CN110016203A

CN110016203A - Resin combination

Info

Publication number: CN110016203A
Application number: CN201811622499.4A
Authority: CN
Inventors: 川合贤司
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2018-01-09
Filing date: 2018-12-28
Publication date: 2019-07-16
Anticipated expiration: 2038-12-28
Also published as: JP2022003125A; TWI811275B; JP2019119819A; JP7296191B2; KR20190084890A; CN110016203B; JP7272392B2; TW201936771A

Abstract

The issue of the present invention is to provide: the resin combination for the solidfied material that dielectric loss angle tangent is low and glue residue removability is excellent can be obtained；Resin sheet with the resin composition layer comprising aforementioned resin；Printed wiring board comprising the insulating layer formed by the solidfied material of aforementioned resin；And the semiconductor device of the solidfied material comprising aforementioned resin.Solution of the invention is a kind of resin combination, is contained: (A) aromatic resins, which contains the aromatic ring as monocycle or condensed ring, and relative to the aromatic ring, with 2 or more the groups containing the oxygen atom for being bonded to aromatic ring；(B) active ester system curing agent.

Description

Resin combination

Technical field

The present invention relates to resin combinations.In turn, the present invention relates to the resin sheet, the printing cloth that have used resin combination Line plate and semiconductor device.

Background technique

In recent years, the miniaturization of electronic equipment, high performance are developing, and in multilayer printed-wiring board, stack (buildup) layer is by multiple stratification, it is desirable that the miniaturization and densification of wiring, in turn, in order to reduce transmission loss, it is desirable that dielectric The low insulating materials of loss angle tangent.

It is active esterifying containing (A) epoxy resin, (B) for example, describing a kind of resin combination in patent document 1 It closes object and (C) glue residue inhibits the resin combination of ingredient, when the nonvolatile component of the resin combination is set as 100 mass %, (C) it is 0.001~10 mass % that glue residue, which inhibits ingredient,.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2014-5464 bulletin.

Summary of the invention

Problems to be solved by the invention

When the insulating layer to multilayer printed-wiring board carries out aperture processing, (smear, resin are residual for generation glue residue in through-hole Slag), it is desirable that glue residue is removed in roughening treatment process.However, the understanding of people etc. according to the present invention, using including active ester The resin combination of the low-dielectric loss angle tangent of compound is come when making multilayer printed-wiring board, even if in the aperture of insulating layer To being roughened in through-hole after processing, the removing of the glue residue (gum residue) in through-hole is sometimes also insufficient, at For the through-hole of minor diameter, then glue residue removing becomes to be more difficult to.

Therefore, project to be solved by this invention is designed to provide: can be obtained that dielectric loss angle tangent is low and glue The resin combination of the excellent solidfied material of slag removability；Resin sheet with the resin composition layer comprising aforementioned resin Material；Printed wiring board comprising the insulating layer formed by the solidfied material of aforementioned resin；And it is combined comprising aforementioned resin The semiconductor device of the solidfied material of object.

Means for solving the problems

The present inventor has made intensive studies to solve aforementioned problems, as a result, it has been found that, it include (A) aromatic resins using combination (aromatic resins contain the aromatic ring as monocycle or condensed ring, and relative to the aromatic ring, contain key with 2 or more Together in the group of the oxygen atom of the aromatic ring) and (B) active ester system curing agent resin combination, can solve aforementioned problems, thus Complete the present invention.

That is, the present invention includes following the description,

[1] a kind of resin combination, contains:

(A) aromatic resins, the aromatic resins contain the aromatic ring as monocycle or condensed ring, and relative to the aromatic ring, have 2 A above group containing the oxygen atom for being bonded to the aromatic ring；With

(B) active ester system curing agent；

[2] resin combination described in [1], wherein (A) ingredient has structure shown in following formula (1),

[chemical formula 1]

(in formula (1), R¹¹Each independently represent 1 valence group.)

[3] resin combination described in [1] or [2], wherein (A) ingredient has structure shown in following formula (2),

[chemical formula 2]

(in formula (2), R²¹Each independently represent 1 valence group.)

[4] resin combination described in [1] or [2], wherein (A) ingredient by following formula (3) indicate,

[chemical formula 3]

(in formula (3), R³¹Each independently represent 1 valence group, R³²Each independently represent divalent alkyl.N3 indicate 0~10 it is whole Number.)

[5] resin combination described in any one of [1]~[4], wherein (A) ingredient by following formula (6) indicate,

[chemical formula 4]

(in formula (6), R⁶¹Each independently represent 1 valence group.N6 indicates 0~10 integer.)

[6] resin combination described in any one of [1]~[5], wherein the group containing the oxygen atom for being bonded to aromatic ring is Alkylenepoxy oxygroup, alkoxy or hydroxyl；

[7] resin combination described in any one of [1]~[6], wherein also contain (C) epoxy resin；

[8] resin combination described in [7], wherein when the total content of (A) ingredient and (C) ingredient is set as 100 mass %, (A) The content of ingredient is 5 mass % or more and 50 mass % or less；

[9] resin combination described in any one of [1]~[8], wherein be set as the nonvolatile component in resin combination When 100 mass %, the content of (B) ingredient is 1 mass % or more and 30 mass % or less；

[10] resin combination described in any one of [1]~[9], wherein also contain (D) inorganic filling material；

[11] resin combination described in [10], wherein when the nonvolatile component in resin combination is set as 100 mass %, (D) content of ingredient is 50 mass % or more；

[12] resin combination described in any one of [1]~[11], is the insulating layer for being used to form multilayer printed-wiring board Resin combination；

[13] resin combination described in any one of [1]~[12], be used to form with top diameter be 35 μm or less Through-hole insulating layer resin combination；

[14] resin combination described in any one of [1]~[13], be used to form thickness (μm) with insulating layer with The resin combination of the insulating layer for the through-hole that the radius-thickness ratio (thickness/top diameter of insulating layer) of top diameter (μm) is 0.5 or more Object；

[15] a kind of resin sheet, it includes: supporting mass and be set on the supporting mass comprising any one of [1]~[14] The resin composition layer of the resin combination；

[16] resin sheet described in [15], wherein resin composition layer with a thickness of 20 μm or less；

[17] a kind of printed wiring board, it includes the solidfied materials of the resin combination as described in any one of [1]~[14] to be formed Insulating layer；

[18] a kind of semiconductor device, it includes the printed wiring boards described in [17].

The effect of invention

Through the invention, it is possible to provide: the resin for the solidfied material that dielectric loss angle tangent is low and glue residue removability is excellent can be obtained Composition；Resin sheet with the resin composition layer comprising aforementioned resin；Comprising by aforementioned resin The printed wiring board for the insulating layer that solidfied material is formed；And the semiconductor device of the solidfied material comprising aforementioned resin.

Specific embodiment

Hereinafter, showing embodiment and illustrative material, the present invention is explained 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 without departing from claims of the present invention and its equivalents To implement.

[resin combination]

Resin combination of the invention contains: (A) aromatic resins, which contains the aromatic ring as monocycle or condensed ring, and And relative to the aromatic ring, with 2 or more the groups containing the oxygen atom for being bonded to the aromatic ring；And (B) active ester system Curing agent.By using such resin composition layer, the following desired effect of the present invention can be obtained, dielectric can be obtained The solidfied material that loss angle tangent is low, glue residue removability is excellent.Therefore, flexibly sharp for the solidfied material of the resin combination With its excellent characteristic, can be used as the insulating layer of multilayer printed-wiring board and it is preferable to use.

In addition, aforementioned resin other than comprising (A)~(B) ingredient, can also include arbitrary ingredient.As Arbitrary ingredient can enumerate such as (C) epoxy resin, (D) inorganic filling material, (E) curing agent, (F) thermoplastic resin, (G) Curing accelerator and (H) other additives etc..Hereinafter, each ingredient for including in the resin combination that the present invention will be described in detail.

< (A) aromatic resins, the aromatic resins contain the aromatic ring as monocycle or condensed ring, and relative to the virtue Ring, with 2 or more the group > containing the oxygen atom for being bonded to the aromatic ring

Resin combination contains (A) aromatic resins, which contains the aromatic ring as monocycle or condensed ring, and relative to one A aromatic ring, with 2 or more the groups containing the oxygen atom for being bonded to the aromatic ring.For aromatic ring, it is easy by containing There is the supplied for electronic of the oxygen atom in the group for the oxygen atom for being bonded to the aromatic ring and is oxidized.In addition, due to relative to a virtue Ring includes 2 or more the groups, therefore aromatic ring is easier to be oxidized.Therefore, because (A) ingredient is oxidized easily, therefore can improve The glue residue removability of the solidfied material of resin combination.

Herein, term " aromatic ring " includes: phenyl ring etc as the aromatic ring of monocycle and the virtue as condensed ring of naphthalene nucleus etc Any one of ring.From the viewpoint of significantly obtaining the desired effect of the present invention, the aforementioned virtue that includes in each (A) ingredient The carbon atom number of ring is preferably 6 or more, and more preferably 10 or more, preferably 20 are hereinafter, more preferably 14 or less.

As the example of aromatic ring, the monocycles such as phenyl ring, cyclohexyl biphenyl can be enumerated；The condensed ring such as naphthalene nucleus, anthracene nucleus；Etc., from further From the viewpoint of improving glue residue removability, preferred condensed ring.In addition, the type for the aromatic ring for including in a molecule aromatic resins can be 1 kind, or two or more.

At least one aromatic ring in aromatic ring that aromatic resins as (A) ingredient are included, relative to the aromatic ring, tool There are 2 or more the groups containing the oxygen atom for being bonded to the aromatic ring.From the viewpoint for significantly obtaining the desired effect of the present invention Consider, is preferably 4 hereinafter, more preferably relative to aromatic ring, group containing the oxygen atom for being bonded to aromatic ring number For 3 hereinafter, particularly preferably 2.

Each molecule (A) ingredient, virtue with 2 or more " groups containing the oxygen atom for being bonded to aforementioned aromatic ring " The number of ring is usually 1 or more, from the viewpoint of significantly obtaining the desired effect of the present invention, preferably 2 or more, more Preferably 3 or more.The upper limit is not particularly limited, from the reactive viewpoint for inhibiting steric hindrance and raising and epoxy resin Consider, preferably 6 hereinafter, more preferably 5 or less.

As the example of the group containing the oxygen atom for being bonded to aromatic ring, alkylenepoxy oxygroup, alkoxy, hydroxyl can be enumerated Base etc..From the viewpoint of significantly obtaining the desired effect of the present invention, alcoxyl that the preferred carbon atom number of alkoxy is 1~10 Base, the alkoxy that more preferable carbon atom number is 1~6, the alkoxy that further preferred carbon atom number is 1~3, particularly preferred carbon are former The alkoxy (methoxyl group) that subnumber is 1.From the viewpoint of significantly obtaining the desired effect of the present invention, alkylenepoxy oxygroup In the carbon atom number of alkylidene be preferably 1~10, carbon atom number is more preferably 1~6, further preferred carbon atom number is 1~ 3, particularly preferred carbon atom number is 1 (glycidyl ether).

As (A) ingredient, for example, it is preferable to the aromatic resins with structure shown in following formula (1)；

[chemical formula 5]

(in formula (1), R¹¹Each independently represent 1 valence group).

In formula (1), R¹¹Each independently represent 1 valence group.Group containing the oxygen atom for being bonded to aromatic ring is in formula (1) "-OR¹¹".As the example of 1 valence group, can enumerate: hydrogen atom；Epoxy alkyl, can having with 1 valence such as substituted alkyl Machine group etc..The carbon atom number of alkyl and alkyl in epoxy alkyl is same as the carbon atom number of alkoxy above-mentioned.As The substituent group of alkyl can be enumerated such as halogen atom, hydroxyl, epoxy group.In addition, 2 or more substituent groups can be bonded and Form ring.Wherein, from the viewpoint of improving glue residue removability, R¹¹Preferably epoxy alkyl, hydrogen atom, more preferably epoxy Base alkyl, further preferably glycidyl.

Structure shown in formula (1) is preferably indicated by following formula (2)；

[chemical formula 6]

(in formula (2), R²¹Each independently represent 1 valence group).

In formula (2), R²¹Indicate 1 valence group, R²¹With the R in formula (1)¹¹Meaning is identical.As formula (2), by naphthalene nucleus 1 and 6 bonding containing be bonded to aromatic ring oxygen atom group, can be further improved glue residue removability.

As (A) ingredient, for example, it is preferable to for aromatic resins shown in following formula (3)；

[chemical formula 7]

(in formula (3), R³¹Each independently represent 1 valence group, R³²Each independently represent divalent alkyl.N3 indicate 0~10 it is whole Number).

In formula (3), R³¹Indicate 1 valence group, R³¹With the R in formula (1)¹¹Meaning is identical.

In formula (3), R³²Indicate divalent alkyl.Divalent alkyl can be aliphatic alkyl, or aryl, or The group that aliphatic alkyl and aryl are composed.The carbon atom number of divalent alkyl is usually 1 or more, obtains this from significant It can be preferably 3 or more, more preferably 5 or more, further preferably 7 or more from the viewpoint of inventing desired effect.It is right For the upper limit of carbon atom number above-mentioned, from the viewpoint of significantly obtaining the desired effect of the present invention, preferably can be 20 or less, 15 or less or 10 or less.

As R³²Concrete example, following divalent alkyls can be enumerated.

[chemical formula 8]

。

In formula (3), n3 indicates 0~10 integer.From the viewpoint of significantly obtaining the desired effect of the present invention, n3 is excellent 0 or more, more preferably 2 or more, further preferably 3 or more, preferably 10 are selected as hereinafter, more preferably 5 or less.

Aromatic resins shown in formula (3) are preferably aromatic resins shown in following formula (4)；

[chemical formula 9]

(in formula (4), R⁴¹Each independently represent 1 valence group, R⁴²Each independently represent alkylidene.N4 indicate 0~10 it is whole Number).

In formula (4), R⁴¹Indicate 1 valence group, R⁴¹With the R in formula (1)¹¹Meaning is identical.

In formula (4), R⁴²Indicate alkylidene.As the carbon atom number of alkylidene, preferably 10 hereinafter, more preferably 6 hereinafter, Further preferably 3 hereinafter, can be 1 or more for lower limit.Wherein, the desired effect of the present invention is obtained from significant From the viewpoint of, preferably methylene, dimethylethylene.

In formula (4), n4 indicates that 0~10 integer, n4 are identical as the n3 meaning in formula (3).

Phenylene in formula (4) is preferably in 1 and 4 and 2 by R⁴²The alkylene of expression.

Aromatic resins shown in formula (4) are preferably aromatic resins shown in following formula (5)；

[chemical formula 10]

(in formula (5), R⁵¹Each independently represent 1 valence group, R⁵²Each independently represent alkylidene.N5 indicate 0~10 it is whole Number).

In formula (5), R⁵¹Indicate 1 valence group, R⁵¹With the R in formula (1)¹¹Meaning is identical.

In formula (5), R⁵²Indicate alkylidene.R⁵²With the R in formula (4)⁴²Meaning is identical.

In formula (5), n5 indicates that 0~10 integer, n5 are identical as the n3 meaning in formula (3).

Wherein, as (A) ingredient, preferably aromatic resins shown in following formula (6)；

[chemical formula 11]

(in formula (6), R⁶¹Each independently represent 1 valence group.N6 indicates 0~10 integer).

In formula (6), R⁶¹Indicate 1 valence group, R⁶¹With the R in formula (1)¹¹Meaning is identical.

In formula (6), n6 indicates that 0~10 integer, n6 are identical as the n3 meaning in formula (3).

As the commercially available product of (A) ingredient, can enumerate for example: Nippon Steel live aurification corporation " ESN375 ", " HP4032 " of " SN395 ", DIC corporation, " HP4032D ", " HP4032SS ", " HP4032H ", " HP4700 ", " HP4710 ", " NC3500 " etc. of Japanese chemical drug corporation.

Aromatic resins as (A) ingredient can be used alone, and also can be used in combination two or more.

(A) ingredient containing when to be bonded to the group of the oxygen atom of aromatic ring include epoxy group, from significantly obtaining institute of the present invention From the viewpoint of desired effect, the epoxide equivalent of (A) ingredient is preferably 50~5000g/eq., more preferably 50~3000g/ Eq., further preferably 80~2000g/eq. is even more preferably 90~1000g/eq..Epoxide equivalent is to include 1 equivalent The quality of the resin of epoxy group.The epoxide equivalent can be measured according to JIS K7236.

(A) ingredient containing when to be bonded to the group of the oxygen atom of aromatic ring include hydroxyl, be used as resin combination from improving The viewpoint of the crosslink density of the insulating layer of the solidfied material of layer and from the viewpoint of significantly obtaining the desired effect of the present invention, (A) The hydroxyl equivalent of ingredient is preferably 50g/eq. or more, more preferably 60g/eq. or more, further preferably 70g/eq. or more, Also, preferably 250g/eq. hereinafter, more preferably 150g/eq. hereinafter, particularly preferably 120g/eq. or less.Hydroxyl equivalent For the quality of the resin comprising 1 equivalent of hydroxyl groups.

In addition, (A) ingredient containing when to be bonded to the group of the oxygen atom of aromatic ring include hydroxyl, by (C) epoxy resin Epoxy radix when being set as 1, from the viewpoint of obtaining the superior solidfied material of glue residue removability, (A) ingredient contains bonding In the group number of the oxygen atom of aromatic ring be preferably 1 or more, more preferably 5 or more, further preferably 10 or more, preferably 30 with Under, more preferably 25 hereinafter, further preferably 20 or less.Herein, so-called " the epoxy radix of (C) epoxy resin ", refer to by Divided by value obtained by epoxide equivalent, all adduction obtains the quality of the nonvolatile component of (C) ingredient present in resin combination Value.In addition, so-called " the group number containing the oxygen atom for being bonded to aromatic ring of (A) ingredient ", referring to will deposit in resin combination (A) ingredient nonvolatile component quality divided by containing be bonded to aromatic ring oxygen atom group equivalent obtained by value entirely It is worth obtained from portion's adduction.

From the viewpoint of obtaining the excellent solidfied material of glue residue removability, the nonvolatile component in resin combination is set as When 100 mass %, the content of (A) ingredient is preferably 0.5 mass % or more, more preferably 0.8 mass % or more, and further preferably 1 Quality % or more, preferably 15 mass % hereinafter, more preferably 10 mass % hereinafter, further preferably 8 mass % or less or 5 matter Measure % or less；

It should be noted that in the present invention, about the content of each ingredient in resin combination, as long as no separately specifically It is bright, refer to the value when nonvolatile component in resin combination to be set as to 100 mass %.

In addition, from the viewpoint of obtaining the superior solidfied material of glue residue removability, by (A) ingredient and aftermentioned (C) ring When the total content of oxygen resin is set as 100 mass %, the content of (A) ingredient is preferably 2 mass % or more, more preferably 5 mass % with On, further preferably 15 mass % or more, preferably 50 mass % hereinafter, more preferably 40 mass % hereinafter, further preferably 30 mass % or less.

< (B) active ester system curing agent >

Resin combination contains (B) active ester system curing agent.When using active ester system curing agent, dielectric loss angle can be usually reduced Tangent, but then, glue residue removability are poor.However, resin combination of the invention thus can be obtained due to containing (A) ingredient To following resin combination: available to reduce dielectric loss angle tangent and the excellent solidfied material of glue residue removability.

As (B) active ester system curing agent, it is usually preferred to use phenolic ester class (phenol ester), thiophenol esters (thiophenol ester), N- hydroxylamine esters, the esters of heterocycle hydroxyl compound etc. are anti-with 2 or more in a molecule The compound for the ester group for answering activity high.For the active ester system curing agent, preferably pass through carboxylic acid compound and/or thiocarboxylic It closes the condensation reaction of object and hydroxy compounds and/or mercaptan compound and obtains.Especially from the viewpoint of heat resistance raising, It is preferred that the active ester system curing agent obtained by carboxylic acid compound and hydroxy compounds, more preferably by carboxylic acid compound and phenol chemical combination The active ester system curing agent that object and/or naphthol compound obtain.As carboxylic acid compound, can enumerate for example: benzoic acid, acetic acid, Succinic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc..As phenolated Object or naphthol compound are closed, can be enumerated for example: hydroquinone, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, methylation Bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, alpha-Naphthol, β-naphthalene Phenol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, four hydroxyls Base benzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type bisphenol compounds, phenol novolacs (phenol Novolac) etc..Herein, so-called " dicyclopentadiene-type bisphenol compounds " refer to the bicyclopentadiene and two molecules of a molecule Phenol condensation obtained from bisphenol compounds.

Specifically, it is preferable that dicyclopentadiene-type active ester system curing agent, the active ester system curing agent comprising naphthalene structure, packet The active ester of the active ester system curing agent of acetylate containing phenol novolacs, benzoylate comprising phenol novolacs It is curing agent, wherein more preferable includes active ester system curing agent, the dicyclopentadiene-type active ester system curing agent of naphthalene structure, into One step preferred dicyclopentadiene-type active ester system curing agent.As dicyclopentadiene-type active ester system curing agent, two are preferably comprised The active ester system curing agent of Cyclopeutadiene type biphenol structure.So-called " dicyclopentadiene-type biphenol structure " is indicated by sub- benzene The structural unit for the divalent that-two cyclopentylenes of base-phenylene is formed.

For the commercially available product of (B) active ester system curing agent, as the work comprising dicyclopentadiene-type biphenol structure Property ester system curing agent, can enumerate " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-65T ", " HPC-8000H- 65TM ", " EXB8000L-65TM " (DIC corporation)；As the active ester system curing agent comprising naphthalene structure, can enumerate " EXB8150-60T ", " EXB9416-70BK " (DIC corporation)；Activity as the acetylate comprising phenol novolacs Ester system curing agent can enumerate " DC808 " (Mitsubishi Chemical Ind's system)；Work as the benzoylate comprising phenol novolacs Property ester system curing agent, can enumerate " YLH1026 " (Mitsubishi Chemical Ind's system)；Work as the acetylate for being phenol novolacs Property ester system curing agent, can enumerate " DC808 " (Mitsubishi Chemical Ind's system)；Work as the benzoylate for being phenol novolacs Property ester system curing agent, can enumerate " YLH1026 " (Mitsubishi Chemical Ind's system), " YLH1030 " (Mitsubishi Chemical Ind's system), " YLH1048 " (Mitsubishi Chemical Ind's system)；Etc..

(B) the amount ratio of active ester system curing agent and (A) and (C) ingredient is with [sum of the epoxy group of (A) and (C) ingredient]: The ratiometer of [sum of the reactive group of active ester system curing agent] is preferably the range of 1:0.01~1:5, more preferably 1:0.05 ~1:2, further preferably 1:0.1~1:1.8.Herein, the reactive group of so-called active ester system curing agent refers to active ester groups.Separately Outside, the sum of the epoxy group of so-called (A) and (C) ingredient refers to, the solid component quality of each ingredient is obtained divided by epoxide equivalent Value all adduction obtained from be worth；The sum of the reactive group of so-called active ester system curing agent refers to, for whole active esters It is curing agent, by the solid component quality of each active ester system curing agent divided by obtained from value adduction obtained by reactive group equivalent Value.By making the amount ratio above range of epoxy resin Yu active ester system curing agent, so that the solidfied material of resin combination is resistance to It is hot to further increase.

When nonvolatile component in resin combination is set as 100 mass %, the content of (B) active ester system curing agent is preferred For 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more.In addition, the upper limit is preferably 30 mass % Hereinafter, more preferably 20 mass % are hereinafter, further preferably 15 mass % or less.By the above-mentioned model of content for making (B) ingredient In enclosing, so as to obtain the excellent solidfied material of glue residue removability.

< (C) epoxy resin >

Resin combination can contain (C) epoxy resin.It but does not include the substance for belonging to (A) ingredient in (C) ingredient.

It as (C) epoxy resin, can enumerate for example: union II cresols (bixylenol) type epoxy resin, bisphenol type epoxy Resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, three Phenol-type epoxy resin, naphthol novolac (naphthol novolac) type epoxy resin, phenol novolac (phenol novolac) type Epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, Glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac (cresol novolac) type epoxy resin, It is biphenyl type epoxy resin, linear aliphatic epoxy resin, the epoxy resin with butadiene structure, cycloaliphatic epoxy resin, miscellaneous Ring type epoxy resin contains whorled epoxy resin, 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 One kind also can be used in combination two or more.

In resin combination, as (C) epoxy resin, it preferably is contained in the ring in a molecule with 2 or more epoxy groups Oxygen resin.Nonvolatile component from the viewpoint of significantly obtaining the desired effect of the present invention, relative to (C) epoxy resin For 100 mass %, the ratio of the epoxy resin in a molecule with 2 or more epoxy groups is preferably 50 mass % or more, more Preferably 60 mass % or more, particularly preferably 70 mass % or more.

Include in epoxy resin 20 DEG C at a temperature of be liquid epoxy resin (hereinafter sometimes referred to " liquid epoxy tree Rouge ") and 20 DEG C at a temperature of be solid epoxy resin (hereinafter sometimes referred to " solid epoxy resin ").For resin combination For object, it can only include liquid-state epoxy resin as (C) epoxy resin, can also only include solid epoxy resin, but preferably It in combination include liquid-state epoxy resin and solid epoxy resin.By using liquid-state epoxy resin and solid epoxy resin in combination As (C) epoxy resin, the flexibility of resin composition layer can be improved, alternatively, the disconnected of the solidfied material of resin composition layer can be improved Resistance to spalling.

As liquid-state epoxy resin, with the liquid-state epoxy resin of 2 or more epoxy groups preferably in a molecule, more preferably The liquid-state epoxy resin of aromatics system in a molecule with 2 or more epoxy groups.Herein, the epoxy resin of so-called " aromatics system " Refer to the epoxy resin that there is aromatic ring in its intramolecular.

As liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type asphalt mixtures modified by epoxy resin Rouge, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy, Cycloaliphatic epoxy resin, hexamethylene type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine with ester skeleton Type epoxy resin and epoxy resin with butadiene structure；More 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: " 828US " of Mitsubishi Chemical Ind, " jER828EL ", " 825 ", " Epikote 828EL " (bisphenol A type epoxy resin)；" jER807 ", " 1750 " (Bisphenol F of Mitsubishi Chemical Ind Type epoxy resin)；" jER152 " (phenol novolak type epoxy) of Mitsubishi Chemical Ind；Mitsubishi Chemical Ind " 630 ", " 630LSD " (glycidyl amine type epoxy resin)；" ZX1059 " (bisphenol-A type ring of aurification corporation is lived by Nippon Steel The melange of oxygen resin and bisphenol f type epoxy resin)；" EX-721 " (glycidyl ester type of Nagase ChemteX corporation Epoxy resin)；" Celloxide 2021P " (cycloaliphatic epoxy resin with ester skeleton) of Co., Ltd.'s Daicel；Strain " PB-3600 " (epoxy resin with butadiene structure) of formula commercial firm Daicel；Aurification corporation is lived by Nippon Steel " ZX1658 ", " ZX1658GS " (liquid 1,4- glycidol butylcyclohexane type ring oxygen resin) etc..They can be used alone one Kind, it also can be used in combination two or more.

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

As solid epoxy resin, preferably union II first phenol-type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional 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.

It as the concrete example of solid epoxy resin, can enumerate: " N-690 " (cresol novolak type epoxy tree of DIC corporation Rouge)；" N-695 " (the cresol novolak type epoxy resin) of DIC corporation；" HP-7200 " of DIC corporation, " HP-7200HH ", " HP-7200H " (dicyclopentadiene-type epoxy resin)；" EXA-7311 ", " EXA-7311-G3 ", " EXA- of DIC corporation 7311-G4 ", " EXA-7311-G4S ", " HP6000 " (naphthylene ether type epoxy)；" the EPPN- of Japanese chemical drug corporation 502H " (tris phenol type epoxy)；" NC7000L " (the naphthol novolac type epoxy resin) of Japanese chemical drug corporation；Japanese chemical drug " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin) of corporation；Aurification is lived by Nippon Steel " ESN475V " (naphthol type epoxy resin) of corporation；" ESN485 " (naphthol novolac type ring of aurification corporation is lived by Nippon Steel Oxygen resin)；" YX4000H ", " YX4000 ", " YL6121 " (biphenyl type epoxy resin) of Mitsubishi Chemical Ind；Mitsubishi Chemical " YX4000HK " (the union II first phenol-type epoxy resin) of corporation；" YX8800 " (anthracene type asphalt mixtures modified by epoxy resin of Mitsubishi Chemical Ind Rouge)；" PG-100 ", " CG-500 " of Osaka combustion gas chemistry corporation；" YL7760 " (bisphenol AF type ring of Mitsubishi Chemical Ind Oxygen resin)；" YL7800 " (the fluorenes type epoxy resin) of Mitsubishi Chemical Ind；" jER1010 " (solid-state of Mitsubishi Chemical Ind Bisphenol A type epoxy resin)；" jER1031S " (the tetraphenyl ethane type epoxy resin) of Mitsubishi Chemical Ind etc..They can be with One kind is used alone, also can be used in combination two or more.

When using liquid-state epoxy resin and solid epoxy resin in combination as (C) epoxy resin, their amount ratio (liquid Epoxy resin: solid epoxy resin) by quality ratio be preferably 1:1~1:20, more preferably 1:1~1:15, particularly preferably 1:1~1:10.In amount ratio above range by making liquid-state epoxy resin and solid epoxy resin, the present invention can be significantly obtained Desired effect.In addition, in general, in the form of resin sheet in use, appropriate adhesiveness can be brought.In addition, in general, In use, sufficient flexibility can be obtained, treatability is improved in the form of resin sheet.In addition, in general, can obtain having abundant Breaking strength solidfied material.

(C) epoxide equivalent of epoxy resin is preferably 50~5000g/eq., more preferably 50~3000g/eq., further Preferably 80~2000g/eq. is even more preferably 110~1000g/eq..By becoming above range, resin combination The crosslink density of the solidfied material of layer becomes that sufficiently, the small insulating layer of surface roughness can be formed.Epoxide equivalent is to include 1 equivalent ring The quality of the resin of oxygroup.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 (C) epoxy resin is excellent It is selected as 100~5000, more preferably 250~3000, further preferably 400~1500.

The weight average molecular weight of resin can using gel permeation chromatography (GPC) method, as the value by weight of polystyrene To measure.

When resin combination contains (C) epoxy resin, from the insulation for obtaining showing good mechanical strength, insulating reliability From the viewpoint of layer, when the nonvolatile component in resin combination is set as 100 mass %, the content of (C) epoxy resin is preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more.It is desired from the present invention is significantly obtained From the viewpoint of effect, the upper limit of the content of epoxy resin is preferably 30 mass % hereinafter, more preferably 25 mass % are hereinafter, especially Preferably 20 mass % or less.

< (D) inorganic filling material >

Resin combination can contain (D) inorganic filling material.As the material of inorganic filling material, inorganic compound is used. The example of material as inorganic filling material can be enumerated: silica, aluminium oxide, glass, cordierite, Si oxide, sulfuric acid Barium, barium carbonate, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, carbonic acid Magnesium, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, oxidation Titanium, zirconium oxide, barium titanate, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc..It is especially excellent in these Select silica.As silica, can enumerate for example: amorphous silica, fused silica, crystalline silica, Synthetic silica, hollow silica etc..In addition, as silica, preferred spherical silicon dioxide.(D) inorganic fill material Material can be used alone, and also can be used in combination two or more.

It as the commercially available product of (D) inorganic filling material, can enumerate for example: " the SP60- of Zhu Jin Materials Co., Ltd, Nippon Steel 05","SP507-05"；" YC100C ", " YA050C ", " YA050C-MJE ", " YA010C " of Admatechs corporation；Electrification (Denka) " UFP-30 " of corporation；" Silfil (the シ Le Off ィ Le) NSS-3N " of moral mountain (Tokuyama) corporation, "Silfil NSS-4N","Silfil NSS-5N"；" SC2500SQ " of Admatechs corporation, " SO-C4 ", " SO-C2 ", "SO-C1"；Etc..

From the viewpoint of significantly obtaining the desired effect of the present invention, the average grain diameter of (D) inorganic filling material is preferred It is 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm hereinafter, more preferably 2 μm Hereinafter, further preferably 1 μm or less.

(D) average grain diameter of inorganic filling material is using the laser diffraction-scattering method for being based on Michaelis (Mie) scattering theory To measure.Specifically, can measure in the following manner: laser diffraction and scattering formula particle size distribution analyzer is utilized, with volume The particle diameter distribution of inorganic filling material is made in benchmark, using its median particle diameter as average grain diameter.About measurement sample, it can be used and claim Measure inorganic filling material 100mg, dispersing agent (Sannopco corporation " SN9228 ") 0.1g, methyl ethyl ketone 10g to phial In (vial container), sample obtained from dispersion in 20 minutes is carried out using ultrasonic wave.For measurement sample, laser is used Diffraction-type particle size distribution analyzer (Shimadzu Scisakusho Ltd's system " SALD-2200 "), with pond in batches (batch cell) Mode measures particle diameter distribution, calculates average grain diameter as median particle diameter.

From the shape for being easy to control through-hole and from the viewpoint of realizing good shape, the ratio table of (D) inorganic filling material Area is preferably 1m²/ g or more, more preferably 2m²/ g or more, particularly preferably 5m²/ g or more.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 using BET method.

For (D) inorganic filling material, from the viewpoint of improving moisture-proof and dispersibility, preferably with surface treatment Agent is handled.It as surface treating agent, can enumerate for example: fluorine containing silane coupling agent, amino silicone methane series coupling agent, epoxy group silicon Methane series coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, alkoxy silane, organic silazane hydride compounds, titanate esters system Coupling agent etc..In addition, surface treating agent can be used alone, can also arbitrarily be applied in combination two or more.

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

It, preferably will be at the surface that carried out using surface treating agent from the viewpoint of the dispersibility for improving inorganic filling material The degree of reason is limited in defined range.Specifically, for 100 mass parts of inorganic filling material, preferably with 0.2 mass parts~ The surface treating agent of 5 mass parts is surface-treated, and is preferably surface-treated with 0.2 mass parts~3 mass parts, is preferably used 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 of inorganic filling material Long-pending carbon amounts is preferably 0.02mg/m²More than, more preferably 0.1mg/m²More than, further preferably 0.2mg/m²More than.It is another Aspect, from the viewpoint of the melt viscosity rising under the melt viscosity and sheet form for inhibiting resin varnish, preferably 1mg/ m²Hereinafter, more preferably 0.8mg/m²Hereinafter, further preferably 0.5mg/m²Below.

The carbon amounts of per unit surface area about inorganic filling material, can be in utilization solvent (for example, methyl ethyl ketone (MEK)) it is measured after carrying out carrying out washing treatment to the inorganic filling material after surface treatment.Specifically, by as solvent Enough MEK are added in the inorganic filling material being surface-treated with surface treating agent, in 25 DEG C of progress, 5 minutes ultrasounds Wave washing.Supernatant is removed, keeps solid component dry, then, using carbon analysis meter, every list of inorganic filling material can be measured The carbon amounts of bit surface area.As carbon analysis meter, Horiba Ltd's system " EMIA-320V " etc. can be used.

When resin combination contains (D) inorganic filling material, examined from the viewpoint for the dielectric loss angle tangent for reducing insulating layer Consider, relative to the 100 mass % of nonvolatile component in resin combination, the content of (D) inorganic filling material is preferably 50 mass % More than, more preferably 60 mass % or more, further preferably 65 mass % or more, preferably 90 mass % are hereinafter, more preferably 85 Quality % is hereinafter, further preferably 80 mass % or less.

< (E) curing agent >

Resin combination can contain (E) curing agent.It but does not include (B) active ester system curing agent in (E) curing agent.As (E) Curing agent can be enumerated for example: phenol system curing agent, naphthols system curing agent, benzoxazine system curing agent, cyanate system curing agent, And carbodiimide system curing agent etc..Wherein, from the viewpoint of improving insulating reliability, (E) curing agent is preferably that phenol system is solid More than any in agent, naphthols system curing agent, cyanate system curing agent and carbodiimide system curing agent, more preferably include Phenol system curing agent.Curing agent can be used alone, or can also and with two or more.

As phenol system curing agent and naphthols system curing agent, from the viewpoint of heat resistance and water resistance, preferably there is phenol The phenol system curing agent of aldehyde structure or naphthols system curing agent with phenolic structure.In addition, from the sight of the adaptation with conductor layer Point consideration, preferably nitrogenous phenol system curing agent, further preferably the phenol system curing agent of triazine skeleton.

It as phenol system curing agent and the concrete example of naphthols system curing agent, can enumerate for example: bright and chemical conversion corporation Gold is lived by " MEH-7700 ", " MEH-7810 ", " MEH-7851 ", " NHN " of Japanese chemical drug corporation, " CBN ", " GPH ", Nippon Steel " SN170 " of chemical company, " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495 ", " SN-495V ", " SN375 ", " SN395 ", " TD-2090 " of DIC corporation, " LA-7052 ", " LA-7054 ", " LA-1356 ", " LA-3018- 50P ", " EXB-9500 " etc..

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.

It as cyanate system curing agent, can enumerate for example: bisphenol A dicyanate, polyphenol cyanate (polyphenol Cyanate), oligomeric (3- methylene -1,5- phenylenecyanate), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- 3,5-dimethylphenyl cyanate), Bis- (4- cyanate) phenyl-propanes of 4,4 '-ethylidenediphenyl dicyanates, hexafluoro bisphenol-a dicyanate, 2,2-, 1,1- are bis- (4- cyanate phenylmethane), bis- (4- cyanate -3,5- 3,5-dimethylphenyl) methane, bis- (the 4- cyanate phenyl -1- (first of 1,3- Base ethylidene)) the two function cyanate ester resins such as benzene, bis- (4- cyanate phenyl) thioethers and bis- (4- cyanate phenyl) ethers, by benzene Multifunctional cyanate ester resin derived from phenol phenolic resin and cresol novolac resin etc., these cyanate ester resins carry out a part of triazine Prepolymer obtained from change etc..As the concrete example of cyanate system curing agent, " PT30 " of Lonza Japan corporation can be enumerated And " PT60 " (phenol novolak type multifunctional cyanate ester resin), " ULL-950S " (multifunctional cyanate ester resin), " BA230 ", " BA230S75 " (part or all of bisphenol A 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.

When resin combination contains (E) curing agent, the amount ratio of (A) and (C) ingredient and (E) curing agent with [(A) and (C) at The sum for the epoxy group divided]: the ratiometer of [sum of the reactive group of curing agent] is preferably the range of 1:0.01~1:2, more excellent It is selected as 1:0.01~1:1, further preferably 1:0.03~1:0.5.Herein, the reactive group of so-called curing agent refers to activity hydroxy Deng different according to the type of curing agent.The sum of the reactive group of so-called curing agent refers to, for whole curing agent, will be each The solid component quality of curing agent is worth divided by obtained from value adduction obtained by reactive group equivalent.By make (A) and (C) ingredient with The amount ratio of curing agent is above range, so that the heat resistance of the solidfied material of resin combination further increases.

When resin combination contains (B) active ester system's curing agent and (E) curing agent, (A) and (C) ingredient and (B) active ester It is the amount ratio of curing agent and (E) curing agent with [sum of the epoxy group of (A) and (C) ingredient]: [reactive group of (B) and (E) ingredient Sum] ratiometer be preferably 1:0.01~1:5 range, more preferably 1:0.05~1:2, further preferably 1:0.1 ~1:1.By making above-mentioned amount ratio above range, so that the heat resistance of the solidfied material of resin combination further increases.

When resin combination contains (E) curing agent, when the nonvolatile component in resin combination is set as 100 mass %, (E) content of curing agent is preferably 0.1 mass % or more, further preferably 0.3 mass % or more, more preferably 0.5 mass % with On.The upper limit is preferably 5 mass % hereinafter, more preferably 3 mass % are hereinafter, further preferably 1 mass % or less.By keeping (E) solid The content of agent is in above range, so that the heat resistance of the solidfied material of resin combination further increases.

< (F) thermoplastic resin >

Resin combination can contain (F) thermoplastic resin.About the thermoplastic resin as (F) ingredient, can enumerate for example: benzene Oxygroup resin, polyvinyl acetal resin, polyolefin resin, polybutadiene, polyimide resin, polyamidoimide tree Rouge, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyether-ether-ketone resin, gathers polyetherimide resin Ester resin etc..Wherein, from the viewpoint for significantly obtaining the desired effect of the present invention and obtain that surface roughness is small and and conductor From the viewpoint of the especially excellent insulating layer of adaptation of layer, preferred phenoxy resin.In addition, thermoplastic resin can individually make With one kind, or also can be used in combination two or more.

It as phenoxy resin, can enumerate for example: have selected from by bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, double Phenol acetophenone skeleton, phenolic aldehyde skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, enb skeleton, naphthalene skeleton, anthracene bone The phenoxy group tree of the skeleton of one or more of the group of frame, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton composition Rouge.The end of phenoxy 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 (be containing The phenoxy resin of bisphenol A skeleton)；" YX8100 " (phenoxy resin containing bisphenol S skeleton) of Mitsubishi Chemical Ind；Three " YX6954 " (phenoxy resin containing bis-phenol acetophenone skeleton) of water chestnut chemical company；Aurification corporation is lived by Nippon Steel " FX280 " and " FX293 "；" YL7500BH30 " of Mitsubishi Chemical Ind, " YX6954BH30 ", " YX7553 ", " YX7553BH30 ", " YL7769BH30 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 "；Etc..

It as polyvinyl acetal resin, can enumerate for example: vinyl-formal resin, polyvinyl butyral tree Rouge, preferably polyvinyl butyral resin.As the concrete example of polyvinyl acetal resin, can enumerate: electrochemically industry is public Take charge of system " Denka Butyral 4000-2 ", " Denka Butyral 5000-A ", " Denka Butyral 6000-C ", "Denka Butyral 6000-EP"；The S-LEC BH series of ponding chemical industrial company, BX series (such as BX-5Z), KS Serial (such as KS-1), BL series, BM series；Etc..

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 make two functional hydroxyl groups end polybutadiene, Diisocyanate cpd and quaternary acid anhydrides linear polyimides (Japanese Unexamined Patent Publication 2006-37083 public affairs obtained from being reacted Report the polyimides recorded), (Japanese Unexamined Patent Publication 2002-12667 bulletin and Japan are special for polyimides containing silicone matrix Open 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, 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 (F) thermoplastic resin Preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 70,000 hereinafter, more excellent 60,000 is selected as hereinafter, particularly preferably 50,000 or less.

When resin combination contains (F) thermoplastic resin, from the viewpoint of significantly obtaining the desired effect of the present invention, When nonvolatile component in resin combination is set as 100 mass %, the content of (F) thermoplastic resin be preferably 0.1 mass % with On, more preferably 0.2 mass % or more, further preferably 0.3 mass % or more, preferably 1.5 mass % are hereinafter, more preferably 1 Quality % is hereinafter, further preferably 0.5 mass % or less.

< (G) curing accelerator >

Resin combination can contain (G) curing accelerator.As (G) curing accelerator, can enumerate for example: the solidification of phosphorus system promotes Agent, amine system curing accelerator, imidazoles system curing accelerator, guanidine system curing accelerator, metal system curing accelerator etc..Wherein, excellent Select phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator, metal system curing accelerator, more preferable amine system Curing accelerator, imidazoles system curing accelerator, metal system curing accelerator.Curing accelerator can be used alone, can also It is applied in combination two or more.

It as phosphorus system curing accelerator, can enumerate for example: 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.

It as amine system curing accelerator, can enumerate for example: 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.

It as imidazoles system curing accelerator, can enumerate for example: 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, the inclined benzene front three of 1- cyano ethyl -2- phenylimidazole Hydrochlorate, 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-undecyls Imidazole radicals-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl-equal three Piperazine, 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanide Urea acid addition product, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole, 2,3- dihydro - 1H- pyrrolo- [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2- The adduct of the imidazolium compounds such as benzylimidazoline and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- Benzyl -2- phenylimidazole.

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

It as guanidine system curing accelerator, can enumerate for example: 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, the organic metal network of the metal such as cobalt, copper, zinc, iron, nickel, manganese, tin can be enumerated Close object or organic metal salt.It as the concrete example of metal-organic complex, can enumerate: acetylacetone cobalt (II), acetylacetone cobalt (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..It as organic metal salt, can enumerate for example: zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, hard Resin acid tin, zinc stearate etc..

When resin combination contains (G) curing accelerator, from the viewpoint of significantly obtaining the desired effect of the present invention, When nonvolatile component in resin combination is set as 100 mass %, the content of (G) curing accelerator be preferably 0.01 mass % with On, more preferably 0.05 mass % or more, further preferably 0.1 mass % or more, preferably 3 mass % are hereinafter, more preferably 2 Quality % is hereinafter, further preferably 1.5 mass % or less.

The arbitrary additive > of < (H)

It,, can also be comprising arbitrary as arbitrary ingredient other than comprising above-mentioned ingredient for resin combination Additive.As such additive, can enumerate for example: organic filler material；Organocopper compound, organic zinc compound and have The organo-metallic compounds such as machine cobalt compound；Fire retardant, thickener, defoaming agent, levelling agent, adaptation imparting agent, colorant etc. Resin additive；Etc..These additives can be used alone, and also can be used in combination two or more.

The physical property of < resin combination, purposes >

Keep resin combination solid in 100 DEG C of progress heat cure in 30 minutes, then obtained from 170 DEG C of progress heat cure in 30 minutes Compound usually shows the excellent such characteristic of glue residue removability.Therefore, even if forming through-hole on solidfied material above-mentioned, also To maximum insulating layer of the glue residue length less than 5 μm of via bottoms.Glue residue removability can be according to recording in aftermentioned embodiment Method measurement.

Resin combination solidfied material obtained from 200 DEG C of progress heat cure in 90 minutes is set to show dielectric loss angle tangent Low such characteristic.Therefore, the low insulating layer of dielectric loss angle tangent is obtained.As dielectric loss angle tangent, preferably 0.01 Hereinafter, more preferably 0.008 hereinafter, further preferably 0.005 or less.Lower limit is not particularly limited, can for 0.0001 with It is first-class.Dielectric loss angle tangent can be measured according to the method recorded in aftermentioned embodiment.

Resin combination of the invention can obtain the insulating layer that dielectric loss angle tangent is low, glue residue removability is excellent.Therefore, Resin combination of the invention may be adapted to resin combination (the multilayer print as the insulating layer for being used to form multilayer printed-wiring board The resin compositions for insulating layer of brush wiring plate) it uses, it can be more suitable as being used to form the interlayer insulating film of printed wiring board Resin combination (the interlayer insulating film resin combination of printed wiring board) use.In addition, due to resin group of the invention It closes object and obtains the good insulating layer of component imbedibility, therefore when printed wiring board is component internal circuit board, it can also be suitably It uses.

Especially, the insulation that dielectric loss angle tangent is low, glue residue removability is excellent can be obtained in resin combination of the invention Layer, therefore, can form the small insulating layer of the diameter of through-hole.Therefore, aforementioned resin is suitable for being used to form having and lead to The resin combination (resin combination of the insulating layer formation with through-hole) of the insulating layer in hole, wherein be particularly suitable as The resin combination of insulating layer formation with 35 μm of through-holes below of top diameter；It is particularly suitable as that there is insulating layer The insulating layer for the through-hole that the radius-thickness ratio (thickness/top diameter of insulating layer) of thickness (μm) and top diameter (μm) is 0.5 or more The resin combination of formation.Herein, term " top diameter " is indicated when forming through-hole on the insulating layer on substrate, in through-hole The maximum gauge of opening that is formed of the side opposite with substrate；" thickness of insulating layer " indicates the thickness, i.e. of insulating layer entirety The depth of through-hole.

The radius-thickness ratio (thickness/top diameter of insulating layer) of thickness (μm) and top diameter (μm) as insulating layer, from From the viewpoint of the miniaturization of electronic equipment, high performance, preferably 0.5 or more, more preferably 0.6 or more, further preferably It is 0.7 or more, preferably 3 hereinafter, more preferably 2 hereinafter, further preferably 1 or less.

[resin sheet]

Resin sheet of the invention includes supporting mass and is set to being formed by resin combination of the invention on the supporting mass Resin composition layer.

For the thickness of resin composition layer, it can be provided from the slimming of printed wiring board and for film From the viewpoint of the excellent solidfied material of insulating properties is such, preferably 40 μm hereinafter, more preferably 35 μm hereinafter, further preferably 25 μm or less, 20 μm or less.The lower limit of the thickness of resin composition layer is not particularly limited, typically 3 μm or more, 5 μm Above, 7 μm with first-class.

As supporting mass, can enumerate for example: film, metal foil, the processing release paper being molded of plastic material, preferably by plastic material The film of formation, metal foil.

It when using the film being molded of plastic material as supporting mass, as plastic material, can enumerate for example: poly- to benzene two Formic acid glycol ester (hereinafter sometimes referred to simply as " PET "), polyethylene naphthalate (hereinafter sometimes referred to simply as " PEN ") etc. are poly- The acrylics, cyclic polyolefin such as ester, polycarbonate (hereinafter sometimes referred to simply as " PC "), polymethyl methacrylate (PMMA) Hydrocarbon, triacetyl cellulose (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferred poly terephthalic acid Glycol ester, polyethylene naphthalate, particularly preferably cheap polyethylene terephthalate.

When using metal foil as supporting mass, as metal foil, can enumerate such as copper foil, aluminium foil, preferably copper foil.Make For copper foil, the foil formed by individual metallic copper can be used, 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, the face that engages with resin composition layer can be implemented matte management, sided corona treatment, prevent it is quiet Electric treatment.

In addition, maying be used on the face engaged with resin composition layer as supporting mass and having demoulding with release layer The supporting mass of layer.Release agent used in release layer as the supporting mass with release layer, can enumerate for example selected from by alkyd The release agent of one or more of the group of resin, polyolefin resin, polyurethane resin and organic siliconresin composition.With release layer Supporting mass can be used commercially available product, can enumerate for example: have with the PET of alkyd resin system release agent release layer as main component Film, that is, Lin get Ke corporation " SK-1 ", " AL-5 ", " AL-7 ", " the LUMIRROR T60 " of Toray, Supreme Being people's corporation " Purex ", " Unipeel " of UNITIKA corporation etc..

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 of release layer using the supporting mass for having release layer It is whole with a thickness of above range.

In one embodiment, as needed, resin sheet can also include other layers.It, can as other described layers It enumerates for example: being set to the face (that is, face of the side opposite with supporting mass) of resin composition layer not engaged with supporting mass The protective film etc. selected according to supporting mass.The thickness of protective film is not particularly limited, and for example, 1 μm~40 μm.It is protected by stacking Cuticula can inhibit dust etc. and be attached to the surface of resin composition layer or generate damage on the surface of resin composition layer.

Resin sheet can be for example manufactured in the following manner: made of resin combination is dissolved in organic solvent by preparation The resin varnish is coated on supporting mass by resin varnish using die coater (die coater) etc., and then keeps it dry It is dry, form resin composition layer.

It as organic solvent, can enumerate for example: the ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone；Ethyl acetate, The acetate esters such as butyl acetate, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate；Cellosolve and butyl The carbitols class such as carbitol；The aromatic hydrocarbons such as toluene and dimethylbenzene；Dimethylformamide, dimethyl acetamide (DMAc) and N- methyl Acid amides series solvents such as pyrrolidones etc..Organic solvent can be used alone, and also can be used in combination two or more.

Drying can be implemented by method well known to heating, blowing hot-air etc..Drying condition is not particularly limited, and can use makes The content of organic solvent in resin composition layer becomes 10 mass % or less, preferably 5 mass % modes below are dried.Though It is so different according to the boiling point of the organic solvent in resin varnish, such as include the organic molten of 30 mass of mass %~60 % using It, can be by 50 DEG C~150 DEG C progress drying in 3 minutes~10 minutes, to form resin group in the case where the resin varnish of agent Close nitride layer.

Resin sheet can wound into rolls save.Resin sheet have protective film when, can by will protect film stripping come It uses.

[printed wiring board]

Printed wiring board of the invention includes the insulating layer formed by the solidfied material of resin combination of the invention.

Printed wiring board for example can be used above-mentioned resin sheet, utilize the method for the process including following (I) and (II) It manufactures,

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

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

" internal substrate " used in process (I) refers to the component of the substrate as printed wiring board, can enumerate for example: glass Glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate etc..Separately Outside, which can have conductor layer in its one or both sides, can carry out pattern processing to the conductor layer.It sometimes will be in substrate One or both sides on form conductor layer (circuit) internal substrate be known as " internal layer circuit substrate ".In addition, being printed in manufacture Insulating layer to be further formed and/or the intermediate manufacture object of conductor layer are also included in the present invention described " interior when wiring plate In laminar substrate ".When printed wiring board is component internal circuit board, the internal substrate for being built-in with component can be used.

The stacking of internal substrate and resin sheet for example can be by heating from bearing side by the inside laminar substrate of resin sheet It crimps to carry out.As by the component (hereinafter also referred to " heating crimping component ") of resin sheet inside laminar substrate heating crimping, It can enumerate such as heated metal plate (SUS panelling) or metallic roll (SUS roller) etc..It should be noted that it is preferred that not will Heating crimps component to resin sheet direct pressing, but in order to make resin sheet sufficiently follow the concave-convex surface of internal substrate, It is suppressed across heat resistant rubber elastomeric material.

The stacking of internal substrate and resin sheet can be implemented using vacuum layer platen press.In vacuum layer platen press, heating crimping temperature Degree preferably 60 DEG C~160 DEG C, more preferably 80 DEG C~140 DEG C of range, heating crimping pressure be preferably 0.098MPa~ 1.77MPa, the more preferably range of 0.29MPa~1.47MPa, the heating crimping time is preferably 20 seconds~400 seconds, more preferably 30 seconds~300 seconds ranges.Stacking is preferably implemented in the case where pressure is 26.7hPa reduced pressure below.

Stacking can be carried out using commercially available vacuum laminator.It as commercially available vacuum laminator, can enumerate for example: strain formula meeting Society's name mechanism makees the vacuum pack system device (vacuum of made vacuum pressure type laminating machine, Nikko-Materials corporation Applicator), intermittent vacuum pressurization laminating machine etc..

After stacking, under normal pressure (under atmospheric pressure), such as it can be suppressed by the way that crimping component will be heated from bearing side, To carry out smoothing techniques to the resin sheet of stacking.About the pressing conditions of smoothing techniques, may be set to and above-mentioned layer The folded same condition of heating crimping condition.Smoothing techniques can be carried out using commercially available laminating machine.It should be noted that stacking Above-mentioned commercially available vacuum laminator can be used continuously to carry out with smoothing techniques.

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

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

The heat cure condition of resin composition layer is not particularly limited, when maying be used at the insulating layer to form printed wiring board The condition generallyd use.

For example, the heat cure condition of resin composition layer is different according to type of resin combination etc., solidification temperature is excellent It is selected as 120 DEG C~240 DEG C, more preferably 150 DEG C~220 DEG C, further preferably 170 DEG C~200 DEG C.Curing time can be excellent It is selected as 5 minutes~120 minutes, more preferably 10 minutes~100 minutes, further preferably 15 minutes~90 minutes.

It can be before making resin composition layer heat cure, to resin composition layer at temperature more lower than solidification temperature It is preheated.For example, can be before making resin composition layer heat cure, at 50 DEG C more than or lower than 120 DEG C (preferably 60 DEG C Above and 115 DEG C hereinafter, more preferable 70 DEG C or more and 110 DEG C or less) at a temperature of, to resin composition layer carry out 5 minutes with It preheats within upper (preferably 5 minutes~150 minutes, more preferable 15 minutes~120 minutes, further preferred 15 minutes~100 minutes).

When manufacturing printed wiring board, can further implement (III) on the insulating layer the process of aperture, (IV) to insulation The process of process, (V) formation conductor layer that layer is roughened.Above-mentioned operation (III) ~ process (V) can be according to printing cloth It is available in the manufacture of line plate that well known to a person skilled in the art various methods to implement.It should be noted that at process (II) In the case where supporting mass is removed later, the removing of the supporting mass can be between process (II) and process (III), process (III) implement between process (IV) or between process (IV) and process (V).In addition, as needed, can be repeated Process (II)~insulating layer of process (V) and the formation of conductor layer and implement, formed multiwiring board.

Process (III) is the process of aperture on the insulating layer, and the holes such as through-hole, open-work thus can be formed on the insulating layer.It is right For process (III), the composition etc. of the resin combination according to used in the formation of insulating layer can be used such as drill bit, swash Light, plasma etc. are implemented.The size or shape in hole can be suitably determined according to the design of printed wiring board.

As the top diameter of through-hole, from the viewpoint of the miniaturization of electronic equipment, high performance, preferably 70 μm with Under, more preferably 60 μm hereinafter, further preferably 55 μm or less or 35 μm or less.Lower limit is not particularly limited, it can be with For 10 μm with first-class.For example SEM can be used to measure for the top diameter of through-hole.

Process (IV) is the process being roughened to insulating layer.In general, also carrying out glue residue in the process (IV) It removes.The step of roughening treatment, condition are not particularly limited, and can be used usually makes when forming the insulating layer of printed wiring board Known step, condition.For example, can successively implement the swelling treatment based on swelling solution, the roughening based on oxidant Processing, the neutralisation treatment based on neutralizer, are roughened insulating layer.As the swelling solution for roughening treatment, It is not particularly limited, aqueous slkali, surfactant solution etc., preferably aqueous slkali can be enumerated, as the aqueous slkali, more preferable hydrogen Sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling solution, such as ATOTECH JAPAN corporation can be enumerated " Swelling Dip Securiganth P ", " Swelling Dip Securiganth SBU " etc..Based on the molten of swelling solution Swollen processing is not particularly limited, such as can be by impregnating 1 minute~20 minutes insulating layer in 30 DEG C~90 DEG C of swelling solution Come carry out.Inhibit from the viewpoint of appropriate level from by the swelling of the resin of insulating layer, preferably by insulating layer 40 DEG C~80 DEG C swelling solution in impregnate 5 minutes~15 minutes.It as the oxidant for roughening treatment, is not particularly limited, can enumerate Such as alkalinity permanganic acid solution made of potassium permanganate or sodium permanganate is dissolved in the aqueous solution of sodium hydroxide.Based on alkalinity The roughening treatment of the oxidants such as permanganic acid solution is preferably by molten in the oxidant for being heated to 60 DEG C~80 DEG C by insulating layer 10 minutes~30 minutes are impregnated in liquid to carry out.In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 matter Measure the mass of %~10 %.As commercially available oxidant, " the Concentrate of such as ATOTECH JAPAN corporation can be enumerated The alkalinity permanganic acid solution such as Compact CP ", " Dosing Solution Securiganth P ".In addition, as coarse Change the neutralizer of processing, the aqueous solution of preferred acidic can enumerate such as ATOTECH JAPAN corporation as commercially available product "Reduction Solution Securiganth P".Processing based on neutralizer can be by that will complete based on oxidant The process face of roughening treatment impregnates 5 minutes~30 minutes in 30 DEG C~80 DEG C of neutralizer to carry out.From the side such as operability Face considers, the object for completing the roughening treatment based on oxidant is preferably impregnated 5 in 40 DEG C~70 DEG C of neutralizer Minute~20 minutes methods.

In one embodiment, the arithmetic average roughness (Ra) of the surface of insulating layer after roughening treatment is preferably 400nm hereinafter, more preferably 350nm hereinafter, further preferably 300nm or less.Lower limit is not particularly limited, Ke Yiyou 0.5nm or more, more preferably 1nm are selected as with first-class.In addition, the r.m.s. roughness of the surface of insulating layer after roughening treatment It (Rq) is preferably 400nm hereinafter, more preferably 350nm is hereinafter, further preferably 300nm or less.It is not special for lower limit Limitation can be preferably 0.5nm or more, more preferably 1nm with first-class.The arithmetic average roughness (Ra) of surface of insulating layer and Non-contact type surface roughness meter can be used to measure for root mean square roughness (Rq).

Process (V) is the process to form conductor layer, and conductor layer is formed on the insulating layer.Conductor material used in conductor layer It is not particularly limited.In a preferred embodiment, conductor layer include selected from by gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, The metal of one or more of the group of nickel, titanium, tungsten, iron, tin and indium composition.Conductor layer can be single metal layer, be also possible to alloy Layer, as alloy-layer, can enumerate for example by the alloy of two or more metal in above-mentioned group (for example, nickel-chromium alloy, Copper-nickel alloy and copper-titanium alloy) formed layer.Wherein, versatility, cost, the easiness of pattern formation formed from conductor layer Etc. viewpoints consider, preferred chromium, nickel, titanium, aluminium, zinc, gold, palladium, the single metal layer or nickel-chromium alloy of silver or copper, copper-nickel alloy, Copper-titanium alloy alloy-layer, more preferable chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper single metal layer or nickel-chromium alloy conjunction Layer gold, the single metal layer of further preferred copper.

Conductor layer can be single layer structure, be also possible to the single metal layer formed by different types of metal or alloy or conjunction Multilayered structure made of layer gold is laminated 2 layers or more.When conductor layer is multilayered structure, the layer contacted with insulating layer is preferably chromium, zinc Titanium single metal layer or nickel-chromium alloy alloy-layer.

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

In one embodiment, conductor layer can be formed by plating.For example, using semi-additive process, fully-additive process etc. Existing known technology carries out plating on the surface of insulating layer, the conductor layer with desired wiring pattern is formed, from system From the viewpoint of the simplicity made, formed preferably by semi-additive process.Hereinafter, showing the example for forming conductor layer using semi-additive process Son.

Firstly, forming plating seed layer on the surface of insulating layer using chemical plating (electroless plating).Next, in shape At plating seed layer on, correspond to desired wiring pattern, formed make plating seed layer a part expose mask artwork Case.On the plating seed layer of exposing, metal layer is formed using electrolytic coating, then removes mask pattern.Then, erosion is utilized Quarter etc. removes unwanted plating seed layer, can form the conductor layer with desired wiring pattern.

For resin sheet of the invention, due to obtaining component imbedibility also good insulating layer, printing When wiring plate is component internal circuit board, can also suitably it use.Component internal circuit board can utilize well known manufacturer's legal system Make.

It can be using the printed wiring board that resin sheet of the invention manufactures such as under type, that is, have: resin sheet Solidfied material, that is, insulating layer of resin composition layer and the buried wiring layer being embedded in insulating layer.

[semiconductor device]

Semiconductor device of the invention includes printed wiring board of the invention.Semiconductor device of the invention can be used of the invention Printed wiring board manufactures.

As semiconductor device, can enumerate: be available for electric product (for example, computer, mobile phone, digital camera and Television set etc.) and the vehicles (for example, motorcycle, automobile, electric car, ship and aircraft etc.) etc. various semiconductor devices.

Semiconductor device of the invention can be and conduction position installing component (semiconductor chip) in printed wiring board Manufacture.So-called " conduction position " refers to " position of the transmitting electric signal in printed wiring board ", and position is surface or is The position being embedded in.In addition, as long as semiconductor chip using semiconductor as the electrical circuit components of material, does not then have special Limitation.

For the installation method of semiconductor chip when manufacturing semiconductor device, as long as sending out semiconductor chip effectively Function is waved, then is not particularly limited, specifically, can enumerate: wire bonding installation method, uses flip-chip installation method The installation method of solderless buildup layer (BBUL), using the installation method of anisotropic conductive film (ACF), using non-conductive film (NCF) installation method etc..Here, " installation method for using solderless buildup layer (BBUL) " refers to " semiconductor chip is direct It is embedded to the recess portion of printed wiring board, makes the installation method of the wiring connection on semiconductor chip and printed wiring board ".

[embodiment]

Hereinafter, showing embodiment specifically describes the present invention.But the present invention is not limited to embodiments below.In the following description In, as long as no separately clearly stating, " part " and " % " of expression amount refers respectively to " mass parts " and " quality % ".As long as in addition, It does not clearly state separately, operation described below carries out in the environment of normal temperature and pressure.

[embodiment 1]

By bisphenol-type epoxy resin, (aurification corporation " ZX1059 ", bisphenol A-type and Bisphenol F are lived by Nippon Steel while stirring The 1:1 melange of type, epoxide equivalent 169) (aurification corporation is lived by Nippon Steel for 10 parts and naphthol type epoxy resin " ESN475V ", about 330) 30 parts of epoxide equivalent dissolve by heating in 40 parts of solvent naphtha.It is cooled to room temperature, prepares ring The dissolved composition of oxygen resin (X).

In addition, the aromatic resins of structure will be shown below while stirring, (aurification corporation is lived by Nippon Steel " ESN375 ", about 171) 10 parts of epoxide equivalent dissolve by heating in 10 parts of MEK, and then are cooled to room temperature, prepare aromatic hydrocarbons tree The solution of rouge (Y).

[chemical formula 12]

(n indicates 1~10 integer).

In the dissolved composition of the epoxy resin (X), phenoxy resin (Mitsubishi Chemical Ind's system is mixed " YX7553BH30 ", the MEK of 30 mass % of solid component and the 1:1 solution of cyclohexanone) 5 parts, there is triazine skeleton and phenolic structure Phenol system curing agent (DIC corporation " LA-3018-50P ", active group equivalent about 151, the 2- methoxy propyl of solid component 50% Alcoholic solution) 5 parts, active ester system curing agent (DIC corporation " HPC-8000-65T ", active group equivalent about 223, solid component 65 The toluene solution of quality %) 50 parts, curing accelerator (1- benzyl -2- phenylimidazole (1B2PZ), the MEK of 10 mass % of solid component Solution) 5 parts, the ball that is surface-treated with amine system alkoxysilane compound containing trialkylsilyl group in molecular structure (chemical industrial company, SHIN-ETSU HANTOTAI system " KBM573 ") The solution 20 of 220 parts of shape silica (0.77 μm of average grain diameter, Admatechs corporation " SO-C2 ") and aromatic resins (Y) Part, it is evenly dispersed with high speed rotation mixing machine, make resin varnish.

As supporting mass, the polyethylene terephthalate film for preparing to have release layer (Lin get Ke corporation " AL5 ", 38 μm of thickness, PET film).It is in such a way that the thickness of the resin composition layer after drying becomes 15 μm, resin varnish above-mentioned is equal It is even to be coated on the release layer of the supporting mass.Then, resin varnish is made do within 3 minutes in 80 DEG C~100 DEG C (90 DEG C average) It is dry, resin sheet of the production comprising supporting mass and resin composition layer.

[embodiment 2]

In embodiment 1, by active ester system curing agent (DIC corporation " HPC-8000-65T ", active group equivalent about 223, solid at The toluene solution of point 65 mass %) 50 parts be changed to active ester system curing agent (DIC corporation " EXB8000L-65TM ", active group Equivalent 220, the toluene-MEK mixed solution of solid component 65%) 50 parts.Other than above item, similarly to Example 1 Operation makes resin varnish, resin sheet.

[embodiment 3]

In embodiment 1, by active ester system curing agent (DIC corporation " HPC-8000-65T ", active group equivalent about 223, solid at The toluene solution of point 65 mass %) 50 parts be changed to active ester system curing agent (DIC corporation " EXB8150-60T ", active group worked as Amount 230, the toluene solution of solid component 60%) 55 parts.It other than above item, operates similarly with example 1, makes Resin varnish, resin sheet.

[embodiment 4]

By bisphenol-type epoxy resin, (aurification corporation " ZX1059 ", bisphenol A-type and Bisphenol F are lived by Nippon Steel while stirring The 1:1 melange of type, epoxide equivalent 169) (aurification corporation is lived by Nippon Steel for 10 parts and naphthol type epoxy resin " ESN475V ", about 330) 20 parts of epoxide equivalent dissolve by heating in 40 parts of solvent naphtha.It is cooled to room temperature, prepares ring The dissolved composition of oxygen resin (X2)；

In addition, by aromatic resins, (Nippon Steel is lived aurification corporation " ESN375 ", epoxide equivalent about 171) 20 while stirring Part dissolves by heating in 20 parts of MEK, and then is cooled to room temperature, prepares the solution of aromatic resins (Y2).

In the dissolved composition of the epoxy resin (X2), phenoxy resin (Mitsubishi Chemical Ind's system is mixed " YX7553BH30 ", the MEK of 30 mass % of solid component and the 1:1 solution of cyclohexanone) 5 parts, curing agent (DIC company, active ester system Make " EXB8150-60T ", active group equivalent 230, the toluene solution of solid component 60%) 80 parts, curing accelerator (1- benzyl -2- Phenylimidazole (1B2PZ), the MEK solution of 10 mass % of solid component) 5 parts, with amine system alkoxysilane compound containing trialkylsilyl group in molecular structure (SHIN-ETSU HANTOTAI's chemistry Industrial group's system " KBM573 ") be surface-treated preparing spherical SiO 2 (0.77 μm of average grain diameter, Admatechs company Make " SO-C2 ") 40 parts of solution of 250 parts and aromatic resins (Y2), evenly dispersed with high speed rotation mixing machine, production resin is clear Paint.And then operate similarly with example 1, make resin sheet.

[embodiment 5]

In embodiment 3,

1) by aromatic resins, (Nippon Steel is lived aurification corporation " ESN375 ", and about 171) 20 parts of amount becomes epoxide equivalent from 20 parts More 5 parts,

2) by naphthol type epoxy resin, (Nippon Steel is lived aurification corporation " ESN475V ", and the amount of epoxide equivalent about 330) is from 30 parts 40 parts are changed to,

3) ball that will be surface-treated with amine system alkoxysilane compound containing trialkylsilyl group in molecular structure (chemical industrial company, SHIN-ETSU HANTOTAI system " KBM573 ") The amount of shape silica (0.77 μm of average grain diameter, Admatechs corporation " SO-C2 ") is changed to 230 parts from 220 parts；

It other than above item, operates similarly with example 1, makes resin varnish, resin sheet.

[embodiment 6]

By bisphenol-type epoxy resin, (aurification corporation " ZX1059 ", bisphenol A-type and Bisphenol F are lived by Nippon Steel while stirring The 1:1 melange of type, epoxide equivalent 169) (aurification corporation is lived by Nippon Steel for 10 parts and naphthol type epoxy resin " ESN475V ", about 330) 50 parts of epoxide equivalent dissolve by heating in 40 parts of solvent naphtha.It is cooled to room temperature, prepares ring The dissolved composition of oxygen resin (X3)；

In addition, the aromatic resins of structure will be shown below while stirring, (aurification corporation is lived by Nippon Steel " SN395-50M ", active group equivalent 107, the use in the form of the MEK solution of solid component 50%) 3 parts and aromatic resins it is (new Day, iron was lived aurification corporation " ESN375 ", and about 171) 5 parts of epoxide equivalent dissolve by heating in 10 parts of MEK, and then are cooled to Room temperature prepares the solution of aromatic resins (Y3).

[chemical formula 13]

(n indicates 1~10 integer).

In the dissolved composition of the epoxy resin (X3), phenoxy resin (Mitsubishi Chemical Ind's system is mixed " YX7553BH30 ", the MEK of 30 mass % of solid component and the 1:1 solution of cyclohexanone) 5 parts, there is triazine skeleton and phenolic structure Phenol system curing agent (DIC corporation " LA-3018-50P ", active group equivalent about 151, the 2- methoxy propyl of solid component 50% Alcoholic solution) 2 parts, active ester system curing agent (DIC corporation " EXB8150-60T ", active group equivalent 230, solid component 60% Toluene solution) 55 parts, curing accelerator (1- benzyl -2- phenylimidazole (1B2PZ), the MEK solution of 10 mass % of solid component) 5 Part, the spherical dioxy being surface-treated with amine system alkoxysilane compound containing trialkylsilyl group in molecular structure (chemical industrial company, SHIN-ETSU HANTOTAI system " KBM573 ") 13 parts of solution of 240 parts of SiClx (0.77 μm of average grain diameter, Admatechs corporation " SO-C2 ") and aromatic resins (Y3) are used High speed rotation mixing machine is evenly dispersed, makes resin varnish.And then operate similarly with example 1, make resin sheet.

[comparative example 1]

In embodiment 1,

1) ball that will be surface-treated with amine system alkoxysilane compound containing trialkylsilyl group in molecular structure (chemical industrial company, SHIN-ETSU HANTOTAI system " KBM573 ") The amount of shape silica (0.77 μm of average grain diameter, Admatechs corporation " SO-C2 ") is changed to 240 parts from 220 parts,

2) by naphthol type epoxy resin, (Nippon Steel is lived aurification corporation " ESN475V ", and the amount of epoxide equivalent about 330) is from 40 parts 50 parts are changed to,

3) be not used aromatic resins (Nippon Steel lives aurification corporation " ESN375 ", about 171) 10 parts of epoxide equivalent；

[comparative example 2]

In embodiment 2,

It other than above item, operates similarly to Example 2, makes resin varnish, resin sheet.

[comparative example 3]

In embodiment 3,

It other than above item, operates similarly to Example 3, makes resin varnish, resin sheet.

The evaluation > of < glue residue removability

(1) base treatment of internal substrate

As internal substrate, prepare the glass cloth base material epoxy resin two sides copper-clad laminated board that there is copper foil on surface (copper foil 18 μm of thickness, the thickness 0.8mm of substrate, Panasonic Corporation system " R1515A ").Using micro-etching agent (MEC A/S's system " CZ8101 "), The copper foil on the surface of the internal substrate is etched with 1 μm of copper etch quantity, is roughened.Then, in 190 DEG C into Row drying in 30 minutes.

(2) stacking, solidification of resin sheet

It is pressurizeed laminating machine (2 grades of stacking laminating machinees " CVP700 " of Nikko-Materials corporation) using intermittent vacuum, with tree The mode that oil/fat composition layer is engaged with internal substrate above-mentioned, by resin sheet layer obtained in the above embodiments and comparative example It is pressed in the two sides of internal substrate.The lamination is implemented in the following manner: depressurize within 30 seconds, so that air pressure is become 13hPa hereinafter, so It carries out crimping for 30 seconds under conditions of temperature is 100 DEG C, pressure is 0.74MPa afterwards；

Next, under atmospheric pressure, 100 DEG C, laminated resin sheet is subjected to hot pressing in 60 seconds under conditions of pressure 0.5MPa, Make its smoothing.In turn, it is put into 100 DEG C of baking oven, heat within 30 minutes, next, moving to 170 DEG C of baking oven In, heat within 30 minutes, forms insulating layer.

(3) through-hole is formed:

Use sub- machinery (Via Mechanics) the corporation CO of dimension₂Laser machine (LK-2K212/2C), with the frequency of 2000Hz Rate processes insulating layer under conditions of pulse width is 6 μ seconds, output power 0.24mJ, irradiation (shot) number are 3, Formed surface of insulating layer in top diameter be 25 μm, the through-hole that the diameter in insulating layer bottom surface is 19 μm.It in turn, then will branch Hold the PET film removing of body.

(4) roughening treatment

In 60 DEG C by internal substrate the ATOTECH JAPAN corporation as swelling solution Swelling Dip It is impregnated 5 minutes in Securiganth P.Next, in 80 DEG C in the ATOTECH JAPAN corporation as roughening liquid Concentrate Compact P(KMnO₄: the aqueous solution of 60g/L, NaOH:40g/L) middle dipping 20 minutes.Finally, in 40 DEG C 5 points are impregnated in the Reduction Solution Securiganth P of the ATOTECH JAPAN corporation as neutralizer Clock.

(5) the residue evaluation of via bottoms

With scanning electron microscope (SEM) to being observed around via bottoms, by obtained determining image from via bottoms Wall surface rise maximum glue residue length, evaluated according to benchmark below；

Zero: maximum glue residue length is less than 5 μm

×: maximum glue residue length is 5 μm or more.

The measurement > of < dielectric loss angle tangent

So that resin sheet obtained in each embodiment and each comparative example is carried out heat cure in 90 minutes in 200 DEG C, PET film removed, Obtain the solidfied material of sheet.The solidfied material is cut into the test piece that width is 2mm, length is 80mm, uses Northeast applying electronic The resonant cavity perturbation method dielectric constant measurement device " CP521 " and Agilent Technologies (Agilent of development company Technologies) corporation " Network Analyzer (Network Analyzer) E8362B ", using Resonant-cavity Method, with 5.8GHz Measurement frequency carry out dielectric loss angle tangent (tan δ) measurement.It is measured for 2 test pieces, calculates average value.

[table 1]

In table, when the total content of (A) ingredient and (C) ingredient is set as 100 mass parts by " content (quality %) of (A) ingredient " expression (A) ingredient content, " content (quality %) of (D) ingredient " indicates the nonvolatile component in resin combination being set as 100 matter The content of (D) ingredient when amount %.

In Examples 1 to 6, it is thus identified that even if in the case where not containing (C) ingredient~(G) ingredient, although degree exists Difference, but also it is attributed to result same as above-described embodiment.

Claims

1. a kind of resin combination, contains:

(A) aromatic resins, the aromatic resins contain the aromatic ring as monocycle or condensed ring, and relative to the aromatic ring, have 2 or more the groups containing the oxygen atom for being bonded to the aromatic ring；With

(B) active ester system curing agent.

2. resin combination according to claim 1, wherein (A) ingredient has structure shown in following formula (1),

In formula (1), R¹¹Each independently represent 1 valence group.

3. resin combination according to claim 1, wherein (A) ingredient has structure shown in following formula (2),

In formula (2), R²¹Each independently represent 1 valence group.

4. resin combination according to claim 1, wherein (A) ingredient by following formula (3) indicate,

In formula (3), R³¹Each independently represent 1 valence group, R³²Each independently represent divalent alkyl, n3 indicate 0~10 it is whole Number.

5. resin combination according to claim 1, wherein (A) ingredient by following formula (6) indicate,

In formula (6), R⁶¹1 valence group is each independently represented, n6 indicates 0~10 integer.

6. resin combination according to claim 1, wherein the group containing the oxygen atom for being bonded to aromatic ring is epoxy Asia Alkyl oxy, alkoxy or hydroxyl.

7. resin combination according to claim 1, wherein also contain (C) epoxy resin.

8. resin combination according to claim 7, wherein the total content of (A) ingredient and (C) ingredient is set as 100 matter When measuring %, the content of (A) ingredient is 5 mass % or more and 50 mass % or less.

9. resin combination according to claim 1, wherein the nonvolatile component in resin combination is set as 100 matter When measuring %, the content of (B) ingredient is 1 mass % or more and 30 mass % or less.

10. resin combination according to claim 1, wherein also contain (D) inorganic filling material.

11. resin combination according to claim 10, wherein the nonvolatile component in resin combination is set as 100 When quality %, the content of (D) ingredient is 50 mass % or more.

12. resin combination according to claim 1 is the resin for being used to form the insulating layer of multilayer printed-wiring board Composition.

It is that be used to form with top diameter be 35 μm of through-holes below 13. resin combination according to claim 1 Insulating layer resin combination.

It is to be used to form thickness (μm) with insulating layer and top is straight 14. resin combination according to claim 1 The resin combination of the insulating layer for the through-hole that the radius-thickness ratio (thickness/top diameter of insulating layer) of diameter (μm) is 0.5 or more.

15. a kind of resin sheet, it includes:

Supporting mass and

The resin combination comprising resin combination described in any one of claim 1~14 being set on the supporting mass Layer.

16. resin sheet according to claim 15, wherein resin composition layer with a thickness of 20 μm or less.

17. a kind of printed wiring board, it includes the solidfied material shapes of the resin combination as described in any one of claim 1~14 At insulating layer.

18. a kind of semiconductor device, it includes the printed wiring boards described in claim 17.