CN104842609B - Resin sheet with supporter - Google Patents

Resin sheet with supporter Download PDF

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Publication number
CN104842609B
CN104842609B CN201510076938.6A CN201510076938A CN104842609B CN 104842609 B CN104842609 B CN 104842609B CN 201510076938 A CN201510076938 A CN 201510076938A CN 104842609 B CN104842609 B CN 104842609B
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resin
supporter
layer
mass
composition layer
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CN104842609A (en
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西村嘉生
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

The present invention provides a kind of technology, which can keep subject characteristic as inorganic filling material content height, while can be formed in the insulating layer for showing excellent peel strength after roughening treatment to conductor layer.A kind of resin sheet with supporter, the resin sheet with supporter contain supporter；The resin composition layer for being 50 mass % or more with engaged with the supporter, inorganic filling material content, wherein, resin area A in the section in the direction vertical with supporting body surface of resin composition layer, in the region that the boundary apart from supporter and resin composition layer is 0 μm to 1 μm0‑1And the resin area A in the region for being 1 μm to 2 μm apart from above-mentioned boundary1‑2Meet A0‑1/A1‑2The relationship of > 1.1.

Description

Resin sheet with supporter
Technical field
The present invention relates to the resin sheets with supporter.
Background technique
Manufacturing technology as printed wiring board, it is known that use insulating layer and conductor layer alternately stacked stacking (ビ Le De ア ッ プ) mode manufacturing method.Using in the manufacturing method of stack manner, in general, insulating layer passes through resin combination heat It is solidified to form.For example, Patent Document 1 discloses following technologies: use is comprising supporter and is arranged on the supporter The resin composition layer containing silicon dioxide granule the resin sheet with supporter, resin composition layer is stacked in internal substrate After upper, by resin composition layer heat cure, resulting solidified body be roughened and forms insulating layer.
In the further densification for seeking wiring, there is the stacking due to printed wiring board and increase lamination number The tendency added, along with the increase of lamination number, due to the thermal expansion of insulating layer and conductor layer difference caused by crackle or electricity The generation that road deforms (the askew body of circuit) becomes problem.As technology the problem of inhibiting the crackle or circuit modifications, for example, patent Following technologies are disclosed in document 2: the content by improving the inorganic filling materials such as the silicon dioxide granule in resin combination, To which the thermal expansion coefficient for being formed by insulating layer is suppressed to reduced levels.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2010/35451
Patent document 2: Japanese Unexamined Patent Publication 2010-202865 bulletin.
Summary of the invention
Technical problems to be solved by the inivention
In technology described in Patent Document 1, the silicon dioxide granule on solidified body surface is detached from roughening treatment, thus Realize the insulating layer that sufficient peel strength is showed to conductor layer.But if to form the low insulating layer of thermal expansion coefficient, Using the high resin combination of the content of the inorganic filling materials such as silicon dioxide granule, even if then in the art, sometimes also not It is avoided that the peel strength for being formed by insulating layer and conductor layer reduces.
The technical problem to be solved in the present invention is to provide a kind of technology, which can keep inorganic filling material content high Such main body (bulk) characteristic, while excellent peel strength is showed to conductor layer after roughening treatment can be formed in Insulating layer.
Solve the means of technical problem
The inventors of the present invention have made intensive studies above-mentioned technical problem, as a result, it has been found that, by using contain resin group The resin sheet with supporter for closing nitride layer, can solve above-mentioned technical problem, and the resin composition layer is, on the support side In region near surface, the amount ratio (inorganic filling material/resin component) of inorganic filling material and resin component has gradient The resin combination of (hook is matched) (that is, the positive draft for having certain value or more from the engagement surface with supporter towards thickness direction) Layer, so as to complete the present invention.
That is, the present invention includes content below,
[1] with the resin sheet of supporter, which contains:
Supporter；With
Engage with the supporter, inorganic filling material content is the resin composition layer of 50 mass % or more,
Wherein, in the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and tree The resin area A in region that the boundary of oil/fat composition layer is 0 μm to 1 μm0-1It and is being 1 μm to 2 μm apart from above-mentioned boundary Resin area A in region1-2Meet A0-1/A1-2The relationship of > 1.1；
[2] with the resin sheet of supporter, which contains:
Supporter；With
Engage with the supporter, inorganic filling material content is the resin composition layer of 50 mass % or more,
Wherein, in the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and tree The resin area A in region that the boundary of oil/fat composition layer is 0 μm to 0.5 μm0-0.5It and is being 0.5 μm to 1 apart from above-mentioned boundary μm region in resin area A0.5-1Meet A0-0.5/A0.5-1The relationship of > 1.1；
[3] resin sheet with supporter described in [1] or [2], wherein resin composition layer and supporting body surface Resin in the section in vertical direction, in the region that the boundary apart from supporter and resin composition layer is 0.5 μm to d μm Area A0.5-dAnd the resin area A in the region for being d μm to 0.5D μm apart from above-mentioned boundaryd-0.5DMeet 0.9≤kA0.5-d/ Ad-0.5D≤ 1.1 relationship,
Wherein, k be meet k=|d-0.5D|/| the coefficient of 0.5-d|, d be meet 0.5 < d < 0.5D number, D is resin The thickness of composition layer；
[4] manufacturing method of the resin sheet with supporter, which includes the following steps: will be by the first resin group Close first layer of the thickness less than 2 μm and set in a manner of being interconnected by the second layer that the second resin combination is constituted that object is constituted It sets, forms integrated resin composition layer,
Wherein, the inorganic filling material content in resin composition layer is 50 mass % or more,
The surface of the side from first layer in resin composition layer is engaged with supporter,
In the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and resin combination The resin area A in region that the boundary of nitride layer is 0 μm to 1 μm0-1And in the region for being 1 μm to 2 μm apart from above-mentioned boundary Resin area A1-2Meet A0-1/A1-2The relationship of > 1.1；
[5] method described in [4], wherein the step of forming above-mentioned resin composition layer include:
(A1) the step of preparing the interim resin sheet with supporter, the interim resin sheet with supporter contains support Body and first layer of the thickness being made of the first resin combination less than 2 μm engaged with the supporter；And
(B1) it is coated with the second resin combination on the first layer, the second layer is arranged in coated film drying, forms integration Resin composition layer the step of；
[6] method described in [4] or [5], wherein the thickness of first layer is less than 1 μm；
[7] method described in any one of [4]~[6], wherein the first resin combination contain average grain diameter 500nm with Under inorganic filling material；
[8] method described in any one of [4]~[7], wherein the inorganic filling material in the first resin combination contains Amount is 40 mass % or less；
[9] method described in any one of [4]~[8], wherein the inorganic filling material in the second resin combination contains Amount is greater than 50 mass %；
[10] printed wiring board, the printed wiring board include to use the tree with supporter described in any one of [1]~[3] The insulating layer that rouge piece is formed；
[11] semiconductor device, the semiconductor device include printed wiring board described in [10].
Invention effect
Resin sheet according to the present invention with supporter can keep subject characteristic as inorganic filling material content height (バ Le Network characteristic), while the insulation for showing excellent peel strength after roughening treatment to conductor layer can be formed in Layer.
Detailed description of the invention
Fig. 1 is for illustrating resin area ratio (kAd1-d2/Ad2-d3Than) calculation method ideograph.
Specific embodiment
Before the resin sheet of the invention with supporter is described in detail, the band for forming of the invention is supported " the first resin combination " and " the second resin combination " used when resin composition layer contained in the resin sheet of body carries out Explanation.
The first resin combination of < >
First resin combination is used to be formed in resin composition layer and the region near the engagement surface of supporter.
As long as the resin composition layer with required composition gradient can be obtained, the first resin combination is not particularly limited, Its solidfied material has sufficient hardness and insulating properties.As the resin combination, such as can enumerate containing curable resin With the composition of its curing agent.As curable resin, can be used formed printed wiring board insulating layer when use with Toward well known curable resin, wherein preferred epoxy.Therefore, in one embodiment, the first resin combination contains (a) Epoxy resin and (b) curing agent.In first resin combination, as needed, can further contain (c) inorganic filling material, (d) additives such as thermoplastic resin, (e) curing accelerator, (f) fire retardant and (g) rubber particles.
Hereinafter, the epoxy resin, curing agent and additive for the materials'use that can be used as the first resin combination carry out Explanation.
(a) epoxy resin-
It as epoxy resin, such as can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy Resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol (trisphenol) type epoxy resin, naphthols Novolaks (naphthol novolak) type epoxy resin, phenol novolacs (phenol novolak) type epoxy resin, Tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine Type epoxy resin, glycidyl ester type epoxy resin, cresol novolak (cresol novolak) type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resins, the epoxy resin with butadiene structure, alicyclic epoxy resin, hetero ring type ring Oxygen resin, the epoxy resin containing loop coil, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy and trihydroxy methyl type Epoxy resin etc..Epoxy resin can be used alone, or can be used in combination two or more.
Preferred epoxy includes the epoxy resin in a molecule with more than two epoxy groups.It is preferred that with epoxy resin Nonvolatile component be 100 mass % in the case where, at least 50 mass % or more are that have more than two epoxy groups in a molecule Epoxy resin.Wherein, it preferably comprises: the asphalt mixtures modified by epoxy resin that there are more than two epoxy groups in a molecule and be in a liquid state at 20 DEG C of temperature Tool there are three the above epoxy group and is in solid-state at 20 DEG C of temperature in rouge (hereinafter referred to as " liquid-state epoxy resin ") and a molecule Epoxy resin (hereinafter referred to as " solid epoxy resin ").By by liquid-state epoxy resin and solid epoxy resin and being used as ring Oxygen resin can obtain the resin combination with excellent flexibility.Moreover, the insulating layer that resin combination is formed by curing is disconnected Resistance to spalling also improves.
As liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type ring Oxygen resin and naphthalene type epoxy resin, more preferable bisphenol A type epoxy resin, bisphenol f type epoxy resin and naphthalene type epoxy resin, into The preferred bisphenol A type epoxy resin of one step, bisphenol f type epoxy resin.As the concrete example of liquid-state epoxy resin, can enumerate: DIC " HP4032 " of (strain) system, " HP4032D ", " HP4032SS " (naphthalene type epoxy resin), Mitsubishi Chemical's (strain) make " jER828EL " (bisphenol A type epoxy resin), " jER807 " (bisphenol f type epoxy resin), " jER152 " (phenol novolak type Epoxy resin), Nippon Steel live aurification (strain) system " ZX1059 " (bisphenol A type epoxy resin and bisphenol f type epoxy resin it is mixed Conjunction product), Na ガ セ ケ system テ ッ Network ス (strain) system " EX-721 " (glycidyl ester type epoxy resin).They can individually make With one kind, or can be used in combination two or more.
As solid epoxy resin, preferably 4 functional epoxy resins of naphthalene type, cresol novolak type epoxy resin, two rings penta Diene type epoxy resin, triphen phenol-type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin or sub- naphthalene Base ether type epoxy, more preferable 4 functional epoxy resins of naphthalene type, biphenyl type epoxy resin or naphthylene ether type epoxy, into Preferred 4 functional epoxy resins of naphthalene type of one step, biphenyl type epoxy resin.As the concrete example of solid epoxy resin, can enumerate: DIC " HP-4700 ", " HP-4710 " (4 functional epoxy resins of naphthalene type), " N-690 " (cresol novolak type epoxy tree of (strain) system Rouge), " N-695 " (cresol novolak type epoxy resin), " HP-7200 " (dicyclopentadiene-type epoxy resin), " EXA7311 ", " EXA7311-G3 ", " EXA7311-G4 ", " EXA7311-G4S ", " HP6000 " (naphthylene ether type asphalt mixtures modified by epoxy resin Rouge), Japanese chemical drug (strain) " EPPN-502H " (trisphenol epoxy resin), " NC7000L " (naphthol novolac novalac epoxy tree for making Rouge), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), Nippon Steel live aurification (strain) " ESN475 " (naphthol novolac type epoxy resin), " ESN485V " (the naphthol novolac type epoxy resin), Mitsubishi of system Learn (strain) system " YX4000H ", " YL6121 " (biphenyl type epoxy resin), " YX4000HK " (union II first phenol-type epoxy resin), " YL7800 " (fluorenes type asphalt mixtures modified by epoxy resin that " PG-100 " of Osaka ガ ス ケ ミ カ Le (strain) system, " CG-500 ", Mitsubishi Chemical's (strain) make Rouge) etc..
When as epoxy resin and with liquid-state epoxy resin and solid epoxy resin, they amount ratio (liquid-state epoxy resin: Solid epoxy resin) by quality ratio be preferably 1:0.1~1:5 range.By making liquid-state epoxy resin and solid epoxidic tree In the range, can get has cementability appropriate, ii to the amount ratio of rouge when i) using in the form of resin sheet) with resin sheet Form using when obtain it is sufficient it is flexible, operability improves and iii) insulating layer with sufficient breaking strength can be obtained And other effects.From it is above-mentioned i)~iii) effect from the viewpoint of, amount ratio (the liquid ring of liquid-state epoxy resin and solid epoxy resin Oxygen resin: solid epoxy resin) by quality ratio be more preferably 1:0.3~1:4.5 range, further preferably 1:0.6~ The range of 1:4, the particularly preferably range of 1:0.8~1:4.
The content of epoxy resin in first resin combination be preferably 5 mass % or more, more preferably 10 mass % with Upper, further preferably 20 mass % or more or 30 mass % or more.The upper limit of epoxy resin content is not particularly limited, preferably For 99 mass % or less, more preferably 95 mass % or less, further preferably 90 mass % or less, 85 mass % or less, 80 Quality % or less, 75 mass % or less or 70 mass % or less.
It should be noted that the content for constituting each ingredient of resin combination is by not waving in resin combination in the present invention The total amount of hair ingredient is set as value when 100 mass %.
The epoxide equivalent of epoxy resin is preferably 50~3000, more preferably 80~2000, further preferably 110~ 1000.By making the epoxide equivalent of epoxy resin in the range, so that the crosslink density of solidfied material becomes that sufficiently, table can be formed The small insulating layer of surface roughness.It should be noted that epoxide equivalent can be measured according to JIS K7236, epoxide equivalent refers to containing 1 The quality of the resin of equivalent epoxy group.
The weight average molecular weight of epoxy resin is preferably 100~5000, is more preferably 250~3000, is more preferably 400~1500.Here, the weight average molecular weight of epoxy resin is changed using the polystyrene of gel permeation chromatography (GPC) method measurement The weight average molecular weight of calculation.
(b) curing agent-
As curing agent, as long as having the function of that cured epoxy resin is not particularly limited, such as can enumerate: phenol (Off ェ ノ ー Le) is curing agent, naphthols system curing agent, active ester system curing agent, benzoxazine system curing agent and cyanate system Curing agent.Curing agent can be used alone, or can be used in combination two or more.
As phenol system curing agent and naphthols system curing agent, from the viewpoint of heat resistance and water resistance, preferably there is phenol The phenol system curing agent of Novolac structure (ノ ボ ラ ッ Network construction) or naphthols system curing agent with novolac structure.This Outside, from the viewpoint of the adaptation with conductor layer, preferably nitrogenous phenol system curing agent, the further preferably phenol of triazine skeleton It is curing agent.Wherein, from highly meeting heat resistance, water resistance and examined with the viewpoint of the adaptation (peel strength) of conductor layer Consider, preferably comprises the phenol resol resins of triazine skeleton.
It as the concrete example of phenol system curing agent and naphthols system curing agent, such as can enumerate: bright and chemical conversion (strain) system " NHN ", " CBN ", " GPH ", Dongdu chemical conversion that " MEH-7700 ", " MEH-7810 ", " MEH-7851 ", Japanese chemical drug (strain) are made " SN170 ", " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495 ", " SN375 ", " SN395 ", DIC of (strain) system " LA7052 ", " LA7054 ", " LA3018 " etc. of (strain) system.
From obtaining from the viewpoint of roughening treatment rear surface roughness small insulating layer, further preferably active ester system solidifies Agent.It as active ester system curing agent, is not particularly limited, it is usually preferred to use phenol esters (phenol esters), benzenethiol Esters (thiophenol esters), N- hydroxylamine esters, esters of heterocycle hydroxyl compound etc. in 1 molecule have 2 with The compound of the high ester group of upper reactivity.It is preferred that the active ester system curing agent are as follows: by carboxylic acid compound and/or thiocarboxylic Close active ester system curing agent obtained from the condensation reaction of object and hydroxy compounds and/or mercaptan compound.Especially from raising From the viewpoint of heat resistance, the active ester system curing agent preferably obtained by carboxylic acid compound and hydroxy compounds, more preferably by carboxylic The active ester system curing agent that acid compound and oxybenzene compound and/or naphthol compound obtain.As carboxylic acid compound, such as can It enumerates: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), equal benzene four Acid etc..It as oxybenzene compound or naphthol compound, such as can enumerate: quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenol Phthalein quinoline, methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, Alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxy two Benzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolacs (phenol novolak) etc..Herein, " dicyclopentadiene-type diphenol compound " refers to, 1 molecule bicyclopentadiene and 2 molecules Diphenol compound obtained by phenol condensation.
Specifically, it is preferable that the active ester compound containing dicyclopentadiene-type biphenol structural, the work containing naphthalene structure Active ester compound, the benzoyl containing phenol novolacs of property ester compounds, acetylate containing phenol novolacs The active ester compound of compound, wherein the active ester compound of further preferably naphthalene structure, contain dicyclopentadiene-type xenol The active ester compound of structure." dicyclopentadiene-type biphenol structural " refers to, by-two ring pentalene of phenylene (ジ シ Network ロ ペ Application タ レ Application)-phenylene formed divalent structural units.
As the commercially available product of active ester system curing agent, the active ester compound containing dicyclopentadiene-type biphenol structural can Enumerate " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-65T " (DIC (strain) system)；Activity containing naphthalene structure Ester compounds can enumerate " EXB9416-70BK " (DIC (strain) system)；Acetylate containing phenol novolacs it is active esterifying " DC808 " (Mitsubishi Chemical's (strain) system) can be enumerated by closing object；The active ester compound of benzoylate containing phenol novolacs " YLH1026 " (Mitsubishi Chemical's (strain) system) etc. can be enumerated.
As the concrete example of benzoxazine system curing agent, " HFB2006M ", the four countries of Showa macromolecule (strain) system can be enumerated " P-d ", " F-a " of chemical conversion industry (strain) system.
It as cyanate system curing agent, such as can enumerate: bisphenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene- 1,5- phenylenecyanate), 4,4' methylene bis (2,6- 3,5-dimethylphenyl cyanate), two cyanic acid of 4,4'- ethylene phenyl Bis- (4- cyanate) phenyl-propanes of ester, hexafluoro bisphenol-a dicyanate, 2,2-, 1,1- bis- (4- cyanate phenylmethanes), bis- (4- Cyanate -3,5- 3,5-dimethylphenyl) methane, 1,3- bis- (4- cyanate phenyl -1- (methyl ethylidene)) benzene, bis- (4- cyanates Phenyl) the two function cyanate ester resins such as thioether and bis- (4- cyanate phenyl) ethers, by phenol novolacs and cresol novolak The prepolymer etc. that multifunctional cyanate ester resin, these cyanate ester resin part triazineizations Deng derived from are formed.As cyanate system The concrete example of curing agent can be enumerated: " PT30 " and " PT60 " of ロ Application ザ ジ ャ パ Application (strain) system (is phenol novolak type Multifunctional cyanate ester resin), " BA230 " (bisphenol A dicyanate part or all of triazine chemical conversion tripolymer and pre-polymerization for being formed Object) etc..
The amount of epoxy resin and curing agent ratio, with [the epoxy group sum of epoxy resin]: [the reactive group sum of curing agent] Ratiometer, preferably the range of 1:0.2~1:2, more preferably 1:0.3~1:1.5, further preferably 1:0.4~1: 1.2.Here, the reactive group of curing agent refers to activity hydroxy, active ester groups etc., different according to the type of curing agent.In addition, ring The epoxy group sum of oxygen resin refers to, for whole epoxy resin, by with the solid component quality of each epoxy resin divided by ring Value obtained by the resulting value of oxygen equivalent is amounted to；The reactive group sum of curing agent refers to, for whole curing agent, will use each Value obtained by the solid component quality of curing agent is amounted to divided by the resulting value of reactive group equivalent.By making epoxy resin and consolidating The amount ratio of agent within the above range, to further increase the heat resistance of the solidfied material of resin combination.
In one embodiment, the first resin combination contains above-mentioned (a) epoxy resin and (b) curing agent.Preferably It is, in the first resin combination, as (a) epoxy resin, the mixture (liquid containing liquid-state epoxy resin and solid epoxy resin State epoxy resin: the mass ratio of solid epoxy resin is preferably the range of 1:0.1~1:5, more preferably 1:0.3~1:4.5 Range, is even more preferably the range of 1:0.8~1:4 at the range of further preferably 1:0.6~1:4)；Solidify as (b) Agent, containing a kind in phenol system curing agent, naphthols system curing agent, active ester system curing agent and cyanate system curing agent with Upper (being preferably selected from one or more of phenol system curing agent, naphthols system curing agent and active ester system curing agent).
(c) inorganic filling material-
First resin combination can contain inorganic filling material in turn.It as inorganic filling material, such as can enumerate: two Silica, aluminium oxide, glass, cordierite, Si oxide, barium sulfate, talcum, clay, mica powder, aluminium hydroxide, magnesium hydroxide, Calcium carbonate, magnesium carbonate, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, barium titanate, strontium titanates, calcium titanate, magnesium titanate, Bismuth titanates, titanium oxide, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc..Wherein, amorphous silicas, dissolve The silica such as silica, crystalline silica, synthetic silica, hollow silica are particularly suitable for.In addition, as two The preferred spherical silicon dioxide of silica.Inorganic filling material can be used alone, and can also be used in combination of two or more.
The average grain diameter of inorganic filling material used in first resin combination, as long as the composition for having required can be obtained The resin composition layer of gradient is not particularly limited, and preferably 500nm or less, is more preferably 300nm or less, is further preferred For 200nm or less, be even more preferably 150nm or less, 100nm or less, 90nm or less, 80nm or less, 70nm or less, 60nm Below or 50nm or less.The lower limit of the average grain diameter is not particularly limited, usually 5nm or more.As with such average The commercially available product of the inorganic filling material of partial size, such as can enumerate: (strain) ア De マ テ ッ Network ス system " YC100C ", " YA050C ", " YA050C-MJE ", " YA010C ", electrochemically industrial (strain) system " UFP30 ", ト Network ヤ マ system " シ Le Off ィ Le NSS-3N ", "シルフィルNSS-4N","シルフィルNSS-5N".The average grain diameter of inorganic filling material is using based on Michaelis (Mie) laser diffraction scattering method of scattering theory is measured.It specifically can be by using laser diffraction and scattering formula granularity point The size distribution of inorganic filling material is made by volume reference for cloth measurement device, is carried out its median diameter as average grain diameter Measurement.Inorganic filling material is preferably dispersed in water the sample to be formed using using ultrasonic wave by measurement sample.As laser Diffraction scattering formula particle size distribution device can be used (strain) hole field and make made " LA-500 " etc..
From the viewpoint of improving moisture-proof and dispersibility, inorganic filling material preferably uses amino silicone methane series coupling agent, ring Oxosilane system coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, organic silazane hydride compounds, titanate esters system coupling agent Deng a kind or more of surface treating agent handled.It as the commercially available product of surface treating agent, such as can enumerate: SHIN-ETSU HANTOTAI's chemistry work Industry (strain) makes " KBM403 " (3- glycidoxy-propyltrimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) makes " KBM803 " (3- mercapto Base propyl trimethoxy silicane), SHIN-ETSU HANTOTAI's chemical industry (strain) make " KBE903 " (3-aminopropyltriethoxysilane), SHIN-ETSU HANTOTAI Learn industrial (strain) system " KBM573 " (N- phenyl -3- TSL 8330), SHIN-ETSU HANTOTAI's chemical industry (strain) system " SZ-31 " (hexamethyldisilazane) etc..
The degree of the surface treatment carried out using surface treating agent can pass through the per unit surface area of inorganic filling material Carbon amounts evaluated.From the viewpoint of the dispersibility for improving inorganic filling material, the per unit table of inorganic filling material The carbon amounts of area is preferably 0.02mg/m2Above, it is more preferably 0.1mg/m2It above, is more preferably 0.2mg/m2More than.Separately On the one hand, from the viewpoint of preventing the dissolving dissolving under viscosity or lamellar morphology viscosity rises of resin varnish, preferably 1mg/m2Below, it is more preferably 0.8mg/m2It below, is more preferably 0.5mg/m2Below.
The carbon amounts of the per unit surface area of inorganic filling material can with solvent (for example, methyl ethyl ketone (MEK)) to surface Treated, and inorganic filling material be measured after cleaning processing.Specifically, can be carried out to surface treating agent Enough MEK are added in inorganic filling material after surface treatment as solvent, ultrasonic cleaning 5 minutes at 25 DEG C.In removing Clear liquid is measured after solid component drying using carbon amounts of the carbon analysis meter to inorganic filling material per unit surface area.Make For carbon analysis meter, (strain) hole field can be used and make made " EMIA-320V " etc..
The content of inorganic filling material in first resin combination, as long as the tree for the composition gradient for having required can be obtained Oil/fat composition layer is not particularly limited, and preferably 40 mass % or less, more preferably 30 mass % or less, is more preferably 25 mass % or less, even more preferably for 20 mass % or less, 18 mass % or less, 16 mass % or less, 14 mass % with Under, 12 mass % or less, 10 mass % or less, 8 mass % or less, 6 mass % or less, 4 mass % or less or 2 mass % with Under.The content lower limit of inorganic filling material in first resin combination is not particularly limited, and can be 0 mass %.
(d) thermoplastic resin-
First resin combination can contain thermoplastic resin in turn.It as thermoplastic resin, such as can enumerate: phenoxy group Resin, polyvinyl acetal resin, acrylic resin, polyolefin resin, polybutadiene, polyimide resin, polyamide- Imide resin, polyethersulfone resin, polyphenylene oxide resin and polysulfone resin etc..Thermoplastic resin can be used alone, or can To be used in combination two or more.
Thermoplastic resin polystyrene conversion weight average molecular weight be preferably 8000~70000 range, more preferably 10000~60000 range, further preferably 20000~60000 range.The polystyrene conversion of thermoplastic resin Weight average molecular weight can be used gel permeation chromatography (GPC) method and be measured.Specifically, the polystyrene of thermoplastic resin converts Weight average molecular weight can calculate as follows: use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as measurement device, make as column It uses Showa electrician (strain) Shodex K-800P/K-804L/K-804L processed, use chloroform etc. as mobile phase, at 40 DEG C of column temperature It is measured, is calculated using the standard curve of standard polystyren.
It as phenoxy resin, such as can enumerate: have selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol Acetyl benzene skeleton, novolaks (ノ ボ ラ ッ Network) skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, norbornene bone The benzene of the skeleton of one or more of frame, naphthalene skeleton, anthracene skeleton, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton Oxygroup resin.The end of phenoxy resin can be any functional group such as phenolic hydroxyl group, epoxy group.Phenoxy resin can be independent Using one kind, or can be used in combination two or more.It as the concrete example of phenoxy resin, can enumerate: Mitsubishi Chemical's (strain) system " 1256 " and " 4250 " (being the phenoxy resin containing bisphenol A skeleton), " YX8100 " (phenoxy group containing bisphenol S skeleton Resin) and " YX6954 " (phenoxy resin containing bis-phenol acetyl benzene skeleton), it is other to enumerate Dongdu chemical conversion (strain) system " FX280 " and " FX293 ", Mitsubishi Chemical's (strain) system " YL7553 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc..
As acrylic resin, the acrylic resin of functional group, the acrylic acid tree of further preferably epoxy group are preferably comprised The acrylate copolymer resin of rouge, further preferably epoxy group.Third containing functional group is used as acrylic resin When olefin(e) acid resin, functional equivalent is preferably 1000~50000, more preferably 2500~30000.
As the concrete example of acrylic resin, " SG-80H ", " SG- of Na ガ セ ケ system テ ッ Network ス (strain) system can be enumerated P3 " (acrylate copolymer resin containing epoxy group).
As the concrete example of polyvinyl acetal resin, the electrochemical Block チ ラ ー Le of electrochemically industrial (strain) system can be enumerated 4000-2,5000-A, 6000-C, 6000-EP, the エ ス レ ッ Network BH of ponding chemical industry (strain) system is serial, BX is serial, KS system Column, BL series, BM series etc..
As the concrete example of polyimide resin, " the リ カ コ ー ト SN20 " and " リ カ of new Japan Chemical (strain) system can be enumerated コートPN20".As the concrete example of polyimide resin, 2 functional hydroxyl groups end polybutadiene, diisocyanate can be also enumerated Linear polyimides obtained by ester compounds and quaternary anhydride reaction (Japanese Unexamined Patent Publication 2006-37083 bulletin) contain poly- silicon oxygen Polyimides (Japanese Unexamined Patent Publication 2002-12667 bulletin and Japanese Unexamined Patent Publication 2000-319386 bulletin etc.) of alkane skeleton etc. is modified Polyimides.
As the concrete example of polyamide-imide resin, " the バ イ ロ マ ッ Network ス of Japan's weaving (strain) system can be enumerated HR11NN " and " バ イ ロ マ ッ Network ス HR16NN ".As the concrete example of polyamide-imide resin, Hitachi's chemical conversion can be also enumerated Modified polyamides-the acyl such as the polyamide-imides " KS9100 " containing silicone matrix of industrial (strain) system, " KS9300 " is sub- Amine.
As the concrete example of polyethersulfone resin, " PES5003P " etc. of Sumitomo Chemical (strain) system can be enumerated.
As the concrete example of polysulfone resin, the polysulfones of ソ Le ベ イ ア De バ Application ス ト Port リ マ ー ズ (strain) system can be enumerated " P1700 ", " P3500 " etc..
The content of thermoplastic resin in first resin combination, as long as the resin for the composition gradient for having required can be obtained Composition layer is not particularly limited, preferably 0.1 mass % or more, more preferably 1 mass % or more, further preferably 3 Quality % or more, 5 mass % or more or 7 mass % or more.The upper content limit of thermoplastic resin is not particularly limited, and preferably 50 Quality % or less, more preferably 40 mass % or less, further preferably 30 mass % or less.
(e) curing accelerator-
First resin combination can contain curing accelerator in turn.As curing accelerator, such as can enumerate: phosphorus system is solid Change promotor, amine system curing accelerator, imidazoles system curing accelerator, guanidine system curing accelerator etc., preferably phosphorus system curing accelerator, Amine system curing accelerator, imidazoles system curing accelerator, more preferable amine system curing accelerator, imidazoles system curing accelerator.Solidification promotees It can be used alone, two or more can also be applied in combination into agent.
It as phosphorus system curing accelerator, such as can enumerate: triphenylphosphine, Peng Suan phosphonium compounds, tetraphenylphosphoniphenolate tetraphenyl boron Hydrochlorate, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyl) triphenyl phosphonium thiocyanate, four benzene Ji Phosphonium thiocyanate, Ding base triphenyl phosphonium thiocyanate etc., triphenylphosphine, 4-butyl-phosphonium caprate.
It as amine system curing accelerator, such as can enumerate: the trialkylamines such as triethylamine, tri-butylamine, 4- dimethylamino Yl pyridines, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol, 1,8- diazabicyclo (5,4,0)-hendecene Deng, preferably 4-dimethylaminopyridine, 1,8- diazabicyclo (5,4,0)-hendecene.
It as imidazoles system curing accelerator, such as can enumerate: 2-methylimidazole, 2- undecyl imidazole, 2- heptadecyl Imidazoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl Imidazoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2- methyl Imidazoles, 1- cyano ethyl -2- undecyl imidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenyl Imidazoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acid salt, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt, 2,4- diamino -6- [2'- methylimidazolyl-is (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- undecyl imidazole Base-is (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- ethyl -4'- methylimidazolyl-is (1')]-ethyl-s-triazine, 2, 4- diamino -6- [2'- methylimidazolyl-is (1')]-ethyl-s-triazine isocyanuric acid addition product, 2- phenylimidazole isocyanuric acid Addition product, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole, 2,3- dihydro -1H- pyrrole Cough up simultaneously [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2- phenyl The adduct of the imidazolium compounds such as imidazoline and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- benzyl Base -2- phenylimidazole.
It as guanidine system curing accelerator, such as can enumerate: dicyandiamide, 1- methylguanidine, 1- ethyl guanidine, 1- cyclohexyl guanidine, 1- Guanidines, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethylguanidine, pentamethyl guanidine, tri- nitrogen of 1,5,7- Miscellaneous bicyclic [4.4.0] ten carbon -5- alkene, 7- methyl-1, tri- azabicyclo of 5,7- [4.4.0], ten carbon -5- alkene, 1- methyl biguanides, 1- Ethyl biguanides, 1- normal-butyl biguanides, 1- n-octadecane base biguanides, 1,1- dimethylbiguanide, 1,1- diethyl biguanides, 1- cyclohexyl Biguanides, 1- allyl biguanides, 1- phenyl biguanide, 1- (o-tolyl) biguanides etc., preferably dicyandiamide, 1,5,7- tri- azabicyclos [4.4.0] ten carbon -5- alkene.
The content of curing accelerator in first resin combination, as long as the resin for the composition gradient for having required can be obtained Composition layer is not particularly limited, when the nonvolatile component total amount of epoxy resin and curing agent is set as 100 mass %, preferably It is used in the range of the 0.05 mass % of mass %~3.
(f) fire retardant-
First resin combination can contain fire retardant in turn.As fire retardant, such as can enumerate: organic phosphorus flame retardant, The nitrogenous phosphorus compound of organic system, nitrogen compound, silicone flame retardant, metal hydroxides etc..Fire retardant can be used alone One kind, or can be used in combination two or more.The content of fire retardant in first resin composition layer, as long as can obtain having required The resin composition layer of composition gradient be not particularly limited, preferably 0.5 mass of mass %~20 %, more preferably 1 matter Measure the mass of %~15 %, further preferably 1.5 mass of mass %~10 %.
(g) rubber particles-
First resin combination can contain rubber particles in turn.As rubber particles, can be used for example in following trees Insoluble and above-mentioned epoxy resin, curing agent and thermoplastic resin etc. in organic solvent used in the preparation of rouge varnish Incompatible rubber particles.Such rubber particles are generally by increasing to the molecular weight of rubber constituent in organic solvent or tree In rouge it is undissolved it is horizontal, form particle shape to prepare.
As rubber particles, such as core-sheath-type rubber particles, crosslink propylene nitrile butadiene rubber particle, crosslinking benzene can be enumerated Ethylene-butylene rubber particles, acrylic rubber particle etc..Core-sheath-type rubber particles are the rubber granules with sandwich layer and sheaths Son, for example, 2 layers of structure that the sheaths of outer layer are made of glassy polymers, the sandwich layer of internal layer is made of rubber-like polymer；Or Person, the sheaths of outer layer are made of glassy polymers, middle layer is made of rubber-like polymer, sandwich layer is by glassy polymers structure At 3-tier architecture rubber particles etc..Glassy polymeric nitride layer is for example made of methylmethacrylate polymer etc., rubber-like Polymeric layer is for example made of butyl acrylate object (butyl rubber) etc..Rubber particles can be used alone, or can To be used in combination two or more.
The average grain diameter of rubber particles is preferably 0.005 μm~1 μm of range, more preferably 0.2 μm~0.6 μm of model It encloses.The average grain diameter of rubber particles can be used dynamic light scattering method and be measured.Such as make rubber particles using ultrasonic wave etc. It is evenly dispersed in suitable organic solvent, uses dense system's particle size analyzer (FPAR-1000；Big tomb electronics (strain) system), With the size distribution of quality criteria production rubber particles, using its median diameter as average grain diameter, it is possible thereby to measure.First tree The content of rubber particles in oil/fat composition be preferably 1 mass of mass %~20 %, more preferably 2 mass of mass %~10 %, Further preferably 2 mass of mass %~5 %.
Other ingredients-
First resin combination can also contain other additives as needed, as other additive, such as It can enumerate: the organo-metallic compounds such as organocopper compound, organic zinc compound and organic cobalt compounds；And organic filler, Resin additives such as thickener, defoaming agent, levelling agent, adaptation imparting agent and colorant etc..
The second resin combination of < >
Second resin combination be used to formed in resin composition layer except with the region near the engagement surface of supporter it Outer remaining region (main part (バ Le Network part)).
Second resin combination influences the subject characteristic of resin composition layer and then influences the subject characteristic of insulating layer.From It reduces the thermal expansion coefficient of resulting insulating layer, prevent from splitting caused by the difference due to the thermal expansion of insulating layer and conductor layer From the viewpoint of the generation of line or circuit modifications, the second resin combination contains inorganic filling material with high-content.
Inorganic fill from the viewpoint of reducing the thermal expansion coefficient of resulting insulating layer, in the second resin combination The content of material is greater than 50 mass %, preferably 52 mass % or more, more preferably 54 mass % or more, further preferably 56 Quality % or more, even more preferably for 58 mass % or more, 60 mass % or more, 62 mass % or more, 64 mass % or more, 66 mass % or more, 68 mass % or more or 70 mass % or more.From the viewpoint of the mechanical strength of resulting insulating layer, the The upper content limit of inorganic filling material in two resin combinations be preferably smaller than 96 mass %, more preferably 95 mass % or less, Further preferably 90 mass % or less or 85 mass % or less.
As inorganic filling material, such as can enumerate for inorganic filling material illustrated by the first resin combination, In preferably silica, more preferable spherical silicon dioxide.Sufficient circuit is realized from the mobility for improving resin composition layer From the viewpoint of landfill property (circuit Mai め Write body), the average grain diameter of inorganic filling material contained in the second resin combination Preferably 0.01 μm~5 μm of range, more preferably 0.05 μm~2 μm of range, further preferably 0.1 μm~1 μm of model It encloses, be even more preferably 0.2 μm~0.8 μm.As the commercially available product of the inorganic filling material with such average grain diameter, example (strain) ア De マ テ ッ Network ス system " SOC2 ", " SOC1 " can such as be enumerated.
Inorganic filling material contained in second resin combination is preferably handled with surface treating agent.Surface treating agent Type and surface treatment degree as illustrated in the column < the first resin combination >.
As other materials contained in the second resin combination, such as it can enumerate in the column < the first resin combination > and say Bright, using (a) epoxy resin as the curable resin of representative and (b) curing agent.Therefore, in one embodiment, the second resin Composition contains (a) epoxy resin, (b) curing agent and (c) inorganic filling material.Preferable such as the first resin of < group of each ingredient It closes illustrated in the column object >, wherein preferably, in the second resin combination, as (a) epoxy resin, contain liquid ring Oxygen resin and solid epoxy resin mixture (liquid-state epoxy resin: the mass ratio of solid epoxy resin is preferably 1:0.1~1: 5 range, the range of more preferably 1:0.3~1:4.5, the range of further preferably 1:0.6~1:4, particularly preferably 1: The range of 0.8~1:4)；As (b) curing agent, containing selected from phenol system curing agent, naphthols system curing agent, the solidification of active ester system One or more of agent and cyanate system curing agent (it is solid to be preferably selected from phenol system curing agent, naphthols system curing agent and active ester system One or more of agent)；As (c) inorganic filling material, contain silica.
The content of (a) epoxy resin in the second resin combination, as long as the tree for the composition gradient for having required can be obtained Oil/fat composition layer is not particularly limited, preferably 3 mass of mass %~50 %, more preferably 5 mass of mass %~45 %, into One step is preferably 5 mass of mass %~40 %, is even more preferably 7 mass of mass %~35 %.
The amount ratio of (a) epoxy resin in the second resin combination and (b) curing agent can in the first resin combination of < Amount illustrated in the column object > is than identical.
Second resin combination can in turn containing selected from (d) thermoplastic resin, (e) curing accelerator, (f) fire retardant and (g) ingredient of one or more of rubber particles.In the preferable such as column < the first resin combination > of these (d) to (g) ingredient Illustrated.The content of (d) thermoplastic resin in the second resin combination, as long as the composition gradient for having required can be obtained Resin composition layer is not particularly limited, preferably 0.1 mass of mass %~20 %, more preferably 0.5 matter of mass %~10 Measure %.The content of (e) curing accelerator in the second resin combination, by (a) epoxy resin and (b) curing agent it is non-volatile at When point total amount is set as 100 mass %, preferably 0.05 mass of mass %~3 %.(f) fire retardant in second resin combination Content, as long as the resin composition layer that can obtain the composition gradient for having required is not particularly limited, preferably 0.5 mass % ~10 mass %, more preferably 1 mass of mass %~9 %, further preferably 1.5 mass of mass %~8 %.Second resin group The content for closing (g) rubber particles in object, without spy as long as the resin composition layer for the composition gradient that can obtain having required It does not limit, preferably 1 mass of mass %~10 %, more preferably 2 mass of mass %~5 %.
Second resin combination can also contain other additives as needed, as other additive, such as It can enumerate: the organo-metallic compounds such as organocopper compound, organic zinc compound and organic cobalt compounds；And organic filler, Resin additives such as thickener, defoaming agent, levelling agent, adaptation imparting agent and colorant etc..
Hereinafter, explaining the present invention in detail in conjunction with better embodiment of the invention.
[resin sheet with supporter]
Resin sheet with supporter of the invention is characterized in that, contains supporter；With engaged with the supporter, nothing Resin composition layer of the machine packing material content for 50 mass % or more, the resin composition layer, surface on the support side are attached In close region, the amount ratio (inorganic filling material/resin component) of inorganic filling material and resin component have gradient (that is, from There is the positive draft of certain value or more towards thickness direction with the engagement surface of supporter).
In resin composition layer contained in resin sheet with supporter of the invention, in the engagement surface with supporter There are the phases of resin component dense (リ ッ チ), but from the engagement surface with supporter towards the position of thickness direction certain distance In, the ratio of inorganic filling material steeply rises.Here, " thickness direction " refers to the thickness direction of resin composition layer, indicates The direction vertical with resin combination layer surface.From the engagement surface with supporter towards thickness direction preferably 0.05 μm~2 μ In the position of m distance, in the position of more preferable 0.05 μm~1.5 μm distances, the position of further preferred 0.05 μm~1 μm distance In, in the position of particularly preferred 0.05 μm~0.5 μm distance, the ratio of the inorganic filling material in resin composition layer sharply on It rises.
If goed deep into turn to thickness direction, the amount ratio of inorganic filling material and resin component becomes no gradient, at For the phase with uniform composition.According to the resin sheet of the invention with supporter containing resin composition layer, the resin combination There is composition gradient sharply in finite region near the surface of nitride layer only on the support side, keep uniform as subject characteristic Composition, therefore available intensity and heat resistance etc. are excellent, show excellent stripping to conductor layer after roughening treatment simultaneously Insulating layer from intensity.It is described in detail below, the insulating layer formed using the resin sheet of the invention with supporter, although Surface roughness after roughening treatment is smaller, but can confirm and show excellent peel strength to conductor layer, band of the invention The resin sheet of supporter has notable contribution to the fine wiring of printed wiring board.
In the present invention, indicate resin composition layer support body side surface near region in inorganic filling material and When the gradient of the amount ratio of resin component, using following ratio: in the direction vertical with supporting body surface of resin composition layer Section in, be fixed distance d1 (μm) to fixed distance d2 (μm) apart from supporter and the boundary of resin composition layer Region resin area Ad1-d2And in the area apart from above-mentioned boundary for fixed distance d2 (μm) to fixed distance d3 (μm) The resin area A in domaind2-d3Ratio (kAd1-d2/Ad2-d3).Here, d1, d2 and d3 are the numbers of satisfaction 0≤d1 < d2 < d3, and k is Meet k=|d2-d3|/| the coefficient of d1-d2|.
Above-mentioned resin area is such as shown in Fig. 1 mode, to the side vertical with 10 surface of supporter of resin composition layer 20 SEM observation is carried out to the section of (Z-direction in Fig. 1), measures boundary (Fig. 1 apart from supporter 10 and resin composition layer 20 In Z=0 position) be d1 (μm) to d2 (μm) region 21a resin area Ad1-d2And apart from above-mentioned boundary be d2 (μm) To the resin area A of the region 21b of d3 (μm)d2-d3, can be by resulting Ad1-d2Value and Ad2-d3Value calculates.In measurement Ad1-d2Value And Ad2-d3When value, the width for measuring region (the measurement distance on the direction parallel with supporting body surface) is set as equivalent.
It should be noted that " resin area " refers to area shared by resin component in the present invention.For described in resin area " resin component " refers in the ingredient for constituting resin combination, the ingredient after removing inorganic filling material.
In resin sheet with supporter of the invention, resin composition layer is inorganic in the region near surface on the support side The amount of packing material and resin component is than having gradient sharply, above-mentioned kAd1-d2/Ad2-d3Than the value according to d1, d2 and d3 compared with Big variation.
That is, the resin sheet of the invention with supporter is characterized in that, in hanging down with supporting body surface for resin composition layer Resin area in the section in straight direction, in the region that the boundary apart from supporter and resin composition layer is 0 μm to 1 μm A0-1And the resin area A in the region for being 1 μm to 2 μm apart from above-mentioned boundary1-2Meet A0-1/A1-2The relationship of > 1.1.From Subject characteristic as inorganic filling material content height is kept, while obtaining showing conductor layer after roughening treatment excellent Peel strength insulating layer from the viewpoint of, the resin sheet of the invention with supporter preferably satisfies A0-1/A1-2≤ 1.15, more Preferably satisfy A0-1/A1-2≧1.2。
A0-1/A1-2The upper limit of ratio is not particularly limited, usually 20 or less, preferably 15 or less, more preferably 10 with Under, further preferably 5 or less.
In this case, it in the section in the direction vertical with supporting body surface of resin composition layer, is supported in distance The boundary of body and resin composition layer be (resin area)/(entire area) in 0 μm to 1 μm of region than preferably 0.3 with It goes up, be more preferably 0.4 or more, be more preferably 0.5 or more, be even more preferably 0.6 or more, 0.7 or more, 0.8 or more Or 0.9 or more.The upper limit for being somebody's turn to do (resin area)/(entire area) ratio is not particularly limited, and can be 1.
From subject characteristic as uniform composition and high inorganic filling material content is kept, while obtaining at roughening From the viewpoint of the insulating layer for showing excellent peel strength after reason to conductor layer, the resin sheet of the invention with supporter In, in the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and resin composition layer Boundary be resin area A in 0 μm to 0.5 μm of region0-0.5And in the region for being 0.5 μm to 1 μm apart from above-mentioned boundary Resin area A0.5-1Preferably satisfy A0-0.5/A0.5-1The relationship of > 1.1.Conductor layer is presented after roughening treatment from realizing Out from the viewpoint of the insulating layer of more high-peeling strength, the resin sheet of the invention with supporter more preferably meets A0-0.5/A0.5-1 ≤ 1.2, further preferably meet A0-0.5/A0.5-1≤ 1.22, even more preferably meet A0-0.5/A0.5-1≤ 1.24, particularly preferably Meet A0-0.5/A0.5-1≧1.26、A0-0.5/A0.5-1≧1.28、A0-0.5/A0.5-1≤ 1.3 or A0-0.5/A0.5-1≧1.32。
A0-0.5/A0.5-1The upper limit of ratio is not particularly limited, usually 20 or less, preferably 15 or less, more preferably 10 It below, is more preferably 5 or less.
In this case, it in the section in the direction vertical with supporting body surface of resin composition layer, is supported in distance (resin area)/(entire area) in region that the boundary of body and resin composition layer is 0 μm to 0.5 μm is than preferably 0.5 Above, be more preferably 0.6 or more, further preferably 0.7 or more, even more preferably be 0.8 or more or 0.9 or more.It should (tree Rouge area) upper limit of/(entire area) ratio is not particularly limited, and it can be 1.
As described above, in the resin sheet of the invention with supporter, resin composition layer is only on the support side near surface Finite region in there is composition gradient, keep uniform composition as subject characteristic.
In preferable embodiment, the resin sheet of the invention with supporter is constituted as follows: in resin composition layer In the section in the direction vertical with supporting body surface, the area for being 2 μm to d μm on the boundary apart from supporter and resin composition layer Resin area A in domain2-dAnd the resin area A in the region for being d μm to 0.5D μm apart from above-mentioned boundaryd-0.5DMeet 0.9 ≦kA2-d/Ad-0.5D≤ 1.1 (here, k be meet k=|d-0.5D|/| the coefficient of 2-d|, d be meet 2 < d < 0.5D number, D It is the thickness of resin composition layer.) relationship.This indicates, resin combination contained in the resin sheet of the invention with supporter Nitride layer has uniform composition in the region that distance support body side surface is 2 μm or more.
In more preferably embodiment, the resin sheet of the invention with supporter is constituted as follows: in resin composition layer It is 1.5 μm to d μm on the boundary apart from supporter and resin composition layer in the section in the direction vertical with supporting body surface Resin area A in region1.5-dAnd the resin area A in the region for being d μm to 0.5D μm apart from above-mentioned boundaryd-0.5DMeet 0.9≦kA1.5-d/Ad-0.5D≤ 1.1 (here, k be meet k=|d-0.5D|/| the coefficient of 1.5-d|, d be meet 1.5 < d < The number of 0.5D, D are the thickness of resin composition layer.) relationship.This is indicated, contained in the resin sheet of the invention with supporter Resin composition layer, be that there is uniform composition in 1.5 μm or more of region in distance support body side surface.
In further preferably embodiment, the resin sheet of the invention with supporter is constituted as follows: in resin combination It is 1 μm to d on the boundary apart from supporter and resin composition layer in the section in the direction vertical with supporting body surface of nitride layer μm region in resin area A1-dAnd the resin area A in the region for being d μm to 0.5D μm apart from above-mentioned boundaryd-0.5D Meet 0.9≤kA1-d/Ad-0.5D≤ 1.1 (here, k be meet k=|d-0.5D|/| the coefficient of 1-d|, d be meet 1 < d < The number of 0.5D, D are the thickness of resin composition layer.) relationship.This is indicated, contained in the resin sheet of the invention with supporter Resin composition layer, be that there is uniform composition in 1 μm or more of region in distance support body side surface.
In embodiment especially preferably, the resin sheet of the invention with supporter is constituted as follows: in resin combination It is 0.5 μm to d on the boundary apart from supporter and resin composition layer in the section in the direction vertical with supporting body surface of layer μm region in resin area A0.5-dAnd the resin area A in the region for being d μm to 0.5D μm apart from above-mentioned boundaryd-0.5D Meet 0.9≤kA0.5-d/Ad-0.5D≤ 1.1 (here, k be meet k=|d-0.5D|/| the coefficient of 0.5-d|, d be meet 0.5 < d The number of < 0.5D, D are the thickness of resin composition layer.) relationship.This indicates, institute in the resin sheet of the invention with supporter The resin composition layer contained has uniform composition in the region that distance support body side surface is 0.5 μm or more.It should be noted that In above-mentioned resin area ratio, denominator is not required as Ad-0.5D, or Ad-D(that is, being d μm to D μm apart from above-mentioned boundary Region in resin area).Even if by denominator by Ad-0.5DReplace with Ad-DIn the case where, value is repaired by coefficient k Just, therefore the suitable range of resin area ratio is still same as described above.
In resin sheet with supporter of the invention, the content of the inorganic filling material in resin composition layer is 50 matter Measure % or more.It is inorganic in resin composition layer from the viewpoint of the thermal expansion coefficient for fully reducing resulting insulating layer The content of packing material be preferably 55 mass % or more, more preferably 60 mass % or more, further preferably 65 mass % with On.
It should be noted that in the present invention, the content of each ingredient in resin composition layer be by resin composition layer not The total amount of volatile ingredient is set as value when 100 mass %.For example, the content of the inorganic filling material in resin composition layer can be such as Under acquire: by the nothing in the content of the inorganic filling material in above-mentioned first resin combination and above-mentioned second resin combination The content of machine packing material, the amount based on the first and second resin combinations used when forming resin composition layer are weighted It is average.
Resin area A0-1With resin area A1-2The ratio between (A0-1/A1-2) band support of the invention in above-mentioned particular range In the resin sheet of body, it not will lead to the reduction to the peel strength of conductor layer, can be further improved in resin composition layer The content of inorganic filling material.For example, the content of the inorganic filling material in resin composition layer can be improved to 66 mass % with Upper, 68 mass % or more, 70 mass % or more, 72 mass % or more, 74 mass % or more, 76 mass % or more or 78 matter Measure % or more.
From the viewpoint of the mechanical strength of resulting insulating layer, the content of the inorganic filling material in resin composition layer The upper limit is preferably 95 mass % or less, more preferably 90 mass % or less, further preferably 85 mass % or less.
Using inorganic filling material as representative, such as above-mentioned the first resin of < group in detail of each constituent of resin composition layer It closes described in the second column resin combination > object > and <.In one embodiment, in the resin sheet of the invention with supporter Contained resin composition layer contains inorganic filling material, curable resin and curing agent.Resin composition layer can contain in turn Additive selected from one or more of thermoplastic resin, curing accelerator, fire retardant and rubber particles can also contain organic gold Belong to other resin additions such as compound, organic filler, thickener, defoaming agent, levelling agent, adaptation imparting agent and colorant Agent.
As long as the content of inorganic filling material is above-mentioned specific range, other ingredients in resin composition layer contain Amount is not particularly limited, and can be set as range usually used when the insulating layer to form printed wiring board.In the present invention, use Above-mentioned the first and second resin combinations form resin composition layer, but the main part of resin composition layer is substantially by the Two resin combinations are formed, and the first resin combination image degree shared in resin composition layer entirety is limited.Cause This, in the resin sheet of the invention with supporter, the ingredient other than inorganic filling material in resin composition layer preferably contains Amount can be identical as the preferred content of each ingredient described in the column above-mentioned < the second resin combination >.
In resin sheet with supporter of the invention, the thickness of resin composition layer is preferably 3 μm or more, more preferably 5 μ M or more, further preferably 7 μm or more, 8 μm or more, 9 μm or more or 10 μm or more.The upper thickness limit of resin composition layer is excellent Be selected as 100 μm or less, more preferably 80 μm or less, be more preferably 60 μm or less, 50 μm or less, 40 μm or less, 30 μm with It is lower or 20 μm or less.
In resin sheet with supporter of the invention, as supporter, such as it can enumerate: the film that is molded of plastic material, Metal foil, processing release paper, the film being preferably molded of plastic material, metal foil.
When using the film being molded of plastic material as supporter, as plastic material, such as it can enumerate: poly- terephthaldehyde The polyester such as sour second diester (hereinafter sometimes referred to simply as " PET "), polyethylene naphthalate (hereinafter sometimes referred to simply as " PEN ") gather Acrylic acid series, cyclic polyolefin, the triacetyls such as carbonic ester (hereinafter sometimes referred to simply as " PC "), polymethyl methacrylate (PMMA) Base cellulose (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferably polyethylene terephthalate, Polyethylene naphthalate, particularly preferably cheap polyethylene terephthalate.
When using metal foil as supporter, as metal foil, such as it can enumerate: copper foil, aluminium foil etc., preferably copper foil.Make For copper foil, the foil formed by copper monometallic can be used, also can be used by copper and other metals (for example, tin, chromium, silver, magnesium, Nickel, zirconium, silicon, titanium etc.) alloy formed foil.
It can implement delustring processing (マ ッ ト processing), sided corona treatment to the face of supporter engaged with resin composition layer.
In addition, as supporter, can be used the face that is engaged with resin composition layer have release layer with release layer Supporter.As release agent used in the release layer in the supporter with release layer, such as it can enumerate selected from alkyd resin, gather The release agent of one or more of olefin resin, polyurethane resin and organic siliconresin.Supporter with release layer can make With commercially available product, such as it can enumerate and have with the PET film of alkyd resin system release agent release layer as main component, that is, リ Application テ ッ " SK-1 ", " AL-5 ", " AL-7 " etc. of Network (strain) system.
The thickness of supporter is not particularly limited, preferably 5 μm~75 μm of range, more preferably 10 μm~60 μm of model It encloses.It should be noted that when using supporter with release layer, supporter preferably with release layer it is whole with a thickness of above range.
Resin sheet with supporter of the invention, can resin composition layer do not engaged with supporter face (i.e. with branch The face of support body opposite side) further contain protective film.Protective film help to prevent resin combination layer surface adhesive dust etc. or It is scratched.It, can be using material identical with the explanation of supporter is directed to as the material of protective film.The thickness of protective film does not have Especially limitation, for example, 1 μm~40 μm.When manufacturing printed wiring board, protection film stripping can be used into the tree with supporter Rouge piece.
Resin sheet with supporter of the invention can be used to form the insulation of metallisation foil laminate plate (metal laminated plates) Layer (the insulating layer use of metallisation foil laminate plate), the insulating layer (insulating layer of printed wiring board that can be used to form printed wiring board With).Wherein, when using stack manner manufacture printed wiring board, can suitably be used to form the insulating layer (heap of printed wiring board Folded insulating layer use), and then can suitably be used to form conductor layer using plating and (form the printed wiring board of conductor layer using plating Stacking insulating layer use).
[manufacturing method of the resin sheet with supporter]
The manufacturing method of resin sheet with supporter of the invention is characterized in that the manufacturing method includes the following steps: First layer by the thickness being made of the first resin combination less than 2 μm and the second layer being made of the second resin combination are with phase Inter-engaging mode is arranged, and forms integrated resin composition layer, wherein the i) inorganic filling material in resin composition layer Content is 50 mass % or more, ii) surface of the side from first layer in resin composition layer is engaged with supporter, Moreover, iii) in the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and resin group The resin area A in region that the boundary for closing nitride layer is 0 μm to 1 μm0-1And in the region for being 1 μm to 2 μm apart from above-mentioned boundary Interior resin area A1-2Meet A0-1/A1-2The relationship of > 1.1.
It is for example aforementioned for the first resin combination and the second resin combination.In the present invention, in order to meet it is above-mentioned i) extremely Iii condition), first layer by the thickness being made of the first resin combination less than 2 μm and is made of the second resin combination The second layer be arranged in a manner of being interconnected, form integrated resin composition layer (also referred to as " resin combination Layer ".).About above-mentioned condition i), the preferred scope of the inorganic filling material content in resin composition layer such as [band supporter Resin sheet] column described in.Above-mentioned ii) condition indicate the dense Xiang Yuzhi of resin component for being originated from the first resin combination Support body engagement.Supporter is as described in the column of [resin sheet with supporter].In addition, about above-mentioned iii) condition, preferably Resin area ratio (A0-1/A1-2Than, A0-0.5/A0.5-1Than, kA2-d/Ad-0.5DDeng) condition such as [resin sheet with supporter] column Described in.
From the viewpoint of resin area ratio needed for realizing, the thickness for the first layer being made of the first resin combination is small In 2 μm, preferably 1.5 μm or less, more preferably 1 μm or less, be further preferably less than 1.0 μm, 0.8 μm or less, 0.6 μm with It is lower or 0.5 μm or less.The lower thickness limit of first layer is not particularly limited, from obtaining showing conductor layer after roughening treatment It, usually can be with from the viewpoint of the viewpoint of the insulating layer of excellent peel strength, the ease of manufacturing of resin sheet with supporter It is 0.05 μm or more, 0.1 μm with first-class.
The thickness for the second layer being made of the second resin combination is not particularly limited, can be in the thickness for considering first layer In the case where determine so that the thickness of resulting resin composition layer reaches required range.It should be noted that the second layer is to constitute The layer of the main part of resin composition layer, thus it is preferably sufficiently thick compared with first layer.Specifically, the thickness of the second layer Thickness relative to first layer be preferably 2 times or more, more preferably 4 times or more, be more preferably 6 times or more, further more Preferably 8 times or more, 10 times or more, 12 times or more, 14 times or more, 16 times or more, 18 times or more or 20 times or more.The second layer Thickness is relative to typically 2000 times or less, 1000 times of thickness or less of first layer or 500 times or less.In an embodiment party In formula, the thickness of the second layer is preferably 3 μm or more, more preferably 5 μm or more, further preferably 7 μm or more, 8 μm or more, 9 μ M or more or 10 μm or more.The upper thickness limit of the second layer is preferably 100 μm or less, more preferably 80 μm or less, is more preferably 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less or 20 μm or less.
As the method that first layer and the second layer are arranged in a manner of be combineding with each other, if can with meet it is above-mentioned i) extremely Iii the mode of condition) is implemented to be not particularly limited, such as can enumerate: 1) it is on the first layer coated with the second resin combination, By the dry method the second layer is arranged of coated film；2) it is coated with the first resin combination on the second layer, coated film is dry next The method of first layer is set；3) by the method for the first layer prepared respectively and the second layer lamination in a manner of being interconnected.
In a preferable embodiment, the step of forming integrated resin composition layer, includes:
(A1) the step of preparing interim resin sheet with supporter, the interim resin sheet with supporter contain supporter, With first layer of the thickness being made of the first resin combination less than 2 μm engaged with the supporter；And
(B1) it is coated with the second resin combination on the first layer, the second layer is arranged in coated film drying, forms integration Resin composition layer the step of
(embodiment is also referred to as " first embodiment " below.).
In step (A1), prepare the interim resin sheet with supporter, the interim resin sheet with supporter contain supporter, With first layer of the thickness being made of the first resin combination less than 2 μm engaged with the supporter.
Interim resin sheet with supporter can make as follows: for example, being coated with the first resin combination on supporter, will apply Cloth film is dry and first layer is arranged.Specifically, the resin for being dissolved with the first resin combination in organic solvent can be prepared The resin varnish is coated on supporter by varnish using chill coating machine (ダ イ コ ー タ ー) etc., keeps coated film dry To make.
As organic solvent, such as can enumerate: the ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, The acetate esters such as cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, cellosolve and butyl carbitol Aromatic hydrocarbon, dimethylformamide, dimethyl acetamide and the N-Methyl pyrrolidones such as equal carbitols class, toluene and dimethylbenzene Etc. acid amides series solvents etc..Organic solvent can be used alone, or can be used in combination two or more.
The drying of coated film can be implemented by drying means well known to heating, blowing hot-air etc..Although according in resin varnish The boiling point of organic solvent and it is different, but using contain such as resin varnish of the organic solvent of 30 mass of mass %~60 % feelings Under condition, by drying 3 minutes~10 minutes at 50 DEG C~150 DEG C, it can be formed on supporter by the first resin combination The first layer of composition.
Interim resin sheet with supporter, can first layer do not engaged with supporter face (i.e. with supporter opposite side Face) further contain protective film.Protective film in detail as aforementioned.When being used for step (B1), by the way that film stripping will be protected to be The interim resin sheet with supporter can be used.
In step (B1), it is coated with the second resin combination on the first layer, the second layer is arranged in coated film drying, is formed Integrated resin composition layer.
The coating of second resin combination and the drying of coated film can use and the first resin combination in step (A1) The coating of object and the identical method of the drying of coated film are implemented.In addition, the drying condition in step (B1) can be with step (A1) drying condition of the coated film in is identical, can also be different.From the thickness and precision for improving resulting resin composition layer Viewpoint considers, the drying temperature T in step (A1)A1Drying temperature T in (DEG C) and step (B1)B1(DEG C) preferably satisfies TA1< TB1Relationship, more preferably meet TA1+ 10≤TB1Relationship, further preferably meet TA1+ 20≤TB1Relationship.
In another better embodiment, the step of forming integrated resin composition layer, includes:
(A2) the step of preparing interim resin sheet with protective film, the interim resin sheet with protective film contain protective film, With the second layer being made of the second resin combination engaged with the protective film；And
(B2) it is coated with the first resin combination on the second layer, first of thickness less than 2 μm is arranged in coated film drying Layer, the step of forming integrated resin composition layer
(embodiment is also known as " second embodiment " below.).
Protective film used in step (A2) is for example aforementioned.Interim resin sheet with protective film can make as follows: for example, protecting It is coated with the second resin combination on cuticula, the second layer is arranged in coated film drying.The coating and coating of second resin combination The drying of film can be with the coating of the first resin combination in step (A1) and the drying of coated film is same implements.
Interim resin sheet with protective film, can the second layer do not engaged with protective film face (i.e. with protective film opposite side Face) further contain the second protective film.In this case, the interim resin sheet with protective film can protect film stripping for second Afterwards for step (B2).
In step (B2), the coating of the first resin combination and the drying of coated film can be with the first trees in step (A1) The coating of oil/fat composition and the drying of coated film are equally implemented.In addition, the drying condition in step (B2) can be with step (A2) In coated film drying condition it is identical, can also be different.From the viewpoint of the thickness and precision for improving resulting resin composition layer, Drying temperature T from the viewpoint of the flexibility of resulting resin composition layer, in step (A2)A2It is dry in (DEG C) and step (B2) Dry temperature TB2(DEG C) preferably satisfies TA2> TB2Relationship, more preferably meet TA2≧TB2+ 10 relationship further preferably meets TA2≧TB2+ 20 relationship.
In second embodiment, after step (B2), in not engaged with protective film for integrated resin composition layer Face on supporter is set.Supporter in detail as aforementioned.
In yet another embodiment, the step of forming integrated resin composition layer include:
(A3a) the step of preparing the interim resin sheet with supporter, which contains support Body and first layer of the thickness being made of the first resin combination less than 2 μm engaged with the supporter；
(A3b) the step of preparing the interim resin sheet with protective film, which contains protection Film and the second layer being made of the second resin combination engaged with the protective film；And
(B3) the interim resin sheet with supporter and the interim resin sheet with protective film are engaged with first layer and the second layer Mode the step of carrying out lamination
(embodiment is also known as " third embodiment " below.).
In third embodiment, step (A3a) and step (A3b) can respectively with the step (A1) in first embodiment Equally implement with the step (A2) in second embodiment.
In step (B3), by the interim resin sheet with supporter and the interim resin sheet with protective film with first layer and second The mode of layer engagement carries out lamination.
The lamination operation of interim resin sheet with supporter and the interim resin sheet with protective film is good, is easy to get one The contact condition of sample, therefore preferably crimping etc. is connect or pressurizeed to two sheet materials progress lamination treatment using roll-in.Wherein, more preferably exist The vacuum layer platen press being laminated under decompression.The method of lamination can be batch-type or continous way.
Crimping pressure is generally preferably set as 1kgf/cm by lamination treatment2~11kgf/cm2(9.8×104N/m2~107.9 ×104N/m2) range, temperature will be crimped and be set as 70 DEG C~120 DEG C of range, will be set as 5 seconds~180 seconds the crimping time Range, air pressure be 20mmHg (26.7hPa) decompression below under implemented.
Commercially available vacuum laminator can be used to implement in lamination treatment.As commercially available vacuum laminator, such as can arrange (strain) the name mechanism of act makees made vacuum pressure type laminating machine, vacuum pack system device of ニ チ ゴ ー モ ー ト Application (strain) system etc..
It is examined from the viewpoint that can be easily achieved in resin composition layer of the resin sheet whole face with required resin area ratio Consider, as formed integrated resin composition layer the step of, preferably above-mentioned first embodiment or second embodiment, more It is preferred that above-mentioned first embodiment.
[printed wiring board]
Printed wiring board of the invention includes the insulating layer that the resin sheet using of the invention with supporter is formed.
In one embodiment, the resin sheet of the invention with supporter can be used in printed wiring board of the invention, leads to The method containing following step (I) and (II) is crossed to manufacture,
(I) resin sheet of the invention with supporter is stacked on internal substrate, so that resin composition layer and internal layer The step of substrate engages
(II) the step of resin composition layer heat cure being formed into insulating layer.
In step (I), the resin sheet of the invention with supporter is stacked on internal substrate, so that resin composition layer It is engaged with internal substrate.
Used in step (I) " internal substrate ", it is primarily referred to as glass epoxy substrate, metal substrate, polyester substrate, polyamides The substrates such as imines substrate, BT resin substrate, heat curing type polyphenylene oxide substrate are formed with progress in the one or both sides of the substrate The circuit substrate of the conductor layer (circuit) of pattern processing.In addition, when manufacturing printed wiring board, insulating layer to be further formed And/or the internal layer circuit substrate of the intermediate manufacture object of conductor layer is also contained in " internal substrate " described in the present invention.
Known any means can be used in the lamination of the resin sheet with supporter and internal substrate in step (I) Implement, it is preferred to use roll-in connect or pressurize crimp etc., be laminated in a manner of engaging resin composition layer with internal substrate Processing.The condition of lamination treatment can be and condition phase illustrated by the third embodiment for [resin sheet with supporter] Same condition.It should be noted that in order to which the resin sheet with supporter fully follows the concave-convex surface of internal substrate (for example, internal layer The bumps of the surface circuit of circuit substrate), preferably lamination treatment is carried out via heat resistant rubber elastomeric material.
In step (I), the resin sheet with supporter can be stacked in the one side of internal substrate or be stacked in internal layer base The two sides of plate.
After step (I), the resin sheet with supporter of internal substrate superimposed layer can be heated and pressurizeed, be come real Apply smoothing techniques.Smoothing techniques using heated metal plate or metallic roll, prop up band usually under normal pressure (atmospheric pressure) The resin sheet of support body is heated and pressurizeed to implement.The condition being heated and pressurizeed can be using the condition with above-mentioned lamination treatment Same condition.Continuously implement it should be noted that commercially available vacuum laminator can be used in lamination treatment and smoothing techniques.
Supporter can remove between step (I) and step (II), can also remove after step (II).
In step (II), resin composition layer heat cure is formed into insulating layer.
The condition of heat cure is not particularly limited, and can be used and generallys use when forming the insulating layer of printed wiring board Condition.
For example, the heat cure condition of resin composition layer according to constitute resin composition layer resin combination composition and Difference, solidification temperature can be 120 DEG C~240 DEG C of range (preferably 150 DEG C~210 DEG C of range, more preferably 170 DEG C ~190 DEG C of range), curing time can for 5 minutes~90 minutes range (preferably 10 minutes~75 minutes, more preferably It is 15 minutes~60 minutes).
Before by resin composition layer heat cure, can lower than solidification temperature at a temperature of to resin composition layer into Row preheating.For example, can be before by resin composition layer heat cure, at 50 DEG C or more and less than 120 DEG C (preferably 60 DEG C Above and 110 DEG C or less, more preferably 70 DEG C or more and 100 DEG C or less) at a temperature of, by resin composition layer preheating 5 points More than clock (preferably 5 minutes~150 minutes, more preferably 15 minutes~120 minutes).
The insulating layer formed using the resin sheet of the invention with supporter is kept as inorganic filling material content height Subject characteristic, thus it is shown that low thermal coefficient of expansion.In one embodiment, the resin sheet shape using of the invention with supporter At insulating layer, can show preferred 30ppm/ DEG C or less, more preferable 25ppm/ DEG C or less, it is further preferred 22ppm/ DEG C with Under, even more preferably 20ppm/ DEG C or less, 19ppm/ DEG C or less, 18ppm/ DEG C or less, 17ppm/ DEG C or less, 16ppm/ DEG C with Under, 15ppm/ DEG C or less or 14ppm/ DEG C of coefficient of linear thermal expansion below.The lower limit of the coefficient of linear thermal expansion of insulating layer is without spy It does not limit, usually 1ppm/ DEG C or more.
Method well known to thermo-mechanical analysis etc. can be used for example to measure in the coefficient of linear thermal expansion of insulating layer.As heat engine Tool analytical equipment, such as " the Thermo Plus TMA8310 " of (strain) リ ガ Network can be enumerated.In the present invention, the line heat of insulating layer The coefficient of expansion is when carrying out thermo-mechanical analysis using tensile load method, in-plane 25 DEG C~150 DEG C of linear thermal expansion Coefficient.
The insulating layer formed using the resin sheet of the invention with supporter keeps uniform composition as subject characteristic, because This can advantageously show desired characteristic as the insulating layer of printed wiring board.
In one embodiment, the insulating layer that the resin sheet using of the invention with supporter is formed shows preferably 120 DEG C or more, more preferable 140 DEG C or more, further preferred 150 DEG C or more, even more preferably 155 DEG C or more or 160 DEG C or more Glass transition temperature (Tg), shows sufficient intensity.The upper limit of Tg is not particularly limited, and usually 250 DEG C or less.Insulation The Tg of layer, such as method well known to thermo-mechanical analysis can be used etc. measure.As thermo-mechanical analysis device, such as can enumerate " the Thermo Plus TMA8310 " of (strain) リ ガ Network.
In one embodiment, the insulating layer that the resin sheet using of the invention with supporter is formed shows preferably 0.05 Below, more preferably 0.04 or less, further preferred 0.03 or less, even more preferably 0.02 or less or 0.01 medium below declines Consumption factor (lures electricity just to connect), helps to prevent fever, reduction signal delay and signal noise under high frequency.Dielectric loss tangent Lower limit is not particularly limited, and usually 0.001 or more.The dielectric loss tangent of insulating layer can for example be taken the photograph using cavity resonator Method well known to dynamic method etc. measures.As cavity resonator perturbation method dielectric constant measurement device, such as ア ジ レ can be enumerated " HP8362B " of Application ト テ Network ノ ロ ジ ー (strain) system.In the present invention, the dielectric loss tangent of insulating layer be frequency 5.8GHz, The dielectric loss tangent of cavity resonator perturbation method measurement is utilized under conditions of 23 DEG C of measuring temperature.
When manufacturing printed wiring board, it can further implement the step of (III) carries out aperture to insulating layer, (IV) to insulation The step of layer is roughened, (V) are the step of surface of insulating layer forms conductor layer.These steps (III) to (V) can be with According to printed wiring board used in manufacture, well known to a person skilled in the art various methods implements.It should be noted that in step When removing supporter after (II) suddenly, the removing of the supporter can be between step (II) and step (III), step (III) Implement between step (IV) or between step (IV) and step (V).
Step (III) is that the step of carrying out aperture to insulating layer, through-hole (via can be formed on the insulating layer whereby Hole), the holes such as open-work (through hole).It is, for example, possible to use Drillings, laser (carbon dioxide laser, YAG laser Device etc.), plasma etc. hole is formed on the insulating layer.
Step (IV) is the step of being roughened to insulating layer.Program, the condition of roughening treatment be not special It limits, it can be using the well known program usually used when forming the insulating layer of printed wiring board, condition.For example, can be according to It is secondary to implement that the swelling process of swelling liquid is utilized, the roughening treatment of oxidant is utilized, the neutralisation treatment of neutralizer is utilized To be roughened to insulating layer.It is not particularly limited as swelling liquid, aqueous slkali, surfactant solution can be enumerated Deng, preferred aqueous slkali, as the aqueous slkali, more preferable sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling liquid, Such as the ス ウ ェ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ス P of ア ト テ ッ Network ジ ャ パ Application (strain) system, ス ウ ェ リ Application can be enumerated グ デ ィ ッ プ セ キ ュ リ ガ Application ス SBU etc..The swelling process that swelling liquid is utilized is not particularly limited, for example, can by Insulating layer is impregnated 1 minute~20 minutes to carry out in 30 DEG C~90 DEG C of swelling liquid.It is not particularly limited as oxidant, example The alkalinity dissolved with potassinm permanganate or sodium permanganate in the aqueous solution of sodium hydroxide can such as be enumerated and cross mangaic acid solution.Alkali is utilized Property crosses the roughening treatments of the oxidants such as mangaic acid solution preferably in the oxidizing agent solution for being heated to 60 DEG C~80 DEG C for insulating layer 10 minutes~30 minutes are impregnated to carry out.In addition, alkalinity cross mangaic acid solution in permanganate concentration be preferably 5 mass %~ 10 mass %.As commercially available oxidant, such as the U Application セ Application ト レ ー ト U of ア ト テ ッ Network ジ ャ パ Application (strain) system can be enumerated The alkalinity such as Application パ Network ト CP, ド ー ジ Application グ ソ リ ュ ー シ ョ Application セ キ ュ リ ガ Application ス P crosses mangaic acid solution.In addition, as neutralization Liquid, the aqueous solution of preferred acidic as commercially available product, such as can enumerate the リ ダ Network シ ョ Application ソ of ア ト テ ッ Network ジ ャ パ Application (strain) system リューション・セキュリガントP.The processing that neutralizer is utilized can be by that will be roughened through oxidizing agent solution The process face of processing impregnates 5 minutes~30 minutes in 30 DEG C~80 DEG C of neutralizer to carry out.
With patent document 1 above-mentioned for representative in the prior art, in roughening treatment, will be present in insulating layer table The inorganic filling material in face is detached from, and is formed on the surface concave-convex.Think that the bumps play fixed (ア Application カ between conductor layer ー) effect helps to improve the peel strength between insulating layer and conductor layer.But if improve inorganic filling out in insulating layer Material content is filled, even if then having by the bumps bring fixed effect, do not can avoid between insulating layer and conductor layer still sometimes Peel strength reduction, in addition, the surface roughness of insulating layer becomes excessively high after roughening treatment sometimes.
As described above, resin composition layer contained in the resin sheet of the invention with supporter, connect with supporter The composition gradient having in the region near surface sharply is closed, and it is exhausted being formed using the resin sheet of the invention with supporter Still the composition gradient is maintained in edge layer.Therefore, the insulating layer that the resin sheet using of the invention with supporter is formed keeps nothing Subject characteristic as the content height of machine packing material, while the ratio shared by inorganic filling material in the region near surface It is low.Whereby, in the insulating layer that the resin sheet using of the invention with supporter is formed, compared with insulating layer in the prior art, It is difficult to cause the disengaging of the inorganic filling material as caused by roughening treatment.It is formed using the resin sheet of the invention with supporter Insulating layer excellent peel strength is showed to conductor layer after roughening treatment, thus it is speculated that this is because in inorganic filling material In the balance that content and inorganic filling material are detached from, surface as the peel strength facilitated with conductor layer has been reproduced.
In one embodiment, the arithmetic average roughness Ra of the surface of insulating layer after roughening treatment is preferably 180nm Below, it is more preferably 150nm or less, further preferably 120nm or less, is even more preferably 110nm or less.Use this hair The insulating layer that the bright resin sheet with supporter is formed, though Ra be 100nm or less, 90nm or less, 80nm or less, 70nm with Under, in 60nm or less or 50nm or less situation very small in this way, excellent peel strength is still showed to conductor layer.Ra value Lower limit be not particularly limited, preferably 0.5nm or more, more preferably 1nm or more.
Non-contact type surface roughness meter can be used to be measured for the arithmetic average roughness Ra of surface of insulating layer.As The concrete example of non-contact type surface roughness meter can enumerate " the WYKO NT3300 " of ビ ー U イ Application ス Star Le メ Application Star.
Step (V) is the step of surface of insulating layer forms conductor layer.
There is no particular limitation for conductor material used in conductor layer.In preferable embodiment, conductor layer contains choosing From the metal of one or more of gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor layer can be Single metal layer or alloy-layer as alloy-layer, such as can be enumerated by the alloy of the metal of more than two kinds selected from above-mentioned metal The layer that (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) is formed.Wherein, from conductor layer formed versatility, cost, The consideration of the viewpoints such as patterned easiness, the preferably single metal layer or nickel-chrome of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper Alloy, copper-nickel alloy, copper-titanium alloy alloy-layer, the more preferably monometallic of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper The alloy-layer of layer or nickel-chromium alloy, and then the single metal layer of preferably copper.
Conductor layer can be single layer structure, be also possible to 2 layers or more of the Dan Jin comprising different types of metal or alloy Belong to multilayered structure obtained by layer or alloy layer laminate.When conductor layer is multilayered structure, the layer to connect with insulating layer is preferably chromium, zinc Titanium single metal layer or nickel-chromium alloy alloy-layer.
The thickness of conductor layer depends on the design of required printed wiring board, but generally 3 μm~35 μm, preferably 5 μm ~30 μm.
Conductor layer can use plating to be formed.Such as the known skill such as can use semi-additive process, full additive method Art carries out plating on the surface of insulating layer, forms the conductor layer with required wiring pattern.Semi-additive process is utilized hereinafter, showing Form the example of conductor layer.
Firstly, conformal at plating layer (め っ き シ ー De layer) using electroless plating on the surface of insulating layer.Then, in shape At plating layer on, corresponding to required wiring pattern, form the mask pattern for exposing a part of plating layer.In exposing On plating layer, after forming metal layer using plating, mask pattern is removed.Then, unwanted plating layer is removed using etching etc., The conductor layer with required wiring pattern can be formed.
In one embodiment, the peel strength of the insulating layer after roughening treatment and conductor layer is preferably 0.5kgf/cm Above, be more preferably 0.55kgf/cm or more, further preferably 0.60kgf/cm or more, particularly preferably 0.65kgf/cm with On.On the other hand, the upper limit value of peel strength is not particularly limited, and is that 1.2kgf/cm or less, 0.9kgf/cm are such as the following.This hair In bright, although the surface roughness Ra of the insulating layer after roughening treatment is smaller, it can be formed and be showed such as above-mentioned height removing The insulating layer of intensity.Therefore, the present invention has notable contribution for the fine wiring of printed wiring board.
It should be noted that the peel strength of insulating layer and conductor layer refers to, by conductor layer relative to insulation in the present invention Cupping machine progress can be used in peel strength (90 degree of peel strengths) when removing on the vertical direction (90 degree of directions) of layer It measures so as to find out the peel strength by conductor layer when being removed on the direction (90 degree of directions) vertical relative to insulating layer.As Cupping machine, such as " AC-50C-SL " etc. of (strain) TSE can be enumerated.
[semiconductor device]
Using above-mentioned printed wiring board, semiconductor device can be manufactured.
As the semiconductor device, can enumerate for electric product (for example, computer, mobile phone, digital camera and electricity Depending on machine etc.) and the vehicles (for example, motorcycle, automobile, electric car, ship and aircraft etc.) etc. various semiconductor devices.
Embodiment
Specifically describe the present invention by the following examples, but the present invention is not limited to the examples.It should say Bright, in record below, in case of no particular description, " part " and " % " respectively refers to " mass parts " and " quality % ".
It is illustrated firstly for various measuring methods, evaluation method.
(measurement, the preparation of sample for evaluation)
(1) the ground processing of internal layer circuit substrate
Glass cloth base material epoxy resin two-sided copper foil covered laminated plate (the ガ ラ ス cloth base material エ Port of internal layer circuit will be formed with キ シ Shu Zhi both face copper laminated plates) (18 μm of the thickness of copper foil, thickness 0.3mm, パ Na ソ ニ ッ Network electrician (strain) of substrate make " R5715ES ") two sides using メ ッ Network (strain) system " CZ8100 " etch 1 μm, carry out copper surface roughening treatment.
(2) lamination of the resin sheet with supporter
Using batch-type vacuum pressed laminating machine ((strain) name mechanism makees made " MVLP-500 "), by embodiment and comparative example The resin sheet with supporter of middle production internal layer circuit substrate two sides carry out lamination treatment so that resin composition layer with it is interior Layer circuit substrate engagement.Lamination treatment carries out as follows: after progress decompression in 30 seconds makes air pressure reach 13hPa or less, 100 DEG C, crimp 30 seconds under pressure 0.74MPa.
(3) heat cure of resin composition layer
After resin sheet lamination with supporter, under conditions of 170 DEG C, 30 minutes by resin composition layer heat cure and Form insulating layer.Then supporter is removed.
(4) roughening treatment
The internal layer circuit substrate of insulating layer will be provided on two sides in swelling liquid (ア ト テ ッ Network ジ ャ パ Application (strain) system " ス エ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ト P ", the sodium hydrate aqueous solution containing diethylene glycol monobutyl ether) at 60 DEG C Dipping 5 minutes, then in oxidant, (ア ト テ ッ Network ジ ャ パ Application (strain) makes " U Application セ Application ト レ ー ト U Application パ Network ト CP ", mistake The aqueous solution of about 6 mass % of mangaic acid potassium concn, about 4 mass % of naoh concentration) in impregnated 20 minutes at 80 DEG C, finally exist (ア ト テ ッ Network ジ ャ パ Application (strain) makes " リ ダ Network シ ョ Application ソ リ ュ ー シ ョ Application セ キ ュ リ ガ Application ト P ", sulfuric acid hydroxyl to neutralizer Amine aqueous solution) in impregnated 5 minutes at 40 DEG C.Then, 30 minutes dry at 80 DEG C.Resulting substrate is known as " evaluation base Plate A ".
(5) formation of conductor layer
According to semi-additive process, conductor layer is formed on the surface of insulating layer.
That is, evaluation substrate A is being contained PdCl2Electroless plating application solution in impregnated 5 minutes at 40 DEG C, then exist It is impregnated 20 minutes at 25 DEG C in electroless plating copper liquid, forms plating layer in surface of insulating layer.Heated at 150 DEG C 30 minutes into It has gone after annealing, underseal is set on plating layer, so that plating layer is formed pattern by etching.Then sulfuric acid is carried out Copper plating after foring 30 μm of thickness of conductor layer, carries out making annealing treatment for 60 minutes at 190 DEG C.Resulting substrate is claimed For " evaluation substrate B ".
The measurement > of < resin area ratio
For the resin sheet with supporter made in embodiment and comparative example, for resin composition layer and support The section in the vertical direction in body surface face carries out SEM observation, and measurement is d1 (μ on the boundary apart from supporter and resin composition layer M) to the resin area A in the region of d2 (μm)d1-d2It and is being the resin face of d2 (μm) to the region of d3 (μm) apart from above-mentioned boundary Product Ad2-d3.Then, by resulting Ad1-d2Value and Ad2-d3Value calculates resin area ratio (kAd1-d2/Ad2-d3)。
Specifically, by SEM observation as being saved as image, using image analysis software, will be set for resin area Rouge part carries out white black binaryzation as black, using the inorganic filling material part other than resin as white, by black portions Area of the bit number (ビ ッ ト number) as resin portion.It should be noted that the SEM observation of resin combination layer cross section uses focusing Ion beam/scanning ion microscope (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー (strain) system " SMI3050SE ") is implemented, The width for measuring region is 7.5 μm.
The measurement > of < arithmetic average roughness (Ra value)
The arithmetic average roughness (Ra value) of surface of insulating layer after roughening treatment is measured according to following programs. For evaluating substrate A, non-contact type surface roughness meter (ビ ー U イ Application ス Star Le メ Application Star system " WYKO is used NT3300 "), using VSI contact mode, 50 times of lens, it is measured in 121 μ m, 92 μm of measurement range, by resulting number Value acquires Ra value.For each evaluation substrate, randomly selected 10 points of average value is found out.
The measurement > of < peel strength
The peel strength of insulating layer and conductor layer is measured according to following programs.It is cut in the conductor layer of evaluation substrate B One end is peeled and is clamped with fixture by the notch for opening the part of wide 10mm, long 100mm, at room temperature, with 50mm/ minutes Speed peels 35mm in vertical direction, measures loading (kgf/cm) at this time.Cupping machine ((strain) TSE system is used in measurement オ ー ト U system type testing machine " AC-50C-SL ").
The measurement > of < coefficient of linear thermal expansion and glass transition temperature (Tg)
The resin sheet with supporter made in embodiment and comparative example is heated 90 minutes at 190 DEG C, makes resin group Close nitride layer heat cure.Then, supporter removing is obtained into the solidfied material of sheet.The solidfied material of resulting sheet is cut into wide about 5mm, the test film for being about 15mm use thermo-mechanical analysis device ((strain) リ ガ Network system " Thermo Plus TMA8310 "), benefit Thermo-mechanical analysis is carried out with tensile load method.Specifically, after test film being mounted in above-mentioned thermo-mechanical analysis device, METHOD FOR CONTINUOUS DETERMINATION 2 times under loading 1g, 5 DEG C/min of heating rate of determination condition.Then, in the 2nd measurement, 25 DEG C are calculated The coefficient of mean linear thermal expansion (ppm/ DEG C) and glass transition temperature (Tg) in the range of to 150 DEG C.
The measurement of < dielectric loss tangent and evaluation >
The resin sheet with supporter made in embodiment and comparative example is heated 90 minutes at 190 DEG C, makes resin group Close nitride layer heat cure.Then, supporter removing is obtained into the solidfied material of sheet.The solidfied material of resulting sheet is cut into width The test film of 2mm, long 80mm use cavity resonance perturbation method dielectric constant measurement device (ア ジ レ Application ト テ Network ノ ロ ジ ー (strain) makes " HP8362B "), dielectric loss tangent is measured under conditions of measuring frequency 5.8GHz, 23 DEG C of measuring temperature.For 2 Piece test film is measured, and calculates average value.
For example following preparations of the varnish of resin combination 1 to 6 used in embodiment and comparative example.
The preparation of the varnish of 1 > resin combination 1 of < preparation example
By bisphenol-type epoxy resin, (1:1 of aurification (strain) system " ZX1059 ", bisphenol A-type and bisphenol-f type lives in Nippon Steel (Japanese chemical drug (strain) system " NC3000H ", epoxide equivalent are about for about 169) 10 parts of melange, epoxide equivalent, biphenyl type epoxy resin 290) it is dissolved by heating while stirring in 700 parts of methyl ethyl ketone (MEK) for 30 parts.After being cooled to room temperature, mixing contains three thereto Piperazine skeleton phenol novolacs system curing agent (DIC (strain) make " LA-7054 ", 60 mass % of nonvolatile component MEK solution, Phenolic hydroxyl equivalent 124) 20 parts, (4-dimethylaminopyridine (DMAP), the MEK of 10 mass % of solid component are molten for curing accelerator Liquid) 1 part, (ponding chemical industry (strain) makes " KS-1 ", 105 DEG C of glass transition temperature, no to polyvinyl butyral resin solution The ethyl alcohol of 15 mass % of volatile ingredient: toluene mass ratio is the mixed solution of 1:1) 20 parts, prepare the varnish of resin combination 1.
The preparation of the varnish of 2 > resin combination 2 of < preparation example
By 10 parts of bisphenol-type epoxy resin (aurification (strain) system " ZX1059 ", epoxide equivalent about 169 live in Nippon Steel), connection 40 parts of benzene-type epoxy resin (Japanese chemical drug (strain) makes " NC3000H ", epoxide equivalent about 290), phenoxy resin (Mitsubishi Chemical The MEK solution of (strain) system " YL7553BH30 ", 30 mass % of solid component) 30 parts dissolve by heating while stirring in MEK900 In part.Thereto mixed active ester system curing agent (DIC (strain) make " HPC8000-65T ", active group equivalent about 223, it is non-volatile at The toluene solution of point 65 mass %) 60 parts, (DIC (strain) makes " LA- for the phenol novolacs system curing agent of the skeleton containing triazine 7054 ", MEK solution, the phenolic hydroxyl equivalent 124 of 60 mass % of nonvolatile component) 15 parts, N- phenyl -3- aminopropyl trimethoxy 2 parts of base silane (SHIN-ETSU HANTOTAI's chemical industry (strain) makes " KBM-573 "), the curing accelerator (MEK of DMAP, 10 mass % of solid component Solution) 3 parts, 200 parts of cyclohexanone, prepare the varnish of resin combination 2.
The preparation of the varnish of 3 > resin combination 3 of < preparation example
Using the acrylate copolymer containing epoxy group, (it is non-volatile that Na ガ セ ケ system テ ッ Network ス (strain) makes " SG-80H " The MEK solution of 18 mass % of ingredient) 50 parts to replace polyvinyl butyral resin solution, (ponding chemical industry (strain) makes " KS- 1 ", the ethyl alcohol of 105 DEG C of glass transition temperature, 15 mass % of nonvolatile component: toluene mass ratio is the mixed solution of 1:1) 20 Part, the varnish of resin combination 3 is in addition to this prepared with the equally operation of preparation example 1.
The preparation of the varnish of 4 > resin combination 4 of < preparation example
Using active ester system curing agent, (DIC (strain) makes " HPC8000-65T ", active group equivalent about 223, nonvolatile component The toluene solution of 65 mass %) 30 parts and nano silica filler slurry (Na ノ シ リ カ Off ィ ラ ー ス ラ リ ー) ((strain) ア De マ テ ッ Network ス system " YA050C-MJE ", average grain diameter 50nm, at metering system acyloxy silane (メ タ Network リ Le シ ラ Application) surface The MEK slurry of reason, 50 mass % of solid component) 40 parts come replace active ester system curing agent (DIC (strain) make " HPC8000-65T ", The toluene solution of active group equivalent about 223,65 mass % of nonvolatile component) 60 parts, in addition to this come with the equally operation of preparation example 2 Prepare the varnish of resin combination 4.
The preparation of the varnish of 5 > resin combination 5 of < preparation example
By 15 parts of bisphenol-type epoxy resin (aurification (strain) system " ZX1059 ", epoxide equivalent about 169 live in Nippon Steel), connection 30 parts of benzene-type epoxy resin (Japanese chemical drug (strain) makes " NC3000H ", epoxide equivalent about 290), 4 functional epoxy resins' (ring of naphthalene type Oxygen equivalent 162, DIC (strain) system " HP-4700 ") 5 parts dissolve by heating while stirring and mixed at MEK20 part and 10 parts of cyclohexanone In bonding solvent.After being cooled to room temperature, mixing the phenol novolacs system curing agent of the skeleton containing triazine thereto, (phenolic hydroxyl equivalent is about 124, DIC (strain) makes the MEK solution of " LA-7054 ", 60 mass % of nonvolatile component) 30 parts, curing accelerator (DMAP, solid The MEK solution of 10 mass % of ingredient) 1 part, the ball that is surface-treated through amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemistry system " KBM573 ") Shape silica ((strain) ア De マ テ ッ Network ス system " SOC2 ", 0.5 μm of average grain diameter, per unit surface area carbon amounts 0.39mg/ m2) 125 parts, polyvinyl butyral resin solution (ponding chemical industry (strain) make " KS-1 ", 105 DEG C of glass transition temperature, The ethyl alcohol of 15 mass % of nonvolatile component: toluene mass ratio is the mixed solution of 1:1) 10 parts, it is uniform with high speed rotation blender Dispersion, prepares the varnish of resin combination 5.
The preparation of the varnish of 6 > resin combination 6 of < preparation example
By 20 parts of bisphenol-type epoxy resin (aurification (strain) system " ZX1059 ", epoxide equivalent about 169 live in Nippon Steel), connection 40 parts of benzene-type epoxy resin (Japanese chemical drug (strain) makes " NC3000H ", epoxide equivalent about 290), phenoxy resin (Mitsubishi Chemical The MEK solution of (strain) system " YL7553BH30 ", 30 mass % of solid component) 15 parts dissolve by heating while stirring in solvent naphtha In 20 parts.(DIC (strain) makes " HPC8000-65T ", active group equivalent about 223, non-volatile to mixed active ester system curing agent thereto The toluene solution of 65 mass % of ingredient) 60 parts, (DIC (strain) makes " LA- for the phenol novolacs system curing agent of the skeleton containing triazine MEK solution, the phenolic hydroxyl equivalent 124 of 7054 " nonvolatile component, 60 mass %) 15 parts, curing accelerator (DMAP, solid component The MEK solution of 10 mass %) 3 parts, spherical two through amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemistry system " KBM573 ") surface treatment Silica ((strain) ア De マ テ ッ Network ス system " SOC1 ", 0.24 μm of average grain diameter, per unit surface area carbon amounts 0.36mg/m2) It is 375 parts, evenly dispersed with high speed rotation blender, prepare the varnish of resin combination 6.
[table 1]
。
The production of resin sheet 1 of 1 > of < embodiment with supporter
As supporter, prepare 38 μm of thickness of PET film (リ Application テ ッ Network (strain) makes " AL5 ").Existed with chill coating machine The varnish of resin combination 1 is equably coated on the supporter, coated film is 3 minutes dry at 80 DEG C, form 0.5 μm of thickness First layer.Then, the varnish of resin combination 5 is equably coated on the first layer with chill coating machine, so that after dry The overall thickness of resin composition layer reach 10 μm, 4 minutes dry, the production under 80~120 DEG C (100 DEG C average) by coated film Resin sheet 1 with supporter.
The production of resin sheet 2 of 2 > of < embodiment with supporter
Replace the varnish of resin combination 1 to form first layer using the varnish of resin combination 2, in addition to this with implementation The equally operation of example 1 is to make the resin sheet 2 with supporter.
The production of resin sheet 3 of 3 > of < embodiment with supporter
Replace the varnish of resin combination 5 to form the second layer using the varnish of resin combination 6, in addition to this with implementation The equally operation of example 1 is to make the resin sheet 3 with supporter.
The production of resin sheet 4 of 4 > of < embodiment with supporter
Using the varnish of resin combination 2 first layer is formed instead of the varnish of resin combination 1, using resin combination The varnish of object 6 replaces the varnish of resin combination 5 to form the second layer, in addition to this operates similarly to Example 1 to make band The resin sheet 4 of supporter.
The production of resin sheet 5 of 5 > of < embodiment with supporter
Using the varnish of resin combination 3 first layer is formed instead of the varnish of resin combination 1, using resin combination The varnish of object 6 replaces the varnish of resin combination 5 to form the second layer, in addition to this operates similarly to Example 1 to make band The resin sheet 5 of supporter.
The production of resin sheet 6 of 6 > of < embodiment with supporter
Using resin varnish 4 replace resin varnish 1, using resin varnish 6 replace resin varnish 5, in addition to this with it is above-mentioned " (production of the resin sheet 1 with supporter) " equally operates, and obtains the resin sheet 6 with supporter.
The production of resin sheet 7 of 1 > of < comparative example with supporter
As supporter, prepare 38 μm of thickness of PET film (リ Application テ ッ Network (strain) AL5 processed).Then, chill coating is used Machine is equably coated with the varnish of resin combination 5 on the supporter, so that the thickness of the resin composition layer after dry reaches It is 10 μm, coated film is 4 minutes dry under 80~120 DEG C (100 DEG C average), make the resin sheet 7 with supporter.
The production of resin sheet 8 of 2 > of < comparative example with supporter
The varnish of resin combination 5 is replaced using the varnish of resin combination 6, is in addition to this equally operated with comparative example 1 To make the resin sheet 8 with supporter.
Evaluation result is shown in table 2.
[table 2]
。

Claims (25)

1. the resin sheet with supporter, which contains:
Supporter；With
Engage with the supporter, inorganic filling material content is 50 mass % or more and containing curable resin and curing agent Resin composition layer,
Wherein, in the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and resin group The resin area A in region that the boundary for closing nitride layer is 0 μm to 1 μm0-1And in the region for being 1 μm to 2 μm apart from above-mentioned boundary Interior resin area A1-2Meet A0-1/A1-2The relationship of > 1.1.
2. the resin sheet with supporter, which contains:
Supporter；With
Engage with the supporter, inorganic filling material content is 50 mass % or more and containing curable resin and curing agent Resin composition layer,
Wherein, in the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and resin group The resin area A in region that the boundary for closing nitride layer is 0 μm to 0.5 μm0-0.5It and is being 0.5 μm to 1 μm apart from above-mentioned boundary Resin area A in region0.5-1Meet A0-0.5/A0.5-1The relationship of > 1.1.
3. the resin sheet of any of claims 1 or 2 with supporter, wherein
In the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and resin composition layer Boundary be resin area A in 0.5 μm to d μm of region0.5-dAnd in the region for being d μm to 0.5D μm apart from above-mentioned boundary Interior resin area Ad-0.5DMeet 0.9≤kA0.5-d/Ad-0.5D≤ 1.1 relationship,
Wherein, k be meet k=|d-0.5D|/| the coefficient of 0.5-d|, d be meet 0.5 < d < 0.5D number, D is resin combination The thickness of nitride layer.
4. the manufacturing method of the resin sheet with supporter, which includes the following steps: will be by the first resin combination structure At first layer of the thickness less than 2 μm and be arranged in a manner of being interconnected by the second layer that the second resin combination is constituted, shape The resin composition layer integrally changed,
Wherein, the first resin combination contains curable resin and curing agent,
Inorganic filling material content in resin composition layer is 50 mass % or more,
The surface of the side from first layer in resin composition layer is engaged with supporter,
In the section in the direction vertical with supporting body surface of resin composition layer, apart from supporter and resin composition layer Boundary be resin area A in 0 μm to 1 μm of region0-1And the tree in the region for being 1 μm to 2 μm apart from above-mentioned boundary Rouge area A1-2Meet A0-1/A1-2The relationship of > 1.1.
5. method as claimed in claim 4, wherein the step of forming above-mentioned resin composition layer include:
(A1) the step of preparing interim resin sheet with supporter, the interim resin sheet with supporter contain supporter and First layer of the thickness being made of the first resin combination less than 2 μm engaged with the supporter；And
(B1) it is coated with the second resin combination on the first layer, the second layer is arranged in coated film drying, forms integrated tree The step of oil/fat composition layer.
6. method as claimed in claim 4, wherein the second resin combination contains curable resin and curing agent.
7. method as claimed in claim 4, wherein the thickness of first layer is less than 1 μm.
8. method as claimed in claim 4, wherein first layer with a thickness of 0.05 μm or more.
9. method as claimed in claim 4, wherein the first resin combination contains average grain diameter 500nm inorganic fill below Material.
10. method as claimed in claim 4, wherein the first resin combination contains average grain diameter 300nm inorganic fill below Material.
11. method as claimed in claim 4, wherein the first resin combination contains average grain diameter 200nm inorganic fill below Material.
12. method as claimed in claim 4, wherein the first resin combination contains average grain diameter 150nm inorganic fill below Material.
13. method as claimed in claim 4, wherein the first resin combination contains average grain diameter 100nm inorganic fill below Material.
14. method as claimed in claim 4, wherein the first resin combination contains average grain diameter 50nm inorganic fill below Material.
15. method as claimed in claim 4, wherein the first resin combination contains the inorganic fill material of average grain diameter 5nm or more Material.
16. method as claimed in claim 4, wherein the inorganic filling material content in the first resin combination is 40 mass % Below.
17. method as claimed in claim 4, wherein the inorganic filling material content in the first resin combination is 30 mass % Below.
18. method as claimed in claim 4, wherein the inorganic filling material content in the first resin combination is 25 mass % Below.
19. method as claimed in claim 4, wherein the inorganic filling material content in the first resin combination is 20 mass % Below.
20. method as claimed in claim 4, wherein inorganic filling material content in the first resin combination be 0 mass % with On.
21. method as claimed in claim 4, wherein the inorganic filling material content in the second resin combination is greater than 50 matter Measure %.
22. method as claimed in claim 4, wherein the inorganic filling material content in the second resin combination is 60 mass % More than.
23. method as claimed in claim 4, wherein the inorganic filling material content in the second resin combination is 95 mass % Below.
24. printed wiring board, which includes to be formed using the resin sheet with supporter described in as claimed in claim 1 or 22 Insulating layer.
25. semiconductor device, which includes printed wiring board described in claim 24.
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