CN105017721A

CN105017721A - Resin composition for insulating layer of printed wiring board

Info

Publication number: CN105017721A
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: 2015-11-04
Anticipated expiration: 2035-04-17
Also published as: JP6269294B2; KR102293385B1; CN105017721B; TWI666268B; JP2015211086A; KR20150123179A; TW201542710A

Abstract

The invention provides a resin composition for insulating layer of printed circuit boards, which has excellent dispersion stabiltiy and proper melt viscosity and can inhibit bending of parts in installation. The resin composition for printed wiring board is an insulating layer, wherein when the resin composition is set to a non-volatile content 100% by volume, the content of the inorganic filler is 40 to 75% by volume, represented by the formula: A = SR[rho]/6 [wherein, S represents a specific surface area of the inorganic filler (m2/g), R represents an average particle diameter of the inorganic filler ([mu]m), [rho] is the density of the inorganic filler (g/cm3)] represented by inorganic filling material geometry parameters a meet 20 <= 6A <= 40.

Description

The resin compositions for insulating layer of printed-wiring board (PWB)

Technical field

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

Background technology

As the manufacturing technology of printed-wiring board (PWB), known employing replaces the manufacture method of the stack manner of lapped insulation layer and conductor layer on internal substrate.In the manufacture method adopting stack manner, insulation layers is as formed by using the adhesive film etc. containing resin composition layer to be stacked on by resin composition layer on internal substrate and making resin composition layer solidify.The resin combination used in the formation of insulation layer, the angle of the crackle reduce from making the thermal expansivity of the insulation layer of gained, prevented from being caused by the difference of the thermal expansion of insulation layer and conductor layer, the generation of circuit modifications is considered, generally contains inorganic filling material.As this inorganic filling material, be applicable to using spherical inorganic filling material (patent documentation 1).

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2010-238667 publication.

Summary of the invention

Adjoint in recent years by the replacement of leaded solder to lead-free solder, solder Reflow Soldering (reflow) temperature in the installation procedure of parts raises.In addition in recent years, in order to realize the miniaturization of electronics, carry out the further slimming of printed-wiring board (PWB).

Along with the propelling of the slimming of printed-wiring board (PWB), in the installation procedure of parts, sometimes produce the problems such as the loose contact of printed-wiring board (PWB) generation warpage, circuit modifications or parts.The present inventor etc. find by using the inorganic filling material of broken shape to replace spherical inorganic filling material, can warpage in the installation procedure of suppression component.But dispersion stabilization is poor sometimes for the resin combination of the inorganic filling material containing broken shape, is easy to get back to high melt viscosity, causes lamination bad simultaneously.

Problem of the present invention be to provide the good dispersion stabilization of display and suitable melt viscosity, simultaneously can warpage in the installation procedure of suppression component, the resin compositions for insulating layer of printed-wiring board (PWB).

The present inventor etc. have carried out making great efforts research for above-mentioned problem, found that the inorganic filling material with specified shape by using specified amount, can solve above-mentioned problem, thus completing the present invention.

That is, the present invention contains following content,

[1] resin combination, it is the resin compositions for insulating layer of printed-wiring board (PWB), wherein,

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

By formula: [in formula, S represents the specific surface area (m of inorganic filling material in A=SR ρ/6 ²/ g), R represents the median size (μm) of inorganic filling material, and ρ represents the density (g/cm of inorganic filling material ³)] the geometric shape parameters A of inorganic filling material that represents meets 20≤6A≤40;

[2] resin combination, it is the resin compositions for insulating layer of printed-wiring board (PWB), wherein,

By formula: B=Lc/L is [in formula, L represents the girth (μm) of the inorganic filling material in the cross section of regulation, and Lc represents with the sectional area of the inorganic filling material in above-mentioned cross section to be the girth (μm) of the positive round of homalographic] mean value of the geometric shape parameters B of inorganic filling material that represents is more than 0.8 and less than 0.9;

[3] according to [1] or the resin combination described in [2], wherein, the Average crystallite diameter of inorganic filling material is below 1800 dusts;

[4] according to the resin combination according to any one of [1] ~ [3], wherein, the specific surface area of inorganic filling material is 3 ~ 10m ²/ g;

[5] according to the resin combination according to any one of [1] ~ [4], wherein, the median size of inorganic filling material is less than 4 μm;

[6] according to the resin combination according to any one of [1] ~ [5], wherein, the median size of inorganic filling material is less than 3 μm;

[7] according to the resin combination according to any one of [1] ~ [6], wherein, inorganic filling material be make Average crystallite diameter be the crystallite particles of below 1800 dusts tufted agglutinator dispersion obtain, the maximum particle diameter of this tufted agglutinator is less than 20 μm;

[8] according to the resin combination according to any one of [1] ~ [7], wherein, inorganic filling material contains crystallinity inorganic filling material, and when whole inorganic filling material is set to 100 quality %, the content of this crystallinity inorganic filling material is more than 50 quality %;

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

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

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

[12] sheet laminated material, it contains the resin composition layer that the resin combination according to any one of [1] ~ [11] is formed;

[13] printed-wiring board (PWB), the insulation layer that its cured article containing the resin combination according to any one of utilization [1] ~ [11] is formed;

[14] semiconductor device, the printed-wiring board (PWB) that it contains described in [13].

The effect of invention

According to the present invention, can provide the resin compositions for insulating layer of printed-wiring board (PWB), it can show good dispersion stabilization and suitable melt viscosity, simultaneously can warpage in the installation procedure of suppression component.

Embodiment

[resin compositions for insulating layer of printed-wiring board (PWB)]

The feature of the resin compositions for insulating layer (hereinafter also referred to as " resin combination of the present invention ") of printed-wiring board (PWB) of the present invention is, containing specified amount to have with the inorganic filling material of current known spherical inorganic filling material, broken shape be difform inorganic filling material.

The inorganic filling material used in the present invention is different from spherical inorganic filling material, has corner angle shape.In this respect, the inorganic filling material of broken shape has sharp-pointed corner angle shape, and the inorganic filling material used in the present invention, a little with in circular this point, has the shape also different from the inorganic filling material of broken shape.

When comparing for projection of shape in the plane, different from clearly not identifying the spherical inorganic filling material of corner angle, the inorganic filling material used in the present invention can identify corner angle clearly.Wherein, " for projection of shape in the plane; can identify corner angle " refers to for projection of shape in the plane, identifiable design straight line or roughly straight line and with this straight line or roughly straight line there is certain angle θ (angle inside projection of shape) and the straight line connected or roughly straight line.About the inorganic filling material used in the present invention, the mean value of this angle θ is larger compared with the inorganic filling material of broken shape.Such as, the inorganic filling material used in the present invention compared with the inorganic filling material of broken shape, the mean value of this angle θ preferably large 5 °, more preferably large 7.5 °, and then preferably large 10 °, 12.5 °, 15 °, 17.5 ° or 20 °.

Below, use 2 geometric shape parameterses (shape パラメータ), i.e. geometric shape parameters A and geometric shape parameters B that the shape of the inorganic filling material used in the present invention is described.Should illustrate, it is the difference of the parameter derived by the method for three-dimensional or the parameter derived by the method for two dimension that geometric shape parameters A and geometric shape parameters B exist, but both for inorganic filling material shape, represent the parameter of the degree of distortion compared with ball.

< geometric shape parameters A >

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

Formula (1): A=SR ρ/6

[in formula,

S represents the specific surface area (m of inorganic filling material ²/ g),

R represents the median size (μm) of inorganic filling material,

ρ represents the density (g/cm of inorganic filling material ³)].

Consider the system (hereinafter also referred to " ball model system ") that there is multiple ball.When the median size (diameter) of these balls is for R, the average surface area of the multiple balls existed in ball model system is by π R ²represent, average-volume is by π R ³/ 6 represent.In addition, when the density of ball is ρ, the average quality of the multiple balls existed in ball model system is by π ρ R ³/ 6 represent.

Then, the system of the inorganic filling material of consideration and ball model system average-volume and equal density.If have the such fact of minimum surface-area based on for the object of same volume, ball, then the average surface area of the inorganic filling material of the volume existed in the system of described inorganic filling material can use A π R ²represent.Wherein, A is the geometric shape parameters of inorganic filling material, and its lower limit is 1 (inorganic filling material is the situation of ball).In addition, if based on the condition with ball model system average-volume and equal density, then the average quality of the inorganic filling material of the volume existed in the system of inorganic filling material can by π ρ R ³/ 6 represent.So in the system of inorganic filling material, the specific surface area S of inorganic filling material can use [average surface area (the A π R of the inorganic filling material of the volume existed in the system of inorganic filling material ²)]/[average quality (the π ρ R of the inorganic filling material of the volume existed in the system of inorganic filling material ³/ 6)] represent, it is 6A/ (R ρ).That is, the relational expression of S=6A/ (R ρ) is set up, and when this formula being out of shape for geometric shape parameters A, can obtain above-mentioned formula (1).

The feature of the inorganic filling material used in the present invention is, the geometric shape parameters A represented by above-mentioned formula (1) meets 20≤6A≤40.For the suitable scope of geometric shape parameters A, describe later.

The specific surface area S of the inorganic filling material needed when obtaining geometric shape parameters A can utilize BET method to measure.Particularly, the known molecule of absorption occupied area is adsorbed on inorganic filling material sample at the temperature of liquid nitrogen, the specific surface area of inorganic filling material sample can be tried to achieve by its adsorptive capacity.As the molecule that absorption occupied area is known, be applicable to using the rare gas element such as nitrogen, helium.The specific surface area S of inorganic filling material can use automatic specific area measuring device to measure, and as this automatic specific area measuring device, can enumerate such as (strain) マウ Application テッ Network system " Macsorb HM-1210 ".

In addition, the median size R of inorganic filling material is by measuring based on the laser diffraction-scattering method of Michaelis (Mie) scattering theory.Specifically, laser diffraction formula particle size distribution device can be utilized with volume reference to be made the size-grade distribution of inorganic filling material, its median particle diameter is measured as median size.Working sample can preferably use the sample utilizing ultrasonic wave that inorganic filling material is dispersed in water.As laser diffraction formula particle size distribution device, (strain) Shimadzu Seisakusho Ltd. system " SALD2200 " can be enumerated such as, (strain) hole field makes made " LA-500 ", " LA-750 ", " LA-950 ".

< geometric shape parameters B >

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

Formula (2): B=Lc/L

[in formula,

L represents the girth (μm) of the inorganic filling material in the cross section of regulation,

Lc represents with the sectional area of the inorganic filling material in above-mentioned cross section to be the girth (μm) of the positive round of homalographic.]。

Geometric shape parameters B is based on positive round in figure of the same area and has the such fact of minimum girth and the parameter that derives, and its upper limit is 1 (in the cross section of regulation, the cross-sectional shape of inorganic filling material is the situation of positive round).

Geometric shape parameters B is the parameter set up for each particle of inorganic filling material, by trying to achieve geometric shape parameters B for the particle of the quantity sufficient forming inorganic filling material, can grasp the characteristic of the entirety relevant with the shape of inorganic filling material.In an embodiment of the invention, for the particle of the quantity sufficient of formation inorganic filling material, try to achieve geometric shape parameters B, according to its mean value, give characteristic to the shape of inorganic filling material.In said embodiment, the feature of the inorganic filling material used in the present invention is, the mean value of the geometric shape parameters B represented by above-mentioned formula (2) is more than 0.8 and less than 0.9.For the OK range of the mean value of geometric shape parameters B, describe later.

Or, in addition for the particle of the quantity sufficient of formation inorganic filling material, try to achieve geometric shape parameters B, based on the value of the geometric shape parameters B of gained, also can grasp the distribution of shapes of the particle forming inorganic filling material.In the inorganic filling material used in the present invention, the content that the value of the geometric shape parameters B represented by above-mentioned formula (2) is less than the particle of 0.8 is generally below 50 number %.In addition, in the inorganic filling material used in the present invention, the content that the value of the geometric shape parameters B represented by above-mentioned formula (2) is greater than the particle of 0.9 is generally below 30 number %.For the OK range of these content, describe later.

The sectional area of the inorganic filling material in the perimeter L of that need when obtaining geometric shape parameters B, in regulation cross section inorganic filling material and this cross section, can by for the layer using resin combination of the present invention to be formed, carry out cross-section to measure.In cross-section, be applicable to using FIB-SEM set composite.By the FIB-SEM image of gained, the image processing softwares such as (strain) Leica system " QWin V3 " can be used, try to achieve girth and the area (sectional area) of the inorganic filling material be present in layer.As FIB-SEM set composite, such as SII Na ノテ Network ノロジー (strain) system " SMI3050SE " can be enumerated.

For Lc, as long as calculating and the sectional area of the inorganic filling material of gained are the girth (circumference) of the positive round of homalographic.

In one embodiment, the feature of resin combination of the present invention is, when nonvolatile component in resin combination is set to 100 volume %, the content of inorganic filling material is 40 ~ 75 volume %, and the geometric shape parameters A of the inorganic filling material represented by above-mentioned formula (1) meets 20≤6A≤40 (hereinafter also referred to " resin combination of the 1st embodiment ").

Consider from the angle obtaining the resin combination showing good dispersion stabilization and suitable melt viscosity, importantly the value of above-mentioned 6A is less than 40.And then consider from the angle obtaining the resin combination showing good dispersion stabilization and melt viscosity, the value of above-mentioned 6A is preferably less than 39.8, less than 39.6, less than 39.4, less than 39.2, less than 39, less than 38, less than 37, less than 36, less than 35, less than 34, less than 33, less than 32, less than 31 or less than 30.Consider from the angle of the warpage the installation procedure of suppression component fully, importantly the lower limit of above-mentioned 6A is more than 20.From can the angle of warpage the installation procedure of suppression component further consider, the lower value of above-mentioned 6A is preferably more than 21, more than 22 or more than 23.

In other embodiments, the feature of resin combination of the present invention is, when nonvolatile component in resin combination is set to 100 volume %, the content of inorganic filling material is 40 ~ 75 volume %, and the mean value of the geometric shape parameters B of the inorganic filling material represented by above-mentioned formula (2) is more than 0.8 and less than 0.9 (hereinafter also referred to " resin combination of the 2nd embodiment ").

Consider from the angle obtaining the resin combination showing good dispersion stabilization and suitable melt viscosity, importantly the mean value of geometric shape parameters B is more than 0.8.And then consider from the angle obtaining the resin combination showing good dispersion stabilization and melt viscosity, the mean value of geometric shape parameters B is preferably more than 0.81 or more than 0.82.Consider from the angle of the warpage the installation procedure of suppression component fully, importantly the upper limit of the mean value of geometric shape parameters B is less than 0.9.From can the angle of warpage the installation procedure of suppression component further consider, the upper limit of the mean value of geometric shape parameters B is preferably less than 0.89, less than 0.88, less than 0.87, less than 0.86 or less than 0.85.

No matter the difference of the 1st embodiment and the 2nd embodiment, from the angle of the warpage the installation procedure of abundant suppression component, the angle that the thermal expansivity of the insulation layer of gained is fully reduced is considered, when the nonvolatile component in resin combination is set to 100 volume %, the content of inorganic filling material is 40 more than volume %, be preferably 42 more than volume %, be more preferably 44 more than volume %, and then be preferably 46 more than volume %, and then be more preferably 48 more than volume %, be particularly preferably 50 more than volume %, 52 more than volume %, 54 more than volume %, 56 more than volume %, 58 more than volume %, or 60 more than volume %.When using the inorganic filling material of broken shape, along with the content of this inorganic filling material uprises, there is the tendency that melt viscosity too raises.In contrast, about use in the present invention, the inorganic filling material that meets specific geometric shape parameters condition, good melt viscosity can be realized, and then content can be improved simultaneously.Such as in resin combination of the present invention, the content of this inorganic filling material can be increased to 62 more than volume %, 64 more than volume %, 66 more than volume % or 68 more than volume %.Consider from the angle obtaining the resin combination showing suitable melt viscosity, the angle that obtains little and excellent with the dhering strength (stripping strength) of the conductor layer insulation layer of surfaceness, the upper limit of the content of this inorganic filling material is 75 below volume %, be preferably 74 below volume %, be more preferably 73 below volume %, and then be preferably 72 below volume %, and then be more preferably 71 below volume %, be particularly preferably 70 below volume %.Especially, when utilizing vacuum layer platen press to implement the lamination of resin composition layer and internal substrate in the manufacture of printed-wiring board (PWB), the upper limit of the content of this inorganic filling material is suitably for 70 below volume %.The content (volume %) of inorganic filling material can calculate based on the quality of the nonvolatile component beyond the quality of the inorganic filling material used in the preparation of resin combination and density and the inorganic filling material used in the preparation of resin combination and density.

No matter the difference of the 1st embodiment and the 2nd embodiment, consider from the angle obtaining the resin combination showing good dispersion stabilization and melt viscosity, preferably, the content that the value of geometric shape parameters B in inorganic filling material, that represented by above-mentioned formula (2) is less than the particle of 0.8 is lower.In resin combination of the present invention, the content that the value of geometric shape parameters B in inorganic filling material, that represented by above-mentioned formula (2) is less than the particle of 0.8 is generally below 50 number %, be preferably below 48 number %, be more preferably below 46 number %, and then be preferably below 44 number %, and then be more preferably below below 42 number % or 40 number %.Especially, the value of geometric shape parameters B is that the content of the particle of less than 0.75 is preferably below below 20 number %, below 18 number % or 16 number %.

No matter the difference of the 1st embodiment and the 2nd embodiment, consider from the angle of the warpage the installation procedure of abundant suppression component, preferably, the content that the value of geometric shape parameters B in inorganic filling material, that represented by above-mentioned formula (2) is greater than the particle of 0.9 is lower.In resin combination of the present invention, the content that the value of geometric shape parameters B in inorganic filling material, that represented by above-mentioned formula (2) is greater than the particle of 0.9 is generally below 30 number %, be preferably below 28 number %, be more preferably below 26 number %, and then be preferably below 24 number %, and then be more preferably below below 22 number % or 20 number %.Especially, the value of geometric shape parameters B is that the content of the particle of more than 0.94 is preferably below 6 number %, below 4 number %, below 2 number %, below 1 number %, below 0.8 number %, below 0.6 number %, below 0.4 number %, below 0.2 number %.

In resin combination of the present invention, the material of inorganic filling material is not particularly limited, such as silicon-dioxide can be enumerated, aluminum oxide, glass, trichroite, Si oxide, barium sulfate, barium carbonate, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, magnesium oxide, boron nitride, aluminium nitride, nitrogenized manganese, aluminum borate, Strontium carbonate powder, strontium titanate, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, zirconium white, barium titanate, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, with phosphoric acid tungsten wire array etc., silicon-dioxide is particularly suitable.Inorganic filling material can be used alone a kind, also two or more can be combinationally used.When inorganic filling material of more than two kinds is combinationally used, as the median size needed when obtaining geometric shape parameters A (R), specific surface area (S) and density (ρ), use the median size of the inorganic filling material mixture of gained, specific surface area and density respectively.

The median size (R) of inorganic filling material, considers from the angle of the miniaturization of circuit layout, is preferably less than 4 μm, is more preferably less than 3.5 μm, and then is preferably less than 3 μm.The lower limit of the median size of inorganic filling material, the angle obtaining having suitable viscosity, operability good resinous varnish when forming resinous varnish from using resin combination is considered, be preferably more than 0.01 μm, be more preferably more than 0.03 μm, and then be preferably more than 0.05 μm, and then be more preferably more than 0.07 μm, be particularly preferably more than 0.1 μm.

The specific surface area (S) of inorganic filling material with the relation of median size (R) and density (ρ) in, as long as meet above-mentioned geometric shape parameters condition, be just not particularly limited.The specific surface area of inorganic filling material can be such as 3 ~ 10m ²the scope of/g, is preferably 3 ~ 8m ²the scope of/g.

As long as inorganic filling material meets above-mentioned geometric shape parameters condition, can be amorphism, crystalline any one.In one embodiment, resin combination of the present invention contains crystallinity inorganic filling material.The content of the crystallinity inorganic filling material in inorganic filling material, when whole inorganic filling material is set to 100 quality %, be preferably more than 50 quality %, be more preferably more than 60 quality %, and then be preferably more than 70 quality %, and then be more preferably more than 80 quality %, be particularly preferably more than more than 90 quality %, more than 92 quality %, more than 94 quality %, more than 96 quality %, more than 98 quality % or 99 quality %.Inorganic filling material can be remove unavoidably contain impurity, be made up of crystallinity inorganic filling material in fact.In said embodiment, the Average crystallite diameter of inorganic filling material is preferably 1800 dusts () below, is more preferably less than 1600, and then is preferably less than 1400.The lower limit of this Average crystallite diameter is not particularly limited, and can be more than 100,200 with first-class usually.The crystallite diameter of inorganic filling material can use X-ray diffraction (XRD) device to measure.As XRD device, (strain) リガ Network system " Multi FLEX " can be enumerated such as.

Wherein, as crystallinity inorganic filling material, preferably crystalline silica is used.

Meet the inorganic filling material of above-mentioned geometric shape parameters condition, the method such as can carrying out physical property and/or chemical grinding by the surface of the inorganic filling material utilizing the broken shape by having sharp-pointed corner angle shape, the method etc. of heat-treating, make it prepare with circle a little.The method of physical property grinding and chemical grinding is not particularly limited, and can use current known any means.As the commercially available product of broken silicon-dioxide, can enumerate such as imperial gloomy (strain) system " VX-SR " etc.

In addition, in the inorganic oxide of natural output, there is the inorganic oxide meeting above-mentioned geometric shape parameters condition suitably.Such as, it is the native silicon dioxide (particularly the maximum particle diameter of tufted agglutinator is the situation of less than 20 μm) of the tufted agglutinator output of the crystallite particles of less than 1800 as Average crystallite diameter, when preparing resin combination through scatter operation, tufted agglutinator is untied thus, meets above-mentioned geometric shape parameters condition.Therefore, in one embodiment, the feature of the inorganic filling material contained in resin combination of the present invention is, make Average crystallite diameter be the crystallite particles of less than 1800 tufted agglutinator dispersion obtain, the maximum particle diameter of this tufted agglutinator is less than 20 μm.As the commercially available product of described native silicon dioxide, such as Unimin society system " IMSIL A-8 ", " IMSIL A-10 ", " IMSIL A-15 ", " IMSIL A-25 " etc. can be enumerated.

The inorganic filling material used in resin combination of the present invention is considered from the angle making dispersiveness, wet fastness improve, and preferably carries out surface treatment with surface treatment agent.As surface treatment agent, 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, titanic acid ester system coupling agent can be enumerated.Surface treatment agent can be used alone a kind, also two or more can be combinationally used.As the commercially available product of surface treatment agent, such as SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 " (3-glycidoxypropyltrime,hoxysilane) can be enumerated, SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM803 " (3-mercaptopropyi Trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBE903 " (APTES), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 " (N-phenyl-3-TSL 8330), SHIN-ETSU HANTOTAI's chemical industry (strain) system " SZ-31 " (hexamethyldisilazane) etc.

After the surface treatment carrying out inorganic filling material, the carbon amounts of the per unit surface-area that the surface of inorganic filling material combines is preferably 0.05mg/m ²above, 0.08mg/m is more preferably ²above, so be preferably 0.11mg/m ²above, and then be more preferably 0.14mg/m ²above, 0.17mg/m is particularly preferably ²above, 0.20mg/m ²above, 0.23mg/m ²above or 0.26mg/m ²above.The upper limit of this carbon amounts is preferably 1.00mg/m ²below, 0.75mg/m is more preferably ²below, so be preferably 0.70mg/m ²below, and then be more preferably 0.65mg/m ²below, 0.60mg/m ²below, 0.55mg/m ²below, 0.50mg/m ²below.

The carbon amounts of the per unit area that the surface of inorganic filling material combines can calculate by following step.Add the methyl ethyl ketone (MEK) of the substantial amount as solvent in inorganic filling material after surface treatment, carry out ultrasonic washing.Removing supernatant liquor, after making solid state component drying, uses carbon analysis meter to be determined at the carbon amounts that the surface of inorganic filling material combines.By by the carbon amounts of gained divided by the specific surface area of inorganic filling material, calculate the carbon amounts of the per unit surface-area combined in inorganic filling material.As carbon analysis meter, (strain) hole field can be enumerated such as and make made " EMIA-320V " etc.

Resin combination of the present invention is preferred and then contain thermosetting resin and solidifying agent.As thermosetting resin, preferably epoxy resin.Therefore in one embodiment, resin combination of the present invention contains inorganic filling material, but also containing epoxy resin and solidifying agent.

-epoxy resin-

As epoxy resin, such as bisphenol A type epoxy resin can be enumerated, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, tris phenol type epoxy, naphthol novolac type (Na フトー 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-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresoform type (Network レゾー Le ノボラッ Network type) epoxy resin, biphenyl type epoxy resin, wire aliphatic epoxy resin, there is the epoxy resin of butadiene structure, alicyclic epoxy resin, hetero ring type epoxy resin, containing whorled epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylidene ether type epoxy, trishydroxymethyl type epoxy resin, tetraphenyl ethane type epoxy resin etc.Epoxy resin can be used alone a kind, also two or more can be combinationally used.

Epoxy resin preferably contains the epoxy resin of the epoxy group(ing) in 1 molecule with more than 2.When the nonvolatile component of epoxy resin is set to 100 quality %, preferably more than at least 50 quality % are the epoxy resin of the epoxy group(ing) in 1 molecule with more than 2.Wherein, be preferably the epoxy resin (hereinafter referred to as " liquid-state epoxy resin ") of liquid state temperature 20 DEG C and there is the epoxy group(ing) of more than 3 in 1 molecule and be solid-state epoxy resin (hereinafter referred to as " solid epoxy resin ") temperature 20 DEG C containing the epoxy group(ing) in 1 molecule with more than 2.As epoxy resin, by by liquid-state epoxy resin and solid epoxy resin and use, the resin combination with excellent flexibility can be obtained.In addition, the breaking tenacity of the cured article of resin combination also improves.

As liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, novolac type epoxy resin and have the epoxy resin of butadiene structure, is more preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin and naphthalene type epoxy resin.As the object lesson of liquid-state epoxy resin, can enumerate " HP4032 " that DIC (strain) makes, " HP4032H ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin), " jER828EL " (bisphenol A type epoxy resin) that Mitsubishi Chemical's (strain) makes, " jER807 " (bisphenol f type epoxy resin), " jER152 " (novolac type epoxy resin), " ZX1059 " (melange of bisphenol A type epoxy resin and bisphenol f type epoxy resin) that aurification (strain) is made is lived by Nippon Steel, " EX-721 " (glycidyl ester type epoxy resin) that Na ガセケ system テッ Network ス (strain) makes, " PB-3600 " (there is the epoxy resin of butadiene structure) that ダイセ Le chemical industry (strain) makes.They can be used alone a kind, also two or more can be combinationally used.

As solid epoxy resin, preferably 4 officials' energy naphthalene type epoxy resin, cresoform type epoxy resin, dicyclopentadiene-type epoxy resin, tris phenol type epoxy, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylidene ether type epoxy, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenyl ethane type epoxy resin, being more preferably 4 officials can naphthalene type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylidene ether type epoxy, bisphenol A type epoxy resin, tetraphenyl ethane type epoxy resin.As the object lesson of solid epoxy resin, can enumerate " HP-4700 " that DIC (strain) makes, " HP-4710 " (4 officials' energy naphthalene type epoxy resin), " N-690 " (cresoform type epoxy resin), " N-695 " (cresoform type epoxy resin), " HP-7200 " (dicyclopentadiene-type epoxy resin), " EXA7311 ", " EXA7311-G3 ", " EXA7311-G4 ", " EXA7311-G4S ", " HP6000 " (naphthylidene ether type epoxy), " EPPN-502H " (tris phenol type epoxy) that Japan's chemical drug (strain) makes, " NC7000L " (naphthol novolac type epoxy resin), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), " ESN475V " (naphthol type epoxy resin) that aurification (strain) is made is lived by Nippon Steel, " ESN485 " (naphthol novolac type epoxy resin), " YX4000H " that Mitsubishi Chemical's (strain) makes, " YL6121 " (biphenyl type epoxy resin), " YX4000HK " (di-cresols type (PVC キシレノー Le type) epoxy resin), " YX8800 " (anthracene type epoxy resin), " PG-100 " that Osaka ガスケミカ Le (strain) is made, " CG-500 ", " YL7800 " (fluorenes type epoxy resin) that Mitsubishi Chemical's (strain) makes, " jER1010 " (solid-state bisphenol A type epoxy resin) that Mitsubishi Chemical's (strain) makes, " jER1031S " (tetraphenyl ethane type epoxy resin) etc.

As epoxy resin, by liquid-state epoxy resin and solid epoxy resin and the used time, preferably their usage ratio (liquid-state epoxy resin: solid epoxy resin) is the scope of 1:0.1 ~ 1:4 by quality ratio.By making the usage ratio of liquid-state epoxy resin and solid epoxy resin be described scope, following effect can be obtained: when i) using with the form of sheet laminated material, bring suitable cementability; Sufficient flexibility can be obtained when ii) using with the form of sheet laminated material, operability improves; And iii) cured article etc. with sufficient breaking tenacity can be obtained.From above-mentioned i) ~ iii) effect angle consider, the usage ratio (liquid-state epoxy resin: solid epoxy resin) of liquid-state epoxy resin and solid epoxy resin is more preferably the scope of 1:0.3 ~ 1:3.5, the more preferably scope of 1:0.6 ~ 1:3 by quality ratio.

The content of the epoxy resin in resin combination, when the nonvolatile component in resin combination is set to 100 quality %, is preferably 3 quality % ~ 40 quality %, is more preferably 5 quality % ~ 35 quality %, and then be preferably 10 quality % ~ 30 quality %.

The epoxy equivalent (weight) of epoxy resin is preferably 50 ~ 5000, is more preferably 50 ~ 3000, and then is preferably 80 ~ 2000, and then is more preferably 110 ~ 1000.By being this scope, the cross-linking density of cured article becomes abundant, can form the insulation layer that surfaceness is little.Should illustrate, epoxy equivalent (weight) can measure according to JIS K7236, and it is the quality of the resin containing 1 equivalent epoxy group(ing).The weight-average molecular weight of epoxy resin is preferably 100 ~ 5000, is more preferably 250 ~ 3000, and more preferably 400 ~ 1500.Wherein, the weight-average molecular weight of epoxy resin is the weight-average molecular weight of the polystyrene conversion utilizing gel permeation chromatography (GPC) method to measure.

-solidifying agent-

As solidifying agent, as long as have the function of epoxy resin cure, just be not particularly limited, can enumerate such as phenol (phenol) is solidifying agent, naphthols system solidifying agent, active ester system solidifying agent, benzoxazine system solidifying agent and cyanate system solidifying agent.Solidifying agent can be used alone a kind, also two or more can be combinationally used.

As phenol system solidifying agent and naphthols system solidifying agent, consider preferably there is the phenol system solidifying agent of novolac structure (novolac structure) or there is the naphthols system solidifying agent of novolac structure from the angle of thermotolerance and water tolerance.In addition, consider from the angle of the dhering strength with conductor layer, preferably nitrogenous phenol system solidifying agent or nitrogenous naphthols system solidifying agent, be more preferably the phenol system solidifying agent containing triazine skeleton or the naphthols system solidifying agent containing triazine skeleton.Wherein, from highly meeting thermotolerance, water tolerance and considering with the angle of the dhering strength of conductor layer, preferably containing the lacquer resins of triazine skeleton.They can be used alone a kind, also two or more can be combinationally used.

As the object lesson of phenol system solidifying agent and naphthols system solidifying agent, can enumerate such as bright and change into " MEH-7700 " that (strain) make, " MEH-7810 ", " MEH-7851 ", " NHN " that Japan's chemical drug (strain) makes, " CBN ", " GPH ", " SN-170 " that aurification (strain) is made lives in Nippon Steel, " SN-180 ", " SN-190 ", " SN-475 ", " SN-485 ", " SN-495 ", " SN-375 ", " SN-395 ", " LA-7052 " that DIC (strain) makes, " LA-7054 ", " LA-3018 ", " LA-1356 ", " TD2090 " etc.

Active ester system solidifying agent has no particular limits, and usually preferably uses the ester class etc. of phenolic ester class (phenol esters), thiophenol ester (thiophenol esters) class, N-oxyamine ester class, heterocycle hydroxyl compound in 1 molecule, have the compound of the high ester group of more than 2 reactive behavioies.This active ester system solidifying agent preferably by carboxylic acid cpd and/or thiocarboxylic acid compound and oxy-compound and/or mercaptan compound condensation reaction and obtain.Consider from the angle improving thermotolerance especially, the active ester system solidifying agent preferably obtained by carboxylic acid cpd and oxy-compound.More preferably the active ester system solidifying agent obtained by carboxylic acid cpd and oxybenzene compound and/or naphthol compound.As carboxylic acid cpd, can enumerate such as: phenylformic acid, acetic acid, succsinic acid, toxilic acid, methylene-succinic acid, phthalic acid, m-phthalic acid, terephthalic acid, Pyromellitic Acid etc.As oxybenzene compound or naphthol compound, can enumerate such as: quinhydrones, Resorcinol, dihydroxyphenyl propane, Bisphenol F, bisphenol S, phenolphthalin, methylate dihydroxyphenyl propane, methylate Bisphenol F, methylate bisphenol S, phenol, ortho-cresol, meta-cresol, p-cresol, catechol, naphthyl alcohol, 2-Naphthol, 1, 5-dihydroxy naphthlene, 1, 6-dihydroxy naphthlene, 2, 6-dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, Phloroglucinol, benzenetriol (benzenetriol), dicyclopentadiene-type bisphenol compounds, lacquer resins (phenol novolac) etc.Wherein, " dicyclopentadiene-type bisphenol compounds " refers to 2 molecule phenol and 1 molecule Dicyclopentadiene (DCPD) condensation and the bisphenol compounds obtained.

As active ester system solidifying agent; the active ester compound of the active ester compound preferably containing dicyclopentadiene-type biphenol structure, the active ester compound containing naphthalene structure, the active ester compound of the acetylate containing lacquer resins, the benzoylate containing lacquer resins, wherein more preferably containing the active ester compound of naphthalene structure, the active ester compound containing dicyclopentadiene-type biphenol structure.They can be used alone a kind, also two or more can be combinationally used.Should illustrate, " dicyclopentadiene-type biphenol structure " represents the divalent structural unit comprising phenylene-two ring pentalene (ジシ Network ロペ Application タレ Application)-phenylene.

As the commercially available product of active ester system solidifying agent, active ester compound containing dicyclopentadiene-type biphenol structure can be enumerated " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-65T " (DIC (strain) system), active ester compound containing naphthalene structure can enumerate " EXB9416-70BK " (DIC (strain) system), the active ester compound of the acetylate containing lacquer resins can enumerate " DC808 " (Mitsubishi Chemical's (strain) system), the active ester compound of the benzoylate containing lacquer resins can enumerate " YLH1026 " (Mitsubishi Chemical's (strain) system) etc.

As the object lesson of benzoxazine system solidifying agent, " HFB2006M " that Showa polymer (strain) makes can be enumerated, four countries change into " P-d ", " F-a " that industry (strain) is made.

As cyanate system solidifying agent, have no particular limits, such as phenol aldehyde type (ノボラッ Network type) (novolac type, alkyl novolac type etc.) cyanate system solidifying agent, dicyclopentadiene-type cyanate system solidifying agent, bisphenol type (bisphenol A-type, bisphenol-f type, bisphenol S type etc.) cyanate system solidifying agent and their prepolymer etc. that with a portion of triazine can be enumerated.As concrete example, bisphenol A dicyanate can be enumerated, polyphenol cyanate (oligomeric (3-methylene radical-1, 5-phenylenecyanate)), 4, 4'-methylene-bis (2, 6-3,5-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluoro bisphenol-a dicyanate, 2, two (4-cyanate) phenyl-propane of 2-, 1, 1-two (4-cyanate phenylmethane), two (4-cyanate-3, 5-3,5-dimethylphenyl) methane, 1, two (4-cyanate phenyl-1-(methyl the ethylidene)) benzene of 3-, two (4-cyanate phenyl) thioether, can cyanate ester resins with two (4-cyanate phenyl) ether etc. 2 officials, the multifunctional cyanate ester resin derivative by line style phenolic aldehyde and cresoform etc., a part for these cyanate ester resins is by the prepolymer etc. of triazine.As the commercially available product of cyanate system solidifying agent, " PT30 " and " PT60 " (being novolac type multifunctional cyanate ester resin), " BA230 " (part or all of bisphenol A dicyanate is become trimerical prepolymer by triazine) etc. that ロ Application ザジャパ Application (strain) makes can be enumerated.

The amount ratio of epoxy resin and solidifying agent, consider from the angle making the physical strength of the insulation layer of gained, water tolerance improves, with [total number of the epoxy group(ing) of epoxy resin]: the ratiometer of [total number of the reactive group of solidifying agent] is preferably the scope of 1:0.2 ~ 1:2, be more preferably the scope of 1:0.3 ~ 1:1.5, and then be preferably the scope of 1:0.4 ~ 1:1.Wherein, the reactive group of solidifying agent is activity hydroxy, active ester groups etc., different from the kind of solidifying agent.In addition, the total number of the epoxy group(ing) of epoxy resin refers to for all epoxy resin, the value that the solid state component quality of each epoxy resin obtains divided by epoxy equivalent (weight) is carried out the value added up to, the total number of the reactive group of solidifying agent refers to for all solidifying agent, the value that the solid state component quality of each solidifying agent obtains divided by reactive group equivalent is carried out the value added up to.

In one embodiment, resin combination of the present invention contains above-mentioned inorganic filling material, epoxy resin and solidifying agent.Wherein, mixture (the liquid-state epoxy resin: the mass ratio of solid epoxy resin be preferably 1:0.1 ~ 1:4 of resin combination preferably respectively containing the crystalline silica as inorganic filling material, the liquid-state epoxy resin as epoxy resin and solid epoxy resin, be more preferably 1:0.3 ~ 1:3.5, and then be preferably 1:0.6 ~ 1:3), as more than a kind that is selected from phenol system solidifying agent, naphthols system solidifying agent, active ester system solidifying agent and cyanate system solidifying agent of solidifying agent.Even if for the resin composition layer of combination containing described specific composition, the suitable content of inorganic filling material, epoxy resin and solidifying agent also as described above.

Resin combination of the present invention as required can so that containing the additive of more than a kind that is selected from thermoplastic resin, curing catalyst, fire retardant and organic filler material.

-thermoplastic resin-

As thermoplastic resin, such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyether-ether-ketone resin, vibrin can be enumerated.Thermoplastic resin can be used alone a kind, or two or more is combinationally used.

The weight-average molecular weight of the polystyrene conversion of thermoplastic resin is preferably the scope of 8000 ~ 70000, is more preferably the scope of 10000 ~ 60000, and then is preferably the scope of 20000 ~ 60000.The weight-average molecular weight of the polystyrene conversion of thermoplastic resin measures by gel permeation chromatography (GPC) method.Particularly, the weight-average molecular weight of the polystyrene conversion of thermoplastic resin can use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, use Showa electrician (strain) Shodex K-800P/K-804L/K-804L processed as pillar, use chloroform etc. as moving phase, measure column temperature 40 DEG C, use the typical curve of polystyrene standard to calculate.

Phenoxy resin can enumerate the phenoxy resin such as with the skeleton of more than a kind be selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol phenyl methyl ketone skeleton, phenolic aldehyde skeleton, biphenyl backbone, fluorene skeleton, Dicyclopentadiene (DCPD) skeleton, norbornylene skeleton, naphthalene skeleton, anthracene skeleton, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton.The end of phenoxy resin can be the functional group arbitrarily such as phenolic hydroxyl group, epoxy group(ing).Phenoxy resin can be used alone a kind, also two or more can be combinationally used.As the concrete example of phenoxy resin, " 1256 " and " 4250 " (being the phenoxy resin containing bisphenol A skeleton) that Mitsubishi Chemical's (strain) makes, " YX8100 " (phenoxy resin containing bisphenol S skeleton) and " YX6954 " (phenoxy resin containing bis-phenol phenyl methyl ketone skeleton) can be enumerated, other can also be enumerated " FX280 " and " FX293 " that aurification (strain) makes lives in Nippon Steel, Mitsubishi Chemical's (strain) makes " YL7553 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc.

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

As the object lesson of polyimide resin, can enumerate " リカコート SN20 " and " リカコート PN20 " that new Japan Chemical (strain) is made.As the object lesson of polyimide resin, can also enumerate and make 2 functional hydroxyl groups's end polyhutadiene, diisocyanate cpd and tetraprotic acid anhydride reactant and the modified polyimide such as wire polyimide (Japanese Unexamined Patent Publication 2006-37083 publication record material), polyimide (material recorded in Japanese Unexamined Patent Publication 2002-12667 publication and Japanese Unexamined Patent Publication 2000-319386 publication etc.) containing silicone matrix that obtains.

As the object lesson of polyamide-imide resin, can enumerate " バイロマッ Network ス HR11NN " and " バイロマッ Network ス HR16NN " that Japan's weaving (strain) makes.As the object lesson of polyamide-imide resin, the modified polyamide imide such as polyamidoimide " KS9100 ", " KS9300 " containing silicone matrix of Hitachi Chemical Industries (Ltd.) can also be enumerated.

As the object lesson of polyethersulfone resin, " PES5003P " that Sumitomo Chemical (strain) makes etc. can be enumerated.

As the object lesson of polysulfone resin, polysulfones " P1700 ", " P3500 " etc. that ソ Le ベイア De バ Application スト Port リマーズ (strain) makes can be enumerated.

The content of the thermoplastic resin in resin combination, when the nonvolatile component in resin combination is set to 100 quality %, is preferably 0.1 quality % ~ 20 quality %, is more preferably 0.5 quality % ~ 10 quality %, and then be preferably 1 quality % ~ 5 quality %.

-curing catalyst-

Curing catalyst can enumerate such as phosphorus system curing catalyst, amine system curing catalyst, imidazoles system curing catalyst, guanidine system curing catalyst etc., preferably phosphorus system curing catalyst, amine system curing catalyst, imidazoles system curing catalyst.Curing catalyst can be used alone a kind, also two or more can be combinationally used.The content of curing catalyst, when the total of the nonvolatile component by epoxy resin and solidifying agent is set to 100 quality %, preferably uses with the scope of 0.05 quality % ~ 3 quality %.

-fire retardant-

As fire retardant, phosphorus compound, nitrogen compound, silicone flame retardant, metal hydroxides etc. that such as organic phosphorus flame retardant, organic system are nitrogenous can be enumerated.Fire retardant can be used alone a kind, or two or more is combinationally used.The content of the fire retardant in resin combination is not particularly limited, but when the nonvolatile component in resin combination is set to 100 quality %, is preferably 0.5 quality % ~ 10 quality %, is more preferably 1 quality % ~ 9 quality %.

-organic filler material-

As organic filler material, spendable arbitrary organic filler material when forming the insulation layer of printed-wiring board (PWB) can be used in, such as rubber particles, polyamide particles, organosilicon particle etc. can be enumerated, preferably rubber particles.

As rubber particles, as long as implement chemical crosslinking Treatment to the resin of display caoutchouc elasticity, be insoluble in organic solvent and the microsome of not molten resin, just be not particularly limited, such as acrylonitrile-butadiene rubber particle, divinyl rubber particle, acrylic rubber particle etc. can be enumerated.As rubber particles, particularly, XER-91 (Japan synthesis go system (strain) system), スタ Off ィロイ De AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, アイカ industry (strain) system) パラロイ De EXL2655, EXL2602 (more than, Wu Yu chemical industry (strain) is made) etc. can be enumerated.

The median size of organic filler material is preferably the scope of 0.005 μm ~ 1 μm, is more preferably the scope of 0.2 μm ~ 0.6 μm.The median size of rubber particles can use dynamic light scattering determination.Ultrasonic wave etc. such as can be utilized to make rubber particles be evenly dispersed in suitable organic solvent, dense system particle size analyzer (great mound electronics (strain) is used to make " FPAR-1000 "), be made the size-grade distribution of rubber particles with quality criteria, its median particle diameter is measured as median size.The content of the rubber particles in resin combination is preferably 1 quality % ~ 10 quality %, is more preferably 2 quality % ~ 5 quality %.

-other composition-

Resin combination of the present invention as required can containing other composition.As other composition described, the resin additive etc. such as the organometallic compounds such as such as organocopper compound, organic zinc compound and organic cobalt compounds and thickening material, defoamer, flow agent, adaptation imparting agent, tinting material and curable resin can be enumerated.

The preparation method of resin combination of the present invention is not particularly limited, and can enumerate such as gradation composition to be added as required solvent etc., use impeller etc. to carry out the method etc. mixing, disperse.

Resin combination of the present invention shows good dispersion stabilization and suitable melt viscosity, simultaneously can warpage in the installation procedure of suppression component.The resin combination (the interlayer insulating film resin combination of printed-wiring board (PWB)) that resin combination of the present invention can be suitable as the interlayer insulating film for the formation of printed-wiring board (PWB) uses, and then the resin combination (utilizing plating to form the interlayer insulating film resin combination of the printed-wiring board (PWB) of conductor layer) be suitable as the formation of utilizing plating to form the interlayer insulating film of conductor layer thereon uses.Resin combination of the present invention can also be used for the sheet such as adhesive film, prepreg laminated material, solder resist, underfill, bonding (die bonding) material, semiconductor-encapsulating material, filling perforation resin, parts potting resin etc., need the extensive use of resin combination.

[sheet laminated material]

Resin combination of the present invention also can carry out being coated with, using with varnish state, but industrially general being applicable to uses with the form of the sheet laminated material of the resin composition layer formed containing this resin combination useful.

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

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

The thickness of resin composition layer, considers from the angle of the slimming of printed-wiring board (PWB), is preferably less than 100 μm, is more preferably less than 80 μm, and then is preferably less than 60 μm, and then is more preferably less than 50 μm or less than 40 μm.The lower limit of the thickness of resin composition layer is not particularly limited, and is generally more than 10 μm.

As supporter, the film, tinsel, the release paper that are such as formed by plastic material can be enumerated, the film, the tinsel that are preferably formed by plastic material.

When the film that use is formed by plastic material is as supporter, plastic material can enumerate acrylic acid series, cyclic polyolefin, tri acetyl cellulose (TAC), polyether sulfides (PES), polyetherketone, the polyimide etc. such as the such as polyester such as polyethylene terephthalate (below sometimes referred to as " PET "), Polyethylene Naphthalate (below sometimes referred to as " PEN "), polycarbonate (below sometimes referred to as " PC "), polymethylmethacrylate (PMMA).Wherein, preferred polyethylene terephthalate, Polyethylene Naphthalate, particularly preferably low-cost polyethylene terephthalate.

When using tinsel as supporter, tinsel can enumerate such as Copper Foil, aluminium foil etc., preferably Copper Foil.As Copper Foil, the paper tinsel be made up of the monometallic of copper can be used, also can use the paper tinsel be made up of the alloy of copper and other metal (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium etc.).

Delustring process, corona treatment can be implemented to the surface of the side engaged with resin composition layer of supporter.In addition, as supporter, the surface that can be used in the side engaged with resin composition layer has the supporter with release layer of release layer.As the releasing agent used in the release layer of the supporter with release layer, the releasing agent of more than a kind of being such as selected from Synolac, olefin resin, urethane resin and silicone resin can be enumerated.As the commercially available product of releasing agent, can enumerate such as Synolac system releasing agent, " SK-1 ", " AL-5 ", " AL-7 " etc. that リ Application テッ Network (strain) makes.

The thickness of supporter is not particularly limited, and is preferably the scope of 5 μm ~ 75 μm, is more preferably the scope of 10 μm ~ 60 μm.Should illustrate, when supporter is the supporter with release layer, the thickness preferably with the supporter entirety of release layer is above-mentioned scope.

Adhesive film such as can manufacture as follows, that is, preparation is dissolved with the resinous varnish of resin combination in organic solvent, uses die coating machine etc. to be coated on supporter by this resinous varnish, and then make it dry and form resin composition layer, manufacture thus.

Organic solvent can enumerate the acid amides series solvents etc. such as Trivalin SF class, toluene and the dimethylbenzene etc. such as the acetate esters such as ketone, ethyl acetate, butylacetate, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, cellosolve and diethylene glycol monobutyl ether such as such as acetone, methyl ethyl ketone (MEK) and pimelinketone are aromatic hydrocarbon based, dimethyl formamide, N,N-DIMETHYLACETAMIDE (DMAc) and N-Methyl pyrrolidone.Organic solvent can be used alone a kind, or two or more is combinationally used.

Drying can utilize the known methods such as heating, blowing hot-air to implement.Drying conditions is not particularly limited, but carries out drying, is below 10 quality %, preferably below 5 quality % to make the content of the organic solvent in resin composition layer.Different according to the boiling point of the organic solvent in resinous varnish, such as, when using the resinous varnish of the organic solvent containing 30 quality % ~ 60 quality %, by 50 DEG C ~ 150 DEG C dryings 3 minutes ~ 10 minutes, can resin composition layer be formed.

In adhesive film, on the face face of supporter opposition side (that is, with) do not engaged with supporter of resin composition layer, can so that the stacked protective membrane conformed to supporter.The thickness of protective membrane is not particularly limited, such as, be 1 μm ~ 40 μm.By stacked guard film, dust etc. can be prevented to the attachment on the surface of resin composition layer or prevent scar.Adhesive film can be rolled into web-like to preserve, and when adhesive film has protective membrane, can use by peeling off protective membrane.

In one embodiment, prepreg is formed in sheet-like fiber base material by making resin combination of the present invention infiltrate.

The sheet-like fiber base material used in prepreg is not particularly limited, and can be used as the sheet-like fiber base material that the prepreg base materials such as woven fiber glass, aramid nonwoven fabric, liquid crystalline polymers non-woven fabrics are conventional.Consider from the angle of the slimming of printed-wiring board (PWB), the thickness of sheet-like fiber base material is preferably less than 50 μm, is more preferably less than 40 μm, and then is preferably less than 30 μm, and then is more preferably less than 20 μm.The lower limit of the thickness of sheet-like fiber base material is not particularly limited, and is generally more than 10 μm.

Prepreg can utilize the known method manufacture such as hot melt process, solvent method.

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

In sheet laminated material, the lowest melt viscosity of resin composition layer, from suppressing the angle of oozing out of resin to be considered when manufacturing printed-wiring board (PWB), is preferably more than 300 pools, be more preferably more than 500 pools, and then be preferably that 700 pools are above, 900 pools are above or more than 1000 pools.The upper limit of the lowest melt viscosity of resin composition layer, consider from the angle realizing good lamination (circuit landfill) when manufacturing printed-wiring board (PWB), be preferably below 30000 pools, be more preferably below 25000 pools, and then be preferably that 20000 pools are following, 15000 pools are following, 10000 pools are following, 5000 pools are following or below 3500 pools.When utilizing vacuum layer platen press to implement the lamination of resin composition layer and internal substrate especially in the manufacture of printed-wiring board (PWB), the upper limit of the lowest melt viscosity of resin composition layer is suitably for below below 5000 pools or 3500 pools.Wherein, " lowest melt viscosity " of resin composition layer refers to the minimum viscosity that resin composition layer presents when the resin melting of resin composition layer.In detail, when resin composition layer heating being made resin melting with certain heat-up rate, the melt viscosity while temperature rises of stage in the early stage reduces, and when then exceeding certain temperature, while temperature rises, melt viscosity raises." lowest melt viscosity " refers to the melt viscosity of described minimal point.The lowest melt viscosity of resin composition layer can utilize dynamic viscoelastic method to measure, such as, can measure according to the method recorded in the mensuration > of following < lowest melt viscosity.

Meet in the present invention of the inorganic filling material of specific geometric shape parameters condition what employ specified amount, the resin composition layer of the lowest melt viscosity showing above-mentioned suitable scope can being advantageously generated, the sheet laminated material showing good lamination when manufacturing printed-wiring board (PWB) can being brought.In addition, resin combination of the present invention owing to showing good dispersion stabilization, thus for the sheet laminated material of gained, can suppress thick agglutination particle to be separated out in resin composition layer.

Sheet laminated material of the present invention can be suitable for the insulation layer (insulation layer of printed-wiring board (PWB) is used) in order to form printed-wiring board (PWB), can be more suitable for for the interlayer insulating film (interlayer insulating film of printed-wiring board (PWB) is used) in order to form printed-wiring board (PWB), and then the resin combination that can be suitable for form interlayer insulating film, described interlayer insulating film forms conductor layer (interlayer insulating film being formed the printed-wiring board (PWB) of conductor layer by plating is used) thereon by plating.

[printed-wiring board (PWB)]

Printed-wiring board (PWB) of the present invention contains the insulation layer utilizing the cured article of resin combination of the present invention to be formed.

In one embodiment, printed-wiring board (PWB) of the present invention can use above-mentioned adhesive film, utilize the method for the operation containing following (I) and (II) to manufacture,

(I) on internal substrate by adhesive film lamination, the operation that makes the resin composition layer of this adhesive film engage with internal substrate;

(II) resin composition layer thermofixation is formed the operation of insulation layer.

" internal substrate " that use in operation (I) mainly refers to that the substrates such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, heat curing-type polyphenylene oxide substrate or the one or both sides at this substrate form the circuit substrate of the conductor layer (circuit) having carried out pattern processing.In addition, when manufacturing printed-wiring board (PWB), and then the middle internal layer circuit substrate manufacturing thing that should form insulation layer and/or conductor layer is also contained in said in the present invention " internal substrate ".

The thickness of internal substrate, considers from the angle of the slimming of printed-wiring board (PWB), is preferably less than 800 μm, is more preferably less than 400 μm, and then is preferably less than 200 μm.According to the present invention, even and if then when using thin internal substrate, also can suppress the warpage of printed-wiring board (PWB) in installation procedure.Even if such as when using thickness to be the internal substrate of less than 190 μm, less than 180 μm, less than 170 μm, less than 160 μm, less than 150 μm, less than 140 μm, less than 130 μm, less than 120 μm, less than 110 μm or less than 100 μm, the warpage in installation procedure also can be suppressed.The lower limit of the thickness of internal substrate is not particularly limited, but the angle that operability when manufacturing from printed-wiring board (PWB) improves is considered, is preferably more than 10 μm, is more preferably more than 20 μm.

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

The lamination of internal substrate and adhesive film such as can by adding hot pressing to carry out at internal substrate from supporting side by adhesive film.As the component (hereinafter also referred to " adding hot pressing component ") adhesive film being added on internal substrate hot pressing, such as warmed-up metal sheet (SUS wallboard etc.) or metallic roll (SUS roller) etc. can be enumerated.Should illustrate, be not preferably directly pressurize adding hot pressing component on adhesive film, but clip heat resistant rubber elastomeric material and pressurize, with the concave-convex surface making adhesive film comply with internal substrate fully.

The lamination of internal substrate and adhesive film can utilize vacuum layer platen press to implement.In vacuum layer platen press, heating pressing-in temp is preferably 60 DEG C ~ 160 DEG C, be more preferably the scope of 80 DEG C ~ 140 DEG C, heating pressing pressure is preferably 0.098MPa ~ 1.77MPa, be more preferably the scope of 0.29MPa ~ 1.47MPa, heating pressing time is preferably 20 seconds ~ 400 seconds, is more preferably the scope of 30 seconds ~ 300 seconds.Lamination is preferably implement under the reduced pressure of below 26.7hPa at pressure.

Lamination can utilize commercially available vacuum laminator to carry out.As commercially available vacuum laminator, the vacuum pack system device etc. that (strain) name mechanism makes made vacuum pressure type laminating machine, ニチゴーモート Application (strain) makes can be enumerated such as.

After lamination, by (under normal atmosphere) at ambient pressure, such as will add hot pressing component from the pressurization of support side, the smoothing techniques of the adhesive film of lamination can be carried out.It is same condition that the pressurized conditions of smoothing techniques can be set to the hot pressing condition that adds of above-mentioned lamination.Smoothing techniques can be undertaken by commercially available laminating machine.Should illustrate, lamination and smoothing techniques can use above-mentioned commercially available vacuum laminator to carry out continuously.

The lamination of internal substrate and adhesive film can also use vacuum hotpressing machine to implement.By using vacuum hotpressing machine, even if when the resin combination using inorganic filling material content high, good lamination (circuit landfill) also can be realized.Heating and pressurization can be carried out with 1 stage, but from suppressing the angle of oozing out of resin to be considered, preferably condition are divided into more than 2 stages to carry out.Such as preferred adding of 1st stage, is pressed in the scope that temperature is 70 ~ 150 DEG C, pressure is 0.098MPa ~ 1.77MPa and carries out, adding of the 2nd stage is pressed in the scope that temperature is 150 ~ 200 DEG C, pressure is 0.098MPa ~ 3.92MPa and carries out.The time in each stage is preferably 30 ~ 120 minutes.Pressurization is usually 1 × 10 ^-2below MPa, preferably 1 × 10 ^-3implement under the decompression of below MPa.As commercially available vacuum hotpressing machine, (strain) name mechanism can be enumerated such as and make made " MNPC-V-750-5-200 ", Beichuan essence machine (strain) system " VH1-1603 " etc.When using vacuum hotpressing machine to implement operation (I), this operation can have the thermofixation (that is, operation (II)) of resin composition layer concurrently.

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

In operation (II), resin composition layer is carried out thermofixation and forms insulation layer.

The thermofixation condition of resin composition layer is not particularly limited, the condition usually adopted when can be used in the insulation layer forming printed-wiring board (PWB).

Such as, the thermofixation condition of resin composition layer is different according to kind of resin combination etc., but solidification value can be scope (the preferably scope of 150 ~ 210 DEG C of 120 ~ 240 DEG C, be more preferably the scope of 170 ~ 190 DEG C), set time can be the scope (be preferably 10 ~ 75 minutes, be more preferably 15 ~ 60 minutes) of 5 ~ 90 minutes.

Before making resin composition layer thermofixation, resin composition layer can be preheated at the temperature lower than solidification value.Such as before making resin composition layer thermofixation, more than 50 DEG C, under being less than the temperature of 120 DEG C (preferably more than 60 DEG C more than and 110 DEG C below, more preferably 70 DEG C and 100 DEG C below), resin composition layer can be carried out preheating of 5 minutes more than (preferably 5 ~ 150 minutes, more preferably 15 ~ 120 minutes).

The insulation layer formed by the cured article of resin combination of the present invention shows low thermal expansivity.In one embodiment, the insulation layer formed by the cured article of resin combination of the present invention has less than preferred 30ppm/ DEG C, the more preferably coefficient of linear thermal expansion of less than 28ppm/ DEG C.The lower limit of the coefficient of linear thermal expansion of insulation layer is not particularly limited, and is generally more than 1ppm/ DEG C.The coefficient of linear thermal expansion of insulation layer such as can utilize the known methods such as thermo-mechanical analysis to measure.As thermo-mechanical analysis device, " the Thermo Plus TMA8310 " of (strain) リガ Network can be enumerated such as.In the present invention, when the coefficient of linear thermal expansion tension load method of insulation layer carries out thermo-mechanical analysis, the coefficient of linear thermal expansion of 25 ~ 150 DEG C of in-plane.

When manufacturing printed-wiring board (PWB), (III) and then can be implemented and insulation layer carried out at the operation of insulating layer perforating, (IV) operation of roughened, (V) to form conductor layer operation at surface of insulating layer.These operations (III) to (V) can according to use in the manufacture of printed-wiring board (PWB), well known to a person skilled in the art various method to implement.Should illustrate, by supporter when operation (II) removes afterwards, the removing of this supporter can be implemented between operation (II) and operation (III), between operation (III) and operation (IV) or between operation (IV) and operation (V).

Operation (III) is the operation of perforate on the insulating layer, can form the hole such as through hole (via hole), open-work (through hole) thus on the insulating layer.Operation (III) according to the composition etc. of the resin combination used in the formation of insulation layer, such as, can use drill bit, laser apparatus, plasma body etc. to implement.Size, the shape in hole suitably can determine according to the design of printed-wiring board (PWB).As previously mentioned, resin combination of the present invention owing to showing good dispersion stabilization, thus can to suppress in resin composition layer and then the precipitation of thick agglutination particle in insulation layer.Have in the insulation layer of homogeneous composition described, the hole with required cross-sectional shape can be formed in operation (III).Therefore, even if when hole being filled with conductor metal and forms filling via (Off ィ Le De PVC ア), also can successfully fill in hole with conductor metal.In this, as used the situation of the inorganic filling material of broken shape, point have the inorganic filling material of corner angle or its thick agglutination particle to be present in the wall in hole time, with this inorganic filling material or its thick agglutination particle for starting point, plating preferentially extends, and therefore sometimes in filling via, produces space.Meet in the present invention of the inorganic filling material of specific geometric shape parameters condition in use, described agglutination particle etc. can be suppressed to be present in the wall in hole, therefore at the whole wall in hole, plating extends equably, advantageously can suppress the generation in the space of filling in via.

Operation (IV) is the operation of insulation layer being carried out roughened.Step, the condition of roughened are not particularly limited, and can adopt normally used known step, condition when forming the insulation layer of printed-wiring board (PWB).Such as can implement the neutralizing treatment adopting the swelling process of swelling liquid, adopt the roughened of oxygenant, adopt neutralizer successively, insulation layer is carried out roughened.As swelling liquid, be not particularly limited, can enumerate alkaline solution, surfactant soln etc., preferably alkaline solution, as this alkaline solution, is more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling liquid, スウェリ Application グディップセキュリガ Application ス P, スウェリ Application グディップセキュリガ Application ス SBU etc. that such as アトテッ Network ジャパ Application (strain) is made can be enumerated.The swelling process of swelling liquid is adopted to be not particularly limited, such as can by insulation layer being flooded 1 minute ~ 20 minutes to carry out in the swelling liquid of 30 ~ 90 DEG C.As oxygenant, be not particularly limited, the alkaline permanganic acid solution such as having dissolved potassium permanganate, sodium permanganate in the aqueous solution of sodium hydroxide can be enumerated.The roughened of the oxygenants such as alkaline permanganic acid solution is adopted preferably to be heated in the oxidizing agent solution of 60 DEG C ~ 80 DEG C varnished insulation layer 10 minutes ~ 30 minutes.In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 quality % ~ 10 quality %.As commercially available oxygenant, the alkaline permanganic acid solutions such as the コ Application セ Application トレートコ Application パ Network ト CP, ドージ Application グソリューショ Application セキュリガ Application ス P that such as アトテッ Network ジャパ Application (strain) makes can be enumerated.In addition, as neutralizer, be preferably the acid aqueous solution, as commercially available product, the リダ Network ショ Application ソリューショ Application セキュリガ Application ト P that such as アトテッ Network ジャパ Application (strain) is made can be enumerated.Adopt the process of neutralizer within 5 minutes ~ 30 minutes, can carry out by making to have carried out adopting the treated side of the roughened of oxidizing agent solution to flood in the neutralizer of 30 ~ 80 DEG C.

The insulation layer using resin combination of the present invention to be formed shows low surfaceness after roughened.In one embodiment, the arithmetic average roughness Ra of the surface of insulating layer after roughened is preferably below 500nm, is more preferably below 480nm, and then is preferably below 450nm, and then is more preferably below 400nm, below 360nm or below 320nm.Even if the insulation layer using resin combination of the present invention to be formed, when Ra is little like this, also presents the dhering strength of the excellence for conductor layer.The lower limit of Ra value is not particularly limited, and is preferably more than 0.5nm, is more preferably more than 1nm.The arithmetic average roughness Ra of surface of insulating layer can use non-contact type surface roughness meter to measure.As the object lesson of non-contact type surface roughness meter, " the WYKO NT3300 " of PVC ーコイ Application スツルメン Star society can be enumerated.

Operation (V) is the operation forming conductor layer on surface of insulating layer.

The conductor material used in conductor layer is not particularly limited.In suitable embodiment, conductor layer contains the metal of more than a kind of being selected from gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor layer can be single metal layer or alloy layer, as alloy layer, can enumerate such as by be selected from above-mentioned in the layer that formed of the alloy (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) of metal of more than two kinds.Wherein, from conductor layer formed versatility, cost, pattern formed easiness angularly consider, be preferably the alloy layer of 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, be 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 be preferably the single metal layer of copper.

Conductor layer can be single layer structure, also can be the single metal layer formed by different types of metal or alloy of more than 2 layers or the multilayered structure of alloy layer lamination.When conductor layer is multilayered structure, the layer connected with insulation layer is preferably the single metal layer of chromium, zinc or titanium or the alloy layer of nickel-chromium alloy.

The thickness dependence of conductor layer in the design of the printed-wiring board (PWB) expected, but is generally 3 μm ~ 35 μm, is preferably 5 μm ~ 30 μm.

Conductor layer can utilize plating to be formed.The known technology such as semi-additive process, full additive method such as can be utilized to carry out plating on the surface of insulation layer, form the conductor layer with required Wiring pattern.Below, the example utilizing semi-additive process to form conductor layer is shown.

First, utilize non-electrolytic plating to form plating layer (メッキシー De Layer) on the surface of insulation layer.Then, on the plating layer formed, corresponding to required Wiring pattern, the mask pattern that a part for plating layer is exposed is formed.On the plating layer exposed, after utilizing plating to form metal level, removing mask pattern.Then, utilize etching to wait the unwanted plating layer of removing, the conductor layer with required Wiring pattern can be formed.

The insulation layer using resin combination of the present invention to be formed shows sufficient dhering strength for conductor layer.In one embodiment, the dhering strength of insulation layer and conductor layer is preferably more than 0.50kgf/cm, is more preferably more than 0.55kgf/cm, and then is preferably more than 0.60kgf/cm.The higher limit of dhering strength is not particularly limited, for below 1.2kgf/cm, 0.90kgf/cm are such as the following.In the present invention, although the surface roughness Ra of the insulation layer after roughened is little, also can form the insulation layer presenting high dhering strength like this, therefore significantly contribute to the miniaturization of circuit layout.Should illustrate, in the present invention, the dhering strength of insulation layer and conductor layer to refer to conductor layer relative to insulation layer with the stripping strength (90 degree of stripping strengths) during vertical direction (90 degree of directions) tearing, tensile testing machine can be utilized to be tried to achieve with stripping strength during vertical direction (90 degree of directions) tearing relative to insulation layer by conductor layer by mensuration.As tensile testing machine, " AC-50C-SL " of (strain) TSE etc. can be enumerated such as.

In other embodiments, printed-wiring board (PWB) of the present invention can use above-mentioned prepreg to manufacture.Manufacture method is substantially same with using the situation of adhesive film.

[semiconductor device]

Use printed-wiring board (PWB) of the present invention, can semiconductor device be manufactured.Although printed-wiring board (PWB) of the present invention is slim, even if in the installation procedure of parts adopting high solder Reflow Soldering temperature, also warpage can be suppressed, the problem such as loose contact of circuit modifications, parts advantageously can be alleviated.

In one embodiment, printed-wiring board (PWB) of the present invention is in the installation procedure of solder Reflow Soldering temperature of 260 DEG C high like this at employing peak temperature, the warpage of printed-wiring board (PWB) can be suppressed for being less than 40 μm.In the present invention, the warpage of printed-wiring board (PWB) is the value of when utilizing image moire device to observe the buckling behavior of the square part of 10mm of printed-wiring board (PWB) central authorities, the maximum height of displacement data and the difference of minimum constructive height.During mensuration, printed-wiring board (PWB) is being reappeared Reflow Soldering temperature profile (lead free manufacture (lead-free assembly) distribution plan recorded in IPC/JEDEC J-STD-020C (" Moisture/Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devices ", in July, 2004); Peak temperature 260 DEG C) reflow soldering apparatus in by after 1 time, according to the Reflow Soldering temperature profile based on above-mentioned IP C/JEDEC J-STD-020C, the one side of printed-wiring board (PWB) is carried out heat treated, for the gridline of another side being arranged at printed-wiring board (PWB), try to achieve displacement data.Should illustrate, as reflow soldering apparatus, such as Japanese ア Application ト system (strain) system " HAS-6116 " can be enumerated, as image moire device, such as Akrometrix system " TherMoire AXP " can be enumerated.Utilize the cured article meeting the resin combination of the inorganic filling material of geometry in particular Parameter Conditions containing specified amount and form insulation layer, even if the printed-wiring board (PWB) of the present invention containing this insulation layer is slim, the warpage in installation procedure also advantageously can be suppressed.

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

Semiconductor device of the present invention can by manufacturing at conducting position installation parts (semi-conductor chip) of printed-wiring board (PWB) of the present invention." conducting position " refers to " position of electrical signal in conduction printed-wiring board (PWB) ", and its position can be any one of the position of surface or landfill.In addition, as long as semi-conductor chip take semi-conductor as the circuit element of material, be not particularly limited.

As long as the installation method of semi-conductor chip when manufacturing semiconductor device of the present invention makes semi-conductor chip effectively play function, be not particularly limited, particularly, wire-bonded installation method, flip-chip installation method can be enumerated, adopt bumpless build up layer (バ Application プな PVC Le De アップ Layer; BBUL) installation method, adopt the installation method of anisotropic conductive film (ACF), adopt the installation method etc. of non-conductive film (NCF).Wherein, " adopting the installation method of bumpless build up layer (BBUL) " is " by direct for semi-conductor chip landfill in the recess of printed-wiring board (PWB), making the installation method that semi-conductor chip is connected with the distribution on printed-wiring board (PWB) ".

[embodiment]

By embodiment, the present invention is specifically described below, but the present invention is not by the restriction of these embodiments.Should illustrate, " part " and " % " in below recording refers to " mass parts " and " quality % " respectively as long as no other explanation.

First various measuring method, evaluation method are described.

(evaluating the preparation with substrate 1)

(1) preparation of internal layer circuit substrate

Utilize メッ Network (strain) to make " CZ8100 " on the two sides of the woven fiber glass base material epoxy resin two-sided copper foil covered plywood (thickness 18 μm of Copper Foil, the thickness 0.3mm of substrate, SUNX (strain) system " R5715ES ") defining internal layer circuit to etch 1 μm, carry out the roughened on copper surface.

(2) lamination of adhesive film

Use intermittent vacuum pressure level press ((strain) name mechanism is done made " MVLP-500 "), the mode engaged with internal layer circuit substrate with resin composition layer by the adhesive film made in embodiment and comparative example, the two sides being stacked on internal layer circuit substrate.Lamination by carry out 30 seconds decompression, make air pressure be below 13hPa after, 100 DEG C, under the condition of pressure 0.74MPa pressing within 30 seconds, carry out.

(3) solidification of resin composition layer

After lamination, from the two sides of substrate, supporter is peeled off.Then, make resin composition layer carry out thermofixation with the condition of cure of 100 DEG C, 30 minutes and then 170 DEG C, 30 minutes, form insulation layer.

(4) roughened

After forming insulation layer, by substrate, at 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 of dippings 5 minutes, at oxygenant, (アトテッ Network ジャパ Application (strain) makes " コ Application セ Application トレートコ Application パ Network ト CP ", KMnO ₄: the aqueous solution of 60g/L, NaOH:40g/L) in 80 DEG C dipping 10 minutes, finally in 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 flood 5 minutes.Then, its dry 30 minutes are made at 80 DEG C.The substrate of gained is called " substrate 1a ".

Should illustrate, about embodiment 6 and comparative example 5, as following, implement the operation of above-mentioned (2) ~ (4), obtain substrate 1a;

Use vacuum pressure device (Beichuan essence machine (strain) system " VH1-1603 "), the adhesive film made is stacked on the two sides of internal layer circuit substrate in embodiment and comparative example in the mode that resin composition layer engages with internal layer circuit substrate.Lamination passes through at 1x10 ^-3under the decompression of MPa, 100 DEG C, pressing 30 minutes under the condition of pressure 1.0MPa, after being then warming up to 180 DEG C with 10 minutes, 180 DEG C, under the condition of pressure 1.0MPa pressing within 30 minutes, carry out.Thus, resin composition layer thermofixation is formed insulation layer.Roughened except in swelling liquid in 60 DEG C dipping 5 minutes, in oxygenant in 80 DEG C dipping 5 minutes except, other is same with above-mentioned (4).

(5) formation of conductor layer

According to semi-additive process, as described below at surface of insulating layer formation conductor layer;

By substrate 1a containing PdCl ₂non-electrolytic plating solution in, 40 DEG C dipping 5 minutes after, in non-electrolytic copper plating solution, 25 DEG C dipping 20 minutes.Then, 150 DEG C of heating 30 minutes, after carrying out anneal, form erosion shield, utilize etching to form pattern.Then, carry out copper sulfate bath plating, form the conductor layer of thickness 25 μm, carry out the anneal of 30 minutes at 180 DEG C.The substrate of gained is called " substrate 1b ".

(evaluating the preparation with substrate 2)

(1) preparation of internal substrate

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

(2) lamination of adhesive film

Use intermittent vacuum pressure level press (2 stages stack layer press " CVP700 " that ニチゴーモート Application (strain) makes), in the mode making resin composition layer connect with internal substrate, the adhesive film made in embodiment and comparative example is laminated in the two-sided of internal substrate.Stackedly to implement as follows: reduce pressure 30 seconds, make air pressure be after below 13hPa, 100 DEG C, make its pressing 30 seconds under the condition of pressure 0.74MPa.Then, 100 DEG C, the condition of pressure 0.5MPa carries out the hot pressing of 60 seconds.

(3) solidification of resin composition layer

After lamination, from substrate, supporter is peeled off.Then, with the condition of cure of 190 DEG C, 90 minutes, resin composition layer is carried out thermofixation, form insulation layer.The substrate of gained is called " substrate 2a ".

The mensuration > 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 "), utilizes nitrogen BET method to try to achieve.

The mensuration > of the median size (R) of < inorganic filling material

In the bottle of 20ml, add inorganic filling material 0.01g, nonionic system dispersion agent (Nippon Yushi (Co., Ltd.) " T208.5 ") 0.2g, pure water 10g, the ultrasonic wave dispersion utilizing sonic washing machine to carry out 10 minutes, prepares sample.Then, drop into sample in the laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system " SALD2200 "), make it circulate to irradiate the ultrasonic wave of 10 minutes.Then, stop ultrasonic wave, under the state of circulation maintaining sample, carry out the mensuration of size-grade distribution, try to achieve the median size (R) of inorganic filling material.Should illustrate, specific refractory power during mensuration is set as 1.45-0.001i.

< geometric shape parameters A calculates >

The value of the specific surface area (S) of inorganic filling material, median size (R) and density (ρ) is substituted into following formula (1), calculates geometric shape parameters A,

Formula (1): A=SR ρ/6.

< geometric shape parameters B calculates >

For the insulation layer be stacked in the one side of substrate 1a, use FIB-SEM set composite (SII Na ノテ Network ノロジー (strain) makes " SMI3050SE "), carry out cross-section with the observation multiplying power of 14000 times.By the FIB-SEM picture of gained, use image processing software ((strain) Leica system " QWin V3 "), be determined at girth (L) and the area of the inorganic filling material particle existed in insulation layer.Should illustrate, for avoid general image unclear inorganic filling material particle, profile feint inorganic filling material particle, the inorganic filling material particle of any 50 of every 1 sample measures.By the area of the inorganic filling material particle of gained, calculate the girth (circumference with the positive round of its homalographic; Lc).The value of L and Lc is substituted into following formula (2), for each inorganic filling material particle, calculates geometric shape parameters B, obtain mean value and its distribution of geometric shape parameters B,

Formula (2): B=Lc/L.

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

The Average crystallite diameter of inorganic filling material is tried to achieve according to following step.First, fixed inorganic packing material on glass specimen plate, preparation sample panel.This sample panel is arranged in Wide angle X-ray diffraction device ((strain) リガ Network system " Multi FLEX "), utilizes Wide angle X-ray diffraction reflection method to measure diffractogram.X-ray source is CuK α, and detector is scintillation detector, and power is 40kV, 40mA.By the SiO of the diffractogram based on gained ₂the diffracted ray in Quarts (101) face, use is thanked to the formula of strangling (Scherrer) and is calculated crystallite diameter.

The evaluation > of < dispersion stabilization

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

Metewand:

The agglutination particle of more than zero: 10 μm is less than 2 in 10 visuals field

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

The mensuration > of < lowest melt viscosity

For the resin composition layer of the adhesive film made in embodiment and comparative example, ((strain) ユービーエ system system " Rheosol-G3000 ") measures melt viscosity to use Measurement of Dynamic Viscoelasticity device.For sample resin combination 1g, use the parallel plate of diameter 18mm, 200 DEG C are warming up to from starting temperature 60 DEG C with the heat-up rate of 5 DEG C/min, to measure, temperature interval is 2.5 DEG C, the condition determination of vibration 1Hz, measure of skewness (askew body) 1deg measures dynamic viscoelastic modulus, measures lowest melt viscosity.Lamination is evaluated according to following benchmark,

Metewand:

Zero: lowest melt viscosity is below 30000 pools

×: lowest melt viscosity is higher than 30000 pools.

The evaluation > of < warpage

Substrate 2a (n=5) is passed through once (Reflow Soldering temperature profile is according to IPC/JEDEC J-STD-020C) in the reflow soldering apparatus (Japanese ア Application ト system (strain) system " HAS-6116 ") of solder Reflow Soldering temperature reappearing peak temperature 260 DEG C.Then, use image moire device (Akrometrix society system " TherMoire AXP "), utilize and heat below substrate according to the Reflow Soldering temperature profile of IPC/JEDEC J-STD-020C (peak temperature 260 DEG C), measure the displacement of the square part of 10mm of substrate center based on the gridline configured at thereon.Warpage is evaluated according to following metewand,

Metewand:

Zero: for whole 5 samples, the maximum height of the displacement data of whole temperature range and the difference of minimum constructive height are less than 40 μm

×: at least 1 sample, the maximum height of the displacement data of whole temperature range and the difference of minimum constructive height are more than 40 μm.

The mensuration > of < arithmetic average roughness (Ra)

For substrate 1a, use non-contact type surface roughness meter (PVC ーコイ Application スツルメン Star society's system " WYKO NT3300 "), utilizing VSI contact mode, 50 times of lens, is that 121 μm × 92 μm numerical value obtained try to achieve Ra value by measurement range.By obtain Stochastic choice the mean value of 10 and as measured value.

The mensuration > of the dhering strength of < conductor layer

The mensuration of the dhering strength of insulation layer and conductor layer, for evaluation substrate 1b, carries out according to JIS C6481.Particularly, in the conductor layer of substrate 1b, introduce the otch of part of width 10mm, length 100mm, its one end is peeled off, catches with fixture, measure at room temperature with the speed of 50mm/ minute vertically tearing 35mm time loading (kgf/cm), try to achieve dhering strength.

The mensuration > of < coefficient of linear thermal expansion

The adhesive film made in embodiment and comparative example is heated 90 minutes at 190 DEG C, makes resin composition layer carry out thermofixation.Then, supporter is peeled off, obtains the cured article of sheet.The cured article of the sheet of gained is cut into the test film that width is about 5mm, length is about 15mm, uses thermo-mechanical analysis device ((strain) リガ Network system " Thermo Plus TMA8310 "), carry out thermo-mechanical analysis by tension load method.In detail, test film is assemblied in after on above-mentioned thermo-mechanical analysis device, METHOD FOR CONTINUOUS DETERMINATION 2 times under the condition determination of load 1g, heat-up rate 5 DEG C/min.Calculate the mean coefficient of linear thermal expansion from the scope of 25 DEG C to 150 DEG C in measuring for the 2nd time.

< fills the evaluation > in the space of via

The evaluation of filling the space of via is carried out according to following step:

(1) formation of through hole

Use CO2 Laser Processing Equipment for Joining ((strain) Hitachi system " LC-2E21B/1C "), on insulation layer in the one side being stacked on substrate 1a, form the through hole of top diameter (トップ footpath) 60 μm, base diameter (ボト system footpath) 50 μm;

(2) formation of via is filled

After forming through hole, insulation layer is carried out roughened, form conductor layer.The formation of roughened and conductor layer is same with (preparation of evaluation substrate 1) to be carried out.Thus, also fill conductor metal in through hole inside, obtain filling via;

(3) evaluation in space

Scanning electron microscope (SEM) ((strain) Hitachi Ha イテ Network ノロジーズ system, model " SU-1500 ") is used to carry out cross-section to the filling via formed.The situation that the number in 10 spaces of filling in via is less than 2 is set to "○", and the situation being more than 2 by the number in 10 spaces of filling in via is set to "×".

Each physical property of the inorganic filling material used in embodiment and comparative example and geometric shape parameters A, B gather and are shown in table 1.

[table 1]

。

Should illustrate, for IMSIL A-8, the content that geometric shape parameters B is less than the particle of 0.8 is 36 number %, especially, geometric shape parameters B is the content of the particle of less than 0.75 is 16 number %, the content that geometric shape parameters B is greater than the particle of 0.9 is 12 number %, and especially, geometric shape parameters B is the content of the particle of more than 0.94 is 0 number %.In addition, for IMSIL A-25, the content that geometric shape parameters B is less than the particle of 0.8 is 26 number %, especially, geometric shape parameters B is the content of the particle of less than 0.75 is 20 number %, the content that geometric shape parameters B is greater than the particle of 0.9 is 14 number %, and especially, geometric shape parameters B is the content of the particle of more than 0.94 is 0 number %.

< embodiment 1 >

(1) preparation of resinous varnish

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 187, Mitsubishi Chemical's (strain) system " jER828EL ") 20 parts, biphenyl type epoxy resin (epoxy equivalent (weight) 276, Japan's chemical drug (strain) system " NC3000 ") 30 parts, tetraphenyl ethane type epoxy resin (epoxy equivalent (weight) 198, Mitsubishi Chemical's (strain) system " jER1031S ") 5 parts, curable type bisphenol A type epoxy resin (epoxy equivalent (weight) about 3000 ~ 5000, Mitsubishi Chemical's (strain) system " jER1010 ") mass ratio that is dissolved in methyl ethyl ketone (MEK) and pimelinketone is the resin solution forming nonvolatile component 50 quality % in the mixed solvent of 1:1, stir while make resin solution 5 parts of heating for dissolving of this nonvolatile component 50 quality % in the mixed solvent of MEK20 part and pimelinketone 10 parts.Mixing is containing the line style phenolic aldehyde system solidifying agent (hydroxyl equivalent 125 of triazine skeleton wherein, DIC (strain) makes " LA-7054 ", the MEK solution of solid state component 60%) 10 parts, line style phenolic aldehyde system solidifying agent (hydroxyl equivalent 105, DIC (strain) makes " TD2090 ") 6 parts, amine system curing catalyst (4-dimethylaminopyridine (DMAP), the MEK solution of solid state component 5 quality %) 3 parts, surface-treated crystalline silica (Unimin society system " IMSIL A-8 " has been carried out by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 "), median size 1.38 μm, maximum particle diameter 20 μm, specific surface area 6.54m ²/ g, density 2.65g/cm ³, Average crystallite diameter 1000) 180 parts, fire retardant (three light (strain) system " HCA-HQ ", 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, median size 2 μm) 5 parts, utilize high speed rotating mixing tank to disperse equably, prepare resinous varnish.Should illustrate, the global density of the nonvolatile component beyond the inorganic filling material used in the preparation of resinous varnish is about 1.2g/cm ³.

(2) making of adhesive film

As supporter, prepare the polyethylene terephthalate film (thickness 38 μm, リ Application テッ Network (strain) system, " AL5 ") with Synolac system release layer.On this supporter, utilize die coating machine to be coated with the resinous varnish of above-mentioned preparation equably, make its dry 6 minutes at 80 ~ 120 DEG C (average 100 DEG C), form resin composition layer.The thickness of resin composition layer is 40 μm, and the residual solvent amount in resin combination is about 2 quality %.Then, on the surface of resin composition layer, as protective membrane, laminating polypropylene screen (make, the even surface side of " ア Le Off ァ Application MA-411 ", thickness 15 μm, simultaneously wound into rolls by the special paper of prince (strain).The adhesive film of web-like is cut into width 507mm, obtains the adhesive film of 507mm × 336mm size.

< embodiment 2 >

Replace except biphenyl type epoxy resin (epoxy equivalent (weight) 276, Japanese chemical drug (strain) system " NC3000 ") 30 parts except using biphenyl type epoxy resin (epoxy equivalent (weight) 276, Japanese chemical drug (strain) system " NC3000 ") 10 parts and naphthylidene ether type epoxy (epoxy equivalent (weight) 250, DIC (strain) make " HP6000 ") 18 parts, other prepares resinous varnish similarly to Example 1, makes adhesive film.

< embodiment 3 >

Replace 6 parts, line style phenolic aldehyde system solidifying agent (hydroxyl equivalent 105, DIC (strain) make " TD2090 ") except using 12 parts, naphthol novolac system solidifying agent (aurification (strain) system " SN485 " is lived by hydroxyl equivalent 215, Nippon Steel) and the usage quantity of having carried out surface-treated crystalline silica (Unimin society system " IMSIL A-8 ") by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") is changed into except 210 parts, other prepares resinous varnish similarly to Example 1, makes adhesive film.

< embodiment 4 >

Replace except curable type bisphenol A type epoxy resin (epoxy equivalent (weight) about 3000 ~ 5000, Mitsubishi Chemical's (strain) system " jER1010 ") except using phenoxy resin (MEK/ pimelinketone=1/1 solution of Mitsubishi Chemical's (strain) system " YL7553BH30 ", solid state component 30 quality %) 8 parts, other prepares resinous varnish similarly to Example 1, makes adhesive film.

< embodiment 5 >

Except use N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") has carried out surface-treated crystalline silica (Unimin society system " IMSIL A-25 ", median size 2.55 μm, maximum particle diameter 20 μm, specific surface area 5.87m ²/ g, density 2.65g/cm ³, Average crystallite diameter 1400), replace having been undertaken beyond surface-treated crystalline silica (Unimin society system " IMSIL A-8 ") 180 parts by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 "), other prepares resinous varnish similarly to Example 1, makes adhesive film.

< embodiment 6 >

Except surface-treated crystalline silica (Unimin society system " IMSIL A-8 ", median size 1.38 μm, maximum particle diameter 20 μm, specific surface area 6.54m will have been carried out with N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") ²/ g, density 2.65g/cm ³, Average crystallite diameter 1000) usage quantity change into beyond 400 parts, other prepares resinous varnish similarly to Example 1, make adhesive film.

< comparative example 1 >

Except use N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") has carried out surface-treated spherical silicon dioxide, (ア De マテッ Network ス (strain) makes " SO-C2 ", median size 0.90 μm, specific surface area 5.75m ²/ g, density 2.2g/cm ³) 150 parts replace having been undertaken beyond surface-treated crystalline silica (Unimin society system " IMSIL A-8 ") 180 parts by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 "), other prepares resinous varnish similarly to Example 1, makes adhesive film.

< comparative example 2 >

Except use N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") has carried out surface-treated spherical silicon dioxide, (ア De マテッ Network ス (strain) makes " SO-C6 ", median size 2.06 μm, specific surface area 2.15m ²/ g, density 2.2g/cm ³) 150 parts replace having been undertaken beyond surface-treated crystalline silica (Unimin society system " IMSIL A-8 ") 180 parts by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 "), other prepares resinous varnish similarly to Example 1, makes adhesive film.

< comparative example 3 >

Except use N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") has carried out the broken shape silicon-dioxide of surface-treated (dragon gloomy (strain) system " VX-SR ", median size 1.30 μm, specific surface area 11.94m ²/ g, density 2.65g/cm ³, Average crystallite diameter 1900) 180 parts replace having been undertaken beyond surface-treated crystalline silica (Unimin society system " IMSIL A-8 ") 180 parts by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 "), other prepares resinous varnish similarly to Example 1, makes adhesive film.

< comparative example 4 >

Except the usage quantity of having carried out surface-treated crystalline silica (Unimin society system " IMSIL A-8 ") by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") is changed into except 80 parts, other prepares resinous varnish similarly to Example 1, makes adhesive film.

< comparative example 5 >

Except the usage quantity of having carried out surface-treated crystalline silica (Unimin society system " IMSIL A-8 ") by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") is changed into except 480 parts, other prepares resinous varnish similarly to Example 1, makes adhesive film.

[table 2]

。

Claims

1. resin combination, it is the resin compositions for insulating layer of printed-wiring board (PWB), wherein,

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

In formula, S represents the specific surface area (m of inorganic filling material ²/ g), R represents the median size (μm) of inorganic filling material, and ρ represents the density (g/cm of inorganic filling material ³).

2. resin combination, it is the resin compositions for insulating layer of printed-wiring board (PWB), wherein,

By formula: the mean value of the geometric shape parameters B of the inorganic filling material that B=Lc/L represents is more than 0.8 and less than 0.9,

In formula, L represents the girth (μm) of the inorganic filling material in the cross section of regulation, and Lc represents with the sectional area of the inorganic filling material in above-mentioned cross section to be the girth (μm) of the positive round of homalographic.

3. resin combination according to claim 1 and 2, wherein, the Average crystallite diameter of inorganic filling material is below 1800 dusts.

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

5. resin combination according to claim 1 and 2, wherein, the median size of inorganic filling material is less than 4 μm.

6. resin combination according to claim 1 and 2, wherein, the median size of inorganic filling material is less than 3 μm.

7. resin combination according to claim 1 and 2, wherein, inorganic filling material be make Average crystallite diameter be the crystallite particles of below 1800 dusts tufted agglutinator dispersion obtain, the maximum particle diameter of this tufted agglutinator is less than 20 μm.

8. resin combination according to claim 1 and 2, wherein, inorganic filling material contains crystallinity inorganic filling material, and when whole inorganic filling material is set to 100 quality %, the content of this crystallinity inorganic filling material is more than 50 quality %.

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

10. resin combination according to claim 1 and 2, it is further containing epoxy resin and solidifying agent.

11. resin combinations according to claim 1 and 2, it is interlayer insulating film resin combination.

12. sheet laminated materials, it contains the resin composition layer formed by the resin combination described in claim 1 or 2.

13. printed-wiring board (PWB)s, the insulation layer that its cured article containing the resin combination utilized described in claim 1 or 2 is formed.

14. semiconductor devices, it contains printed-wiring board (PWB) according to claim 13.