CN108727942A

CN108727942A - Resin combination

Info

Publication number: CN108727942A
Application number: CN201810365456.6A
Authority: CN
Inventors: 藤岛祥平
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2017-04-24
Filing date: 2018-04-23
Publication date: 2018-11-02

Abstract

The resin combination etc. that the issue of the present invention is to provide minimum melt viscosities is low, plyability is excellent, even if the resin combination if average grain diameter is small or the inorganic filling material of large specific surface area using can obtain the solidfied material that fine circuits Forming ability is excellent, dielectric loss angle tangent is low.The solution of the present invention is a kind of resin combination, is contained：(A) epoxy resin, (B) active ester system curing agent, (C) polyimide resin and (D) average grain diameter are 100nm inorganic filling materials below, wherein, when resin component is set as 100 mass %, the content of (C) ingredient is 0.1 mass % or more and 6 mass % or less.

Description

Resin combination

Technical field

The present invention relates to resin combinations.Further relate to the resin sheet comprising the resin combination, containing by resin group Close the printed wiring board and semiconductor device of the insulating layer of the solidfied material formation of object.

Background technology

As the manufacturing technology of printed wiring board, stacking (buildup) side based on alternately laminated insulating layer and conductor layer The manufacturing method of formula is known.In manufacturing method based on stack manner, usual insulating layer be make resin combination cure and It is formed.For example, having been recorded in patent document 1 makes comprising epoxy resin, active ester compound, carbodiimide compound, thermoplastic The resin combination of property resin and inorganic filling material is solidified to form insulating layer.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2016-27097 bulletins.

Invention content

Problems to be solved by the invention

The inventors of the present invention are further studied resin combination, as a result obtain following understanding.If in resin combination Contain a large amount of inorganic filling materials in object, then the minimum melt viscosity of resin combination rises, and the imbedibility of film declines.Its result It recognizes：Control plyability becomes difficult.Especially, consider from viewpoints such as filmings, average grain is contained in resin combination When diameter is small or the inorganic filling material of large specific surface area, the minimum melt viscosity of resin combination is further up, imbedibility Decline notable.

The resin combination that the issue of the present invention is to provide minimum melt viscosities is low, plyability is excellent；Including the resin The resin sheet of composition；Have the printed wiring board and semiconductor device of the insulating layer formed using the resin combination, institute It is formed even if stating resin combination using fine circuits can be obtained if average grain diameter is small or the inorganic filling material of large specific surface area The solidfied material that ability is excellent, dielectric loss angle tangent is low.

Means for solving the problems

In order to reach the project of the present invention, the inventors of the present invention have made intensive studies, as a result, it has been found that, if containing in resin combination (C) ingredient for having specified amount, then can be obtained the resin combination that minimum melt viscosity is low, plyability is excellent；The resin combination Even if using that can be obtained if average grain diameter is small or the inorganic filling material of large specific surface area, fine circuits Forming ability is excellent, is situated between The low solidfied material of matter loss angle tangent, so as to complete the present invention.

That is, the present invention includes content below；

[1] resin combination contains：

(A) epoxy resin,

(B) active ester system curing agent,

(C) polyimide resin and

(D) inorganic filling material,

Wherein, the average grain diameter of (D) ingredient be 100nm hereinafter,

When resin component is set as 100 mass %, the content of (C) ingredient is 0.1 mass % or more and 6 mass % or less；

[2] resin combination contains：

(A) epoxy resin,

(B) active ester system curing agent,

(C) polyimide resin and

(D) inorganic filling material,

Wherein, the specific surface area of (D) ingredient is 15m²/ g or more,

[3] according to the resin combination described in [1] or [2], wherein (C) ingredient is the polyimides with polycyclic aromatic hydrocarbon skeleton Resin；

[4] according to the resin combination described in [3], wherein polycyclic aromatic hydrocarbon skeleton is that 5-membered ring compounds are formed with aromatic ring fusion Aromatic hydrocarbons skeleton；

[5] according to the resin combination described in [3] or [4], wherein polycyclic aromatic hydrocarbon skeleton be in indane skeleton and fluorene skeleton extremely It is few any；

[6] according to the resin combination described in any one of [1]~[5], wherein the weight average molecular weight of (C) ingredient be 5000 with On；

[7] resin combination according to any one of [1]~[6], wherein (C) ingredient has：With polycyclic aromatic hydrocarbon skeleton Repetitive unit and repetitive unit with imide structure；

[8] according to the resin combination described in [7], wherein repetitive unit with polycyclic aromatic hydrocarbon skeleton and with acid imide knot Mass ratio (the quality of the repetitive unit with the polycyclic aromatic hydrocarbon skeleton/repetition list with imide structure of the repetitive unit of structure The quality of member) it is 0.5 or more and 2 or less；

[9] resin combination according to any one of [1]~[8], wherein set the nonvolatile component in resin combination For 100 mass % when, the content of (C) ingredient is 0.1 mass % or more and 3 mass % or less；

[10] resin combination according to any one of [1]~[9], wherein by the nonvolatile component in resin combination When being set as 100 mass %, the content of (B) ingredient is 1 mass % or more and 25 mass % or less；

[11] resin combination according to any one of [1]~[10], wherein by the nonvolatile component in resin combination When being set as 100 mass %, the content of (D) ingredient is 30 mass % or more and 80 mass % or less；

[12] resin combination according to any one of [1]~[11], wherein also contain (E) curing agent；

[13] according to the resin combination described in [12], wherein (E) curing agent is that phenol (phenol) is curing agent；

[14] according to the resin combination described in any one of [1]~[13], be used to form insulating layer, the insulating layer be in order to Form the insulating layer of conductor layer；

[15] resin combination according to any one of [1]~[14], is used to form the insulating layer of printed wiring board；

[16] resin combination according to any one of [1]~[15], is used to form the layer insulation of printed wiring board Layer；

[17] resin sheet, it includes the resins described in any one of supporting mass and [1] that is set on the supporting mass~[16] Composition layer；

[18] printed wiring board it includes the first conductor layer, the second conductor layer and is formed in the first conductor layer and the second conductor layer Between insulating layer, wherein

The insulating layer is the solidfied material of the resin combination described in any one of [1]~[16]；

[19] semiconductor device, it includes the printed wiring boards described in [18].

The effect of invention

Through the invention, it is possible to provide the resin combination that minimum melt viscosity is low, plyability is excellent；Including the resin combination Resin sheet；Printed wiring board with the insulating layer formed using the resin combination and semiconductor device, the resin group Even if it is excellent using that can obtain fine circuits Forming ability if average grain diameter is small or the inorganic filling material of large specific surface area to close object Solidfied material different, dielectric loss angle tangent is low.

Description of the drawings

Fig. 1 is the phantom of an example for schematically showing printed wiring board.

Specific implementation mode

Hereinafter, being carried out specifically to the resin combination of the present invention, resin sheet, printed wiring board and semiconductor device It is bright.

[resin combination]

The resin combination of the first embodiment of the present invention contains (A) epoxy resin, (B) active ester system curing agent, (C) polyamides Imide resin and (D) inorganic filling material, the average grain diameter of (D) ingredient are 100nm hereinafter, resin component is set as 100 matter When measuring %, the content of (C) ingredient is 0.1 mass % or more and 6 mass % or less.By the resin combination for making first embodiment Containing (C) ingredient, to which the resin combination that minimum melt viscosity is low, plyability is excellent can be obtained, even if the resin combination It is 100nm inorganic filling materials below containing (D) average grain diameter, can also obtains that fine circuits Forming ability is excellent, medium damage Consume the low solidfied material of angle tangent.In addition, the resin combination of second embodiment is containing (A) epoxy resin, (B) active ester system The specific surface area of the resin combination of curing agent, (C) polyimide resin and (D) inorganic filling material, (D) ingredient is 15m²/ G or more, when resin component is set as 100 mass %, the content of (C) ingredient is 0.1 mass % or more and 6 mass % or less.By making The resin combination of second embodiment contains (C) ingredient, to which the resin that minimum melt viscosity is low, plyability is excellent can be obtained Composition, even if the resin combination is 15m containing (D) specific surface area²The inorganic filling material of/g or more can also obtain fine The solidfied material that circuit Forming ability is excellent, dielectric loss angle tangent is low.

As needed, resin combination also may include that (E) curing agent (except active ester system curing agent), (F) solidification promote The ingredients such as agent, (G) thermoplastic resin and (H) other additives.Hereinafter, the first embodiment and second to the present invention are real Each ingredient for including is applied in the resin combination of mode to be described in detail.Here, sometimes by the resin group of first embodiment The resin combination for closing object and second embodiment is referred to as " resin combination ".

< (A) epoxy resin >

Resin combination includes (A) epoxy resin.As epoxy resin, can enumerate for example：Union II cresols (bixylenol) type ring Oxygen resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, two rings Pentadiene type epoxy resin, tris phenol type epoxy, naphthol novolac (naphthol novolac) type epoxy resin, phenol novolac (phenol novolac) type epoxy resin, tertiary butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy Resin, anthracene type epoxy resin, glycidyl group amine type epoxy resin, glycidyl esters type epoxy resin, cresol novolac (cresol novolac) type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resins, with butadiene structure Epoxy resin, cycloaliphatic epoxy resin, hetero ring type epoxy resin, the epoxy resin containing loop coil, hexamethylene type epoxy resin, hexamethylene Alkane dimethanol type epoxy resin, naphthylene ether type epoxy, trihydroxy methyl type epoxy resin, tetraphenyl ethane type epoxy resin Deng.Epoxy resin can be used alone a kind, also can be used in combination two or more.

Epoxy resin preferably is contained in the epoxy resin with 2 or more epoxy groups in 1 molecule.By epoxy resin not When volatile ingredient is set as 100 mass %, preferably at least 50 mass % or more are the epoxy with 2 or more epoxy groups in 1 molecule Resin.Wherein, resin combination preferably in combination be included in 20 DEG C of temperature when for liquid epoxy resin (hereinafter referred to as " liquid Epoxy resin ".) and in 20 DEG C of temperature be solid epoxy resin (hereinafter also referred to " solid epoxy resin ".).As liquid Epoxy resin, the liquid-state epoxy resin with 2 or more epoxy groups preferably in 1 molecule, has 2 more preferably in 1 molecule The aromatics system liquid-state epoxy resin of the above epoxy group.As solid epoxy resin, there are 3 or more epoxies preferably in 1 molecule The solid epoxy resin of base, the aromatics system solid epoxy resin with 3 or more epoxy groups more preferably in 1 molecule.The present invention In, the epoxy resin of so-called aromatics system refers to the epoxy resin for having 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 Fat, naphthalene type epoxy resin, glycidyl esters type epoxy resin, glycidyl group amine type epoxy resin, phenol novolak type epoxy Resin, the cycloaliphatic epoxy resin with ester skeleton, hexamethylene type epoxy resin, cyclohexanedimethanol type epoxy resin and tool There are the epoxy resin of butadiene structure, more preferable bisphenol A type epoxy resin, bisphenol f type epoxy resin and hexamethylene type asphalt mixtures modified by epoxy resin Fat, further preferred bisphenol A type epoxy resin.As the concrete example of liquid-state epoxy resin, DIC corporations can be enumerated " HP4032 ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin), Mitsubishi Chemical Ind " 828US ", " jER828EL ", " 825 ", " Epikote 828EL " (bisphenol A type epoxy resin), " jER807 ", " 1750 " (bisphenol F type epoxy Resin), " jER152 " (phenol novolak type epoxy), " 630 ", " 630LSD " (glycidyl group amine type epoxy resin), new Day iron lives " ZX1059 " (melange of bisphenol A type epoxy resin and bisphenol f type epoxy resin), the Nagase of aurification corporation " EX-721 " (the glycidyl esters type epoxy resin) of ChemteX the corporations, " Celloxide of Daicel corporation 2021P " (cycloaliphatic epoxy resin with ester skeleton), " PB-3600 " (epoxy resin with butadiene structure), Nippon Steel Firmly " ZX1658 ", " ZX1658GS " (liquid 1,4- glycidol butylcyclohexane type ring oxygen resin) of aurification corporation, Mitsubishi " 630LSD " (the glycidyl group amine type epoxy resin) of chemical company etc..They can be used alone a kind, also can be used in combination Two or more.

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 Fat, 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, Naphthol type epoxy resin, biphenyl type epoxy resin and naphthylene ether type epoxy, further preferred union II cresols type asphalt mixtures modified by epoxy resin Fat, naphthol type epoxy resin, biphenyl type epoxy resin.As the concrete example of solid epoxy resin, DIC corporations can be enumerated " HP4032H " (naphthalene type epoxy resin), " HP-4700 ", " HP-4710 " (naphthalene type tetrafunctional epoxy resin), " N-690 " (cresols Phenol aldehyde type epoxy resin), " N-695 " (cresol novolak type epoxy resin), " HP-7200 " (dicyclopentadiene-type epoxy resin), “HP-7200HH”、“HP-7200H”、“EXA-7311”、“EXA-7311-G3”、“EXA-7311-G4”、“EXA-7311-G4S”、 " EPPN-502H " (tris phenol type epoxy) of " HP6000 " (naphthylene ether type epoxy), Japanese chemical drug corporation, " NC7000L " (naphthol novolac type epoxy resin), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type ring Oxygen resin), Nippon Steel live " ESN475V " (naphthalene type epoxy resin) of aurification corporation, " ESN485 " (naphthol novolac type ring oxygen Resin), " YX4000H " of Mitsubishi Chemical Ind, " YX4000 ", " YL6121 " (biphenyl type epoxy resin), " YX4000HK " (union II first phenol-type epoxy resin), " YX8800 " (anthracene type epoxy resin), chemical (Osaka ガスケミカ Le) company of Osaka combustion gas System " PG-100 ", " CG-500 ", Mitsubishi Chemical Ind " YL7760 " (bisphenol AF type epoxy resin), " YL7800 " (fluorenes Type epoxy resin), " jER1010 " (solid-state bisphenol A type epoxy resin resin), " jER1031S " (tetraphenyl of Mitsubishi Chemical Ind Ethane type epoxy resin) etc..They can be used alone a kind, also can be used in combination two or more.

And when using liquid-state epoxy resin and solid epoxy resin as (A) ingredient, their amount ratio (liquid epoxy tree Fat：Solid epoxy resin) it is preferably 1 by quality ratio：0.1~1：20 range.By making liquid-state epoxy resin and solid-state ring The amount ratio of oxygen resin is above range, and following effects can be obtained：I) in the form of resin sheet in use, can bring appropriate Adhesiveness；Ii) in use, sufficient flexibility can be obtained, treatability improves in the form of resin sheet；And iii) can obtain To the solidfied material with sufficient fracture strength；Etc..From it is above-mentioned i)~iii) effect from the viewpoint of, liquid-state epoxy resin With the amount ratio (liquid-state epoxy resin of solid epoxy resin：Solid epoxy resin) it is more preferably 1 by quality ratio：0.2~1：5 Range, further preferably 1：0.3~1：1 range.

For the content of (A) ingredient in resin combination, from obtaining showing that good mechanical strength, insulation are reliable From the viewpoint of the insulating layer of property, when the nonvolatile component in resin combination is set as 100 mass %, preferably 15 mass % with On, more preferably 20 mass % or more, further preferably 25 mass % or more.For the upper limit of the content of epoxy resin, Be not particularly limited, if can play the present invention effect, preferably 60 mass % hereinafter, more preferably 45 mass % with Under, 40 mass % or less or 35 mass % or less.

(A) epoxide equivalent of ingredient is preferably 50~5000, more preferably 50~3000, further preferably 80~ 2000, it is even more preferably 110~1000.It, can to make the crosslink density of solidfied material become abundant by the range Form the small insulating layer of surface roughness.It should be noted that epoxide equivalent can be measured according to JIS K7236, it includes 1 to be The quality of the resin of the epoxy group of equivalent.

(A) weight average molecular weight of ingredient is preferably 100~5000, more preferably 250~3000, further preferably 400 ~1500.Herein, the weight average molecular weight of epoxy resin is changed according to polystyrene using what gel permeation chromatography (GPC) method measured The weight average molecular weight of calculation.

< (B) active esters system curing agent >

Resin combination includes (B) active ester system curing agent.Active ester system curing agent is to have 1 or more activity in 1 molecule The active ester compound of ester group.As active ester system curing agent, the activity with 2 or more active ester groups preferably in 1 molecule Ester system curing agent, for instance, it may be preferable to using phenolic ester (phenol ester) class, benzenethiol ester (thiophenol ester) class, The activity with 2 or more the high ester groups of reactivity in 1 molecule such as N- hydroxylamines esters, esters of heterocycle hydroxyl compound Ester system curing agent.Active ester system curing agent can be used alone a kind, also can be used in combination two or more.

From the viewpoint of improving heat resistance, preferably pass through carboxylic acid compound and/or thiocarboxylic acid compound and hydroxylating Close active ester system curing agent obtained from the condensation reaction of object and/or mercaptan compound.Wherein, more preferably make carboxylic acid compound with Selected from one or more of phenol (phenol, phenol) compound, naphthol compound and mercaptan compound reacted obtained from it is living Property ester system curing agent, obtained from so that carboxylic acid compound is reacted with the aromatic compounds with phenolic hydroxyl In 1 molecule with 2 or more active ester groups aromatic compounds, even more preferably make in 1 molecule have at least two with The carboxylic acid compound of upper carboxyl reacted with the aromatic compounds with phenolic hydroxyl obtained from 1 molecule with 2 The aromatic compounds of the above active ester groups.Active ester system curing agent can be straight-chain, or branched.In addition, at 1 point When the carboxylic acid compound with the above carboxyl of at least two is compound comprising aliphatic chain in son, it can be improved and resin combination The compatibility of object, for compound with aromatic ring when, heat resistance can be improved.

As carboxylic acid compound, the virtue of such as aliphatic carboxylic acid of carbon atom number 1~20, carbon atom number 7~20 can be enumerated Race's carboxylic acid.As aliphatic carboxylic acid, preferably carbon atom number is 1~20, and more preferable carbon atom number is 2~10, further preferred carbon Atomicity is 2~8, specifically, acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid etc. can be enumerated.As aromatic carboxylic acid, It is preferred that carbon atom number be 7~20, more preferable carbon atom number be 7~10, specifically, can enumerate benzoic acid, phthalic acid, Phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc..Wherein, from the viewpoint of heat resistance, preferably succinic acid, maleic acid, clothing Health acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), more preferable M-phthalic acid, terephthalic acid (TPA).

It as thiocarboxylic acid compound, is not particularly limited, can enumerate such as thioacetic acid, thiobenzoate.

As phenol (phenol) compound, such as preferred carbon atom number is 6~40, and more preferable carbon atom number is 6~30, into The preferred carbon atom number of one step is 6~23, and still more preferably carbon atom number is 6~22.As the preferred specific of phenolic compounds Example, can enumerate hydroquinone, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, the bisphenol-A that methylates, the Bisphenol F that methylates, Methylate bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, dihydroxy benaophenonel, trihydroxybenzophenone, Tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type biphenol etc..As phenolic compounds, phenol also can be used Phenolic resin (phenol novolac), Japanese Unexamined Patent Publication 2013-40270 bulletins are recorded former containing phosphorus with phenolic hydroxyl The oligomer of son.

As naphthol compound, such as preferred carbon atom number is 10~40, and more preferable carbon atom number is 10~30, further It is preferred that carbon atom number is 10~20.As the preferred concrete example of naphthol compound, alpha-Naphthol, betanaphthol, 1,5- bis- can be enumerated Hydroxyl naphthalene, 1,6- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes etc..As naphthol compound, naphthol novolac resin also can be used (naphthol novolac)。

Wherein, preferably bisphenol-A, Bisphenol F, bisphenol S, the bisphenol-A that methylates, the Bisphenol F that methylates, the bisphenol S that methylates, adjacent benzene two Phenol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes, dihydroxy benaophenonel, trihydroxy Benzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type biphenol, phenol novolacs, has tetrahydroxybenzophenone The oligomer containing phosphorus atoms of phenolic hydroxyl, more preferable catechol, 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes, 2,6- bis- Hydroxyl naphthalene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, two rings penta 2 Ene-type biphenol, phenol novolacs, the oligomer containing phosphorus atoms with phenolic hydroxyl, further preferred 1,5- dihydroxy Naphthalene, 1,6- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, two Cyclopeutadiene type biphenol, phenol novolacs, the oligomer containing phosphorus atoms with phenolic hydroxyl, even more preferably 1, 5- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes, dicyclopentadiene-type biphenol, phenol novolacs, have phenolic at 1,6- dihydroxy naphthlenes The oligomer containing phosphorus atoms of hydroxyl, especially more preferable 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes, two Cyclopeutadiene type biphenol, the oligomer containing phosphorus atoms with phenolic hydroxyl, particularly preferred dicyclopentadiene-type biphenol.

It as mercaptan compound, is not particularly limited, can enumerate such as dimercaptobenzene, two mercaptan of triazine.

As the preferred concrete example of active ester system curing agent, the work for including dicyclopentadiene-type biphenol structure can be enumerated The active ester system of property ester system curing agent, the active ester system curing agent comprising naphthalene structure, the acetylate comprising phenol novolacs Curing agent, benzoylate comprising phenol novolacs active ester system curing agent, make aromatic carboxylic acid and there is phenolic hydroxyl The oligomer reaction containing phosphorus atoms obtained from active ester system curing agent etc., wherein more preferably include dicyclopentadiene-type The active ester system curing agent of biphenol structure, the active ester system curing agent comprising naphthalene structure make aromatic carboxylic acid and have phenolic hydroxyl Active ester system curing agent obtained from the oligomer reaction containing phosphorus atoms of base.It should be noted that in the present invention, it is so-called " dicyclopentadiene-type biphenol structure " expression is formed by-two cyclopentylene of phenylene (dicyclopentylene)-phenylene Divalent structural unit.

As active ester system curing agent, Japanese Unexamined Patent Publication 2004-277460 bulletins, Japanese Unexamined Patent Publication 2013-40270 can be used Active ester system curing agent disclosed in number bulletin, in addition, it is possible to use commercially available active ester system curing agent.It is solid as active ester system The commercially available product of agent can enumerate " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000- of such as DIC corporations 65T ", " HPC-8000L-65M " (the active ester system curing agent for including dicyclopentadiene-type biphenol structure), DIC corporations " DC808 " of " EXB9416-70BK " (the active ester system curing agent for including naphthalene structure), Mitsubishi Chemical Ind (includes phenol phenol The active ester system curing agent of the acetylate of urea formaldehyde), " YLH1026 " of Mitsubishi Chemical Ind (include phenol novolacs Benzoylate active ester system curing agent), " EXB9050L-62M " (active ester systems containing phosphorus atoms of DIC corporations Curing agent).

For the content of active ester system curing agent, from obtain fine circuits Forming ability is excellent, dielectric loss angle just From the viewpoint of cutting low solidfied material, when the nonvolatile component in resin combination is set as 100 mass %, preferably 1 mass % More than, more preferably 5 mass % or more, further preferably 10 mass % or more.For active ester system curing agent content it is upper For limit, be not particularly limited, preferably 25 mass % hereinafter, more preferably 20 mass % hereinafter, further preferably 15 mass % Below.

In addition, when the epoxy radix of (A) epoxy resin is set as 1, from obtaining the viewpoint of the good insulating layer of mechanical strength Considering, the reactive group number of (B) active ester system curing agent is preferably 0.1~10, and more preferably 0.1~5, further preferably 0.1~1.Herein, so-called " the epoxy radix of epoxy resin " refers to being calculated for whole epoxy resin in resin combination The summation that is worth obtained from the solid constituent quality divided by epoxide equivalent of each epoxy resin present in resin combination and obtain The value arrived.In addition, so-called " reactive group " refer to can with the functional group of epoxy reaction, it is so-called " active ester system curing agent it is anti- Answer group number " refer to the solid constituent quality of active ester system curing agent divided by reaction present in resin combination by all It is worth obtained from value adduction obtained from group equivalent.

< (C) polyimide resins >

The resin combination of the present invention includes (C) polyimide resin.If in resin combination containing average grain diameter it is small or ratio The big inorganic filling material of surface area, then the melt viscosity rising of usual resin combination.In contrast, including (C) ingredient The resin combination of the present invention can inhibit the rising of the melt viscosity of resin combination.Think the rising to melt viscosity Inhibition be due to polyimide resin for the high effect of the compatibility of low polarity and epoxy resin and polyimide resin and It obtains.In addition, for the thermoplastic resin comprising phenoxy resin, aliphatic etc., usually easy tod produce in solidification The high ingredient of alcohol isopolarity, as a result, the dielectric loss angle tangent of the solidfied material of resin combination is got higher sometimes.In contrast, The case where solidfied material of the resin combination of the present invention containing (C) ingredient is with containing thermoplastic resins such as phenoxy resins phase Than polarity is lower, and result thinks that the dielectric loss angle tangent of solidfied material is lower.In addition, for the resin combination of the present invention For, it is believed that since the rough surface comprising minute asperities can be formed by roughening treatment, thus even if fine foring In the case of circuit, adequately anchoring (anchor) effect, result also can be obtained, fine circuits Forming ability is made to become excellent It is different.

For the content of (C) ingredient, when the resin component of resin combination is set as 100 mass %, it is situated between from reducing From the viewpoint of matter loss angle tangent, be 0.1 mass % or more, preferably 0.3 mass % or more, more preferably 0.5 mass % with On, further preferably 0.8 mass % or more.For the upper limit, from obtaining the excellent solidfied material of fine circuits Forming ability Viewpoint considers, is 6 mass % hereinafter, preferably 5.8 mass % are hereinafter, more preferably 5.5 mass % are hereinafter, further preferably 5.2 Quality % or less.

So-called " resin component " refer to constitute resin combination nonvolatile component in other than inorganic filling material Ingredient.

It as (C) ingredient, is not particularly limited, as long as polyimide resin.As (C) ingredient, example can be enumerated " RIKACOAT SN20 ", " RIKACOAT PN20 " polyimide resin of such as new Japan Chemical corporation；Make two functionalities Linear polyimides (Japanese Unexamined Patent Publication obtained from C-terminal polybutadiene, diisocyanate cpd and quaternary anhydride reaction 2006-37083 bulletins record polyimides), polyimides (the Japanese Unexamined Patent Publication 2002-12667 containing silicone matrix Polyimides described in number bulletin and Japanese Unexamined Patent Publication 2000-319386 bulletins etc.) etc. modified polyimides；Including making dimerization The polyimide resin of structure is (hereinafter, sometimes obtained from object diamines (dimer diamine) and polycarboxylic compounds' reaction Referred to as " dimer diamines polyimide resin ".)；Polyimide resin with polycyclic aromatic hydrocarbon skeleton.Wherein, as (C) at Point, from the viewpoint of further increasing fine circuits Forming ability, further decreasing minimum melt viscosity, preferred dimer two Amine polyimide resin and polyimide resin with polycyclic aromatic hydrocarbon skeleton, the more preferably polyamides with polycyclic aromatic hydrocarbon skeleton are sub- Polyimide resin.

(dimer diamines polyimide resin)

Dimer diamines polyimide resin includes in its molecular structure：The knot for being polymerize with dimer diamines and being formed The structural unit of structure and polymerize with polycarboxylic compounds and the structural unit of structure that is formed.In the following description In, the structural unit of structure that will be polymerize sometimes with dimer diamines and formed is known as " dimer diamine unit ".Separately Outside, the structural unit of structure that will polymerize sometimes with polycarboxylic compounds and formed is known as " polybasic carboxylic acid unit ". In general, in the molecule of dimer diamines polyimide resin, dimer diamine unit passes through cyclic annular acyl Asia with polybasic carboxylic acid unit Amine key and be bonded.

Dimer diamines is the dimer of aliphatic amine, includes 2 amino in 1 molecule.These amino be usually by- NH₂The primary amino group of expression.

The carbon atom number of every 1 molecular dimer diamines is preferably 19 or more, more preferably 27 or more, preferably 49 hereinafter, More preferably 41 or less.In addition, the aliphatic group that dimer diamines is included can be saturated aliphatic groups, or Unsaturated aliphatic group.In addition, dimer diamine unit can have carbon-to-carbon unsaturated bond.Every 1 dimer diamine unit The number of carbon-to-carbon unsaturated bond be preferably 0~3, more preferably 0~1, particularly preferably 0.

Dimer diamines generally comprises the main chain that is formed of aliphatic alkyl by connecting 2 amino and aforementioned by being bonded to The side chain that 2 aliphatic alkyls of main chain are formed.Therefore, for dimer diamine unit, usual every 1 dimer diamines Unit includes 2 side chains formed by aliphatic alkyl, and the aliphatic alkyl as side chain is preferably the straight chain fat of not branch Fat race alkyl.In addition, from the viewpoint of significantly obtaining the desired effect of the present invention, every 1 aliphatic hydrocarbon as side chain The carbon atom number of base is preferably 2 or more, and preferably 19 hereinafter, more preferably 18 or less.In addition, from institute's phase of the present invention is significantly obtained From the viewpoint of the effect of prestige, for every 1 dimer diamine unit, 1 or more side chain in preferably 2 side chains is Saturated aliphatic hydrocarbons, particularly preferred all side chains are saturated aliphatic hydrocarbons.

Dimer diamines can wrap ring-containing alicyclic diamine in the molecule, can also be not include ring in the molecule Chain fatty race diamines.Therefore, the aliphatic group that dimer diamine unit is included can include ring in its molecular structure.

About specific dimer diamines, the dimer diamines described in No. 5534378 bulletins of Japanese Patent No. can refer to.

Dimer diamines such as can by making dimeric dibasic acid unsaturated fatty acid or its ester, advanced unsaturated nitrile or advanced Unsaturated alcohol carries out reduction amination, then carries out dimerization to manufacture.In addition, dimer diamines for example can by make it is above-mentioned not It is sour, polynary to obtain polyhydric aliphatic that saturated fatty acid or its ester, advanced unsaturated nitrile or advanced unsaturated alcohol carry out dimerization Then nitrile or polyalcohol carry out reduction amination to manufacture.In turn, the manufacturing method of dimer diamines may include implementing hydrogenation instead It answers.About the manufacturing method of dimer diamines, the method described in Japanese Unexamined Patent Publication 9-12712 bulletins can refer to.

Polycarboxylic compounds refer to the carboxylic acid compound of 2 yuan or more of first number, and can enumerate for example every 1 molecule has The carboxylic acid and its acid anhydride (acid anhydrides) of 2 or more carboxyls.Wherein, from the viewpoint of significantly obtaining the desired effect of the present invention, make For polybasic carboxylic acid, preferably tetracarboxylic compound, particularly preferred aromatic acid's compound.

As aromatic acid's compound, such as Pyromellitic Acid, pyromellitic acid anhydride, 4,4 '-oxygroups two can be enumerated O-phthalic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides, 3, 3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydrides, 1,2,3,4- benzene tetracarboxylic acids acid anhydride, 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride, 2,3,6,7- naphthalenes four Formic anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 2,3,3 ', 4 '-bibenzene tetracarboxylics Dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydrides, 2,3,3 ', 4 '-diphenyl ether tetracarboxylic dianhydrides, 2,3,3 ', 4 '-hexichol Bis- (3,3 ', 4,4 '-tetracarboxylic phenyl) the tetrafluoropropane dianhydrides of base sulfone tetracarboxylic dianhydride, 2,2-, 2,2 '-bis- (3,4- dicarboxyl benzene Phenyl) sulfone dianhydride, bis- (2,3- dicarboxyphenyis) propane dianhydrides of 2,2-, bis- (3,4- dicarboxyphenyis) propane two of 2,2- Acid anhydride, pentamethylene tetracarboxylic anhydride, butane -1,2,3,4- tetrabasic carboxylic acids, 2,3,5- tricarboxylic cyclopentyls acetic anhydride, 4,4 '-[propane -2, 2- diyls are bis- (1,4- phenylene oxygens)] two O-phthalic acid dianhydrides etc..

About the particularly preferred structural unit that dimer diamines polyimide resin is included, Japanese Patent No. can refer to No. 5534378 bulletins.

In dimer diamines polyimide resin, the amount ratio of dimer diamine unit and polybasic carboxylic acid unit is arbitrary, As long as the effect of the present invention is not significantly impaired.In general, the dimer diamine unit in dimer diamines polyimide resin With the amount ratio of polybasic carboxylic acid unit, with the dimer diamines as the raw material for manufacturing the dimer diamines polyimide resin Charging with polycarboxylic compounds is than identical.For by " mole of the molal quantity of polybasic carboxylic acid unit/dimer diamine unit For the amount ratio that number " indicates, and specifically, it is preferable to be 0.6 or more, particularly preferably 0.8 or more, preferably 1.4 are hereinafter, especially excellent It is selected as 1.2 or less.By the way that aforementioned quantities than controlling in aforementioned range, can significantly be obtained the desired effect of the present invention.

As needed, dimer diamines polyimide resin may include except dimer diamine unit and polybasic carboxylic acid unit with Outer arbitrary structural unit.For dimer diamines polyimide resin, it can be used alone a kind, it can also be with arbitrary Ratio combine use two or more.

Dimer diamines polyimide resin for example can be by making dimer diamines polymerize by system with polycarboxylic compounds It makes.In addition, dimer diamines polyimide resin for example can be by by making dimer diamines polymerize with polycarboxylic compounds After obtaining polyamic acid, polyamic acid progress imidizate is set to manufacture by being dehydrated and being cyclized.In addition, for dimer two For the manufacturing method of amine polyimide resin, it can be obtained with polymerizeing for polycarboxylic compounds by dimer diamines After polyimide resin, the chain extending reaction based on chain extender is carried out.The manufacturing method of dimer diamines polyimide resin is for example It can refer to No. 5534378 bulletins of Japanese Patent No..

(polyimide resin with polycyclic aromatic hydrocarbon skeleton)

So-called polycyclic aromatic hydrocarbon refers in 1 molecule comprising at least one in 2 or more cyclic structures and the cyclic structure For the hydrocarbon of aromatic ring, 2 or more cyclic structures can be condensed, can not also be condensed.

Polycyclic aromatic hydrocarbon skeleton can not have substituent group, it is possible to have substituent group.As substituent group, do not limit especially System, can enumerate such as halogen atom ,-OH ,-O-C_1-6Alkyl ,-N (C_1-6Alkyl)₂、C_1-6Alkyl, C_6-10Aryl ,-NH₂、-CN、-C (O)O-C_1-6Alkyl ,-COOH ,-C (O) H ,-NO₂Deng preferably C_1-6Alkyl, more preferable methyl.Substituent group can only have a kind, Can also have a variety of.

Herein, term " C_p-q" (p and q are positive integer, meet p < q.) indicate to follow the organic group recorded after the term closely Carbon atom number be p~q.For example, " C_1-6The such expression of alkyl " indicates the alkyl of carbon atom number 1~6.

As polycyclic aromatic hydrocarbon skeleton, the indane skeleton and fluorenes for example including 1,1,3- trimethyl indane skeleton etc. can be enumerated Aromatic hydrocarbons skeleton made of the 5-membered ring compounds and aromatic ring fusion of skeleton etc.；Made of the aromatic ring fusion of naphthalene skeleton and anthracene skeleton etc. Aromatic hydrocarbons skeleton；Biphenyl backbone etc. has the aromatic hydrocarbons skeleton (non-condensed type aromatic hydrocarbons skeleton) that 2 or more condensed aromatic rings do not occur Deng, from the viewpoint of further increasing fine circuits Forming ability, further decreasing minimum melt viscosity, preferred five-membered ring Close object and aromatic hydrocarbons skeleton made of aromatic ring fusion.Wherein, from the coefficient of linear thermal expansion for the solidfied material for reducing resin combination, raising From the viewpoint of glass transition temperature and peel strength, polycyclic aromatic hydrocarbon skeleton be preferably in indane skeleton and fluorene skeleton at least It is any.

As the imide resin with polycyclic aromatic hydrocarbon skeleton, from further increasing fine circuits Forming ability, further From the viewpoint of reducing minimum melt viscosity, it is however preferred to have the polyimides tree of polycyclic aromatic hydrocarbon skeleton and cyclic imide structure Fat.

As cyclic imide structure, such as phthalimide, succinimide, glutarimide, 3- can be enumerated Polydimethyl glutarimide, maleimide, dimethylmaleimide, inclined benzene trimellitic imide, equal diimides, preferably Phthalimide, succinimide can be enumerated, wherein the preferably polyimide resin with aromatic imide structure, more It is preferred that phthalimide.

For (C) ingredient, coefficient of linear thermal expansion, raising glass transition from the solidfied material for reducing resin combination From the viewpoint of temperature and peel strength, preferably have：Repetitive unit with polycyclic aromatic hydrocarbon skeleton and with imide structure Repetitive unit.

As the repetitive unit with polycyclic aromatic hydrocarbon skeleton, for example, preferably the following general formula (1) indicate repetitive unit；

(in formula (1), A indicates that polycyclic aromatic hydrocarbon skeleton, D indicate the linking group of singly-bound or divalent.).

A in formula (1) indicates that polycyclic aromatic hydrocarbon skeleton, the details of polycyclic aromatic hydrocarbon skeleton are as described above.

D in formula (1) indicates the linking group of singly-bound or divalent, the preferably linking group of divalent.Linker as divalent Group, can enumerate for example oxygen atom, sulphur atom, alkylidene, arlydene ,-NH- ,-C (=O)-,-SO- or by 2 in them with On the group etc. that is formed of combination.

As alkylidene, the preferably alkylidene of carbon atom number 1~10, the alkylidene of more preferable carbon atom number 1~6, into one Walk the alkylidene of preferred carbon atom number 1~3.Alkylidene can be the arbitrary form in straight chain, branch, ring-type.As such Alkylidene can be enumerated such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, preferably methylene.

As arlydene, the preferably arlydene of carbon atom number 6~14, the arlydene of more preferable carbon atom number 6~10.As Arlydene can be enumerated such as phenylene, naphthylene, anthrylene, preferably phenylene.

Alkylidene and arlydene can not have substituent group, it is possible to have substituent group.As substituent group, with polycyclic aromatic hydrocarbon The substituent group that skeleton can have is same.

As the group formed by the combination of 2 or more in them, preferably by oxygen atom, arlydene and alkylidene 2 or more combination formed group.As such group, such as 1 or more arlydene and 1 or more alkylene can be enumerated Group (group is formed by the combination of arlydene and alkylidene), 1 or more oxygen atom and 1 or more arlydene made of base bonding Group made of bonding (group formed by the combination of oxygen atom and arlydene) etc..As 1 or more arlydene and 1 or more Group made of alkylene can enumerate the group of the divalent for example formed by phenylene-methylene, by phenylene-dimethyl The group etc. for the divalent that methylene is formed.Group made of being bonded with 1 or more arlydene as 1 or more oxygen atom, can enumerate Such as the group of the divalent formed by phenylene-oxygen atom-phenylene, the divalent formed by oxygen atom-phenylene group, by oxygen The group etc. for the divalent that atom-naphthylene is formed.

As the preferred example of the repetitive unit with polycyclic aromatic hydrocarbon skeleton, repetitive unit below can be enumerated；

。

As the repetitive unit with imide structure, be not particularly limited, if having imide structure, from into One step improves fine circuits Forming abilities, further decrease minimum melt viscosity from the viewpoint of, it is however preferred to have cyclic annular acyl is sub- The repetitive unit of amine structure.

As cyclic imide structure, such as phthalimide, succinimide, glutarimide, 3- can be enumerated Polydimethyl glutarimide, maleimide, dimethylmaleimide, inclined benzene trimellitic imide, equal diimides, preferably Phthalimide, succinimide can be enumerated, wherein preferred aromatic imide structure, more preferable phthalimide. Repetitive unit with imide structure can also be the form that above-mentioned imide structure is bonded with the linking group of divalent.Make It is same as the linking group of divalent represented by the D in general formula (1) for the linking group of divalent.

As the preferred example of the repetitive unit with imide structure, repetitive unit below can be enumerated；

。

Mass ratio as repetitive unit and the repetitive unit with imide structure with polycyclic aromatic hydrocarbon skeleton (has The quality of the quality of the repetitive unit of polycyclic aromatic hydrocarbon skeleton/repetitive unit with imide structure), preferably 0.5 or more, more Preferably 0.6 or more, further preferably 0.8 or more, preferably 2 are hereinafter, more preferably 1.8 hereinafter, further preferably 1.5 Below.By making the mass ratio within the above range, the coefficient of linear thermal expansion of the solidfied material of resin combination can be reduced, improves glass Glass transition temperature and peel strength.

The manufacturing method of polyimide resin with polycyclic aromatic hydrocarbon skeleton is not particularly limited, can be according to various method systems It makes.As a preferred embodiment, can by using as the repetitive unit with imide structure monomer and become The monomer of repetitive unit with polycyclic aromatic hydrocarbon skeleton, which is polymerize, to be obtained.When being polymerize, as needed, polymerization can be used Initiator etc..

For the weight average molecular weight of (C) ingredient, from further increasing fine circuits Forming ability, further decrease most From the viewpoint of low melt viscosity, preferably 5000 or more, more preferably 10000 or more, further preferably 11000 or more, Preferably 100000 hereinafter, more preferably 50000 hereinafter, further preferably 30000 or less.Herein, (C) ingredient is divided equally again Son amount is the weight average molecular weight to convert according to polystyrene measured using gel permeation chromatography (GPC).

< (D) inorganic filling materials >

The resin combination of first embodiment includes that (D) average grain diameter is 100nm inorganic filling materials below.In addition, the The resin combination of two embodiments includes that (D) specific surface area is 15m²The inorganic filling material of/g or more.(D) material of ingredient It is not particularly limited, such as silica, aluminium oxide, glass, cordierite, Si oxide, barium sulfate, barium carbonate, cunning can be enumerated Stone, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesia, nitrogen Change boron, aluminium nitride, nitrogenized manganese, aluminium borate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, zirconium oxide, titanium Sour barium, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc..In these, particularly preferred 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.Inorganic filling material can be used alone a kind, Also it can be used in combination two or more.

It is micro- from the viewpoint of filming and raising for the average grain diameter of the inorganic filling material in first embodiment It is 100nm hereinafter, preferably 90nm is hereinafter, more preferably 80nm or less from the viewpoint of thin circuit Forming ability.For average It for the lower limit of grain size, is not particularly limited, can be preferred 1nm or more, more preferable from the viewpoint of improving plyability 5nm or more, further preferred 10nm are with first-class.

In addition, for the average grain diameter of the inorganic filling material in second embodiment, from the viewpoint of filming and Improve fine circuits Forming ability from the viewpoint of, preferably 100nm hereinafter, more preferably 90nm hereinafter, further preferably 80nm or less.For the lower limit of average grain diameter, be not particularly limited, can be preferred 1nm or more, more preferable 5nm or more, Further preferred 10nm is with first-class.

As the commercially available product of the inorganic filling material with such average grain diameter, can enumerate for example electrochemically industrial public Department's system " UFP-30 " etc..

The average grain diameter of inorganic filling material can utilize the laser diffraction-scattering method of Michaelis (Mie) scattering theory.Tool For body, using laser diffraction and scattering formula particle size distribution device, the grain of inorganic filling material is made according to volume reference Degree distribution, using its median particle diameter as average grain diameter, is thus measured.For determination sample, preferably using utilization Product obtained from inorganic filling material is scattered in methyl ethyl ketone by ultrasonic wave.As laser diffraction and scattering formula size distribution Ku Chang manufacturing companies system " LA-500 ", Shimadzu Seisakusho Ltd.'s corporation " SALD-2200 " etc. can be used in measurement device.

For the specific surface area of the inorganic filling material in second embodiment, from raising fine circuits Forming ability From the viewpoint of, it is 15m²/ g or more, more preferably 20m²/ g or more, further preferably 30m²/ g or more.For upper limit value Speech, from the viewpoint of improving plyability, preferably 60m²/ g is hereinafter, more preferably 50m²/ g is hereinafter, further preferably 40m²/ g or less.

In addition, for the specific surface area of the inorganic filling material in first embodiment, from raising fine circuits shape From the viewpoint of ability, preferably 15m²/ g or more, more preferably 20m²/ g or more, further preferably 30m²/ g or more.It is right It is not particularly limited in the upper limit, preferably 60m²/ g is hereinafter, more preferably 50m²/ g is hereinafter, further preferably 40m²/ g or less.

Specific surface area can be obtained by following manner：According to BET method, using specific area measuring device, (Mountech is public Department Macsorb HM-1210 processed), make specimen surface absorption nitrogen, specific surface area is calculated using BET multipoint methods.

For inorganic filling material, from the viewpoint of improving moisture-proof and dispersibility, preferably with fluorine containing silane idol Join agent, amino silicone methane series coupling agent, epoxy radicals silicone hydride system coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, alkoxy 1 kind or more of surface conditioning agent of silane, organic silazane hydride compounds, titanate esters system coupling agent etc. is handled, more preferably It is handled with amino silicone methane series silane coupling agent.As the commercially available product of surface conditioning agent, such as SHIN-ETSU HANTOTAI's chemistry work can be enumerated Industry corporation " KBM403 " (3- glycidoxypropyltrime,hoxysilanes), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM803 " (3- Mercaptopropyi trimethoxy silane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBE903 " (3-aminopropyltriethoxysilane), SHIN-ETSU HANTOTAI Chemical industrial company's system " KBM573 " (N- phenyl -3- TSL 8330s), chemical industrial company of SHIN-ETSU HANTOTAI system " SZ- 31 " (hexamethyldisilazane), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM103 " (phenyltrimethoxysila,e), SHIN-ETSU HANTOTAI's chemical industry Corporation " KBM-4803 " (long-chain epoxy type silane coupling agent), chemical industrial company of SHIN-ETSU HANTOTAI system " KBM-7103 " (3,3,3- tri- Fluoropropyl trimethoxy silane) etc..

For the degree of the surface treatment carried out using surface conditioning agent, from the dispersibility for improving inorganic filling material From the viewpoint of, relative to 100 mass parts of (D) ingredient, preferably carried out with the surface conditioning agent of the mass parts of 0.2 mass parts~5 Surface treatment is preferably surface-treated with the mass parts of 0.2 mass parts~4, is preferably carried out with the mass parts of 0.3 mass parts~3 Surface treatment.

The degree of the surface treatment carried out using surface conditioning agent can pass through the inorganic filling material of per unit surface area Carbon amounts is evaluated.For the carbon amounts of the inorganic filling material of per unit surface area, from raising inorganic filling material From the viewpoint of dispersibility, preferably 0.02mg/m²More than, more preferably 0.1mg/m²More than, further preferably 0.2mg/m² More than.On the other hand, from the viewpoint of the rising of the melt viscosity 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 the inorganic filling material of per unit surface area can be right using solvent (for example, methyl ethyl ketone (MEK)) Inorganic filling material after surface treatment is measured after carrying out carrying out washing treatment.Specifically, by enough MEK as solvent It is added in the inorganic filling material being surface-treated with surface conditioning agent, 5 minutes ultrasonic washings is carried out in 25 DEG C.It removes Supernatant is removed, solid constituent is made to dry, carbon analysis meter then can be used, measures the carbon of the inorganic filling material of per unit surface area Amount.As carbon analysis meter, Ku Chang manufacturing companies system " EMIA-320V " etc. can be used.

It, will be in resin combination from the viewpoint of reducing dielectric loss angle tangent for the content of (D) ingredient When nonvolatile component is set as 100 mass %, preferably 30 mass % or more, more preferably 35 mass % or more, further preferably 40 Quality % or more.For the upper limit, from the viewpoint of improving insulation performance, preferably 80 mass % are hereinafter, more preferably 70 Quality % is hereinafter, further preferably 65 mass % or less.

< (E) curing agent >

In one embodiment, resin combination can contain (E) curing agent.But (E) curing agent so-called herein does not include (B) Active ester system curing agent.It as (E) ingredient, is not particularly limited, as long as with the cured function of (A) ingredient is made, can lift It is curing agent, naphthols system curing agent, benzoxazine system curing agent, cyanate system curing agent and carbon two to go out such as phenol (phenol) Imines system curing agent etc..Wherein, as (E) ingredient, preferably phenol system curing agent.Curing agent can be used alone a kind, or also can be simultaneously Use 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 phenolic aldehyde The phenol system curing agent of structure or naphthols system curing agent with phenolic structure.In addition, being examined from the viewpoint of the adaptation with conductor layer Consider, preferably nitrogenous phenol system curing agent, further preferably the phenol system curing agent of triazine skeleton.

As phenol system curing agent and the concrete example of naphthols system curing agent, for example bright and chemical conversion corporation " MEH- can be enumerated 7700 ", aurification is lived by " MEH-7810 ", " MEH-7851 ", " NHN " of Japanese chemical drug corporation, " CBN ", " GPH ", Nippon Steel " SN170 " of corporation, " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495 ", " SN-495V " " SN375 ", " TD-2090 " of " SN395 ", DIC corporations, " 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.

As cyanate system curing agent, such as bisphenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene-can be enumerated 1,5- phenylenecyanates), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- 3,5-dimethylphenyls cyanate), 4,4 '-ethylene phenyl, two cyanic acid It is bis- (4- cyanates) phenyl-propanes of ester, hexafluoro bisphenol-a dicyanate, 2,2-, 1,1- bis- (4- cyanatephenyls methane), double Bis- (4- cyanatephenyls -1- (methyl the ethylidene)) benzene of (4- cyanic acid ester group -3,5- 3,5-dimethylphenyls) methane, 1,3-, bis- (4- Cyanatephenyl) the two function cyanate ester resins such as thioether and bis- (4- cyanatephenyls) ethers, by phenol novolacs and first Multifunctional cyanate ester resin derived from phenol phenolic resin etc., these cyanate ester resins carry out prepolymer obtained from the triazine of part Deng.As the concrete example of cyanate system curing agent, " PT30 " and " PT60 " (phenol phenol of Lonza Japan corporations can be enumerated Aldehyde type multifunctional cyanate ester resin), " ULL-950S " (multifunctional cyanate ester resin), " BA230 ", " BA230S75 " (bisphenol-A two Part or all of cyanate carries out triazine and forms the prepolymer of tripolymer) etc..

As the concrete example of carbodiimide system curing agent, can enumerate Nisshinbo Chemical Inc. " V-03 ", " V-07 " etc..

When resin combination contains (E) ingredient, for the amount ratio of (A) ingredient and (E) ingredient, with [the ring of (A) ingredient The sum of oxygroup]：The ratiometer of [sum of the reactive group of (E) ingredient], preferably 1：0.01~1：2 range, more preferably It is 1：0.05~1：1.5, further preferably 1：0.08~1：1.The reactive group of (E) ingredient so-called herein, refers to active hydroxyl Base etc., it is different with the difference of the type of (E) ingredient.In addition, the sum of the epoxy group of so-called (A) ingredient, refers to for complete (A) ingredient in portion calculates the value obtained by the summation being worth obtained from the respectively solid constituent quality of (A) ingredient divided by epoxide equivalent, institute The sum for calling the reactive group of (E) ingredient refers to that the solid constituent quality of each (E) ingredient of (E) ingredient calculating for being directed to whole is removed With the value obtained by the summation that is worth obtained from reactive group equivalent.By making the amount ratio of (A) ingredient and (E) ingredient in above range It is interior, so as to further decrease resin combination solidfied material coefficient of linear thermal expansion, can further improve peel strength.

In addition, when resin combination contains (E) ingredient, (A) epoxy resin and the amount ratio of (B) ingredient and (E) ingredient with [sum of the epoxy group of (A) ingredient]：The ratiometer of [sum of the reactive group of (B) ingredient and the reactive group of (E) ingredient] Preferably 1：0.01~1：3 range, more preferably 1：0.005~1：2, further preferably 1：0.1~1：1.5.

When resin combination contains (E) ingredient, from further increasing fine circuits Forming ability, further decrease most eutectic From the viewpoint of body viscosity, for the content of (E) ingredient, the nonvolatile component in resin combination is set as 100 mass % When, preferably 15 mass % hereinafter, more preferably 10 mass % hereinafter, further preferably 5 mass % or less.In addition, for lower limit For, it is not particularly limited, preferably 1 mass % or more, more preferably 2 mass % or more, further preferably 3 mass % or more.

< (F) curing accelerators >

In one embodiment, resin combination can contain (F) curing accelerator.As curing accelerator, can enumerate for example Phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator, guanidine system curing accelerator, metal system solidification promote Agent etc., preferably phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator, metal system curing accelerator, it is more excellent Select amine system curing accelerator.Curing accelerator can be used alone a kind, also can be used in combination two or more.

As phosphorus system curing accelerator, such as triphenylphosphine, Phosphonium borate compound, tetraphenylphosphoniphenolate tetraphenyl boron can be enumerated Hydrochlorate, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyls) triphenyl phosphonium rhodanate, tetraphenyl Phosphonium rhodanate, Ding base triphenyl phosphonium rhodanates etc., triphenylphosphine, 4-butyl-phosphonium caprate.

As amine system curing accelerator, the trialkylamine such as triethylamine, tri-butylamine, 4- dimethylaminos can be enumerated Pyridine, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol, 1,8- diazabicyclos (5,4,0)-endecatylene Deng, preferably 4-dimethylaminopyridine, 1,8- diazabicyclos (5,4,0)-endecatylene.

As imidazoles system curing accelerator, such as 2-methylimidazole, 2- undecyl imidazoles, 2- heptadecyl miaows can be enumerated Azoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl miaows Azoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazoles, 1- cyano ethyl -2- methyl miaows Azoles, 1- cyano ethyl -2- undecyl imidazoles, 1- cyano ethyls -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenyl miaows Azoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acids salt, 1- cyano ethyl -2- phenylimidazole trimellitic acids salt, 2, 4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-undecyl imidazole bases - (1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2,4- Diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acids add At object, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles, 2,3- dihydro -1H- pyrroles And [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazoles chloride, 2-methylimidazole quinoline, 2- phenyl miaows The adduct of the imidazolium compounds such as oxazoline and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- benzyls- 2- phenylimidazoles.

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

As guanidine system curing accelerator, such as dicyandiamide, 1- methylguanidines, 1- ethyl guanidines, 1- cyclohexyl guanidine, 1- benzene can be enumerated Base guanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethylguanidine, pentamethyl guanidine, tri- azepines of 1,5,7- Bicyclic [4.4.0] decyl- 5- alkene, 7- methyl-1s, tri- azabicyclos of 5,7- [4.4.0] decyl- 5- alkene, 1- methyl biguanides, 1- ethyls are double Guanidine, 1- normal-butyls biguanides, 1- n-octadecane bases biguanides, 1,1- dimethylbiguanides, 1,1- diethyl biguanides, 1- cyclohexyl biguanides, 1- allyls biguanides, 1- phenyl biguanides, 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.As the concrete example of metal-organic complex, acetylacetone cobalt (II), acetylacetone cobalt can be enumerated (III) the organic zincs complexing such as organic copper complex, zinc acetylacetonate (II) such as organic cobalt complex, acetylacetone copper (II) such as Organic nickel complexes such as the Organic-iron complexes such as object, ferric acetyl acetonade (III), nickel acetylacetonate (II), manganese acetylacetonate (II) Etc. organic manganese complex etc..As organic metal salt, such as zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, hard can be enumerated Resin acid tin, zinc stearate etc..

It, will be in resin combination for the content of curing accelerator when resin combination contains curing accelerator When nonvolatile component is set as 100 mass %, preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably For 0.1 mass % or more.For the upper limit, preferably 3 mass % are hereinafter, more preferably 2 mass % are hereinafter, further preferably 1 Quality % or less.Content by making curing accelerator within the above range, can further improve fine circuits Forming ability, into One step reduces minimum melt viscosity.

< (G) thermoplastic resins >

In one embodiment, resin combination can contain (G) thermoplastic resin.But (G) thermoplastic resin so-called herein It does not include (C) polyimide resin.

As thermoplastic resin, such as phenoxy resin, polyvinyl acetal resin, vistanex, poly- fourth can be enumerated Diene resin, polyamide-imide resin, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyethers ether Ketone resin, polyester resin etc., preferably phenoxy resin.Thermoplastic resin can be used alone a kind, or also can be used in combination 2 kinds More than.

The weight average molecular weight according to polystyrene conversion of thermoplastic resin is preferably 8,000 or more, more preferably 10, 000 or more, further preferably 20,000 or more, particularly preferably 40,000 or more.For the upper limit, do not limit especially System, preferably 70,000 hereinafter, more preferably 60, and 000 or less.The Weight-average molecular of thermoplastic resin to convert according to polystyrene Amount can utilize gel permeation chromatography (GPC) to measure.Specifically, for the weight of thermoplastic resin to convert according to polystyrene For average molecular weight, it can be used Shimadzu Seisakusho Ltd. corporation LC-9A/RID-6A as measurement device, use Showa electrician company Shodex K-800P/K-804L/K-804L processed are as column, using chloroform etc. as mobile phase, surveyed in 40 DEG C of column temperatures It is fixed, it is calculated using the standard curve of standard polystyren.

As phenoxy resin, can enumerate for example with selected from by bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-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 Fat.The end of phenoxy resin can be the arbitrary functional group in phenolic hydroxyl, epoxy group etc..Phenoxy resin can be used alone 1 kind, it also can be used in combination two or more.As the concrete example of phenoxy resin, can enumerate Mitsubishi Chemical Ind " 1256 " and " 4250 " (being the phenoxy resin containing bisphenol A skeleton), " YX8100 " (phenoxy resin containing bisphenol S skeleton) and " YX6954 " (phenoxy resin containing bis-phenol acetophenone skeleton), in addition, can enumerate Nippon Steel lives aurification corporation " FX280 " and " FX293 ", " YL7500BH30 " of Mitsubishi Chemical Ind, " YX6954BH30 ", " YX7553 ", " YX7553BH30 ", " YL7769BH30 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc..

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

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

As the concrete example of polyethersulfone resin, can enumerate " PES5003P " of sumitomo chemical company etc..As polyphenylene oxide The concrete example of resin can enumerate oligomeric phenylate-styrene resin " OPE- with vinyl of gas chemical company of Mitsubishi 2St 1200 " etc..

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

It, will be in resin combination for the content of thermoplastic resin when resin combination contains thermoplastic resin When nonvolatile component is set as 100 mass %, preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more.For the upper limit, preferably 10 mass % are hereinafter, more preferably 5 mass % are hereinafter, further preferably 3 Quality % or less.

< (H) others additives >

In one embodiment, as needed, resin combination also may include other additives, as the others Additive, can enumerate phosphorus compound, nitrogen compound, organo-silicon compound that for example organophosphorus compound, organic system are nitrogenous and The fire retardants such as metal hydroxides；The organic filler materials such as rubber particles；Organocopper compound, organic zinc compound and organic cobalt The organo-metallic compounds such as compound；The resin additives such as thickener, antifoaming agent, levelling agent, adaptation imparting agent and colorant Deng.

The physical property of < resin combinations, purposes >

The resin combination of the present invention brings the insulating layer (resin that fine circuits Forming ability is excellent, dielectric loss angle tangent is low The solidfied material of composition layer).Therefore, resin combination of the invention can suitably serve as the resin composition layer of insulation applications. Specifically, resin combination of the invention can suitably serve as：It is used to form the resin combination of the insulating layer of printed wiring board (resin compositions for insulating layer of printed wiring board)；Can more suitably it be used as：It is used to form the layer insulation of printed wiring board The resin combination (the interlayer insulating film resin combination of printed wiring board) of layer.In addition, the resin combination band of the present invention Carry out the good insulating layer of component imbedibility, therefore also can suitably make in the case where printed wiring board is component internal circuit board With.In addition, the resin combination of the present invention can suitably serve as：Be used to form in order to formed on the insulating layer conductor layer (including Wiring layer again) the insulating layer resin combination (in order to form the insulating layer formation resin combination of conductor layer).

Resin combination is set to carry out heat cure in 30 minutes in 100 DEG C and then carry out heat cure in 30 minutes in 180 DEG C and obtain Solidfied material show the excellent such characteristic of fine circuits Forming ability.That is, the insulation for bringing fine circuits Forming ability excellent Layer.Since fine circuits Forming ability is excellent, minimum L (lines：Wiring width)/(spaces S：Interval width) it is preferably 8 μ M/8 μm hereinafter, more preferably 7 μm/7 μm hereinafter, further preferably 6 μm/6 μm or less.For lower limit, do not limit especially System can be 1 μm/1 μm with first-class.In addition, minimum wiring spacing be preferably 10 μm hereinafter, more preferably 8 μm hereinafter, into one Preferably 6 μm or less of step.For lower limit, it is not particularly limited, it can be for 1 μm with first-class.Fine circuits Forming ability can It is measured according to the method for aftermentioned < fine circuits Forming ability measured described in >.

Solidfied material display medium loss angle tangent is low obtained from so that resin combination is carried out heat cure in 90 minutes in 200 DEG C Such characteristic.That is, the insulating layer for bringing dielectric loss angle tangent low.As dielectric loss angle tangent, preferably 0.1 hereinafter, More preferably 0.05 hereinafter, further preferably 0.015 or less.It for lower limit, is not particularly limited, can be 0.0001 With first-class.Measuring for dielectric loss angle tangent can be surveyed according to the method for aftermentioned < dielectric loss angle tangents measured described in > It is fixed.

For minimum melt viscosity when 120 DEG C of resin combination, from the viewpoint of improving plyability, preferably For 7000 pools hereinafter, more preferably 6000 pools are hereinafter, further preferably 5000 pools are following.For lower limit, without special Limitation can be 100 pools with first-class.Minimum melt viscosity can be surveyed according to the method described in the evaluation > of aftermentioned < plyabilities It is fixed.

Characteristic below is presented in resin combination：Since minimum melt viscosity is low, thus imbedibility improves, and result can press down The generation of system empty (void).For example, even if resin combination to be laminated to comb shape (Comb Dentistry) pattern of L/S=160 μm/160 μm On, also do not generate cavity.The presence or absence of cavity can be measured according to the method described in the evaluation > of aftermentioned < plyabilities.

[resin sheet]

The resin sheet of the present invention includes that supporting mass and the resin combination by the present invention being set on the supporting mass are formed Resin composition layer.

For the thickness of resin composition layer, from the viewpoint of the slimming of printed wiring board, preferably 200 μm Hereinafter, more preferably 100 μm hereinafter, further preferably 50 μm hereinafter, even more preferably be 20 μm or less, 15 μm or less, Or 10 μm or less.It for the lower limit of the thickness of resin composition layer, is not particularly limited, typically 1 μm or more, 3 μ M is with first-class.

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

In the case where using the film being molded of plastic material as supporting mass, as plastic material, can enumerate for example poly- Ethylene glycol terephthalate is (hereinafter sometimes referred to simply as " PET ".), polyethylene naphthalate (hereinafter sometimes referred to simply as "PEN".) etc. polyester, makrolon (hereinafter sometimes referred to simply as " PC ".), the acrylic acid series such as polymethyl methacrylate (PMMA), Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferably poly- pair Ethylene terephthalate, polyethylene naphthalate, particularly preferably cheap polyethylene terephthalate.

In the case where using metal foil as supporting mass, as metal foil, can enumerate such as copper foil, aluminium foil, preferably Copper foil.As 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.

It, can pair face engaged with resin composition layer implementation matte management, sided corona treatment, antistatic for supporting mass Processing.

In addition, as supporting mass, it may be used at the face engaged with resin composition layer and carries release layer with release layer Supporting mass.As the releasing agent used in the release layer of the supporting mass with release layer, can enumerate for example selected from by alkyd The releasing agent of one or more of the group of resin, vistanex, polyurethane resin and organic siliconresin composition.With release layer Supporting mass commercially available product can be used, can enumerate for example with using alkyd resin system releasing agent as the PET film of the release layer of principal component, That is " SK-1 ", " AL-5 ", " AL-7 " of Lin get Ke corporations, " dew Miller T60 " of Toray, Supreme Being people's corporation " UNIPEEL " etc. of " Purex ", UNITIKA corporations.

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 when using the supporting mass for carrying release layer, the supporting mass entirety of release layer is preferably carried Thickness is within the above range.

In one embodiment, as needed, resin sheet also may include other layers.As other described layers, can lift Go out for example to be arranged on the face (that is, face with supporting mass opposite side) of resin composition layer not engaged with supporting mass, press According to the protective film etc. of supporting mass.The thickness of protective film is not particularly limited, for example, 1 μm~40 μm.By the way that protective film is laminated, from And it 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 for example be manufactured by following manner：Prepare the resin for being dissolved with resin combination in organic solvent The resin varnish is coated on supporting mass using metal mold coating machine (die coater) etc., and then made it dry, shape by varnish At resin composition layer.

As organic solvent, ketone, ethyl acetate, second such as acetone, methyl ethyl ketone (MEK) and cyclohexanone can be enumerated The acetate esters such as acid butyl ester, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, cellosolve and butyl The aromatic hydrocarbons such as the carbitols such as carbitol class, toluene and dimethylbenzene, dimethylformamide, dimethylacetylamide (DMAc) and N- methyl Acid amides series solvents such as pyrrolidones etc..For organic solvent, it can be used alone a kind, also can be used in combination two or more.

Drying can utilize method well known to heating, blowing hot-air etc. to implement.Drying condition is not particularly limited, and is dried, So that the content of the organic solvent in resin composition layer becomes 10 mass % or less, preferably 5 mass % or less.Although also with The difference of the boiling point of organic solvent in resin varnish and it is different, but for example using including the organic molten of 30 mass of mass %~60 % It, can be by carrying out drying in 3 minutes~10 minutes in 50 DEG C~150 DEG C, to form resin composition layer when the resin varnish of agent.

For resin sheet, can wound into rolls and preserved.Resin sheet have protective film when, can pass through by It protects film stripping and uses.

[printed wiring board]

The printed wiring board of the present invention includes insulating layer, the first conductor formed by the solidfied material of the resin combination of the present invention Layer and the second conductor layer.Insulating layer is arranged between the first conductor layer and the second conductor layer, and the first conductor layer and second are led Body layer insulate (conductor layer is known as wiring layer sometimes).

The thickness of insulating layer between first conductor layer and the second conductor layer be preferably 6 μm hereinafter, more preferably 5.5 μm with Under, further preferably 5 μm or less.It for lower limit, is not particularly limited, can be 0.1 μm or more.As shown in Figure 1 Shown in an example, the interval (insulating layer between the first conductor layer and the second conductor layer of so-called first conductor layer and the second conductor layer Thickness), refer to the thickness t1 of the insulating layer 3 between the interarea 11 of the first conductor layer 1 and the interarea 21 of the second conductor layer 2.The One conductor layer and the second conductor layer are across the adjacent conductor layer of insulating layer, and interarea 11 and interarea 21 are opposite.

It should be noted that the thickness t2 of insulating layer entirety be preferably 15 μm hereinafter, more preferably 13 μm hereinafter, further Preferably 10 μm or less.It for lower limit, is not particularly limited, usually can be 1 μm or more, 1.5 μm or more, 2 μm or more Deng.

For printed wiring board, above-mentioned resin sheet can be used, utilize the process including following (I) and (II) Method manufactures,

(I) in such a way that the resin composition layer of resin sheet is engaged with internal substrate resin sheet is folded on internal substrate upper layer Process；

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

" internal substrate " used in process (I) is the component of the substrate as printed wiring board, can enumerate such as glass Epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrates, thermohardening type polyphenylene oxide substrate etc..In addition, The substrate can have conductor layer in its one or both sides, can carry out pattern processing to the conductor layer.It sometimes also will be the one of substrate The internal substrate that face or two sides form conductor layer (circuit) is known as " internal layer circuit substrate ".In addition, " interior described in the present invention Laminar substrate " further includes that should be further formed insulating layer when manufacturing printed wiring board and/or the intermediate of conductor layer manufactures object.Print When brush wiring plate 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 being crimped on internal layer from bearing side by resin sheet heating Substrate and carry out.As by resin sheet heating be crimped on internal substrate component (hereinafter also referred to as " and heating crimping structure Part ".), can enumerate such as heated metallic plate (SUS end plate (Mirror plates)) or metallic roll (SUS rollers) etc..It needs to illustrate Be, it is preferred that and it is indirect will heating crimping component to resin sheet pressurize, but across heat resistant rubber elastomeric material into Row pressurization, so that resin sheet fully follows the concave-convex surface of internal substrate.

The stacking of internal substrate and resin sheet can utilize vacuum layer platen press to implement.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 pressures below.

Stacking can be carried out using commercially available vacuum laminator.As commercially available vacuum laminator, such as name mechanism can be enumerated Make the vacuum pressure type laminating machine of institute's corporation, the vacuum pack system device (vacuum of Nikko-Materials corporations Applicator), intermittent vacuum pressurization laminating machine etc..

After stacking, under normal pressure (under atmospheric pressure), for example, heating crimping component is pressurizeed from bearing side, by The smoothing techniques of this resin sheet that can be laminated.The pressurized conditions of smoothing techniques may be set to and above-mentioned stacking Heat the same condition of crimping condition.Smoothing techniques can be carried out using commercially available laminating machine.It should be noted that being laminated and putting down Above-mentioned commercially available vacuum laminator can be used continuously to carry out for cunningization processing.

It for supporting mass, can remove between process (I) and process (II), can also be removed 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 of generally use.

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

Before making resin composition layer heat cure, resin composition layer can be carried out at a temperature of less than solidification temperature Preheating.For example, before making resin composition layer heat cure, in 50 DEG C less than 120 DEG C (preferably 60 DEG C or more and 115 DEG C hereinafter, more preferably 70 DEG C or more and 110 DEG C or less) temperature, 5 minutes or more are carried out (preferably to resin composition layer It is 5 minutes~150 minutes, more preferably 15 minutes~120 minutes, further preferably 15 minutes~100 minutes) preheating.

When manufacturing printed wiring board, can also implementing (III), the process of trepanning, (IV) carry out insulating layer on the insulating layer The process that the process of roughening treatment, (V) form conductor layer.Above-mentioned operation (III) ~ process (V) can be according to can be in printed wiring Utilized in the manufacture of plate well known to a person skilled in the art the implementations of various methods.It should be noted that after process (II) When removing supporting mass, the removing of the supporting mass can between process (II) and process (III), process (III) and process (IV) it Between or process (IV) and process (V) between implement.In addition, as needed, the exhausted of process (II)~process (V) can be implemented repeatedly The formation of edge layer and conductor layer, to form multiwiring board.In this case, the thickness of the insulating layer between each conductor layer (t1 of Fig. 1) preferably within the above range.

Process (III) is the process of trepanning on the insulating layer, thus can be formed on the insulating layer through-hole (via hole), thoroughly The holes such as hole (through hole).Process (III) can be according to the composition etc. of the resin combination used in the formation of insulating layer Use the implementations such as such as drill bit, laser, plasma.Size, the shape in hole can be suitably determined according to the design of printed wiring board.

Process (IV) is the process being roughened to insulating layer.The step of roughening treatment, condition be not special The known step usually used when forming the insulating layer of printed wiring board, condition can be used in limitation.For example, can be real successively Apply swelling treatment, the roughening treatment using oxidant, the neutralisation treatment using neutralizer using swelling solution, to insulating layer into Row roughening treatment.It as the swelling solution for roughening treatment, is not particularly limited, aqueous slkali, surfactant can be enumerated Solution etc., preferably aqueous slkali, as the aqueous slkali, more preferable sodium hydroxide solution, potassium hydroxide solution.As commercially available molten Swollen liquid can enumerate " Swelling Dip Securiganth P ", " Swelling of such as ATOTECH JAPAN corporations Dip Securiganth SBU " etc..It is not particularly limited using the swelling treatment of swelling solution, such as can be by soaking insulating layer Stain in 30 DEG C~90 DEG C of swelling solution 1 minute~20 minutes and carry out.It is suitable from the swelling of the resin of insulating layer can be suppressed to From the viewpoint of the level of degree, preferably insulating layer is impregnated in 40 DEG C~80 DEG C of swelling solution 5 minutes~15 minutes.As with In the oxidant of roughening treatment, be not particularly limited, for example, can enumerate in the aqueous solution of sodium hydroxide dissolve potassium permanganate, Alkaline permanganic acid solution made of sodium permanganate.Using the roughening treatment of the oxidants such as alkaline permanganic acid solution preferably pass through by Insulating layer, which is impregnated in, to be heated in 60 DEG C~80 DEG C of oxidizing agent solution 10 minutes~30 minutes and has carried out.In addition, alkalinity is high The concentration of permanganate in mangaic acid solution is preferably 5 mass of mass %~10 %.As commercially available oxidant, can enumerate for example " the Concentrate Compact CP " of ATOTECH JAPAN corporations, " Dosing Solution Securiganth P " Deng alkaline permanganic acid solution.In addition, as the neutralizer for roughening treatment, the aqueous solution of preferred acidic, as commercially available product, It can enumerate " the Reduction Solution Securiganth P " of such as ATOTECH JAPAN corporations.Utilize neutralizer Processing can be by will carry out being impregnated in using the process face of the roughening treatment of oxidant 5 in 30 DEG C~80 DEG C of neutralizer Minute~30 minutes and carry out.Consider from operability etc., preferably will utilize pair of the roughening treatment of oxidant The method for being impregnated in 5 minutes~20 minutes in 40 DEG C~70 DEG C of neutralizer as object.

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.For lower limit, it is not particularly limited, Can be preferred 0.5nm or more, more preferable 1nm with first-class.In addition, the root mean square roughness of the surface of insulating layer after roughening treatment Degree (Rq) is preferably 400nm hereinafter, more preferably 350nm is hereinafter, further preferably 300nm or less.For lower limit, do not have There is special limitation, can be preferred 0.5nm or more, more preferable 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 be measured for r.m.s. roughness (Rq).

Process (V) is the process to form conductor layer.Not when forming conductor layer on internal substrate, process (V) is to form the The process of one conductor layer, when foring conductor layer on internal substrate, which is the first conductor layer, and process (V) is to be formed The process of second conductor layer.

The conductor material used in conductor layer is not particularly limited.In a preferred embodiment, conductor layer includes and is selected from The metal of one or more of the group being made of gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor Layer can be single metal layer, can also be alloy-layer, as alloy-layer, can enumerate for example by 2 kinds in above-mentioned group with On metal alloy (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) formed layer.Wherein, it is formed from conductor layer Versatility, cost, the pattern viewpoints such as easiness that are formed consider, preferably chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper The alloy-layer of single metal layer or nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably chromium, nickel, titanium, aluminium, zinc, gold, The alloy-layer of palladium, the single metal layer of silver or copper or nickel-chromium alloy, the further preferably single metal layer of copper.

Conductor layer can be single layer structure, or 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 Or the single metal layer of titanium or the alloy-layer of nickel-chromium alloy.

The thickness of conductor layer depends on the design of desired printed wiring board, 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 using semi-additive process formation conductor layer Son.

First, plating seed layer is formed 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, etching is utilized Deng the unwanted plating seed layer of removing, the conductor layer with desired wiring pattern can be formed.

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

Printed wiring board using the resin sheet manufacture of the present invention can be the resin composition layer for having resin sheet Solidfied material, that is, insulating layer and the buried wiring layer being embedded in insulating layer form.

[semiconductor device]

The semiconductor device of the present invention includes the printed wiring board of the present invention.The semiconductor device of the present invention can be used the present invention's Printed wiring board manufactures.

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

The semiconductor device of the present invention can be by conduction position installing component (semiconductor chip) in printed wiring board Manufacture.So-called " conduction position " refers to " position of the transmission electric signal in printed wiring board ", and position is surface or is to be buried The place entered.In addition, as long as semiconductor chip does not just limit especially using semiconductor as the electrical circuit components of material System.

For the installation method of semiconductor chip when manufacturing semiconductor device, as long as semiconductor chip is made effectively to send out Function is waved, is not particularly limited, specifically, wire bonding installation method can be enumerated, flip-chip installation method, utilized The installation method of solderless buildup layer (Bump less Build-Up Layer, BBUL) utilizes anisotropic conductive film (ACF) Installation method, utilize the installation method etc. of non-conductive film (NCF).It is so-called herein " to utilize solderless buildup layer (BBUL) Installation method " refers to " semiconductor chip being directly embedded to the recess portion of printed wiring board, makes semiconductor chip and printed wiring board On wiring connection installation method ".

Embodiment

Hereinafter, specifically describing the present invention using embodiment.The present invention is not restricted by the embodiments.It needs to illustrate It is in the following record, for " part " and " % " of expression amount, as long as no separately clearly stating, to indicate " matter respectively Measure part " and " quality % ".

First, various assay methods, evaluation method are illustrated.

The measurement > of < fine circuits Forming abilities

(preparation of test sample)

(1) base treatment of internal layer circuit substrate

Prepare be formed with internal layer circuit glass cloth base material epoxy resin two sides copper-clad laminated board (thickness of copper foil be 18 μm, base The thickness of plate is 0.8mm, Panasonic Corporation system " R1766 ") it is used as internal layer circuit substrate, its two sides is impregnated in MEC A/S's system In " CZ8101 ", roughening treatment (the copper etch quantity on copper surface is carried out：1.0μm).

(2) stacking of resin sheet

The resin sheet for being 10 μm for thickness made in Examples and Comparative Examples, resin composition layer, use are intermittent (Nikko Materials corporations, 2 stages stack laminating machine (2-Stage Buildup to vacuum pressed laminating machine Laminator), CVP700), in such a way that resin composition layer is engaged with internal layer circuit substrate, the two of internal layer circuit board Face carries out lamination treatment.Lamination treatment is implemented by following manner：Depressurize within 30 seconds, air pressure is made to become 13hPa hereinafter, then It carries out crimping for 30 seconds in 100 DEG C, under the pressure of 0.74MPa.Next, being carried out 60 seconds in 100 DEG C, under the pressure of 0.5MPa Hot pressing.

(3) solidification of resin composition layer

After resin sheet is laminated, be 100 DEG C carry out 30 minutes, next in 180 DEG C carry out 30 minutes under conditions of, make tree Oil/fat composition layer heat cure forms insulating layer.Then, supporting mass is removed, exposes insulating layer.

(4) roughening treatment

In 60 DEG C, the substrate for exposing insulating layer is impregnated in swelling solution (ATOTECH JAPAN corporations " Swelling Dip Securiganth P ", the sodium hydrate aqueous solution containing diethylene glycol monobutyl ether) in 10 minutes, next, in 80 DEG C leaching Stain in oxidant (ATOTECH JAPAN corporations " Concentrate Compact CP ", about 6 mass % of potassium permanganate concentration, The aqueous solution of about 4 mass % of naoh concentration) in 20 minutes, finally, neutralizer is impregnated in 40 DEG C, and (ATOTECH JAPAN are public Department system " Reduction Solution Securiganth P ", hydroxylamine sulfate solution) in 5 minutes.Then, in 80 DEG C of progress Drying in 15 minutes.Obtained substrate is known as " substrate a ".

(5) formation of conductor layer (circuit)

According to semi-additive process, conductor layer is formed on the roughening face of insulating layer.That is, carry out include following 1~6 process plating Process (the plating copper process for having used the liquid of ATOTECH JAPAN corporations) is covered, conductor layer is formed.

1. alkali cleaning (washing and charge for being provided with the surface of the insulating layer of through-hole are adjusted)

Using Cleaning Cleaner Securiganth 902 (trade name), carried out 5 minutes in 60 DEG C of surfaces to substrate a Washing.

2. soft etching (washing in through-hole)

Using sulfuric acid peroxy-disulfuric acid sodium water solution, in 30 DEG C of surfaces to substrate a handle within 1 minute.

3. preimpregnation (in order to assign Pd and carrying out the adjusting of charge on the surface of insulating layer)

Using Pre. Dip Neoganth B (trade name), at room temperature the surface of substrate a handle within 1 minute.

4. activator assigns and (assigns Pd to the surface of insulating layer)

Using Activator Neoganth 834 (trade name), in 35 DEG C of surfaces to substrate a handle within 5 minutes.

5. reduction (restores the Pd for being imparted to insulating layer)

Use the mixed of Reducer Neoganth WA (trade name) and 810 mod. of Reducer Acceralator (trade name) Liquid is closed, in 30 DEG C of surfaces to substrate a handle within 5 minutes.

6. electroless copper process (makes Cu be precipitated on the surface (surfaces Pd) of insulating layer)

Use Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth The mixing of MSK (trade name), Stabilizer Printganth MSK-DK (trade name) and Reducer Cu (trade name) Liquid in 35 DEG C of surfaces to substrate a handle within 30 minutes.The thickness of the chemical plating copper layer of formation is 1 μm.

(6) formation of wiring pattern

After chemical plating, substrate surface handle within 30 seconds with 5% aqueous sulfuric acid.Next, being pressurizeed using intermittent vacuum Laminating machine (name mechanism makees institute's corporation " MVLP-500 "), by pattern formation, with dry film, (Hitachi is melted into corporation " PHOTEC RY- 3600 ", thickness is 19 μm) it is laminated in the two sides of substrate.Stacking carries out in the following manner：Carry out 30 seconds depressurize, make air pressure at For 13hPa hereinafter, then carrying out pressurizeing for 20 seconds in 70 DEG C, under the pressure of 0.1MPa.

Then, wiring pattern will be formed with (details is as follows.) glass mask (photomask) be configured at dry film On, carry out light irradiation using projection exposure machine (USHIO INC. systems " UX-2240 ").It will next, being pressed with the injection of 0.15MPa 30 DEG C of 1% aqueous sodium carbonate carries out 30 seconds spraying treatments.Then it is washed, is developed (pattern is formed).

The wiring pattern of glass mask (glass mask)：

Using with it is following i) ~ vii) each 10 glass masks of comb pattern；

I) L/S=2 μm/2 μm connect up the comb pattern (cloth line length 15mm, 16 lines (line)) of 4 μm of spacing

Ii) L/S=3 μm/3 μm connect up the comb pattern (cloth line length 15mm, 16 lines) of 6 μm of spacing

Iii) L/S=4 μm/4 μm connect up the comb pattern (cloth line length 15mm, 16 lines) of 8 μm of spacing

Iv) L/S=5 μm/5 μm connect up the comb pattern (cloth line length 15mm, 16 lines) of 10 μm of spacing

V) L/S=6 μm/6 μm connect up the comb pattern (cloth line length 15mm, 16 lines) of 12 μm of spacing

Vi) L/S=7 μm/7 μm connect up the comb pattern (cloth line length 15mm, 16 lines) of 14 μm of spacing

Vii) L/S=8 μm/8 μm connect up the comb pattern (cloth line length 15mm, 16 lines) of 16 μm of spacing.

After development, electrolytic copper plating is carried out, forms electrolytic copper plated layer (conductor layer) (conjunction with chemical plating copper layer of 5 μm of thickness It is about 6 μm to count thickness).

Next, 50 DEG C of 3% sodium hydroxide solution is carried out spraying treatment with 0.2MPa injection pressures, shelled from substrate two sides From dry film.It carries out heating for 60 minutes in 190 DEG C, be made annealing treatment, then use fast-etching (flash etching) erosion Agent (the SAC techniques etchant of weak former electricity production corporation) is carved, unwanted conductor layer (layers of copper) is removed, electricity is consequently formed Road.Obtained substrate is known as " evaluation substrate A ".

(7) evaluation of fine circuits Forming ability

For evaluation substrate A it is above-mentioned i) ~ vii) comb pattern, with light microscope confirm whether there is or not the strippings of circuit, and Confirm that whether there is or not the residues of unwanted chemical plating copper layer by measuring the insulation resistance of comb pattern.Moreover, will be combed at 10 The case where having 9 or more in shape pattern there is no problem, is determined as qualification.It is when connected up by the minimum L/S for being judged as qualified Spacing evaluates fine circuits Forming ability.In the evaluation, being judged as qualified minimum L/S, when to connect up spacing smaller, Then fine circuits Forming ability is more excellent.

The evaluation > of < plyabilities

(measurement of minimum melt viscosity)

For the resin composition layer (25 μm of thickness) of the resin sheet of pre-production, measurement of dynamic viscoelasticity device (UBM is used Corporation " Rheosol-G3000 "), measure minimum melt viscosity.For sample resin combination 1g, the flat of diameter 18mm is used Andante is warming up to 200 DEG C for 60 DEG C with 5 DEG C/min of heating rate from initial temperature, and 2.5 DEG C, vibration are divided between measuring temperature Dynamic viscoelastic modulus is measured under the determination condition for being 5deg for 1Hz, strain, measures the melt viscosity at 120 DEG C.

(whether there is or not the evaluations in cavity)

It, will using intermittent vacuum pressurization laminating machine (Nikko Materials corporations, 2 stages stack laminating machine, CVP700) The thickness of the resin composition layer made in Examples and Comparative Examples is 25 μm, area is 240 × 320mm²Resin sheet layer It is pressed in L (lines：Wiring width)/(spaces S：Interval width) in=160 μm/160 μm of comb pattern (18 μm of thickness).Lamination is logical Cross following manner progress：Depressurize within 30 seconds, air pressure is made to become 13hPa hereinafter, then in 100 DEG C, under the pressure of 0.74MPa Pressurize within 30 seconds.Next, in 100 DEG C, 0.5MPa pressure carry out hot pressing in 60 seconds.It admits air into, confirms after lamination Hole (cavity) whether is generated in resin composition layer.The situation for not generating cavity after laminating is denoted as "○", will be produced The situation in cavity is denoted as "×".

The measurement > of < dielectric loss angle tangents

In 200 DEG C, the resin sheet that the thickness to the resin composition layer made in Examples and Comparative Examples is 25 μm carries out 90 Minute heating, makes resin composition layer heat cure, then removes supporting mass, obtain evaluation solidfied material.Evaluation is cured Object cuts into the test piece that width is 2mm, length is 80mm.For the test piece, Agilent Technologies corporations are used " HP8362B " measures medium using resonant cavity perturbation method under conditions of measurinng frequency is 5.8GHz, measuring temperature is 23 DEG C Loss angle tangent.It is measured for 2 test pieces, calculates its average value.

< synthesis examples 1：The synthesis > of polyimide resin 1

Prepare the removable of the 500mL with the water and basis weight receiver for being connected with reflux condenser, nitrogen ingress pipe and blender Formula flask.4,4 '-oxygroup diphthalic anhydrides (ODPA) 20.3g, gamma-butyrolacton 200g, toluene are added into the flask 20g and 5- (4- amino-benzene oxygens) -3- [4- (4- amino-benzene oxygens) phenyl] -1,1,3- trimethyl indane 29.6g, in nitrogen Under air-flow, stirs 2 hours, reacted in 45 DEG C.

Next, the reaction solution is heated up, remain about 160 DEG C on one side, on one side under stream of nitrogen gas by condensed water with Toluene is azeotroped off together.To the water of specified amount is retained in water and basis weight receiver and no longer observe the outflow of water into Row confirms.After confirmation, reaction solution is further heated up, carries out stirring for 1 hour in 200 DEG C.Then it is cooled down, including The varnish of the polyimide resin (polyimide resin 1) with 1,1,3- trimethyl indane skeletons of 20 mass %.What is obtained is poly- Imide resin 1 has the repetitive unit that the repetitive unit of following formula (X1) expression and formula (X2) indicate.In addition, polyimides tree The weight average molecular weight of fat 1 is 12000；

。

< synthesis examples 2：The synthesis > of polyimide resin 2

In synthesis example 1, by 5- (4- amino-benzene oxygens) -3- [4- (4- amino-benzene oxygens) phenyl] -1,1,3- trimethyl indane 29.6g is changed to bis- (4- aminophenyls) the fluorenes 22.9g of 9,9-.Other than above item, operated in the same manner as synthesis example 1, Obtain the varnish of the polyimide resin (polyimide resin 2) with fluorene skeleton comprising 20 mass %.Obtained polyimides Resin 2 has the repetitive unit that the repetitive unit of following formula (X3) expression and previously described formula (X2) indicate.In addition, polyimide resin 2 weight average molecular weight is 14000；

。

< synthesis examples 3：The synthesis > of polyimide resin 3

Into the reaction vessel with blender, water knockout drum, thermometer and nitrogen ingress pipe, it is packed into aromatic tetracarboxylic acid dianhydride (SABIC Japan corporations " BisDA-1000 ") 65.0g, cyclohexanone 266.5g and hexahydrotoluene 44.4g, by solution plus Heat is to 60 DEG C.Next, dimer diamines (Croda Japan corporations " PRIAMINE 1075 ") 43.7g and 1,3- is added dropwise Then double aminomethyl cyclohexane 5.4g spend 1 hour in 140 DEG C and carry out imidization reaction.Thus it obtains including dimer The varnish (polyimide resin 3,30 mass % of nonvolatile component) of diamines polyimide resin.In addition, polyimide resin 3 Weight average molecular weight is 25000.

1 > of < embodiments

Stir on one side, on one side by bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " 828US ", about 180) 30 parts of epoxide equivalent, (Japanese chemical drug corporation " NC3000H ", about 269) 30 parts of epoxide equivalent are dissolved by heating in solvent naphtha biphenyl type epoxy resin The in the mixed solvent of 40 parts and 15 parts of cyclohexanone, then cools to room temperature.The mixing amino silicone methane series idol in the mixed solution Connection agent (chemical industrial company of SHIN-ETSU HANTOTAI system " KBM573 ") be surface-treated preparing spherical SiO 2 (0.078 μm of average grain diameter, Specific surface area 30.7m²/ g, Denki Kagaku Kogyo kabushiki's system " UFP-30 ") 100 parts, the phenol system curing agent containing triazine skeleton 14 parts of (DIC corporations " LA-3018-50P ", hydroxyl equivalent about 151, the 2- methoxy propyls alcoholic solution of solid constituent 50%), activity (toluene of DIC corporations " HPC-8000-65T ", active group equivalent about 223,65 mass % of nonvolatile component is molten for ester system curing agent Liquid) 40 parts, (gamma-butyrolacton of 20 mass % of solid constituent is molten for the varnish comprising polyimide resin 1 that synthesizes in synthesis example 1 Liquid) 25 parts, curing accelerator (" DMAP ", 4-dimethylaminopyridine, methyl ethyl ketone (the following letter of 5 mass % of solid constituent Referred to as " MEK ") solution) 6 parts, it is evenly dispersed with high speed rotation mixing machine, prepare resin varnish 1.

Prepare 2 PET films (Lin get Ke corporations " AL5 ", 38 μm of thickness) with alkyd resin system release layer as branch Hold body.In such a way that the thickness of the resin composition layer after drying becomes 10 μm, 25 μm, on the release layer of each supporting mass uniformly It is coated with resin varnish 1, drying in 2 minutes is carried out in 70~95 DEG C, makes resin sheet 1.

2 > of < embodiments

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) amount be changed to 15 parts from 25 parts.Other than above item, implement similarly to Example 1, makes resin Varnish 2, resin sheet 2.

3 > of < embodiments

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) amount be changed to 5 parts from 25 parts.Other than above item, implement similarly to Example 1, makes resin Varnish 3, resin sheet 3.

4 > of < embodiments

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) 25 parts be changed to the varnish comprising polyimide resin 2 synthesized in synthesis example 2 (20 mass %'s of solid constituent Gamma-butyrolacton solution) 15 parts.Other than above item, implement similarly to Example 1, makes resin varnish 4, resin Sheet material 4.

5 > of < embodiments

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) 25 parts be changed to the varnish (ring of 30 mass % of solid constituent comprising polyimide resin 3 synthesized in synthesis example 3 The mixed solution of hexanone and hexahydrotoluene) 10 parts.Other than above item, implement similarly to Example 1, makes tree Fat varnish 5, resin sheet 5.

1 > of < comparative examples

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) amount be changed to 50 parts from 25 parts.Other than above item, implement similarly to Example 1, makes resin Varnish 6, resin sheet 6.

2 > of < comparative examples

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) 25 parts be changed to the varnish comprising polyimide resin 2 synthesized in synthesis example 2 (20 mass %'s of solid constituent Gamma-butyrolacton solution) 50 parts.Other than above item, implement similarly to Example 1, makes resin varnish 7, resin Sheet material 7.

3 > of < comparative examples

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) 25 parts be changed to the varnish (ring of 30 mass % of solid constituent comprising polyimide resin 3 synthesized in synthesis example 3 The mixed solution of hexanone and hexahydrotoluene) 33 parts.Other than above item, implement similarly to Example 1, makes tree Fat varnish 8, resin sheet 8.

4 > of < comparative examples

In embodiment 1, varnish (γ-fourth of 20 mass % of solid constituent comprising polyimide resin 1 for will being synthesized in synthesis example 1 Lactone solution) 25 parts be changed to phenoxy resin (Mitsubishi Chemical Ind's system " YX6954BH30 ", the MEK of 30 mass % of solid constituent With the 1 of cyclohexanone：1 solution) 10 parts.Other than above item, implement similarly to Example 1, making resin varnish 9, Resin sheet 9.

The ingredient used in the preparation of resin combination 1~9 and its use level (fixedness point conversion) are shown in following In table.It should be noted that " content (quality %) of (C) ingredient " is indicated the resin component in resin combination in following tables The content of (C) ingredient when being set as 100 mass %, " content (quality %) of (D) ingredient " are indicated not waving in resin combination Send out into the content of (D) ingredient when being divided into 100 mass %.

[table 1]

。

In Examples 1 to 5, it is thus identified that even if without containing (E) ingredient~(F) ingredient, although existing in degree Difference, but it is attributed to result same as above-described embodiment.

Reference sign

1 first conductor layer

The interarea of 11 first conductor layers

2 second conductor layers

The interarea of 21 second conductor layers

3 insulating layers

Interval (the thickness of the insulating layer between the first conductor layer and the second conductor layer of the first conductor layers of t1 and the second conductor layer Degree)

The thickness of t2 insulating layer entirety.

Claims

1. resin combination contains：(A) epoxy resin, (B) active ester system curing agent, (C) polyimide resin and (D) nothing Machine packing material, wherein

(D) average grain diameter of ingredient be 100nm hereinafter,

When resin component is set as 100 mass %, the content of (C) ingredient is 0.1 mass % or more and 6 mass % or less.

2. resin combination contains：(A) epoxy resin, (B) active ester system curing agent, (C) polyimide resin and (D) nothing Machine packing material, wherein

(D) specific surface area of ingredient is 15m²/ g or more,

3. resin combination according to claim 1 or 2, wherein (C) ingredient is that the polyamides with polycyclic aromatic hydrocarbon skeleton is sub- Polyimide resin.

4. resin combination according to claim 3, wherein polycyclic aromatic hydrocarbon skeleton is 5-membered ring compounds and aromatic ring fusion Made of aromatic hydrocarbons skeleton.

5. resin combination according to claim 3, wherein polycyclic aromatic hydrocarbon skeleton be in indane skeleton and fluorene skeleton extremely It is few any.

6. resin combination according to claim 1 or 2, wherein the weight average molecular weight of (C) ingredient is 5000 or more.

7. resin combination according to claim 1 or 2, wherein (C) ingredient has：Weight with polycyclic aromatic hydrocarbon skeleton Multiple unit and the repetitive unit with imide structure.

8. resin combination according to claim 7, wherein repetitive unit with polycyclic aromatic hydrocarbon skeleton with it is sub- with acyl The mass ratio of the repetitive unit of amine structure, i.e., the quality of the repetitive unit with polycyclic aromatic hydrocarbon skeleton/with imide structure The quality of repetitive unit is 0.5 or more and 2 or less.

9. resin combination according to claim 1 or 2, wherein the nonvolatile component in resin combination is set as 100 When quality %, the content of (C) ingredient is 0.1 mass % or more and 3 mass % or less.

10. resin combination according to claim 1 or 2, wherein the nonvolatile component in resin combination to be set as When 100 mass %, the content of (B) ingredient is 1 mass % or more and 25 mass % or less.

11. resin combination according to claim 1 or 2, wherein the nonvolatile component in resin combination to be set as When 100 mass %, the content of (D) ingredient is 30 mass % or more and 80 mass % or less.

12. resin combination according to claim 1 or 2, wherein also contain (E) curing agent.

13. resin combination according to claim 12, wherein (E) curing agent is phenol system curing agent.

14. the resin combination according to any one of claim 1 ~ 13, is used to form insulating layer, the insulating layer be for Form the insulating layer of conductor layer.

15. resin combination according to claim 1 or 2 is used to form the insulating layer of printed wiring board.

16. resin combination according to claim 1 or 2 is used to form the interlayer insulating film of printed wiring board.

17. resin sheet, described in any one of supporting mass and the claim 1~16 being set on the supporting mass Resin composition layer.

18. printed wiring board it includes the first conductor layer, the second conductor layer and is formed in the first conductor layer and the second conductor layer Between insulating layer, wherein

The insulating layer is the solidfied material of the resin combination described in any one of claim 1~16.

19. semiconductor device, it includes the printed wiring boards described in claim 18.