CN108449868A - The manufacturing method of surface treatment copper foil, the copper foil with carrier, layered product, the manufacturing method of printing distributing board and e-machine - Google Patents

Abstract

Copper foil, layered product, the manufacturing method of printing distributing board the present invention relates to surface treatment copper foil, with carrier and the manufacturing method of e-machine.A kind of surface treatment copper foil is provided in particular, even if being used for high-frequency circuit board, can also reduce transmission loss well, and acid resistance is good.A kind of surface treatment copper foil, with copper foil and in one or two face of copper foil with the surface-treated layer for including roughening treatment layer, surface-treated layer includes Ni, and the containing ratio of the Ni in surface-treated layer is 8 mass % or less (except 0 mass %), 10 mean roughness Rz of the most surface of surface-treated layer are 1.4 μm or less.

Description

The manufacturer of surface treatment copper foil, the copper foil with carrier, layered product, printing distributing board The manufacturing method of method and e-machine

Technical field

The present invention relates to a kind of surface treatment copper foil, the copper foil with carrier, layered product, printing distributing board manufacturing method and The manufacturing method of e-machine.

Background technology

After this half a century, printing distributing board has obtained prodigious progress, nowadays has reached in almost all of electronics The degree used in machine.With the miniaturization of e-machine in recent years, the increase of high performance demand, the height of part is carried The high frequency progress of density installationization or signal requires excellent high frequency to correspond to printing distributing board.

In high frequency substrate, in order to ensure the quality of output signal, it is desirable that transmission loss reduces.Transmission loss includes mainly The dielectric loss caused by resin (substrate-side) and the conductor losses caused by conductor (copper foil side).The dielectric constant of resin and Dielectric loss angle tangent becomes smaller, and dielectric loss is more reduced.In high-frequency signal, the main reason for conductor losses, is：Due to frequency Rate becomes higher, and electric current is only in the skin effect of the surface of conductor circulation, and the sectional area of current flowing is reduced, resistance liter It is high.

As the technology for the purpose of the transmission loss for reducing high frequency copper foil, for example, Patent Document 1 discloses such as Under high-frequency circuit metal foil, the one or two sides of metal foil surface it is coating silver or silver alloy, in the silver or silver alloy On coating, to be applied with the coating other than silver or silver alloy than above-mentioned silver-colored or silver alloy coating thickness thin thickness.And And record, also reduce in the superelevation frequency domain that may be provided in whereby used in satellite communication and is lost caused by skin effect Metal foil.

In addition, disclosing following high-frequency circuit roughening treatment rolled copper foil in patent document 2, it is characterised in that： Integrated intensity (the I in (200) face found out by X-ray diffraction on the calendering face after the recrystallization annealing of rolled copper foil (200)) it is I relative to the integrated intensity (I0 (200)) in (200) face of micropowder copper found out by X-ray diffraction (200)/I0 (200) ＞ 40, the arithmetic that the roughening treatment face after the roughening treatment by plating is carried out to the calendering face are flat Equal roughness (being set as Ra below) is 0.02 μm~0.2 μm, and 10 mean roughness (being set as Rz below) are 0.1 μm~1.5 μm, And above-mentioned high-frequency circuit is printed circuit board raw material with roughening treatment rolled copper foil.And record, whereby can The printed circuit board that can be used at high frequencies over ighz is provided.

In turn, following electrolytic copper foil is disclosed in patent document 3, it is characterised in that：The part on the surface of copper foil is The male and fomale(M＆F) for being 2 μm~4 μm by the surface roughness that strumae is constituted.And record, high-frequency transmission spy can be provided whereby The excellent electrolytic copper foil of property.

In turn, following surface treatment copper foil is disclosed in patent document 4, is to be formed with surface at least one surface The surface treatment copper foil of process layer, and surface-treated layer includes roughening treatment layer, Co, Ni, Fe's in surface-treated layer Total adhesion amount is 300 μ g/dm²Hereinafter, surface-treated layer has Zn metal layers or the alloy treatment layer comprising Zn, at surface Reason layer surface with laser microscope come the three-dimensional table area that measures relative to bivariate table area ratio for 1.0~1.9, at least one The surface roughness Rz JIS on a surface are 2.2 μm hereinafter, being formed with above-mentioned surface-treated layer, and above-mentioned two surface on two surfaces Surface roughness Rz JIS be 2.2 μm or less.And record, even if can provide whereby also good for high-frequency circuit board Ground inhibits the surface treatment copper foil of transmission loss.

[existing technical literature]

[patent document]

No. 4161304 bulletins of [patent document 1] Japanese Patent No.

No. 4704025 bulletins of [patent document 2] Japanese Patent No.

[patent document 3] Japanese Unexamined Patent Publication 2004-244656 bulletins

No. 5710737 bulletins of [patent document 4] Japanese Patent No..

Invention content

[problem to be solved by the invention]

The control of transmission loss about copper foil when being used in high-frequency circuit board, though it has carried out as described above a variety of Research, but still there are prodigious exploitation leeway.In addition, existing using acid etc. to circuit (copper when high-frequency circuit board manufactures Wiring) carry out soft etching the case where, therefore also still expect copper foil acid resistance improve.

[technical means to solve problem]

Present inventors found that with copper foil and in one or two face of copper foil with including roughening treatment layer Surface-treated layer surface treatment copper foil in, pass through the containing ratio of the Ni in control surface process layer and surface treatment 10 mean roughness Rz of the most surface of layer can also reduce transmission loss well even if being then used for high-frequency circuit board, and Acid resistance becomes good.

The present invention is completed based on above-mentioned opinion, is on the one hand a kind of surface treatment copper foil, with copper foil, with And there is the surface-treated layer for including roughening treatment layer in one or two face of above-mentioned copper foil, above-mentioned surface-treated layer includes The containing ratio of Ni, the Ni in above-mentioned surface-treated layer are 8 mass % or less (except 0 mass %), and above-mentioned surface-treated layer Most surface 10 mean roughness Rz be 1.4 μm or less.

The surface treatment copper foil of the present invention in an implementation form, total adhesion amount of above-mentioned surface-treated layer is 1.0~ 5.0g/m²。

For the surface treatment copper foil of the present invention in another implementation form, above-mentioned surface-treated layer includes Co, and above-mentioned surface The containing ratio of Co in process layer is 15 mass % or less (except 0 mass %).

The surface treatment copper foil of the present invention is in another implementation form in turn, the adhesion amount of the Co in above-mentioned surface-treated layer For 30~2000 μ g/dm²。

For the surface treatment copper foil of the present invention in another implementation form in turn, above-mentioned surface-treated layer includes Ni, and above-mentioned The adhesion amount of Ni in surface-treated layer is 10~1000 μ g/dm²。

In another implementation form in turn, above-mentioned surface-treated layer has more selected from by resistance to the surface treatment copper foil of the present invention The layer of one or more of the group that thermosphere, antirust coat, chromating layer and silane coupled process layer are formed.

The surface treatment copper foil of the present invention is in another implementation form in turn, the copper clad layers pressure for high-frequency circuit board Plate or printing distributing board.

The present invention is a kind of surface treatment copper foil of tape tree lipid layer on the other hand, has the surface treatment of the present invention Copper foil and resin layer.

The present invention is a kind of copper foil with carrier, in one or two face of carrier has in another aspect in turn Interbed and very thin layers of copper, and the surface of the tape tree lipid layer for the surface treatment copper foil or the present invention that above-mentioned very thin layers of copper is the present invention Handle copper foil.

The present invention is a kind of layered product in another aspect in turn, surface treatment copper foil, the present invention with the present invention The surface treatment copper foil of tape tree lipid layer or the copper foil with carrier of the present invention.

The present invention is a kind of layered product in another aspect in turn, and it includes the copper foils and resin with carrier of the present invention, and And part or all of the end face of the above-mentioned copper foil with carrier is covered by above-mentioned resin.

The present invention is a kind of layered product in another aspect in turn, and there are two the copper foils with carrier of the present invention for tool.

On the other hand the present invention, is being a kind of manufacturing method of printing distributing board, is using the surface for having the present invention in turn Handle the copper foil with carrier of copper foil, the surface treatment copper foil of tape tree lipid layer of the invention or the present invention.

The present invention is a kind of manufacturing method of printing distributing board in another aspect in turn comprising：By the surface of the present invention The surface treatment copper foil of the tape tree lipid layer of processing copper foil or the present invention is laminated with insulating substrate and forms copper clad laminate The step of, or after the copper foil with carrier and the insulating substrate of the present invention are laminated, peel the above-mentioned copper foil with carrier Carrier and the step of form copper clad laminate；And utilize semi-additive process (セ ミ ア デ ィ テ ィ Block method), subtractive process (サ Block ト ラ Network テ ィ Block method), part addition process (パ ー ト リ ー ア デ ィ テ ィ Block method) or modified form semi-additive process (モ デ ィ Off ァ イ De セ ミ ア デ ィ テ ィ Block method) in either method come the step of forming circuit.

The present invention is a kind of manufacturing method of printing distributing board in another aspect in turn comprising：On the surface of the present invention The step of handling the above-mentioned surface-treated layer side surface formation circuit of copper foil, or in the above-mentioned of the copper foil with carrier of the invention The step of very thin layers of copper side surface or above-mentioned carrier side circuit forming surface；In a manner of burying foregoing circuit, on above-mentioned surface Handle the above-mentioned surface-treated layer side surface of copper foil or the above-mentioned very thin layers of copper side surface or above-mentioned of the above-mentioned copper foil with carrier Carrier side surface forms the step of resin layer；And by after forming above-mentioned resin layer, removing above-mentioned surface treatment copper foil, or Person makes to be buried in by after removing above-mentioned carrier or above-mentioned very thin layers of copper, removing above-mentioned very thin layers of copper or above-mentioned carrier The step of stating the circuit exposing of resin layer.

The present invention is a kind of manufacturing method of printing distributing board in another aspect in turn comprising：It is carried in the band of the present invention The step of above-mentioned carrier side surface of the copper foil of body or above-mentioned very thin layers of copper side surface laminated resin substrate；Above-mentioned with carrier The step of surface with the side opposite side for being laminated with resin substrate of copper foil, at least 1 time setting resin layer and circuit；And After forming above-mentioned resin layer and circuit, the step of removing above-mentioned carrier or above-mentioned very thin layers of copper from above-mentioned copper foil with carrier.

The present invention is a kind of manufacturing method of printing distributing board in another aspect in turn comprising：With the present invention's One or two face of the layered product of copper foil with carrier or the layered product of the present invention, at least 1 time setting resin layer and circuit The step of；And after forming above-mentioned resin layer and circuit, above-mentioned load is removed from the copper foil with carrier for constituting above-mentioned layered product The step of body or above-mentioned very thin layers of copper.

On the other hand the present invention, is being a kind of manufacturing method of e-machine, is using the side having using the present invention in turn Printing distributing board made of method.

[The effect of invention]

According to the present invention, it is possible to provide even if a kind of can also reduce transmission loss well for high-frequency circuit board, and it is resistance to Acid good surface treatment copper foil.

Description of the drawings

Figure 1A~C is involved by the concrete example using the manufacturing method of the printing distributing board of the copper foil with carrier of the present invention To circuit plating resist (レ ジ ス ト) remove until the step of in distributing board section schematic diagram.

Fig. 2 D~F are involved by the concrete example using the manufacturing method of the printing distributing board of the copper foil with carrier of the present invention The copper foil of slave resin and the second layer with carrier the step of being laminated to until laser boring in distributing board section schematic diagram.

Fig. 3 G~I are involved by the concrete example using the manufacturing method of the printing distributing board of the copper foil with carrier of the present invention Slave through-hole filling (ビ ア Off ィ Le) formed to the 1st layer carrier stripping until the step of in distributing board section schematic diagram.

Fig. 4 J~K are involved by the concrete example using the manufacturing method of the printing distributing board of the copper foil with carrier of the present invention From dodge erosion (Off ラ ッ シ ュ エ ッ チ Application グ) to convex block copper post formed until the step of in distributing board section schematic diagram.

Fig. 5 is the cross section of the width direction of circuit pattern and the calculating of etching factor (エ ッ チ Application グ Off ァ ク タ ー) The generalized schematic of method.

Fig. 6 is the schematic cross-section of the polyimide resin substrate and copper circuit in the acid resistance evaluation test of embodiment.

Fig. 7 is the schematic surface of the polyimide resin substrate and copper circuit in the acid resistance evaluation test of embodiment.

Specific implementation mode

＜ surface treatment copper foils ＞

The surface treatment copper foil of the present invention has a copper foil, and at least one face of copper foil, i.e. one or two of copper foil A face has surface-treated layer.It, can be by surface treatment copper foil after the surface treatment copper foil of the present invention is fitted on insulating substrate It is etched to the conductive pattern as target, can finally manufacture printing distributing board.The surface treatment copper foil of the present invention also can be used as height The surface treatment copper foil of frequency circuit substrate uses.Herein, so-called high-frequency circuit board refers to the electricity using the circuit board Road is come the circuit board that the frequency of the signal transmitted is 1GHz or more.Additionally, it is preferred that the frequency for above-mentioned signal is 3GHz or more, More preferably 5GHz or more, more preferably 8GHz or more, more preferably 10GHz or more, more preferably 15GHz or more, more preferably For 18GHz or more, more preferably 20GHz or more, more preferably 30GHz or more, more preferably 38GHz or more, more preferably 40GHz or more, more preferably 45GHz or more, more preferably 48GHz or more, more preferably 50GHz or more, more preferably 55GHz More than, more preferably 58GHz or more.

＜ copper foils ＞

For the form of workable copper foil in the present invention, there is no particular restriction, for typical, the copper that is used in the present invention Foil can be any one of electrolytic copper foil or rolled copper foil.In general, electrolytic copper foil is from the bath of copper sulphate plating, to titanium or stainless The bucket of steel powers on parsing copper to manufacture, and rolled copper foil is that the plastic processing and heat treatment using roll is repeated to manufacture. It is more the case where the use for requiring bendability applies rolled copper foil on the way.

As copper foil material, (JIS H3100 are closed the tough pitch copper used in addition to the conductive pattern usually as printing distributing board Gold number C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloys number C1011) or phosphorus it is de- Other than the copper of high-purities such as oxygen copper (JIS H3100 alloys numbers C1201, C1220 or C1221) or cathode copper, such as can also it make With：Be added Sn copper, the copper of Ag is added, added with Sn, Ag, In, Au, Cr, Fe, P, Ti, Sn, Zn, Mn, Mo, Co, Ni, Si, The copper alloy of Zr, P and/or Mg etc., the copper alloy of gloomy (U Le ソ Application) series copper alloy of section added with Ni and Si etc. etc.Separately Outside, it is possible to use copper foil and copper alloy foil with known composition.In addition, when term " copper foil " being used alone in this specification, Also include copper alloy foil.

In addition, the plate thickness of copper foil is without being particularly limited to, such as 1~1000 μm or 1~500 μm or 1~300 μm or 3~ 100 μm or 5~70 μm or 6~35 μm or 9~18 μm.

In addition, the present invention on the other hand, is a kind of at least one face of carrier, the i.e. face or two faces of carrier The copper foil with carrier with middle layer, very thin layers of copper successively, and the surface treatment copper foil that very thin layers of copper is the present invention.This hair In bright in the case where using the copper foil with carrier, the surface treatments such as roughening treatment layer below are set on very thin layers of copper surface Layer.In addition, being illustrated hereinafter to another implementation form of the copper foil with carrier.

＜ surface-treated layers ＞

The surface-treated layer of the surface treatment copper foil of the present invention includes Ni.Include in the surface-treated layer of surface treatment copper foil In the case of Ni, has the effect of acid resistance raising.In addition, being set as 8 matter by the containing ratio of the Ni in surface-treated layer % or less (except 0 mass %) is measured, frequency transfer characteristic is can further improve.If the containing ratio of the Ni is more than 8 mass %, There are the misgivings that the frequency transfer characteristic for generating surface treatment copper foil deteriorates.Ni in the surface-treated layer containing than Rate be preferably 7.5 mass % hereinafter, more preferably 7 mass % hereinafter, more preferably 6.5 mass % hereinafter, more preferably 6 matter Measure % hereinafter, more preferably 5.5 mass % hereinafter, more preferably 5 mass % hereinafter, more preferably 4.8 mass % are hereinafter, more excellent Be selected as 4.5 mass % hereinafter, more preferably 4.2 mass % hereinafter, more preferably 4.0 mass % hereinafter, more preferably 3.8 matter Measure % hereinafter, more preferably 3.5 mass % hereinafter, more preferably 3.0 mass % hereinafter, more preferably 2.5 mass % are hereinafter, more Preferably 2.0 mass % hereinafter, more preferably 1.9 mass % hereinafter, in turn be more preferably 1.8 mass % or less.In addition, just resistance to For acid viewpoint, the containing ratio of the Ni in the surface-treated layer is preferably 0 mass % or more, preferably greater than 0 matter %, preferably 0.01 mass % or more, preferably 0.02 mass % or more, preferably 0.03 mass % or more are measured, preferably 0.04 mass % or more, preferably 0.05 mass % or more, preferably 0.06 mass % or more, preferably 0.07 mass % with On, preferably 0.08 mass % or more, preferably 0.09 mass % or more, preferably 0.10 mass % or more, preferably 0.11 Quality % or more, preferably 0.15 mass % or more, preferably 0.18 mass % or more, preferably 0.20 mass % or more, it is excellent It is selected as 0.25 mass % or more, preferably 0.50 mass % or more, preferably 0.80 mass % or more, preferably 0.90 mass % More than, preferably 1.0 mass % or more, preferably 1.1 mass % or more, preferably 1.2 mass % or more, preferably 1.3 matter Measure % or more, preferably 1.4 mass % or more, preferably 1.5 mass % or more.

The adhesion amount of Ni in surface-treated layer is preferably 10 μ g/dm²More than.It is set as 10 μ g/ by the adhesion amount of the Ni dm²More than, there is the acid proof situation that can further improve surface treatment copper foil.In addition, Ni's in surface-treated layer is attached The amount of wearing is preferably 1000 μ g/dm²Below.It is set as 1000 μ g/dm by the adhesion amount of the Ni²Hereinafter, there are frequency transfer characteristic into And the case where improving.For the acid proof viewpoint of surface treatment copper foil, the adhesion amount of the Ni is preferably 20 μ g/dm²More than, Preferably 30 μ g/dm²More than, preferably 40 μ g/dm²More than, preferably 50 μ g/dm²More than, preferably 55 μ g/dm²More than, it is excellent It is selected as 60 μ g/dm²More than, preferably 70 μ g/dm²More than, preferably 75 μ g/dm²More than, preferably 100 μ g/dm²More than, it is excellent It is selected as 110 μ g/dm²More than, preferably 120 μ g/dm²More than, preferably 130 μ g/dm²More than, preferably 140 μ g/dm²More than, Preferably 160 μ g/dm²More than, preferably 180 μ g/dm²More than, preferably 200 μ g/dm²More than, preferably 220 μ g/dm²With On, preferably 240 μ g/dm²More than, preferably 260 μ g/dm²More than, preferably 280 μ g/dm²More than, preferably 530 μ g/dm² More than.In addition, for the viewpoint of the frequency transfer characteristic of surface treatment copper foil, the adhesion amount of the Ni is preferably 950 μ g/dm² Hereinafter, preferably 900 μ g/dm²Hereinafter, preferably 850 μ g/dm²Hereinafter, preferably 800 μ g/dm²Hereinafter, preferably 750 μ g/ dm²Hereinafter, preferably 700 μ g/dm²Hereinafter, preferably 650 μ g/dm²Hereinafter, preferably 600 μ g/dm²Hereinafter, preferably 550 μ g/dm²Hereinafter, preferably 500 μ g/dm²Hereinafter, preferably 450 μ g/dm²Hereinafter, preferably 400 μ g/dm²Hereinafter, preferably 350μg/dm²Hereinafter, preferably 300 μ g/dm²Hereinafter, preferably 250 μ g/dm²Hereinafter, preferably 200 μ g/dm²Hereinafter, it is preferred that For 180 μ g/dm²Hereinafter, preferably 160 μ g/dm²Hereinafter, preferably 150 μ g/dm²Hereinafter, preferably 140 μ g/dm²Hereinafter, excellent It is selected as 130 μ g/dm²Hereinafter, preferably 125 μ g/dm²Hereinafter, preferably 120 μ g/dm²Hereinafter, preferably 115 μ g/dm²Hereinafter, Preferably 110 μ g/dm²Hereinafter, preferably 105 μ g/dm²Hereinafter, preferably 100 μ g/dm²Hereinafter, preferably 95 μ g/dm²With Under, preferably 90 μ g/dm²Hereinafter, preferably 85 μ g/dm²Hereinafter, preferably 80 μ g/dm²Below.

The surface-treated layer of the surface treatment copper foil of the present invention preferably includes Co, and Co in surface-treated layer contains Ratio is 15 mass % or less (except 0 mass %).It is set as 15 mass % by the containing ratio of the Co hereinafter, in the presence of can be into one Step improves the case where frequency transfer characteristic.The containing ratio of the Co is more preferably 14 mass % hereinafter, more preferably 13 mass % Hereinafter, more preferably 12 mass % hereinafter, more preferably 11 mass % hereinafter, more preferably 10 mass % are hereinafter, more preferably 9 Quality % hereinafter, more preferably 8 mass % hereinafter, more preferably 7.5 mass % hereinafter, more preferably 7 mass % are hereinafter, in turn More preferably 6.5 mass % hereinafter, be more preferably 6.0 mass % hereinafter, being more preferably 5.5 mass % or less in turn in turn.Separately Outside, include Co by the surface-treated layer of surface treatment copper foil, the case where raising there are fine circuits formative.Surface-treated layer In the containing ratio of Co be preferably 0 mass % or more, preferably greater than 0 mass %, preferably 0.01 mass % or more, preferably For 0.02 mass % or more, preferably 0.03 mass % or more, preferably 0.05 mass % or more, preferably 0.09 mass % with On, preferably 0.1 mass % or more, preferably 0.11 mass % or more, preferably 0.15 mass % or more, preferably 0.18 matter % or more, preferably 0.2 mass % or more, preferably 0.3 mass % or more, preferably 0.5 mass % or more are measured, preferably 0.8 mass % or more, preferably 0.9 mass % or more, preferably 1.0 mass % or more, preferably 1.5 mass % or more, it is excellent Be selected as 2.0 mass % or more, preferably 2.5 mass % or more, preferably 3.0 mass % or more, preferably 3.5 mass % with On, preferably 4.0 mass % or more, preferably 4.5 mass % or more.

The adhesion amount of Co in surface-treated layer is preferably 30 μ g/dm²More than.It is set as 30 μ g/ by the adhesion amount of the Co dm²More than, the case where dissolubility of etching solution when existing for circuit production improves, and there are fine wiring formatives to become Better situation.In addition, the adhesion amount of the Co in surface-treated layer is preferably 2000 μ g/dm²Below.In addition, passing through the Co Adhesion amount be set as 2000 μ g/dm²Hereinafter, the case where in the presence of can further improve frequency transfer characteristic.With regard to surface treatment copper foil Fine wiring formative viewpoint for, the adhesion amount of the Co in the surface-treated layer is preferably 35 μ g/dm²More than, preferably For 40 μ g/dm²More than, preferably 45 μ g/dm²More than, preferably 50 μ g/dm²More than, preferably 55 μ g/dm²More than, preferably 60μg/dm²More than, preferably 70 μ g/dm²More than, preferably 80 μ g/dm²More than, preferably 90 μ g/dm²More than, preferably 100μg/dm²More than, preferably 150 μ g/dm²More than, preferably 200 μ g/dm²More than, preferably 250 μ g/dm²More than, preferably For 300 μ g/dm²More than, preferably 350 μ g/dm²More than, preferably 400 μ g/dm²More than, preferably 450 μ g/dm²More than, it is excellent It is selected as 500 μ g/dm²More than, preferably 550 μ g/dm²More than, preferably 600 μ g/dm²More than, preferably 650 μ g/dm²More than, Preferably 700 μ g/dm²More than, preferably 940 μ g/dm²More than.In addition, the sight of the frequency transfer characteristic with regard to surface treatment copper foil For point, the adhesion amount of the Co in the surface-treated layer is preferably 1950 μ g/dm²Hereinafter, preferably 1900 μ g/dm²Hereinafter, excellent It is selected as 1850 μ g/dm²Hereinafter, preferably 1800 μ g/dm²Hereinafter, preferably 1750 μ g/dm²Hereinafter, preferably 1700 μ g/dm² Hereinafter, preferably 1650 μ g/dm²Hereinafter, preferably 1600 μ g/dm²Hereinafter, preferably 1550 μ g/dm²Hereinafter, preferably 1500 μg/dm²Hereinafter, preferably 1450 μ g/dm²Hereinafter, preferably 1400 μ g/dm²Hereinafter, preferably 1350 μ g/dm²Hereinafter, it is preferred that For 1300 μ g/dm²Hereinafter, preferably 1250 μ g/dm²Hereinafter, preferably 1200 μ g/dm²Hereinafter, preferably 1150 μ g/dm²With Under, preferably 1100 μ g/dm²Hereinafter, preferably 1050 μ g/dm²Hereinafter, preferably 1000 μ g/dm²Hereinafter, preferably 950 μ g/ dm²Hereinafter, preferably 900 μ g/dm²Hereinafter, preferably 730 μ g/dm²Hereinafter, preferably 700 μ g/dm²Hereinafter, preferably 600 μ g/dm²Hereinafter, preferably 570 μ g/dm²Hereinafter, preferably 550 μ g/dm²Hereinafter, preferably 500 μ g/dm²Hereinafter, preferably 475μg/dm²Below.

Total adhesion amount that the surface treatment copper foil of the present invention is preferably surface-treated layer is 1.0g/m²More than.The surface Total adhesion amount of process layer is the total amount of the adhesion amount for the element for constituting surface-treated layer.Constitute the member of the surface-treated layer Element can for example be enumerated：Cu, Ni, Co, Cr, Zn, W, As, Mo, P, Fe etc..It is set as by total adhesion amount of surface-treated layer 1.0g/m²More than, there is the case where adhesiveness that surface treatment copper foil and resin can be improved.The surface-treated layer adds up to Adhesion amount is preferably 5.0g/m²Below.It is set as 5.0g/m by total adhesion amount of surface-treated layer²Hereinafter, in the presence of can be further The case where improving frequency transfer characteristic.For the viewpoint of the adhesiveness of surface treatment copper foil and resin, the surface-treated layer Total adhesion amount is preferably 1.05g/m²More than, preferably 1.1g/m²More than, preferably 1.15g/m²More than, preferably 1.2g/ m²More than, preferably 1.25g/m²More than, preferably 1.3g/m²More than, preferably 1.35g/m²More than, preferably 1.4g/m²With On, preferably 1.5g/m²More than.In addition, for the viewpoint of the frequency transfer characteristic of surface treatment copper foil, the surface-treated layer Total adhesion amount be preferably 4.8g/m²Hereinafter, preferably 4.6g/m²Hereinafter, preferably 4.5g/m²Hereinafter, preferably 4.4g/ m²Hereinafter, preferably 4.3g/m²Hereinafter, preferably 4.0g/m²Hereinafter, preferably 3.5g/m²Hereinafter, preferably 3.0g/m²Hereinafter, Preferably 2.5g/m²Hereinafter, preferably 2.0g/m²Hereinafter, preferably 1.9g/m²Hereinafter, preferably 1.8g/m²Hereinafter, preferably 1.7g/m²Hereinafter, preferably 1.65g/m²Hereinafter, preferably 1.60g/m²Hereinafter, preferably 1.55g/m²Hereinafter, preferably 1.50g/m²Hereinafter, preferably 1.45g/m²Hereinafter, being more preferably 1.43 μ g/dm in turn²Hereinafter, being more preferably 1.4g/m in turn² Below.

In addition, in the present invention, in the case where surface-treated layer is present in two faces of copper foil, surface-treated layer adds up to The adhesion amount of the elements such as the containing ratio of the Co in adhesion amount, surface-treated layer, the containing ratio of Ni and Co, Ni is wherein one side Equivalent in surface-treated layer is not formed at the conjunction of the element (such as Co etc.) contained in the surface-treated layer in two faces Evaluation.

In addition, the attachment of the element (Co and/or Ni) contained by total adhesion amount of surface-treated layer, surface-treated layer Amount, the containing ratio of Co in surface-treated layer and the containing ratio of the Ni in surface-treated layer can increase in the following manner Or increase：The concentration for forming element when surface-treated layer in used surface treatment liquid is improved, and/or is being surface-treated In the case of plating, improve current density and/or extend the surface treatment time (carrying out conduction time when plating) etc..Separately Outside, total adhesion amount of surface-treated layer, the adhesion amount of element (Co and/or Ni) contained by surface-treated layer, surface treatment The containing ratio of Co in layer and the containing ratio of the Ni in surface-treated layer can reduce and/or reduce in the following manner：Drop The low concentration for forming element when surface-treated layer in used surface treatment liquid, and/or be surface-treated as plating In the case of, reduce current density and/or shorten the surface treatment time (carrying out conduction time when plating) etc..

The present invention surface treatment copper foil surface-treated layer most surface 10 mean roughness Rz be 1.4 μm with Under.If 10 mean roughness Rz of the most surface of surface-treated layer are more than 1.4 μm, exist and generate frequency transfer characteristic deterioration The problem of misgivings.10 mean roughness Rz of the most surface of surface-treated layer are more preferably 1.3 μm hereinafter, more preferably 1.2 μm hereinafter, in turn be more preferably 1.1 μm hereinafter, in turn be more preferably 1.0 μm hereinafter, in turn be more preferably 0.9 μm hereinafter, And then more preferably 0.8 μm or less.So-called " most surface of surface-treated layer ", in multiple layers by being formed by surface treatment Refer to the surface of the layer of multiple layer of outermost (most surface) in the case of forming surface-treated layer.Moreover, more for this 10 mean roughness Rz of surface measurements of the layer of a layer of outermost (most surface).10 points of the most surface of surface-treated layer are flat The lower limit of equal roughness Rz is without being particularly limited to, for typical, for example, 0.01 μm or more, for example, 0.05 μm or more, such as It is 0.1 μm or more.

In addition, in the case where surface treatment is plating, 10 mean roughness Rz of the most surface of surface-treated layer can Increase in the following manner：Current density is improved, and/or extends the surface treatment time (carrying out conduction time when plating) Deng.In addition, in the case where surface treatment is plating, 10 mean roughness Rz of the most surface of surface-treated layer can by with Under type and reduce：Reduce current density, and/or shorten the surface treatment time (carrying out conduction time when plating) etc..

The surface-treated layer of the surface treatment copper foil of the present invention has roughening treatment layer.Roughening treatment layer typically exists The face Nian Jie with resin base material, that is, roughening face of copper foil, by improve be laminated after copper foil peel strength for the purpose of, by The surface of copper foil after degreasing carries out the electro-deposition of " plethora " shape and is formed.Sometimes it carries out common copper facing etc. and is used as roughening Preceding pretreatment also carries out the finishing that common copper facing etc. is used as after roughening sometimes for falling off for electrodeposit is prevented Processing.In the present invention, also including the pretreatment and finishing processing, referred to as " roughening treatment ".

Roughening treatment layer in the surface treatment copper foil of the present invention can for example be formed primary by using condition below After particle, offspring is formed to make.

(plating condition of primary particle)

If enumerating an example of the plating condition of primary particle, as described below.

Liquid forms：10~20g/L of copper, 50~100g/L of sulfuric acid

Liquid temperature：25~50 DEG C

Current density：1~58A/dm²

Coulomb amount：1.5~70As/dm²

(plating condition of offspring)

If enumerating an example of the plating condition of offspring, as described below.

Liquid forms：10~20g/L of copper, 5~15g/L of nickel, 5~15g/L of cobalt

pH：2~3

Liquid temperature：30~50 DEG C

Current density：20~50A/dm²

Coulomb amount：12~50As/dm²

In addition, surface-treated layer can also have more selected from by refractory layer, antirust coat, chromating layer and silane coupled The layer of one or more of the group that reason layer is formed.In addition, the refractory layer, antirust coat, chromating layer, silane coupled place Reason layer can also form (such as 2 layers or more, 3 layers with first-class) by multiple layers respectively.In addition, surface-treated layer can also have：By Ni with selected from by one or more of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Ti group formed element structure At alloy-layer and/or chromating layer and/or silane coupled process layer and/or Ni-Zn alloy-layers.

Well known refractory layer, antirust coat can be used in refractory layer, antirust coat.For example, refractory layer and/or antirust coat can be by selecting From nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group in a kind with The layer that upper element is constituted, or by being selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family One or more of group the element metal layer or alloy-layer that constitute of element, iron, tantalum.In addition, refractory layer and/or antirust coat Also contain the oxide comprising the element, nitride, silicide.In addition, refractory layer and/or antirust coat are alternatively and include The layer of nickel-zinc alloy.In addition, refractory layer and/or antirust coat are alternatively nickel-zinc alloy-layer.Above-mentioned nickel-zinc alloy-layer is in addition to containing Other than inevitable impurity, the also zinc of the nickel containing 50wt%~99wt%, 50wt%~1wt%.Above-mentioned nickel-zinc alloy The zinc of layer and total adhesion amount of nickel can be 5~1000mg/m², preferably 10~500mg/m², preferably 20~100mg/m²。 In addition, the adhesion amount of the adhesion amount and zinc of the nickel of the layer comprising above-mentioned nickel-zinc alloy or above-mentioned nickel-zinc alloy-layer ratio (= The adhesion amount of adhesion amount/zinc of nickel) it is preferably 1.5~10.In addition, the above-mentioned layer comprising nickel-zinc alloy or above-mentioned nickel-zinc are closed The adhesion amount of the nickel of layer gold is preferably 0.5mg/m²~500mg/m², more preferably 1mg/m²~50mg/m².In refractory layer and/or In the case that antirust coat is the layer comprising nickel-zinc alloy, when via hole (ス ル ー ホ ー Le) or through-hole (ビ ア ホ ー Le) etc. Inner wall part and decontamination (デ ス ミ ア) liquid when contacting, the interface of copper foil and resin substrate is difficult to be corroded by decontamination liquid, copper foil with The adhesiveness of resin substrate improves.

Such as it is 1mg/m that refractory layer and/or antirust coat, which can be by adhesion amount,²~100mg/m², preferably 5mg/m²~ 50mg/m²Nickel or nickel alloy layer, with adhesion amount be 1mg/m²~80mg/m², preferably 5mg/m²~40mg/m²Tin layers successively It is laminated and winner, above-mentioned nickel alloy layer also can be by appointing in nickel-molybdenum alloy, nickel-zinc alloy, nickel-molybdenum-cobalt alloy, nickel-tin alloy It is a kind of to be constituted.

In this specification, so-called chromating layer refers to included anhydrous chromic acid, chromic acid, two chromic acid, chromate or two The layer that the solution of chromate is handled.Chromating layer also may include Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, The elements such as As and Ti (can be any forms such as metal, alloy, oxide, nitride, sulfide).Chromating layer it is specific Example can be enumerated：The chromating layer or included anhydrous chromic acid that are handled through anhydrous chromic acid or two chromic acid aqueous solutions of potassium or The chromating layer etc. that the treatment fluid of two potassium chromates and zinc is handled.

Well known silane coupling agent can be used to be formed for silane coupled process layer, it is possible to use epoxy silane, amino system The silane such as silane, methacryloxy system silane, sulfydryl system silane, ethylene base system silane, imidazoles system silane, triazine system silane Coupling agent etc. is formed.In addition, silane coupling agent as described above can also mix two or more to use.Wherein, it is preferable to use Amino system silane coupling agent or epoxy silane coupling agent are come the layer that is formed.

In addition, can to copper foil, very thin layers of copper, roughening treatment layer, refractory layer, antirust coat, silane coupled process layer or The surface of chromating layer carries out well known surface treatment.

In addition, can to copper foil, very thin layers of copper, roughening treatment layer, refractory layer, antirust coat, silane coupled process layer or The surface of chromating layer carries out International Publication number WO2008/053878, Japanese Unexamined Patent Publication 2008-111169, Japan specially Profit the 5024930th, International Publication number WO2006/028207, Japanese Patent No. 4828427, International Publication number WO2006/134868, Japanese Patent No. 5046927, International Publication number WO2007/105635, Japanese Patent No. 5180815 Number, the surface treatment described in Japanese Unexamined Patent Publication 2013-19056.

＜ transmission loss ＞

In the case where transmission loss is small, it is suppressed with high frequency to carry out the decaying of signal when signal transmission, therefore In the circuit with high frequency to carry out signal transmission, stable signal transmission can be carried out.Therefore, the small person of the value of transmission loss is suitble to Circuit purposes for carrying out signal transmission with high frequency, so it is preferred that.By surface treatment copper foil and commercially available liquid crystal polymer Resin (50 μm of the Vecstar CTZ- thickness of Kuraray (Network ラ レ) limited liability company manufacture, hydroxybenzoic acid (ester) and hydroxyl The resin of the copolymer of base naphthoic acid (ester)) fitting after, by etching, form micro-strip in such a way that characteristic impedance reaches 50 Ω Line measures penetrating coefficient, to find out the damage of the transmission under frequency 40GHz in the Network Analyzer HP8720C manufactured using Hewlett-Packard Corporation In the case of consumption, the transmission loss under frequency 40GHz is preferably less than 7.5dB/10cm, more preferably less than 7.3dB/10cm, More preferably less than 7.1dB/10cm, more preferably less than 7.0dB/10cm, more preferably less than 6.9dB/10cm, more preferably Less than 6.8dB/10cm, more preferably less than 6.7dB/10cm, more preferably less than 6.6dB/10cm, so it is more preferably small In 6.5dB/10cm.

Copper foil ＞s of the ＜ with carrier

The copper foil with carrier of another implementation form of the present invention at least one face of a carrier, i.e. face of carrier or Two faces have middle layer, very thin layers of copper successively.Moreover, above-mentioned very thin layers of copper is the table of the implementation form of the present invention Surface treatment copper foil.

＜ carriers ＞

For workable carrier typical case it is metal foil or resin film in the present invention, such as with copper foil, copper alloy foil, nickel Foil, nickel alloy foil, iron foil, ferroalloy foil, stainless steel foil, aluminium foil, alloy foil, insulating resin film, polyimide film, LCP (liquid Crystalline polymer) film, fluororesin film, PET (polyethylene terephthalate) film, PP (polypropylene) film, PA membrane, polyamide acyl The form of imines film provides.

For workable carrier typical case provided in the form of rolled copper foil or electrolytic copper foil in the present invention.In general, Electrolytic copper foil is to power on parsing copper to the bucket of titanium or stainless steel to manufacture from the bath of copper sulphate plating, and rolled copper foil is will to utilize The plastic processing of roll is repeated to manufacture with heat treatment.As the material of copper foil, in addition to tough pitch copper (compile by JIS H3100 alloys Number C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloys number C1011) or phosphorized copper or Other than the copper of the high-purities such as cathode copper, such as it can also be used：The copper of Sn is added, the copper of Ag is added, added with Cr, Zr or Mg etc. Copper alloy, the copper alloy of gloomy series copper alloy of section added with Ni and Si etc. etc.In addition, it is possible to use well known copper alloy.This Outside, also include copper alloy foil when term " copper foil " is used alone in this specification.

Also there is no particular restriction for the thickness of workable carrier in the present invention, as long as appropriate be adjusted to be suitable for playing conduct The thickness of the effect of carrier, such as 5 μm or more can be set as.But if blocked up, increased production cost, so generally preferably To be set as 35 μm or less.Therefore, for the thickness typical case of carrier be 8~70 μm, it is more typical for be 12~70 μm, it is more typical and Speech is 18~35 μm.In addition, for reducing the viewpoint of cost of material, the thickness of carrier is preferably small.Therefore, the thickness of carrier For typical case be 5 μm or more 35 μm hereinafter, preferably 5 μm or more 18 μm hereinafter, preferably 5 μm or more 12 μm hereinafter, preferably 5 μm or more 11 μm hereinafter, preferably 5 μm or more 10 μm or less.In addition, in the case where the thickness of carrier is small, in the logical foil of carrier When easy to produce it is pleated.Pleated generation in order to prevent, such as effectively make the carrying roller of the copper foil manufacturing device with carrier Smoothly or shorten carrying roller at a distance from next carrying roller.In addition, burying in one of manufacturing method as printing distributing board Enter in the case of using the copper foil with carrier in technique (エ Application ベ ッ テ ィ De methods (Enbedded Process)), the rigidity of carrier It must be high.Therefore, for being embedded to technique, the thickness of carrier is preferably 18 μm or more 300 μm hereinafter, preferably 25 μm or more 150 μm hereinafter, preferably 35 μm or more 100 μm hereinafter, in turn be more preferably 35 μm or more 70 μm or less.

In addition, also can be in the surface setting primary particle layer with the surface opposite side for the side that very thin layers of copper is arranged of carrier And offspring layer.In the surface setting primary particle layer and two with the surface opposite side for the side that very thin layers of copper is arranged of carrier Secondary particle layer, this has the following advantages that：When carrier is laminated from the surface side with the primary particle layer and offspring layer When on the supports such as resin substrate, carrier is difficult to remove with resin substrate.

Hereinafter, showing an example for using electrolytic copper foil as the manufacturing condition in the case of carrier.

＜ electrolyte forms ＞

Copper：90~110g/L

Sulfuric acid：90~110g/L

Chlorine：50~100ppm

Levelling agent 1 (bis- (3- sulfapropyls) disulphide)：10~30ppm

Levelling agent 2 (amine compounds)：10~30ppm

The amine compounds of following below formula can be used in above-mentioned amine compounds.

As long as in addition, not stating clearly especially, then the processing used in electrolysis, surface treatment or plating used in the present invention etc. The remainder of liquid is water.

[changing 1]

(in above-mentioned chemical formula, R₁And R₂For selected from by hydroxy alkyl, ether, aryl, the alkyl through aromatic series substitution, insatiable hunger Person in the group formed with alkyl, alkyl)

＜ manufacturing conditions ＞

Current density：70~100A/dm²

Electrolyte temperature：50~60 DEG C

Electrolyte linear speed：3~5m/sec

Electrolysis time：0.5~10 minute

＜ middle layers ＞

Middle layer is set on carrier.Other layers can be also set between carrier and middle layer.In being used in the present invention Interbed is not particularly limited if being constructed as follows:：Before lamination step of the copper foil with carrier on insulating substrate, it is difficult to from load Body removes very thin layers of copper, on the other hand, very thin layers of copper can be removed from carrier after the lamination step on insulating substrate.For example, this The middle layer of the copper foil with carrier of invention may include selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, their conjunction One or more of the group that gold, their hydrate, their oxide, organic matter are formed.In addition, middle layer It is alternatively multiple layers.

In addition, for example, middle layer can be constituted in the following way：Formed from carrier side by be selected from by Cr, Ni, Co, The single metal layer that a kind of element in the element group that Fe, Mo, Ti, W, P, Cu, Al, Zn are constituted is constituted, or by being selected from One or more of the element group being made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn element is constituted Alloy-layer, and be formed on by the element group being made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn The layer that the hydrate or oxide or organic matter of one or more kinds of elements are constituted, or by be selected from by Cr, Ni, Co, The single metal layer that a kind of element in the element group that Fe, Mo, Ti, W, P, Cu, Al, Zn are constituted is constituted, or by being selected from One or more of the element group being made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn element is constituted Alloy-layer.

In the case where middle layer is provided only in single side, preferably the antirusts such as Ni layers are plated in the setting of the opposing face of carrier Layer.In addition, being handled come in the case of middle layer is arranged by chromic acid salt treatment or zinc chromate processing or plating, it is believed that there are chromium Or a part for the metal accompanying by zinc etc. becomes the case where hydrate or oxide.

In addition, for example, middle layer can be sequentially laminated nickel, nickel-phosphor alloy or nickel-cobalt alloy and chromium and structure on carrier At.Since the bonding force of nickel and copper is higher than the bonding force of chromium and copper, so when removing very thin layers of copper, in very thin layers of copper and chromium Interface peel.In addition, the nickel for middle layer expects barriering effect, that is, prevent copper component from being spread from carrier to very thin layers of copper.In The adhesion amount of nickel in interbed is preferably 100 μ g/dm²The above 40000 μ g/dm²Hereinafter, more preferably 100 μ g/dm²Above 4000 μg/dm²Hereinafter, more preferably 100 μ g/dm²The above 2500 μ g/dm²Hereinafter, more preferably 100 μ g/dm²Less than 1000 μg/dm², the adhesion amount of the chromium in middle layer is preferably 5 μ g/dm²The above 100 μ g/dm²Below.

The very thin layers of copper ＞ of ＜

Very thin layers of copper is set on the intermediate layer.Other layers can be also set between middle layer and very thin layers of copper.Very thin layers of copper It can be formed by using the plating of the electrobaths such as copper sulphate, cupric pyrophosphate, sulfamic acid copper, copper cyanider, it is general from can be used for Electrolytic copper foil, and can be with high current density come for forming the aspect of copper foil, preferably copper sulphate is bathed.The thickness of very thin layers of copper There is no particular restriction, usually thinner than carrier, for example, 12 μm or less.It is 0.5~12 μm for typical case, is 1 for more typical ~5 μm, and then be 1.5~4 μm for typical case, and then be 2~3.5 μm for typical case.In addition, can also be arranged on the two sides of carrier Very thin layers of copper.

The surface treatment copper foil and/or the copper foil with carrier of the present invention application method of itself of the present invention is this field Known to technical staff, such as the surface of surface treatment copper foil and/or very thin layers of copper fitted in into paper base material phenol resin, paper substrate Material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth paper composite base material epoxy resin, glass cloth glass non-woven Cloth composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film, liquid crystal polymer, fluororesin, The insulating substrates such as polyamide, low dielectric polyimide film (in the case of the copper foil with carrier, load are peeled after thermo-compression bonding Body) copper clad laminate is formed, the surface treatment copper foil for being adhered to insulating substrate and/or very thin layers of copper are etched to as target Conductive pattern, can finally manufacture printing distributing board.

＜ resin layers ＞

The surface treatment copper foil of the present invention can be to have the tape tree of resin layer on the surface of surface-treated layer or most surface The surface treatment copper foil of lipid layer.In addition, also can by Ni with selected from by Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As and Alloy-layer or chromate coating or silane coupling layer that one or more of the group that Ti is formed element is constituted or The surface of Ni-Zn alloy-layers has resin layer.Resin layer is more preferably the most surface for being formed in surface treatment copper foil.

The copper foil with carrier of the present invention also can be on primary particle layer or offspring layer, refractory layer, antirust coat, chromic acid Has resin layer in salt treatment layer or silane coupled process layer.

Above-mentioned resin layer can be the insulating resin layer of the semi-cured state (B-stage) of bonding agent or bonding.It is so-called Semi-cured state (B-stage), including following state：Its surface is touched with finger, has no adhesion sense, it can be by the insulating resin layer weight Folded keeping, if heated processing in turn, generates curing reaction.

In addition, above-mentioned resin layer may include heat-curing resin or thermoplastic resin.In addition, above-mentioned resin layer It may include thermoplastic resin.Its type is not particularly limited, such as can be enumerated comprising selected from one or more of following group Resin is used as preferred person：Epoxy resin, polyimide resin, multi-functional cyanate esters, maleimide compound, Polymaleimide compounds, maleimide amine system resin, aromatic series maleimide resin, polyvinyl acetal resin, poly- ammonia Carbamate resin, polyether sulfone, polyethersulfone resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubbery Resin, polyamines, aromatic polyamine, polyamide-imide resin, rubber modified epoxy resin, phenoxy resin, carboxy-modified third Alkene nitrile-butadiene resin, polyphenylene oxide, bismaleimide-triazine resin, Thermocurable polyphenylene oxide resin, cyanate ester system tree Fat, the acid anhydride of carboxylic acid, the acid anhydride of polybasic carboxylic acid, the linear polymer with crosslinkable functional group, poly (phenylene ether) resin, 2,2- are bis- (4- cyanic acid bases phenyl) propane, phosphorous phenolic compounds, manganese naphthenate, bis- (4- glycidyl phenyls) propane of 2,2-, poly- Asia Phenyl ether-cyanate ester based resin, silicone-modified polyamide-imide resin, cyano ester resin, phosphonitrile system resin, modified rubber Polyamide-imide resin, isoprene, hydrogenation type polybutadiene, polyvinyl butyrate, phenoxy group, high-molecular-weight epoxy, fragrance Polyamide, fluororesin, bis-phenol, block copolymerization polyimide resin and cyano ester resin.

In addition, above-mentioned epoxy resin can be the resin that intramolecular has 2 or more epoxy groups, if can be used for electrical electricity The resin of sub- material applications can be used then without special problem.In addition, above-mentioned epoxy resin preferably has 2 using intramolecular The compound of the above glycidyl carries out epoxidised epoxy resin.In addition, can be by a kind or 2 in following group Kind or more be used in mixed way：Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A D-ring oxygen tree Fat, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol Phenolic resin varnish type epoxy resin, naphthalene type epoxy resin, brominated bisphenol a type epoxy resin, o-cresol phenolic epoxy varnish, Modified rubber bisphenol A type epoxy resin, glycidyl group amine type epoxy resin, triglycidyl group isocyanuric acid ester, N, N- bis- The ethylene oxidic esters chemical combination such as the glycidyls such as glycidyl aniline amine compounds, tetrahydrophthalic acid 2-glycidyl ester Object, phosphorous epoxy resin, biphenyl type epoxy resin, biphenyl phenolic resin varnish type epoxy resin, trihydroxy benzene methylmethane type ring oxygen Resin, tetraphenyl ethane type epoxy resin；Or the hydrogenation body or halogenation body of above-mentioned epoxy resin can be used.

The well known epoxy resin containing phosphorus can be used in above-mentioned phosphorous epoxy resin.In addition, above-mentioned phosphorous asphalt mixtures modified by epoxy resin Fat is preferably：Such as the miscellaneous -10- phospho hetero phenanthrenes -10- oxygen of 9,10- dihydro-9-oxies by intramolecular with 2 or more epoxy groups Compound and the derivative that comes and the epoxy resin that obtains.

Above-mentioned resin layer may include：Well known resin, resin curing agent, compound, curing accelerator, dielectric substance (also may be used Use any Jie such as the dielectric substance comprising inorganic compound and/or organic compound, the dielectric substance comprising metal oxide Electric body), catalysts, crosslinking agent, polymer, prepreg, framework material etc..In addition, above-mentioned resin layer is usable following special Substance (resin, resin curing agent, compound, curing accelerator, dielectric substance, catalysts, crosslinking described in sharp document Agent, polymer, prepreg, framework material etc.) and/or the forming method of resin layer, forming apparatus formed, such as：It is international public The number of beginning the compilation of WO2008/004399, International Publication number WO2008/053878, International Publication number WO2009/084533, Japan Unexamined Patent 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 No. 2002-179772, Japanese Unexamined Patent Publication 2002-359444, Japanese Unexamined Patent Publication 2003-304068, Japanese Patent No. 3992225 Number, Japanese Unexamined Patent Publication 2003-249739, Japanese Patent No. 4136509, Japanese Unexamined Patent Publication 2004-82687, Japanese Patent No. No. 4025177, Japanese Unexamined Patent Publication 2004-349654, Japanese Patent No. 4286060, Japanese Unexamined Patent Publication No. 2005-262506, day This patent the 4570070th, Japanese Unexamined Patent Publication 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415 Number, International Publication number WO2004/005588, Japanese Unexamined Patent Publication 2006-257153, Japanese Unexamined Patent Publication 2007-326923, Japan Special open 2008-111169, Japanese Patent No. 5024930, International Publication number WO2006/028207, Japanese Patent No. No. 4828427, Japanese Unexamined Patent Publication 2009-67029, International Publication number WO2006/134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication 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 above-mentioned resins are dissolved in such as methyl ethyl ketone (MEK), toluene equal solvent and resin liquid is made, are utilized Such as roll-coater method etc., by above-mentioned resin liquid be coated on above-mentioned surface treatment copper foil and/or above-mentioned very thin layers of copper on, or Include the surface-treated layer of above-mentioned refractory layer, antirust coat or above-mentioned chromate skin membrane or above-mentioned silane coupling agent layer etc. On, it is then optionally thermally dried and removes solvent, become B-stage state.Such as hot-air drying stove is used when dry Can, drying temperature is if 100~250 DEG C, preferably 130~200 DEG C.

Have the surface treatment copper foil of above-mentioned resin layer and/or the copper foil with carrier (has the copper with carrier of resin Foil) it is to be used with following embodiment：After the resin layer is overlapped on base material, entirety is thermally compressed and makes the tree Lipid layer carries out heat cure, then in the case of the copper foil with carrier, removes carrier and very thin layers of copper exposing is made (to expose certainly It is the surface of the middle layer side of the very thin layers of copper), form set Wiring pattern on surface treatment copper foil or very thin layers of copper.

If having the surface treatment copper foil of resin using this and/or with the copper foil of carrier, it is multi-sheet printed that manufacture can be reduced The use the piece number of prepreg material when wiring substrate.Moreover, the thickness of resin layer is set as to can ensure that the thickness of layer insulation, i.e., Just prepreg material is not used completely, can manufacture copper clad laminate yet.In addition, at this time also can be in the surface primary coat insulating resin of base material Further to improve the flatness on surface.

In addition, without using prepreg material, the material cost of prepreg material is saved, in addition lamination step also becomes It obtains simply, therefore becomes advantageous in terms of economy, and there are following advantages：Only correspondingly manufactured with the thickness of prepreg material Multilayer printed wiring board thickness it is thinning, can manufacture 1 layer thickness be 100 μm of very thin multi-sheet printed wiring bases below Plate.

The thickness of the resin layer is preferably 0.1~80 μm.If the thickness of resin layer is thinner than 0.1 μm, bonding force declines, when When the copper foil with carrier with resin being laminated on the base material for having internal layer material in the case where not being situated between every prepreg material, The case where in the presence of the 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, extra fee of material and working hour can be spent, therefore become unfavorable in terms of economy.In turn, it is formed by resin Layer is due to its pliability deterioration, so there are following situations：Cracking etc. is easy tod produce when operation, in addition, being thermally compressed with internal layer material When will produce superfluous resin flowing, to be difficult to the lamination being well on.

In turn, as another product form of the copper foil with carrier with resin, can also be had in above-mentioned very thin layers of copper On some surface-treated layers or above-mentioned refractory layer, antirust coat or above-mentioned chromating layer or above-mentioned silane coupled It is coating by resin layer in process layer, after forming semi-cured state, carrier is then removed, with there is no the copper with resin of carrier The form of foil manufactures.

By the electronic component mounting class on printing distributing board, to complete printed circuit board.In the present invention, " printed wiring Also include printing distributing board as described above equipped with electronic component class and printed circuit board and printed base plate in plate ".

In addition, the printing distributing board can be used to make e-machine, it is possible to use should the print equipped with electronic component class Printed circuit board makes e-machine, it is possible to use should printed base plate equipped with electronic component class make e-machine.With Under, several examples of the manufacturing step of the printing distributing board of the copper foil with carrier using the present invention are shown.In addition, using this hair Very thin layers of copper of the bright surface treatment copper foil as the copper foil with carrier, can similarly manufacture printing distributing board.

In one implementation form of the manufacturing method of the printing distributing board of the present invention, including：Prepare the present invention with carrier Copper foil by " copper foil with carrier " and " very thin layers of copper " (hereinafter, also can be referred to as surface treatment copper foil, in addition by " very thin layers of copper Side " is referred to as " surface-treated layer side ", to manufacture printing distributing board；In the case of antonomasia as described above, as not recording load Body person can also manufacture printing distributing board) and the step of insulating substrate；The above-mentioned copper foil with carrier is laminated with insulating substrate The step of；In such a way that very thin layers of copper side and insulating substrate are opposite, the above-mentioned copper foil with carrier is laminated with insulating substrate Afterwards, by peeling the carrier of the above-mentioned copper foil with carrier the step of, forms copper clad laminate, then, using semi-additive process, Either method in modified form semi-additive process, part addition process and subtractive process is come the step of forming circuit.Insulating substrate can also be set For the substrate for having internal layer circuit is added.

In the present invention, so-called semi-additive process, refer to carried out on insulating substrate or copper foil seed (シ ー De) layer it is thin non- It is electrolysed plating, after forming pattern, using plating and is etched the method that forms conductive pattern.

Therefore, using semi-additive process the present invention printing distributing board manufacturing method an implementation form in, including：It is accurate The step of copper foil and insulating substrate with carrier of the standby present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated；

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

By using the methods of the etching of the etchant solutions such as acid or plasma, above-mentioned carrier will be peeled and exposed very thin The step of layers of copper all removes；

Setting via hole and/or blind hole on the above-mentioned resin exposed to remove above-mentioned very thin layers of copper by using etching The step of；

The step of decontamination processing is carried out to the region comprising above-mentioned via hole and/or blind hole；

The step of electroless plating coating is set to above-mentioned resin and comprising the region of above-mentioned via hole and/or blind hole；

In the step of plating resist coating (め っ I レ ジ ス ト) is arranged on above-mentioned electroless plating coating；

Above-mentioned plating resist coating is exposed, then, will be formed the region of circuit plating resist coating removal the step of；

In the region for the above-mentioned formation circuit for eliminating above-mentioned plating resist coating the step of setting electrolysis plating layer；

The step of removing above-mentioned plating resist coating；And

By dodging erosion etc., by the step of the electroless plating coating removal in the region other than the region of above-mentioned formation circuit Suddenly.

In another implementation form using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including：Prepare The step of copper foil and insulating substrate with carrier of the present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated；

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

Peel above-mentioned carrier and on the very thin layers of copper exposed and above-mentioned insulating resin substrate be arranged via hole and/or The step of blind hole；

The step of decontamination processing is carried out to the region comprising above-mentioned via hole and/or blind hole；

By using the methods of the etching of the etchant solutions such as acid or plasma, above-mentioned carrier will be peeled and exposed very thin The step of layers of copper all removes；

To the above-mentioned resin exposed to remove above-mentioned very thin layers of copper by using etching etc. and comprising above-mentioned via hole And/or the step of electroless plating coating is arranged in the region of blind hole；

In the step of plating resist coating is arranged on above-mentioned electroless plating coating；

Above-mentioned plating resist coating is exposed, then, will be formed the region of circuit plating resist coating removal the step of；

In the region for the above-mentioned formation circuit for eliminating above-mentioned plating resist coating the step of setting electrolysis plating layer；

The step of removing above-mentioned plating resist coating；And

By dodging erosion etc., by the step of the electroless plating coating removal in the region other than the region of above-mentioned formation circuit Suddenly.

In another implementation form using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including：Prepare The step of copper foil and insulating substrate with carrier of the present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated；

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

Peel above-mentioned carrier and on the very thin layers of copper exposed and above-mentioned insulating resin substrate be arranged via hole and/or The step of blind hole；

By using the methods of the etching of the etchant solutions such as acid or plasma, above-mentioned carrier will be peeled and exposed very thin The step of layers of copper all removes；

The step of decontamination processing is carried out to the region comprising above-mentioned via hole and/or blind hole；

To the above-mentioned resin exposed to remove above-mentioned very thin layers of copper by using etching etc. and comprising above-mentioned via hole And/or the step of electroless plating coating is arranged in the region of blind hole；

In the step of plating resist coating is arranged on above-mentioned electroless plating coating；

Above-mentioned plating resist coating is exposed, then, will be formed the region of circuit plating resist coating removal the step of；

In the region for the above-mentioned formation circuit for eliminating above-mentioned plating resist coating the step of setting electrolysis plating layer；

The step of removing above-mentioned plating resist coating；And

By dodging erosion etc., by the step of the electroless plating coating removal in the region other than the region of above-mentioned formation circuit Suddenly.

In another implementation form using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including：Prepare The step of copper foil and insulating substrate with carrier of the present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated,

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

By using the methods of the etching of the etchant solutions such as acid or plasma, above-mentioned carrier will be peeled and exposed very thin The step of layers of copper all removes；

Non-electrolytic plating is arranged to the surface of the above-mentioned resin exposed to remove above-mentioned very thin layers of copper by using etching The step of layer；

In the step of plating resist coating is arranged on above-mentioned electroless plating coating；

Above-mentioned plating resist coating is exposed, then, will be formed the region of circuit plating resist coating removal the step of；

In the region for the above-mentioned formation circuit for eliminating above-mentioned plating resist coating the step of setting electrolysis plating layer；

The step of removing above-mentioned plating resist coating；And

By dodging erosion etc., by the electroless plating coating in the region other than the region of above-mentioned formation circuit and very thin copper The step of layer removal.

In the present invention, so-called modified form semi-additive process refers to following method：Laminated metal foil on the insulating layer, using anti- Plating layer protects inverter circuit forming portion, after being electrolysed plating thickness copper of the plating carrying out circuit forming portion, removes resist, leads to (flash of light (Off ラ ッ シ ュ)) etching is crossed to remove the metal foil other than foregoing circuit forming portion, forms electricity on the insulating layer whereby Road.

Therefore, using modified form semi-additive process the present invention printing distributing board manufacturing method an implementation form in, Including：The step of preparing the copper foil and insulating substrate with carrier of the present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated；

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

Peeling above-mentioned carrier and setting via hole and/or the step of blind hole in the very thin layers of copper and insulating substrate exposed；

The step of decontamination processing is carried out to the region comprising above-mentioned via hole and/or blind hole；

The step of electroless plating coating is arranged to the region comprising above-mentioned via hole and/or blind hole；

In the step of plating resist coating is arranged in the very thin layers of copper surface for peeling above-mentioned carrier and exposing；

After above-mentioned plating resist coating is arranged, by being electrolysed plating come the step of forming circuit；

The step of removing above-mentioned plating resist coating；And

The step of being lost by dodging, the very thin layers of copper exposed by removing above-mentioned plating resist coating removed.

In another implementation form using the manufacturing method of the printing distributing board of the present invention of modified form semi-additive process, packet It includes：The step of preparing the copper foil and insulating substrate with carrier of the present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated；

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

Peel above-mentioned carrier and the step of plating resist coating is set in the very thin layers of copper exposed；

Above-mentioned plating resist coating is exposed, then, will be formed the region of circuit plating resist coating removal the step of；

In the region for the above-mentioned formation circuit for eliminating above-mentioned plating resist coating the step of setting electrolysis plating layer；

The step of removing above-mentioned plating resist coating；And

By dodging erosion etc., by the electroless plating coating in the region other than the region of above-mentioned formation circuit and very thin copper The step of layer removal.

In the present invention, so-called part addition process refers to following method：The substrate made of conductor layer is arranged optionally is beaten Go out on substrate made of the hole of via hole or through-hole and assign catalyst core, is etched and forms conductor circuit, optionally set After setting solder mask (ソ Le ダ レ ジ ス ト) or plating resist coating, on above-mentioned conductor circuit, by non-electrolytic plating handle come pair Via hole or through-hole etc. carry out thick plating, manufacture printing distributing board whereby.

Therefore, using part addition process the present invention printing distributing board manufacturing method an implementation form in, including： The step of preparing the copper foil and insulating substrate with carrier of the present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated；

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

Peeling above-mentioned carrier and setting via hole and/or the step of blind hole in the very thin layers of copper and insulating substrate exposed；

The step of decontamination processing is carried out to the region comprising above-mentioned via hole and/or blind hole；

The step of catalyst core being assigned to the region comprising above-mentioned via hole and/or blind hole；

Peel above-mentioned carrier and expose very thin layers of copper surface setting resistant layer (エ ッ チ Application グ レ ジ ス ト) step Suddenly；

The step of above-mentioned resistant layer is exposed and forms circuit pattern；

By using the methods of the etching of the etchant solutions such as acid or plasma, above-mentioned very thin layers of copper and above-mentioned catalysis are removed Agent core and the step of form circuit；

The step of removing above-mentioned resistant layer；

By using etchant solutions such as acid etching or the methods of plasma remove above-mentioned very thin layers of copper and above-mentioned Catalyst core and the above-mentioned insulating substrate surface exposed, the step of solder mask or plating resist coating are set；And

In the step of electroless plating coating is arranged in the region that above-mentioned solder mask or plating resist coating are not arranged.

In the present invention, so-called subtractive process refers to by etching etc., being optionally removed copper foil on copper clad laminate not The method for needing part and forming conductive pattern.

Therefore, using subtractive process the present invention printing distributing board manufacturing method an implementation form in, including：Prepare The step of copper foil and insulating substrate with carrier of the present invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated,

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

Peeling above-mentioned carrier and setting via hole and/or the step of blind hole in the very thin layers of copper and insulating substrate exposed；

The step of decontamination processing is carried out to the region comprising above-mentioned via hole and/or blind hole；

The step of electroless plating coating is arranged to the region comprising above-mentioned via hole and/or blind hole；

On the surface of above-mentioned electroless plating coating the step of setting electrolysis plating layer；

In the step of resistant layer is arranged in the surface of above-mentioned electrolysis plating layer and/or above-mentioned very thin layers of copper；

The step of above-mentioned resistant layer is exposed and forms circuit pattern；

By using the methods of the etching of the etchant solutions such as acid or plasma, above-mentioned very thin layers of copper, above-mentioned non-electrical are removed The step of solving plating layer and above-mentioned electrolysis plating layer and forming circuit；And

The step of removing above-mentioned resistant layer.

In another implementation form using the manufacturing method of the printing distributing board of the present invention of subtractive process, including：Prepare this The step of copper foil and insulating substrate with carrier of invention；

The step of above-mentioned copper foil with carrier and insulating substrate are laminated；

After the above-mentioned copper foil with carrier and insulating substrate are laminated, the step of the carrier of the above-mentioned copper foil with carrier is peeled Suddenly；

Peeling above-mentioned carrier and setting via hole and/or the step of blind hole in the very thin layers of copper and insulating substrate exposed；

The step of decontamination processing is carried out to the region comprising above-mentioned via hole and/or blind hole；

The step of electroless plating coating is arranged to the region comprising above-mentioned via hole and/or blind hole；

In the step of surface of above-mentioned electroless plating coating forms mask；

On the surface for the above-mentioned electroless plating coating for not forming mask the step of setting electrolysis plating layer；

In the step of resistant layer is arranged in the surface of above-mentioned electrolysis plating layer and/or above-mentioned very thin layers of copper；

The step of above-mentioned resistant layer is exposed and forms circuit pattern；

By using the methods of the etching of the etchant solutions such as acid or plasma, above-mentioned very thin layers of copper and above-mentioned non-electrical are removed The step of solving plating layer and forming circuit；And

The step of removing above-mentioned resistant layer.

Be arranged via hole and/or the step of blind hole, with and subsequent decontamination step also can be without.

Herein, using schema, the manufacturing method of the printing distributing board of the copper foil with carrier to using the present invention it is specific Example is described in detail.

First, as shown in Fig. 1-A, prepare surface have the very thin layers of copper for being formed with roughening treatment layer with carrier Copper foil (the 1st layer).

Then, as shown if figure 1-b, it is coated with resist on the roughening treatment layer of very thin layers of copper, is exposed development, Resist is etched to set shape.

Then, as shown in Fig. 1-C, after forming the plating layer of circuit, resist is removed, forms the electricity of set shape whereby Road plating layer.

Then, as depicted in fig. 2-d, in a manner of covering circuit plating layer (in such a way that circuit plating layer buries), in pole Setting embedment resin carrys out laminated resin layer on thin copper layer, then from another copper foil (second with carrier of very thin layers of copper side bonds Layer).

Then, as shown in Fig. 2-E, carrier is peeled from the copper foil with carrier of the second layer.

Then, as shown in Fig. 2-F, laser boring is carried out in the commitment positions of resin layer, circuit plating layer is made to expose and shape At blind hole.

Then, as shown in Fig. 3-G, it is embedded to copper in blind hole, forms through-hole filling.

Then, as shown in Fig. 3-H, in through-hole filling, circuit plating layer is formed as described in above-mentioned Fig. 1-B and Fig. 1-C.

Then, as shown in Fig. 3-I, carrier is peeled from the 1st layer of the copper foil with carrier.

Then, as shown in Fig. 4-J, the very thin layers of copper on two surfaces is removed by dodging erosion, makes the circuit plating in resin layer Expose on the surface of layer.

Then, as shown in Fig. 4-K, convex block is formed on the circuit plating layer in resin layer, copper post is formed on the solder. So come make using the present invention the copper foil with carrier printing distributing board.

In addition, in the manufacturing method of above-mentioned printing distributing board, " very thin layers of copper " can be also referred to as to carrier, and " will carry Body " is referred to as very thin layers of copper, in the circuit forming surface of the carrier side of the copper foil with carrier, circuit is embedded to resin, to manufacture Printing distributing board.In addition, in the manufacturing method of above-mentioned printing distributing board, it also can be " coarse with being formed on surface by inciting somebody to action Change the copper foil with carrier of the very thin layers of copper of process layer " it is referred to as surface treatment copper foil, in the surface treatment of surface treatment copper foil The circuit forming surface with surface-treated layer opposite side of layer side surface or surface treatment copper foil is embedded to circuit, so with resin Afterwards, surface treatment copper foil is removed, to manufacture printing distributing board.In addition, so-called in this specification " at the surface of surface treatment copper foil Manage layer side surface ", refer to the surface of the side with surface-treated layer of surface treatment copper foil, or the one of surface-treated layer Refer to the surface treatment copper foil after part or all of surface-treated layer is removed in the case of being partly or entirely removed The surface of side with surface-treated layer.That is, so-called " the surface-treated layer side surface of surface treatment copper foil ", it includes " table to be Part or all of the most surface of surface treatment layer " and surface-treated layer be removed after surface treatment copper foil surface it is general It reads.

The copper foil with carrier of the present invention can be used in above-mentioned another copper foil (second layer) with carrier, it is possible to use pervious Copper foil with carrier, and then common copper foil can also be used.In addition, on the circuit of the second layer shown in Fig. 3-H, it also can be in turn The circuit for forming 1 layer or multilayer, can also be used in semi-additive process, subtractive process, part addition process or modified form semi-additive process Either method is formed to carry out these circuits.

If using the manufacturing method of printing distributing board as described above, the structure in circuit plating layer embedment resin layer is formed At, therefore, as shown in such as Fig. 4-J, by dodge erosion make a return journey depolarization thin copper layer when, circuit plating layer is protected by resin layer, Its shape is kept, is easy to form fine circuits whereby.In addition, since circuit plating layer is protected by resin layer, so resistance to migration Property improve, the conducting of the wiring of circuit inhibited well.Therefore, it is easy to form fine circuits.In addition, when such as Fig. 4-J and figure Shown in 4-K, by dodge erosion make a return journey depolarization thin copper layer when, the exposed surface of circuit plating layer becomes the shape being recessed from resin layer, because This is easy to form convex block on the circuit plating layer, and then is formed on copper post, and manufacture efficiency improves.

In addition, well known resin, prepreg can be used in embedment resin.Such as it can be used：BT(スマレイミドトリアジ Application, Bismaleimide Triazine) resin or as prepreg, aginomoto fine chemistry share containing the glass cloth for being soaked with BT resins The ABF films or ABF of Co., Ltd's manufacture.In addition, resin layer and/or tree described in this specification can be used in above-mentioned embedment resin Fat and/or prepreg.

In addition, the copper foil with carrier used in above-mentioned first layer also can have substrate on the surface of the copper foil with carrier Or resin layer.By having the substrate or resin layer, the copper foil with carrier used in first layer is supported, it is difficult to generate pleat Wrinkle, therefore have the advantages that productivity raising.In addition, in aforesaid substrate or resin layer, as long as with supporting in above-mentioned first layer All substrate or resin layer may be used in the effect of the copper foil with carrier used.Such as present application specification can be used Described in carrier, prepreg, resin layer or well known carrier, prepreg, resin layer, metallic plate, metal foil, inorganic compound Plate, the foil of inorganic compound, the plate of organic compound, organic compound foil be used as aforesaid substrate or resin layer.

In addition, the manufacturing method of the printing distributing board of the present invention can be the manufacturer of the printing distributing board included the following steps Method (centreless (U ア レ ス) technique)：By the above-mentioned very thin layers of copper side surface of the copper foil with carrier of the present invention or above-mentioned carrier side The step of surface is laminated with resin substrate；With the very thin layers of copper side surface or above-mentioned carrier that are laminated with above-mentioned resin substrate The step of surface of the copper foil with carrier of side surface opposite side, at least 1 time setting resin layer and circuit；And it is above-mentioned being formed After 2 layers of resin layer and circuit, the step of removing above-mentioned carrier or above-mentioned very thin layers of copper from the above-mentioned copper foil with carrier.About this Centreless technique, concrete example are：First, by the present invention the copper foil with carrier very thin layers of copper side surface or carrier side surface with Resin substrate is laminated to manufacture layered product (also referred to as copper clad laminate, copper-clad laminate).Then, with resin substrate The very thin layers of copper side surface of lamination or the surface of the copper foil with carrier of above-mentioned carrier side surface opposite side form resin layer.In shape At on the resin layer of carrier side surface or very thin layers of copper side surface, also can and then be laminated from carrier side or very thin layers of copper side another Copper foil with carrier.In addition, layered product below can be also used for the manufacturing method (centreless technique) of above-mentioned printing distributing board： With centered on resin substrate or resin or prepreg, in two surface sides of the resin substrate or resin or prepreg, with The sequence of carrier/middle layer/very thin layers of copper or the sequence of very thin layers of copper/middle layer/carrier carry out the copper foil of laminating strips carrier The layered product of composition；Or with " carrier/middle layer/very thin layers of copper/resin substrate or resin or prepreg/carrier/centre The sequence of layer/very thin layers of copper " is come the layered product for the composition being laminated；Or with " carrier/middle layer/very thin layers of copper/resin base The sequence of plate/carrier/middle layer/very thin layers of copper " is come the layered product for the composition being laminated；Or with " very thin layers of copper/centre The sequence of layer/carrier/resin substrate/carrier/middle layer/very thin layers of copper " is come the layered product for the composition being laminated.Moreover, in the layer The surface of the very thin layers of copper at the both ends of laminate or the exposing of carrier, also can be by being arranged another resin layer, and then copper is arranged Layer is either processed the layers of copper or metal layer after metal layer and forms circuit.In turn, the side of the circuit can also be embedded to Another resin layer is set on the circuit by formula.In addition, can by the formation of circuit as described above and resin layer carry out 1 time with Upper (increasing layer (ビ Le De ア ッ プ) technique).Moreover, about the layered product formed in the above described manner (hereinafter also referred to as layered product B), the very thin layers of copper or carrier that can make each copper foil with carrier make coreless substrate from carrier or the stripping of very thin layers of copper.This Outside, in the making of the coreless substrate, it is possible to use 2 copper foils with carrier, make it is aftermentioned have very thin layers of copper/in The layered product of the composition of interbed/carrier/carrier/middle layer/very thin layers of copper or with carrier/middle layer/very thin layers of copper/very thin The layered product of the composition of layers of copper/middle layer/carrier has carrier/middle layer/very thin layers of copper/carrier/middle layer/very thin copper The layered product is used for center by the layered product of the composition of layer.It can be in the both sides of these layered products (hereinafter also referred to as layered product A) Very thin layers of copper or carrier surface, the resin layer and circuit of setting 1 time or more, the resin layer and circuit of setting 1 time or more Afterwards, the very thin layers of copper or carrier for making each copper foil with carrier make coreless substrate from carrier or the stripping of very thin layers of copper.It is described Layered product also can between the surface of very thin layers of copper, the surface of carrier, carrier and carrier, very thin layers of copper and very thin layers of copper it Between, there are other layers between very thin layers of copper and carrier.Other layers can be resin substrate or resin layer.In addition, in this specification, In very thin layers of copper, carrier, layered product in the case where very thin layers of copper surface, carrier surface, laminate surface have other layers, " surface of very thin layers of copper ", " very thin layers of copper side surface ", " very thin layers of copper surface ", " surface of carrier ", " carrier side surface ", " carrier surface ", " surface of layered product ", " laminate surface " are set as the concept on the surface (most surface) comprising other layers.Separately Outside, layered product is preferably the composition with very thin layers of copper/middle layer/carrier/carrier/middle layer/very thin layers of copper.Its reason exists In, when using the layered product come when making coreless substrate, due to configuring very thin layers of copper in coreless substrate side, so use modified form Semi-additive process is easy to form circuit on coreless substrate.Another reason is, since the thickness of very thin layers of copper is thin, so the pole Thin copper layer easily removes, and semi-additive process is used after removing very thin layers of copper, is easy to form circuit on coreless substrate.

In addition, in this specification, " layered product " expression for not recording " layered product A " or " layered product B " especially includes at least The layered product of layered product A and layered product B.

In addition, in the manufacturing method of above-mentioned coreless substrate, by (including by the copper foil with carrier or above-mentioned layered product Layered product A) part or all of end face covered with resin, when manufacturing printing distributing board, can prevent using increasing layer technique Only liquid penetrates between 1 copper foil with carrier and another 1 copper foil with carrier of middle layer or composition layered product, can prevent The separation of very thin layers of copper and carrier caused by infiltration by liquid or the corrosion of the copper foil with carrier, can be improved yield.Herein " by resin of part or all of covering of the end face of the copper foil with carrier " used is or " by one of the end face of layered product The resin for dividing or all covering " can be used for the resin of resin layer or well known resin.In addition, above-mentioned coreless substrate In manufacturing method, the laminated portion of the copper foil with carrier or layered product when being overlooked in the copper foil with carrier either layered product (carrier and the laminated portion of very thin layers of copper or the laminated portion of 1 copper foil with carrier and another 1 copper foil with carrier) At least part of periphery can be covered by resin or prepreg.In addition, using the manufacturing method of above-mentioned coreless substrate come shape At layered product (layered product A) a pair of copper foil with carrier can be made to be contacted in a manner of it can be separated from each other and constituted.In addition, at this When being overlooked in the copper foil with carrier, laminated portion (carrier and the very thin layers of copper of the copper foil with carrier or layered product can be also spread Laminated portion or 1 copper foil with carrier and another 1 copper foil with carrier laminated portion) periphery entirety or The entire surface of laminated portion, is covered by resin or prepreg.In addition, in the case of vertical view, resin or prepreg are excellent It is selected as being more than the laminated portion of the either layered product either layered product of the copper foil with carrier preferably by the resin or prepreg The two sides for being pressed on the either layered product of the copper foil with carrier is formed with the copper foil with carrier or layered product by resin or preimpregnation Material the composition of packed (package) layered product.By being set as constituting as described above, when copper foil or layer of the vertical view with carrier When laminate, the laminated portion of the either layered product of the copper foil with carrier is covered by resin or prepreg, can prevent other components It is that lateral direction is collided from the side direction of the part, i.e. for laminating direction, as a result can reduces the carrier in operation The mutual peeling of copper foil with very thin layers of copper or with carrier.In addition, by not expose the copper foil or layered product with carrier The mode of periphery of laminated portion covered by resin or prepreg, can prevent in liquid processing step as described above Immersion of the liquid to the interface of the laminated portion, can anti-stop-band carrier copper foil corrosion or erosion.In addition, working as from layered product A pair isolates a copper foil with carrier on the copper foil with carrier when or by the carrier of the copper foil with carrier and copper foil (pole Thin copper layer) separation when, by the resin copper foil with carrier or layered product that either prepreg is covered laminated portion (carry Body and the laminated portion of very thin layers of copper or the laminated portion of 1 copper foil with carrier and another 1 copper foil with carrier) it utilizes Resin or prepreg etc. and in the case of secure adhesion, the feelings of the laminated portion etc. must be removed by cutting off etc. by existing Condition.

Also the copper foil with carrier of the present invention can be laminated to the band of another present invention from carrier side or very thin layers of copper side The carrier side of the copper foil of carrier or very thin layers of copper side, to constitute layered product.In addition, or copper foil of the said one with carrier Above-mentioned carrier side surface or above-mentioned very thin layers of copper side surface, with the above-mentioned carrier side surface of another above-mentioned copper foil with carrier or Above-mentioned very thin layers of copper side surface, optionally via bonding agent, contact laminating and the layered product that obtains.In addition, said one band carries It is the carrier of the copper foil of body or very thin layers of copper, also engageable with the carrier of another above-mentioned copper foil with carrier or very thin layers of copper.This Place, in the case where carrier or very thin layers of copper have surface-treated layer, it includes phase via the surface-treated layer to be somebody's turn to do " engagement " also Inter-engaging embodiment.In addition, part or all of the end face of the layered product can also be covered by resin.

Carrier each other, very thin layers of copper each other, carrier and very thin layers of copper, the mutual lamination of the copper foil with carrier is in addition to merely Other than overlapping, such as it can be carried out using the following method.

(a) metallurgical joint method：((タ Application グ ス テ Application イ ナ ー ト ガ ス, tungsten are lazy by arc welding, TIG for welding Property gas) welding, MIG (メ タ Le イ ナ ー ト ガ ス, Metallic Inert Gas) welding, resistance welding, seam weld Connect, be spot welded), crimping (ultrasonic bonding, friction stir weld), soldering；

(b) mechanicalness joint method：Ca(u)lk (passes through the engagement of self-piercing riveting, connecing by riveting using the engagement of rivet Close), quilter；

(c) physical joint method：Bonding agent, (two sides) adhesive tape.

By using above-mentioned joint method, by part or all of part with another carrier of carrier or complete Part or all of portion or very thin layers of copper are engaged, and a carrier and another carrier or very thin layers of copper are carried out layer Pressure, can manufacture makes carrier each other or carrier contacts in a detachable fashion with very thin layers of copper and the layered product that constitutes.At one Carrier is lightly engaged with another carrier or very thin layers of copper, and a carrier is laminated with another carrier or very thin layers of copper In the case of, even if not removing a carrier and another carrier or the joint portion of very thin layers of copper, a carrier and another carrier Or very thin layers of copper also separates.In addition, in the case where a carrier is strongly engaged with another carrier or very thin layers of copper, lead to Cross cut-out or chemical grinding (etching etc.), mechanical lapping etc., the portion that a carrier is engaged with another carrier or very thin layers of copper Position removal, can detach a carrier with another carrier or very thin layers of copper.

In addition, the printing distributing board without core can be made by implementing the steps of：What is constituted in the above described manner At least 1 time setting resin layer and the step of circuit on layered product；And after at least 1 time forms above-mentioned resin layer and circuit, from The step of copper foil with carrier of above-mentioned layered product removes above-mentioned very thin layers of copper or carrier.In addition, also can the layered product extremely One or two surface of a few face, i.e. layered product, is arranged resin layer and circuit.

The resin substrate, resin layer, resin, the prepreg that are used in the layered product can be the resin described in this specification Layer, also may include this specification record resin layer used in resin, resin curing agent, compound, curing accelerator, Jie Electric body, catalysts, crosslinking agent, polymer, prepreg, framework material etc..In addition, the copper foil with carrier or lamination Body can be less than resin either prepreg or resin substrate or resin layer when looking down.

In addition, as long as resin substrate has the characteristic for being applicable to printing distributing board etc., then it is not particularly limited, for example, Rigid PWB with can be used on the way：Paper base material phenol resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass Cloth paper composite base material epoxy resin, glass cloth glass non-woven fabric composite base material epoxy resin and glass cloth base material asphalt mixtures modified by epoxy resin Fat etc., FPC usable polyester film or polyimide film, LCP (liquid crystal polymer) film, fluororesin etc. on the way.In addition, using In the case of LCP films or fluororesin film, for there is the case where relatively using polyimide film, the stripping of the film and surface treatment copper foil The tendency to become smaller from intensity.Therefore, using LCP films or fluororesin film, by after forming copper circuit, to cover Layer covers copper circuit, then the film is difficult to peel off with copper circuit, can prevent from declining the caused film by peel strength electric with copper The stripping on road.

[embodiment]

Hereinafter, being illustrated based on Examples and Comparative Examples.In addition, the present embodiment always as an example of, not only limit Due to the example.That is, including other embodiment contained in the present invention or deformation.

The former foil of embodiment 6 and comparative example 4 is that (JIS H3100 C1100 are advised using the rolled copper foil TPC of 12 μm of thickness Fixed tough pitch copper, JX metals manufacture, 10 Rz=0.7 μm of mean roughness on surface).The former foil of embodiment 7 and comparative example 5 is to make With 12 μm of electrolytic copper foil (the HLP foils that JX metals manufacture, 10 mean roughness Rz=on the surface of precipitation face (faces M) of thickness 0.7 μm), face (faces M) is precipitated, surface-treated layer is set.

In addition, Examples 1 to 5,8~15 and the former foil of comparative example 1~3 are carried using using band made of following methods The copper foil of body.

Examples 1 to 5,8,10~15, comparative example 1~3 be prepare 18 μm of thickness electrolytic copper foil (JX metals manufacture JTC foils) it is used as carrier, embodiment 9 is to prepare the standard rolled copper foil TPC of above-mentioned 18 μm of thickness to be used as carrier.And profit With following conditions, middle layer is formed on the surface of carrier, and (1 μm or 3 μ of thickness recorded in table 1 is formed on the surface of middle layer M) very thin layers of copper.In addition, in the case where carrier is electrolytic copper foil, middle layer is formed in glassy surface (faces S).

Examples 1 to 5,8~15 and comparative example 1~3

＜ middle layers ＞

(1) Ni layers (plating Ni)

Carrier is electroplated on the continuous plating wiring of roll-to-roll type by using condition below, forms 3000 μ g/dm²Adhesion amount Ni layers.Specific plating condition is recorded below.

Nickel sulfate：270~280g/L

Nickel chloride：35~45g/L

Nickel acetate：10~20g/L

Boric acid：30~40g/L

Polishes：Saccharin, butynediols etc.

Lauryl sodium sulfate：55~75ppm

pH：4~6

Liquid temperature：55~65 DEG C

Current density：10A/dm²

(2) Cr layers (electrolytic chromate processing)

Then, after the Ni layer surfaces formed in (1) being carried out washing and pickling, then, in the continuous plating of roll-to-roll type On line, electrolytic chromate processing is carried out by using condition below, 11 μ g/dm are adhered on Ni layers²Adhesion amount Cr layers.

1~10g/L of potassium bichromate, zinc 0g/L

pH：7~10

Liquid temperature：40~60 DEG C

Current density：2A/dm²

The very thin layers of copper ＞ of ＜

Then, after the Cr layer surfaces formed in (2) being carried out washing and pickling, then, in the continuous plating of roll-to-roll type It on line, is electroplated by using condition below, forms the very thin copper of the thickness (1 μm or 3 μm) recorded in table 1 on Cr layers Layer makes the copper foil with carrier.

Copper concentration：90~110g/L

Sulfuric acid concentration：90~110g/L

Chloride ion concentration：50~90ppm

Levelling agent 1 (bis- (3- sulfapropyls) disulphide)：10~30ppm

Levelling agent 2 (amine compounds)：10~30ppm

In addition, using following amine compounds as levelling agent 2.

[changing 2]

(in above-mentioned chemical formula, R₁And R₂For selected from by hydroxy alkyl, ether, aryl, the alkyl through aromatic series substitution, insatiable hunger Person in the group formed with alkyl, alkyl)

Electrolyte temperature：50~80 DEG C

Current density：100A/dm²

Electrolyte linear speed：1.5~5m/sec

＜ roughening treatments 1,2 ＞ of roughening treatment

Then, it is bathed using the plating recorded in table 3, is roughened 1 as described in Table 1.About embodiment 3, 12~14, comparative example 1,4,5 are bathed after roughening treatment 1 using the plating recorded in table 3, are carried out as described in Table 1 Roughening treatment 2.

The resistance to heat treatments of ＜, antirust treatment ＞

Then, it about embodiment 2,3,9~14, is bathed using the plating recorded in table 4, it is heat-resisting to carry out as described in Table 1 Processing.In turn, it about embodiment 9,11, is bathed using the plating recorded in table 4, carries out antirust treatment as described in Table 1.

＜ chromic acid salt treatment, silane coupled processing ＞

Then, electrolytic chromate processing below is carried out to Examples 1 to 5,8~15, the Comparative Examples 1 to 5.

Electrolytic chromate processing

Liquid forms：Potassium bichromate 1g/L

Liquid temperature：40~60 DEG C

pH：0.5~10

Current density：0.01~2.6A/dm²

Conduction time：0.05~30 second

Then, the silane below using diamino silanes is carried out for Examples 1 to 5,7,9~15, the Comparative Examples 1 to 5 Coupling processing.

Silane coupled processing

Silane coupling agent：N-2- (amino-ethyl) -3- TSL 8330s

Silane coupled agent concentration：0.5~1.5vol%

Treatment temperature：20~70 DEG C

Processing time：0.5~5 second

(total adhesion amount of surface-treated layer)

The determination of roughening particle number before etching

Using scanning electron microscope (SEM), with 10000 times to embodiment, comparative example with surface-treated layer Surface side shoots photo.Of roughening particle is counted in arbitrary 3 visuals field of 5 μm of 5 μ m of size of the photo obtained Number.Also, using the arithmetic mean of instantaneous value of the roughening particle in 3 visuals field as the number of the roughening particle in every 1 visual field.This Outside, the roughening particle about the part comprising roughening particle in the visual field, also counts as roughening particle.

The implementation of etching

Using condition below, etching in 0.5 second is carried out.

(etching condition)

Etching form：Spraying etching

Spray nozzle：Solid-cone (Off ル コ ー Application) type

Spraying pressure：0.10MPa

Etching solution temperature：30℃

Etching solution forms：

H₂O₂ 18g/L

H₂SO₄ 92g/L

Cu 8g/L

The FE-830IIW3C of additive JCU limited liability companies manufacture is appropriate

Remainder water

In addition, corroded caused by etching solution in order to prevent, the face of the side not being etched is with resistance to acid band or pre- Material etc. is soaked to cover.

The measurement of the roughening particle number of sample surfaces after etching and the decision for etching the end time

By with it is described it is identical in a manner of measure etching after sample surfaces roughening particle number.

Moreover, becoming 5% or more 20% below of the roughening particle number before etching in roughening particle number In the case of number, terminate etching.

In addition, the roughening particle number whether be etching before roughening particle number 5% or more 20% with Under number judgement, be to be carried out according to whether the value A of the following formula is 5% or more 20% or less.

Roughening particle number after A (%)=etching is (a/25 μm²Roughening particle number (a/25 μ before)/etching m²) × 100%

The reason of setting the benchmark that the etching terminates is, at the position that the roughening particle of sample surfaces is not present, There are under surface-treated layer copper foil or very thin layers of copper be etched the case where.It is thick before roughening particle number is more than etching In the case of the 20% of roughening particle number, etching in 0.5 second is carried out again.Moreover, by the survey of the roughening particle number It is fixed, be repeated with the etching in 0.5 second, until roughening particle number becomes the particle number that is roughened before etching Until 20% number below.In addition, when carrying out initial etching in 0.5 second, becomes in roughening particle number and be less than etching In the case of the 5% of preceding roughening particle number, be set as to times of 0.4 second 0.05 second or more range below the time of etching One time (such as 0.05 second, 0.1 second, 0.15 second, 0.2 second, 0.25 second, 0.3 second, 0.35 second or 0.4 second), to carry out the erosion The measurement of the roughening particle number of sample surfaces after quarter.Moreover, the roughening before particle number becomes etching will be roughened Total etching period of 5% or more 20% number below of particle number is as the etching end time.

The weight of sample before etching measures

The size of sample：The sheet material (sheet material for carrying out the 10cm square of punching press with press) of 10cm square

The acquisition of sample：Arbitrary 3 positions

In addition, the weight of sample uses the 4th after can measuring to decimal point precision balance in measuring.Moreover, by gained The measured value of weight be directly used in above-mentioned calculating.

Precision balance is the IBA-200 using sub- prosperous (the ア ズ ワ Application) limited liability company of speed.Press is to use Noguchi pressure The HAP-12 of machine (Noguchi プ レ ス) limited liability company manufacture.

In addition, also may include that the resistance to acid band used when following etchings is implemented or prepreg etc. cover component to carry out The weight stated measures.In this case, in the measurement of the example weight after aftermentioned etching also weight is carried out including covering component It is fixed to measure.In addition, in the case where sample is the copper foil with carrier, it also may include carrier and measured to carry out above-mentioned weight. In this case, also carrying out weight measurement including carrier in the measurement of example weight after aftermentioned etching.

The weight of sample after etching measures

After the face cover with the side opposite side with surface-treated layer of sample, to sample between etching the end time The surface treatment surface side of product is etched.Then the weight of determination sample.In addition, when being observed using scanning electron microscope When, the sample observed using scanning electron microscope is due to noble metals such as vapor deposition platinum, so example weight is also greater than reality Sample weight.Therefore, the weight of the sample after etching is measured using not observed using scanning electron microscope Sample.Roughening treatment layer is substantially evenly formed in copper foil or very thin layers of copper.Therefore, judge to be advisable using not using sweeping The sample that the type electron microscope of retouching is observed.

The calculating of total adhesion amount of surface-treated layer

Total adhesion amount (g/m of surface-treated layer²)={ (weight (the g/ of the sample of the sheet material of the 10cm square before etching 100cm²))-(weight (g/100cm of the sample of the sheet material of the 10cm square after etching²))}×100(m²/100cm²)

Using the arithmetic mean of instantaneous value of total adhesion amount of the surface-treated layer at 3 positions as total attachment of surface-treated layer The value of amount.

(measurement of Co containing ratios, Ni containing ratios, Co, Ni adhesion amount in surface-treated layer)

The adhesion amount of Co, Ni are the samples of size 10cm × 10cm by embodiment, comparative example, with 20 mass %'s of concentration Aqueous solution of nitric acid dissolves 1 μm from surface of thickness, the ICP emission spectrophotometer (models manufactured using SII companies： SPS3100), it is measured by ICP luminesceence analyses.By the arithmetic mean of instantaneous value of the adhesion amount of Co, Ni of the sample at 3 positions The value of adhesion amount as Co, Ni.

In addition, be provided in the embodiment of surface-treated layer, comparative example on the two sides of copper foil, it is acidproof by being attached in single side Band or thermo-compression bonding prepregs such as FR4 etc. are covered, and the surface-treated layer of single side are dissolved to measure the attached of Co, Ni and other elements The amount of wearing.Then, the cover is removed, Co, Ni and the adhesion amount of other elements is measured to another single side, or use another sample Product measure Co, Ni of another single side and the adhesion amount of other elements.In addition, the value described in table 2 is set as the value of single side.For Two sides is provided with the copper foil of surface-treated layer, Co, the Ni on two sides and the adhesion amount of other elements become identical value.This Outside, in the aqueous solution of nitric acid that Co, Ni and other elements are not dissolved in 20 mass % of concentration in the case of, can also be used can make Co, Ni and the liquid of other elements dissolving are (for example, concentration of nitric acid：20 mass %, concentration of hydrochloric acid：The nitric acid and salt of 12 mass % The mixed aqueous solution etc. of acid) and after dissolving, it is measured by above-mentioned ICP luminesceence analyses.In addition, Co, Ni can be made to dissolve Liquid well known liquid or well known Acidic Liquid or well known alkalies can be used.

In addition, copper foil either very thin layers of copper bumps it is big when copper foil or very thin layers of copper thickness be 1.5 μm it is below Situation etc., when only dissolving 1 μm of the thickness from the surface of surface-treated layer side, the face with above-mentioned surface-treated layer opposite side Surface treatment compounds or the ingredient of middle layer of copper foil with carrier can also dissolve.Therefore, in this case, from copper foil Either the surface of the surface-treated layer side of very thin layers of copper plays the 30% of dissolving copper foil or the thickness of very thin layers of copper.

In addition, " adhesion amount " of so-called element, refers to every sample unit area (1dm²Or 1m²) the element adhesion amount (quality).

In addition, the Co containing ratios, Ni containing ratios in surface-treated layer are calculated using following formula.

Co containing ratios (%)=Co adhesion amounts (μ g/dm in surface-treated layer²Total adhesion amount of)/surface-treated layer (g/m²)×10^-4(g/m²)/(μg/dm²)×100

Ni containing ratios (%)=Ni adhesion amounts (μ g/dm in surface-treated layer²Total adhesion amount of)/surface-treated layer (g/m²)×10^-4(g/m²)/(μg/dm²)×100

(measurement of 10 mean roughness Rz)

According to JIS B0601-1982, the contact roughmeter manufactured using limited liability company of little Ban research institutes Surfcorder SE-3C contact pin type roughmeters, come the surface roughness Rz that measures roughening treatment layer side surface, (10 points flat Equal roughness).The Rz for arbitrarily measuring 10 positions, using the average value at 10 positions of the Rz as the value of Rz.

(measurement of transmission loss)

For each sample, with liquid crystal polymer resin substrate (the Vecstar CTZ- of Kuraray Co., Ltd's manufacture 50 μm of thickness, the resin as hydroxybenzoic acid (ester) and the copolymer of hydroxynaphthoic acid (ester)) be bonded after, by etching, with Characteristic impedance forms microstrip line as the mode of 50 Ω, and the Network Analyzer N5247A manufactured using Hewlett-Packard Corporation is to measure to penetrate Number, finds out the transmission loss under frequency 40GHz.In addition, by after the sample and the lamination of liquid crystal polymer resin substrate, for copper The thickness of foil is thinner than 3 μm of sample, and the aggregate thickness of copper foil and copper plate is set as 3 μm by carrying out copper facing.In addition, by institute After stating the lamination of sample and liquid crystal polymer resin substrate, in the case where the thickness of copper foil is thicker than 3 μm, copper foil is etched and Thickness is set as 3 μm.

(measurement of peel strength)

For each sample, from surface-treated layer side with liquid crystal polymer resin substrate (Kuraray Co., Ltd's system 50 μm of the Vecstar CTZ- thickness made, the resin as hydroxybenzoic acid (ester) and the copolymer of hydroxynaphthoic acid (ester)) patch It closes.Then, carrier is peeled in the case where sample is the copper foil with carrier.Moreover, the copper foil in sample or very thin layers of copper In the case that thickness is thinner than 18 μm, to copper foil, either very thin layers of copper surface carries out copper facing by copper foil or very thin layers of copper and copper facing The aggregate thickness of layer is set as 18 μm.In addition, in the case where the thickness of the copper foil of sample or very thin layers of copper is thicker than 18 μm, carry out It etches and the thickness of copper foil or very thin layers of copper is set as 18 μm.Moreover, peel strength is to utilize load sensor (ロ ー De セ Le), liquid crystal polymer resin substrate side stretching is measured according to 90 ° of stripping methods (JIS C 6,471 8.1).In addition, stripping Intensity is to measure 3 samples to each embodiment, each comparative example.Moreover, by each embodiment, the stripping of 3 samples of each comparative example The arithmetic mean of instantaneous value of intensity is as each embodiment, the value of the peel strength of each comparative example.In addition, peel strength is preferably 0.5kN/m or more.

(fine wiring formative)

By each sample of Examples and Comparative Examples and liquid crystal polymer resin substrate, (Kuraray Co., Ltd manufactures 50 μm of Vecstar CTZ- thickness, the resin as hydroxybenzoic acid (ester) and the copolymer of hydroxynaphthoic acid (ester)) it is bonded.So Afterwards, in the case where sample is the copper foil with carrier, very thin layers of copper is peeled from carrier.Then, for the copper foil of sample or pole The thickness of thin copper layer is thinner than 3 μm of sample, by copper foil or the aggregate thickness of very thin layers of copper and copper plate by carrying out copper facing It is set as 3 μm.In addition, in the case where the thickness of copper foil or very thin layers of copper is thicker than 3 μm, copper foil is etched and sets thickness It is 3 μm.Then, either very thin layers of copper or copper facing layer surface coating photonasty are anti-for the copper foil on liquid crystal polymer resin substrate Lose agent after, 50 L/S=5 μm/5 μm wide circuits are printed by step of exposure, using spraying etching condition below come Into be about to copper foil either the unnecessary portion of very thin layers of copper or copper facing layer surface removal etching process.

(spraying etching condition)

Etching solution：Ferric chloride in aqueous solution (Baume degrees (ボ ー メ degree)：40 degree)

Liquid temperature：60℃

Spraying pressure：2.0MPa

Continue to etch, the circuit bottom width (length of bottom edge X) when to circuit top width as 4 μm and erosion Quarter, factor evaluated.Etching factor is to work as that (recess (ダ will be generated the case where be etched into gradually extension shape (last Wide Ga り) レ) the case where), assume circuit be etched vertically in the case of the intersection point from vertical line and resin substrate from copper foil upper surface In the case that the distance of the recess length risen is set as a, the ratio of the thickness b of a and copper foil is indicated：B/a, the numerical value is bigger, refers to Inclination angle becomes bigger, and etch residue does not remain, and recess becomes smaller.The cross section of the width direction of circuit pattern is shown in Fig. 5 The outline of the computational methods of the etching factor of schematic diagram and the use schematic diagram.The X is seen by the SEM above circuit It examines to measure, calculates etching factor (EF=b/a).In addition, being calculated with a=(X (μm) -4 (μm))/2.By using the erosion Quarter factor, can simply judge the quality of etching.In the present invention, etching factor is evaluated as etching for 6 or more：◎ ◎, By 5 etching is evaluated as less than 6：◎ is evaluated as etching by 4 less than 5：00, by 3 less than 4 It is evaluated as etching：Zero, 3 will be less than or can not calculate and be evaluated as etching：×.In addition, in table in " length of bottom edge X " " connection " indicates at least to link in bottom edge part and adjacent circuit, can not form circuit.

(acid resistance)

Polyamic acid (U- varnish-A, the BPDA (ビ of the emerging production manufacture in space portion is coated in each sample of Examples and Comparative Examples Off ェ ニ Le テ ト ラ カ Le ボ Application Suan bis- No water objects, biphenyl tetracarboxylic dianhydride) system), in 100 DEG C of dryings, make it at 315 DEG C It is solidified to form and covers copper with polyimide resin substrate (BPDA (biphenyl tetracarboxylic dianhydride) is polyimides) and copper foil Laminate.Then, in the case where sample is the copper foil with carrier, very thin layers of copper is peeled from carrier.Then, for the copper of sample The thickness of foil either very thin layers of copper is thinner than 3 μm of sample by carrying out copper facing by copper foil or very thin layers of copper and copper plate Aggregate thickness is set as 3 μm.In addition, in the case where the thickness of copper foil or very thin layers of copper is thicker than 3 μm, copper foil is etched and Thickness is set as 3 μm.Then, either very thin layers of copper or the coating sense of copper facing layer surface of the copper foil on polyimide resin substrate After photosensitiveness resist, 50 L/S=5 μm/5 μm wide circuits (wiring) are printed by step of exposure, utilize spray below Mist etching condition come into be about to copper foil either the unnecessary portion of very thin layers of copper or copper facing layer surface removal etching process.

(spraying etching condition)

Etching solution：Ferric chloride in aqueous solution (Baume degrees：40 degree)

Liquid temperature：60℃

Spraying pressure：2.0MPa

Continue to be etched to circuit top width as until 4 μm.Then, make the polyimide resin substrate with copper circuit After being impregnated 1 minute in the aqueous solution being made of sulfuric acid 10wt%, hydrogen peroxide 2wt%, observed using light microscope poly- The interface of imide resin substrate and copper circuit.(with reference to Fig. 6, Fig. 7) is moreover, invade the aqueous solution through sulfuric acid and hydrogen peroxide The width of the circuit of erosion observed, and evaluates acid resistance as follows.In addition, the aqueous solution institute through sulfuric acid and hydrogen peroxide Length of the width of the circuit of erosion as the width direction of the circuit for being etched part of circuit.Moreover, by observed sample The maximum value of the width for the circuit that the aqueous solution through sulfuric acid and hydrogen peroxide is corroded in the circuit of product, as the sample through sulphur The width for the circuit that the aqueous solution of acid and hydrogen peroxide is corroded.

Acid proof evaluation is as described below.“◎◎”：The width for the circuit that aqueous solution through sulfuric acid and hydrogen peroxide is corroded Degree is less than 0.6 μm；“◎”：The width for the circuit that aqueous solution through sulfuric acid and hydrogen peroxide is corroded be 0.6 μm less than 0.8μm；“○○”：The width for the circuit that aqueous solution through sulfuric acid and hydrogen peroxide is corroded is 0.8 μm less than 1.0 μ m；“○”：The width for the circuit that aqueous solution through sulfuric acid and hydrogen peroxide is corroded is 1.0 μm less than 1.2 μm；“×”： The width for the circuit that aqueous solution through sulfuric acid and hydrogen peroxide is corroded is 1.2 μm or more.

By above-mentioned manufacturing condition and evaluation result is shown in table in 1~4.

[table 3]

[table 4]

(evaluation result)

Embodiment 1~15 inhibits transmission loss well, and acid resistance is good.

The containing ratio of Ni in the surface-treated layer of comparative example 1,4,5 is 0 mass %, in addition, surface-treated layer is most 10 mean roughness Rz on surface are more than 1.4 μm, and transmission loss is big, and acid resistance is bad.

The containing ratio of Ni in the surface-treated layer of comparative example 2 is more than 8 mass %, and transmission loss is big.

The containing ratio of Ni in the surface-treated layer of comparative example 3 is 0 mass %, and acid resistance is bad.

In addition, present application is advocated based on 2 7th, the 2017 Japanese patent application 2017-020508 to file an application Number priority, the full content of the Japanese patent application case is incorporated in present application.

Claims (20)

1. a kind of surface treatment copper foil, has：

Copper foil and

There is the surface-treated layer for including roughening treatment layer in one or two face of above-mentioned copper foil；

Above-mentioned surface-treated layer includes Ni, and the containing ratio of the Ni in above-mentioned surface-treated layer is 8 mass % or less (0 mass % Except),

10 mean roughness Rz of the most surface of above-mentioned surface-treated layer are 1.4 μm or less.

2. surface treatment copper foil according to claim 1, wherein total adhesion amount of above-mentioned surface-treated layer be 1.0~ 5.0g/m²。

3. surface treatment copper foil according to claim 1, wherein above-mentioned surface-treated layer includes Co, above-mentioned surface treatment The containing ratio of Co in layer is 15 mass % or less (except 0 mass %).

4. surface treatment copper foil according to claim 2, wherein above-mentioned surface-treated layer includes Co, above-mentioned surface treatment The containing ratio of Co in layer is 15 mass % or less (except 0 mass %).

5. surface treatment copper foil according to any one of claim 1 to 4, wherein Co's in above-mentioned surface-treated layer Adhesion amount is 30~2000 μ g/dm²。

6. surface treatment copper foil according to any one of claim 1 to 4, wherein above-mentioned surface-treated layer includes Ni, and The adhesion amount of Ni in above-mentioned surface-treated layer is 10~1000 μ g/dm²。

7. surface treatment copper foil according to any one of claim 1 to 4 meets in (7-1) below~(7-6) Either one or two or three or four or five or six,

The containing ratio of Ni in (7-1) above-mentioned surface-treated layer meet any of (7-1-1) and (7-1-2) below or Two,

The containing ratio of Ni in (7-1-1) above-mentioned surface-treated layer meet it is below any one：

More than 0 mass %,

0.01 mass % or more,

0.02 mass % or more,

0.03 mass % or more,

0.04 mass % or more,

0.05 mass % or more,

0.06 mass % or more,

0.07 mass % or more,

0.08 mass % or more,

0.09 mass % or more,

0.10 mass % or more,

0.11 mass % or more,

0.15 mass % or more,

0.20 mass % or more,

0.25 mass % or more,

The containing ratio of Ni in (7-1-2) above-mentioned surface-treated layer meet it is below any one：

7.5 mass % or less,

7 mass % or less,

6.5 mass % or less,

6 mass % or less,

5.5 mass % or less,

5 mass % or less,

4.8 mass % or less,

4.5 mass % or less,

4.0 mass % or less,

3.5 mass % or less,

3.0 mass % hereinafter,

2.5 mass % or less,

2.0 mass % or less,

1.9 mass % or less,

1.8 mass % or less；

10 mean roughness Rz of the most surface of (7-2) above-mentioned surface-treated layer meet in (7-2-1) and (7-2-2) below Either one or two of,

10 mean roughness Rz of the most surface of (7-2-1) above-mentioned surface-treated layer meet it is below any one：

1.3 μm or less,

1.2 μm or less,

1.1 μm or less,

1.0 μm or less,

0.9 μm or less,

0.8 μm hereinafter,

10 mean roughness Rz of the most surface of (7-2-2) above-mentioned surface-treated layer meet it is below any one：

0.01 μm or more,

0.05 μm or more,

0.1 μm or more；

Total adhesion amount of (7-3) above-mentioned surface-treated layer meets any of (7-3-1) and (7-3-2) below or two It is a,

Total adhesion amount of (7-3-1) above-mentioned surface-treated layer meet it is below any one：

·1.05g/m²Above,

·1.1g/m²Above,

·1.2g/m²Above,

·1.3g/m²Above,

·1.4g/m²Above,

·1.5g/m²More than,

Total adhesion amount of (7-3-2) above-mentioned surface-treated layer meet it is below any one：

·4.5g/m²Below,

·4.0g/m²Below,

·3.5g/m²Below,

·3.0g/m²Below；

The containing ratio of Co in (7-4) above-mentioned surface-treated layer meet any of (7-4-1) and (7-4-2) below or Two,

The containing ratio of Co in (7-4-1) above-mentioned surface-treated layer meet it is below any one：

More than 0 mass %,

0.01 mass % or more,

0.02 mass % or more,

0.03 mass % or more,

0.05 mass % or more,

0.1 mass % or more,

0.11 mass % or more,

0.15 mass % or more,

0.2 mass % or more,

0.3 mass % or more,

0.5 mass % or more,

1.0 mass % or more,

1.5 mass % or more,

2.0 mass % or more,

2.5 mass % or more,

3.0 mass % or more,

3.5 mass % or more,

4.0 mass % or more,

4.5 mass % or more,

The containing ratio of Co in (7-4-2) above-mentioned surface-treated layer meet it is below any one：

14 mass % or less,

13 mass % or less,

12 mass % or less,

11 mass % or less,

10 mass % or less,

9 mass % or less,

8 mass % or less,

7 mass % or less,

7.5 mass % or less,

6.5 mass % or less,

6.0 mass % or less,

5.5 mass % or less；

The adhesion amount of Co in (7-5) above-mentioned surface-treated layer meets any of (7-5-1) and (7-5-2) below,

The adhesion amount of Co in (7-5-1) above-mentioned surface-treated layer meets any in (7-5-1-1) and (7-5-1-2) below It is a or two,

The adhesion amount of Co in (7-5-1-1) above-mentioned surface-treated layer meet it is below any one：

·40μg/dm²Above,

·50μg/dm²Above,

·60μg/dm²Above,

·70μg/dm²Above,

·80μg/dm²Above,

·90μg/dm²Above,

·100μg/dm²Above,

·200μg/dm²Above,

·300μg/dm²Above,

·400μg/dm²Above,

·500μg/dm²Above,

·600μg/dm²Above,

·650μg/dm²Above,

·700μg/dm²Above,

·940μg/dm²More than,

The adhesion amount of Co in (7-5-1-2) above-mentioned surface-treated layer meet it is below any one：

·1500μg/dm²Below,

·1400μg/dm²Below,

·1300μg/dm²Below,

·1200μg/dm²Below,

·1100μg/dm²Below,

·1000μg/dm²Below,

·950μg/dm²Hereinafter,

The adhesion amount of Co in (7-5-2) above-mentioned surface-treated layer meets any in (7-5-2-1) and (7-5-2-2) below It is a or two,

The adhesion amount of Co in (7-5-2-1) above-mentioned surface-treated layer meet it is below any one：

·40μg/dm²Above,

·50μg/dm²Above,

·60μg/dm²Above,

·70μg/dm²Above,

·80μg/dm²Above,

·90μg/dm²Above,

·100μg/dm²Above,

·200μg/dm²Above,

·300μg/dm²Above,

·400μg/dm²More than,

The adhesion amount of Co in (7-5-2-2) above-mentioned surface-treated layer meet it is below any one：

·1500μg/dm²Below,

·1400μg/dm²Below,

·1300μg/dm²Below,

·1200μg/dm²Below,

·1100μg/dm²Below,

·1000μg/dm²Below,

·950μg/dm²Below,

·900μg/dm²Below,

·730μg/dm²Below,

·700μg/dm²Below,

·600μg/dm²Below,

·570μg/dm²Below,

·550μg/dm²Hereinafter,

·500μg/dm²Below,

·475μg/dm²Below；

The adhesion amount of Ni in (7-6) above-mentioned surface-treated layer meets any of (7-6-1) and (7-6-2) below,

The adhesion amount of Ni in (7-6-1) above-mentioned surface-treated layer meets any in (7-6-1-1) and (7-6-1-2) below It is a or two,

The adhesion amount of Ni in (7-6-1-1) above-mentioned surface-treated layer meet it is below any one：

·20μg/dm²Above,

·55μg/dm²Above,

·60μg/dm²Above,

·70μg/dm²Above,

·75μg/dm²Above,

·110μg/dm²More than,

·120μg/dm²Above,

·130μg/dm²Above,

·530μg/dm²More than,

The adhesion amount of Ni in (7-6-1-2) above-mentioned surface-treated layer meet it is below any one：

·800μg/dm²Below,

·700μg/dm²Below,

·650μg/dm²Below,

·600μg/dm²Below,

·550μg/dm²Hereinafter,

The adhesion amount of Ni in (7-6-2) above-mentioned surface-treated layer meets any in (7-6-2-1) and (7-6-2-2) below It is a or two,

The adhesion amount of Ni in (7-6-2-1) above-mentioned surface-treated layer meet it is below any one：

·20μg/dm²Above,

·55μg/dm²Above,

·60μg/dm²Above,

·70μg/dm²Above,

·75μg/dm²More than,

The adhesion amount of Ni in (7-6-2-2) above-mentioned surface-treated layer meet it is below any one：

·800μg/dm²Below,

·700μg/dm²Below,

·650μg/dm²Below,

·600μg/dm²Below,

·550μg/dm²Below,

·800μg/dm²Below,

·700μg/dm²Below,

·650μg/dm²Below,

·600μg/dm²Below,

·550μg/dm²Below,

·500μg/dm²Below,

·450μg/dm²Below,

·400μg/dm²Below,

·350μg/dm²Below,

·300μg/dm²Below,

·250μg/dm²Below,

·200μg/dm²Below,

·160μg/dm²Below,

·150μg/dm²Below,

·140μg/dm²Below,

·130μg/dm²Below,

·125μg/dm²Below,

·120μg/dm²Below,

·115μg/dm²Below,

·110μg/dm²Below,

·105μg/dm²Below,

·100μg/dm²Below,

·95μg/dm²Below,

·90μg/dm²Below,

·85μg/dm²Below,

·80μg/dm²Below.

8. surface treatment copper foil according to any one of claim 1 to 4, wherein above-mentioned surface-treated layer is with more choosing The layer of one or more of the group that free refractory layer, antirust coat, chromating layer and silane coupled process layer are formed.

9. surface treatment copper foil according to any one of claim 1 to 4 is used for the copper clad layers of high-frequency circuit board Pressing plate or printing distributing board.

10. a kind of surface treatment copper foil of tape tree lipid layer, has：

Surface treatment copper foil according to any one of claim 1 to 9 and

Resin layer.

11. a kind of copper foil with carrier has middle layer and very thin layers of copper in a face of carrier or two faces, above-mentioned Very thin layers of copper is the surface treatment copper foil or band according to claim 10 according to any one of claim 1 to 9 The surface treatment copper foil of resin layer.

12. a kind of layered product has any of (12-1) below~(12-3)：

(12-1) surface treatment copper foil according to any one of claim 1 to 9,

The surface treatment copper foil of (12-2) tape tree lipid layer according to claim 10 and

(12-3) copper foil according to claim 11 with carrier.

13. a kind of layered product, it includes according to claim 11 copper foil and resin with carrier, the above-mentioned copper with carrier Part or all of the end face of foil is covered by above-mentioned resin.

14. a kind of layered product, there are two the copper foils according to claim 11 with carrier for tool.

15. a kind of manufacturing method of printing distributing board, using there is any of (15-1) below~(15-3)：

(15-1) surface treatment copper foil according to any one of claim 1 to 9,

The surface treatment copper foil of (15-2) tape tree lipid layer according to claim 10 and

(15-3) copper foil according to claim 11 with carrier.

16. a kind of manufacturing method of printing distributing board, including：The step of (16-1) or (16-2) below,

(16-1) is by surface treatment copper foil according to any one of claim 1 to 9 or according to claim 10 Tape tree lipid layer surface treatment copper foil, the step of be laminated with insulating substrate and form copper clad laminate,

After copper foil according to claim 11 with carrier and insulating substrate are laminated by (16-2), peel with carrier The carrier of copper foil and the step of form copper clad laminate；And

Utilize semi-additive process (セ ミ ア デ ィ テ ィ Block method), subtractive process (サ Block ト ラ Network テ ィ Block method), part addition process (パ ー ト リ ー ア デ ィ テ ィ Block method) or modified form semi-additive process (モ デ ィ Off ァ イ De セ ミ ア デ ィ テ ィ Block method) in either method come The step of forming circuit.

17. a kind of manufacturing method of printing distributing board, including：

Electricity is formed in the above-mentioned surface-treated layer side surface of surface treatment copper foil according to any one of claim 1 to 9 The step of road or in the above-mentioned very thin layers of copper side surface of the copper foil according to claim 11 with carrier or above-mentioned carrier Side surface forms the step of circuit；

In a manner of burying foregoing circuit, in the above-mentioned surface-treated layer side surface of above-mentioned surface treatment copper foil or above-mentioned band The step of above-mentioned very thin layers of copper side surface of the copper foil of carrier or above-mentioned carrier side surface form resin layer；And

By after forming above-mentioned resin layer, removing above-mentioned surface treatment copper foil, or by removing above-mentioned carrier or above-mentioned After very thin layers of copper, above-mentioned very thin layers of copper or above-mentioned carrier are removed, and the step of making the circuit for being buried in above-mentioned resin layer expose.

18. a kind of manufacturing method of printing distributing board, including：

By the above-mentioned carrier side surface of the copper foil according to claim 11 with carrier or above-mentioned very thin layers of copper side surface, with The step of resin substrate is laminated；

On the above-mentioned copper foil with carrier and with the side opposite side of resin substrate lamination surface, at least 1 time setting resin layer And the step of circuit；And

After forming above-mentioned resin layer and circuit, the step of above-mentioned carrier or above-mentioned very thin layers of copper is removed from the above-mentioned copper foil with carrier Suddenly.

19. a kind of manufacturing method of printing distributing board, including：

On any surface of the layered product with the copper foil according to claim 11 with carrier or two sides or according to right It is required that any surface or the two sides of layered product described in 13 or 14, the step of at least 1 time setting resin layer and circuit；And

After forming above-mentioned resin layer and circuit, above-mentioned carrier or above-mentioned is removed from the copper foil with carrier for constituting above-mentioned layered product The step of very thin layers of copper.

20. a kind of manufacturing method of e-machine, using having with the method system according to any one of claim 15 to 19 At printing distributing board.