CN108864654A

CN108864654A - Resin composition layer

Info

Publication number: CN108864654A
Application number: CN201810436857.6A
Authority: CN
Inventors: 鹤井彦; 鹤井一彦
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2017-05-10
Filing date: 2018-05-09
Publication date: 2018-11-23
Anticipated expiration: 2038-05-09
Also published as: CN108864654B

Abstract

The subject of the invention is to provide a kind of resin composition layer, the insulating layer of the available through-hole that can inhibit halo phenomenon thinner thickness and excellent in shape can be formed of the resin composition layer.Solution of the invention is a kind of resin composition layer, is comprising resin combination with a thickness of 15 μm of resin composition layers below, wherein resin combination includes：(A) epoxy resin；(B) containing the aromatic resins of aromatic ring, which is with 2 or more hydroxyls as monocycle or the aromatic ring of condensed ring；(C) has 100nm average grain diameter below and 15m²The inorganic filling material of at least one of the specific surface area of/g or more.

Description

Resin composition layer

Technical field

The present invention relates to resin composition layers.In turn, the present invention relates to the resin sheets comprising the resin composition layer；With And printed wiring board and semiconductor device containing the insulating layer formed by the solidfied material of resin composition layer.

Background technique

In recent years, in order to realize the miniaturization of electronic equipment, the further slimming of printed wiring board is being in progress.With It, the miniaturization of the wired circuit in internal substrate is being in progress.For example, describing in patent document 1 comprising supporting mass and tree The resin sheet (adhesive film) for being suitable for fine wiring of oil/fat composition layer.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2014-36051 bulletin.

Summary of the invention

Subject to be solved by the invention

The present inventor is in order to realize the miniaturising of electronic equipment, be thinned, for making the resin combination of resin sheet Layer is that the scheme of thinner layer is studied.Research as a result, the inventors discovered that, be applicable in relatively thin resin in a insulating layer When composition layer, haloing (haloing) phenomenon is generated after through-hole is formed.Here, halo phenomenon refers to, around through-hole, The phenomenon that resin discoloration of insulating layer.Such halo phenomenon is typically due to the deterioration of the resin around through-hole and generates.And then Know, if to produce halo phenomenon insulating layer implement roughening treatment, produce halo phenomenon insulating layer part (with Down sometimes referred to as " haloing portion ".) resin be etched in roughening treatment, interlayer occurs between insulating layer and internal substrate Removing.

In turn, the inventors discovered that, when being applicable in relatively thin resin composition layer in a insulating layer, the control of shape of through holes becomes It is difficult, it is difficult to obtain the through-hole of excellent in shape.Here, the shape " good " of through-hole refers to, taper ratio (the テーパー of through-hole Rate) close to 1.In addition, the taper ratio of through-hole refers to, ratio of the base diameter of through-hole relative to top diameter.

Above-mentioned project is the project generated for the first time with a thickness of relatively thin degree due to making resin composition layer, be with Toward unknown new project.From the viewpoint of the conducting reliability of interlayer for improving printed wiring board, waits in expectation and solve these Project.

The present invention is the invention carried out in view of aforementioned problems, the purpose is to provide a kind of resin composition layer, the resin The insulating layer of the available through-hole that can inhibit halo phenomenon thinner thickness and excellent in shape can be formed of composition layer； The object of the invention is also to provide the resin sheets comprising aforementioned resin layer；Comprising halo phenomenon, energy shape can be inhibited At the printed wiring board of the relatively thin insulating layer of the through-hole of excellent in shape；And the semiconductor dress comprising aforementioned printed wiring board It sets.

Solve the means of project

The present inventor has made intensive studies to solve aforementioned problems, as a result, it has been found that, it can be solved using following resin combination Certainly aforementioned problems, in the resin combination combination include：(A) epoxy resin；(B) containing the aromatic resins of aromatic ring, which is With 2 or more hydroxyls as monocycle or the aromatic ring of condensed ring；And (C) has 100nm average grain diameter below and 15m²/g The inorganic filling material of at least one of above specific surface area, has thus completed the present invention.

That is, the present invention includes following the description：

[1] resin composition layer is comprising resin combination with a thickness of 15 μm of resin composition layers below,

Wherein, resin combination includes：(A) epoxy resin；(B) containing the aromatic resins of aromatic ring, which is to have 2 or more Hydroxyl as monocycle or the aromatic ring of condensed ring；(C) average grain diameter is 100nm inorganic filling material below；

[2] resin composition layer is comprising resin combination with a thickness of 15 μm of resin composition layers below,

Wherein, resin combination includes：(A) epoxy resin；(B) containing the aromatic resins of aromatic ring, which is to have 2 or more Hydroxyl as monocycle or the aromatic ring of condensed ring；(C) specific surface area is 15m²The inorganic filling material of/g or more；

[3] resin composition layer according to [1] or [2], wherein (B) ingredient indicates by following formula (1) or formula (2),

(in formula (1), R⁰The alkyl of divalent is each independently represented, n1 indicates 0~6 integer.)

(in formula (2), R¹~R⁴Each independently represent the alkyl of hydrogen atom or 1 valence.)；

[4] resin composition layer according to any one of [1]~[3], wherein (B) ingredient is by following formula (3) or formula (4) It indicates,

(in formula (3), n2 indicates 0~6 integer.)

(in formula (4), R¹~R⁴Each independently represent the alkyl of hydrogen atom or 1 valence.)；

[5] resin composition layer according to any one of [1]~[4], wherein relative to the resin in resin combination 100 mass % of ingredient, the amount of (B) ingredient are 5 mass of mass %~50 %；

[6] resin composition layer according to any one of [1]~[5], wherein relative to not waving in resin combination 100 mass % of ingredient is sent out, the amount of (C) ingredient is 50 mass % or more；

[7] resin composition layer according to any one of [1]~[6], wherein the resin composition layer is used to be formed as Form the insulating layer of conductor layer (for forming the insulating layer for forming conductor layer)；

[8] resin composition layer according to any one of [1]~[7], wherein the resin composition layer is used to form print The interlayer insulating film of brush wiring plate；

[9] resin composition layer according to any one of [1]~[8], wherein the resin composition layer is used to form tool Having top diameter is the insulating layer of 35 μm of through-holes below；

[10] resin sheet, it includes：Resin described in any one of supporting mass and [1] that is set on supporting mass~[9] Composition layer；

[11] printed wiring board is formed it includes the solidfied material of the resin composition layer as described in any one of [1]~[9] Insulating layer；

[12] printed wiring board it includes the first conductor layer, the second conductor layer and is formed in the first conductor layer and second and leads Insulating layer between body layer, wherein

Insulating layer with a thickness of 15 μm hereinafter,

It is 35 μm of through-holes below that insulating layer, which has top diameter,

The taper ratio of the through-hole is 80% or more,

The slave bottom sides genesis of the through-hole haloing distance be 5 μm hereinafter,

The haloing ratio relative to bottom radius of the through-hole is 35% or less；

[13] printed wiring board according to [12], wherein the haloing ratio relative to bottom radius of the through-hole be 5% with On；

[14] semiconductor device, it includes the printed wiring boards described in any one of [11]~[13].

The effect of invention

It can provide a kind of resin composition layer according to the present invention, which can get can inhibit thinner thickness Halo phenomenon and can be formed excellent in shape through-hole insulating layer；The resin comprising aforementioned resin layer can also be provided Sheet material；Printed wiring board comprising the relatively thin insulating layer of halo phenomenon, the through-hole that excellent in shape can be formed can be inhibited；And Semiconductor device comprising aforementioned printed wiring board.

Detailed description of the invention

Fig. 1 be schematically show the resin composition layer of first embodiment of the invention is solidified obtained by insulating layer, And the cross-sectional view of internal substrate；

Fig. 2 be schematically show the resin composition layer of first embodiment of the invention is solidified obtained by insulating layer with lead The plan view (top view) in the face of body layer opposite side；

Fig. 3 be schematically show the resin composition layer of first embodiment of the invention is solidified obtained by after roughening treatment Insulating layer and internal substrate cross-sectional view；

Fig. 4 is the schematic cross sectional views of the printed wiring board of second embodiment of the invention.

Specific embodiment

Embodiment and illustrative material described below, the present invention is described in detail.But the present invention is not limited to be exemplified below Embodiment and illustrative material, can arbitrarily be changed in the range of not departing from scope of the presently claimed invention and its equivalents And implement.

In the following description, " resin component " of resin combination refers to, resin combination include it is non-volatile at Ingredient in point in addition to inorganic filling material.

[summaries of 1. resin composition layers]

Resin composition layer of the invention is the relatively thin resin composition layer with institute's definite value thickness below.In addition, this hair Resin combination contained by bright resin composition layer includes：

(A) epoxy resin；

(B) containing the aromatic resins of aromatic ring, which is with 2 or more hydroxyls as monocycle or the aromatic ring (monocycle of condensed ring Or the aromatic ring of condensed ring form)；And

(C) there is 100nm average grain diameter below and 15m²The inorganic fill material of at least one of the specific surface area of/g or more Material.

It therefore, may include the first following resin combinations in resin combination contained by resin composition layer of the invention With the second resin combination any one.

First resin combination includes (A) epoxy resin；(B) containing the aromatic resins of aromatic ring, the aromatic ring be have 2 with Upper hydroxyl as monocycle or the aromatic ring of condensed ring；And (C) average grain diameter is 100nm inorganic filling material below.

Second resin combination includes (A) epoxy resin；(B) containing the aromatic resins of aromatic ring, the aromatic ring be have 2 with Upper hydroxyl as monocycle or the aromatic ring of condensed ring；And (C) specific surface area is 15m²The inorganic filling material of/g or more.

By using such resin composition layer, relatively thin insulating layer can get.Then, it can get the following present invention Desired effect：It can be in the through-hole for forming excellent in shape on resulting insulating layer while inhibiting halo phenomenon.

[2. (A) ingredients：Epoxy resin]

As the epoxy resin of (A) ingredient, such as can enumerate：Union II cresols (bixylenol) type epoxy resin, bisphenol-A type ring Oxygen resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, Tris phenol type epoxy, naphthol novolac (naphthol novolac) type epoxy resin, phenol novolac (phenol novolac) Type epoxy resin, tert butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, Glycidyl group amine type epoxy resin, glycidyl esters type epoxy resin, cresol novolac (cresol novolac) type ring oxygen Resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, the epoxy resin with butadiene structure, cycloaliphatic epoxy resin, Hetero ring type epoxy resin, the epoxy resin containing loop coil, hexamethylene type epoxy resin, cyclohexanedimethanol type epoxy resin, sub- naphthalene Base ether type epoxy, trihydroxy methyl type epoxy resin, tetraphenyl ethane type epoxy resin etc..Epoxy resin can be used alone 1 Kind, two or more can also be applied in combination.

Preferably, in resin combination, as (A) epoxy resin, being included in 1 molecule has 2 or more epoxy groups Epoxy resin.From the viewpoint of significantly obtaining the desired effect of the present invention, relative to (A) epoxy resin it is non-volatile at Point 100 mass %, the ratio of the epoxy resin in 1 molecule with 2 or more epoxy groups are preferably 50 mass % or more, more preferably For 60 mass % or more, particularly preferably 70 mass % or more.

Epoxy resin includes epoxy resin (hereinafter sometimes referred to " liquid epoxy tree at a temperature of 20 DEG C for liquid Rouge ".) and be solid epoxy resin (sometimes referred to as " solid epoxy resin " at a temperature of 20 DEG C.).In resin combination, make It can only include liquid-state epoxy resin for (A) epoxy resin, can also only include solid epoxy resin, preferably combination includes liquid ring Oxygen resin and solid epoxy resin.As (A) epoxy resin, by the way that liquid-state epoxy resin and solid epoxy resin is applied in combination, The flexibility of resin composition layer can be improved, or improve the breaking strength of the solidfied material of resin composition layer.

As liquid-state epoxy resin, with the liquid-state epoxy resin of 2 or more epoxy groups preferably in 1 molecule, more preferably With the aromatics system liquid-state epoxy resin of 2 or more epoxy groups in 1 molecule.Here, the epoxy resin of " aromatics system " refers to Its intramolecular has the epoxy resin of aromatic ring.

As liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type asphalt mixtures modified by epoxy resin Rouge, naphthalene type epoxy resin, glycidyl esters type epoxy resin, glycidyl group amine type epoxy resin, phenol novolak type epoxy Resin, hexamethylene type epoxy resin, cyclohexanedimethanol type epoxy resin, shrinks at the cycloaliphatic epoxy resin with ester skeleton Glyceryl amine type epoxy resin and epoxy resin with butadiene structure；More preferable bisphenol A type epoxy resin, bisphenol-f type Epoxy resin and hexamethylene type epoxy resin.

As the concrete example of liquid-state epoxy resin, can enumerate：" HP4032 " of DIC corporation, " HP4032D ", " HP4032SS " (naphthalene type epoxy resin)；" 828US " of Mitsubishi Chemical Ind, " jER828EL ", " 825 ", " EPIKOTE 828EL " (bisphenol A type epoxy resin)；" jER807 ", " 1750 " (bisphenol f type epoxy resin) of Mitsubishi Chemical Ind；Mitsubishi " jER152 " (phenol novolak type epoxy) of chemical company；" 630 " of Mitsubishi Chemical Ind, " 630LSD " (shrink Glyceryl amine type epoxy resin)；" ZX1059 " (bisphenol A type epoxy resin and Bisphenol F type ring of aurification corporation is lived by Nippon Steel The melange of oxygen resin)；" EX-721 " (the glycidyl esters type epoxy resin) of Nagase ChemteX corporation；Daicel " CELLOXIDE 2021P " (cycloaliphatic epoxy resin with ester skeleton) of corporation；" PB-3600 " of Daicel corporation (epoxy resin with butadiene structure)；" ZX1658 " of aurification corporation, " ZX1658GS " (liquid 1,4- live in Nippon Steel Glycidol butylcyclohexane type ring oxygen resin) etc..These can be used alone a kind, two or more can also be applied in combination.

As solid epoxy resin, with the solid epoxy resin of 3 or more epoxy groups preferably in 1 molecule, more preferably With the aromatics system solid epoxy resin of 3 or more epoxy groups in 1 molecule.

As solid epoxy resin, preferably union II first phenol-type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional asphalt mixtures modified by epoxy resin Rouge, cresol novolak type epoxy resin, dicyclopentadiene-type epoxy resin, tris phenol type epoxy, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthylene ether type epoxy, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, Tetraphenyl ethane type epoxy resin；More preferable union II first phenol-type epoxy resin, naphthalene type epoxy resin, bisphenol AF type epoxy resin, And naphthylene ether type epoxy.

As the concrete example of solid epoxy resin, can enumerate：" HP4032H " (naphthalene type epoxy resin) of DIC corporation； " HP-4700 ", " HP-4710 " (the naphthalene type tetrafunctional epoxy resin) of DIC corporation；" N-690 " (cresols phenol of DIC corporation Aldehyde type epoxy resin)；" N-695 " (the cresol novolak type epoxy resin) of DIC corporation；" HP-7200 " (two of DIC corporation Cyclopeutadiene type epoxy resin)；" HP-7200HH ", " HP-7200H ", " EXA-7311 ", " EXA-7311- of DIC corporation G3 ", " EXA-7311-G4 ", " EXA-7311-G4S ", " HP6000 " (naphthylene ether type epoxy)；Japanese chemical drug corporation " EPPN-502H " (tris phenol type epoxy)；" NC7000L " (the naphthol novolac type epoxy resin) of Japanese chemical drug corporation； " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin) of Japanese chemical drug corporation；Nippon Steel Firmly " ESN475V " (naphthalene type epoxy resin) of aurification corporation；" ESN485 " (naphthols phenol of aurification corporation is lived by Nippon Steel Aldehyde type epoxy resin)；" YX4000H ", " YX4000 ", " YL6121 " (biphenyl type epoxy resin) of Mitsubishi Chemical Ind；Three " YX4000HK " (the union II first phenol-type epoxy resin) of water chestnut chemical company；" YX8800 " (anthracene type ring of Mitsubishi Chemical Ind Oxygen resin)；" PG-100 ", " CG-500 " of Osaka combustion gas chemistry corporation；" YL7760 " (bisphenol AF of Mitsubishi Chemical Ind Type epoxy resin)；" YL7800 " (the fluorenes type epoxy resin) of Mitsubishi Chemical Ind；" jER1010 " of Mitsubishi Chemical Ind (solid-state bisphenol A type epoxy resin resin)；" jER1031S " (the tetraphenyl ethane type epoxy resin) of Mitsubishi Chemical Ind etc..These It can be used alone a kind, two or more can also be applied in combination.

In the case where using liquid-state epoxy resin and solid epoxy resin as (A) epoxy composite, their amount ratio (liquid-state epoxy resin：Solid epoxy resin) it is by quality ratio preferably 1：1~1：20, it is more preferably 1：2~1：15, especially excellent It is selected as 1：5~1：13.Amount ratio by making liquid-state epoxy resin and solid epoxy resin within the above range, can significantly obtain this Invent desired effect.In turn, usually in the form of resin sheet in use, appropriate adherence can be brought.In addition, logical Often, in use, obtaining adequately flexible, operability improves in the form of resin sheet.In turn, being commonly available has sufficiently Breaking strength solidfied material.

(A) epoxide equivalent of epoxy resin be preferably 50~5000, more preferably 50~3000 and then preferably 80~ And then more preferably 110~1,000 2000,.By making epoxide equivalent in the range, the solidfied material of resin composition layer can be made Crosslink density become sufficiently, the insulating layer that surface roughness can be brought small.Epoxide equivalent refers to the tree comprising 1 equivalent epoxy group The quality of rouge.The epoxide equivalent can be measured according to JIS K7236.

From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of (A) epoxy resin is excellent It is selected as 100~5000, more preferably 250~3000 and then preferably 400~1500.

The weight average molecular weight of resin can utilize gel permeation chromatography (GPC) method, come as the value by weight of polystyrene Measurement.

From the viewpoint of the insulating layer for obtaining showing good mechanical strength, insulating reliability, relative to resin combination 100 mass % of resin component in object, the amount of (A) epoxy resin in resin combination are preferably 10 mass % or more, more preferably For 20 mass % or more and then preferably 30 mass % or more.From the viewpoint of significantly obtaining the desired effect of the present invention, ring The upper limit of the content of oxygen resin be preferably 90 mass % or less, more preferably 85 mass % or less, particularly preferably 80 mass % with Under.

[3. (B) ingredients：Aromatic resins containing aromatic ring, the aromatic ring are conduct monocycle or condensed ring with 2 or more hydroxyls Aromatic ring]

In resin combination, as (B) ingredient, comprising the aromatic resins containing aromatic ring, which has 2 or more hydroxyls.It is logical Often, (B) ingredient can be reacted by hydroxyl possessed by aromatic ring with (A) epoxy resin, thus (B) ingredient can be used as makes resin combination The curing agent of solidification works.Then, due to the effect of (B) ingredient, halo phenomenon can be inhibited.

Here, term " aromatic ring " includes the aromatic ring of the monocyclic form as phenyl ring and the condensed ring shape as naphthalene nucleus The aromatic ring of formula it is any.From the viewpoint of significantly obtaining the desired effect of the present invention, (B) ingredient included every 1 The carbon atom number of aforementioned aromatic ring is preferably 6 or more, and preferably 14 or less, more preferably 10 or less.

As the example of aromatic ring, can enumerate：Phenyl ring, naphthalene nucleus, anthracene nucleus etc..In addition, aromatic ring contained in every 1 molecule of aromatic resins Type can be a kind, be also possible to two or more.

At least one in aromatic ring contained by aromatic resins as (B) ingredient is that every 1 aromatic ring is with 2 or more Hydroxyl.From the viewpoint of significantly obtaining the desired effect of the present invention, the number of the hydroxyl of every 1 aromatic ring be preferably 3 with Under, particularly preferably 2.

(B) number of the aromatic ring with 2 or more hydroxyls of every 1 molecule of ingredient is usually 1 or more, from significantly obtaining From the viewpoint of the desired effect of the present invention, preferably 2 or more, more preferably 3 or more.The upper limit is not limited especially System, from inhibit steric hindrance and from the viewpoint of improving the reactivity with epoxy resin, preferably 6 or less, be more preferably 5 Below.

As the example of suitable (B) ingredient, the aromatic resins indicated by following formula (1) can be enumerated and by following formula (2) The aromatic resins of expression；

。

In formula (1), R⁰Each independently represent the alkyl of divalent.The alkyl of divalent can be aliphatic hydrocarbyl, be also possible to virtue Alkyl can also be group made of combination aliphatic hydrocarbyl and aryl.The carbon atom number of the alkyl of divalent is usually 1 or more, from It is preferably 3 or more, 6 or more or 7 or more from the viewpoint of the desired effect of the significant acquisition present invention.This is obtained from significant From the viewpoint of inventing desired effect, the upper limit of aforementioned carbon atom number is preferably 20 or less, 15 or less or 10 or less.

As R⁰Concrete example, following alkyl can be enumerated；

。

In formula (1), n1 indicates 0 or more and 6 integers below.Wherein, from significantly obtaining the desired effect of the present invention Viewpoint considers that n1 is preferably 1 or more, more preferably 2 or more, preferably 4 or less, more preferably 3 or less.

If can particularly effectively inhibit halo phenomenon using the aromatic resins indicated by formula (1).

In formula (2), R¹~R⁴Each independently represent the alkyl of hydrogen atom or 1 valence.The alkyl of 1 valence can be aliphatic hydrocarbyl, It is also possible to aryl, can also be group made of combination aliphatic hydrocarbyl and aryl.Wherein, from significantly obtaining institute of the present invention From the viewpoint of desired effect, preferred aliphatic series alkyl, more preferable radical of saturated aliphatic alkyl, particularly preferred chain saturated aliphatic hydrocarbon Base.The carbon atom number of the alkyl of 1 valence is usually 1 or more, from the viewpoint of significantly obtaining the desired effect of the present invention, preferably It is 20 or less, more preferably 15 or less, 10 or less or 8 or less.As R¹~R⁴Preference, can enumerate：Hydrogen atom；Methyl, second The alkyl such as base, propyl, butyl, hexyl.If can particularly effectively be inhibited by coarse using the aromatic resins indicated by formula (2) The removing in haloing portion caused by erosion when changing processing.

Wherein, as the particularly preferred aromatic resins of (B) ingredient, can enumerate by following formula (3) indicate aromatic resins, with And the aromatic resins indicated by following formula (4).In formula (3), n2 indicates the integer defined same as the n1 of formula (1), preferred model It encloses also the same.In addition, R in formula (4)¹~R⁴With the R in formula (2)¹~R⁴Meaning is identical；

。

As the commercially available product of the aromatic resins indicated by formula (3), such as it can enumerate and be lived by the Nippon Steel that following formula (5) indicate The naphthols system curing agent " SN395 " of aurification corporation.In formula (5), n3 indicates 2 or 3.In addition, as the virtue indicated by formula (4) The commercially available product of hydrocarbon resin, such as can enumerate the phenol (phenol) of Qun Rong chemical industrial company is curing agent " GRA13H "；

。

Aromatic resins as (B) ingredient can be used alone a kind, two or more can also be applied in combination.

This hair is obtained as the viewpoint of the crosslink density of the insulating layer of resin composition layer solidfied material and significantly from raising From the viewpoint of bright desired effect, the hydroxyl equivalent of (B) ingredient be preferably 50g/eq or more, more preferably 60g/eq with Upper and then preferably 70g/eq or more, and preferably 200g/eq or less, more preferably 150g/eq or less, particularly preferably 120g/eq or less.Hydroxyl equivalent refers to the quality of the resin comprising 1 equivalent of hydroxyl groups.

Relative to the 100 mass % of resin component in resin combination, the amount of (B) ingredient in resin combination is preferably 5 Quality % or more, more preferably 7 mass % or more, particularly preferably 9 mass % or more, preferably 50 mass % or less, are more preferably 40 mass % or less, 30 mass % or less or 20 mass % or less.By making the amount of (B) ingredient in aforementioned range, can effectively press down Halo phenomenon processed.

Relative to 100 mass % of (A) epoxy resin, the amount of (B) ingredient is preferably 5 mass % or more, more preferably 8 mass % Above, 10 mass % or more are particularly preferably, preferably 100 mass % or less, more preferably 50 mass % or less, are particularly preferably 30 mass % or less.By making the amount of (B) ingredient in aforementioned range, halo phenomenon can be effectively inhibited.

When the epoxy radix of (A) epoxy resin is set as 1, the hydroxyl value of (B) ingredient is preferably 0.1 or more, is more preferably 0.2 or more, so preferably 0.3 or more, preferably 2 or less, more preferably 1.5 or less, and then preferably 1 or less, it is especially excellent It is selected as 0.5 or less.Here, " the epoxy radix of (A) epoxy resin " refers to, will use (A) ingredient present in resin combination Nonvolatile component quality all amounts to resulting value divided by value obtained by epoxide equivalent.In addition, " hydroxyl value of (B) ingredient " is Refer to, will all be amounted to the nonvolatile component quality of (B) ingredient present in resin combination divided by value obtained by hydroxyl equivalent Resulting value.The hydroxyl value of (B) ingredient when the epoxy radix by making (A) epoxy resin is set as 1 can have in aforementioned range Effect ground inhibits halo phenomenon.

[4. (C) ingredients：With 100nm average grain diameter below and 15m²At least one of the specific surface area of/g or more Inorganic filling material]

It include inorganic filling material as (C) ingredient in resin combination.Using inorganic filling material, resin combination can be reduced The thermal expansion coefficient of the solidfied material of nitride layer, therefore can get the repressed insulating layer of Reflow Soldering warpage.In addition, as (C) ingredient Inorganic filling material have 100nm average grain diameter below and 15m²At least one of the specific surface area of/g or more.As nothing Machine packing material, by that will have (C) ingredient of at least one of the average grain diameter of above range and specific surface area and (B) ingredient It is applied in combination, can be realized the insulating layer that can form the through-hole of excellent in shape.

As the material of inorganic filling material, inorganic compound is used.The example of material as inorganic filling material, can It enumerates：Silica, aluminium oxide, glass, cordierite, Si oxide, barium sulfate, barium carbonate, talcum, clay, mica powder, oxidation Zinc, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, Aluminium borate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, zirconium oxide, barium titanate, metatitanic acid barium zirconate, zirconium Sour barium, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc..Among these, silica is especially suitable.As silica, example It can such as enumerate：Amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica Deng.In addition, as silica, preferred spherical silicon dioxide.Inorganic filling material can be used alone a kind, and can also combine makes Use two or more.

From the viewpoint and controllable shape of through holes that make insulating layer thin layer and from the viewpoint of realizing excellent in shape, (C) The average grain diameter of ingredient is usually 100nm or less, preferably 90nm or less, more preferably 80nm or less.Under the average grain diameter Limit is not particularly limited, preferably 50nm or more, 60nm or more or 70nm or more.As with the inorganic of above-mentioned average grain diameter The commercially available product of packing material, such as Denki Kagaku Kogyo kabushiki's system " UFP-30 ", " UFP-40 " etc. can be enumerated.

The average grain diameter of inorganic filling material can by laser diffraction-scattering method based on Michaelis (Mie) scattering theory come Measurement.Specifically, being made inorganic filling material using laser diffraction and scattering formula particle size distribution analyzer with volume reference Particle diameter distribution be thus measured using its median particle diameter as average grain diameter.Measurement sample, which preferably uses, utilizes ultrasonic wave Sample made of dispersing inorganic filling material in methyl ethyl ketone.It is filled as laser diffraction and scattering formula particle size distribution measuring It sets, Ku Chang manufacturing company system " LA-500 ", Shimadzu Seisakusho Ltd.'s corporation " SALD-2200 " etc. can be used.

From the viewpoint of being easy to control shape of through holes and realizing excellent in shape, the specific surface area of (C) ingredient is usually 15m²/ g or more, preferably 20m²/ g or more, particularly preferably 30m²/ g or more.In addition, biggish for such specific surface area (C) for ingredient, usual partial size is smaller, therefore can make insulating layer thin layer.The upper limit is not particularly limited, preferably 60m²/ g or less, 50m²/ g or less or 40m²/ g or less.The specific surface area of inorganic filling material can be measured by BET method.

From the viewpoint of improving moisture-proof and dispersibility, the inorganic filling material as (C) ingredient is preferably at surface Reason agent is handled.As surface treating agent, such as can enumerate：Fluorine-containing silane coupling agent, amino silicone methane series coupling agent, ring Oxysilane system coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, alkoxy silane, organic silazane hydride compounds, titanium Acid esters system coupling agent etc..In addition, surface treating agent can be used alone a kind, two or more can also be used in any combination.

As the commercially available product of surface treating agent, such as can enumerate：Chemical industrial company of SHIN-ETSU HANTOTAI system " KBM403 " (3- epoxy third Oxygroup propyl trimethoxy silicane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM803 " (3-mercaptopropyi trimethoxy silane), SHIN-ETSU HANTOTAI Chemical industrial company's system " KBE903 " (3-aminopropyltriethoxysilane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM573 " (N- Phenyl -3- TSL 8330), chemical industrial company of SHIN-ETSU HANTOTAI system " SZ-31 " (hexamethyldisilazane), SHIN-ETSU HANTOTAI Learn industrial group's system " KBM103 " (phenyltrimethoxysila,e), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM-4803 " (long-chain epoxy Fundamental mode silane coupling agent), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM-7103 " (3,3,3- trifluoro propyl trimethoxy silane) etc..

From the viewpoint of the dispersibility for improving inorganic filling material, the journey for the surface treatment that surface treating agent carries out is utilized Degree is preferably in fixed range.Specifically, for 100 mass parts of inorganic filling material, preferably with 0.2 mass parts~5 The surface treating agent of mass parts is surface-treated, and is preferably surface-treated with 0.2 mass parts~3 mass parts, preferably with 0.3 Mass parts~2 mass parts are surface-treated.

The degree of the surface treatment carried out using surface treating agent can pass through the per unit surface area of inorganic filling material Carbon amounts is evaluated.From the viewpoint of the dispersibility for improving inorganic filling material, the per unit surface area of inorganic filling material Carbon amounts be preferably 0.02mg/m²Above, it is more preferably 0.1mg/m²And then preferably 0.2mg/m above,²More than.Another party Face, from the viewpoint of the rising of the melt viscosity under the melt viscosity and sheet form for inhibiting resin varnish, preferably 1mg/m²Below, it is more preferably 0.8mg/m²And then preferably 0.5mg/m below,²Below.

It, can be by the inorganic filling material after surface treatment for the carbon amounts of the per unit surface area of inorganic filling material It is measured after carrying out carrying out washing treatment with solvent (for example, methyl ethyl ketone (MEK)).Specifically, can be with surface treating agent Enough MEK are added in the inorganic filling material being surface-treated as solvent, are washed in 25 DEG C of progress, 5 minutes ultrasonic waves It washs.Supernatant is removed, after keeping solid component dry, the per unit surface area of inorganic filling material is measured using carbon analysis meter Carbon amounts.As carbon analysis meter, Ku Chang manufacturing company system " EMIA-320V " etc. can be used.

From the viewpoint of the dielectric loss angle tangent for reducing insulating layer, relative to the nonvolatile component in resin combination 100 mass %, the amount of (C) ingredient in resin combination are preferably 30 mass % or more, more preferably 35 mass % or more, in turn Preferably 40 mass % or more.In addition, being in the past thin layer in the resin composition layer containing this large amount of inorganic filling material In the case of, it is difficult to the through-hole of excellent in shape is formed, particularly, if relative to 100 matter of nonvolatile component in resin combination % is measured, it is especially difficult for forming the through-hole of excellent in shape when the amount of inorganic filling material is 50 mass % or more.Therefore, From effectively with the through-hole that can form excellent in shape（This is previous especially difficult thing as described above）Such present invention From the perspective of advantage, relative to the 100 mass % of nonvolatile component in resin combination, the amount of (C) ingredient is preferably 50 matter Measure % or more, particularly preferably 54 mass % or more.From the viewpoint of the mechanical strength for improving insulating layer, relative to resin combination 100 mass % of nonvolatile component in object, the upper limit of the amount of (C) ingredient be preferably 90 mass % or less, more preferably 85 mass % with Under, and then preferably 80 mass % or less or 75 mass % or less.

[5. (D) ingredients：Thermoplastic resin]

In resin combination, other than containing mentioned component, as arbitrary ingredient, it can also contain (D) thermoplastic resin in turn Rouge.

As the thermoplastic resin of (D) ingredient, such as can enumerate：Phenoxy resin, polyvinyl acetal resin, polyolefin Resin, polybutadiene, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethers Sulphone resin, polyphenylene oxide resin, polycarbonate resin, polyether-ether-ketone resin, polyester resin etc..Wherein, the present invention is obtained from significant The viewpoint of desired effect and the sight for obtaining the especially excellent insulating layer of the small and adaptation with conductor layer of surface roughness Point consideration, preferably phenoxy resin.In addition, thermoplastic resin can be used alone a kind, or it can be used in combination two or more.

As phenoxy resin, such as it can enumerate to have and be selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol benzene Ethyl ketone skeleton, phenolic aldehyde skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, enb skeleton, naphthalene skeleton, anthracene skeleton, The phenoxy resin of the skeleton of one or more of adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton.Phenoxy group The end of resin can be any functional group of phenolic hydroxyl, epoxy group etc..

As the concrete example of phenoxy resin, can enumerate：" 1256 " and " 4250 " of Mitsubishi Chemical Ind (are to contain There is the phenoxy resin of bisphenol A skeleton)；" YX8100 " (phenoxy resin containing bisphenol S skeleton) of Mitsubishi Chemical Ind； " YX6954 " (phenoxy resin containing bis-phenol acetophenone skeleton) of Mitsubishi Chemical Ind；Aurification corporation is lived by Nippon Steel " FX280 " and " FX293 "；" YL7500BH30 " of Mitsubishi Chemical Ind, " YX6954BH30 ", " YX7553 ", " YX7553BH30 ", " YL7769BH30 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 "；Deng.

As polyvinyl acetal resin, such as vinyl-formal resin, polyvinyl butyral resin can be enumerated, It is preferred that polyvinyl butyral resin.As the concrete example of polyvinyl acetal resin, Denki Kagaku Kogyo kabushiki's system can be enumerated " Denka Butyral 4000-2 ", " Denka Butyral 5000-A ", " Denka Butyral 6000-C ", " Denka Butyral 6000-EP"；S-LEC BH series, BX serial (such as BX-5Z), the serial (example of KS of ponding chemical industrial company Such as KS-1), BL series, BM series；Deng.

As the concrete example of polyimide resin, can enumerate new Japan Chemical corporation " RIKACOAT SN20 " and "RIKACOAT PN20".As the concrete example of polyimide resin, can also enumerate by two functional hydroxyl groups end polybutadiene, Linear polyimides obtained by diisocyanate cpd and quaternary anhydride reaction (record by Japanese Unexamined Patent Publication 2006-37083 bulletin Polyimides), polyimides (Japanese Unexamined Patent Publication 2002-12667 bulletin and Japanese Unexamined Patent Publication containing silicone matrix The polyimides recorded in 2000-319386 bulletin etc.) etc. modified polyimides.

As the concrete example of polyamide-imide resin, can enumerate Dongyang spinning company " VYLOMAX HR11NN " and "VYLOMAX HR16NN".As the concrete example of polyamide-imide resin, Hitachi's chemical conversion corporation can be also enumerated The modified polyamide imides such as " KS9100 ", " KS9300 " (polyamidoimide containing silicone matrix).

As the concrete example of polyethersulfone resin, " PES5003P " of sumitomo chemical company etc. can be enumerated.

As the concrete example of polyphenylene oxide resin, oligomeric phenylate-styrene resin of gas chemical company of Mitsubishi can be enumerated " OPE-2St 1200 " etc..

As the concrete example of polysulfone resin, the polysulfones of Solvay Advanced Polymers corporation can be enumerated " P1700 ", " P3500 " etc..

From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of (D) thermoplastic resin Preferably 8,000 or more, it is more preferably 10,000 or more, 20,000 or more, preferably 70,000 or less is particularly preferably, is more excellent It is selected as 60,000 or less, particularly preferably 50,000 or less.

In the case where use (D) thermoplastic resin, for the amount of (D) thermoplastic resin in resin combination, From the viewpoint of significantly obtaining the desired effect of the present invention, relative to the 100 mass % of resin component in resin combination, Preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and then preferably 1 mass % or more, preferably 15 mass % with Under, more preferably 12 mass % or less, and then preferably 10 mass % or less.

[6. (E) ingredients：Curing agent]

It, can also be in turn containing in addition to (B) ingredient as arbitrary ingredient in resin combination other than containing mentioned component (E) curing agent.

As the curing agent of (E) ingredient, can be used with the substance for making the cured effect of (A) ingredient.Solidify as (E) Agent, such as can enumerate：Active ester system curing agent, phenol (phenol) are curing agent, naphthols system curing agent, the solidification of benzoxazine system Agent, cyanate system curing agent and carbodiimide system curing agent etc..In addition, curing agent can be used alone a kind, or can and with 2 kinds More than.Wherein, from the viewpoint of significantly obtaining the desired effect of the present invention, preferred active ester system curing agent.

As active ester system curing agent, it may be used at the compound in 1 molecule with 1 or more active ester groups.Wherein, As active ester system curing agent, preferably phenolic ester (phenol ester) class, benzenethiol ester (thiophenol ester) class, N- hydroxyl The compound with the high ester group of 2 or more reactivities in 1 molecule such as base amine esters, esters of heterocycle hydroxyl compound. The active ester system curing agent preferably passes through carboxylic acid compound and/or thiocarboxylic acid compound and hydroxy compounds and/or Thiolation It closes the condensation reaction of object and obtains.It, preferably can be by carboxylic acid compound and hydroxyl especially from the viewpoint of improving heat resistance The active ester system curing agent that compound obtains, more preferably can be by carboxylic acid compound and phenol (phenol) compound and/or naphthalene The active ester system curing agent that phenolic compounds obtains.

As carboxylic acid compound, it can be mentioned, for example benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc..

As oxybenzene compound or naphthol compound, such as can enumerate：Hydroquinone, resorcinol, bisphenol-A, Bisphenol F, Bisphenol S, phenolphthalin, methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, youngster Tea phenol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, three hydroxyls Base benzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type bisphenol compounds, phenol novolac tree Rouge (phenol novolac) etc..So-called herein " dicyclopentadiene-type bisphenol compounds " refer in 1 molecule bicyclopentadiene Bisphenol compounds obtained from 2 molecule phenol of upper condensation.

As the preferred concrete example of active ester system curing agent, can enumerate：Work comprising dicyclopentadiene-type biphenol structure Property ester compounds, the active ester compound comprising naphthalene structure, the acetylate comprising phenol novolacs active ester compound, The active ester compound of benzoylate comprising phenol novolacs.Wherein, more preferably active esterifying comprising naphthalene structure Close object, the active ester compound comprising dicyclopentadiene-type biphenol structure.So-called " dicyclopentadiene-type biphenol structure " table Show the structural unit of the divalent formed by-two cyclopentylene of phenylene (dicyclopentylene)-phenylene.

As the commercially available product of active ester system curing agent, the active ester compound comprising dicyclopentadiene-type biphenol structure can Enumerate " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-65T ", " HPC-8000H-65TM ", " EXB- 8000L-65TM ", " EXB-8150-65T " (DIC corporation)；Active ester compound comprising naphthalene structure can enumerate " EXB9416- 70BK " (DIC corporation)；The active ester compound of acetylate comprising phenol novolacs can enumerate " DC808 " (Mitsubishi Learn corporation)；The active ester compound of benzoylate comprising phenol novolacs can enumerate " YLH1026 " (Mitsubishi Chemical Corporation)；The active ester system curing agent of acetylate as phenol novolacs can enumerate " DC808 " (Mitsubishi Chemical Ind System)；The active ester system curing agent of benzoylate as phenol novolacs can enumerate " YLH1026 " (Mitsubishi Chemical Ind System), " YLH1030 " (Mitsubishi Chemical Ind's system), " YLH1048 " (Mitsubishi Chemical Ind's system)；Deng.

As phenol system curing agent and naphthols system curing agent, from the viewpoint of heat resistance and water resistance, preferably there is phenol The curing agent of aldehyde (novolac) structure.In addition, from the viewpoint of the adaptation with conductor layer, preferably nitrogenous phenol system solidification Agent, more preferably the phenol system curing agent of the skeleton containing triazine.

As the concrete example of phenol system curing agent and naphthols system curing agent, such as can enumerate：It is bright and chemical conversion corporation "MEH-7700","MEH-7810","MEH-7851"；" NHN ", " CBN ", " GPH " of Japanese chemical drug corporation；Gold is lived by Nippon Steel " SN170 ", " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495 ", " SN-495V " " SN375 " of chemical company； " TD-2090 ", " LA-7052 ", " LA-7054 ", " LA-1356 ", " LA-3018-50P ", " EXB-9500 " of DIC corporation； Deng.

As the concrete example of benzoxazine system curing agent, " HFB2006M ", the four countries of Showa high score subsidiary system can be enumerated " P-d ", " F-a " of chemical conversion industry corporation.

As cyanate system curing agent, such as can enumerate：Bisphenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene- 1,5- phenylenecyanate), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- 3,5-dimethylphenyl cyanate), 4,4 '-ethylene phenyl, two cyanic acid It is bis- (the 4- cyanic acid ester group) phenyl-propanes of ester, hexafluoro bisphenol-a dicyanate, 2,2-, 1,1- bis- (4- cyanatephenyl methane), double (4- cyanic acid ester group -3,5- 3,5-dimethylphenyl) methane, 1,3- bis- (4- cyanatephenyl -1- (methyl ethylidene)) benzene, bis- (4- Cyanatephenyl) the two function cyanate ester resins such as thioether and bis- (4- cyanatephenyl) ethers；By phenol novolacs and Multifunctional cyanate ester resin derived from cresol novolac resin etc.；These cyanate ester resins carry out pre-polymerization obtained from the triazine of part Object；Deng.As the concrete example of cyanate system curing agent, " PT30 " and " PT60 " (phenol of Lonza Japan corporation can be enumerated Phenol aldehyde type multifunctional cyanate ester resin), " ULL-950S " (multifunctional cyanate ester resin), " BA230 ", " BA230S75 " (bisphenol-A Part or all of dicyanate carries out triazine and forms the prepolymer of tripolymer) etc..

As the concrete example of carbodiimide system curing agent, chemical (Nisshinbo Chemical) company of Nisshinbo can be enumerated " V-03 ", " V-07 " etc. of system.

In the case where use (E) curing agent, for the amount of (E) curing agent in resin combination, from significantly obtaining From the viewpoint of desired effect of the invention, relative to the resin component 100 mass % in resin combination, preferably 0.1 Quality % or more, more preferably 0.5 mass % or more, and then preferably 1 mass % or more, preferably 20 mass % or less, more preferably For 15 mass % or less and then preferably 12 mass % or less.

In addition, in the case where use (E) curing agent, for the amount of (E) curing agent in resin combination, from aobvious It writes from the viewpoint of obtaining the desired effect of the present invention, relative to 100 mass % of (B) ingredient, preferably 40 mass % or more, more Preferably 50 mass % or more, particularly preferably 60 mass % or more, preferably 120 mass % or less, more preferably 100 mass % with Under, particularly preferably 90 mass % or less.

In turn, when the epoxy radix of (A) epoxy resin being set as 1, the active radix of (E) ingredient is preferably 0.1 or more, more Preferably 0.2 or more, preferably 2 or less, it is more preferably 1.5 or less and then preferably 1 or less, particularly preferably 0.5 or less. Here, " the active radix of (E) ingredient " refers to, the nonvolatile component quality of (E) ingredient present in resin combination is removed Resulting value is all amounted to value obtained by active group equivalent.When being set as 1 by making the epoxy radix by (A) epoxy resin (E) the active radix of ingredient is in aforementioned range, to can get the especially excellent insulating layer of mechanical strength.

[7. (F) ingredients：Curing accelerator]

In resin combination other than containing mentioned component, as arbitrary ingredient, (F) curing accelerator can be contained in turn.

As curing accelerator, such as can enumerate：Phosphorus system curing accelerator, amine system curing accelerator, the solidification of imidazoles system promote Into agent, guanidine system curing accelerator, metal system curing accelerator etc..Wherein, preferably phosphorus system curing accelerator, amine system solidification promote Agent, imidazoles system curing accelerator, metal system curing accelerator, more preferable amine system curing accelerator, imidazoles system curing accelerator, gold Category system curing accelerator.Curing accelerator can be used alone a kind, also can be used in combination two or more.

As phosphorus system curing accelerator, such as can enumerate：Triphenylphosphine, Phosphonium borate compound, tetraphenylphosphoniphenolate tetraphenyl Borate, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyl) triphenyl phosphonium rhodanate, four benzene Ji Phosphonium rhodanate, Ding base triphenyl phosphonium rhodanate etc., triphenylphosphine, 4-butyl-phosphonium caprate.

As amine system curing accelerator, such as can enumerate：The trialkylamines such as triethylamine, tri-butylamine, 4- dimethylamino Yl pyridines, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol, (5,4,0)-ten one carbon of 1,8- diazabicyclo Alkene etc., preferably 4-dimethylaminopyridine, 1,8- diazabicyclo (5,4,0)-endecatylene.

As imidazoles system curing accelerator, such as can enumerate：2-methylimidazole, 2- undecyl imidazole, 2- heptadecyl Imidazoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl Imidazoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2- methyl Imidazoles, 1- cyano ethyl -2- undecyl imidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenyl Imidazoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acid salt, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt, 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-undecyl imidazoles Base-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2, 4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid Addition product, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole, 2,3- dihydro -1H- pyrrole Cough up simultaneously [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2- phenyl The adduct of the imidazolium compounds such as imidazoline and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- benzyl Base -2- phenylimidazole.

As imidazoles system curing accelerator, commercially available product can be used, such as " the P200- of Mitsubishi Chemical Ind can be enumerated H50 " etc..

As guanidine system curing accelerator, such as can enumerate：Dicyandiamide, 1- methylguanidine, 1- ethyl guanidine, 1- cyclohexyl guanidine, 1- Guanidines, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethylguanidine, pentamethyl guanidine, tri- nitrogen of 1,5,7- Miscellaneous bicyclic [4.4.0] decyl- 5- alkene, 7- methyl-1, tri- azabicyclo of 5,7- [4.4.0] decyl- 5- alkene, 1- methyl biguanides, 1- ethyl Biguanides, 1- normal-butyl biguanides, 1- n-octadecane base biguanides, 1,1- dimethylbiguanide, 1,1- diethyl biguanides, 1- cyclohexyl are double Guanidine, 1- allyl biguanides, 1- phenyl biguanide, 1- (o-tolyl) biguanides etc., preferably dicyandiamide, 1,5,7- tri- azabicyclos [4.4.0] decyl- 5- alkene.

As metal system curing accelerator, such as the organic metal network of the metals such as cobalt, copper, zinc, iron, nickel, manganese, tin can be enumerated Close object or organic metal salt.As the concrete example of metal-organic complex, acetylacetone cobalt (II), acetylacetone cobalt can be enumerated (III) the organic zincs complexing such as organic copper complex, zinc acetylacetonate (II) such as organic cobalt complex, acetylacetone copper (II) such as Organic nickel complexes such as the Organic-iron complexes such as object, ferric acetyl acetonade (III), nickel acetylacetonate (II), manganese acetylacetonate (II) Etc. organic manganese complex etc..As organic metal salt, such as zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, hard can be enumerated Resin acid tin, zinc stearate etc..

In the case where use (F) curing accelerator, for the amount of (F) curing accelerator in resin combination, It is excellent relative to the resin component 100 mass % of resin combination from the viewpoint of significantly obtaining the desired effect of the present invention Be selected as 0.01 mass % or more, more preferably 0.05 mass % or more, and then preferably 0.1 mass % or more, preferably 3 mass % with Under, more preferably 2 mass % or less, and then preferably 1.5 mass % or less.

[8. (G) ingredients：Arbitrary additive]

In resin combination other than containing mentioned component, as arbitrary ingredient, arbitrary additive can be contained in turn. As above-mentioned additive, such as can enumerate：Organic filler material；Organocopper compound, organic zinc compound and organic cobalt Close the organo-metallic compounds such as object；The resins such as fire retardant, thickener, defoaming agent, levelling agent, adaptation imparting agent, colorant add Add agent；Deng.These additives can be used alone a kind, two or more can also be applied in combination.

[thickness of 9. resin composition layers]

Resin composition layer is the layer formed by above-mentioned resin combination, has institute's definite value thickness below.Resin combination The specific thickness of layer is usually 15 μm or less, preferably 14 μm or less and then preferably 12 μm or less.In the past, printed wiring board Insulating layer formation resin composition layer thickness it is usually thicker than above-mentioned thickness.In contrast, the present inventor will lead to When thin layer as described above is made in the resin composition layer often formed, find in such relatively thin resin composition layer, Following project can be generated, i.e. previous unknown project as the shape of generation halo phenomenon and uncontrollable through-hole.From solution Certainly such new issue simultaneously facilitates from the viewpoint of the filming of printed wiring board, and resin composition layer of the invention is set For thin layer as the aforementioned.The lower limit of the thickness of resin composition layer is arbitrary, and may be, for example, 1 μm or more, 3 μm or more.

[characteristics of 10. resin composition layers]

By solidifying resin composition layer of the invention, can get formed by the solidfied material of resin composition layer it is relatively thin exhausted Edge layer.The through-hole of excellent in shape can be formed on the insulating layer.In addition, it is existing to can inhibit haloing when forming through-hole on which insulating layer As.These effects are illustrated referring to the drawings.

Fig. 1 is to schematically show insulating layer obtained by making the resin composition layer solidification of first embodiment of the invention 100 and internal substrate 200 cross-sectional view.Shown in the Fig. 1, the center 120C by the bottom 120 of through-hole 110 and with In the parallel plane of the thickness direction of insulating layer 100, section made of insulating layer 100 is truncated.

As shown in Figure 1, the insulating layer 100 of first embodiment of the invention is, in the internal substrate comprising conductor layer 210 What is formed on 200 makes layer obtained by resin composition layer solidification, is formed by the solidfied material of aforementioned resin layer.In addition, Through-hole 110 is formed on insulating layer 100.For through-hole 110, be usually formed following shape, i.e., closer to 210 phase of conductor layer The face 100U of the insulating layer 100 of anti-side then diameter it is bigger, closer to the then smaller positive cone (Cis テー of diameter of conductor layer 210 パ shape), it is generally desirable to it is formed in the column on the thickness direction of insulating layer 100 with constant diameter.The through-hole 110 is usually such as Lower formation：Laser is irradiated on the face 100U of the insulating layer 100 with 210 opposite side of conductor layer, removes one of insulating layer 100 Point.

The bottom of 210 side of conductor layer of aforementioned through-hole 110 is properly termed as " via bottoms ", is indicated with symbol 120.In It is that the diameter of the via bottoms 120 is known as base diameter Lb.In addition, by through-hole 110 with conductor layer 210 opposite side The opening of formation is properly termed as " via top ", is indicated with symbol 130.Then, the diameter of the via top 130 is known as top Diameter Lt.In general, via bottoms 120 and via top 130 are formed as the flat shape from the thickness direction of insulating layer 100 It is circle but it is also possible to be ellipse.In the case that the flat shape of via bottoms 120 and via top 130 is ellipse, Base diameter Lb and top diameter Lt respectively indicates the major diameter of aforementioned ellipse.

At this moment, with base diameter Lb divided by the resulting taper ratio Lb/Lt (%) of top diameter Lt about close to 100%, then should The shape of through-hole 110 is better.If can easily control the shape of through-hole 110, therefore using resin composition layer of the invention Taper ratio Lb/Lt can be achieved close to 100% through-hole 110.

For example, in mask diameters 1mm, 16 μ s of pulsewidth, energy 0.2mJ/ transmitting (shot), transmitting number 2, group schema Under conditions of (burst mode) (10kHz), for resin composition layer to be heated to 30 minutes in 100 DEG C, then in 180 DEG C plus Insulating layer 100 obtained by heat solidifies it irradiates CO₂Laser forms the through-hole that top diameter Lt is 30 μm ± 2 μm 110, in this case, the taper ratio Lb/Lt of the through-hole 110 is formed as preferably 60%~100%, it is more preferable 70%~100%, Particularly preferred 80%~100%.

The taper ratio Lb/Lt of through-hole 110 can be calculated by the base diameter Lb and top diameter Lt of through-hole 110.In addition, The base diameter Lb and top diameter Lt of through-hole 110 can be measured in the following way, that is, FIB (focused ion beam) be used, to exhausted Edge layer 100 is cut so as to show center that is parallel with the thickness direction of the insulating layer 100 and passing through via bottoms 120 Thus the section of 120C is measured then with the electron microscope observation section.

Fig. 2 is to schematically show insulating layer obtained by making the resin composition layer solidification of first embodiment of the invention 100 it is (in Fig. 2 not shown with conductor layer 210.) opposite side face 100U plan view.

As shown in Fig. 2, if observation is formed with the insulating layer 100 of through-hole 110, the sometimes meeting around the through-hole 110 Observe the haloing portion 140 that insulating layer 100 has changed colour.It the haloing portion 140 can be by the halo phenomenon institute shape when forming through-hole 110 At, and be usually continuously formed from through-hole 110.In addition, in most cases, haloing portion 140 becomes albefaction part.

By using resin composition layer of the invention, aforementioned halo phenomenon can inhibit.Therefore, haloing portion 140 can be reduced Size, can ideally make haloing portion 140 disappear.The size in haloing portion 140 can pass through the slave via top of through-hole 110 The haloing distance Wt at 130 edge 150 is evaluated.

The edge 150 of via top 130 is equivalent to the edge part of the inner circumferential side in haloing portion 140.From the side of via top 130 Haloing distance Wt that edge 150 rises indicate from the edge of via top 130 150 to haloing portion 140 peripheral side edge part 160 Until distance.Haloing distance Wt from the edge of via top 130 150 is smaller, then can be evaluated more to effectively inhibit Halo phenomenon.

For example, in mask diameters 1mm, 16 μ s of pulsewidth, energy 0.2mJ/ transmitting, transmitting number 2, group schema (10kHz) Under the conditions of, solidify it for resin composition layer to be heated to 30 minutes in 100 DEG C, is then heated in 180 DEG C and obtain Insulating layer 100, irradiate CO₂Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm, in this case, from The haloing distance Wt that the edge 150 of via top 130 rises is formed as preferably 6 μm or less, more preferable 5 μm or less.

Haloing distance Wt from the edge of via top 130 150 can be measured by being observed by optical microscopy.

In addition, according to the present invention the research of people and distinguish, the diameter of usual through-hole 110 is bigger, then there is haloing portion 140 The trend that size more tends to get bigger.Therefore, it is evaluated by the size in haloing portion 140 relative to the ratio of the diameter of through-hole 110 The inhibition level of halo phenomenon.Such as it being evaluated relative to the haloing ratio Ht of top radius Lt/2 by through-hole 110. Here, the top radius Lt/2 of through-hole 110 refers to the radius of the via top 130 of through-hole 110.In addition, through-hole 110 relative to The haloing ratio Ht of top radius Lt/2 is, with the haloing distance Wt from the edge of via top 130 150 divided by through-hole 110 The resulting ratio of top radius Lt/2.The haloing ratio Ht relative to top radius Lt/2 of through-hole 110 is smaller, then it represents that can more have Effect ground inhibits halo phenomenon.

For example, in mask diameters 1mm, 16 μ s of pulsewidth, energy 0.2mJ/ transmitting, transmitting number 2, group schema (10kHz) Under the conditions of, solidify it for resin composition layer to be heated to 30 minutes in 100 DEG C, is then heated in 180 DEG C and obtain Insulating layer 100, irradiate CO₂Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm, in this case, leads to The haloing ratio Ht relative to top radius Lt/2 in hole 110 is formed as preferably 45% or less, more preferable 40% or less and then preferably 35% or less.

The haloing ratio Ht relative to top radius Lt/2 of through-hole 110 can be by top diameter Lt, Yi Jitong of through-hole 110 The haloing distance Wt from the edge of via top 130 150 in hole 110 is calculated.

Fig. 3 is at roughening obtained by the resin composition layer solidification schematically shown first embodiment of the invention The cross-sectional view of insulating layer 100 and internal substrate 200 after reason.It is shown in the Fig. 3, in the via bottoms for passing through through-hole 110 Section made of insulating layer 100 is truncated in 120 center 120C and the plane parallel with the thickness direction of insulating layer 100.

As shown in figure 3, if implementing roughening treatment, sometimes haloing portion to the insulating layer 100 for foring through-hole 110 140 insulating layer 100 is removed from conductor layer 210, forms the continuous clearance portion 180 from the edge of via bottoms 120 170.It should The usually haloing portion 140 in roughening treatment of clearance portion 180 is etched and is formed.

By using resin composition layer of the invention, as previously mentioned, can inhibit halo phenomenon.Therefore, haloing can be reduced The size in portion 140 can ideally make haloing portion 140 disappear.Therefore, it can inhibit insulating layer 100 to remove from conductor layer 210, Therefore the size of clearance portion 180 can be reduced.

The edge 170 of via bottoms 120 is equivalent to the edge part of the inner circumferential side of clearance portion 180.Therefore, from via bottoms 120 edge 170 rises, to the end (side farther out center 120C i.e. apart from via bottoms 120 of the peripheral side of clearance portion 180 End) distance Wb until 190, be equivalent to the size in direction in the face of clearance portion 180.Here, in face direction refer to absolutely The vertical direction of the thickness direction of edge layer 100.In addition, in the following description, sometimes by afore-mentioned distance Wb be known as through-hole 110 from The haloing distance Wb that the edge 170 of via bottoms 120 rises.

Pass through the evaluable journey for inhibiting clearance portion 180 to be formed of haloing distance Wb from the edge of via bottoms 120 170 Degree.Specifically, the haloing distance Wb from the edge of via bottoms 120 170 is smaller, then can be evaluated more to effectively inhibit The formation of clearance portion 180.

In addition, clearance portion 180 is to remove the insulating layer 100 in haloing portion 140 and formed, therefore its size and halo phenomenon 140 size is related.Therefore, the haloing distance Wb from the edge of via bottoms 120 170 is smaller, then can be evaluated more to have Effect ground inhibits halo phenomenon.

For example, in mask diameters 1mm, 16 μ s of pulsewidth, energy 0.2mJ/ transmitting, transmitting number 2, group schema (10kHz) Under the conditions of, solidify it for resin composition layer to be heated to 30 minutes in 100 DEG C, is then heated in 180 DEG C and obtain Insulating layer 100, irradiate CO₂Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm.Then, it is soaked at 60 DEG C Stain is then impregnated at 80 DEG C in oxidizing agent solution 20 minutes 10 minutes in swelling solution, is then impregnated at 40 DEG C With in liquid after five minutes, dry 15 minutes at 80 DEG C.In the case where implementing such roughening treatment, from via bottoms 120 The haloing distance Wb that rises of edge 170 be formed as preferably 60 μm or less, more preferable 50 μm or less, particularly preferred 40 μm or less.

Haloing distance Wb from the edge of via bottoms 120 170 can be measured in the following way, i.e., (focused using FIB Ion beam), insulating layer 100 is cut so as to show parallel with the thickness direction of the insulating layer 100 and pass through through-hole bottom Thus the section of the center 120C in portion 120 is measured then with the electron microscope observation section.

In turn, according to the present invention the research of people and distinguish, the diameter of usual through-hole 110 is bigger, then there is haloing portion 140 Size more tend to get bigger thus the size of clearance portion 180 also more the trend that tends to get bigger.Therefore, pass through the size phase of clearance portion 180 For the ratio of the diameter of through-hole 110, the inhibition level of halo phenomenon, and then evaluable inhibition clearance portion 180 formation can be evaluated Degree.For example, can evaluating relative to the haloing ratio Hb of bottom radius Lb/2 by through-hole 110.Here, through-hole 110 Bottom radius Lb/2 refers to the radius of the via bottoms 120 of through-hole 110.In addition, through-hole 110 relative to bottom radius Lb/2's Haloing ratio Hb is, with the haloing distance Wb from the edge of via bottoms 120 170 divided by the bottom radius Lb/2 institute of through-hole 110 The ratio obtained.The haloing ratio Hb relative to bottom radius Lb/2 of through-hole 110 is smaller, then shows more effectively inhibit clearance portion 180 formation.

For example, in mask diameters 1mm, 16 μ s of pulsewidth, energy 0.2mJ/ transmitting, transmitting number 2, group schema (10kHz) Under the conditions of, solidify it for resin composition layer to be heated to 30 minutes in 100 DEG C, is then heated in 180 DEG C and obtain Insulating layer 100, irradiate CO₂Laser forms the through-hole 110 that top diameter Lt is 30 μm ± 2 μm.Then, it is soaked at 60 DEG C Stain is then impregnated at 80 DEG C in oxidizing agent solution 20 minutes 10 minutes in swelling solution, is then impregnated at 40 DEG C With in liquid after five minutes, dry 15 minutes at 80 DEG C.In the case where implementing such roughening treatment, through-hole 110 it is opposite Be formed as preferably 60% or less, more preferable 50% or less and then preferably 40% or less in the haloing ratio Hb of bottom radius Lb/2.

The haloing ratio Hb relative to bottom radius Lb/2 of through-hole 110 can be by the base diameter Lb and through-hole of through-hole 110 The 110 haloing distance Wb from the edge of via bottoms 120 170 is calculated.

In the manufacturing process of printed wiring board, through-hole 110 is usually formed in the state of following, i.e., with conductor layer The state of not set other conductor layer (not shown) on the face 100U of the insulating layer 100 of 210 opposite side.Therefore, if clearly The manufacturing process of Chu's printed wiring board then can clearly recognize following structures, i.e., in 210 side of conductor layer, there are via bottoms 120, it is open with 210 opposite side via top 130 of conductor layer.But in the printed wiring board of completion, it is possible to exhausted Conductor layer is arranged in the two sides of edge layer 100., in which case it is possible to be difficult to distinguish through-hole bottom by the positional relationship with conductor layer Portion 120 and via top 130.However, the top diameter Lt of usually via top 130 is the base diameter Lb of via bottoms 120 Above size.Therefore, in the previous case, via bottoms 120 and via top 130 can be distinguished by the size of diameter.

For obtaining the construction of effect as the aforementioned by resin composition layer of the invention, the present inventor makees following supposition. But technical scope of the invention is not limited by the construction of following the description.

In general, assigning heat, light etc. for the part of through-hole 110 of insulating layer 100 will be formed when forming through-hole 110 Energy.At this moment a part of the energy assigned is transmitted to around the part that will form through-hole 110, it is possible to produce resin Oxidation.If generating this oxidation, resin deterioration may show as halo phenomenon.But since (B) ingredient includes tool There is an aromatic ring of 2 or more hydroxyls, therefore is able to suppress the oxidation reaction of resin since the steric hindrance of aforementioned hydroxy acts on It carries out.Therefore, the insulating layer 100 obtained using resin composition layer of the invention can inhibit halo phenomenon.

In addition, as the explanation of average grain diameter and specific surface area it is found that the partial size of (C) ingredient contained in resin composition layer It is usually smaller.Since the partial size of (C) ingredient is smaller, the energy for assigning insulating layer 100 can be along the thickness side of insulating layer 100 To transmitting well.For example, if assigning thermal energy or luminous energy, the energy to the face 100U of insulating layer 100 can not generate Through-thickness transmits under conditions of big decaying.Therefore, it can easily form the big through-hole 110 of taper ratio, therefore can make to lead to The shape in hole 110 is good.

[purposes of 11. resin composition layers]

Resin composition layer of the invention can suitably serve as the resin composition layer of insulation applications.Specifically, of the invention Resin composition layer can suitably serve as：It is used to form the resin composition layer (printed wiring board of the insulating layer of printed wiring board Insulating layer formation resin composition layer)；And then it can suitably serve as：It is used to form the interlayer insulating film of printed wiring board Resin composition layer (resin composition layer of the interlayer insulating film formation of printed wiring board).In addition, resin of the invention Composition layer can suitably serve as：It is used to form the insulating layer for conductor layer (including again wiring layer) is formed on the insulating layer Resin composition layer (for forming the insulating layer formation resin composition layer of conductor layer).

Particularly, from effectively with " halo phenomenon can be inhibited and the through-hole of excellent in shape can be formed " the advantages of it is such Viewpoint considers that aforementioned resin layer is suitable as：The resin composition layer for being used to form the insulating layer with through-hole (has The resin composition layer of the insulating layer formation of through-hole), wherein particularly suitable as：With 35 μm of through-holes below of top diameter Insulating layer formation resin composition layer.

[12. resin sheet]

Resin sheet of the invention includes supporting mass and the resin composition layer of the invention being set on the supporting mass.

As supporting mass, such as the film being molded of plastic material, metal foil, processing release paper can be enumerated, preferably by plastic material The film of formation, metal foil.

When using the film that is molded of plastic material as supporting mass, as plastic material, such as poly- terephthaldehyde can be enumerated Sour glycol ester (hereinafter sometimes referred to simply as " PET ".), polyethylene naphthalate (hereinafter sometimes referred to simply as " PEN ".) etc. it is poly- Ester, polycarbonate (hereinafter sometimes referred to simply as " PC ".), the propylene such as polymethyl methacrylate (hereinafter sometimes referred to simply as " PMMA ") Acids polymers, cyclic polyolefin, triacetyl cellulose (hereinafter sometimes referred to simply as " TAC "), polyether sulfides are (sometimes simple below Referred to as " PES "), polyether-ketone, polyimides etc..Wherein, preferably polyethylene terephthalate, poly- naphthalenedicarboxylic acid ethylene glycol Ester, particularly preferably cheap polyethylene terephthalate.

When using metal foil as supporting mass, as metal foil, such as copper foil, aluminium foil can be enumerated etc., preferably copper foil.As The foil that is formed by individual metallic copper can be used in copper foil, it is possible to use by copper and other metals (for example, tin, chromium, silver, magnesium, nickel, Zirconium, silicon, titanium etc.) alloy formed foil.

For supporting mass, delustring processing, sided corona treatment, antistatic can be implemented to the face engaged with resin composition layer The processing such as processing.

In addition, maying be used at the face engaged with resin composition layer with release layer with release layer as supporting mass Supporting mass.As release agent used in the release layer in the supporting mass with release layer, such as can enumerate selected from alkyd tree The release agent of one or more of rouge, polyolefin resin, polyurethane resin and organic siliconresin.Supporting mass with release layer can It using commercially available product, such as can enumerate with using alkyd resin system release agent as the PET film of the release layer of principal component, i.e. Lin get Ke is public Take charge of " SK-1 ", " AL-5 ", " AL-7 " of system；" the dew Miller T60 " of Toray；" Purex " of Supreme Being people's corporation； " UNIPEEL " of UNITIKA corporation；Deng.

It as the thickness of supporting mass, is not particularly limited, preferably 5 μm~75 μm of range, more preferably 10 μm~60 μ The range of m.It should be noted that preferably having the supporting mass entirety of release layer when using the supporting mass for having release layer With a thickness of above range.

In addition, resin sheet can be as needed containing the arbitrary layer in addition to supporting mass and resin composition layer.As The arbitrary layer, for example, can enumerate resin composition layer and supporting mass asynthetic face (i.e. with supporting mass opposite side Face) on the protective film etc. based on supporting mass that is arranged.The thickness of protective film is not particularly limited, and for example, 1 μm ~ 40 μm.It utilizes Protective film can prevent from adhering to dirt etc. on the surface of resin composition layer or generate scar.

Resin sheet can for example be manufactured by following manner：Resin of the preparation comprising organic solvent and resin combination is clear The resin varnish, is coated on supporting mass, and then make it by paint using apparatus for coating such as metal mold coating machines (die coater) It is dry, form resin composition layer.

As organic solvent, such as the ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone can be enumerated；Ethyl acetate, acetic acid The acetate solvents such as butyl ester, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate；Cellosolve and butyl The carbitols solvent such as carbitol；The aromatic solvents such as toluene and dimethylbenzene；Dimethylformamide, dimethyl acetamide (DMAc) and N- The acid amides series solvents such as methyl pyrrolidone；Deng.For organic solvent, can be used alone a kind, also can be used in combination 2 kinds with On.

Drying can be implemented using the methods of heating, blowing hot-air.Drying condition is not particularly limited, and is dried, so that The content of organic solvent becomes usual 10 mass % or less, preferably 5 mass % or less in resin composition layer.Although also with resin The difference of the boiling point of organic solvent in varnish and it is different, but for example using the tree of the organic solvent comprising 30 mass of mass %~60 % It, can be by 50 DEG C~150 DEG C progress drying in 3 minutes~10 minutes, to form resin composition layer when rouge varnish.

Resin sheet can be rolled into a roll to be saved.It, usually can be by the way that protective film be shelled when resin sheet has protective film From using.

[13. printed wiring board]

Printed wiring board of the invention has the insulating layer formed such as the above-mentioned solidfied material by relatively thin resin composition layer.This Outside, which can inhibit halo phenomenon when forming through-hole, and can form the through-hole of excellent in shape.Therefore, by using Resin composition layer of the invention can inhibit reduced performance caused by being deteriorated by halo phenomenon or shape of through holes on one side, real on one side The slimming of existing printed wiring board.

In general, in order to make to be set to the conducting of the conductor layer of the insulating layer two sides with through-hole, so that the through-hole be arranged.Cause This, printed wiring board of the invention generally comprises the first conductor layer, the second conductor layer and is formed in the first conductor layer and second Insulating layer between conductor layer.Then, through-hole is formed on the insulating layer, it can be by the first conductor layer and the second conductor by the through-hole Layer conducting.

By with the excellent of resin composition layer as " halo phenomenon can be inhibited and the through-hole of excellent in shape can be formed " Point, so as to realize the specific printed wiring board being difficult to realize in the past.The specific printed wiring board be comprising the first conductor layer, The printed wiring board of second conductor layer and the insulating layer being formed between the first conductor layer and the second conductor layer meets following Whole important document (i)~(v),

(i) insulating layer with a thickness of 15 μm or less；

(ii) it is 35 μm of through-holes below that insulating layer, which has top diameter,；

(iii) the taper ratio of the through-hole is 80% or more；

(iv) the haloing distance from the edge of via bottoms of the through-hole is 5 μm or less；

(v) the haloing ratio relative to bottom radius of the through-hole is 35% or less.

Attached drawing described below is illustrated specific printed wiring board.Fig. 4 is the printing of second embodiment of the invention The schematic cross sectional views of wiring plate 300.Shown in the Fig. 4, the center 120C by the via bottoms 120 of through-hole 110 and with Section made of the parallel plane truncation printed wiring board 300 of the thickness direction of insulating layer 100.In addition, being equivalent in Fig. 4 It encloses and same symbol used in FIG. 1 to FIG. 3 at the position for the element recorded in FIG. 1 to FIG. 3.

As shown in figure 4, the specific printed wiring board 300 of second embodiment of the invention includes：First conductor layer 210, Two conductor layers 220 and the insulating layer 100 being formed between the first conductor layer 210 and the second conductor layer 220.In insulating layer 100 Upper formation through-hole 110.In addition, usual second conductor layer 220 is the layer being arranged after foring through-hole 110.Therefore, it second leads Body layer 220 is usually not only formed in the face 100U of insulating layer 100, but also is also formed in through-hole 110, passes through the through-hole 110 First conductor layer 210 and the second conductor layer 220 are connected.

The thickness T of insulating layer 100 contained by specific printed wiring board 300 is usually 15 μm or less, preferably 12 μm or less, More preferably 10 μm or less, particularly preferably 5 μm or less.Specific printed wiring board 300 has above-mentioned relatively thin insulating layer 100, therefore can realize the slimming of specific printed wiring board 300 itself.It is examined from the viewpoint for the insulation performance for improving insulating layer 100 Consider, the lower limit of the thickness T of insulating layer 100 is preferably 1 μm or more, more preferably 2 μm or more, particularly preferably 3 μm or more.This In, the thickness T of insulating layer 100 indicates the size of the insulating layer 100 between the first conductor layer 210 and the second conductor layer 220, is not Indicate that there is no the sizes of the insulating layer 100 at the position of the first conductor layer 210 or the second conductor layer 220.For insulating layer 100 Thickness T for, usually with the interarea 210U and the second conductor layer 220 across opposite the first conductor layer 210 of the insulating layer 100 The distance between interarea 220D it is consistent and consistent with the depth of through-hole 110.

The top diameter Lt of through-hole 110 possessed by insulating layer 100 contained by specific printed wiring board 300 is usually 35 μm It below, is preferably 33 μm or less, particularly preferably 32 μm or less.Specific printed wiring board 300 includes straight with above-mentioned top The insulating layer 100 of the lesser through-hole 110 of diameter Lt, therefore can promote the wiring comprising the first conductor layer 210 and the second conductor layer 220 Miniaturization.From the viewpoint of through-hole 110 easy to form, the lower limit of the top diameter Lt of through-hole 110 is preferably 3 μm or more, More preferably 10 μm or more, particularly preferably 15 μm or more.

The taper ratio Lb/Lt (%) of through-hole 110 possessed by insulating layer 100 contained by specific printed wiring board 300 is usual It is 80%~100%.Specific printed wiring board 300 includes the through-hole with the above-mentioned higher excellent in shape of taper ratio Lb/Lt 110 insulating layer 100.Therefore, specific printed wiring board 300 usually can be improved the first conductor layer 210 and the second conductor layer 220 it Between conducting reliability.

The edge of the slave via bottoms 120 of through-hole 110 possessed by insulating layer 100 contained by specific printed wiring board 300 170 haloing distance Wb are usually 5 μm or less, preferably 4 μm or less.For specific printed wiring board 300, from through-hole The haloing distance Wb that the edge 170 of bottom 120 rises is above-mentioned smaller value, therefore insulating layer 100 is from the stripping of the first conductor layer 210 From smaller.Therefore, the conducting between the first conductor layer 210 and the second conductor layer 220 usually can be improved in specific printed wiring board 300 Reliability.

Through-hole 110 possessed by insulating layer 100 contained by specific printed wiring board 300 relative to bottom radius Lb/2's Haloing ratio Hb is usually 35% or less, preferably 33% or less and then preferably 31% or less.For specific printed wiring board 300 Speech, the haloing ratio Hb relative to bottom radius Lb/2 is above-mentioned smaller value, therefore insulating layer 100 is from the first conductor layer 210 It removes smaller.Specific printed wiring board 300 comprising the above-mentioned lesser insulating layer 100 of haloing ratio Hb usually can be improved first and lead The reliability of conducting between body layer 210 and the second conductor layer 220.The lower limit of haloing ratio Hb relative to bottom radius Lb/2 is managed It is zero in the case of thinking, but usually 5% or more.

The number of through-hole 110 possessed by insulating layer 100 contained by specific printed wiring board 300 can be 1, can also be with It is 2 or more.When insulating layer 100 has 2 or more through-holes 110, it can be part of it and meet important document (ii)~(v), but It is preferred that its whole meets important document (ii)~(v).It is furthermore preferred that the through-hole for example from insulating layer 100 randomly selected 5 110 meet important document (ii)~(v) in terms of averagely.

Insulating layer 100 is formed by the solidfied material using resin composition layer of the invention, to can realize above-mentioned Specific printed wiring board 300.At this moment, the via bottoms 120 of the through-hole 110 formed on insulating layer 100 and putting down for via top 130 Face shape is arbitrary, but generally circular or oval, preferably circular.

The printed wiring boards such as specific printed wiring board can for example manufacture as follows：Using resin sheet, implement to include following works Sequence (I)~process (III) manufacturing method,

(I) in such a way that resin composition layer is engaged with internal substrate, the process that resin sheet is stacked on internal substrate；

(II) process for making resin composition layer heat cure and forming insulating layer；

(III) process of through-hole is formed on the insulating layer.

" internal substrate " used in process (I) is the component of the substrate as printed wiring board.As internal substrate, example Glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide can such as be enumerated Substrate etc..Usually as internal substrate, the internal substrate in its one or two sides with conductor layer is used.Then, it leads at this Insulating layer is formed on body layer.For the conductor layer, such as in order to work as circuit, pattern processing can be carried out.In base The internal substrate for being formed with conductor layer as circuit in the one or two sides of plate is sometimes referred to as " internal layer circuit substrate ".In addition, When manufacturing printed wiring board, the intermediate manufacture object that be further formed insulating layer and/or conductor layer is also contained in " internal substrate " It is interior.When printed wiring board is component internal circuit board, the internal substrate for being built-in with component can be used.

The lamination of internal substrate and resin sheet can for example carry out as follows：It is crimped on from bearing side by resin sheet heating Thus resin composition layer is fitted in internal substrate by internal substrate.Internal substrate is crimped on as by resin sheet heating Component (hereinafter sometimes referred to " heating crimping component ".), such as heated metal plate (SUS end plate (Mirror plate) can be enumerated etc.) or Metallic roll (SUS roller) etc..It should be explained that, it is preferred that and the indirect crimping component that will heat pressurizes to resin sheet, but be So that the resin sheet is sufficiently followed the concave-convex surface of internal substrate, pressurizes across heat resistant rubber elastomeric material.

The lamination of internal substrate and resin sheet is for example implemented using vacuum layer platen press.In vacuum layer platen press, heating pressure Jointing temp is preferably 60 DEG C ~ 160 DEG C, more preferably 80 DEG C ~ 140 DEG C of range, heating crimping pressure be preferably 0.098MPa ~ The range of 1.77MPa, more preferably 0.29MPa ~ 1.47MPa, heating crimping time are preferably 20 seconds ~ 400 seconds, more preferably 30 Second ~ 300 seconds ranges.Lamination is preferably implemented in the case where pressure is 26.7hPa reduced pressure below.

Lamination can be carried out using commercially available vacuum laminator.As commercially available vacuum laminator, such as can enumerate：Name mechanism Make the vacuum pressure type laminating machine of institute's corporation, the vacuum pack system device (vacuum of Nikko-Materials corporation Applicator), batch-type vacuum pressed laminating machine etc..

After lamination, under normal pressure (under atmospheric pressure), for example, can pressurize from bearing side to heating crimping component, Thus the smoothing techniques of the resin sheet of lamination are carried out.The pressurized conditions of smoothing techniques may be set to and above-mentioned lamination Heat the same condition of crimping condition.Smoothing techniques can be carried out using commercially available laminating machine.It should be noted that on can be used It states commercially available vacuum laminator and continuously carries out lamination and smoothing techniques.

In process (II), makes resin composition layer heat cure and form insulating layer.The heat cure condition of resin composition layer It is not particularly limited, can arbitrarily use the used condition when forming the insulating layer of printed wiring board.

For example, the heat cure condition of resin composition layer is different according to type of resin combination etc., solidification temperature is logical Range (preferably 150 DEG C~220 DEG C of the range, more preferably 170 DEG C~200 DEG C of model that 120 DEG C~240 DEG C of Chang Kewei Enclose), curing time generally can be 5 minutes~120 minutes range (preferably 10 minutes~100 minutes, more preferably 15 minutes ~90 minutes).

Before making resin composition layer heat cure, can make resin composition layer lower than solidification temperature at a temperature of into Row preheating.For example, before making resin composition layer heat cure, usual 50 DEG C more than or lower than 120 DEG C (preferably 60 DEG C with It is upper and 115 DEG C or less, more preferable 70 DEG C or more and 110 DEG C or less) at a temperature of, resin composition layer is preheated usual 5 points It is more than clock (preferably 5 minutes~150 minutes, it is 15 minutes~120 minutes more preferable, and then preferably 15 minutes~100 minutes).

In process (III), through-hole is formed on the insulating layer.As the forming method of through-hole, laser irradiation, erosion can be enumerated Quarter, machine drilling etc..Wherein, laser irradiation is typically easy to generate halo phenomenon.Therefore, from effectively with inhibition halo phenomenon From the viewpoint of such effect, preferred laser irradiation.

For the laser irradiation, such as the laser machine with laser light source can be used to carry out, the laser It is carbon dioxide laser, YAG laser, excimer laser etc. as light source in light source.As workable laser machine, example Via Mechanics corporation CO can such as be enumerated₂Laser machine " LC-2k212/2C ", Mitsubishi Electric Corporation 605GTWIII (- P), laser machine of Panasonic Welding Systems corporation etc..

There is no particular limitation for the irradiation condition of the laser of wavelength, umber of pulse, pulsewidth, the output power of laser etc., can set It is set to suitable condition corresponding with the type of laser light source.

But supporting mass can remove between process (I) and process (II), can be between process (II) and process (III) It removes, can also be removed after process (III).Wherein, it from the viewpoint of the generation for further suppressing recess portion, is preferably insulating The process (III) that through-hole is formed on layer removes later.For example, if being formed on the insulating layer after through-hole again using laser irradiation Supporting mass is removed, then the through-hole of excellent in shape easy to form.

The manufacturing method of printed wiring board can further include the process that (IV) is roughened insulating layer and (V) process of conductor layer is formed.These processes (IV) and process (V) can be according to the various sides used in manufacture of printed wiring board Method is implemented.It should be noted that the removing of the supporting mass can be in process in the case where removing supporting mass after process (III) (III) implement between process (IV), can also implement between process (IV) and process (V).

Process (IV) is the process being roughened to insulating layer.The step of roughening treatment and condition be not special The used arbitrary Step By Condition when forming the insulating layer of printed wiring board can be used in limitation.For example, can sequentially implement Using the swelling treatment of swelling solution, the roughening treatment using oxidant and the neutralisation treatment using neutralizer, thus to exhausted Edge layer is roughened.

It is not particularly limited as swelling solution, such as aqueous slkali, surfactant solution can be enumerated etc., preferably alkali soluble Liquid.As the aqueous slkali, more preferable sodium hydroxide solution and potassium hydroxide solution.As commercially available swelling solution, such as can enumerate " Swelling Dip Securiganth P ", " the Swelling Dip Securiganth of ATOTECH JAPAN corporation SBU " etc..In addition, swelling solution can be used alone a kind, two or more can also be applied in combination with arbitrary ratio.Utilize the molten of swelling solution Swollen processing is not particularly limited, such as can be by being impregnated in insulating layer in 30 DEG C~90 DEG C of swelling solution 1 minute~20 minutes Come carry out.It is controlled from the viewpoint of appropriate level from by the swelling of the resin of insulating layer, insulating layer is preferably impregnated in 40 DEG C 5 minutes~15 minutes in~80 DEG C of swelling solution.

Be not particularly limited as oxidant, for example, can enumerate in the aqueous solution of sodium hydroxide dissolved with potassium permanganate or The alkaline permanganic acid solution of sodium permanganate.In addition, oxidant can be used alone a kind, can also be applied in combination with arbitrary ratio 2 kinds with On.Preferably insulating layer is impregnated in using the roughening treatment of the oxidants such as alkaline permanganic acid solution and is heated to 60 DEG C~80 DEG C It carries out within 10 minutes~30 minutes in oxidizing agent solution.In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 The mass of quality %~10 %.As commercially available oxidant, such as " the Concentrate of ATOTECH JAPAN corporation can be enumerated The alkaline permanganic acid solution of Compact CP ", " Dosing solution Securiganth P " etc..

As the aqueous solution of neutralizer preferred acidic, as commercially available product, such as ATOTECH JAPAN corporation can be enumerated "Reduction Solution Securiganth P".In addition, neutralizer can be used alone a kind, it can also be with arbitrary ratio group It closes and uses two or more.Using the processing of neutralizer by the way that the process face dipping using the roughening treatment of oxidant will be completed It carries out within 5 minutes~30 minutes in 30 DEG C~80 DEG C of neutralizer.Consider from operability etc., will preferably complete utilization The method that the object of the roughening treatment of oxidant is impregnated in 5 minutes~20 minutes in 40 DEG C~70 DEG C of neutralizer.

Process (V) is the process to form conductor layer.Conductor material used in conductor layer is not particularly limited.Suitable In embodiment, conductor layer includes a kind in gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Above metal.Conductor layer can be single metal layer, be also possible to alloy-layer.As alloy-layer, such as can enumerate by selected from upper State the layer that the alloy (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) of the metal of more than two kinds in metal is formed.Its In, the viewpoints such as easiness that the versatility that is formed from conductor layer, cost, pattern are formed consider, preferably chromium, nickel, titanium, aluminium, zinc, Gold, palladium, silver or copper single metal layer；Or, nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy alloy-layer.More preferably chromium, Nickel, titanium, aluminium, zinc, gold, palladium, silver or copper single metal layer；Or the alloy-layer of nickel-chromium alloy；The particularly preferably monometallic of copper Layer.

Conductor layer can be single layer structure, and being also possible to lamination, two or more is formed by different types of metal or alloy Multilayered structure obtained from single metal layer or alloy-layer.Conductor layer be multilayered structure when, the layer to connect with insulating layer be preferably chromium, The alloy-layer of the single metal layer or nickel-chromium alloy of zinc or titanium.

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

Conductor layer can be formed using plating.Such as using the technologies such as semi-additive process, fully-additive process the surface of insulating layer into Row plating can form the conductor layer with desired wiring pattern.Wherein, from the viewpoint of the simplicity of manufacture, preferably It is formed using semi-additive process.

The example described below that conductor layer is formed using semi-additive process.Firstly, using electroless plating (chemical plating) exhausted Plating seed layer (めっきシー De Layer) is formed on edge layer surface.It is and desired next, on the plating seed layer of formation Wiring pattern it is corresponding, form the mask pattern for exposing a part of plating seed layer.Using electrolytic coating exposing plating It covers after forming metal layer on seed layer, mask pattern is removed.Then, unwanted plating seed layer can be removed by etching etc. It goes, forms the conductor layer with desired wiring pattern.

In addition, as needed, repeat and implement the step of forming insulating layer and conductor layer using process (I)~process (V), Manufacture multilayer printed-wiring board.

[14. semiconductor device]

Semiconductor device of the invention includes aforementioned printed wiring board.Printed wiring board can be used to manufacture in the semiconductor device.

As semiconductor device, can enumerate for electric product (for example, computer, mobile phone, digital camera and electricity Depending on machine etc.) and the vehicles (for example, motorcycle, automobile, electric car, ship and aircraft etc.) etc. various semiconductor devices.

For example, semiconductor dress can be manufactured by the conducting position installing component (semiconductor chip) in printed wiring board It sets." conducting position " refers to " position of the electric signal in conduction printed wiring board ", and position can be the portion on surface or embedment Any one of position.In addition, semiconductor chip can arbitrarily use the electrical circuit components using semiconductor as material.

As long as the installation method of semiconductor chip when manufacturing semiconductor device functions semiconductor chip effectively , be not particularly limited, as the example of installation method, can enumerate wire bonding installation method, flip-chip installation method, Using the installation method of solderless buildup layer (BBUL), using the installation method of anisotropic conductive film (ACF), using non-conductive The installation method etc. of film (NCF).Here, " installation method for using solderless buildup layer (BBUL) " refers to " semiconductor chip is straight The recess portion for connecing embedment printed wiring board makes the installation method of the wiring connection on semiconductor chip and printed wiring board ".

[embodiment]

Hereinafter, showing embodiment for the present invention to be specifically described.But the present invention is not limited by following embodiment.With Under explanation in, as long as no other explanation, " part " and " % " of expression amount respectively refers to " mass parts " and " quality % ".In addition, only Without other explanation, operation described below carries out in the environment of normal temperature and pressure.

[explanation of inorganic filling material]

The measuring method > of the average grain diameter of < inorganic filling material

Weigh inorganic filling material 100mg, dispersing agent (Sannopco corporation " SN9228 ") 0.1g and methyl ethyl ketone 10g is dispersed 20 minutes into bottle using ultrasonic wave.Using laser diffraction formula particle size distribution analyzer, (Shimadzu Seisakusho Ltd. is public Department's system " SALD-2200 "), with the particle diameter distribution of volume reference measurement inorganic filling material in a manner of pond in batches (return and divide セ Le). Then, by gained particle diameter distribution, the average grain diameter of inorganic filling material is calculated as median particle diameter.

The measuring method > of the specific surface area of < inorganic filling material

Using the full-automatic specific area measuring device of BET (Mountech corporation " Macsorb HM-1210 "), inorganic fill out is measured Fill the specific surface area of material.

The type > of < inorganic filling material

Inorganic filling material 1：For spherical silicon dioxide (Denki Kagaku Kogyo kabushiki's system " UFP-30 ", 0.078 μ of average grain diameter M, specific surface area 30.7m²/ g) 100 parts, with N- phenyl -3- TSL 8330 (chemical industrial company of SHIN-ETSU HANTOTAI system, KBM573 it) is surface-treated for 2 parts；

Inorganic filling material 2：For preparing spherical SiO 2 (Admatechs corporation " SC2500SQ ", 0.77 μm of average grain diameter, Specific surface area 5.9m²/ g) 100 parts, with N- phenyl -3- TSL 8330 (chemical industrial company of SHIN-ETSU HANTOTAI system, KBM573 it) is surface-treated for 1 part.

[preparation of 1. resin combination 1 of embodiment]

It stirs on one side, on one side by union II first phenol-type epoxy resin (Mitsubishi Chemical Ind's system " YX4000HK ", epoxide equivalent about 185) 6 parts, 5 parts of naphthalene type epoxy resin (aurification corporation " ESN475V ", epoxide equivalent about 332 are lived by Nippon Steel), bisphenol AF type ring oxygen 15 parts of resin (Mitsubishi Chemical Ind's system " YL7760 ", epoxide equivalent about 238), hexamethylene type epoxy resin (Mitsubishi Chemical Ind Making " ZX1658GS ", about 135) 2 parts of epoxide equivalent and phenoxy resin, (Mitsubishi Chemical Ind's system " YX7553BH30 " is not waved Send out the cyclohexanone of 30 mass % of ingredient：The 1 of methyl ethyl ketone (MEK)：1 solution, Mw=35000) 2 parts dissolve by heating in solvent stone The in the mixed solvent that 20 parts and 10 parts of cyclohexanone of cerebrol.Acquired solution is cooled to room temperature.Then, conduct is mixed into the solution (B) the naphthols system curing agent (aromatic resins indicated by formula (5) of ingredient.Aurification corporation " SN395 ", hydroxyl are lived by Nippon Steel Equivalent 107) 5 parts, active ester system curing agent (DIC corporation " EXB-8000L-65TM ", active group equivalent about 220, it is non-volatile at Divide the toluene of 65 mass %：The 1 of MEK：1 solution) 6 parts, inorganic filling material 1 (50 parts) and amine system curing accelerator (4- bis- Dimethylaminopyridine (DMAP)) 0.05 part, it is evenly dispersed with high speed rotation mixing machine, obtain mixture.By the mixture cylinder Formula filter (ROKITECHNO corporation " SHP020 ") filtering, obtains resin combination 1.

[preparation of 2. resin combination 2 of embodiment]

The type of used reagent and amount are changed like that as shown in table 1, in addition to this carried out with embodiment 1 similarly Operation, prepares resin combination 2.The specific variation point carried out from embodiment 1 is as described below,

Using bisphenol-type epoxy resin, (aurification corporation " ZX1059 ", epoxide equivalent about 169, bisphenol A-type and double are lived by Nippon Steel The 1 of phenol F type：1 melange) (DIC corporation " EXA-7311-G4 ", epoxide equivalent are about for 4 parts and naphthylene ether type epoxy 213) 2 parts, to substitute 2 parts of hexamethylene type ring oxygen resin (Mitsubishi Chemical Ind's system " ZX1658GS ", epoxide equivalent about 135)；

In addition, using the phenoxy resin (cyclohexanone of Mitsubishi Chemical Ind's system " YL7500BH30 ", 30 mass % of nonvolatile component： The 1 of methyl ethyl ketone (MEK)：1 solution, Mw=44000) 2 parts, to substitute phenoxy resin (Mitsubishi Chemical Ind's system The cyclohexanone of 30 mass % of " YX7553BH30 ", nonvolatile component：The 1 of methyl ethyl ketone (MEK)：1 solution, Mw=35000) 2 Part；

In turn, as (B) ingredient, the phenol system curing agent (aromatic resins indicated by formula (4) are used.Qun Rong chemical industrial company " GRA13H ", about 75) 4 parts of hydroxyl equivalent are made, (aurification corporation " SN395 ", hydroxyl are lived by Nippon Steel to substitute naphthols system curing agent Base equivalent 107) 5 parts.

[preparation of 1. resin combination 3 of comparative example]

The type of used reagent and amount are changed like that as shown in table 1, in addition to this carried out with embodiment 1 similarly Operation, prepares resin combination 3.The specific variation point carried out from embodiment 1 is as described below,

In turn, used as the cresol novolac system curing agent (DIC corporation " LA-3018- of the skeleton containing triazine of (E) ingredient The 2- methoxy propyl alcoholic solution of 50P ", hydroxyl equivalent about 151, nonvolatile component 50%) 10 parts, it is (new to substitute naphthols system curing agent Day iron lives aurification corporation " SN395 ", hydroxyl equivalent 107) 5 parts.

[preparation of 2. resin combination 4 of comparative example]

The type of used reagent and amount are changed like that as shown in table 1, in addition to this carried out with embodiment 1 similarly Operation, prepares resin combination 4.The specific variation point carried out from embodiment 1 is as described below,

Cresol novolac system curing agent (the DIC corporation " LA-3018-50P ", hydroxyl of the skeleton containing triazine used as (E) ingredient The 2- methoxy propyl alcoholic solution of equivalent about 151, nonvolatile component 50%) 4 parts, to substitute naphthols system curing agent, (aurification is lived by Nippon Steel Learn corporation " SN395 ", hydroxyl equivalent 107) 5 parts；

In turn, using inorganic filling material 2（80 parts）To substitute using inorganic filling material 1（50 parts）.

[preparation of 3. resin combination 5 of comparative example]

The type of used reagent and amount are changed like that as shown in table 1, in addition to this carried out with embodiment 1 similarly Operation, prepares resin combination 5.The specific variation point carried out from embodiment 1 is as described below,

Naphthols system curing agent (aurification corporation " SN485 ", hydroxyl equivalent about 215 are lived by Nippon Steel) 4 used as (E) ingredient The cresol novolac system curing agent of part and the skeleton containing triazine (hydroxyl equivalent about 151, do not wave by DIC corporation " LA-3018-50P " Send out the 2- methoxy propyl alcoholic solution of ingredient 50%) 4 parts, to substitute naphthols system curing agent, (aurification corporation is lived by Nippon Steel " SN395 ", hydroxyl equivalent 107) 5 parts.

[preparation of 4. resin combination 6 of comparative example]

The type of used reagent and amount are changed like that as shown in table 1, in addition to this carried out with embodiment 1 similarly Operation, prepares resin combination 6.The specific variation point carried out from embodiment 1 is as described below,

As curing agent, for 5 parts of naphthols system curing agent (aurification corporation " SN395 ", hydroxyl equivalent 107 are lived by Nippon Steel), And active ester system curing agent (DIC corporation " EXB-8000L-65TM ", active group equivalent about 220,65 matter of nonvolatile component Measure the toluene of %：The 1 of MEK：1 solution) 6 parts be further combined it is solid used as the cresol novolac system of the skeleton containing triazine of (E) ingredient Agent (DIC corporation " LA-3018-50P ", hydroxyl equivalent about 151, nonvolatile component 50% 2- methoxy propyl alcoholic solution) 4 Part.

In addition, using inorganic filling material 2（80 parts）To substitute using inorganic filling material 1（50 parts）.

[composition of resin combination]

Ingredient used in the preparation of resin combination 1~6 and its use level (mass parts of non-volatile content) are shown in following table 1. Abbreviation in following tables is as follows；

The containing ratio of curing agent：The content of curing agent relative to the 100 mass % of resin component in resin combination；

The containing ratio of active ester system curing agent：Active ester system relative to the 100 mass % of resin component in resin combination solidifies The content of agent；

The containing ratio of inorganic filling material：Inorganic filling material relative to the 100 mass % of nonvolatile component in resin combination Content.

[table 1]

。

[manufacture of resin sheet]

As supporting mass, preparation implements poly- pair of demoulding processing with alkyd resin system release agent (Lin get Ke corporation " AL-5 ") Ethylene terephthalate film (Toray system " dew Miller R80 ", 38 μm of thickness, 130 DEG C of softening point).

Using metal mold coating machine, resin combination 1~6 is equably coated on supporting mass respectively, so that after dry Resin composition layer with a thickness of 10 μm, dry 2 minutes at 70 DEG C ~ 95 DEG C, to form resin combination on supporting mass Nitride layer.Then, resin composition layer be bonded polypropylene screen (the Oji F- as protective film on the asynthetic face of supporting mass Tex corporation " ALPHAN MA-411 ", 15 μm of thickness) asperities.Thus obtain sequentially have supporting mass, resin composition layer, And the resin sheet A of protective film.

[measuring method of thickness]

The thickness of the layer of resin composition layer etc. is measured using contact film thickness gauge (Mitutoyo corporation " MCD-25MJ ").

[evaluation of the through-hole after laser punching processing]

Using the resin sheet A that the manufacture of resin combination 1~6 is respectively adopted, the insulation with through-hole is formed by the following method Layer, carries out the evaluation of the through-hole.

The production > of < sample for evaluation

(1) preparation of internal substrate：

As internal substrate, prepare the glass cloth base material epoxy resin two sides copper-coated laminated board (copper foil that there is copper foil layer on two sides 3 μm of thickness, substrate thickness 0.15mm, gas chemical company of Mitsubishi system " HL832NSF LCA ", 255 × 340mm size).

(2) lamination of resin sheet：

Protective film is removed from resin sheet A, exposes resin composition layer.Use batch-type vacuum pressed laminating machine (Nikko- Materials corporation, 2 stages stack laminating machine (2-stage buildup laminator) " CVP700 "), with resin group The mode that nitride layer connects with internal substrate is closed, the two sides of internal substrate is laminated to.Lamination is implemented as follows：Carrying out decompression in 30 seconds makes gas Pressure is adjusted to after 13hPa or less, is crimped 45 seconds under conditions of 130 DEG C, pressure 0.74MPa.Then in 120 DEG C, pressure Hot pressing in 75 seconds is carried out under conditions of 0.5MPa.

(3) heat cure of resin composition layer：

Then, the internal substrate for being laminated with resin sheet is put into 100 DEG C of baking oven and is heated 30 minutes, next move to 180 DEG C Baking oven in heat 30 minutes, make resin composition layer heat cure, form insulating layer.Insulating layer with a thickness of 10 μm.Thus To the solidification substrate A sequentially with supporting mass, insulating layer, internal substrate, insulating layer and supporting mass.

(4) laser punching is processed：

Use CO₂Laser machine (Mitsubishi Electric Corporation's system " 605GTWIII (- P) ") irradiates insulating layer by supporting mass and swashs Multiple through-holes that top diameter (diameter) is about 30 μm are formed on the insulating layer in light.The irradiation condition of laser is mask diameters 1mm, 16 μ s of pulsewidth, energy 0.2mJ/ transmitting, transmitting number 2, group schema (10kHz).

(5) roughening treatment：

After through-hole is formed on the insulating layer, supporting mass is removed, obtains pore-forming sequentially with insulating layer, internal substrate and insulating layer Process substrate A.Then, this is carried out boring dirty (desmear) processing as the removing of roughening treatment at hole machined substrate A.Make Dirty processing is bored to remove, implements following wet type removings and bores dirty processing.

(wet type, which is removed, bores dirty processing)

Swelling solution (ATOTECH JAPAN corporation " Swelling Dip will be impregnated at hole machined substrate A in 60 DEG C The aqueous solution of Securiganth P ", diethylene glycol monobutyl ether and sodium hydroxide) in 10 minutes, be then impregnated in oxygen in 80 DEG C Agent solution (ATOTECH JAPAN corporation " Concentrate Compact CP ", potassium permanganate concentration about 6%, hydroxide The aqueous solution of na concn about 4%) in 20 minutes, neutralizer (ATOTECH JAPAN corporation is then impregnated in 40 DEG C " Reduction Solution Securiganth P ", aqueous sulfuric acid) in 5 minutes, it is then 15 minutes dry in 80 DEG C.It will Implement the dirty processing of wet type removing brill is known as roughening substrate A at hole machined substrate A.

The dimension measurement > of through-hole before < roughening treatment

As sample, before preparing roughening treatment at hole machined substrate A.For this at hole machined substrate A, FIB-SEM is used Set composite (SII Nano Technology corporation " SMI3050SE ") carries out cross-section observation.Specifically, using FIB (focused ion beam) cuts insulating layer to show via bottoms parallel with the thickness direction of the insulating layer and by through-hole The section at center.The section is observed using SEM (scanning electron microscope), by the top of observed determining image through-hole Diameter and base diameter.

Aforementioned measurement is carried out to the through-hole at randomly selected 5.Then, using the top diameter of through-hole at 5 measured Measured value the average through-hole as the sample top diameter Lt1.In addition, straight using the bottom of through-hole at 5 measured The base diameter Lb1 of the average through-hole as the sample of the measured value of diameter.

The dimension measurement > of through-hole after < roughening treatment

As sample, hole machined substrate A is replaced into using roughening substrate A.Other than the above item, carry out and aforementioned < The identical operation of dimension measurement > of through-hole before roughening treatment, the top diameter Lt2 of the through-hole after measuring roughening treatment And base diameter Lb2.

The measurement > of haloing distance before < roughening treatment

With optical microscopy (Hirox corporation " KH8700 ") observe roughening treatment before at hole machined substrate A.In detail and Speech, using optical microscopy (CCD), the insulating layer of bore periphery from the top at hole machined substrate A.For the observation Speech makes the focus of optical microscopy be directed at via top to carry out.Observation as a result, being seen around through-hole from the through-hole The edge of via top play the haloing portion that continuous and insulating layer becomes the annular of white.Therefore, by observed image The peripheral radius r2 of radius (the inner circumferential radius for being equivalent to haloing portion) r1 and haloing portion of the via top of through-hole is measured, is calculated Haloing distance from the edge of via top of the difference r2-r1 of the grade radiuses r1 and radius r2 as the measurement place.

Aforementioned measurement is carried out to the through-hole at randomly selected 5.Then, using the haloing distance of through-hole at 5 measured Measured value the average haloing distance Wt from the edge of via top as the sample.

The dimension measurement > of haloing distance after < roughening treatment

For being roughened substrate A, use FIB-SEM set composite (SII Nano Technology corporation " SMI3050SE ") Carry out cross-section observation.Specifically, using FIB (focused ion beam), insulating layer is cut to show the thickness with the insulating layer Direction is parallel and passes through the section at the center of the via bottoms of through-hole.The section is observed using SEM (scanning electron microscope). Observation as a result, observing that from the edge of via bottoms, continuous and insulating layer is removed from the copper foil layer of internal substrate and formed Clearance portion.The distance at the edge by observed determining image from the center of via bottoms to via bottoms (is equivalent to dizzy The inner circumferential radius in circle portion) distance of end in relatively distal side in r3 and center from via bottoms to aforementioned gap portion (is equivalent to dizzy The peripheral radius in circle portion) r4, the difference r4-r3 of the equidistant r3 and distance r4 is calculated as the slave via bottoms in the measurement place The haloing distance that edge rises.

Aforementioned measurement is carried out to the through-hole at randomly selected 5.Then, using the haloing distance of through-hole at 5 measured Measured value the average haloing distance Wb from the edge of via bottoms as the sample.

[result]

The evaluation result of Examples and Comparative Examples above-mentioned is shown in following table 2.

In table 2, taper ratio indicates the ratio of the top diameter Lt1 and base diameter Lb1 of the through-hole before roughening treatment "Lb1/Lt1".If the taper ratio Lb1/Lt1 is 75% or more, pore-forming processability is determined as " good "；If taper ratio Rate Lb1/Lt1 is lower than 75%, then pore-forming processability is determined as " bad ".

In table 2, the haloing ratio Ht before roughening treatment indicates the swooning from the edge of via top before roughening treatment The ratio " Wt/ (Lt1/2) " of the radius (Lt1/2) of via top of the circle remote from the through-hole before Wt and roughening treatment.If should Haloing ratio Ht is 35% hereinafter, haloing evaluation is then determined as " good "；If haloing ratio Ht is greater than 35%, haloing is evaluated and is determined For " bad ".

In table 2, the haloing ratio Hb after roughening treatment indicates the swooning from the edge of via bottoms after roughening treatment The ratio " Wb/ (Lb2/2) " of the radius (Lb2/2) of via bottoms of the circle remote from the through-hole after Wb and roughening treatment.If should Haloing ratio Hb is 35% hereinafter, haloing evaluation is then determined as " good "；If haloing ratio Hb is greater than 35%, haloing is evaluated and is determined For " bad ".

[table 2]

。

[discussion]

As shown in Table 2, in embodiment, insulating layer is formed using with a thickness of relatively thin resin composition layer as 10 μm, simultaneously The biggish through-hole of taper ratio can be formed on which insulating layer.It can be confirmed by the result, resin composition layer through the invention, It can be realized the insulating layer that the through-hole of excellent in shape can be formed thinner thickness.

In addition, as shown in Table 2, in embodiment, formed absolutely using with a thickness of relatively thin resin composition layer as 10 μm Edge layer, while the haloing in the haloing portion generated with through-hole formation is than small.It can be confirmed by the result, resin through the invention Composition layer can be realized the insulating layer that can inhibit halo phenomenon thinner thickness.

Particularly, as it is obtained in previous embodiment 1 and 2, with a thickness of 15 μm or less, through-hole top diameter be 35 μm Below, the phase that the taper ratio of through-hole is 80% or more, the haloing distance of the slave bottom sides genesis of through-hole is 5 μm or less and through-hole For bottom radius haloing than cannot achieve for 35% insulating layer below in the past.Therefore, such exhausted for being able to achieve For edge layer, there is significant technical meaning in the printed wiring board in recent years of slimming for expecting insulating layer.

In Examples 1 to 2, it is not explicitly shown concrete outcome when foring conductor layer on the insulating layer of roughening substrate A, But from the point of view of the result of above-described embodiment, those skilled in the art can be clearly understood that by the exhausted of roughening substrate A Conductor layer is formed in edge layer to obtain meeting the specific printed wiring board of important document (i)~(v).

In addition, in Examples 1 to 2, in the case where being free of (D) ingredient~(F) ingredient, although being had differences in degree But confirmation is attributed to same result with above-described embodiment.

[explanation of symbol]

100 insulating layers

The face of 100U and the insulating layer of conductor layer opposite side

110 through-holes

120 via bottoms

The center of 120C via bottoms

130 via tops

140 haloing portions

The edge of the via top of 150 through-holes

The edge part of the peripheral side in 160 haloing portions

The edge of the via bottoms of 170 through-holes

180 clearance portions

The end of the peripheral side of 190 clearance portions

200 internal substrates

210 conductor layers (the first conductor layer)

220 second conductor layers

300 printed wiring boards

The base diameter of Lb through-hole

The top diameter of Lt through-hole

The thickness of T insulating layer

Haloing distance of the Wt from the edge of via top

Haloing distance of the Wb from the edge of via bottoms.

Claims

It is comprising resin combination with a thickness of 15 μm of resin composition layers below 1. resin composition layer,

Wherein, resin combination includes：(A) epoxy resin；(B) containing the aromatic resins of aromatic ring, which is to have 2 or more Hydroxyl as monocycle or the aromatic ring of condensed ring；(C) average grain diameter is 100nm inorganic filling material below.
It is comprising resin combination with a thickness of 15 μm of resin composition layers below 2. resin composition layer,

Wherein, resin combination includes：(A) epoxy resin；(B) containing the aromatic resins of aromatic ring, which is to have 2 or more Hydroxyl as monocycle or the aromatic ring of condensed ring；(C) specific surface area is 15m²The inorganic filling material of/g or more.
3. resin composition layer according to claim 1 or 2, wherein (B) ingredient indicates by following formula (1) or formula (2),

In formula (1), R⁰The alkyl of divalent is each independently represented, n1 indicates 0~6 integer；

In formula (2), R¹~R⁴Each independently represent the alkyl of hydrogen atom or 1 valence.
4. resin composition layer according to claim 1 or 2, wherein (B) ingredient indicates by following formula (3) or formula (4),

In formula (3), n2 indicates 0~6 integer；

In formula (4), R¹~R⁴Each independently represent the alkyl of hydrogen atom or 1 valence.
5. resin composition layer according to claim 1 or 2, wherein relative to the resin component 100 in resin combination Quality %, the amount of (B) ingredient are 5 mass of mass %~50 %.
6. resin composition layer according to claim 1 or 2, wherein relative to the nonvolatile component in resin combination 100 mass %, the amount of (C) ingredient are 50 mass % or more.
7. resin composition layer according to claim 1 or 2, wherein the resin composition layer is used to be formed to be formed The insulating layer of conductor layer.
8. resin composition layer according to claim 1 or 2, wherein the resin composition layer is used to form printed wiring The interlayer insulating film of plate.
9. resin composition layer according to claim 1 or 2, wherein the resin composition layer is used to be formed with top Diameter is the insulating layer of 35 μm of through-holes below.
10. resin sheet, it includes：

Supporting mass and

The resin composition layer according to any one of claims 1 to 9 being set on supporting mass.
11. printed wiring board is formed it includes the solidfied material by resin composition layer according to any one of claims 1 to 9 Insulating layer.
12. printed wiring board it includes the first conductor layer, the second conductor layer and is formed in the first conductor layer and the second conductor Insulating layer between layer, wherein

Insulating layer with a thickness of 15 μm hereinafter,

It is 35 μm of through-holes below that insulating layer, which has top diameter,

The taper ratio of the through-hole is 80% or more,

The slave bottom sides genesis of the through-hole haloing distance be 5 μm hereinafter,

The haloing ratio relative to bottom radius of the through-hole is 35% or less.
13. printed wiring board according to claim 12, wherein the haloing ratio relative to bottom radius of the through-hole is 5% More than.
14. semiconductor device, it includes the printed wiring boards described in any one of claim 11~13.