CN108696998A

CN108696998A - The copper foil of attached release layer, the manufacturing method of laminate, the manufacturing method of printing distributing board and e-machine

Info

Publication number: CN108696998A
Application number: CN201810294290.3A
Authority: CN
Inventors: 森山晃正
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2017-03-31
Filing date: 2018-03-30
Publication date: 2018-10-23
Also published as: KR20180111659A; JP2018171899A; TWI684522B; TW201838817A

Abstract

The present invention relates to the manufacturing methods of the copper foil of attached release layer, laminate, the manufacturing method of printing distributing board and e-machine.A kind of copper foil of attached release layer is provided, embedment circuit can be made, and can favorably inhibit and corrode embedment circuit when so that the embedment circuit is exposed using etching.The copper foil of the attached release layer of the present invention sequentially has release layer, copper foil and barrier layer.

Description

Copper foil, laminate, the manufacturing method of printing distributing board and the e-machine of attached release layer Manufacturing method

Technical field

The present invention relates to a kind of copper foil of attached release layer, laminate, the manufacturing method of printing distributing board and e-machines Manufacturing method.

Background technology

Printing distributing board realizes big progress between this halfth century, is nowadays almost used for all e-machines.With close The miniaturization of e-machine, the increase of high performance demand, carry the high-density installation of part or the high frequency of signal over year Constantly progress requires the miniaturization (micro- spacing) of conductive pattern or high frequency to answer equity printing distributing board.

Printing distributing board is manufactured into copper-cover laminated body first, and the copper-cover laminated body is by copper foil and with glass ring oxygroup Insulating substrate based on plate, BT resins, polyimide film etc. is bonded.Fitting uses following methods:By insulating substrate and copper Foil is overlapped and carries out heating pressurization and the method (laminating method) that is formed;Or by the varnish as the predecessor of dielectric substrate material The method (the tape casting) for being coated on the face with coating of copper foil and being heated, being hardened.

In recent years, it develops the printing distributing board made respectively according to purpose and with various preparation methods and is used.Such as It is known to utilize the circuits embedment substrate such as printing distributing board of so-called implantation manufacture (ETS, Embedded Trace Substrate), the implantation is the circuit forming surface coating in ultrathin copper foil, to cover the circuit coating of the formation Mode (in a manner of burying circuit coating), on ultrathin copper foil setting embedment resin and laminated resin layer, use the quilt The circuit coating of embedment is formed (patent documents 1) such as printing distributing boards.

[Xian Youjishuwenxian ]

[Zhuan Liwenxian ]

[Patent document 1]Japanese Unexamined Patent Publication 2005-101137 bulletins

Invention content

[Invent the Ke Ti &#93 to be solved;

The example that the production method of substrate is embedded to as the circuit forms electricity on the surface of ultrathin copper foil first Road, the laminated resin in a manner of covering the circuit form embedment circuit.It secondly, will be laminated on the carrier copper foil of ultrathin copper foil After stripping, ultrathin copper foil is removed using etching, thus exposes the circuit in embedment resin, thus utilizes the embedment circuit Make printing distributing board.

However, if as described in a manner of covering circuit laminated resin and formed embedment circuit after, utilize etching Ultrathin copper foil is removed and embedment circuit is made to expose, then can be existed because the etching of the ultrathin copper foil causes embedment circuit to be etched The problem of.

In addition, in order to be easy to carry out the various processing to copper foil, supported sometimes by fitting in the supports such as resin The processing is carried out in the state of copper foil.At this point, by being demoulded in the side surface setting that is bonded of the supports such as copper foil and resin Layer, and can after processing easily remove the supports such as resin.About the copper foil of this attached release layer, it had not been used in the past The example of the implantation as described.

[Solve the Ji Shushouduan &#93 of project;

The inventors of the present invention have carried out making great efforts research, as a result, it has been found that, pass through the copper foil in attached release layer and release layer side table Face is that barrier layer is arranged in the surface of opposite side, the copper foil of attached release layer can be used to make embedment circuit, and can favorably inhibit profit Embedment circuit is corroded when so that the embedment circuit is exposed with etching.

It is a kind of copper foil of attached release layer in one form by the present invention completed based on the above opinion, sequentially Have release layer, copper foil and barrier layer.

The copper foil of attached release layer about the present invention, in one embodiment, the barrier layer is C layers, Ni layers, Ti layers, Cr layers, V layers, Zr layers, Ta layers, Au layers, Pt layers, Os layers, Pd layers, Ru layers, Rh layers, Ir layers, W layers, or comprising containing selected from by More than any one of group that Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si and Cr are formed alloy Layer, or comprising containing in the group being made of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si and Cr Any above carbide, oxide or nitride layer.

About the present invention attached release layer copper foil, in another embodiment, the barrier layer by be selected from by Ni, Ti, Any one of group that Cr, titanium oxide, chromium oxide and carbon are formed is above to be constituted.

About the present invention attached release layer copper foil, in yet another embodiment, the barrier layer have selected from by Ni layers, The layer of one or more of the Ti layers and Cr layers group formed.

The copper foil of attached release layer about the present invention, in yet another embodiment, the barrier layer are selected from by Ni layers, Ti Layer more than any one of layer and the Cr layers of group formed.

The barrier layer is selected from the layer by any one of Ni layers, the Ti layers and Cr layers group formed.

The copper foil of attached release layer about the present invention, in yet another embodiment, the thickness of the barrier layer is 0.001 μm Above and 10 μm or less.

The copper foil of attached release layer about the present invention, in yet another embodiment, the thickness of the copper foil is 0.1 μm or more And 100 μm or less.

The copper foil of attached release layer about the present invention, in yet another embodiment, the release layer is a variety of alone or in combination And the hydrolysis production of the hydrolysate, the silane compound with silane compound, the silane compound represented by following formula The condensation product of object.

(in formula, R¹For alkoxy or halogen atom,

R²For in the group being made of alkyl, naphthenic base and aryl alkyl or more than one hydrogen atom by halogen The alkyl of atom substitution,

R³And R⁴Separately by halogen atom or alkoxy or selected from being made of alkyl, naphthenic base and aryl The alkyl that alkyl or more than one hydrogen atom in group are substituted with halogen atoms)

The copper foil of attached release layer about the present invention, in yet another embodiment, the release layer is with intramolecular with 2 The compound of a sulfydryl below.

The copper foil of attached release layer about the present invention, in yet another embodiment, the release layer is a variety of alone or in combination And with the water of aluminate compound, titanate compound, zirconate compounds, the aluminate compound represented by following formula Solve product, the hydrolysate of the titanate compound, the hydrolysate of the zirconate compounds, the aluminate compound The condensation product of hydrolysate, the titanate compound hydrolysate condensation product or the zirconate compounds hydrolysis The condensation product of product.

(R¹)_m-M-(R²)_n

(in formula, R¹For alkoxy or halogen atom, R²For the hydrocarbon in the group being made of alkyl, naphthenic base and aryl The alkyl that base or more than one hydrogen atom are substituted with halogen atoms, M Al, Ti or Zr, n 0,1 or 2, m are 1 or more And the valence mumber integer below of M, R¹It is at least one be alkoxy.M+n is the valence mumber of M, that is, when for Al be 3, when for Ti, For 4) when Zr

The copper foil of attached release layer about the present invention, in yet another embodiment, the release layer have resin coating film, institute Resin coating film is stated by silicone and is selected from epoxy system resin, melamine series resin and fluororesin any one or more of resin It is constituted.

The copper foil of attached release layer about the present invention, in yet another embodiment, between the copper foil and barrier layer, tool By one in the group being made of roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupled process layer Kind or more layer.

The copper foil of attached release layer about the present invention is in yet another embodiment in the barrier layer and copper foil side The face of opposite side has selected from by roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupled process layer institute The layer of one or more of the group of composition.

About the present invention attached release layer copper foil, in yet another embodiment, the roughening treatment layer be by be selected from by Any one of the group that Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Co and Zn are formed simple substance contains any the above The layer that the alloy of simple substance is constituted.

The copper foil of attached release layer about the present invention, in yet another embodiment, between the copper foil and release layer, tool By the layer selected from one or more of the group being made of refractory layer, antirust coat, chromating layer and silane coupled process layer.

The copper foil of attached release layer about the present invention has tree in the release layer side surface in yet another embodiment Lipid layer.

The present invention is a kind of laminate in another form, has the copper foil of the attached release layer of the present invention.

The present invention is a kind of laminate in another form, contains the copper foil and resin of the attached release layer of the present invention, and Part or all of the end face of the copper foil is covered by the resin.

The present invention is a kind of laminate in another form, and there are two the copper foil of the attached release layer of the present invention and trees for tool Fat, and its be by the release layer side surface of the copper foil of the attached release layer in the copper foil of described two attached release layers with it is described One face lamination of resin, by the release layer side surface of copper foil of another attached release layer and the another side lamination of the resin At.

The present invention is a kind of manufacturing method of printing distributing board in another form, is the attached release layer using the present invention Copper foil and manufacture printing distributing board.

The present invention is a kind of manufacturing method of printing distributing board in another form comprising following steps:In the present invention Attached release layer copper foil the release layer side lamination support or the step of insulating substrate 1;In the lamination support Or the step of patterned plating resist coating is arranged in the barrier layer side of the copper foil of the attached release layer of the insulating substrate 1; After copper plate is set on the barrier layer provided with the patterned plating resist coating, the plating resist coating is removed, by This forms the step of copper plating circuit;The copper plating circuit is covered using insulating substrate 2, the step for being thus embedded to the copper plating circuit Suddenly;After the copper plating circuit is embedded to, the support of the release layer side surface or the insulating substrate 1 are removed, by The step of this makes the release layer side surface of the copper foil of the attached release layer expose;Using etching by the copper foil from the exposing The step of release layer side surface removes and the barrier layer surface is made to expose;And the barrier layer of the exposing is gone using etching The step of removing, thus exposing the circuit in the embedment insulating substrate 2.

The present invention is a kind of manufacturing method of printing distributing board in another form, be using the present invention laminate and Manufacture printing distributing board.

The present invention is a kind of manufacturing method of e-machine in another form, is using the method system using the present invention The printing distributing board made and manufacture e-machine.

[Fa Mingxiaoguo ]

The copper foil of attached release layer according to the present invention, can make embedment circuit, and can favorably inhibit and make institute using etching It states when embedment circuit exposes and corrodes embedment circuit.

Description of the drawings

Fig. 1 is the forming method of the embedment circuit for the copper foil for indicating the attached release layer using one embodiment of the present invention The schematic diagram of a part.

Fig. 2 is the forming method of the embedment circuit for the copper foil for indicating the attached release layer using one embodiment of the present invention The schematic diagram of a part.

Fig. 3 is the forming method of the embedment circuit for the copper foil for indicating the attached release layer using one embodiment of the present invention The schematic diagram of a part.

Fig. 4 is the forming method of the embedment circuit for the copper foil for indicating the attached release layer using one embodiment of the present invention The schematic diagram of a part.

Fig. 5 is that another embodiment of the present invention on two surfaces of insulating substrate is respectively provided with the copper foil of attached release layer Laminate schematic diagram.

Specific implementation mode

The copper foil > of the attached release layers of <

Sequentially have release layer, copper foil and barrier layer.Copper foil is typically splashed with rolled copper foil or electrolytic copper foil or utilization The form of the copper foil of the dry type plating methods such as plating manufacture provides.In general, electrolytic copper foil is to keep copper electric from copper sulphate plating bath It parses to manufacturing on the drum of titanium or stainless steel, rolled copper foil is the plastic processing and heat treatment being repeated using stack And it manufactures.As the material of copper foil, except refined copper (JIS H3100 alloys number C1100) or oxygen-free copper (JIS H3100 alloys volume Number C1020 or JIS H3510 alloys number C1011) etc. other than high-purity coppers, also can be used and for example add the copper of Sn, be added The copper alloy of the copper of Ag, the copper alloy for being added to Cr, Zr or Mg etc., the inferior series copper alloy of card for being added to Ni and Si etc. etc.

The thickness of copper foil is not necessarily to be particularly limited to, for example, 0.1 μm or more and 100 μm or less, 1 μm or more and 1000 μm Below or 1 μm or more and 500 μm or less or 1 μm or more and 300 μm or less or 3 μm or more and 100 μm or less or 5 μm or more And 70 μm or less or 6 μm or more and 35 μm or less or 9 μm or more and 18 μm or less.

Barrier layer has dissolubility resistent to copper etchant, that is, has following property:For copper etchant (etching solution of copper), The speed for not readily dissolving or being etched than copper is slower than copper.The speed being etched refers to being etched the thickness of liquid erosion per unit time Degree.Such as the speed being etched can be calculated as follows.

Measure the quality W1 (g) of the sample before etching.Measure the quality W2 (g) of the sample after specific time t (s) is etched. Moreover, calculating the speed being etched using following formula.

Speed (μm/s)={ the quality W2 (g) of quality W1 (g) the ﹣ samples of the sample before the etching }/{ barrier layer being etched (g/ μm of density³Area that) × sample is etched (μm²) × etching period t (s) }

In addition, be etched described in measuring speed when, such as etching of the Sulfuric-acid-hydrogen-peroxide aqueous solution as copper can be used Liquid.

Have the barrier layer of dissolubility resistent, it is preferable to use C layers, Ni layers, Ti layers, Cr layers, V layers, Zr as to copper etchant Layer, Ta layers, Au layers, Pt layers, Os layers, Pd layers, Ru layers, Rh layers, Ir layers, W layers, or comprising containing Ni, Ti, V, Zr, Ta, Au, The layer of alloy more than any one of Pt, Os, Pd, Ru, Rh, Ir, W, Si and Cr, or comprising containing Ni, Ti, V, Zr, Ta, The layer etc. of more than any one of Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si and Cr carbide or oxide or nitride.Make To have the barrier layer of dissolubility resistent to copper etchant, more preferably by being selected from by Ni, Ti, Cr, titanium oxide, chromium oxide and carbon institute Any one of group of composition or two or more constituted barrier layers.In addition, because having the effect of being used as barrier layer, institute Preferably have selected from the layer by one or more of Ni layers, the Ti layers and Cr layers group formed with barrier layer.In addition, because more Have the effect as barrier layer, thus barrier layer be preferably selected from by Ni layers, the Ti layers and Cr layers group formed it is a kind of with On layer.In addition, because having the effect of that barrier layer, barrier layer is used as to be preferably selected from by Ni layers, Ti layers and Cr layers A kind of layer in the group formed.In addition, barrier layer is Ni layers preferred.In addition, barrier layer is Ti layers preferred.In addition, barrier layer is excellent Select Cr layers.

In addition, Ni layers or the alloy-layer comprising Ni are preferably formed as follows.The reason is that, Ni layers or the conjunction comprising Ni The surface of layer gold is smoothened, the barrier of the very thin layers of copper and/or layers of copper that are formed on described Ni layers or the alloy-layer comprising Ni Layer side and also smoothened, therefore the fine circuits formative of very thin layers of copper and/or layers of copper with surface that barrier layer is opposite side It is promoted.

The formation of Ni layers or alloy-layer comprising Ni

Ni layers or the alloy-layer comprising Ni can be formed by carrying out nickel plating or comprising the alloy plating of nickel.At this point, weight What is wanted is finally to be processed into cause dense and uniform and do not have defective plating.As nickel plating or comprising the alloy plating of nickel, with It is carried out under conditions of lower.

Plating liquid

Nickel:20~200g/L

Other elements:0.1~200g/L (only in the case of the alloy plating comprising nickel)

Boric acid:5~60g/L

Liquid temperature:40~65 DEG C

PH value:1.5~5.0, preferably 2.0~3.0.Plating is periodically carried out by keeping pH value relatively low, is generated Hydrogen and cathode surface become reducing environment.Therefore, it can inhibit and generate the generation moisture such as oxide, hydroxide, hydrate Reason element.

Current density:0.5~20A/dm², preferably 2~8A/dm².It is preferred that being handled with low current density, because being not easy Lead to coarse plating, becomes that defect is few and fine and close plating.

It stirs (liquid circulation amount)

100~1000L/ minutes.The defects of liquid circulation amount can mostly make the gas disengaging of the hydrogen of generation improve, pin hole becomes It is few.In addition, having the effect of reducing thickness of diffusion layer, it can inhibit and generate the reason of hydroxide etc. generates moisture element.

Carry out the conveyance speed of the object of plating

2~30m/ minutes, preferably 5~10m/ minutes.Conveyance speed can make smooth and fine and close Ni layers or comprising nickel slowly Alloy-layer is formed.

Additive

It is preferable to use a gloss agent below and secondary gloss agents for additive.It crystallizes as a result, smoothened and fine and close.Cause This, the defect that plating generates is reduced, and the absorption of moisture is reduced.

(gloss agent)

1-5 naphthalenes-sodium disulfonate:2~10g/L, 1-3-6 naphthalene-sodium trisulfonate:10~30g/L, to toluene sulfone-amide:0.5 ~4g/L, saccharin sodium:Any one of 0.5~5g/L.

(secondary gloss agent)

Formalin:0.5~5g/L, gelatin:0.005~0.5g/L, thiocarbamide:0.05~1.0g/L, propargyl alcohol:0.01~ 0.3g/L, 1-4 butynediols:0.05~0.5g/L, ethylene cyanohydrin (ethylene cyanohydrin):In 0.05~0.5g/L It is any.

The lower limit of the thickness of barrier layer is not necessarily to be particularly limited to, for example, be alternatively 0.001 μm or more, preferably 0.01 μm with It is upper and then preferably 0.05 μm or more.In addition, the upper limit of the thickness of barrier layer is not necessarily to be particularly limited to, such as it is alternatively 10 μm Below, preferably 5 μm or less and then preferably 1 μm or less.

The copper foil of attached release layer about the present invention, in the circuit forming surface of copper foil, in a manner of covering the circuit Laminated resin and after forming embedment circuit, when being removed the copper foil using etching and embedment circuit being made to expose, because having pair Copper etchant has the barrier layer of dissolubility resistent, so not corroded because of the etching of copper foil to the worry of embedment circuit.

The release layer of the copper foil of the attached release layer of the present invention can will utilize crimping etc. to make the branch such as resin base material from release layer side Hold the stripping of the supports such as resin base material when showing consideration for conjunction.At this point, the supports such as resin base material pass through demoulding layer separation with copper foil.

(1) silane compound

Release layer can also give birth to the hydrolysis of silane compound or the silane compound with the structure represented by following formula Condensation product (making silane compound hereinafter, being abbreviated) independent or multiple combinations of substance are generated at substance or the hydrolysis and are formed.

Formula:

(in formula, R¹For alkoxy or halogen atom, R²For the hydrocarbon in the group being made of alkyl, naphthenic base and aryl The alkyl that base or more than one hydrogen atom are substituted with halogen atoms, R³And R⁴It is separately halogen atom or alcoxyl Base or alkyl in the group being made of alkyl, naphthenic base and aryl or more than one hydrogen atom are taken by halogen atom The alkyl in generation).

The silane compound must have at least one alkoxy.There is no alkoxy and only by be selected from by alkyl, Alkyl or more than one hydrogen atom in the group that naphthenic base and aryl are formed be substituted with halogen atoms these in any hydrocarbon In the case that base constitutes substituent group, has the tendency that the adhesion excessive descent of resin substrate and copper foil.In addition, the silane chemical combination Object must have at least one alkyl in the group being made of alkyl, naphthenic base and aryl or more than one hydrogen atom Be substituted with halogen atoms these in any alkyl.The reason is that, there is no the alkyl, have resin substrate with The tendency that the adhesion of copper foil rises.In addition, the alkoxy of present invention is also including more than one hydrogen atom by halogen The alkoxy of atom substitution.

There are three alkoxy, alkyl (including more than one hydrogen atom quilts for the preferred tool of the silane compound The alkyl of halogen atom substitution).Above formula carrys out word, refers to R³And R⁴The two is alkoxy.

As alkoxy, do not limit, can enumerate methoxyl group, ethyoxyl, just or isopropoxy, just, exclusive or tert-butoxy, Just, straight-chains, the branched or cricoid such as exclusive or neopentyl oxygen, positive hexyloxy, cyclohexyloxy, positive oxygroup in heptan and n-octyloxy The alkoxy of carbon number 1~20, preferably carbon number 1~10, more preferable carbon number 1~5.

As halogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom can be enumerated.

As alkyl, do not limit, can enumerate methyl, ethyl, just or isopropyl, just, exclusive or tertiary butyl, just, exclusive or it is new The straight-chains such as amyl, n-hexyl, n-octyl, positive decyl or the carbon number 1~20 of branched, preferably carbon number 1~10, more preferable carbon number 1~5 alkyl.

It as naphthenic base, does not limit, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl etc. can be enumerated The naphthenic base of carbon number 3~10, preferably carbon number 5~7.

As aryl, phenyl can be enumerated, through alkyl-substituted phenyl (example:Tolyl, xylyl), 1- or 2- naphthalenes, The aryl of the carbon numbers such as anthryl 6~20, preferably 6~14.

These alkyl also can more than one hydrogen atom be substituted with halogen atoms, such as can be by fluorine atom, chlorine atom or bromine Atom replaces.

As the example of preferred silane compound, methyltrimethoxysilane, ethyl trimethoxy silane, just can be enumerated Or isopropyltri-methoxysilane, just, exclusive or tert-butyl trimethoxy silane, just, exclusive or neopentyl trimethoxy silane, hexyl Trimethoxy silane, octyl trimethoxy silane, ruthenium trimethoxysilane, phenyltrimethoxysila,e;Alkyl-substituted phenyl Trimethoxy silane (for example, to (methyl) phenyltrimethoxysila,e), methyltriethoxysilane, ethyl triethoxy silicane Alkane, just or isopro-pyltriethoxysilane, just, exclusive or t-butyltriethoxysilane, amyl triethoxysilane, three second of hexyl Oxysilane, octyltri-ethoxysilane, ruthenium triethoxysilane, phenyl triethoxysilane, three second of alkyl-substituted phenyl Oxysilane (for example, to (methyl) phenyl triethoxysilane), (3,3,3- trifluoro propyl) trimethoxy silane and ten trifluoros Octyltri-ethoxysilane, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, phenyl trichlorosilane, trimethyl The condensation product of silicon fluoride, two bromo-silicane of dimethyl, dibromodiphenyl silane, these hydrolysate and these hydrolysate Deng.Among these, for the viewpoint for obtaining easiness, preferably propyl trimethoxy silicane, methyltriethoxysilane, hexyl Trimethoxy silane, phenyl triethoxysilane, ruthenium trimethoxysilane.

(2) intramolecular has the compound of 2 sulfydryls below

Release layer can also be used intramolecular to have the compound of 2 sulfydryls below and constitute.

As the intramolecular have 2 sulfydryls below compound, can enumerate mercaptan, two mercaptan, thionothiolic acid or its Salt, dithiocarboxylic acid or its salt, thiosulfonic acid or its salt and two thiosulfonic acids or its salt can be used selected from least one of these.

Mercaptan has in the molecule there are one sulfydryl, such as is indicated by R-SH.Here, R expressions also may include hydroxyl or amido Fatty family or aromatic system alkyl or heterocycle.

Two mercaptan have in the molecule there are two sulfydryl, such as by R (SH)₂It indicates.R indicates also to may include hydroxyl or amido Fatty family or aromatic system alkyl or heterocycle.It, also can be with mutually not phase in addition, two sulfydryls can be bonded with identical carbon respectively Same carbon or nitrogen bond.

Thionothiolic acid is that the hydroxyl of organic carboxyl acid is replaced by sulfydryl, such as is indicated by R-CO-SH.R expressions also may include The fatty family or aromatic system alkyl or heterocycle of hydroxyl or amido.In addition, thionothiolic acid can also salt form use.This Outside, tool also can be used, and there are two the compounds of thionothiolic acid base.

Dithiocarboxylic acid is that two oxygen atoms in the carboxyl of organic carboxyl acid are replaced by Sulfur atom, such as by R- (CS)-SH is indicated.R indicates the fatty family that also may include hydroxyl or amido or aromatic system alkyl or heterocycle.In addition, two sulphur Carboxylic acid can also salt form use.In addition, tool also can be used, there are two the compounds of dithiocarboxylic acid base.

Thiosulfonic acid is that the hydroxyl of organic sulfonic acid is replaced by sulfydryl, such as by R (SO₂)-SH expressions.R expressions can also wrap The fatty family or aromatic system alkyl or heterocycle of hydroxyl or amido.In addition, thiosulfonic acid can also salt form use.

Two thiosulfonic acids are that two hydroxyls of organic-disulfonate are replaced by sulfydryl respectively, such as by R- ((SO₂)-SH)₂Table Show.R indicates the fatty family that also may include hydroxyl or amido or aromatic system alkyl or heterocycle.In addition, two sulphur acidic groups It can be bonded with identical carbon, can be also bonded from mutual different carbon respectively.In addition, two thiosulfonic acids can also salt form use.

Here, as suitable for the fatty family alkyl as R, alkyl, naphthenic base can be enumerated, these alkyl also may include hydroxyl Either one or two of base and amido.

In addition, as alkyl, do not limit, can enumerate methyl, ethyl, just or isopropyl, just, exclusive or tertiary butyl, just, it is different Or the straight-chains such as neopentyl, n-hexyl, n-octyl, positive decyl or the carbon number 1~20 of branched, preferred carbon number 1~10, more preferably The alkyl of carbon number 1~5.

In addition, as naphthenic base, do not limit, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring can be enumerated The naphthenic base of the carbon numbers such as octyl 3~10, preferably carbon number 5~7.

In addition, as suitable for the aromatic hydrocarbyl as R, phenyl can be enumerated, through alkyl-substituted phenyl (example:Tolyl, Xylyl), the aryl of 1- or 2- naphthalenes, the carbon numbers 6~20, preferably 6~14 such as anthryl, these alkyl also may include hydroxyl and amine Either one or two of base.

In addition, as suitable for the heterocycle as R, imidazoles, triazole, tetrazolium, benzimidazole, benzotriazole, thiophene can be enumerated Azoles, benzothiazole, also may include either one or two of hydroxyl and amido.

The preferred example as intramolecular with the compound of 2 sulfydryls below can enumerate 3- sulfydryls -1,2 the third two Alcohol, 2 mercapto ethanol, 1,2- dimercaptoethylsulfides, 6- sulfydryl -1- hexanols, 1- octanethiols, 1- dodecyl mercaptans, 10- hydroxyls -1- Dodecyl mercaptans, 10- carboxyl -1- dodecyl mercaptans, 10- amido -1- dodecyl mercaptans, 1- dodecyl mercaptans sodium sulfonate, benzene sulphur Phenol, thiobenzoate, 4- amidos-benzenethiol, to toluenethiol, 2,4- dimethylbenzene thiols, -1,2,4 triazole of 3- sulfydryls, 2- mercaptos Base-benzothiazole.Among these, for the viewpoint in terms of water-soluble and offal treatment, preferred 3- sulfydryls -1,2 propylene glycol.

(3) metal alkoxide

Release layer also can be by the aluminate compound with the structure represented by following formula, titanate compound, zirconic acid salinization The hydrolysis for closing object or these compounds generates the condensation product of substance or the hydrolysis generation substance (hereinafter, brief note makees metal alkane Oxide) it is independent or it is multiple combination and constitute.

(R¹)_m-M-(R²)_n

In formula, R¹For alkoxy or halogen atom, R²For the hydrocarbon in the group being made of alkyl, naphthenic base and aryl The alkyl that base or more than one hydrogen atom are substituted with halogen atoms, M Al, Ti or Zr, n 0,1 or 2, m are 1 or more And the valence mumber integer below of M, R¹It is at least one be alkoxy.M+n is the valence mumber of M, that is, when for Al be 3, when for Ti, It is 4 when Zr.

The metal alkoxide must have at least one alkoxy.There is no alkoxy and only by being selected from by alkane Alkyl or more than one hydrogen atom in the group that base, naphthenic base and aryl are formed be substituted with halogen atoms these in it is any In the case that alkyl constitutes substituent group, has the tendency that the adhesion excessive descent of resin substrate and copper foil.In addition, the metal alkane Oxide must have 0~2 alkyl in the group being made of alkyl, naphthenic base and aryl or more than one hydrogen former Son be substituted with halogen atoms these in any alkyl.The reason is that, with 3 or more the alkyl, have The tendency of the adhesion excessive descent of resin substrate and copper foil.In addition, the alkoxy of present invention also includes more than one The alkoxy that is substituted with halogen atoms of hydrogen atom.The peel strength of resin substrate and copper foil is just adjusted to the side of the range For face, the metal alkoxide preferably with more than two alkoxies and with alkyl described in one or two (including The alkyl that more than one hydrogen atom is substituted with halogen atoms).

In addition, as suitable for as R²Aromatic hydrocarbyl, phenyl can be enumerated, through alkyl-substituted phenyl (example:Toluene Base, xylyl), the aryl of 1- or 2- naphthalenes, the carbon numbers 6~20, preferably 6~14 such as anthryl, these alkyl also may include hydroxyl Either one or two of with amido.

As the example of preferred aluminate compound, aluminium methoxide, methyl dimethoxy oxygroup aluminium, ethyl diformazan can be enumerated Oxygroup aluminium, just or isopropyl dimethoxy aluminium, just, exclusive or tertiary butyl dimethoxy aluminium, just, exclusive or neopentyl dimethoxy aluminium, Hexyl dimethoxy aluminium, octyl dimethoxy aluminium, decyl dimethyl oxygroup aluminium, phenyl dimethoxy aluminium;Alkyl-substituted phenyl diformazan Oxygroup aluminium (for example, to (methyl) phenyl dimethoxy aluminium), dimethyl aluminum methoxide, aluminium ethoxide, methyl diethoxy aluminium, Ethyl diethoxy aluminium, just or isopropyl diethoxy aluminium, just, exclusive or tertiary butyl diethoxy aluminium, amyl diethoxy aluminium, oneself Base diethoxy aluminium, octyl diethoxy aluminium, decyl diethoxy aluminium, diethylamino phenyl oxygroup aluminium, alkyl-substituted phenyl diethoxy Base aluminium (for example, to (methyl) diethylamino phenyl oxygroup aluminium), dimethyl aluminum ethoxide, aluminium isopropoxide, methyl diisopropoxy Aluminium, ethyl diisopropoxy aluminium, just or isopropyl diethoxy aluminium, just, exclusive or tertiary butyl diisopropoxy aluminium, amyl diisopropyl Oxygroup aluminium, hexyl diisopropoxy aluminium, octyl diisopropoxy aluminium, decyl diisopropoxy aluminium, phenyl diisopropoxy aluminium, alkane Base substituted-phenyl diisopropoxy aluminium (for example, to (methyl) phenyl diisopropoxy aluminium), dimethyl aluminum isopropoxide, (3,3, 3- trifluoro propyls) dimethoxy aluminium and ten trifluoro octyl diethoxy aluminium, methyl dichloro aluminium, dimethyl chloride aluminium, dimethyl chloride Aluminium, phenyl dichloro aluminium, dimethyl fluorine aluminium, diformazan bromide aluminium, hexichol bromide aluminium, these hydrolysate and these hydrolysis production The condensation product etc. of object.Among these, for the viewpoint for obtaining easiness, preferably aluminium methoxide, aluminium ethoxide, three isopropyls Oxygroup aluminium.

As the example of preferred titanate compound, titanium tetramethoxide, methyl trimethoxy oxygroup titanium, ethyl front three can be enumerated Oxygroup titanium, just or isopropyl trimethoxy titanium, just, exclusive or tertiary butyl trimethoxy titanium, just, exclusive or neopentyl trimethoxy titanium, Hexyl trimethoxy titanium, octyl trimethoxy titanium, decyl trimethoxy titanium, phenyl trimethoxy titanium;Alkyl-substituted phenyl front three Oxygroup titanium (for example, to (methyl) phenyl trimethoxy titanium), dimethylformamide dimethyl oxygroup titanium, purity titanium tetraethoxide, methyl triethoxy Titanium, ethyl triethoxy titanium, just or isopropyl triethoxy titanium, just, exclusive or tertiary butyl triethoxy titanium, amyl triethoxy Titanium, hexyl triethoxy titanium, octyl triethoxy titanium, decyl triethoxy titanium, phenyl triethoxy titanium, alkyl-substituted phenyl three Ethanolato-titanium (for example, to (methyl) phenyl triethoxy titanium), dimethyl diethoxy titanium, tetraisopropoxy titanium, methyl three are different Titanium propanolate, three titanium isopropoxide of ethyl, just or isopropyl triethoxy titanium, just, three titanium isopropoxide of exclusive or tertiary butyl, amyl Three titanium isopropoxides, three titanium isopropoxide of hexyl, three titanium isopropoxide of octyl, three titanium isopropoxide of decyl, three isopropyl oxygen of phenyl Base titanium, three titanium isopropoxide of alkyl-substituted phenyl (for example, to three titanium isopropoxide of (methyl) phenyl), dimethyl diisopropoxy Titanium, (3,3,3- trifluoro propyls) trimethoxy titanium and ten trifluoro octyl triethoxy titaniums, methyl trichlorine titanium, dimethyl dichloro titanium, Trimethyl chlorine titanium, phenyl trichlorine titanium, dimethyl difluoro titanium, dimethyl dibromo titanium, diphenyl dibromo titanium, these hydrolysate, And the condensation product etc. of these hydrolysate.Among these, for the viewpoint for obtaining easiness, preferably titanium tetramethoxide, four Ethanolato-titanium, tetraisopropoxy titanium.

As the example of preferred zirconate compounds, tetramethoxy zirconium, methyl trimethoxy oxygroup zirconium, ethyl front three can be enumerated Oxygroup zirconium, just or isopropyl trimethoxy zirconium, just, exclusive or tertiary butyl trimethoxy zirconium, just, exclusive or neopentyl trimethoxy zirconium, Hexyl trimethoxy zirconium, octyl trimethoxy zirconium, decyl trimethoxy zirconium, phenyl trimethoxy zirconium;Alkyl-substituted phenyl front three Oxygroup zirconium (for example, to (methyl) phenyl trimethoxy zirconium), dimethylformamide dimethyl oxygroup zirconium, tetraethoxy zirconium, methyl triethoxy Zirconium, ethyl triethoxy zirconium, just or isopropyl triethoxy zirconium, just, exclusive or tertiary butyl triethoxy zirconium, amyl triethoxy Zirconium, hexyl triethoxy zirconium, octyl triethoxy zirconium, decyl triethoxy zirconium, phenyl triethoxy zirconium, alkyl-substituted phenyl three Ethyoxyl zirconium (for example, to (methyl) phenyl triethoxy zirconium), dimethyl diethoxy zirconium, zirconium tetraisopropoxide, methyl three are different Propoxyl group zirconium, three isopropoxy zirconium of ethyl, just or isopropyl triethoxy zirconium, just, three isopropoxy zirconium of exclusive or tertiary butyl, amyl Three isopropoxy zirconiums, three isopropoxy zirconium of hexyl, three isopropoxy zirconium of octyl, three isopropoxy zirconium of decyl, three isopropyl oxygen of phenyl Base zirconium, three isopropoxy zirconium of alkyl-substituted phenyl (for example, to three titanium isopropoxide of (methyl) phenyl), dimethyl diisopropoxy Zirconium, (3,3,3- trifluoro propyls) trimethoxy zirconium and ten trifluoro octyl triethoxy zirconiums, methyl trichlorine zirconium, dimethyl dichloro zirconium, Trimethyl chlorine zirconium, phenyl trichlorine zirconium, dimethyl difluoro zirconium, dimethyl dibromo zirconium, diphenyl dibromo zirconium, these hydrolysate, And the condensation product etc. of these hydrolysate.Among these, for the viewpoint for obtaining easiness, preferably tetramethoxy zirconium, four Ethyoxyl zirconium, zirconium tetraisopropoxide.

(4) release layer being made of resin coating film

Using by silicone and selected from epoxy system resin, melamine series resin and fluororesin any one or more of Resin substrate is bonded with copper foil, thus moderately adhesion can be made to reduce by the resin coating film that resin is constituted, and will remove strong Degree is adjusted to the range as aftermentioned.

It is this realizing that the adjusting of the peel strength of adhesion by silicone and is selected from by the use as aftermentioned Resin coating film that epoxy system resin, melamine series resin and fluororesin any one or more of resin are constituted and carry out. The reason is that, the baking for carrying out the specified conditions as aftermentioned to this resin coating film is handled, it to be used for resin substrate and copper foil Between, it carries out hot pressing and is bonded, thus so that adhesion is reduced, and peel strength is adjusted to the range.

As epoxy system resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, nobolak type epoxy tree can be enumerated Fat, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, bisphenol-A epoxy resin, phenoxy resin, bromination Phenoxy resin etc..

As melamine series resin, can enumerate methyl etherified melamine resin, butylated urea melmac, Butylated melamine resins, methylated melamine resins, butyl alcohol modified melamine resin etc..In addition, melamine It is the hybrid resin that resin is alternatively the resin and butylated urea resins, butylation benzoguanamine resin etc..

In addition, the number average molecular weight of epoxy system resin preferably 2000~3000, the quantity of melamine series resin is flat Average molecular weight preferably 500~1000.It by with this number average molecular weight, and can realize the coating of resin, and hold The Bonding strength of resin coating film is easily adjusted to particular range.

In addition, as fluororesin, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride can be enumerated Deng.

As silicone, methyl phenyl silicone, methylhydrogenpolysi,oxane, dimethyl polysiloxane, modified two can be enumerated Methyl polysiloxane, these mixture etc..Here, so-called modification, such as epoxy-modified, alkyl-modified, amido can be enumerated and changed Property, carboxy-modified, alcohol is modified, fluorine richness, alkyl aralkyl is polyether-modified, epoxidized polyether is modified, polyether-modified, alkyl higher alcohol Ester modified, polyester modification, acyloxyallcyl are modified, halogenated alkyl acyloxyallcyl is modified, halogenated alkyl is modified, amido ethylene glycol Modified, sulfhydryl modified polyester modification etc. containing hydroxyl.

About resin coating film, if film thickness is too small, resin coating film is excessively thin and is difficult to be formed, therefore productivity is easy drop It is low.In addition, even if film thickness has not seen the further promotion of the fissility of resin coating film if being more than fixed size, resin coating film Manufacturing cost is easy to get higher.For this viewpoint, preferably 0.1~10 μm of the film thickness of resin coating film, and then preferably 0.5~5 μm. In addition, the film thickness of resin coating film is by being reached with specific coating weight coating cold coating in aftermentioned program.

In resin coating film, silicone is functioned as the remover of resin coating film.Therefore, if epoxy system resin, three The total amount of paracyanogen amine system resin is excessive compared with silicone, then between resin substrate and copper foil, stripping that resin coating film is assigned Become larger from intensity, therefore the fissility of resin coating film reduces, it is sometimes easily peelable not allow by hand.On the other hand, if epoxy Resin, the total amount of melamine series resin are very few, then the peel strength becomes smaller, therefore sometimes in the copper foil of attached release layer Conveyance when or processing when remove.For this viewpoint, preferably with relative to 100 mass parts of silicone, epoxy system resin, trimerization The amount for adding up to 10~1500 mass parts of cyanamide system resin contains the ingredient, and then preferably with the amount of 20~800 mass parts Contain.

In addition, fluororesin functions in the same manner as silicone as remover, having makes the heat resistance of resin coating film be promoted Effect.If fluororesin is excessive compared with silicone, the peel strength becomes smaller, therefore sometimes in the conveyance of laminate Or removed when processing, in addition, the temperature needed for aftermentioned baking procedure improves, therefore become uneconomical.For this viewpoint, fluorine Resin is relative to 100 mass parts of silicone, preferably 0~50 mass parts, and then preferably 0~40 mass parts.

In resin coating film, in addition to fluororesin except silicone and epoxy resin and/or melmac and optionally, It can further contain and be selected from SiO₂,MgO,Al₂O₃,BaSO₄And Mg (OH)₂One or more of roughing in surface particle.Pass through tree Fat film contains roughing in surface particle, and the surface of resin coating film becomes concave-convex.By the bumps, and it is coated with resin coating film Resin substrate or the surface of copper foil become concave-convex, and become frosting.About the content of roughing in surface particle, as long as making tree Fat film is further provided for contouring, is not particularly limited, relative to 100 mass parts of silicone, preferably 1~10 mass parts.

Preferred 15nm~4 μm of grain size of roughing in surface particle.Here, grain size refers to according to scanning electron microscope (SEM) The average grain diameter (average value of maximum particle diameter and minimum grain size) that photo etc. measures.Grain size by roughing in surface particle is described Range, and it is easily adjusted the concavo-convex amount on the surface of resin coating film, as a result it is easily adjusted the bumps on the surface of resin substrate or copper foil Amount.Specifically, the concavo-convex amount on the surface of resin substrate or copper foil becomes 4.0 μ in terms of maximum height roughness Ry as defined in JIS M or so.

Here, the manufacturing method to laminate illustrates.

The copper foil of the attached release layer is obtained via the program with following steps:Resin substrate or copper foil at least One surface is coated with the step of resin coating film;With the baking procedure for making the resin coating film of the coating harden.Hereinafter, to each step Suddenly it illustrates.

(application step)

The step of application step is the one or two sides coating cold coating in resin substrate and forms resin coating film, it is described Cold coating is by the silicone as host agent, the epoxy system resin as curing agent, melamine series resin and conduct optionally The fluororesin of remover is constituted.Cold coating be in the organic solvents such as alcohol dissolve epoxy system resin, melamine series resin, Fluororesin and silicone form.In addition, the blended amount (additive amount) in cold coating is preferably with respect to 100 mass parts of silicone, epoxy It is that resin, melamine series resin add up to 10~1500 mass parts.In addition, fluororesin is preferably with respect to 100 mass of silicone Part, it is 0~50 mass parts.

As the coating method in application step, as long as resin coating film can be formed, it is not particularly limited, is applied using intaglio plate Cloth method, rod coating method, print roll coating method, showering curtain type plane rubbing method, the method etc. using electrostatic atomizer, with regard to resin coating film Uniformity and operation convenience viewpoint for, preferred gravure coating process.In addition, about coating weight, as amount of resin, preferably 1.0~2.0g/m², so that resin coating film 3 becomes preferred film thickness:0.5~5 μm of mode.

Gravure coating process is to be transferred to resin base by making the cold coating filled up in the recess portion (slot) of roller surface is arranged Plate, and the method for forming resin coating film on the surface of resin substrate.It specifically, will be under the lower side roller that surface is provided with slot Portion is immersed in cold coating, and the rotation by lower side roller will be drawn onto on cold coating in slot.Moreover, existing in lower side roller and configuration Resin substrate is configured between the upper side roller of the upside of lower side roller, resin substrate is pressed against lower side roller using upper side roller on one side, one While lower side roller and upper side roller is made to rotate, resin substrate is thus transported, and is drawn onto the cold coating transfer (coating) in slot by To the single side of resin substrate.

In addition, by moving in side in resin substrate, scraper is configured in a manner of being contacted with the surface of lower side roller, and will be upper The extra cold coating for being drawn onto the roller surface other than slot is removed, and the resin to be coated with specific quantity on the surface of resin substrate applies Material.In addition, in the case of viscosity height in the case where the number (size and depth) of slot is big or in cold coating, it is formed in tree The resin coating film of the single side of aliphatic radical plate is not easy smoothened.Therefore, also flat roll can be configured in the side that moves out of resin substrate, with dimension Hold the smoothness of resin coating film.

In addition, in the case where the two sides of resin substrate forms resin coating film, forms resin in the single side of resin substrate and apply After film, resin substrate is overturn, and is configured again between lower side roller and upper side roller.Moreover, with it is described in the same manner as, by lower side roller Slot in cold coating transfer (coating) to resin substrate the back side.

(baking procedure)

Baking procedure is to implement 125~320 DEG C (baking temperatures) and 0.5~60 to the resin coating film formed in application step The step of baking processing of second (baking time).As described above, passing through the tree formed to the cold coating by specific blended amount Fat film implements the baking processing of specified conditions, and by the peel strength between the resin substrate and copper foil that are assigned by resin coating film Control is in particular range.In the present invention, baking temperature is the limiting temperature of resin substrate.In addition, being handled as baking Heating means, use known device.

Baking become inadequate condition, for example baking temperature not up to 125 DEG C or baking time not up to 0.5 second the case where Under, resin coating film becomes under-ageing, and the peel strength is more than 200gf/cm, and fissility reduces.In addition, in overbaking Condition, in the case that for example baking temperature is more than 320 DEG C, resin coating film deterioration, the peel strength is more than 200gf/cm, and Workability when stripping is deteriorated.Alternatively, the situation for having resin substrate rotten because of high temperature.In addition, being more than 60 seconds in baking time In the case of, productivity is deteriorated.

In the manufacturing method of laminate, the cold coating of the application step is alternatively by silicone, the work as host agent For the epoxy resin of curing agent, melamine series resin, as the fluororesin of remover and selected from SiO₂,MgO,Al₂O₃, BaSO₄And Mg (OH)₂One or more of the cold coating that is constituted of roughing in surface particle.

Specifically, cold coating is in the silicone adds resin solution and then addition roughing in surface particle forms. It is added in cold coating by by this roughing in surface particle, and the surface of resin coating film is made to become concave-convex, passes through institute Stating bumps makes resin substrate or copper foil become concave-convex, and becomes frosting.Moreover, this with frosting in order to obtain Resin substrate or copper foil, the blended amount (additive amount) of the roughing in surface particle in preferred resin coating is relative to 100 mass of silicone Part is 1~10 mass parts.In addition, the grain size of preferred roughing in surface particle is 15nm~4 μm in turn.

The manufacturing method of the present invention is as discussed above, but when carrying out the present invention, will not be to each step Suddenly, also can be between each step or front and back in the range of causing harmful effect, including other steps.For example, can also apply The cleaning step cleaned to the surface of resin substrate is carried out before cloth step.

In addition, the release layer of the present invention is alternatively with selected from the group being made of alloy, metal, organic matter and inorganic matter One or more of layer.As the alloy, metal, organic matter, inorganic matter, it is possible to use described in the description of the present application Alloy, metal, organic matter or inorganic matter.

It can be laminated on the support or resin (aftermentioned insulating substrate 1) of the release layer side of the copper foil of attached release layer

As well known resin can be used laminated on the resin of the release layer side of the copper foil of attached release layer.In addition, described Aftermentioned resin layer can be used in resin.In addition, as can be laminated on the resin of the release layer side of the copper foil of attached release layer, without special Limitation, can be used all resins.In addition, as can be laminated on the resin of the release layer side of the copper foil of attached release layer, such as can make With phenol resin, polyimide resin, epoxy resin, fluororesin, liquid crystal polymer resin, cyclic olefin polymerization resin, polyethylene Resin, polyethylene terephthalate resin, vinyl chloride resin, natural rubber, rosin etc..In addition, can be laminated on attached release layer Copper foil release layer side the preferred thermosetting resin of resin.In addition, as can be laminated on the demoulding of the copper foil of attached release layer The resin of layer side, it is possible to use prepreg.Prepreg before being bonded with copper foil is preferably in the prepreg of the state of B-stage.Such as The linear expansion coefficient of fruit prepreg (C-stage) is 12~18 (× 10^-6/ DEG C), then with the copper foil of the constituent material as substrate 16.5(×10^-6/ DEG C) or SUS pressboards 17.3 (× 10^-6/ DEG C) almost equal, therefore before and after being not likely to produce because of compacting The substrate size phenomenon (dimensional variation) different from substrate size when design caused by circuit position offset in terms of have Profit.In turn, as the synergistic effect of these advantages, the very thin coreless substrate of multilayer can also be produced.Prepreg used herein can From constitute circuit board prepreg it is identical also can be different.

About the prepreg, maintains for the viewpoint of optimum range with regard to by the peel strength after heating, preferably have High glass transition temperature Tg, for example, 120~320 DEG C, preferably 170~240 DEG C of glass transition temperature Tg.In addition, glass turns It moves temperature Tg and is set as the value measured using DSC (differential scanning thermal measurement method).

It is also desirable to which the coefficient of thermal expansion of resin or prepreg or support is+the 10% of the coefficient of thermal expansion of copper foil And within -30%.It can be effectively prevented the position offset of the circuit of the thermal expansion difference due to copper foil and resin as a result, and can So that defective products is generated reduction, makes Yield lmproved.As support, it is possible to use metallic plate or metal foil.

The thickness of resin or support is not particularly limited.In addition, resin or support can be rigidity or flexibility.This Outside, if the thickness of resin or support is blocked up, harmful effect can be caused to the heat distribution in hot pressing, on the other hand, if It is excessively thin, then it is bent sometimes and makes the manufacturing step of printing distributing board that can not carry out, therefore the thickness of resin or support is usual It is preferred that 5 μm or more and 1000 μm or less.In addition, more preferable 50 μm of thickness of resin or support or more and 900 μm are hereinafter, in turn More preferable 100 μm or more and 400 μm or less.

< laminates >

The copper foil of the attached release layer of the present invention can be used to make laminate (copper-cover laminated body etc.).

The laminate of copper foil as the attached release layer for using the present invention, such as it is alternatively sequentially lamination " support or tree The composition of fat or prepreg/release layer/copper foil/barrier layer ".

The support or resin or prepreg can be aftermentioned resin layer, also may include the resin for aftermentioned resin layer, Hardening of resin agent, compound, hardening accelerator, dielectric substance, catalysts, crosslinking agent, polymer, prepreg, framework material Deng.In addition, the copper foil of attached release layer can also be less than support or resin or prepreg when looking down.

< roughening treatments and other surface treatments >

In the copper foil with the copper foil on surface or attached release layer that copper foil is opposite side of the barrier layer of the copper foil of attached release layer Between barrier layer, such as also can roughening treatment layer be set by implementing roughening treatment, so that with insulating substrate or resin Adhesion is good.Roughening treatment for example can form roughening particle by using copper or copper alloy and carry out.Roughening treatment is alternatively Fine roughening treatment.Roughening treatment layer is alternatively by being selected from by Cu (copper), Ni (nickel), P (phosphorus), W (tungsten), As (arsenic), Mo Any one of the group that (molybdenum), Cr (chromium), Ti (titanium), Fe (iron), V (vanadium), Co (cobalt) and Zn (zinc) are formed monomer contains The layer etc. that the alloy of any the above simple substance is constituted.In addition, also can after forming roughening particle using copper or copper alloy, And then it carries out that offspring or the roughening treatment of particle three times is arranged using nickel, cobalt, copper, the simple substance of zinc or alloy etc..Later, Using nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum simple substance and/or Alloy and/or oxide and/or nitride and/or silicide etc. form refractory layer or antirust coat, also can be in turn to described heat-resisting Implement the processing such as chromic acid salt treatment, silane coupled processing in the surface of layer or antirust coat.Alternatively, also can without roughening treatment, and Utilize nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, the simple substance of tantalum and/or conjunction Gold and/or oxide and/or nitride and/or silicide etc. form refractory layer or antirust coat, and then to the refractory layer or prevent Implement the processing such as chromic acid salt treatment, silane coupled processing in the surface of rusty scale.It is selected from that is, can also be formed on the surface of roughening treatment layer The layer of one or more of the group being made of refractory layer, antirust coat, chromating layer and silane coupled process layer, also can be The barrier layer of the copper foil of attached release layer with copper foil and the barrier layer of the copper foil on surface or attached release layer that copper foil is opposite side it Between, it is formed selected from one or more of the group being made of refractory layer, antirust coat, chromating layer and silane coupled process layer Layer.In addition, also can be in the copper foil with surface or attached release layer that copper foil is opposite side of the barrier layer of the copper foil of attached release layer Copper foil and barrier layer between, formed selected from by roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupled The layer of one or more of the group that process layer is formed.In addition, also can between the copper foil and release layer of the copper foil of attached release layer, It is formed selected from one or more of the group's being made of refractory layer, antirust coat, chromating layer and silane coupled process layer Layer.The refractory layer is alternatively layers of copper.The antirust coat is alternatively layers of copper.In addition, at the refractory layer, antirust coat, chromate Reason layer, silane coupled process layer can also form (such as 2 layers or more, 3 layers with first-class) by multiple layers respectively.

For example, as roughening treatment copper-cobalt-nickel alloy plating can by electrolytic coating formed as adhesion amount be 15~ 40mg/dm²Copper -100~3000 μ g/dm²Cobalt -100~1500 μ g/dm²Nickel as 3 yuan be alloy-layer mode it is real It applies.If Co adhesion amounts are not up to 100 μ g/dm², then have heat resistance be deteriorated and etching be deteriorated the case where.If Co adhesion amounts are super Cross 3000 μ g/dm², then not preferably in the case where must take into consideration effect of magnetic influence, there is generation etching spot and acid resistance and resistance to The case where chemicals are deteriorated.If Ni adhesion amounts are not up to 100 μ g/dm², then have the case where heat resistance variation.On the other hand, such as Fruit Ni adhesion amounts are more than 1500 μ g/dm², then etch residue becomes more situations.Preferred Co adhesion amounts are 1000~2500 μ g/ dm², preferred nickel adhesion amount is 500~1200 μ g/dm².Here, so-called etching spot, refers to being etched using copper chloride In the case of, Co is insoluble and remain, moreover, so-called etch residue, refer to using ammonium chloride progress alkaline etching, Ni is insoluble and remains.

To formed this 3 yuan be copper-cobalt-nickel alloy plating general bath and the following institute of an example of plating conditions It states:

Plating bath forms:10~20g/L of Cu, 1~10g/L of Co, 1~10g/L of Ni

PH value:1~4

Temperature:30~50 DEG C

Current density D_k:20~30A/dm²

Plating times:1~5 second

The chromating layer refers to utilizing the liquid comprising chromic anhybride, chromic acid, two chromic acid, chromate or two chromate Processed layer.Chromating layer also may include the elements such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As and Ti ( Can be any forms such as metal, alloy, oxide, nitride, sulfide).As the concrete example of chromating layer, can enumerate Include chromic anhybride or two potassium chromates and zinc using chromic anhybride or the processed chromating layer of two chromic acid aqueous solutions of potassium or utilization The processed chromating layer for the treatment of fluid etc..

The silane coupled process layer can be used well known silane coupling agent and be formed, it is possible to use epoxy silane, amine The silicon such as base system silane, methacryloxy system silane, sulfydryl system silane, ethylene system silane, imidazoles system silane, triazine system silane Alkane coupling agent etc. and formed.In addition, this silane coupling agent can also use two or more mixing.Wherein, it is preferable to use amine Base system silane coupling agent or epoxy silane coupling agent and the silane coupled process layer formed.

In addition, surface that can be to the barrier layer side of the copper foil of attached release layer or roughening treatment layer, refractory layer, antirust coat, silicon The surface of alkane coupling processing layer or chromating layer carries out International Publication number WO2008/053878, Japanese Unexamined Patent Publication 2008- No. 111169, Japanese Patent No. 5024930, International Publication number WO2006/028207, Japanese Patent No. 4828427, state Border discloses number WO2006/134868, Japanese Patent No. 5046927, International Publication number WO2007/105635, Japan specially Surface treatment described in profit the 5180815th, Japanese Unexamined Patent Publication 2013-19056.

In addition, can be in the copper foil and barrier layer of the copper foil on the surface or attached release layer of the barrier layer side of the copper foil of attached release layer Between have roughening treatment layer, can also have on the roughening treatment layer more than one selected from by refractory layer, antirust coat, chromium Layer in the group that hydrochlorate process layer and silane coupled process layer are formed.

In addition, can be in the copper foil and barrier layer of the copper foil on the surface or attached release layer of the barrier layer side of the copper foil of attached release layer Between have roughening treatment layer, can have refractory layer, antirust coat on the roughening treatment layer, can be in the refractory layer, antirust Have chromating layer on layer, can also have silane coupled process layer on the chromating layer.

In addition, copper foil that also can be in the copper foil on the surface or attached release layer of the barrier layer side of the copper foil of attached release layer and barrier Between layer or on the roughening treatment layer or the refractory layer or the antirust coat or the chromating layer or described Has resin layer in silane coupled process layer.The resin layer is alternatively insulating resin layer.

The resin layer can be solid, or the insulating resin layer of semi-hardened state (B-stage) then.It is so-called Semi-hardened state (B-stage state) refers to that finger is used to touch the surface of the resin layer also without adhesion sense, and can will be described Insulating resin layer overlapping is taken care of, and then includes the state that reaction can be hardened if heated processing.

In addition, the resin layer may include thermosetting resin or thermoplastic resin.In addition, the resin layer It may include thermoplastic resin.The type of thermoplastic resin is not particularly limited, for example, as preferred thermoplastic resin, can arrange Lift the resin of one or more of group comprising resin selected from the following:Epoxy resin, polyimide resin, multi-functional cyanic acid Ester compounds, maleimide compounds, polyvinyl acetal resin, amine ester resin, polyether sulfone, polyethersulfone resin, virtue Fragrant polyamide resin, aromatic polyamide resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamidoimide Resin, rubber modified epoxy resin, phenoxy resin, carboxy-modified acrylonitrile-butadiene resin, polyphenylene oxide, double maleoyl-s Imines cyanate resin, thermosetting polyphenylene oxide resin, cyanate ester based resin, the acid anhydrides of carboxylic acid, polybasic carboxylic acid acid anhydrides, have can Bis- (4- cyanatephenyls) propane of linear polymer, polyphenylene oxide resin, 2,2- of crosslinked functional group, phosphorous phenolate are closed Bis- (4- glycidyl phenyls) propane of object, manganese naphthenate, 2,2-, polyphenylene oxide-cyanate ester based resin, silicone-modified polyamide Imide resin, cyano ester resin, phosphonitrile system resin, rubber-modified polyamide imide resin, isoprene, the poly- fourth of hydrogenation type Diene, polyvinyl butyral, phenoxy resin, macromolecule epoxy resin, aromatic polyamide, fluororesin, bis-phenol, block copolymerization polyamides Imide resin and cyano ester resin.

In addition, as long as the epoxy resin with 2 or more epoxy groups and can be used for electrical, electronic material in the molecule Purposes can then use with no particular problem.In addition, it is preferable to use the shrinks that intramolecular has 2 or more for the epoxy resin Glyceryl compound carries out epoxy resin made of epoxidation.In addition, the epoxy resin can be by resin selected from the following One or more of group mixes and uses:Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy tree Fat, bisphenol-A D-ring oxygen resin, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, Bromination (brominated) epoxy resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, bmminated bisphenol-A type epoxy It is resin, o-cresol phenolic epoxy varnish, modified rubber bisphenol A type epoxy resin, glycidyl amine type epoxy resin, different Cyanuric acid three-glycidyl ester, N, the glycidols such as N- diglycidylanilines amine compounds, tetrahydrophthalic acid two contract The epihydric alcohol ester compounds such as water glyceride, phosphorous epoxy resin, biphenyl type epoxy resin, biphenyl nobolak type epoxy tree Fat, trihydroxy benzene methylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, or the hydrogenation of the epoxy resin can be used Body or halogenation body.

As the phosphorous epoxy resin, the well known epoxy resin containing phosphorus can be used.In addition, the phosphorous ring Oxygen resin is for example preferably as the miscellaneous -10- phospho hetero phenanthrenes-of 9,10- dihydro-9-oxies for the epoxy group for having 2 or more from intramolecular The derivative of 10- oxides and the epoxy resin obtained.

The resin layer may include that well known resin, hardening of resin agent, compound, hardening accelerator, dielectric substance (can also make With any dielectric substances such as the dielectric substance comprising inorganic compound and/or organic compound, the dielectric substances comprising metal oxide), Catalysts, crosslinking agent, polymer, prepreg, framework material etc..In addition, document below can also be used in the resin layer In recorded substance it is (resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, catalysts, crosslinking agent, poly- Close object, prepreg, framework material etc.) and/or resin layer forming method, forming apparatus and formed:Such as International Publication number No. WO2008/004399, International Publication number WO2008/053878, International Publication number WO2009/084533, Japanese Unexamined Patent Publication Flat No. 11-5828, Japanese Unexamined Patent Publication 11-140281, Japanese Patent No. 3184485, International Publication number WO97/02728, Japanese Patent No. 3676375, Japanese Unexamined Patent Publication 2000-43188, Japanese Patent No. 3612594, Japanese Unexamined Patent Publication 2002- No. 179772, Japanese Unexamined Patent Publication 2002-359444, Japanese Unexamined Patent Publication 2003-304068, Japanese Patent No. 3992225, Japan it is special Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Unexamined Patent Publication 2004-82687, Japanese Patent No. 4025177, Japanese Unexamined Patent Publication 2004-349654, Japanese Patent No. 4286060, Japanese Unexamined Patent Publication 2005-262506, Japanese Patent No. No. 4570070, it is Japanese Unexamined Patent Publication 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, international public The number of beginning the compilation of WO2004/005588, Japanese Unexamined Patent Publication 2006-257153, Japanese Unexamined Patent Publication 2007-326923, Japanese Unexamined Patent Publication 2008- No. 111169, Japanese Patent No. 5024930, International Publication number WO2006/028207, Japanese Patent No. No. 4828427, day This special open 2009-67029, International Publication number WO2006/134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication No. 2009-173017, International Publication number WO2007/105635, Japanese Patent No. 5180815, International Publication number WO2008/114858, International Publication number WO2009/008471, Japanese Unexamined Patent Publication 2011-14727, International Publication number WO2009/001850, International Publication number WO2009/145179, International Publication number WO2011/068157, Japanese Unexamined Patent Publication No. 2013-19056.

These resins are dissolved in such as methyl ethyl ketone (MEK), toluene equal solvent and resin solution is made, and pass through example Such as the resin solution is coated on the surface of the barrier layer side of the copper foil of attached release layer or the roughening by roll coater method On process layer, the refractory layer, antirust coat or the chromate skin membrane or the silane coupling agent layer, then optionally into Row heat drying removes solvent, and becomes B-stage state.Dry usable such as hot-air drying stove, drying temperature can be 100 ~250 DEG C, preferably 130~200 DEG C.

The copper foil (copper foil of the attached release layer with resin) for having the attached release layer of the resin layer is with following state Sample uses:After the resin layer is overlapped in base material, entirety is thermally compressed and makes the resin layer thermmohardening, in copper The barrier layer side surface of foil forms specific Wiring pattern.

If using the copper foil of the attached release layer with resin, can reduce when manufacturing multilayer printed wiring board The use the piece number of prepreg material.Moreover, the thickness of resin layer can be made to become as thickness as can ensure that layer insulation, or i.e. Make also manufacture copper-cover laminated plate without using prepreg material completely.In addition, at this point, also can the surface of base material by insulating resin into Row priming paint is coated with and further improves the flatness on surface.

In addition, without using prepreg material, have the following advantages that:The material cost of prepreg material has been saved, In addition, layering steps also become simple, therefore economically become advantageous, moreover, correspondingly with the thickness of prepreg material, manufacture The thickness of multilayer printed wiring board is thinning, and the thickness that can manufacture 1 layer is 100 μm of very thin multi-sheet printed wiring bases below Plate.

Preferably 0.1~80 μm of the thickness of the resin layer.If the thickness of resin layer is thinner than 0.1 μm, adhesion reduces, Prepreg material be not interposed by the copper foil laminated when having the base material of internal layer material of the attached release layer with resin, is being existed The case where layer insulation being difficult to ensure between the circuit of internal layer material.

On the other hand, it if the thickness of resin layer is made to be thicker than 80 μm, is difficult to form target thickness by 1 application step Resin layer, and to spend additional fee of material and working hour, therefore economically become unfavorable.In turn, it is formed by resin layer Pliability is deteriorated, therefore easy tos produce slight crack etc. in operation sometimes, in addition, cause in the thermo-compression bonding with internal layer material it is extra Resin flows and is difficult to carry out smoothly lamination.

Another product form of copper foil as the attached release layer with resin, also can be in the resistance of the copper foil of attached release layer The surface of interlayer side or the roughening treatment layer, the refractory layer, antirust coat or the chromating layer or the silane It is coating using resin layer progress on coupling processing layer, after becoming semi-hardened state, made in the form of the copper foil with resin It makes.

In turn, by printing distributing board electronic component mounting class, and printed circuit board is completed.In the present invention, " printing Distributing board " is also comprising the printing distributing board and printed circuit board that are equipped with electronic component class as described and printed base plate.

In addition, the printing distributing board can be used to make e-machine, it is possible to use the electronic component class that is equipped with Also the printed base plate for being equipped with electronic component class can be used to make e-machine for print circuit plates making e-machine.With Under, indicate the example of the manufacturing step of the printing distributing board of the copper foil of several attached release layers using the present invention.

Hereinafter, being illustrated to the example of the manufacturing method of printing distributing board, the manufacturing method packet of the printing distributing board Include the step of forming embedment circuit using the copper foil of the attached release layer of the present invention.In addition, in the present specification, the concept of " circuit " Including wiring.

Fig. 1~Fig. 4 indicates the embedment circuit of the copper foil to illustrate the attached release layer using one embodiment of the present invention Forming method schematic diagram.Use the forming method of the embedment circuit of the copper foil of the attached release layer of one embodiment of the present invention It is the 30 side lamination insulating substrate 1 (Fig. 1 b) of the release layer of the copper foil (Fig. 1 a) of the attached release layer first in the present invention.Secondly, In 10 side of barrier layer of the copper foil of the attached release layer of lamination insulating substrate 1, patterned plating resist coating 40 (Fig. 1 c) is set. Secondly, copper plate 50 (Fig. 2 d) is set on the barrier layer 10 provided with patterned plating resist coating 40.Secondly, by that will resist Coating layer 40 removes and forms copper plating circuit 51 (Fig. 2 e).Secondly, it covers copper plating circuit 51 by using insulating substrate 2 and will plate Copper circuit 51 is embedded to (Fig. 2 f).In addition, at this point, can so on insulating substrate 2 be arranged copper foil 60 (Fig. 3 g), also can be then to institute It states copper foil 60 to be etched, copper plating circuit 61 (Fig. 3 h) is consequently formed.Secondly, by by the insulation base on the surface of 30 side of release layer Plate 1 removes and the surface of 30 side of release layer of the copper foil of attached release layer is made to expose (Fig. 3 i).Secondly, using etching by copper foil 20 from The surface of 30 side of release layer of exposing removes and the surface of barrier layer 10 is made to expose (Fig. 4 j).Secondly, using etching by exposing Barrier layer 10 removes, and the circuit in embedment insulating substrate 2 is thus made to expose (Fig. 4 k).Embedment circuit is obtained in this way, from And the printing distributing board using the embedment circuit can be manufactured.

In addition, after Fig. 1 b the step of, also can on the surface of the copper foil side of the attached release layer of non-lamination of insulating substrate 1, As shown in figure 5, the copper foil of another attached release layer of lamination, that is, make sequentially 10/ copper foil of lamination barrier layer, 20/ release layer 30/ and insulate Laminate made of 1/ release layer of substrate, 31/ copper foil, 21/ barrier layer 11.It in said case, also can be in a table of insulating substrate 1 The copper foil of the attached release layer in face forms embedment circuit in a manner of Fig. 1 c~Fig. 4 k, on the other hand, in the another of insulating substrate 1 The copper foil of the attached release layer on surface also forms embedment circuit with same program.In addition, in the manufacturer of the printing distributing board In method, also the insulating substrate 1 can be renamed as the support.

In addition, embedment resin (RESIN) can be used in insulating substrate 1 and 2.The usable well known resin of the embedment resin, Prepreg.Such as BT (double maleimide triazines) resins or as the preimpregnation containing the glass cloth for being soaked with BT resins can be used The ABF films or ABF that body, Ajinomoto Fine-Techno limited liability companies manufacture.In addition, the insulating substrate 1 and 2 and Resin layer and/or resin described in resin or this specification well known to the embedment resin (RESIN) is usable and/or preimpregnation Body.

The manufacturing method of the printing distributing board of the present invention is alternatively the manufacturing method of the printing distributing board comprised the following steps (called non-sleeve method (coreless method)):By the barrier layer side surface of the copper foil of the attached release layer of the present invention or described de- The step of mold layer side surface carries out lamination with resin substrate;With barrier layer side surface with the resin substrate layer or described Release layer side surface is the surface of the copper foil of the attached release layer of opposite side, and 1 resin layer and circuit this two layers step is at least arranged Suddenly;And after forming this two layers of the resin layer and circuit, from the copper foil of the attached release layer make the resin layer and circuit this two The step of layer stripping.In addition, resin layer, circuit can be sequentially arranged this two layers in resin layer and circuit, circuit, tree also can be sequentially set Lipid layer.About the called non-sleeve method, as specific example, first, by the barrier layer side table of the copper foil of the attached release layer of the present invention Face or release layer side surface and resin substrate layer and manufacture laminate (also referred to as copper-cover laminated plate, copper-cover laminated body).Later, In the copper foil with barrier layer side surface or attached release layer that the release layer side surface is opposite side with resin substrate layer Surface forms resin layer.Also can in the resin layer for being formed in release layer side surface or copper foil side surface, and then from release layer side or The copper foil of another attached release layer of barrier layer side lamination.In addition, can will also match for the printing with the laminate constituted as follows The manufacturing method (called non-sleeve method) of line plate:Centered on resin substrate or resin or prepreg, in the resin substrate or resin or Two surface sides of prepreg, it is attached with the sequential lamination of the sequence of release layer/copper foil/barrier layer or barrier layer/copper foil/release layer The composition of the copper foil of release layer;Or sequentially lamination " release layer/copper foil/barrier layer/resin substrate or resin or prepreg/demoulding The composition of layer/copper foil/barrier layer ";Or sequentially lamination " release layer/copper foil/barrier layer/resin substrate or resin or prepreg/resistance The composition of interlayer/copper foil/release layer ";Or sequentially lamination " barrier layer/copper foil/release layer/resin substrate or resin or prepreg/ The composition of release layer/copper foil/barrier layer ".Moreover, the table that can be also exposed in the barrier layer or release layer at the laminate both ends Face is arranged another resin layer, and then after setting layers of copper or metal layer, is processed to the layers of copper or metal layer, thus shape At circuit or wiring.In turn, the mode that can also be embedded to the circuit or wiring is (by the circuit or the side of wiring burial Formula), another resin layer is set on the circuit or wiring.In addition, also can be in the barrier layer at the laminate both ends or de- The surface that mold layer is exposed is arranged the wiring or circuit of copper or metal, another resin layer is arranged on the wiring or circuit, profit The wiring or circuit are embedded to and (are buried the wiring or circuit) with another resin.It later, also can be in another resin The formation of circuit or wiring and resin layer is carried out on layer.In addition, the formation of this circuit or wiring and resin layer can also carry out 1 time (Layer increasing method) above.It, can will be each attached de- moreover, about the laminate (hereinafter also referred to as laminate B) formed in this way The copper foil of mold layer is removed from the laminate and makes coreless substrate.In addition, the making of the coreless substrate can also be used two The copper foil of attached release layer makes the product of the aftermentioned composition with barrier layer/copper foil/release layer/release layer/copper foil/barrier layer Layer body or the composition with release layer/copper foil/barrier layer/barrier layer/copper foil/release layer laminate or with release layer/copper The laminate is used for center by the laminate of the composition of foil/barrier layer/release layer/copper foil/barrier layer.It can be in these laminations The barrier layer of body (hereinafter also referred to as laminate A) both sides or the surface of release layer, by this two layers setting of resin layer and circuit 1 time More than, after resin layer and the setting 1 time of this two layers of circuit is above, it will be provided with more than once from the copper foil of each attached release layer The resin layer and the stripping of circuit this two layers layer, and make coreless substrate.In addition, this two layers of resin layer and circuit can be sequentially Resin layer, circuit are set, circuit, resin layer also can be sequentially set.The laminate also can be in the surface of barrier layer, release layer Between surface, release layer and release layer, between barrier layer and barrier layer, between barrier layer and release layer have other layers.Other Layer or resin substrate or resin layer.In addition, in the present specification, " surface of copper foil ", " copper foil side surface ", " copper foil table Face ", " surface of release layer ", " release layer side surface ", " demoulding layer surface ", " surface of laminate ", " laminate surface ", " surface of barrier layer ", " barrier layer side surface ", " barrier layer surface " concept, in copper foil, release layer, laminate, barrier layer In the case where copper foil surface, demoulding layer surface, laminate surface, barrier layer surface have other layers, including other described layers Surface (most surface).In addition, laminate preferably have barrier layer/copper foil/release layer/one or more support/release layer/ The composition of copper foil/barrier layer.The reason is that, when making coreless substrate using the laminate, because being configured in coreless substrate side Barrier layer can reduce electricity so in the case where forming circuit on barrier layer and being embedded to the circuit when removing barrier layer The erosion on road.

In addition, in the present specification, " laminate " expression for not being denoted as " laminate A " or " laminate B " especially is at least wrapped The laminate of A containing laminate and laminate B.

In addition, in the manufacturing method of the coreless substrate, by by resin by the copper foil of attached release layer or the lamination Part or all of covering of the end face of body (including laminate A) can prevent medicine when manufacturing printing distributing board using Layer increasing method Between liquid penetrates into peeling layer or constitutes the copper foil and the copper foil of another attached release layer of an attached release layer of laminate, it can prevent The corrosion of the copper foil of attached release layer caused by liquid penetrates into, so as to make Yield lmproved.It " attached will be taken off as used herein The end face of the copper foil of mold layer part or all covering resin " or " by the end face of laminate part or all cover Resin ", can be used for the resin of resin layer or well known resin.In addition, in the manufacturing method of the coreless substrate, When being overlooked in the copper foil or laminate of attached release layer the lamination part of the copper foil of attached release layer or laminate (release layer and copper foil The copper foil of the lamination part or an attached release layer of lamination part or barrier layer and copper foil and the copper foil of another attached release layer Lamination part) at least part of periphery can also be covered by resin or prepreg.In addition, utilizing the manufacture of the coreless substrate The laminate (laminate A) that method is formed can also make the copper foil of a pair of attached release layer that can contact and constitute separated from each other.In addition, Also lamination part (release layer and the copper of the copper foil of attached release layer or laminate when being overlooked in the copper foil of the attached release layer can be spread The copper of the copper foil and another attached release layer of the lamination part or an attached release layer of the lamination part of foil or barrier layer and copper foil The lamination part of foil) the entirety of periphery or the entire surface of lamination part covered by resin or prepreg.Additionally, it is preferred that when overlooking Resin or prepreg are more than the copper foil of attached release layer or the lamination part of laminate or laminate, are preferably made and are constituted with following Laminate:By the resin or prepreg laminated on the copper foil of attached release layer or the two sides of laminate, resin or preimpregnation are utilized The copper foil of attached release layer or laminate are packed (package) by body.By the way that this composition is made, in the copper foil for overlooking attached release layer or The lamination part of the copper foil of attached release layer or laminate is covered by resin or prepreg when laminate, and other component can be prevented from institute It states the side direction of part, i.e. relative to lamination direction from the collision of the direction of horizontal side, as a result can reduce the release layer and copper in operation The mutual peeling of the copper foil of foil or attached release layer.In addition, by not make the copper foil of attached release layer or the lamination part of laminate The mode exposed of periphery covered by resin or prepreg, liquid in liquid processing step as described above can be prevented to described The infiltration at the interface of lamination part thus prevents the corrosion or erosion of the copper foil of attached release layer.In addition, from the one of laminate When detaching the copper foil of an attached release layer to the copper foil of attached release layer, in the copper by resin or the attached release layer of prepreg covering Foil or laminate lamination part (the lamination part or barrier layer of release layer and copper foil and the lamination part of copper foil or one it is attached de- The lamination part of the copper foil of the copper foil of mold layer and another attached release layer) the case where being touched securely by resin or prepreg etc. Under, described lamination part etc. must be passed through the removals such as cut-out sometimes.

Also can be of the invention laminated on another from release layer side or barrier layer side by the copper foil of the attached release layer of the present invention The release layer side or barrier layer side of the copper foil of attached release layer and constitute laminate.In addition, or by one attached release layer Copper foil the release layer side surface or the copper foil side surface and another attached release layer copper foil the demoulding Layer side surface or the barrier layer side surface, the laminate optionally obtained via the direct lamination of solid.In addition, can also incite somebody to action The release layer or resistance of the release layer or barrier layer of the copper foil of one attached release layer with the copper foil of another attached release layer Interlayer engages.Here, " engagement " also includes to be situated between every institute in the case where release layer or barrier layer have surface-treated layer State the aspect that surface-treated layer is interconnected.In addition, also can part or all of end face of the laminate covered by resin.

Release layer each other, barrier layer each other, the mutual lamination of the copper foil of release layer and barrier layer, attached release layer is except simply Other than overlapping, also carried out using for example following method.

(a) metallurgical, bond method:Welding (arc-welding, TIG (tungsten inert gas) welding, MIG (consumable electrode noble gas) welderings Connect, resistance welding, seam weld, spot welding), crimping (ultrasonic welding, friction stir weld), soldering;

(b) mechanical interface method:Riveting (utilizes the engagement of self-piercing riveting, connecing using rivet using the engagement of rivet Close), stitching unstrument;

(c) physical engagement method:Solid, (two sides) adhesive tape

By using the joint method by part or all and another attached release layer of the copper foil of an attached release layer Part or all of engagement of copper foil, can manufacture laminate below, the laminate be by the copper foil of an attached release layer with it is another One attached release layer it is copper foil laminated, so that the copper foil of attached release layer is separably contacted and is constituted each other.In the copper of an attached release layer The weak engagement of copper foil of foil and another attached release layer, and by the copper foil laminated feelings of the copper foil of an attached release layer and another attached release layer Under condition, even if the joint portion of the copper foil of an attached release layer and the copper foil of another attached release layer is not removed, the copper of an attached release layer The copper foil of foil and another attached release layer also separates.In addition, the copper foil in the copper foil and another attached release layer of an attached release layer is strong In the case of engagement, can by using cut-out or chemical grinding (etching etc.), mechanical lapping etc. by the copper foil of an attached release layer with The position removal that the copper foil of another attached release layer engages, by the copper foil of the copper foil of an attached release layer and another attached release layer point From.

In addition, as " barrier layer/copper foil/release layer/resin substrate or resin or prepreg/release layer/copper foil/barrier The laminate that constitutes in this way of layer ", the step of this two layers of 1 resin layer and circuit are at least set, and make the resin layer and electricity After this two layers of road is at least formed 1 time, the resin substrate or resin or pre- are removed from the copper foil of the attached release layer of the laminate After the step of soaking body, release layer and copper foil are removed by etching.Later, using can by barrier layer pass through etch removal erosion It carves liquid to remove barrier layer, thus can make at least foring 1 resin layer and this two layers layer of circuit and do not have There is the printing distributing board of core.In addition, on one or two surface of the laminate, may also set up resin layer and circuit this two Layer.In addition, resin layer, circuit can be sequentially arranged this two layers in resin layer and circuit, circuit, resin layer also can be sequentially set.

Resin substrate, resin layer, resin, prepreg used in the laminate can be the resin described in this specification Layer, also may include resin, hardening of resin agent, compound, hardening accelerator, Jie used in the resin layer described in this specification Electric body, catalysts, crosslinking agent, polymer, prepreg, framework material etc..

In addition, the copper foil or laminate of the attached release layer can also be less than resin or prepreg or resin substrate when looking down Or resin layer.

[Shi Shili ]

Hereinafter, the present invention is described in more detail in embodiment through the invention, but the present invention is not by these embodiments Any restriction.

(embodiment 1:The copper foil of attached release layer)

The electrolytic copper foil JTC foils (35 μm of thickness) that copper foil is manufactured using JX Metallgesellschaft AG, in the cathode copper The faces S (glassy surface) side of foil forms the Ni layers of 1 μm of thickness by plating, as barrier layer under the following conditions.

[Nickel (Ni) Du Fu ]

Plating liquid

Nickel:20~200g/L

Boric acid:5~60g/L

Liquid temperature:40~65 DEG C

PH value:1.5~5.0

Current density:0.5~20A/dm²

Conduction time:1~20 second

It stirs (liquid circulation amount):100~1000L/ minutes

Transport speed:2~30m/ minutes

Additive:Gloss agent (saccharin sodium:0.5~5g/L), secondary gloss agent (thiocarbamide:0.05~1g/L)

Later, under the following conditions, in electrolytic copper foil with barrier layer release layer is formed for the surface of opposite side.

Silane coupled processing

Treatment fluid:

Silane compound:N-propyl trimethoxy silane

Silane concentration:0.4vol%

Treatment fluid mixing time before use:12 hours

Determining alcohol:0vol%

PH value:4~7

Processing time:30 seconds (coating for utilizing spray nozzle)

(test result)

Using the copper foil of the attached release layer of embodiment 1, using prepreg FR-4 as the release layer side table laminated on copper foil The resin (insulating substrate 1) in face can be made into as shown in Figure 1 to 4 using epoxy resin as embedment resin (insulating substrate 2) It is embedded to circuit board (printed wiring version).

Symbol description

1,2:Insulating substrate

10,11:Barrier layer

20,21,60:Copper foil

30,31:Release layer

40:Plating resist coating

50:Copper plate

51,61:Copper plating circuit

Claims

1. a kind of copper foil of attached release layer, sequentially has release layer, copper foil and barrier layer.

2. the copper foil of attached release layer according to claim 1, wherein

The barrier layer is

C layers, Ni layers, Ti layers, Cr layers, V layers, Zr layers, Ta layers, Au layers, Pt layers, Os layers, Pd layers, Ru layers, Rh layers, Ir layers, W layers, Or

Including containing appointing in the group being made of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si and Cr The layer of more than one alloy, or

Including containing appointing in the group being made of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si and Cr More than one carbide, the layer of oxide or nitride.

3. the copper foil of attached release layer according to claim 1, wherein the barrier layer is by being selected from by Ni, Ti, Cr, oxidation Any one of group that titanium, chromium oxide and carbon are formed is constituted for two or three or four kinds or five kinds or six kinds.

4. the copper foil of attached release layer according to claim 2, wherein the barrier layer is by being selected from by Ni, Ti, Cr, oxidation Any one of group that titanium, chromium oxide and carbon are formed is constituted for two or three or four kinds or five kinds or six kinds.

5. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the barrier layer have selected from by The layer of one or more of Ni layers, the Ti layers and Cr layers group formed.

6. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the barrier layer is selected from by Ni Layer more than any one of layer, the Ti layers and Cr layers group formed.

7. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the barrier layer is selected from by Ni The layer of any one of layer, the Ti layers and Cr layers group formed.

8. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the thickness of the barrier layer is 0.001 μm or more and 10 μm or less.

9. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the thickness of the copper foil is 0.1 μm Above and 100 μm or less.

10. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the release layer is alone or in combination The water of a variety of and hydrolysates, the silane compound with silane compound, the silane compound represented by following formula The condensation product of product is solved,

(in formula, R¹For alkoxy or halogen atom,

R²For in the group being made of alkyl, naphthenic base and aryl alkyl or more than one hydrogen atom by halogen atom The alkyl of substitution,

R³And R⁴Separately by halogen atom or alkoxy or in the group being made of alkyl, naphthenic base and aryl Alkyl or the alkyl that is substituted with halogen atoms of more than one hydrogen atom).

11. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the release layer has intramolecular Compound with 2 sulfydryls below.

12. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the release layer is alone or in combination It is a variety of and with aluminate compound, titanate compound, zirconate compounds, the aluminate compound represented by following formula Hydrolysate, the hydrolysate of the titanate compound, the hydrolysate of the zirconate compounds, the aluminate Close the condensation product of the hydrolysate of object, the condensation product of the hydrolysate of the titanate compound or the zirconate compounds The condensation product of hydrolysate,

(R¹)_m-M-(R²)_n

(in formula, R¹For alkoxy or halogen atom,

M be Al, Ti or Zr,

N is 0,1 or 2,

M is the valence mumber integer below of 1 or more and M,

R¹At least one of be alkoxy;

M+n is the valence mumber of M, that is, when for Al is 3, is 4) when for Ti, Zr.

13. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the release layer is applied with resin Film, the resin coating film is by silicone;And selected from any one of epoxy system resin, melamine series resin and fluororesin or more Kind resin is constituted.

14. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the copper foil and barrier layer it Between, have selected from the group being made of roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupled process layer One or more of layer.

15. the copper foil of attached release layer according to claim 14, wherein the roughening treatment layer be by be selected from by Cu, Ni, P, any one of group that W, As, Mo, Cr, Ti, Fe, V, Co and Zn are formed simple substance or contain any simple substance described above The layer that alloy is constituted.

16. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the barrier layer and copper foil Side is the face of opposite side, is had selected from by roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupled processing The layer of one or more of the group that layer is formed.

17. the copper foil of attached release layer according to claim 16, wherein the roughening treatment layer be by be selected from by Cu, Ni, P, any one of group that W, As, Mo, Cr, Ti, Fe, V, Co and Zn are formed simple substance or contain any simple substance described above The layer that alloy is constituted.

18. the copper foil of attached release layer according to any one of claim 1 to 4, wherein the copper foil and release layer it Between, have selected from one or more of the group being made of refractory layer, antirust coat, chromating layer and silane coupled process layer Layer.

19. the copper foil of attached release layer according to any one of claim 1 to 4, wherein have in the release layer side surface Standby resin layer.

20. a kind of laminate, the copper foil with the attached release layer described in any one of claim 1 to 19.

21. a kind of laminate, copper foil and resin containing the attached release layer described in any one of claim 1 to 19, and institute Part or all for stating the end face of copper foil is covered by the resin.

22. a kind of laminate has there are two the copper foil and resin of the attached release layer described in any one of claim 1 to 19, And

It is by the release layer side surface of the copper foil of the attached release layer in the copper foil of described two attached release layers with it is described One face lamination of resin, by another area of the release layer side surface and the resin of the copper foil of another attached release layer Layer forms.

23. a kind of manufacturing method of printing distributing board is using the attached release layer described in any one of claim 1 to 19 Copper foil and manufacture printing distributing board.

24. a kind of manufacturing method of printing distributing board comprising following steps:

The release layer side lamination support of the copper foil of attached release layer described in any one of claim 1 to 19 or insulation The step of substrate 1;

It is arranged through pattern in the barrier layer side of the copper foil of the lamination support or the attached release layer of the insulating substrate 1 The step of plating resist coating of change;

After copper plate is set on the barrier layer provided with the patterned plating resist coating, the plating resist coating is gone The step of removing, copper plating circuit be consequently formed;

The step of copper plating circuit being covered using insulating substrate 2, being thus embedded to the copper plating circuit;

After the copper plating circuit is embedded to, the support of the release layer side surface or the insulating substrate 1 are removed, by The step of this makes the release layer side surface of the copper foil of the attached release layer expose;

The step that the copper foil is removed from the release layer side surface of the exposing using etching and the barrier layer surface is made to expose Suddenly;And

The step of barrier layer of the exposing is removed using etching, thus exposes the circuit in the embedment insulating substrate 2.

25. a kind of manufacturing method of printing distributing board, be using the laminate described in any one of claim 20 to 22 and Manufacture printing distributing board.

26. a kind of manufacturing method of e-machine is matched using using the printing described in any one of claim 23 to 25 Line plate manufacturing method manufacture printing distributing board and manufacture e-machine.