound of further preferably naphthalene structure, contain two rings penta The active ester compound of diene type biphenol structure.They can be used alone, two or more can also be applied in combination.It answers Explanation is given, " dicyclopentadiene-type biphenol structure " indicates to include-two ring pentalene of phenylene (ジシ Network ロペ Application タレ Application)- The divalent structural unit of phenylene.

As the commercially available product of active ester system curing agent, the active ester compound containing dicyclopentadiene-type biphenol structure can To enumerate " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-65T " (DIC (strain) system), the work containing naphthalene structure Property ester compounds can enumerate " EXB9416-70BK " (DIC (strain) system), the activity of the acetylate containing linear phenol-aldehyde resin Ester compounds can enumerate " DC808 " (Mitsubishi Chemical's (strain) system), the active ester of the benzoylate containing linear phenol-aldehyde resin Compound can enumerate " YLH1026 " (Mitsubishi Chemical's (strain) system) etc..

As the specific example of benzoxazine system curing agent, can enumerate Showa macromolecule (strain) system " HFB2006M ", " P-d ", " F-a " of four countries' chemical conversion industry (strain) system.

It as cyanate system curing agent, is not particularly limited, such as phenol aldehyde type (ノボラッ Network type) (line can be enumerated Type phenol aldehyde type, alkyl novolac type etc.) cyanate system curing agent, dicyclopentadiene-type cyanate system curing agent, bisphenol type be (double Phenol A type, bisphenol-f type, bisphenol S type etc.) cyanate system curing agent and their prepolymer that with a portion of triazine Deng.As concrete example, bisphenol A dicyanate, polyphenol cyanate (oligomeric (3- methylene -1,5- phenylene cyanic acid can be enumerated Ester)), 4,4' methylene bis (2,6- 3,5-dimethylphenyl cyanate), 4,4'- ethylidenediphenyl dicyanate, hexafluoro bisphenol-a Bis- (4- cyanate) phenyl-propanes of dicyanate, 2,2-, 1,1- bis- (4- cyanate phenylmethanes), bis- (4- cyanate -3,5- two Aminomethyl phenyl) methane, bis- (4- cyanate phenyl -1- (methyl the ethylidene)) benzene of 1,3-, bis- (4- cyanate phenyl) thioethers and double The 2 function cyanate ester resins, the multifunctional cyanate ester tree as derived from line style phenolic aldehyde and Cresol formaldehyde etc. such as (4- cyanate phenyl) ether Rouge, these cyanate ester resins a part by prepolymer of triazine etc..As the commercially available product of cyanate system curing agent, Ke Yilie " PT30 " and " PT60 " (being novolac type multifunctional cyanate ester resin) of act ロ Application ザジャパ Application (strain) system, " BA230 " (prepolymer that part or all of bisphenol A dicyanate is become tripolymer by triazine) etc..

The amount ratio of epoxy resin and curing agent, from the angle for improving the mechanical strength of resulting insulating layer, water resistance Consider, with [total number of the epoxy group of epoxy resin]: the ratiometer of [total number of the reactive group of curing agent] is preferably 1:0.2 The range of~1:2, the more preferably range of 1:0.3~1:1.5, and then the range of preferably 1:0.4~1:1.Wherein, curing agent Reactive group be activity hydroxy, active ester groups etc., it is different according to the type of curing agent.In addition, the epoxy group of epoxy resin Total number refers to for all epoxy resin, by the solid state component quality of each epoxy resin divided by be worth obtained by epoxide equivalent into The total value of row, the total number of the reactive group of curing agent refers to for all curing agent, by the solid state component matter of each curing agent Amount carries out total value divided by value obtained by reactive group equivalent.

In one embodiment, resin combination of the invention contain above-mentioned inorganic filling material, epoxy resin and Curing agent.Wherein, resin combination preferably contains respectively as the crystalline silica of inorganic filling material, as epoxy resin Liquid-state epoxy resin and the mixture of solid epoxy resin (liquid-state epoxy resin: the mass ratio of solid epoxy resin is preferably 1:0.1~1:4, more preferably 1:0.3~1:3.5, and then preferably 1:0.6~1:3), as curing agent be selected from phenol system One or more of curing agent, naphthols system curing agent, active ester system curing agent and cyanate system curing agent.Contain even for combination There is a resin composition layer of the specific ingredient, the suitable content of inorganic filling material, epoxy resin and curing agent is also such as It is above-mentioned such.

Resin combination of the invention as needed can be in turn containing selected from thermoplastic resin, curing accelerator, fire-retardant The additive of one or more of agent and organic filler material.

Thermoplastic resin-

As thermoplastic resin, such as phenoxy resin can be enumerated, polyvinyl acetal resin, polyolefin resin, gathered Butadiene resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, Polyphenylene oxide resin, polycarbonate resin, polyether-ether-ketone resin, polyester resin.Thermoplastic resin can be used alone, or by 2 Kind combination of the above uses.

The weight average molecular weight of the polystyrene conversion of thermoplastic resin is preferably 8000~70000 range, more preferably 10000~60000 range, and then preferably 20000~60000 range.The weight of the polystyrene conversion of thermoplastic resin Average molecular weight is measured with gel permeation chromatography (GPC) method.Specifically, the weight average molecular weight of the polystyrene conversion of thermoplastic resin Can be used (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as measurement device, using Showa electrician (strain) Shodex K- processed 800P/K-804L/K-804L as pillar, use chloroform etc. as mobile phase, be measured at 40 DEG C of column temperature, it is poly- using standard The standard curve of styrene calculates.

Phenoxy resin can be enumerated for example with 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.Phenoxy resin End can be any functional group such as phenolic hydroxyl group, epoxy group.Phenoxy resin can be used alone, can also by 2 kinds with On be applied in combination.As the concrete example of phenoxy resin, " 1256 " and " 4250 " that can enumerate Mitsubishi Chemical (strain) system (are Phenoxy resin containing bisphenol A skeleton), " YX8100 " (phenoxy resin containing bisphenol S skeleton) and " YX6954 " (contain Have the phenoxy resin of bis-phenol acetyl benzene skeleton), it is other can also enumerate Nippon Steel live aurification (strain) system " FX280 " and " YL7553 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc. of " FX293 ", Mitsubishi Chemical's (strain) system.

As the concrete example of polyvinyl acetal resin, the electrochemical Block チラー of electrochemically industrial (strain) system can be enumerated Le 4000-2,5000-A, 6000-C, 6000-EP, the エスレッ Network BH of ponding chemical industry (strain) system is serial, BX is serial, KS Series, BL series, BM series etc..

As the specific example of polyimide resin, can enumerate new Japan Chemical (strain) system " リカコート SN20 " and "リカコートPN20".As the specific example of polyimide resin, can also enumerate makes 2 functional hydroxyl groups end polybutadienes (the Japanese Unexamined Patent Publication 2006-37083 bulletin of threadiness polyimides obtained by alkene, diisocyanate cpd and quaternary anhydride reaction The substance of record), polyimides (Japanese Unexamined Patent Publication 2002-12667 bulletin and Japanese Unexamined Patent Publication containing silicone matrix The substance recorded in 2000-319386 bulletin etc.) etc. modified polyimides.

As the specific example of polyamide-imide resin, " the バイロマッ Network ス of Japan's weaving (strain) system can be enumerated HR11NN " and " バイロマッ Network ス HR16NN ".As the specific example of polyamide-imide resin, Hitachi can also be enumerated The polyamidoimide " KS9100 " containing silicone matrix, modified polyamides acyl such as " KS9300 " of chemical conversion industry (strain) system Imines.

As the specific example of polyethersulfone resin, " PES5003P " etc. of Sumitomo Chemical (strain) system can be enumerated.

As the specific example of polysulfone resin, the poly- of ソ Le ベイア De バ Application スト Port リマーズ (strain) system can be enumerated Sulfone " P1700 ", " P3500 " etc..

Nonvolatile component in resin combination is being set as 100 matter by the content of the thermoplastic resin in resin combination When measuring %, the preferably 0.1 mass % of mass %~20, the more preferably 0.5 mass % of mass %~10, and then preferably 1 matter of mass %~5 Measure %.

Curing accelerator-

Curing accelerator can enumerate for example phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator, Guanidine system curing accelerator etc., preferably phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator.Solidification promotees It can be used alone, two or more can also be applied in combination into agent.The content of curing accelerator, by epoxy resin and admittedly When the nonvolatile component of agent total is set as 100 mass %, preferably used with the range of 0.05 mass of mass %~3 %.

Fire retardant-

As fire retardant, can enumerate phosphorus compound, nitrogen compound that for example organic phosphorus flame retardant, organic system are nitrogenous, Silicone flame retardant, metal hydroxides etc..Fire retardant can be used alone, or two or more is applied in combination.Resin The content of fire retardant in composition is not particularly limited, but the nonvolatile component in resin combination is set as 100 mass % When, the preferably 0.5 mass % of mass %~10, more preferably 1 mass of mass %~9 %.

Organic filler material-

It is workable when maying be used at the insulating layer to form printed wiring board arbitrary organic to fill out as organic filler material Material is filled, can be enumerated such as rubber particles, polyamide particles, organic silicon particle, preferably rubber particles.

As rubber particles, as long as to the resin of display caoutchouc elasticity implement chemically crosslinking Treatment, for organic molten The microsome of insoluble and insoluble resin in agent, there is no particular limitation, such as acrylonitrile-butadiene rubber grain can be enumerated Son, butadiene rubber particle, acrylic rubber particle etc..As rubber particles, specifically, XER-91 (Japan can be enumerated Synthesize go system (strain) system), スタ Off ィロイ De AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, アイカ industrial (strain) system) パラロイ De EXL2655, EXL2602 (more than, Wu Yu chemical industry (strain) system) etc..

The average grain diameter of organic filler material is preferably 0.005 μm~1 μm of range, more preferably 0.2 μm~0.6 μm Range.Dynamic light scattering determination can be used in the average grain diameter of rubber particles.Such as it can use ultrasonic wave etc. and make rubber granule Son is evenly dispersed in organic solvent appropriate, and using dense system's particle size analyzer, (big tomb electronics (strain) makes " FPAR- 1000 ") it, is made the size distribution of rubber particles with quality criteria, its median particle diameter is measured as average grain diameter.Resin group The content for closing the rubber particles in object is preferably the 1 mass % of mass %~10, more preferably 2 mass of mass %~5 %.

Other ingredients-

Resin combination of the invention can contain other ingredients as needed.As other ingredients, Ke Yilie Citing such as organocopper compound, organic zinc compound and organic cobalt compounds organo-metallic compound and thickener, defoaming Resin additives such as agent, levelling agent, adaptation imparting agent, colorant and curable resin etc..

The preparation method of resin combination of the invention is not particularly limited, and can enumerate for example by gradation composition according to need Solvent etc. is added, is mixed using impeller etc., the method dispersed etc..

Resin combination of the invention shows good dispersion stabilization and suitable melt viscosity, while can be with suppressing portion Warpage in the installation procedure of part.The interlayer that resin combination of the invention can be suitable as being used to form printed wiring board is exhausted The resin combination (interlayer insulating film of printed wiring board resin combination) of edge layer uses, and then is suitable as shape (track of conductor layer is formed using plating at the resin combination for the interlayer insulating film for utilizing plating to form conductor layer on it The interlayer insulating film of road plate resin combination) it uses.Resin combination of the invention can be also used for adhesive film, prepreg Etc. sheets laminated material, solder resist, underfill, bonding (die bonding) material, semiconductor-encapsulating material, filling perforation Resin, component potting resin etc., the extensive use for needing resin combination.

[sheet laminated material]

Resin combination of the invention can also be coated with varnish state, be used, but be industrially generally adapted with The form of the sheet laminated material of the resin composition layer of the formation containing the useful resin combination uses.

As sheet laminated material, adhesive film preferably as shown below, prepreg.

In one embodiment, the resin composition layer that adhesive film contains supporter and engages with the supporter is (Nian Jie Layer), resin composition layer (adhesive layer) is formed by resin combination of the invention.

The thickness of resin composition layer, from the point of view of the slimming of printed wiring board, preferably 100 μm hereinafter, more Preferably 80 μm hereinafter, be preferably 60 μm hereinafter, being more preferably 50 μm or less or 40 μm or less in turn in turn.Resin composition layer The lower limit of thickness be not particularly limited, usually 10 μm or more.

As supporter, the film being for example molded of plastic material, metal foil, processing release paper can be enumerated, preferably by plastics The film of material formation, metal foil.

When using the film that is molded of plastic material as supporter, plastic material can enumerate such as poly terephthalic acid second The polyester, poly- carbonic acid such as diester (hereinafter sometimes referred to simply as " PET "), polyethylene naphthalate (hereinafter sometimes referred to simply as " PEN ") The acrylic acid series such as ester (hereinafter sometimes referred to simply as " PC "), polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl are fine Tie up plain (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferably polyethylene terephthalate, poly- naphthalene Dioctyl phthalate second diester, particularly preferably cheap polyethylene terephthalate.

When using metal foil as supporter, metal foil can be enumerated such as copper foil, aluminium foil, preferably copper foil.As Copper foil, can be used the foil being made of the monometallic of copper, also can be used by copper and other metals (such as tin, chromium, silver, magnesium, Nickel, zirconium, silicon, titanium etc.) alloy constitute foil.

It can implement delustring processing, sided corona treatment to the surface for the side of supporter engaged with resin composition layer.In addition, As supporter, the surface for maying be used at the side engaged with resin composition layer has the support with release layer of release layer Body.As release agent used in the release layer in the supporter with release layer, can enumerate for example selected from alkyd resin, alkene The release agent of one or more of hydrocarbon resin, polyurethane resin and organic siliconresin.As the commercially available product of release agent, can enumerate Such as alkyd resin system release agent, リ Application テッ Network (strain) system " SK-1 ", " AL-5 ", " AL-7 " etc..

The thickness of supporter is not particularly limited, preferably 5 μm~75 μm of range, more preferably 10 μm~60 μm of model It encloses.It should be noted that when supporter is supporter with release layer, preferably the supporter with release layer it is whole with a thickness of upper State range.

Adhesive film can for example manufacture as follows, that is, preparation is dissolved with the resin of resin combination in organic solvent The resin varnish is coated on supporter using chill coating machine etc., and then makes it dry and form resin combination by varnish Thus nitride layer manufactures.

Organic solvent can enumerate ketone, ethyl acetate, acetic acid such as acetone, methyl ethyl ketone (MEK) and cyclohexanone The acetate esters such as butyl ester, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, cellosolve and butyl card It must aromatic hydrocarbon, dimethylformamide, dimethyl acetamide (DMAc) and the N- first such as carbitols class, toluene and the dimethylbenzene such as alcohol Acid amides series solvents such as base pyrrolidones etc..Organic solvent can be used alone, or two or more is applied in combination.

Drying can use method well known to heating, blowing hot-air etc. to implement.Drying condition is not particularly limited, but into Row drying, so that the content of the organic solvent in resin composition layer is 10 mass % or less, preferably 5 mass % or less.According to tree The boiling point of organic solvent in rouge varnish and it is different, such as use the tree of the organic solvent containing 30 mass of mass %~60 % When rouge varnish, by 50 DEG C~150 DEG C drying 3 minutes~10 minutes, resin composition layer can be formed.

In adhesive film, in the face (that is, face with supporter opposite side) of resin composition layer not engaged with supporter On, the protective film being consistent with supporter can be laminated in turn.The thickness of protective film is not particularly limited, and for example, 1 μm~40 μm. By the way that protective film is laminated, dust etc. can be prevented to the attachment on the surface of resin composition layer or prevent scar.Adhesive film can be with It is rolled into a roll to save, when adhesive film has protective film, can be used by removing protective film.

In one embodiment, prepreg is and being impregnated into resin combination of the invention in sheet-like fiber substrate It is formed.

Sheet-like fiber substrate used in prepreg is not particularly limited, and can be used as glass cloth, aromatic polyamides The common sheet-like fiber substrate of the prepregs substrates such as non-woven fabrics, liquid crystal polymer non-woven fabrics.From the slimming of printed wiring board From the point of view of, the thickness of sheet-like fiber substrate be preferably 50 μm hereinafter, more preferably 40 μm hereinafter, in turn be preferably 30 μm with Under, and then more preferably 20 μm or less.The lower limit of the thickness of sheet-like fiber substrate is not particularly limited, and usually 10 μm or more.

Prepreg can use the manufacture of method well known to hot melt, solvent method etc..

The thickness of prepreg can be same range with the resin composition layer in above-mentioned adhesive film.

In sheet laminated material, the lowest melt viscosity of resin composition layer, from inhibition tree when manufacturing printed wiring board From the point of view of the exudation of rouge, it is more than preferably 300 pools, it is more than more preferably 500 pools, so preferably 700 pools are above, 900 More than pool or more than 1000 pools.The upper limit of the lowest melt viscosity of resin composition layer, it is good from being realized when manufacturing printed wiring board From the point of view of good lamination (circuit landfill), preferably 30000 pools are hereinafter, more preferably 25000 moor hereinafter, excellent in turn It is selected as that 20000 pools or less, 15000 pools are following, 10000 pools are following, 5000 pools are following or 3500 pools are following.Especially in printed wire When implementing the lamination of resin composition layer and internal substrate using vacuum layer platen press in the manufacture of plate, resin composition layer it is minimum The upper limit of melt viscosity is suitably for 5000 pools or less or 3500 pools are following.Wherein, " lowest melt viscosity " of resin composition layer Refer to the minimum viscosity that resin composition layer is presented in the resin melting of resin composition layer.In detail, with certain liter When resin composition layer is heated and makes resin melting by warm speed, melt viscosity while temperature rises of stage in the early stage drops Low, when being then more than certain temperature, melt viscosity is increased while temperature rises." lowest melt viscosity " refers to described minimum The melt viscosity of point.The lowest melt viscosity of resin composition layer can use the measurement of dynamic viscoelastic method, such as can be according to The method recorded in the measurement > of following < lowest melt viscosities measures.

It, can in the present invention for the inorganic filling material for meeting specific geometric shape parameters condition for having used specified amount To advantageously generate the resin composition layer for the lowest melt viscosity for showing above-mentioned suitable range, it can bring and be printed in manufacture The sheet laminated material of good lamination is shown when wiring board.In addition, resin combination of the invention is good due to showing Dispersion stabilization can inhibit coarse agglutination particle in resin composition layer hence for resulting sheet laminated material It is precipitated.

Sheet laminated material of the invention can be suitable for the insulating layer (printed wiring board in order to form printed wiring board Insulating layer use), can be particularly suited for form the interlayer insulating film of the printed wiring board (layer insulation of printed wiring board Layer is used), and then can be suitable for the resin combination in order to form interlayer insulating film, the interlayer insulating film is by plating at it It is upper to form conductor layer (the interlayer insulating film use of the printed wiring board of conductor layer is formed by plating).

[printed wiring board]

Printed wiring board of the invention contains the insulating layer formed using the solidfied material of resin combination of the invention.

In one embodiment, above-mentioned adhesive film can be used, using containing following in printed wiring board of the invention (I) it is manufactured with the method for the process of (II),

(I) it will be bonded film lamination on internal substrate, engage the resin composition layer of the adhesive film with internal substrate Process；

(II) process that resin composition layer heat cure is formed into insulating layer.

" internal substrate " used in process (I) is primarily referred to as glass epoxy substrate, metal substrate, polyester substrate, polyamides The substrates such as imines substrate, BT resin substrate, heat curing type polyphenylene oxide substrate are schemed in the one or both sides formation of the substrate The circuit substrate of the conductor layer (circuit) of case processing.In addition, when manufacturing printed wiring board, so should be formed insulating layer and/ Or the internal layer circuit substrate of the intermediate manufacture object of conductor layer is also included in the present invention in described " internal substrate ".

The thickness of internal substrate, from the point of view of the slimming of printed wiring board, preferably 800 μm hereinafter, more preferably For 400 μm hereinafter, being in turn preferably 200 μm or less.According to the present invention, even if in the case where using thin internal substrate in turn, It can also inhibit the warpage of printed wiring board in installation procedure.Such as even if use with a thickness of 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 120 μm or less, 110 μm or less or 100 μm In the case where internal substrate below, the warpage in installation procedure can also be inhibited.The lower limit of the thickness of internal substrate is without spy From the point of view of operability when not limiting, but manufacturing from printed wiring board improves, preferably 10 μm or more, more preferably 20 μm More than.

The bending elastic modulus of internal substrate is not particularly limited.In the present invention, no matter the elasticity of flexure of internal substrate Modulus, can warpage in the installation procedure of suppression component.

The lamination of internal substrate and adhesive film for example can be by heating on internal substrate from support side by adhesive film It presses to carry out.As the component (hereinafter also referred to " heating pressing component ") that adhesive film is heated to pressing on internal substrate, It can enumerate such as warmed-up metal plate (SUS siding) or metallic roll (SUS roller) etc..It should be noted that it is preferred that not being that will add Hot pressing component directly pressurizes on adhesive film, but clips heat resistant rubber elastomeric material and pressurize, so that adhesive film fills Comply with the concave-convex surface of internal substrate with dividing.

The lamination of internal substrate and adhesive film can use the implementation of vacuum layer platen press.In vacuum layer platen press, heating pressing Temperature is preferably 60 DEG C~160 DEG C, more preferably 80 DEG C~140 DEG C of range, heating pressing pressure be preferably 0.098MPa~ 1.77MPa, the more preferably range of 0.29MPa~1.47MPa, heating pressing time is preferably 20 seconds~400 seconds, more preferably 30 seconds~300 seconds ranges.Lamination is preferably implemented in the case where pressure is 26.7hPa reduced pressure below.

Lamination can use commercially available vacuum laminator and carry out.As commercially available vacuum laminator, can enumerate for example (strain) name mechanism makees made vacuum pressure type laminating machine, vacuum pack system device of ニチゴーモート Application (strain) system etc..

After lamination, by pressurizeing (under atmospheric pressure), for example by heating pressing component from support side under normal pressure, it can carry out The smoothing techniques of the adhesive film of lamination.The pressurized conditions of smoothing techniques, which can be set to, presses condition with the heating of above-mentioned lamination For same condition.Smoothing techniques can be carried out by commercially available laminating machine.It should be noted that lamination and smoothing techniques can be with It is continuously carried out using above-mentioned commercially available vacuum laminator.

The lamination of internal substrate and adhesive film can also be implemented using vacuum hotpressing machine.By using vacuum hotpressing machine, i.e., Make using the high resin combination of inorganic filling material content, good lamination also may be implemented, and (circuit is filled out Burying property).Being heated and pressurizeed can be carried out with 1 stage, but from the point of view of the exudation for inhibiting resin, is preferably divided into condition 2 more than the stage carry out.Such as preferably by the pressurization in the 1st stage temperature be 70~150 DEG C, pressure be 0.098MPa~ The range of 1.77MPa carries out, by the pressurization in the 2nd stage temperature is 150~200 DEG C, pressure is 0.098MPa~3.92MPa's Range carries out.The time in each stage is preferably 30~120 minutes.Pressurization is usually 1 × 10^-2MPa or less, preferably 1 × 10^-3MPa Implement under decompression below.As commercially available vacuum hotpressing machine, such as (strain) name mechanism can be enumerated and make made " MNPC-V- 750-5-200 ", Beichuan essence machine (strain) system " VH1-1603 " etc..When implementing process (I) using vacuum hotpressing machine, which can be simultaneous There is the heat cure (that is, process (II)) of resin composition layer.

Supporter can remove between process (I) and process (II), can also remove after process (II).

In process (II), resin composition layer is subjected to heat cure and forms insulating layer.

The heat cure condition of resin composition layer is not particularly limited, and can be used in the insulating layer for forming printed wiring board When the condition that generallys use.

For example, the heat cure condition of resin composition layer is different according to type of resin combination etc., but solidification temperature It can be 120~240 DEG C of range (preferably 150~210 DEG C of range, more preferably 170~190 DEG C of range), when solidification Between can be 5~90 minutes ranges (preferably 10~75 minutes, more preferably 15~60 minutes).

It, can be pre- in the at a temperature of progress lower than solidification temperature by resin composition layer before making resin composition layer heat cure Heating.It, can be at 50 DEG C more than and less than 120 DEG C (preferably 60 DEG C or more and 110 such as before making resin composition layer heat cure DEG C or less, more preferable 70 DEG C or more and 100 DEG C or less) at a temperature of, resin composition layer is carried out 5 minutes or more (preferably 5~ 150 minutes, it is 15~120 minutes more preferable) preheating.

Low thermal expansion coefficient is shown by the insulating layer that the solidfied material of resin combination of the invention is formed.Implement at one In mode, the insulating layer formed by the solidfied material of resin combination of the invention have preferred 30ppm/ DEG C or less, it is more preferable 28ppm/ DEG C of coefficient of linear thermal expansion below.The lower limit of the coefficient of linear thermal expansion of insulating layer is not particularly limited, usually 1ppm/ DEG C or more.The coefficient of linear thermal expansion of insulating layer for example can use the measurement of method well known to thermo-mechanical analysis etc..As thermomechanical Analytical equipment can enumerate " the Thermo Plus TMA8310 " of such as (strain) リガ Network.In the present invention, the line of insulating layer When thermal expansion coefficient carries out thermo-mechanical analysis with tensile load method, 25~150 DEG C of coefficient of linear thermal expansion of in-plane.

When manufacturing printed wiring board, can implement in turn (III) the process of insulating layer perforating, (IV) by insulating layer into The process that the process of row roughening treatment, (V) form conductor layer in surface of insulating layer.These processes (III) to (V) can basis Used in the manufacture of printed wiring board, well known to a person skilled in the art various methods to implement.It should be noted that will support For body when process (II) removes afterwards, the removing of the supporter can be between process (II) and process (III), process (III) and work Implement between sequence (IV) or between process (IV) and process (V).

Process (III) is the process of aperture on the insulating layer, it is possible thereby to be formed on the insulating layer through-hole (via hole), The holes such as open-work (through hole).The composition etc. of process (III) resin combination according to used in the formation of insulating layer, example Drill bit, laser, plasma such as can be used to implement.Size, the shape in hole can be fitted according to the design of printed wiring board Work as decision.As previously mentioned, resin combination of the invention is due to showing good dispersion stabilization, to can inhibit resin combination The precipitation of coarse agglutination particle in nitride layer and then in insulating layer.It, can be in work in the insulating layer with uniform composition The hole with required cross sectional shape is formed in sequence (III).Therefore, even if hole is filled with conductor metal and forms filling conducting In the case where hole (Off ィ Le De ビア), it will successfully can also be filled in hole with conductor metal.At this point, as using broken The case where inorganic filling material of broken shape, is such, and the sharp inorganic filling material for having corner angle or its coarse agglutination particle are present in When the wall surface in hole, using the inorganic filling material or its coarse agglutination particle as starting point, plating preferentially extends, therefore exists sometimes Gap is generated in filling via hole.In the present invention using the inorganic filling material for meeting specific geometric shape parameters condition In, it can inhibit the wall surface that described agglutination particle etc. is present in hole, therefore the entire wall surface in hole, plating equably extend, it can be with Advantageously inhibit the generation in the gap in filling via hole.

Process (IV) is the process for being roughened insulating layer.The step of roughening treatment, condition be not special It limits, it can be using the known step usually used when forming the insulating layer of printed wiring board, condition.Such as it can be successively Implement swelling process, the roughening treatment using oxidant, the neutralisation treatment using neutralizer using swelling liquid, by insulating layer It is roughened.It as swelling liquid, is not particularly limited, aqueous slkali, surfactant solution etc. can be enumerated, preferably Aqueous slkali, as the aqueous slkali, more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling liquid, Ke Yilie スウェリ Application グディップセキュリガ Application ス P, the スウェリ Application グ of citing such as アトテッ Network ジャパ Application (strain) system ディップセキュリガ Application ス SBU etc..Be not particularly limited using the swelling process of swelling liquid, for example, can by 30~ Insulating layer is impregnated 1 minute~20 minutes to carry out in 90 DEG C of swelling liquid.It as oxidant, is not particularly limited, Ke Yilie The alkaline permanganic acid solution of potassium permanganate, sodium permanganate has such as been dissolved in citing in the aqueous solution of sodium hydroxide.Using alkaline high The roughening treatment of the oxidants such as mangaic acid solution varnished insulation layer 10 preferably in the oxidizing agent solution for being heated to 60 DEG C~80 DEG C Minute~30 minutes.In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 mass of mass %~10 %.As Commercially available oxidant, can enumerate such as アトテッ Network ジャパ Application (strain) system U Application セ Application トレート U Application パ Network ト CP, The alkalinity permanganic acid solution such as ドージ Application グソリューショ Application セキュリガ Application ス P.In addition, as neutralizer, preferably Acid aqueous solution can enumerate the リダ Network ショ Application ソリュー of such as アトテッ Network ジャパ Application (strain) system as commercially available product ション・セキュリガントP.It can be by making to have carried out at the roughening using oxidizing agent solution using the processing of neutralizer The process face of reason impregnates 5 minutes~30 minutes in 30~80 DEG C of neutralizer to carry out.

Low surface roughness is shown after roughening treatment using the insulating layer that resin combination of the invention is formed.? In one embodiment, the arithmetic average roughness Ra of the surface of insulating layer after roughening treatment is preferably 500nm hereinafter, more excellent 480nm is selected as hereinafter, being in turn preferably 450nm hereinafter, being more preferably 400nm or less, 360nm or less or 320nm or less in turn. Even if the insulating layer formed using resin combination of the invention is in the case where Ra is small in this way, also in referring now to conductor layer Excellent dhering strength.The lower limit of Ra value is not particularly limited, preferably 0.5nm or more, more preferably 1nm or more.Insulating layer The arithmetic average roughness Ra on surface can be used non-contact type surface roughness meter and be measured.It is thick as non-contact type surface The specific example of roughnessmeter can enumerate " the WYKO NT3300 " of ビー U イ Application スツルメン Star society.

Process (V) is the process that conductor layer is formed on surface of insulating layer.

Conductor material used in conductor layer is not particularly limited.In suitable embodiment, conductor layer, which contains, to be selected from The metal of one or more of gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor layer can be list Metal layer or alloy-layer, as alloy-layer, can enumerate for example by selected from metal of more than two kinds among the above alloy (such as Nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) formed layer.Wherein, versatility, the cost, pattern shape formed from conductor layer At easiness angularly consider, preferably the single metal layer of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper or nickel-chromium alloy, Copper-nickel alloy, copper-titanium alloy alloy-layer, more preferably the single metal layer of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper or The alloy-layer of nickel-chromium alloy, and then the single metal layer of preferably copper.

Conductor layer can be single layer structure, be also possible to 2 layers or more of the list formed by different types of metal or alloy The multilayered structure of metal layer or alloy layer laminate.Conductor layer be multilayered structure when, the layer to connect with insulating layer be preferably chromium, zinc or The single metal layer of titanium or the alloy-layer of nickel-chromium alloy.

The thickness of conductor layer depends on the design of desired printed wiring board, but generally 3 μm~35 μm, preferably 5 μm ~30 μm.

Conductor layer can use plating to be formed.Such as the known skill such as can use semi-additive process, full additive method Art carries out plating on the surface of insulating layer, forms the conductor layer with required Wiring pattern.Semi-additive process is utilized hereinafter, showing Form the example of conductor layer.

Firstly, conformal at plating layer (メッキシー De layer) using electroless plating on the surface of insulating layer.Then, in shape At plating layer on, corresponding to required Wiring pattern, form the mask pattern for exposing a part of plating layer.In exposing On plating layer, after forming metal layer using plating, mask pattern is removed.Then, unwanted plating layer is removed using etching etc., The conductor layer with required Wiring pattern can be formed.

Sufficient dhering strength is shown for conductor layer using the insulating layer that resin combination of the invention is formed.At one In embodiment, the dhering strength of insulating layer and conductor layer is preferably 0.50kgf/cm or more, more preferably 0.55kgf/cm with On, and then preferably 0.60kgf/cm or more.The upper limit value of dhering strength is not particularly limited, be 1.2kgf/cm or less, 0.90kgf/cm is such as the following.In the present invention, it although the surface roughness Ra of the insulating layer after roughening treatment is small, can also be formed The insulating layer of high dhering strength is presented in this way, therefore significantly assists in the miniaturization of circuit layout.It should be noted that in the present invention In, the dhering strength of insulating layer and conductor layer refer to by conductor layer relative to insulating layer with vertical direction (90 degree of directions) tearing when Peel strength (90 degree of peel strengths), can by measurement using cupping machine by conductor layer relative to insulating layer with vertical Peel strength when direction (90 degree of directions) is torn acquires.As cupping machine, it can enumerate such as (strain) TSE's " AC-50C-SL " etc..

In other embodiments, above-mentioned prepreg can be used to manufacture in printed wiring board of the invention.Manufacture Method is substantially same as the case where using adhesive film.

[semiconductor device]

Using printed wiring board of the invention, semiconductor device can be manufactured.Printed wiring board of the invention is although be thin Type can be advantageous even if can also inhibit warpage in the installation procedure using the component of high soft solder Reflow Soldering temperature Ground mitigates the problems such as poor contact of circuit modifications, component.

In one embodiment, printed wiring board of the invention use peak temperature for 260 DEG C of soft solders high in this way In the installation procedure of Reflow Soldering temperature, the warpage of printed wiring board can be suppressed to less than 40 μm.In the present invention, track When the warpage of road plate is the buckling behavior using the 10mm square part in image moire device observation printed wiring board center, position Move the value of the maximum height of data and the difference of minimum constructive height.When measurement, printed wiring board is being reappeared into IPC/JEDEC J-STD- 020C(“Moisture/Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devices ", in July, 2004) in record Reflow Soldering temperature profile (lead free manufacture (lead-free Assembly distribution map) is used；260 DEG C of peak temperature) reflow soldering apparatus in by after 1 time, according to being based on above-mentioned IPC/JEDEC The Reflow Soldering temperature profile of J-STD-020C heats on one side by printed wiring board, for being set to printed wire The gridline of the another side of plate, acquires displacement data.It should be noted that such as Japan ア Application ト can be enumerated as reflow soldering apparatus System (strain), which makes " HAS-6116 " as image moire device, can enumerate such as Akrometrix system " TherMoire AXP ". Using the solidfied material of the resin combination of the inorganic filling material for meeting geometry in particular Parameter Conditions containing specified amount Formed insulating layer, even if the printed wiring board of the invention containing the insulating layer be it is slim, can also advantageously inhibit erector Warpage in sequence.

As semiconductor device, can enumerate for electric product (such as computer, mobile phone, digital camera and TV etc.) With the various semiconductor devices in the vehicles (such as motorcycle, automobile, electric car, ship and aircraft etc.) etc..

Semiconductor device of the invention (can partly be led by the conducting position installing component in printed wiring board of the invention Body chip) it manufactures." conducting position " refers to " position of the electric signal in conduction printed wiring board ", and position can be table Any one of face or the position of landfill.In addition, as long as semiconductor chip does not have using semiconductor as the circuit element of material It is particularly limited to.

As long as the installation method of semiconductor chip when manufacturing semiconductor device of the invention makes semiconductor chip effectively It functions, is not particularly limited, specifically, wire bonding installation method can be enumerated, flip-chip installation method, adopted With (プ layers of アッ of Le De of ビ of プな of バ Application of bumpless build up layer；BBUL installation method), using anisotropic conductive film (ACF) installation method, using installation method of non-conductive film (NCF) etc..Wherein, it " uses bumpless build up layer (BBUL) Installation method " be " semiconductor chip directly to be filled into the recess portion of printed wiring board, semiconductor chip and printed wire are made The installation method of wiring connection on plate ".

[embodiment]

The present invention is specifically described with embodiment below, but the present invention is not restricted by the embodiments.It should Illustrate, " part " and " % " in record refers respectively to " mass parts " and " quality % " as long as no other explanation below.

It is illustrated firstly for various measuring methods, evaluation method.

(preparation that substrate 1 is used in evaluation)

(1) preparation of internal layer circuit substrate

By form internal layer circuit glass cloth base material epoxy resin two-sided copper foil covered plywood (18 μm of the thickness of copper foil, The thickness 0.3mm of substrate, Matsushita Electrician (strain) system " R5715ES ") two sides etch 1 μm using メッ Network (strain) system " CZ8100 ", Carry out the roughening treatment on copper surface.

(2) lamination of adhesive film

It is pressurizeed laminating machine ((strain) name mechanism makees made " MVLP-500 ") using intermittent vacuum, by embodiment and comparative example The adhesive film of middle production in such a way that resin composition layer is engaged with internal layer circuit substrate, be stacked on the two of internal layer circuit substrate Face.Lamination is by carrying out decompression in 30 seconds, pressing air pressure 13hPa or less afterwards, under conditions of 100 DEG C, pressure 0.74MPa It carries out within 30 seconds.

(3) solidification of resin composition layer

After lamination, supporter is removed from the two sides of substrate.Then, with 100 DEG C, 30 minutes and then 170 DEG C, 30 minutes Condition of cure make resin composition layer carry out heat cure, formed insulating layer.

(4) roughening treatment

After forming insulating layer, by substrate, in swelling liquid, (アトテッ Network ジャパ Application (strain) makes " スエリ Application グディップセキュリガ Application ト P ", the aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) in 80 DEG C impregnate 5 minutes, aoxidizing (アトテッ Network ジャパ Application (strain) makes " U Application セ Application トレート U Application パ Network ト CP ", KMnO for agent₄: 60g/L, NaOH:40g/L Aqueous solution) in 80 DEG C impregnate 10 minutes, finally neutralizer (アトテッ Network ジャパ Application (strain) make " リダ Network ショ Application ソリューショ Application セキュリガ Application ト P ", sulfuric acid aqueous hydroxylamine) in 40 DEG C impregnate 5 minutes.Then, make it dry at 80 DEG C Dry 30 minutes.Resulting substrate is known as " substrate 1a ".

It should be noted that implementing the operation of above-mentioned (2)~(4) as described below about embodiment 6 and comparative example 5, obtaining base Plate 1a；

It is viscous by what is made in embodiment and comparative example using vacuum pressure device (Beichuan essence machine (strain) makes " VH1-1603 ") Connect the two sides that film is stacked on internal layer circuit substrate in such a way that resin composition layer is engaged with internal layer circuit substrate.Lamination by 1x10^-3Under the decompression of MPa, 100 DEG C, press 30 minutes under conditions of pressure 1.0MPa, be then warming up to 180 DEG C with 10 minutes Afterwards, 30 minutes are pressed under conditions of 180 DEG C, pressure 1.0MPa to carry out.Resin composition layer heat cure is formed as a result, Insulating layer.Roughening treatment in addition in swelling liquid in 60 DEG C impregnate 5 minutes, in oxidant in 80 DEG C impregnate 5 minutes other than, It is other same as above-mentioned (4).

(5) formation of conductor layer

According to semi-additive process, conductor layer is formed in surface of insulating layer as described below；

Substrate 1a is being contained into PdCl₂Non-electrolytic plating solution in, 40 DEG C dipping after five minutes, in non-electrolytic copper plating It is impregnated 20 minutes in liquid, at 25 DEG C.Then, it is heated 30 minutes at 150 DEG C, after being made annealing treatment, forms underseal, utilize Etching forms pattern.Then, copper sulfate bath plating is carried out, 25 μm of thickness of conductor layer is formed, is carried out at 180 DEG C 30 minutes Annealing.Resulting substrate is known as " substrate 1b ".

(preparation that substrate 2 is used in evaluation)

(1) preparation of internal substrate

As internal substrate, preparation all removes the two-sided copper foil of glass cloth base material epoxy resin two-sided copper foil covered plywood Gone without covering (unclad) plate (100 μm of thickness).As glass cloth base material epoxy resin two-sided copper foil covered plywood, use Mitsubishi ガス chemistry (strain) system " HL832NSF-LCA " (size 100mm × 150mm, 100 μm of the thickness of base substrate, thermal expansion 4ppm/ DEG C of coefficient, bending elastic modulus 34GPa, surface copper circuit 16 μm of thickness).

(2) lamination of adhesive film

Using intermittent vacuum pressurization laminating machine, (2 stages of ニチ go ーモート Application (strain) system stack laminating machine " CVP700 "), in a manner of making resin composition layer connect with internal substrate, the bonding that will make in embodiment and comparative example Film layer is laminated on the two-sided of internal substrate.Implementation of such as getting off is laminated: decompression 30 seconds, after making air pressure 13hPa or less, in 100 DEG C, pressure Press it 30 seconds.Then, hot pressing in 60 seconds is carried out in the condition of 100 DEG C, pressure 0.5MPa.

(3) solidification of resin composition layer

After lamination, supporter is removed from substrate.Then, with 190 DEG C, 90 minutes conditions of cure by resin combination Nitride layer carries out heat cure, forms insulating layer.Resulting substrate is known as " substrate 2a ".

The measurement > of the specific surface area (S) of < inorganic filling material

The specific surface area of inorganic filling material uses automatic specific area measuring device ((strain) マウ Application テッ Network system " Macsorb HM-1210 "), it is acquired using nitrogen BET method.

The measurement > of the average grain diameter (R) of < inorganic filling material

Inorganic filling material 0.01g, nonionic system dispersing agent (Nippon Yushi (Co., Ltd.) are added in the bottle of 20ml " T208.5 ") 0.2g, pure water 10g, are dispersed using the ultrasonic wave that sonic washing machine carries out 10 minutes, prepare sample.Then, exist Sample is put into laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system " SALD2200 "), makes its circulation on one side 10 minutes ultrasonic waves are irradiated on one side.Then, stop ultrasonic wave, size distribution is carried out in the state of maintaining the circulation of sample Measurement, acquires the average grain diameter (R) of inorganic filling material.It should be noted that refractive index when measurement is set as 1.45-0.001i.

The calculating > of < geometric shape parameters A

The value of the specific surface area (S) of inorganic filling material, average grain diameter (R) and density (ρ) is substituted into following formula (1), is calculated Geometric shape parameters A,

Formula (1): ρ/6 A=SR.

The calculating > of < geometric shape parameters B

The insulating layer in one side for being stacked on substrate 1a uses FIB-SEM set composite (SII Na ノテ Network ノロジー (strain) makes " SMI3050SE "), cross-section observation is carried out with 14000 times of observation multiplying power.By resulting FIB-SEM picture, use Image processing software ((strain) Leica system " QWin V3 ") measures the perimeter of the existing inorganic filling material particle in insulating layer (L) and area.It should be noted that for the unclear inorganic filling material particle of general image, the feint nothing of profile is avoided Any 50 inorganic filling material particles of machine packing material particle, every 1 sample are measured.It inorganic is filled out by resulting The area of material particles is filled, the perimeter (circumference with the positive round of its homalographic is calculated；Lc).The value of L and Lc is substituted into following formula (2), For each inorganic filling material particle, geometric shape parameters B is calculated, obtains average value and its distribution of geometric shape parameters B,

Formula (2): B=Lc/L.

The measurement > of the Average crystallite diameter of < inorganic filling material

The Average crystallite diameter of inorganic filling material is acquired according to following step.Firstly, fixed on glass specimen plate Inorganic filling material prepares sample panel.The sample panel is arranged in Wide angle X-ray diffraction device ((strain) リガ Network system " Multi FLEX ") in, diffraction pattern is measured using Wide angle X-ray diffraction bounce technique.X-ray source is CuK α, and detector is scintillation detector, Power is 40kV, 40mA.By the SiO based on resulting diffraction pattern₂The diffracted ray in Quarts (101) face is strangled using thanking (Scherrer) formula calculates crystallite diameter.

The evaluation > of < dispersion stabilization

For the adhesive film made in embodiment and comparative example, using microscope ((strain) KEYENCE system " VH-2250 ") with Agglutination particle in 1000 times of observation multiplying power observation resin composition layer.The dispersion stabilization of resin combination is according to below Benchmark is evaluated,

Evaluation criteria:

Zero: 10 μm or more of agglutination particle is in 10 visuals field less than 2

×: 10 μm or more of agglutination particle is 2 or more in 10 visuals field.

The measurement > of < lowest melt viscosity

Resin composition layer for the adhesive film made in embodiment and comparative example, uses measurement of dynamic viscoelasticity device ((strain) ユービーエ system system " Rheosol-G3000 ") measures melt viscosity.For sample resin combination 1g, use The parallel-plate of diameter 18mm is warming up to 200 DEG C from 60 DEG C of initial temperature with 5 DEG C/min of heating rate, with measuring temperature interval For 2.5 DEG C, the determination condition measurement dynamic viscoelastic modulus of vibration 1Hz, degree of skewness (askew body) 1deg, it is viscous to measure minimum melting Degree.Lamination is evaluated according to benchmark below,

Evaluation criteria:

Zero: lowest melt viscosity is that 30000 pools are following

×: lowest melt viscosity is higher than 30000 pools.

The evaluation > of < warpage

By substrate 2a (n=5) reappear 260 DEG C of peak temperature soft solder Reflow Soldering temperature reflow soldering apparatus (Japanese ア Application ト system (strain) makes " HAS-6116 ") in pass through primary (Reflow Soldering temperature profile is according to IPC/JEDEC J-STD-020C).It connects , using image moire device (Akrometrix society system " TherMoire AXP "), using according to IPC/JEDEC J-STD- Substrate is heated below the Reflow Soldering temperature profile of 020C (260 DEG C of peak temperature), based on the gridline configured in thereon Measure the displacement of the 10mm square part of substrate center.Warpage is evaluated according to evaluation criteria below,

Evaluation criteria:

Zero: for all 5 samples, the maximum height of the displacement data of entire temperature range and the difference of minimum constructive height are small In 40 μm

×: at least one sample, the maximum height of the displacement data of entire temperature range and the difference of minimum constructive height are 40 μm or more.

The measurement > of < arithmetic average roughness (Ra)

For substrate 1a, non-contact type surface roughness meter (ビー U イ Application スツルメン Star society system " WYKO is used NT3300 "), it is that numerical value obtained by 92 μm of 121 μ m acquires Ra value as measurement range using VSI contact mode, 50 times of lens. As measured value and finding out randomly selected 10 points of average value.

The measurement > of the dhering strength of < conductor layer

The measurement of insulating layer and the dhering strength of conductor layer is carried out for evaluating substrate 1b according to JIS C6481.Specifically Ground introduces the notch of the part of width 10mm, length 100mm in the conductor layer of substrate 1b, one end is removed, is grabbed with fixture Firmly, the loading (kgf/cm) when vertically tearing 35mm with 50mm/ minutes speed at room temperature is measured, is acquired closely sealed strong Degree.

The measurement > of < coefficient of linear thermal expansion

The adhesive film made in embodiment and comparative example is heated 90 minutes at 190 DEG C, resin composition layer is made to carry out heat Solidification.Then, supporter is removed, obtains the solidfied material of sheet.By the solidfied material of resulting sheet be cut into width about 5mm, The test film of length about 15mm, using thermo-mechanical analysis device ((strain) リガ Network system " Thermo Plus TMA8310 "), with drawing It stretches load method and carries out thermo-mechanical analysis.In detail, by test film assembly in above-mentioned thermo-mechanical analysis device after, load 1g, METHOD FOR CONTINUOUS DETERMINATION 2 times under the determination condition that 5 DEG C/min of heating rate.Calculate the range from 25 DEG C to 150 DEG C in the 2nd measurement The coefficient of mean linear thermal expansion.

< fills the evaluation > in the gap of via hole

The evaluation for filling the gap of via hole is carried out according to following step:

(1) formation of through-hole

Using CO2 Laser Processing Equipment for Joining ((strain) Hitachi system " LC-2E21B/1C "), it is being stacked on substrate 1a One side on insulating layer on, formed 60 μm of top diameter (トップ diameter), 50 μm of base diameter (ボト system diameter) through-hole；

(2) formation of via hole is filled

After forming through-hole, insulating layer is roughened, forms conductor layer.The formation of roughening treatment and conductor layer It is equally carried out with (the evaluation preparation of substrate 1).Conductor metal is also filled inside through-hole as a result, obtains filling via hole；

(3) evaluation in gap

It uses scanning electron microscope (SEM) ((strain) Hitachi Ha イテ Network ノロジーズ system, model " SU-1500 ") Cross-section observation is carried out to the filling via hole of formation.Situation of the number less than 2 that 10 are filled the gap in via hole is set For "○", the situation that the number that 10 are filled the gap in via hole is 2 or more is set as "×".

Each physical property and geometric shape parameters A, B of inorganic filling material used in embodiment and comparative example, which summarize, is shown in table 1。

[table 1]

。

It should be noted that the content of particle of the geometric shape parameters B less than 0.8 is 36 several %, especially for IMSIL A-8 Ground, geometric shape parameters B are that the content of 0.75 particle below is 16 several %, particle of the geometric shape parameters B greater than 0.9 Content is 12 several %, and particularly, the content for the particle that geometric shape parameters B is 0.94 or more is 0 several %.In addition, for The content of the particle of IMSIL A-25, geometric shape parameters B less than 0.8 is 26 several %, and particularly, geometric shape parameters B is The content of 0.75 particle below is 20 several %, and the content of particle of the geometric shape parameters B greater than 0.9 is 14 several %, especially Ground, the content for the particle that geometric shape parameters B is 0.94 or more are 0 several %.

1 > of < embodiment

(1) preparation of resin varnish

By 20 parts of liquid bisphenol A type epoxy resin (epoxide equivalent 187, Mitsubishi Chemical's (strain) system " jER828EL "), biphenyl 30 parts of type epoxy resin (epoxide equivalent 276, Japanese chemical drug (strain) make " NC3000 "), tetraphenyl ethane type epoxy resin (epoxy Equivalent 198, Mitsubishi Chemical's (strain) system " jER1031S ") 5 parts, curable type bisphenol A type epoxy resin (epoxide equivalent about 3000~ 5000, Mitsubishi Chemical's (strain) system " jER1010 ") it is dissolved in the mixing that the mass ratio of methyl ethyl ketone (MEK) and cyclohexanone is 1:1 The resin solution that 50 mass % of nonvolatile component is formed in solvent makes the tree of 50 mass % of the nonvolatile component while stirring 5 parts of lipoprotein solution dissolve by heating in MEK20 parts and 10 parts of cyclohexanone of in the mixed solvent.The line style of the skeleton containing triazine is mixed thereto 10 parts of phenolic aldehyde system curing agent (the MEK solution that hydroxyl equivalent 125, DIC (strain) make " LA-7054 ", solid state component 60%), line style phenol 6 parts of aldehyde system curing agent (hydroxyl equivalent 105, DIC (strain) system " TD2090 "), amine system curing accelerator (4-dimethylaminopyridine (DMAP), the MEK solution of 5 mass % of solid state component) 3 parts, with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") crystalline silica (the Unimin society system " IMSIL A-8 ", average grain diameter that are surface-treated 1.38 μm, 20 μm of maximum particle diameter, specific surface area 6.54m²/ g, density 2.65g/cm³, Average crystallite diameter 1000) 180 parts, resistance Fire agent (three light (strain) make " HCA-HQ ", 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide, 2 μm of average grain diameter) 5 parts, it is uniformly dispersing using high speed rotation mixer, prepare resin varnish.It should be noted that in resin varnish Preparation used in the global density of nonvolatile component other than inorganic filling material be about 1.2g/cm³。

(2) production of adhesive film

As supporter, prepare the polyethylene terephthalate film (38 μm of the thickness, リ that have alkyd resin system release layer Application テッ Network (strain) system, " AL5 ").On the supporter, the resin for being equably coated with above-mentioned preparation using chill coating machine is clear Paint makes it dry 6 minutes 80~120 DEG C (100 DEG C average), forms resin composition layer.Resin composition layer with a thickness of 40 μm, the residual solvent amount in resin combination is about 2 mass %.Then, on the surface of resin composition layer, as protection Film, fitting polypropylene screen (the special paper of prince (strain) system, roll up simultaneously by the smooth surface side of " ア Le Off ァ Application MA-411 ", 15 μm of thickness It is coiled into web-like.The adhesive film of web-like is cut into width 507mm, obtains the adhesive film of 507mm × 336mm size.

2 > of < embodiment

In addition to using 10 parts of biphenyl type epoxy resin (epoxide equivalent 276, Japanese chemical drug (strain) make " NC3000 ") and sub- naphthalene 18 parts of base ether type epoxy (epoxide equivalent 250, DIC (strain) system " HP6000 ") to replace biphenyl type epoxy resin, (work as by epoxy Amount 276, Japanese chemical drug (strain) make " NC3000 ") other than 30 parts, other to prepare resin varnish similarly to Example 1, production is viscous Connect film.

3 > of < embodiment

In addition to using 12 parts of naphthol novolac system curing agent (hydroxyl equivalent 215, Nippon Steel live aurification (strain) system " SN485 ") To replace 6 parts of line style phenolic aldehyde system curing agent (hydroxyl equivalent 105, DIC (strain) system " TD2090 ") and N- phenyl -3- ammonia will be used Crystalline silica (the Unimin that base propyl trimethoxy silicane (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") is surface-treated Society's system " IMSIL A-8 ") usage amount change into other than 210 parts, other to prepare resin varnish similarly to Example 1, production Adhesive film.

4 > of < embodiment

In addition to using phenoxy resin, (Mitsubishi Chemical's (strain) makes the MEK/ ring of " YL7553BH30 ", 30 mass % of solid state component Hexanone=1/1 solution) 8 parts replace curable type bisphenol A type epoxy resin (epoxide equivalent about 3000~5000, Mitsubishi Chemical's (strain) Make " jER1010 ") other than, it is other to prepare resin varnish similarly to Example 1, make adhesive film.

5 > of < embodiment

It is carried out in addition to using with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") Crystalline silica (Unimin society system " IMSIL A-25 ", 2.55 μm of average grain diameter, 20 μm of maximum particle diameter, the ratio of surface treatment Surface area 5.87m²/ g, density 2.65g/cm³, Average crystallite diameter 1400), to replace with N- phenyl -3- aminopropyl front three Crystalline silica (the Unimin society system " IMSIL that oxysilane (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") is surface-treated A-8 ") other than 180 parts, it is other to prepare resin varnish similarly to Example 1, make adhesive film.

6 > of < embodiment

In addition to table will have been carried out with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") Crystalline silica (Unimin society system " IMSIL A-8 ", 1.38 μm of average grain diameter, 20 μm of the maximum particle diameter, specific surface of surface treatment Product 6.54m²/ g, density 2.65g/cm³, Average crystallite diameter 1000) usage amount change into other than 400 parts, it is other with implement Example 1 is prepared as resin varnish, makes adhesive film.

1 > of < comparative example

It is carried out in addition to using with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") (ア De マテッ Network ス (strain) makes " SO-C2 ", 0.90 μm of average grain diameter, specific surface area to the spherical silicon dioxide of surface treatment 5.75m²/ g, density 2.2g/cm³) 150 parts replace with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) System " KBM573 ") other than 180 parts of crystalline silica (Unimin society system " IMSIL A-8 ") being surface-treated, it is other Resin varnish is prepared similarly to Example 1, makes adhesive film.

2 > of < comparative example

It is carried out in addition to using with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") (ア De マテッ Network ス (strain) makes " SO-C6 ", 2.06 μm of average grain diameter, specific surface area to the spherical silicon dioxide of surface treatment 2.15m²/ g, density 2.2g/cm³) 150 parts replace with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) System " KBM573 ") other than 180 parts of crystalline silica (Unimin society system " IMSIL A-8 ") being surface-treated, it is other Resin varnish is prepared similarly to Example 1, makes adhesive film.

3 > of < comparative example

It is carried out in addition to using with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") (imperial gloomy (strain) makes " VX-SR ", 1.30 μm of average grain diameter, specific surface area 11.94m to the broken shape silica of surface treatment²/g、 Density 2.65g/cm³, Average crystallite diameter 1900) 180 parts replace with N- phenyl -3- TSL 8330 The crystalline silica (Unimin society system " IMSIL A-8 ") that (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") is surface-treated It is other to prepare resin varnish similarly to Example 1 other than 180 parts, make adhesive film.

4 > of < comparative example

In addition to table will have been carried out with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") The usage amount of the crystalline silica (Unimin society system " IMSIL A-8 ") of surface treatment is changed into other than 80 parts, other and implementation Example 1 is prepared as resin varnish, makes adhesive film.

5 > of < comparative example

In addition to table will have been carried out with N- phenyl -3- TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") The usage amount of the crystalline silica (Unimin society system " IMSIL A-8 ") of surface treatment is changed into other than 480 parts, other and implementation Example 1 is prepared as resin varnish, makes adhesive film.

[table 2]

。

Claims

1. resin combination is the resin compositions for insulating layer of printed wiring board, wherein

When nonvolatile component in resin combination is set as 100 volume %, the content of inorganic filling material is 40~75 volume %,

The average grain diameter of inorganic filling material be 0.01 μm or more and 4 μm hereinafter,

By formula: the geometric shape parameters A for the inorganic filling material that A=SR ρ/6 is indicated meets 20≤6A≤40,

In formula, S indicates the specific surface area of inorganic filling material, and R indicates the average grain diameter of inorganic filling material, and ρ indicates inorganic and fills out Fill the density of material；Wherein, the unit of specific surface area is m²/ g, the unit of average grain diameter are μm that the unit of density is g/cm³。

2. resin combination is the resin compositions for insulating layer of printed wiring board, wherein

By formula: B=Lc/L indicate inorganic filling material geometric shape parameters B average value be 0.8 or more and 0.9 hereinafter,

In formula, L indicates that the perimeter of the inorganic filling material in defined section, Lc indicate and the inorganic fill material in above-mentioned section The sectional area of material is the perimeter of the positive round of homalographic；Wherein, the unit of perimeter is μm.

3. resin combination according to claim 1 or 2, wherein the Average crystallite diameter of inorganic filling material is 1800 Angstrom or less.

4. resin combination according to claim 1 or 2, wherein the specific surface area of inorganic filling material is 3~10m²/g。

5. resin combination according to claim 1 or 2, wherein the average grain diameter of inorganic filling material be 0.05 μm with On.

6. resin combination according to claim 1 or 2, wherein the average grain diameter of inorganic filling material is 3 μm or less.

7. resin combination according to claim 1 or 2, wherein inorganic filling material is to make Average crystallite diameter Obtained by the tufted agglutinator dispersion of 1800 angstroms of crystallite particles below, the maximum particle diameter of the tufted agglutinator is 20 μm or less.

8. resin combination according to claim 1 or 2, wherein inorganic filling material contains crystallinity inorganic fill material Material, when whole inorganic filling materials are set as 100 mass %, the content of the crystallinity inorganic filling material is 50 mass % or more.

9. resin combination according to claim 8, wherein crystallinity inorganic filling material is crystalline silica.

10. resin combination according to claim 1 or 2, further contains epoxy resin and curing agent.

11. resin combination according to claim 1 or 2 is interlayer insulating film resin combination.

12. sheet laminated material contains the resin composition layer formed by resin combination of any of claims 1 or 2.

13. printed wiring board contains the insulating layer formed using the solidfied material of resin combination described in as claimed in claim 1 or 22.

14. semiconductor device contains the printed wiring board described in claim 13.