CN104769165B

CN104769165B - Surface treatment copper foil and use its laminated plates, copper-cover laminated plate, printing distributing board and e-machine

Info

Publication number: CN104769165B
Application number: CN201380058515.0A
Authority: CN
Inventors: 新井英太; 三木敦史; 新井康修; 中室嘉郎; 中室嘉一郎
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2012-11-09
Filing date: 2013-11-11
Publication date: 2017-08-25
Anticipated expiration: 2033-11-11
Also published as: TWI484073B; TW201435153A; KR101660663B1; WO2014073694A1; KR20150070380A; CN104769165A

Abstract

The present invention provides a kind of and resin well then, and removes the transparent excellent surface treatment copper foil of the resin after copper foil using etching and use its laminated plates, copper-cover laminated plate, printing distributing board and e-machine.The surface treatment copper foil of the present invention is in an at least surface to be formed with roughening particle by roughening treatment, after copper foil is fitted in into the two sides of polyimide resin substrate, the copper foil on two sides is removed using etching, the printed article for being printed with wire mark is layed in the lower section of the polyimide substrate exposed, using CCD camera when polyimide substrate is shot to printed article, for the image obtained by above-mentioned shooting, in the observation place point brightness curve for being measured and making along brightness of the direction vertical with the direction of observed wire mark extension to each observation place, poor Δ B (Δ B=Bt-Bb) from the top average value Bt and bottom average value Bb of the brightness curve produced by the end of mark to unmarked part is more than 40.

Description

Surface treatment copper foil and using its laminated plates, copper-cover laminated plate, printing distributing board with And e-machine

Technical field

The present invention relates to a kind of surface treatment copper foil and using its laminated plates, requirement erosion is suitable for especially with regard to one kind Carve copper foil after the remnants of defeated troops resin transparent field surface treatment copper foil and using its laminated plates, copper-cover laminated plate, Printing distributing board and e-machine.

Background technology

In the miniature electric machine such as smart mobile phone or tablet PC, for the easness or light weight of distribution, using having Flexible printed wiring board (following, FPC).In recent years, with the multifunction of the grade e-machine, signaling rate is at a high speed Change direction to develop, impedance matching also turns into important key element for FPC.As for the increased impedance matching of signal volume Countermeasure, the resin insulating barrier (for example, polyimides) of the substrate as FPC develops to thick-layer direction.Also, according to distribution Densification requirement, FPC multiple stratification is further in progress.On the other hand, for FPC can implement engagement to liquid crystal substrates or Carrying of IC chips etc. is processed, but position alignment now is via by the copper in the laminated plates to copper foil and resin insulating barrier The resin insulating barrier that paper tinsel is remained after being etched is carried out depending on the registration pattern recognized, therefore the visibility of resin insulating barrier becomes It is important.

Also, also surface can be used to be implemented with roughening plating as copper foil and the copper-cover laminated plate of the laminated plates of resin insulating barrier Rolled copper foil and manufacture.The rolled copper foil typically uses refined copper (the weight ppm of oxygen content 100~500) or oxygen-free copper is (oxygen-containing Measure below 10 weight ppm) as material, the ingot of the grade is carried out after hot rolling, be repeated it is cold rolling be annealed to specific thicknesses and Manufacture.

As above-mentioned technology, for example, there is a kind of invention on copper-cover laminated plate disclosed in patent document 1, it is that lamination gathers Acid imide film is formed with low roughness copper foil, and light transmittance of the film after etching copper foil under wavelength 600nm is more than 40%, mist It is less than 30% to spend (HAZE), and Bonding strength is more than 500N/m.

Also, there is a kind of invention on COF flexible printed wiring boards disclosed in patent document 2, it is that have with lamination In the insulating barrier of the conductor layer formed by electrolytic copper foil, etching area when forming circuit being etched to the conductor layer absolutely The translucency of edge layer uses flexible printed wiring board for more than 50% membrane of flip chip (COF, chip on film), and its feature exists In：Above-mentioned electrolytic copper foil possesses the antirust treatment layer that is formed by nickel-zinc alloy in the commissure then in insulating barrier, and this is then The surface roughness (Rz) in face is that the mirror surface luster under 0.05~1.5 μm, and 60 ° of incidence angle is more than 250.

Also, there is a kind of invention of the processing method on copper foil for printed circuit disclosed in patent document 3, it is printing electricity The processing method of road copper foil, it is characterised in that：The roughening treatment using copper-cobalt-nickel alloy plating is carried out on the surface of copper foil Afterwards, cobalt-nickel alloy plating layer is formed, and then forms zinc-nickel alloy plating layer.

[patent document 1] Japanese Unexamined Patent Publication 2004-98659 publications

[patent document 2] WO2003/096776

No. 2849059 publications of [patent document 3] Japanese Patent No..

The content of the invention

[the problem of invention is to be solved]

In patent document 1, processing is improved to adherence by the organic agent after Darkening process or electroplating processes And the low roughness copper foil obtained has situation about breaking by fatigue in the purposes of pliability is required copper-cover laminated plate, and There is the poor situation of resin perspectivity.

Also, do not carry out roughening treatment in patent document 2, and in the purposes beyond COF flexible printed wiring boards, copper foil Dhering strength with resin is relatively low and not enough.

And then, in the processing method described in patent document 3, although copper foil can be carried out to utilize the fine of Cu-Co-Ni Processing, but for making the copper foil and resin and removing the resin after the copper foil then and using etching, it is impossible to realize excellent The transparency.

The present invention provides a kind of and resin well then, and removes the transparent excellent of the resin after copper foil using etching Surface treatment copper foil and use its laminated plates, copper-cover laminated plate, printing distributing board and e-machine.

[technological means for solving problem]

Effort research is repeated in present inventor et al., is as a result conceived to certainly to be placed in the printed article that affix is remembered and pastes copper foil The lower section of the polyimide substrate removed after conjunction, utilizes CCD camera (charge-coupled device camera, electric charge Coupling element video camera) printed article is shot across polyimide substrate obtained by the mark part image obtain The brightness curve near mark end drawn in observation place-brightness curve, discovery is controlled simultaneously to the brightness curve Do not influenceed by the species of base plate resin film or the thickness of base plate resin film, but to copper foil to be etched to the resin transparent after removing Property produce influence.

The present invention completed based on above-mentioned opinion is a kind of surface treatment copper foil on the one hand, and it is by roughening treatment And roughening particle is formed with an at least surface, after above-mentioned copper foil is fitted in into the two sides of polyimide resin substrate, utilize Etching removes the copper foil on above-mentioned two sides, and the printed article for being printed with wire mark is layed in the above-mentioned polyimide substrate that exposes Lower section, using CCD camera when above-mentioned polyimide substrate is shot to above-mentioned printed article, for passing through above-mentioned shooting The image of acquisition, along the direction vertical with the direction of observed above-mentioned wire mark extension, to the bright of each observation place Spend in the observation place-brightness curve for being measured and making, produced from the end of above-mentioned mark to the part without above-mentioned mark Brightness curve top average value Bt and bottom average value Bb poor Δ B (Δ B=Bt-Bb) be more than 40.

In the another embodiment of the surface treatment copper foil of the present invention, from the end of above-mentioned mark to without above-mentioned mark The top average value Bt and bottom average value Bb of the brightness curve that part is produced poor Δ B (Δ B=Bt-Bb) are more than 50.

In the another embodiment of the surface treatment copper foil of the present invention, from the end of above-mentioned mark to without above-mentioned mark The top average value Bt and bottom average value Bb of brightness curve produced by part poor Δ B (Δ B=Bt-Bb) are more than 60.

, will be bright in above-mentioned observation place-brightness curve in the another embodiment of the surface treatment copper foil of the present invention The interior value represented closest to the position of above-mentioned wire mark intersection point of the intersection point of line and Bt of writing music is set to t1, will be on the basis of Bt from bright Write music line and Bt intersection point into 0.1 Δ B depth bounds, represented in brightness curve and 0.1 Δ B intersection point closest to above-mentioned line When the value of the position of shape mark intersection point is set to t2, Sv defined in following (1) formulas is more than 3.5,

Sv=(Δ B × 0.1)/(t1-t2) (1).

In the another embodiment of the surface treatment copper foil of the present invention, defined in (1) formula in above-mentioned brightness curve Sv is more than 3.9.

In the another embodiment of the surface treatment copper foil of the present invention, defined in (1) formula in above-mentioned brightness curve Sv is more than 5.0.

In the another embodiment of the surface treatment copper foil of the present invention, the TD on above-mentioned roughening treatment surface average roughness It is 0.20~0.80 μm to spend Rz, and the MD on roughening treatment surface 60 degree of glossiness are 76~350%, the surface of above-mentioned roughening particle Product A, with overlooking above-mentioned roughening particle from above-mentioned copper foil surface side when the ratio between the area B that obtains A/B be 1.90~2.40.

In the another embodiment of the surface treatment copper foil of the present invention, above-mentioned MD 60 degree of glossiness are 90~250%.

In the another embodiment of the surface treatment copper foil of the present invention, above-mentioned TD mean roughness Rz for 0.30~ 0.60μm。

In the another embodiment of the surface treatment copper foil of the present invention, above-mentioned A/B is 2.00~2.20.

The present invention surface treatment copper foil another embodiment in, the MD on roughening treatment surface 60 degree glossiness and The ratio C (C=(MD 60 degree of glossiness)/(TD 60 degree of glossiness)) of TD 60 degree of glossiness is 0.80~1.40.

The present invention surface treatment copper foil another embodiment in, the MD on roughening treatment surface 60 degree glossiness and The ratio C (C=(MD 60 degree of glossiness)/(TD 60 degree of glossiness)) of TD 60 degree of glossiness is 0.90~1.35.

In the another embodiment of the surface treatment copper foil of the present invention, possesses resin bed on above-mentioned roughening treatment surface.

In the another embodiment of the surface treatment copper foil of the present invention, above-mentioned resin bed contains dielectric substance.

The present invention at another aspect is a kind of Copper foil with carrier, and it sequentially has carrier, intermediate layer, a very thin layers of copper, and on State surface treatment copper foil of the very thin layers of copper for the present invention.

The present invention at another aspect is a kind of laminated plates, its be surface treatment copper foil and the resin substrate of the lamination present invention and Constitute.

The present invention is a kind of printing distributing board at another aspect, and it uses the surface treatment copper foil for having the present invention.

The present invention at another aspect is a kind of laminated plates, and it is Copper foil with carrier and the resin substrate of the lamination present invention and structure Into.

The present invention is a kind of printing distributing board at another aspect, and it uses the Copper foil with carrier for having the present invention.

The present invention is a kind of e-machine at another aspect, and it uses the printing distributing board for having the present invention.

The present invention is a kind of printing distributing board at another aspect, and it is surface-treated by insulating resin substrate, with passing through certainly Face side lamination is in above-mentioned insulated substrate and is formed with the surface treatment copper foil of copper circuit and is constituted, using CCD camera every The above-mentioned insulating resin substrate from surface treated face side lamination, when being shot to above-mentioned copper circuit, for logical The image that above-mentioned shooting is obtained is crossed, along the direction vertical with the direction of observed above-mentioned copper circuit extension, to each observation In observation place-brightness curve that the brightness in place is measured and made, from the end of above-mentioned copper circuit to without above-mentioned copper electricity The top average value Bt and bottom average value Bb of the brightness curve that the part on road is produced poor Δ B (Δ B=Bt-Bb) be 40 with On.

The present invention is a kind of copper-cover laminated plate at another aspect, and it is surface-treated by insulating resin substrate, with passing through certainly Face side lamination constituted in the surface treatment copper foil of above-mentioned insulated substrate, by etching the above-mentioned of above-mentioned copper-cover laminated plate Surface treatment copper foil is made after the surface treatment copper foil of wire, using CCD camera across from surface treated face side When the above-mentioned insulating resin substrate of lamination is shot, for the image obtained by above-mentioned shooting, along with it is observed upper State the vertical direction in the direction of linear surfaces processing copper foil extension, the sight that the brightness to each observation place is measured and made Examine in place-brightness curve, end to the part that copper foil is handled without above-mentioned linear surfaces of copper foil is handled from above-mentioned linear surfaces The top average value Bt and bottom average value Bb of the brightness curve of generation poor Δ B (Δ B=Bt-Bb) are more than 40.

The present invention is a kind of printing distributing board at another aspect, and it uses the copper-cover laminated plate for having the present invention.

The present invention is a kind of manufacturer for the printing distributing board for manufacturing and being connected with more than 2 printing distributing boards at another aspect Method, it is to connect more than 2 printing distributing boards of the invention and manufacture.

The present invention is a kind of manufacturer for the printing distributing board for manufacturing and being connected with more than 2 printing distributing boards at another aspect Method, it is included by the printing distributing board of at least one present invention, with another printing distributing board of the invention or not quite at this The step of printing distributing board of the printing distributing board of invention is connected.

The present invention is a kind of e-machine at another aspect, and it is matched somebody with somebody using more than 1 more than 2 printings of connection of the invention The printing distributing board of line plate or the printing distributing board of the present invention.

The present invention is a kind of manufacture method of printing distributing board at another aspect, and it, which is comprised at least, will connect at least one sheet The printing distributing board of the printing distributing board of invention or the printing distributing board of the present invention, the step of be connected with part.

The present invention is a kind of manufacturer for the printing distributing board for manufacturing and being connected with more than 2 printing distributing boards at another aspect Method, it is comprised at least：

By the printing distributing board of at least one present invention, with another printing distributing board of the invention or not quite at this The step of printing distributing board of the printing distributing board of invention is connected；And

Will connect at least one the present invention printing distributing board printing distributing board or the present invention printing distributing board, The step of being connected with part.

The present invention is a kind of manufacture method of printing distributing board at another aspect, and it is included：

The step of preparing Copper foil with carrier and the insulated substrate of the present invention；

The step of above-mentioned Copper foil with carrier and insulated substrate are subjected to lamination；And

Above-mentioned Copper foil with carrier and insulated substrate are carried out after lamination, the step of the carrier by peeling off above-mentioned Copper foil with carrier Suddenly copper-cover laminated plate is formed,

Thereafter, semi-additive process (semi additive method), subtractive process (subtractive method), portion are passed through Divide addition process (partly additive method) or improve semi-additive process (modified semi additive method) In either method formation circuit the step of.

The step of circuit being formed in the above-mentioned very thin layers of copper side surface of the Copper foil with carrier of the present invention；

Above-mentioned very thin layers of copper side surface in above-mentioned Copper foil with carrier in the way of burying foregoing circuit forms resin bed Step；

The step of circuit being formed on above-mentioned resin bed；

Formed on above-mentioned resin bed after circuit, the step of above-mentioned carrier is peeled off；And

Peel off after above-mentioned carrier, by removing above-mentioned very thin layers of copper, and make to form burying in above-mentioned very thin layers of copper side surface Not the step of the circuit of above-mentioned resin bed exposes.

[The effect of invention]

According to the present invention, it is possible to provide a kind of and resin is well then, and remove the saturating of the resin after copper foil using etching The excellent surface treatment copper foil of bright property and use its laminated plates, copper-cover laminated plate, printing distributing board and e-machine.

Brief description of the drawings

Fig. 1 is the schematic diagram for defining Bt and Bb.

Fig. 2 is the schematic diagram for defining t1 and t2 and Sv.

Fig. 3 is the assay method of the slope of the composition of camera and brightness curve when representing to evaluate the slope of brightness curve Schematic diagram.

Fig. 4 a are the SEM observation photos of the copper foil surface of (a) comparative example 1 when evaluating Rz.

Fig. 4 b are the SEM observation photos of the copper foil surface of (b) comparative example 3 when evaluating Rz.

Fig. 4 c are the SEM observation photos of the copper foil surface of (c) comparative example 5 when evaluating Rz.

Fig. 4 d are the SEM observation photos of the copper foil surface of (d) comparative example 6 when evaluating Rz.

Fig. 4 e are the SEM observation photos of the copper foil surface of (e) embodiment 1 when evaluating Rz.

Fig. 4 f are the SEM observation photos of the copper foil surface of (f) embodiment 2 when evaluating Rz.

Fig. 5 A~C is the concrete example of the manufacture method of the printing distributing board of the Copper foil with carrier using the present invention, i.e., to electricity The schematic diagram of distributing board section in the step of untill road plating-resist removal.

Fig. 6 D~F is the concrete example of the manufacture method of the printing distributing board of the Copper foil with carrier using the present invention, i.e., from product The schematic diagram of distributing board section in the step of layer resin and the 2nd layer of Copper foil with carrier are untill laser perforate.

Fig. 7 G~I is the concrete example of the manufacture method of the printing distributing board of the Copper foil with carrier using the present invention, i.e. idiomorphism Into filling perforation (via fill) to peel off the 1st layer of carrier untill the step of in distributing board section schematic diagram.

Fig. 8 J~K is the concrete example of the manufacture method of the printing distributing board of the Copper foil with carrier using the present invention, i.e., from sudden strain of a muscle The schematic diagram of distributing board section in losing the step of untill projection-copper pillar is formed.

Fig. 9 is the outward appearance photo of field trash used in embodiment.

Figure 10 is the outward appearance photo of field trash used in embodiment.

Embodiment

[form and manufacture method of surface treatment copper foil]

The copper foil used in the present invention is suitable for then to make laminate with resin substrate, and by etching The copper foil of removal.

The copper foil used in the present invention also can be any of electrolytic copper foil or rolled copper foil.Generally to improve lamination , also can be to face, the i.e. roughening face with resin substrate then of copper foil, after implementing to degreasing for the purpose of the peel strength of copper foil afterwards Copper foil surface carry out knob-like plating roughening treatment.Electrolytic copper foil has bumps during fabrication, but by roughening treatment, The convex portion of electrolytic copper foil can be made to increase and make concavo-convex further become greatly.In the present invention, the roughening treatment can by copper facing-cobalt- The alloy plating such as nickel alloy or copper facing-nickel-phosphor alloy, nickel-zinc alloy electropalting and carry out.Also, being preferably that can be entered by copper-beryllium OK.Bathed as copper-beryllium, for example, be preferably to use the plating bath containing the element beyond copper and more than a kind of copper, more preferably Contain copper and the plating bath more than any of group being made up of cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum.Also, In the present invention, the current density of the roughening treatment is higher than the current density of previous roughening treatment, and shorten the roughening treatment time. Sometimes common copper facing etc. is carried out as the pretreatment before roughening, is also carried out common to prevent coming off for electronplate sometimes Copper facing etc. is used as the final working process after roughening.In the present invention, also comprising above-mentioned pretreatment and final working process, depending on needing To include to roughening of copper foil and related known process, and be referred to as roughening treatment.

Furthermore, the present invention rolled copper foil also include containing more than a kind of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, The copper alloy foil of the elements such as Si, Te, Cr, Nb, V, B.If the concentration of above-mentioned element is uprised and (such as added up to more than 10 mass %), Then there is the situation that conductance is reduced.The conductance of rolled copper foil is preferably more than 50%IACS, more preferably more than 60%IACS, And then preferably more than 80%IACS.Above-mentioned copper alloy foil can also be added up to containing the element beyond copper more than 0mass% and Below 50mass%, can also contain more than 0.0001mass% and below 40mass%, can also contain more than 0.0005mass% And below 30mass%, it can also contain more than 0.001mass% and below 20mass%.

Also, the copper foil used in the present invention also can be for sequentially with carrier, intermediate layer, the appendix body copper of very thin layers of copper Paper tinsel.When using the situation of Copper foil with carrier in the present invention, above-mentioned roughening treatment is carried out on very thin layers of copper surface.Furthermore, to attached The another embodiment of carrier copper foil, is illustrated in detail below.

Also, the implementation available for the manufacturing condition of the electrolytic copper foil of the present invention is illustrated in following.

＜ electrolyte constitutes ＞

Copper：90~110g/L

Sulfuric acid：90~110g/L

Chlorine：50~100ppm

Leveling agent 1 (double (three sulfopropyls) disulphide)：10~30ppm

Leveling agent 2 (amines)：10~30ppm

For above-mentioned amines, the amines of following chemical formula can be used.

(in above-mentioned chemical formula, R₁And R₂To select free hydroxyl alkyl, ether, aryl, aromatic series substitution alkyl, unsaturated hydrocarbons The group that base, alkyl are constituted).

＜ 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

Also, can enumerate JX MiningShi Metallgesellschaft AG manufacture HLP paper tinsels as can be used in the present invention electrolysis Copper foil.

It can be electroplated as copper facing-cobalt-nickel alloy of roughening treatment by being electrolysed, it is 15~40mg/ to form adhesion amount such as dm²The μ g/dm of copper -100~3000²The μ g/dm of cobalt -50~1500²Nickel ternary alloy layer mode carry out, be preferably To be formed if adhesion amount is 15~40mg/dm²The μ g/dm of copper -100~3000²The μ g/dm of cobalt -100~1500²Nickel ternary It is that the mode of alloy-layer is carried out.If Co adhesion amounts are not up to 100 μ g/dm², then have heat resistance variation, the situation that etching is deteriorated.If Co adhesion amounts are more than 3000 μ g/dm², then have not good enough when the influence of magnetic must be considered, and etching spot is produced, also, acid resistance And the situation that chemical-resistant is deteriorated.If Ni adhesion amounts are not up to 50 μ g/dm², then have the situation that heat resistance is deteriorated.On the other hand, If Ni adhesion amounts are more than 1500 μ g/dm², then etch residues become many situations.Co adhesion amounts are preferably 1000~2500 μ g/ dm², nickel adhesion amount is preferably 500~1200 μ g/dm².Herein, so-called etching spot is meant when being etched using copper chloride, Co It is undissolved and remain situation, also, so-called etch residues mean using ammonium chloride progress alkali etching when, Ni it is undissolved and The situation of residual.

Plating bath and plating conditions to form above-mentioned ternary system copper facing-cobalt-nickel alloy is as described below：

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

PH value：1~4

Temperature：30~50 DEG C

Current density D_k：25~50A/dm²

Electroplating time：0.3~3 second

Furthermore, the surface treatment copper foil of an embodiment of the invention is electroplating time is shorter than previously, and makes electric current Density carries out roughening treatment under conditions of being higher than previously.By making electroplating time be shorter than previously, and make current density higher than first Before under conditions of carry out roughening treatment, and in copper foil surface formation than previous trickle roughening particle.

Also, the condition of copper facing-nickel-phosphor alloy as roughening treatment of the present invention is shown in following.

Plating bath is constituted：10~50g/L of Cu, 3~20g/L of Ni, 1~10g/L of P

PH value：1~4

Temperature：30~40 DEG C

Current density D_k：30~50A/dm²

Electroplating time：0.3~3 second

Furthermore, the surface treatment copper foil of an embodiment of the invention is electroplating time is shorter than previously, and makes electric current Density is higher than carried out roughening treatment under conditions of previously.By making electroplating time be shorter than previously, and it is higher than current density Roughening treatment was carried out under conditions of previously, and in copper foil surface formation than previously trickle roughening particle.

Also, the condition of the copper facing as roughening treatment-nickel-cobalt-tungsten alloy of the present invention is shown in following.

Plating bath is constituted：5~20g/L of Cu, 5~20g/L of Ni, 5~20g/L of Co, 1~10g/L of W

PH value：L~5

Temperature：30~50 DEG C

Current density D_k：30~50A/dm²

Electroplating time：0.3~3 second

Also, the condition of copper facing-nickel-molybdenum-phosphorus alloy as roughening treatment of the present invention is shown in following.

Plating bath is constituted：5~20g/L of Cu, 5~20g/L of Ni, 1~10g/L of Mo, 1~10g/L of P

PH value：1~5

Temperature：30~50 DEG C

Current density D_k：30~50A/dm²

Electroplating time：0.3~3 second

After roughening treatment, the layer of the group selected from refractory layer, antirust coat and weatherable layer can be also set on roughening treatment face In more than a kind.Also, each layer also can be 2 layers, multiple layers such as 3 layers, the order of each layer of lamination can be random order, can also replace Each layer of lamination.

Herein, as refractory layer, known refractory layer can be used.Also, following surface treatment for example can be used.

As refractory layer, antirust coat, known refractory layer, antirust coat can be used.For example, refractory layer and/or antirust coat are also Can be containing selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, the group of tantalum The layer of more than a kind of element, also can be by selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum Metal level or alloy-layer that race's element, iron, more than a kind of the element of the group of tantalum are constituted.Also, refractory layer and/or antirust coat are also Can contain comprising selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group More than a kind of element oxide, nitride, silicide.Also, refractory layer and/or antirust coat also can be to contain nickel-zinc alloy Layer.Also, refractory layer and/or antirust coat also can be nickel-zinc alloy-layer.Above-mentioned nickel-zinc alloy-layer also can be except inevitable Outside impurity, contain nickel 50wt%~99wt%, zinc 50wt%~1wt%.Total attachment of zinc and nickel in above-mentioned nickel-zinc alloy-layer Amount also can be 5~1000mg/m², preferably 10~500mg/m², more preferably 20~100mg/m².Also, above-mentioned contain nickel-zinc The ratio between the nickel adhesion amount of the layer of alloy or above-mentioned nickel-zinc alloy-layer and amount of zinc adhesion (=nickel adhesion amount/amount of zinc adhesion) is preferably 1.5~10.Also, the nickel adhesion amount of the above-mentioned layer containing nickel-zinc alloy or above-mentioned nickel-zinc alloy-layer is preferably 0.5mg/m²~ 500mg/m², more preferably 1mg/m²~50mg/m².When refractory layer and/or antirust coat are the layer containing nickel-zinc alloy, when logical The interface of copper foil and resin substrate is difficult to the copper foil by de-smear corrosion when the inner wall part such as hole or guide hole is contacted with de-smear liquid It can be improved with the adaptation of resin substrate.Antirust coat also can be chromic acid process layer.Chromic acid process layer can be used at known chromic acid Manage layer.For example, so-called chromic acid process layer refers to through the liquid processing containing chromic anhybride, chromic acid, dichromic acid, chromate or bichromate Layer.Chromic acid process layer also can (also can be gold containing elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titaniums Any forms such as category, alloy, oxide, nitride, sulfide).As the concrete example of chromic acid process layer, it can enumerate：Pure chromium acid Process layer or zinc chromate process layer etc..In the present invention, by the chromic acid process layer through chromic anhybride or potassium dichromate aqueous solution processing Referred to as pure chromium acid treatment layer.Also, in the present invention, by the chromic acid through the treatment fluid processing containing chromic anhybride or potassium bichromate and zinc Process layer is referred to as zinc chromate process layer.

For example, refractory layer and/or antirust coat also can be 1mg/m for sequentially lamination adhesion amount²~100mg/m², be preferably 5mg/m²~50mg/m²Nickel or nickel alloy layer, with adhesion amount be 1mg/m²~80mg/m², preferably 5mg/m²~40mg/m²'s Tin layers person, above-mentioned nickel alloy layer can be also made up of any of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt.Also, refractory layer and/or anti- The nickel or nickel alloy of rusty scale and total adhesion amount of tin are preferably 2mg/m²~150mg/m², more preferably 10mg/m²~70mg/ m².Also, refractory layer and/or antirust coat are preferably [the nickel adhesion amount in nickel or nickel alloy]/[tin adhesion amount]=0.25~10, more Preferably 0.33~3.If using the refractory layer and/or antirust coat, Copper foil with carrier is processed as into printing distributing board later The peel strength of circuit, chemical-resistant deterioration rate of the peel strength etc. can become good.

Also, adhesion amount can be formed for 200~2000 μ g/dm²The μ g/dm of cobalt -50~700²The cobalt plating of nickel-nickel alloy layer conduct Refractory layer and/or antirust coat.The processing can regard a kind of antirust treatment as in a broad sense.Cobalt plating-the nickel alloy layer must carry out to The degree of the Bonding strength substantially reduction of copper foil and substrate is not made.If cobalt adhesion amount is not up to 200 μ g/dm², then have heat-resisting peel off by force The situation that degree reduction, oxidative resistance and chemical-resistant are deteriorated.Also, as another reason, if cobalt amount is less, processing surface hair It is red, so it is not good enough.

After roughening treatment, adhesion amount can be formed on roughening face for 200~3000 μ g/dm²The μ g/dm of cobalt -100~700²Nickel Cobalt plating-nickel alloy layer.The processing can regard a kind of antirust treatment as in a broad sense.Cobalt plating-the nickel alloy layer must be carried out to not Make the degree of the Bonding strength substantially reduction of copper foil and substrate.If cobalt adhesion amount is not up to 200 μ g/dm², then have heat-resisting peel strength The situation that reduction, oxidative resistance and chemical-resistant are deteriorated.Also, as another reason, if cobalt amount is less, processing surface hair It is red, so it is not good enough.If cobalt adhesion amount is more than 3000 μ g/dm², then it is not good enough when the influence of magnetic must be considered, and have etching spot The situation of generation, also, there is the situation that acid resistance and chemical-resistant are deteriorated.Cobalt adhesion amount is preferably 500~2500 μ g/dm².Separately On the one hand, if nickel adhesion amount is not up to 100 μ g/dm², then heat-resisting peel strength reduces, oxidative resistance and chemical-resistant are deteriorated Situation.If nickel is more than 1300 μ g/dm², then alkali etching be deteriorated.Nickel adhesion amount is preferably 200~1200 μ g/dm²。

Also, an embodiment of the condition of plating cobalt-nickel alloy is as described below：

Plating bath is constituted：1~20g/L of Co, 1~20g/L of Ni

PH value：1.5~3.5

Temperature：30~80 DEG C

Current density D_k：1.0~20.0A/dm²

Electroplating time：0.5~4 second

According to the present invention, plating cobalt-nickel alloy on so that formed adhesion amount be 30~250 μ g/dm²Zinc coat.If zinc Adhesion amount is not up to 30 μ g/dm², then resistance to heat deterioration rate improvement have the situation of disappearance.On the other hand, if amount of zinc adhesion exceedes 250μg/dm², then have the situation that resistance to hydrochloric acid deterioration rate is extremely deteriorated.Amount of zinc adhesion is preferably 30~240 μ g/dm², more preferably 80~220 μ g/dm²。

One embodiment of above-mentioned zinc-plated condition is as described below：

Plating bath is constituted：100~300g/L of Zn

PH value：3~4

Temperature：50~60 DEG C

Current density D_k：0.1~0.5A/dm²

Electroplating time：1~3 second

Furthermore, can also form the galvanized alloy layer such as plating zinc-nickel alloy and replace zinc coat, and then also can pass through chromium in most surface Acid treatment or the coating of silane coupling agent etc. form antirust coat or weatherable layer.

Known weatherable layer can be used to be used as weatherable layer.Also, as weatherable layer, such as known silane can be used Coupling agent process layer, also, the silane coupling agent process layer using following silane formation can be used.

Known silane coupling agent can be used in silane coupling agent used in silane coupling agent processing, for example, amido can be used It is silane coupling agent or epoxy silane coupling agent, sulfydryl system silane coupling agent.Also, vinyl can be used in silane coupling agent Trimethoxy silane, ethenylphenyl trimethoxy silane, γ-metacryloxy propyl trimethoxy silicane, γ-shrink are sweet Oily epoxide propyl trimethoxy silicane, 4- glycidyls butyl trimethoxy silane, γ-aminocarbonyl propyl triethoxysilane, N- β (amido ethyl) γ-aminocarbonyl propyl trimethoxy silane, N-3- (4- (3- amidos propoxyl group) butoxy) propyl group -3- amidos Propyl trimethoxy silicane, imidizole silane, triazine silane, γ mercaptopropyitrimethoxy silane etc..

Above-mentioned silane coupling agent process layer also can be used epoxy silane, amido system silane, metacryloxy system silane, The formation such as silane coupling agents such as sulfydryl system silane.Furthermore, above-mentioned silane coupling agent can also mix two or more and use.Wherein, preferably To be formed using amido system silane coupling agent or epoxy silane coupling agent.

So-called amido system silane coupling agent, or selected from by N- (2- amidos ethyl) -3- aminocarbonyl propyl trimethoxies herein Base silane, 3- (N- styrylmethyl -2- amido ethyls amido) propyl trimethoxy silicane, 3- aminocarbonyl propyl triethoxysilicanes Alkane, double (2- ethoxys) -3- aminocarbonyl propyl triethoxysilanes, aminocarbonyl propyl trimethoxy silane, N- methylaminos propyl group three Methoxy silane, N- phenyl aminocarbonyl propyl trimethoxy silane, the second of N- (3- propenyloxy group -2- hydroxypropyls) -3- aminocarbonyl propyls three TMOS, 4- amido butyl triethoxysilane, (amido ethyl aminomethyl) phenethyl trimethoxy silane, N- (2- amine Base ethyl -3- aminocarbonyl propyls) trimethoxy silane, N- (2- amido ethyl -3- aminocarbonyl propyls) three (2- ethyl hexyl oxies) silane, 6- (aminohexyl aminocarbonyl propyl) trimethoxy silane, aminocarbonyl phenyl trimethoxy silane, 3- (1- amidos propoxyl group) -3,3- two Methyl-1-propylene base trimethoxy silane, 3- aminocarbonyl propyls three (methoxyethoxyethoxy) silane, the second of 3- aminocarbonyl propyls three TMOS, 3- aminocarbonyl propyl trimethoxy silanes, ω-amido undecyltrimethoxysilane, 3- (2-N- benzylamino second Base aminocarbonyl propyl) trimethoxy silane, double (2- ethoxys) -3- aminocarbonyl propyl triethoxysilanes, (N, N- diethyl -3- amine Base propyl group) trimethoxy silane, (N, N- dimethyl -3- aminocarbonyl propyls) trimethoxy silane, N- methylamino propyl group trimethoxies Base silane, N- phenyl aminocarbonyl propyl trimethoxy silane, 3- (N- styrylmethyl -2- amido ethyls amido) propyl group trimethoxy Base silane, γ-aminocarbonyl propyl triethoxysilane, N- β (amido ethyl) γ-aminocarbonyl propyl trimethoxy silane, N-3- (4- (3- amidos propoxyl group) butoxy) group that is constituted of propyl group -3- aminocarbonyl propyl trimethoxy silanes.

More satisfactory silane coupling agent process layer is to be set to 0.05mg/m using silicon atom conversion²~200mg/m², be preferably 0.15mg/m²~20mg/m², more preferably 0.3mg/m²~2.0mg/m²Scope.In above range, substrate resin can be made More improved with the adaptation of surface treatment copper foil.

[surface roughness Rz]

The surface treatment copper foil of the present invention is preferably by roughening treatment at copper foil surface formation roughening particle, and roughening The mean roughness Rz for managing the TD (Transverse Direction, horizontal direction) on surface is 0.20~0.80 μm.By upper Composition is stated, peel strength can be uprised, with resin well then, and the etched transparency for removing the resin after copper foil is uprised. As a result become easier to via position alignment during the IC wafer-carryings carried out by the resin depending on the registration pattern recognized etc..If TD mean roughness Rz then has worry to produce to the misgivings for the manufacturing cost for making ultra-smooth surface not up to 0.20 μm.Separately On the one hand, if TD mean roughness Rz is more than 0.80 μm, there is the concavo-convex change that the resin surface after copper foil is removed using etching Big secret worry, the secret worry that the problem of its result has the hyalinosis of resin bad produces.The TD's on roughening treatment surface is average thick Rugosity Rz is more preferably 0.30~0.70 μm, and then more preferably 0.35~0.60 μm, and then more preferably 0.35~0.55 μm, And then more preferably 0.35~0.50 μm.

Furthermore, when in the purposes that Rz must be made to diminish using the surface treatment copper foil of the present invention, at surface of the invention The mean roughness Rz for managing the TD on the roughening treatment surface of copper foil is preferably 0.20~0.70 μm, more preferably 0.25~0.60 μ M, and then more preferably 0.30~0.60 μm, and then more preferably 0.30~0.55 μm, and then more preferably 0.30~0.50 μm.

Furthermore, in the surface treatment copper foil of the present invention, so-called " roughening treatment surface " refers to after roughening treatment, is used During surface treatment to set refractory layer, antirust coat, weatherable layer etc., the table of the surface treatment copper foil after the surface treatment is carried out Face.Also, when surface treatment copper foil is the very thin layers of copper of Copper foil with carrier, so-called " roughening treatment surface " refers to roughening treatment Afterwards, when carrying out the situation of surface treatment to set refractory layer, antirust coat, weatherable layer etc., carry out after the surface treatment The surface of very thin layers of copper.

[glossiness]

Surface treatment copper foil roughening face rolling direction (MD, Machine direction, longitudinal direction) in incidence Glossiness under 60 degree of angle is affected greatly to the transparency of above-mentioned resin.That is, it is roughened the big copper foil of the glossiness in face, The hyalinosis of above-mentioned resin must be better.Therefore, the glossiness in the roughening face of surface treatment copper foil of the invention is preferably 76 ~350%, more preferably 80~350%, more preferably 90~300%, and then more preferably 90~250%, and then more preferably For 100~250%.

Herein, in order to obtain the present invention visibility effect, also can control surface treatment before copper foil processing side table Face (is the setting intermediate layer side of carrier before intermediate layer is formed when surface treatment copper foil is the very thin layers of copper of Copper foil with carrier Surface or very thin layers of copper surface) TD (vertically in the direction (width of copper foil) of rolling direction, be in surface treatment copper foil Be the direction of advance of the vertical copper foil in electrolytic copper foil manufacture device during electrolytic copper foil) roughness (Rz) and glossiness.Specifically For, the TD of copper foil surface roughness (Rz) is preferably 0.20~0.80 μm before surface treatment, more preferably 0.30~0.80 μ M, and then more preferably 0.30~0.50 μm, and the glossiness under 60 degree of incidence angle of rolling direction (MD) be preferably 350~ 800%, more preferably 500~800%, and if then current density is higher than the current density of previous roughening treatment, and make thick Change processing time and shorten, then the light under 60 degree of incidence angle of the rolling direction (MD) of surface treatment copper foil after being surface-treated Damp degree turns into 90~350%.As such a copper foil, rolled (high glaze calendering) by adjusting the oil film equivalent of rolling oil And make or pass through such as chemical etching chemical grinding or phosphoric acid solution in electrolytic polishing and make.As above, it will locate The TD of copper foil surface roughness (Rz) and glossiness is set to above range before reason, copper foil that thus can easily after control process Surface roughness (Rz) and surface area.

Furthermore, when the surface roughness (Rz) of copper foil after surface treatment to be made becomes smaller (such as Rz=0.20 μm), The TD of the processing side surface of copper foil roughness (Rz) is set to 0.18~0.80 μm, preferably 0.25~0.50 before being surface-treated μm, and glossiness of the rolling direction (MD) under 60 degree of incidence angle is set to 350~800%, preferably 500~800%, enter And current density is higher than previous roughening treatment, and shorten the roughening treatment time.

Also, the MD of copper foil 60 degree of glossiness are preferably 500~800% before roughening treatment, more preferably 501~800%, And then more preferably 510~750%.If the MD of the copper foil before roughening treatment 60 degree of glossiness are not up to 500%, with above-mentioned light Damp degree is compared for more than 500% situation, and the transparency for having above-mentioned resin can become bad doubt, if more than 800%, having The doubt that the problem of being difficult to manufacture produces.

Furthermore, high glaze calendering can be entered by the way that the oil film equivalent of following formula defined is set into less than 13000~24000 OK.Furthermore, the surface roughness (Rz) of the copper foil after surface treatment to be made becomes the situation of smaller (such as Rz=0.20 μm) When, carry out high glaze calendering by the way that the oil film equivalent of following formula defined is set into more than 12000 and less than 24000.

Oil film equivalent={ (calendering oil viscosity [cSt]) × (by speed [mpm]+roller circular velocity [mpm]) }/{ (roller is stung Angle [rad]) × (yield stress [kg/mm of material²])}

It is the kinetic viscosity at 40 DEG C to roll oil viscosity [cSt].

In order to which oil film equivalent is set into 12000~24000, as long as using following known method, i.e., using low viscous The rolling oil of degree, or make by slowing.

Chemical grinding is to utilize the etching solution such as Sulfuric-acid-hydrogen-peroxide-water system or ammonia-hydrogen peroxide-water system, is less than concentration Common concentration, and carry out for a long time.

The MD60 degree glossiness on roughening treatment surface and ratio C (C=(MD 60 degree of glossiness)/(TD of TD60 degree glossiness 60 degree of glossiness)) be preferably 0.80~1.40.If the MD60 degree glossiness on roughening treatment surface and the ratio of TD60 degree glossiness C not up to 0.80, then have with this than C for more than 0.80 situation compared with, the doubt of the transparency reduction of resin.If also, this is super than C Cross 1.40, then have with this than C for less than 1.40 situation compared with, resin the transparency reduction doubt.This is more preferably than C 0.90~1.35, and then more preferably 1.00~1.30.

[brightness curve]

On the surface treatment copper foil of the present invention, after the two sides of polyimide resin substrate is fitted in, gone using etching Except the copper foil on above-mentioned two sides, the printed article for being printed with wire mark is layed in the lower section of the above-mentioned polyimide substrate exposed, Using CCD camera when above-mentioned polyimide substrate is shot to printed article, for by shooting the image obtained, edge The direction vertical with the direction of observed above-mentioned wire mark extension, the brightness to each observation place is measured and made In observation place-brightness curve of work, the top of the brightness curve produced by from the end of mark to the part without above-mentioned mark Average value Bt and bottom average value Bb poor Δ B (Δ B=Bt-Bb) is more than 40.

Also, the surface treatment copper foil on the present invention, in observation place-brightness curve, by brightness curve and Bt friendship Represent to mark the value of position of intersection point to be set to t1 closest to wire in point, by the basis of Bt from brightness curve and Bt intersection point extremely Represented in 0.1 Δ B depth bounds, in brightness curve and 0.1 Δ B intersection point closest to the position of above-mentioned wire mark intersection point When value is set to t2, Sv defined in following (1) formulas preferably turns into more than 3.5.

Sv=(Δ B × 0.1)/(t1-t2) (1)

Furthermore, in above-mentioned observation position-brightness curve, transverse axis represents location information (pixel × 0.1), and the longitudinal axis represents bright Spend the value of (GTG).

Herein, for " the top average value Bt " of brightness curve, " the bottom average value Bb " of brightness curve and following " t1 ", " t2 ", " Sv ", are illustrated using figure.

Represent what Bt and Bb that the width of mark is set to about 0.3mm situations were defined in Fig. 1 (a) and Fig. 1 (b) Schematic diagram.When the width of mark is set into about 0.3mm, situation just like the brightness curve for turning into V-type as Fig. 1 (a) Suo Shi, with such as Turn into the situation of the brightness curve with bottom as shown in Fig. 1 (b)." the top average value Bt " of brightness curve is in any situation When represent from the position of 50 μm of the end position of the both sides of distance mark with 30 μm of measuring spaces 5 when (both sides total 10 at) Brightness average value.On the other hand, " the bottom average value Bb " of brightness curve brightness curve as shown in Fig. 1 (a) as turn into V During type, represent the V words paddy point in brightness minimum, in Fig. 1 (b) situation with bottom, represent about The value of 0.3mm central part.Furthermore, the width of mark can also be set to 0.2mm, 0.16mm, 0.1mm or so.And then, " brightness is bent The top average value Bt " of line can also be set to the position of 100 μm of end position from distance mark both sides, 300 μm of position or 500 μm of position, the average value of brightness when respectively with 30 μm of measuring spaces 5 (at both sides total 10).

Definition t1 and t2 and Sv schematic diagram is represented in fig. 2." t1 (pixel × 0.1) " represents brightness curve and Bt friendship The intersection point and the value for the position for representing the intersection point that closest above-mentioned wire is marked in point be (above-mentioned observation place-brightness curve The value of transverse axis)." t2 (pixel × 0.1) " is shown on the basis of Bt from brightness curve and Bt intersection point to 0.1 Δ B depth model In enclosing, closest above-mentioned wire is marked in brightness curve and 0.1 Δ B intersection point intersection point and the value for the position for representing the intersection point (value of the transverse axis of above-mentioned observation place-brightness curve).Now, on by the oblique of the brightness curve shown in the line of t1 and t2 connections Rate, is defined with the Sv (GTG/pixel × 0.1) calculated using the Δ B of y-axis direction 0.1, x-axis direction (t1-t2).Again Person, equivalent to 10 μm length of 1 pixel of transverse axis.Also, Sv is the both sides for determining mark, using smaller value.And then, in brightness curve Shape unstable and above-mentioned " brightness curve and Bt intersection point " when there are multiple situations, using the intersection point closest to mark.

In the above-mentioned image captured by CCD camera, turn into higher brightness in the part that non-affix is remembered, but one reaches End is marked, brightness is just reduced.If the visibility of polyimide substrate is good, the reduction shape of such a brightness is clearly observed State.On the other hand, if the visibility of polyimide substrate is bad, brightness mark end near not quickly from " height " to " low " rapidly reduces, but the state of reduction is changed into gentle, so that the reduction state of brightness becomes indefinite.

The present invention is to be based on above-mentioned opinion, and near the mark end that control is drawn in observation place-brightness curve Brightness curve, the observation place-brightness curve be from by the printed article that affix is remembered be placed in by the present invention surface treatment copper foil The lower section of the polyimide substrate removed after laminating, using CCD camera shot across polyimide substrate obtained by it is upper State the image of mark part and obtain.More specifically, from the brightness produced by the end of the mark extremely part without above-mentioned mark The top average value Bt and bottom average value Bb of curve poor Δ B (Δ B=Bt-Bb) turn into more than 40.According to above-mentioned composition, Improved using the discernment of the mark across polyimides of CCD camera, not by the species or the shadow of thickness of base plate resin Ring.Therefore, the excellent polyimide substrate of visibility can be made, and to polyimide substrate in electric substrate manufacturing step etc. Improved when carrying out the situation of particular procedure using the positioning precision of mark, thus, yield raising and other effects can be obtained.

Above-mentioned Δ B (Δ B=Bt-Bb) is preferably set to more than 50, is more preferably set to more than 60.Sv be more preferably 3.9 with On, more preferably more than 4.5, more preferably more than 5.0.On the Δ B upper limit, without being particularly limited to, for example, less than 100, Or less than 80 or less than 70.Also, the Sv upper limit need not be particularly limited to, for example, less than 15, less than 10.According to above-mentioned composition, mark Note with and the boundary of part of non-marked becomes more clear and definite, positioning precision raising, using marking the error of image identification to tail off, And can more accurately carry out position alignment.

[surface area of particle]

The surface area A of roughening particle, with overlooking roughening particle from copper foil surface side when the ratio between the area B that obtains A/B can be right The transparency of above-mentioned resin is affected greatly.That is, if surface roughness Rz is identical, copper foil more less than A/B, above-mentioned The hyalinosis of resin must be better.Therefore, this of surface treatment copper foil of the invention than A/B is preferably 1.90~2.40, more Preferably 2.00~2.20.

Current density and electroplating time when being formed by controlling particle, so that the form or formation density of particle are fixed, And the top average value Bt of controllable brightness curve produced by from the end of above-mentioned mark to the part for not drawing above-mentioned mark Compare A/B with the area of bottom average value Bb poor Δ B (Δ B=Bt-Bb), Sv, surface roughness Rz, glossiness and particle.

As described above, the area obtained when can overlook roughening particle by the surface area A of roughening particle and from copper foil surface side The ratio between B A/B controls are 1.90~2.40, and the concavo-convex of surface is become big, can be by the TD on roughening treatment surface mean roughness Rz controls are 0.20~0.80 μm, and make surface without extremely coarse part, on the other hand, can make the light on roughening treatment surface Damp degree becomes a height of 76~350%.By carrying out above-mentioned control, in the surface treatment copper foil that the present invention can be made, roughening treatment surface In the particle diameter of roughening particle diminish.Though the particle diameter of the roughening particle produces shadow to copper foil to be etched to the resin transparency after removing Ring, but above-mentioned control means to make the particle diameter of roughening particle to diminish in proper range, therefore, copper foil is etched into the tree after removing Fat hyalinosis obtains more good, and peel strength also becomes more good.

[etching factor]

During the larger situation of value of etching factor when using copper foil formation circuit, the bottom of the circuit produced in etching The skirt bottom in portion diminishes, therefore the space between circuit can be made to narrow.Therefore, value the greater of etching factor is adapted to using fine The circuit of pattern is formed, so it is preferred that.On the surface treatment copper foil of the present invention, the value of such as etching factor be preferably 1.8 with On, preferably more than 2.0, preferably more than 2.2, preferably more than 2.3, more preferably more than 2.4.

Furthermore, in printing distributing board or copper-cover laminated plate, can by making resin dissolve and remove, and for copper circuit or Copper foil surface determines area ratio (A/B), glossiness, the surface roughness Rz of above-mentioned particle.

[transmission loss]

In the less situation of transmission loss, the decay of signal when carrying out signal transmission with high frequency is inhibited, therefore The transmission for the signal that can be stablized in the circuit for carrying out signal transmission with high frequency.Therefore, the value smaller of transmission loss fits Share in the circuit purposes that signal transmission is carried out with high frequency, so it is preferred that.By surface treatment copper foil and commercially available polymerizable mesogenic After resin (Kuraray (stock) manufacture Vecstar CTZ-50 μm) laminating, turn into 50 Ω side with characteristic impedance using etching Formula formation micro strip line, the network analyzer HP8720C manufactured using Hewlett-Packard Corporation is determined by coefficient, and is obtained in frequency During the situation of the transmission loss under rate 20GHz, the transmission loss under frequency 20GHz does not reach 5.0dB/10cm preferably, more preferably Not reach 4.1dB/10cm, and then do not reach 3.7dB/10cm more preferably.

[Copper foil with carrier]

Sequentially possess carrier, intermediate layer, very thin layers of copper as the Copper foil with carrier of another embodiment of the present invention.And And, above-mentioned very thin layers of copper is the surface treatment copper foil as an above-mentioned embodiment of the invention.

＜ carriers ＞

Be metal foil or resin film for the carrier typical case of the present invention, for example with copper foil, copper alloy foil, nickel foil, Nickel alloy foil, iron foil, ferroalloy paper tinsel, stainless steel foil, aluminium foil, alloy foil, insulating resin film (such as polyimide film, liquid crystal Polymer (LCP, liquid crystal polymer) film, PET (PET, polyethylene Terephthalate) film, PA membrane, polyester film, fluororesin film etc.) form provide.

It is used as the carrier available for the present invention, it is preferable to use copper foil.Its reason is：The conductance of copper foil is higher, because This intermediate layer thereafter, the formation of very thin layers of copper become easy.It is the form with rolled copper foil or electrolytic copper foil for carrier typical case There is provided.Typically, electrolytic copper foil is copper is electrolysed precipitation on the roller of titanium or stainless steel from copper sulfate bath and is manufactured, and is pressed It is to be repeated to manufacture with being heat-treated using the plastic working of stack to prolong copper foil.As the material of copper foil, except refined copper or nothing Beyond the copper of the high-purities such as oxygen copper, such as also can be used such as the copper for adding Sn, addition Ag copper, added with Cr, Zr or Mg Copper alloy, the copper alloy for blocking inferior series copper alloy added with Ni and Si etc..

On the thickness of the carrier available for the present invention, there is no particular restriction, as long as appropriate be adjusted to playing as load Suitable thickness in the aspect of the effect of body, for example, can be set to more than 5 μm.But, if blocked up, production cost is uprised, Therefore less than 35 μm are generally preferably set to.Therefore, be 12~70 μm for the thickness typical case of carrier, it is more typical for, be 18 ~35 μm.

Also, for the present invention carrier be as above, it is necessary to control formed intermediate layer side surface roughness Rz and Glossiness.Its object is to the glossiness and roughening particle on the roughening treatment surface of the very thin layers of copper after control surface processing Size and number.

＜ intermediate layers ＞

Intermediate layer is set on carrier.Other layers can be also set between carrier and intermediate layer.Use in the present invention As long as intermediate layer is then not particularly limited for composition described as follows：Very thin copper the step of Copper foil with carrier is to insulated substrate lamination before Layer is difficult to peel off from carrier, and on the other hand, very thin layers of copper becomes to peel off from carrier to after the step of insulated substrate lamination.Example Such as, the intermediate layer of Copper foil with carrier of the invention also can contain be selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, A1, Zn, should Deng alloy, this etc. hydrate, this etc. oxide, one kind or two or more in the group that is constituted of organic matter.Also, intermediate layer Also can be multiple layers.

Also, for example, intermediate layer can be constituted in the following way：From carrier side formation by selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn constitute groups of elements a kind of element composition single metal level or by selected from by Cr, Ni, Co, Fe, The alloy-layer of the one kind or two or more element composition for the groups of elements that Mo, Ti, W, P, Cu, Al, Zn are constituted, is formed on by selecting The hydrate of the one kind or two or more element for the groups of elements that free Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn are constituted or The layer of oxide composition.

Also, known organic matter can be used as above-mentioned organic matter in intermediate layer, again, it is preferable to use nitrogenous organic compound It is more than any of thing, organic compounds containing sulfur and carboxylic acid.For example, as specific organic compounds containing nitrogen, preferably making It is used as the l, 2,3 triazole, carboxyl benzotriazole, N' of the triazole compounds with substituent, double (the BTA bases of N'- Methyl) urea, 1H-1,2,4- triazoles and 3- amido -1H-1,2,4- triazoles etc..

For organic compounds containing sulfur, it is preferable to use mercaptobenzothiazoler, Vencide, three polysulfide cyanogen Acid and 2- benzimidazole mercaptans etc..

It is preferred especially with monocarboxylic acid as carboxylic acid, wherein, it is preferable to use oleic acid, linolenic acid and secondary linseed oil Acid etc..

Also, for example intermediate layer can on carrier sequentially lamination nickel, nickel-phosphor alloy or nickel-cobalt alloy, constitute with chromium.Nickel Adhesion with copper becomes the interface in very thin layers of copper and chromium higher than chromium and the adhesion of copper, therefore when peeling off very thin layers of copper Peeled off.Also, expecting to prevent the barriering effect that copper component spreads from carrier to very thin layers of copper to the nickel in intermediate layer.In intermediate layer The adhesion amount of nickel is preferably 100 μ g/dm²Above and 40000 μ g/dm²Hereinafter, more preferably 100 μ g/dm²Above and 4000 μ g/ dm²Hereinafter, more preferably 100 μ g/dm²Above and 2500 μ g/dm²Hereinafter, more preferably 100 μ g/dm²Above and not up to 1000 μ g/dm², the adhesion amount of chromium is preferably 5 μ g/dm in intermediate layer²Above and 100 μ g/dm²Below.Intermediate layer only is being set in one side Situation when, be preferably carrier opposing face set plating the antirust coats such as Ni layers.

If the thickness in intermediate layer becomes too much, there is roughening treatment of the thickness in intermediate layer to very thin layers of copper after surface treatment The glossiness on surface and the size of roughening particle produce the situation of influence, therefore the roughening treatment surface of very thin layers of copper with number The thickness in intermediate layer be preferably 1~1000nm, preferably 1~500nm, preferably 2~200nm, preferably 2~100nm, more Preferably 3~60nm.

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 intermediate layer and very thin layers of copper.Should have and carry The very thin layers of copper of body is the surface treatment copper foil of the embodiment as the present invention.The thickness of very thin layers of copper has no special limit System, it is typically, thinner than carrier, for example, less than 12 μm.For typical case be 0.5~12 μm, it is more typical for be 1.5~5 μm. Also, can also set on the intermediate layer before very thin layers of copper, to reduce the pin hole of very thin layers of copper, and beating using copper-phosphorus alloy is carried out Bottom plating (strike plating).In bottoming plating, cupric pyrophosphate electroplate liquid etc. can be enumerated.

Also, the very thin layers of copper of the application is to be formed under the following conditions.Its object is to：By forming smooth very thin copper Layer, and the size and number of the particle of roughening treatment are controlled, and the glossiness after roughening treatment.

Electrolyte is constituted

Copper：80~120g/L

Sulfuric acid：80~120g/L

Chlorine：30~100ppm

Leveling agent 1 (double (three sulfopropyls) disulphide)：10~30ppm

Leveling agent 2 (amines)：10~30ppm

Manufacturing condition

Current density：70~100A/dm²

Electrolyte temperature：50~65 DEG C

Electrolyte linear speed：1.5~5m/sec

Electrolysis time：0.5~10 minute (being adjusted according to the copper of precipitation thickness, current density)

[resin bed on roughening treatment surface]

Also can possess resin bed on the roughening treatment surface of the surface treatment copper foil of the present invention.Above-mentioned resin bed also can be Insulating resin layer.Above-mentioned resin bed also may be disposed at the part or complete on the roughening treatment surface of the surface treatment copper foil of the present invention In portion.Furthermore, so-called " roughening treatment surface " refers to after roughening treatment in the surface treatment copper foil of the present invention, is used to When the situation of surface treatment of refractory layer, antirust coat, weatherable layer etc. is set, the surface treatment copper foil after the surface treatment is carried out Surface.Also, in situation of the surface treatment copper foil for the very thin layers of copper of Copper foil with carrier, so-called " roughening treatment surface " refers to After roughening treatment, when carrying out the situation of surface treatment to set refractory layer, antirust coat, weatherable layer etc., the table is carried out The surface of very thin layers of copper after the processing of face.

Above-mentioned resin bed can be solid, also can be the insulating resin layer of semi-hardened state (B-stage state) then. So-called semi-hardened state (B-stage state) is to include following state：Even if contacting its surface with finger also without adhesion sense, and it can weigh Repeatedly the insulating resin layer is taken care of, and if then heated processing, produce sclerous reaction.

Above-mentioned resin bed also can be semi-hardened state (B-stage state) then then to use resin, i.e. solid Insulating resin layer.So-called semi-hardened state (B-stage state) is to include following state：Even if contacted with finger its surface also without Adhesion sense, and the insulating resin layer that can overlap is taken care of, and if then heated processing, produce sclerous reaction.

Also, above-mentioned resin bed can contain thermosetting resin, also can be thermoplastic resin.Also, above-mentioned resin bed can also contain There is thermoplastic resin.Above-mentioned resin bed can also contain known resin, hardening of resin agent, compound, hardening accelerator, dielectric Body, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material etc..Also, above-mentioned resin bed for example also International Publication can be used to compile Number No. WO2008/004399, International Publication numbering WO2008/053878, International Publication numbering WO2009/084533, Japan it is special Open flat No. 11-5828, Japanese Unexamined Patent Publication 11-140281, Japanese Patent No. 3184485, International Publication numbering WO97/ 02728th, 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, 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 numbering WO2004/005588, Japanese Unexamined Patent Publication 2006-257153, Japanese Unexamined Patent Publication 2007-326923, Japan JP 2008-111169, Japanese Patent No. 5024930, International Publication numbering WO2006/028207, Japanese Patent No. No. 4828427, Japanese Unexamined Patent Publication 2009-67029, International Publication numbering WO2006/134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication 2009-173017, International Publication numbering WO2007/105635, Japanese Patent No. 5180815, International Publication Numbering WO2008/114858, International Publication numbering WO2009/008471, Japanese Unexamined Patent Publication 2011-14727, International Publication numbering WO2009/001850, International Publication numbering WO2009/145179, International Publication numbering WO2011/068157, Japanese Unexamined Patent Publication Material (resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, reaction catalyst, friendship described in No. 2013-19056 Connection agent, polymer, prepreg, skeleton material etc.) and/or resin bed forming method, forming apparatus and formed.

Also, the species of above-mentioned resin bed is not particularly limited, for example, it can enumerate containing selected from epoxy resin, polyimides tree Fat, multi-functional cyanate esters, maleimide compound, polymaleimide compounds, maleimide amine system resin, Aromatic series maleimide resin, polyvinyl acetal resin, amine Ethyl formate resin, acrylic resin, polyether sulfone (polyethersulphone), polyether sulfone (polyethersulphone) resin, aromatic polyamide resin, aromatic series polyamides Polyimide resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamide-imide resin, rubber modified epoxy fat, benzene oxygen Base resin, carboxyl modification acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide-triazine resin, thermosetting polyphenylene oxide tree Fat, cyanate ester based resin, carboxylic acid anhydrides, polybasic acid anhydride, the linear polymer with crosslinkable functional group, polyphenylene oxide resin, Double (4- cyanatephenyls) propane of 2,2-, phosphorous phenolic compounds, manganese naphthenate, double (the 4- glycidyl phenyls) third of 2,2- Alkane, polyphenylene oxide-cyanate ester based resin, siloxanes modification polyamide-imide resin, cyano group ester resin, phosphine nitrile system resin, rubber Modify polyamide-imide resin, isoprene, hydrogenation type polybutadiene, polyvinyl butyral, phenoxy group, high-molecular-weight epoxy base, Aromatic polyamide, fluororesin, bis-phenol, more than a kind of the tree of the group of block copolymerization polyimide resin and cyano group ester resin Fat is as preferred.

Also, above-mentioned epoxy resin is that have more than 2 epoxy radicals persons in intramolecular, as long as available for electric and electronic material Purposes, then can be used and have no special problem.Also, above-mentioned epoxy resin is preferably to be used in intramolecular to shrink sweet with more than 2 The compound of oil base and the epoxy resin of epoxidation.Bisphenol A type epoxy resin, bisphenol F type epoxy tree are selected from also, can be used Fat, bisphenol-s epoxy resin, bisphenol-A D-ring oxygen tree fat, phenolic resin varnish type epoxy resin, cresol novolak type epoxy tree Fat, alicyclic epoxy resin, bromination (brominated) epoxy resin, phenol system phenolic resin varnish type epoxy resin, naphthalene type asphalt mixtures modified by epoxy resin Fat, brominated bisphenol a type epoxy resin, o-cresol phenolic epoxy varnish, rubber modified bisphenol A type epoxy resin, shrink Glycerine amine type epoxy resin, triglycidyl group chlorinated isocyanurates, N, the glycidol amine compounds such as N- diglycidylanilines The epihydric alcohol ester compounds such as thing, tetrahydrophthalic acid 2-glycidyl ester, phosphorous epoxy resin, biphenyl type epoxy resin, Biphenyl phenolic resin varnish type epoxy resin, trihydroxy benzene methylmethane type epoxy resin, a kind of the group of tetraphenyl ethane type epoxy resin Or mix two or more and use, or the hydride or halide of above-mentioned epoxy resin can be used.

Contain the epoxy resin of phosphorus as above-mentioned phosphorous epoxy resin known to can be used.Also, above-mentioned phosphorous epoxy resin For example it is preferably to possess the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of the 9,10- dihydro-9-oxies of more than 2 epoxy radicals from intramolecular The epoxy that the mode of the derivative of (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is obtained Resin.

(resin bed contains the situation of dielectric substance (dielectric substance filler))

Above-mentioned resin bed can also contain dielectric substance (dielectric substance filler).

When containing the situation of dielectric substance (dielectric substance filler) in any of the above-described kind of resin bed or resin combination, it can use In the purposes of formation capacitor layers, and increase the electric capacity of condenser network.For the dielectric substance (dielectric substance filler), use BaTiO₃、SrTiO₃、Pb(Zr-Ti)O₃(common name PZT), PbLaTiO₃- PbLaZrO (common name PLZT), SrBi₂Ta₂O₉(common name ) etc. SBT there is the dielectric substance powder for the composite oxides that perovskite constructs.

Dielectric substance (dielectric substance filler) also can be powdery.When dielectric substance (dielectric substance filler) is the situation of powdery, Jie The powder characteristics of electric body (dielectric substance filler) is preferably that particle diameter is 0.01 μm~3.0 μm, preferably 0.02 μm~2.0 μm of model Enclose.Furthermore, using sweep electron microscope (SEM), photograph taking, the grain of the dielectric substance on the photo are carried out to dielectric substance When the situation of straight line is drawn on son, the length that will travel across the dielectric substance particle of the straight length of dielectric substance particle most long part is set to The diameter of the particle of the dielectric substance.Also, the grain that the average value of the diameter of ken dielectric body particle is set to dielectric substance will be determined Footpath.

Resin and/or resin combination and/or compound contained by above-mentioned resin bed is set to be dissolved in such as Methylethyl Ketone (MEK), cyclopentanone, dimethylformamide, dimethyl acetamide, N- methylpyrrole pyridines ketone, toluene, methanol, ethanol, propane diols Monomethyl ether, dimethylformamide, dimethyl acetamide, cyclohexanone, ethyl Sai Lusu, N- methyl -2- Pyrrolizidines ketone, N, N- diformazans Resin liquid (resin varnish) is made in yl acetamide, DMF equal solvent, such as by print roll coating method, Above-mentioned resin liquid is coated on the roughening treatment surface of above-mentioned surface treatment copper foil, is then optionally thermally dried, is gone B-stage state is made except solvent.In drying, if for example using hot-air drying stove, as long as drying temperature be 100~ 250 DEG C, preferably 130~200 DEG C.Also solvent can be used, the constituent of above-mentioned resin bed is dissolved, and resin is made and consolidates Shape thing composition is 3wt%~70wt%, is preferably 3wt%~60wt%, is more preferably 10wt%~40wt%, more preferably 25wt%~40wt% resin liquid.Furthermore, for the viewpoint of environment, methyl ethyl ketone and ring are most preferably being used at this stage The mixed solvent of pentanone is dissolved.Furthermore, for solvent, it is preferable to use boiling point is molten for 50 DEG C~200 DEG C of scope Agent.

Also, above-mentioned resin bed is preferably resin spillway discharge when being measured according to MIL-P-13949G in MIL standards (resin flow) is in the semi-hardened resin film of 5%~35% scope.

In present specification, so-called resin spillway discharge is to be based on mathematical expression 1, according to according to the MIL- in MIL standards P-13949G, 4 10cm square samples are taken from resin thickness for the surface treatment copper foil of 55 μm of resin, overlap this 4 Under the state (laminate) of piece sample, in 171 DEG C of press temperature, pressing pressure 14kgf/cm², 10 minutes press times condition Fitted, determine the value that the result obtained by resin outflow weight now is calculated.

[mathematical expression 1]

The above-mentioned surface treatment copper foil (surface treatment copper foil of attached resin) with resin bed is to use as follows：Will The resin bed is overlapped in after base material, is thermally compressed to overall, and makes the resin bed thermmohardening, is then in surface treatment copper foil During the situation of the very thin layers of copper of Copper foil with carrier, exposing very thin layers of copper carrier stripping, (what is exposed certainly is the very thin copper The surface of the intermediate layer side of layer), and formed specifically from the surface of the side opposite with the side of roughened processing of surface treatment copper foil Wiring pattern.

If using the surface treatment copper foil of the attached resin, prepreg material when can reduce manufacture multilayer printed wiring board Use piece number.Moreover, the thickness that can make resin bed is the thickness that such as can ensure that layer insulation, even if or completely without using preimpregnation Body material can also manufacture copper-cover laminated plate.Also, now, also can further improve surface in the surface primary coat insulating resin of base material Flatness.

Furthermore, when the situation of prepreg material is not used, have the following advantages that：The material cost of prepreg material is saved, also, Layering steps also become simple, therefore economically become favourable, moreover, with the multi-sheet printed of the thickness manufacture of only prepreg material The thickness of wiring substrate is thinning, and the thickness that can manufacture 1 layer is less than 100 μm of very thin multilayer printed wiring board.

The thickness of the resin bed is preferably 0.1~120 μm.

If the thickness of resin bed becomes to be thinner than 0.1 μm, there is following situation：Adhesion declines, not via prepreg material And by the surface treatment copper foil lamination of the attached resin when possessing the base material of internal layer material, it becomes difficult to ensure internal layer material and circuit Between layer insulation.On the other hand, if making the thickness of resin bed be thicker than 120 μm, there is following situation：Walked with the coating of 1 time The rapid resin bed for being difficult to form target thickness, and unnecessary fee of material and number of steps are expended, therefore economically become unfavorable.

Furthermore, when being used to manufacture the situation of very thin multi-layer printed circuit board by the surface treatment copper foil with resin bed, In order that the thickness of multi-layer printed circuit board diminishes, the thickness for preferably making above-mentioned resin bed is 0.1 μm~5 μm, is more preferably 0.5 μm~5 μm, more preferably 1 μm~5 μm.

Hereinafter, representing the example of the manufacturing step of the printing distributing board of several Copper foil with carrier using the present invention.

In an embodiment of the manufacture method of the printing distributing board of the present invention, comprising：Prepare the appendix body of the present invention The step of copper foil and insulated substrate, the step of above-mentioned Copper foil with carrier and insulated substrate are carried out into lamination and by above-mentioned appendix body Copper foil and insulated substrate by very thin layers of copper side and insulated substrate to being carried out in the way of after lamination, by peeling off above-mentioned appendix body copper The step of carrier of paper tinsel, forms copper-cover laminated plate, thereafter, by semi-additive process, improves and semi-additive process, part addition process and subtracts into Either method in method and the step of form circuit.Insulated substrate can also be set to add internal layer circuit.

In the present invention, so-called semi-additive process refer to carry out on insulated substrate or copper foil crystal seed layer (seed layer) compared with Thin electroless-plating, is formed after pattern, the method for forming conductive pattern using plating and etching.

Therefore, in the embodiment using the manufacture method of the printing distributing board of the invention of semi-additive process, comprising： The step of preparing Copper foil with carrier and the insulated substrate of the present invention；Above-mentioned Copper foil with carrier and insulated substrate are carried out to the step of lamination Suddenly；After the above-mentioned Copper foil with carrier of lamination and insulated substrate, the step of carrier of above-mentioned Copper foil with carrier is peeled off；By using acid The methods such as etching or plasma-based Deng etchant solution, the step of very thin layers of copper peeled off above-mentioned carrier and exposed all is removed； The step of above-mentioned resin that above-mentioned very thin layers of copper is removed and exposed is set into through hole and/or blind hole by using etching；For containing The step of region for having above-mentioned through hole and/or blind hole carries out removing glue Slag treatment；For containing above-mentioned resin and above-mentioned through hole and/or The step of region of blind hole sets electroless plating layer；The step of plating resist is set in above-mentioned electroless plating layer；To above-mentioned electricity Plating resist is exposed, the step of plating resist that will form the region of circuit thereafter is removed；Formed through removing above-mentioned plating The step of region of the foregoing circuit of resist sets electrolysis electrodeposited coating；The step of above-mentioned plating resist is removed；And lost by dodging Deng will be present in being formed the step of electroless plating layer in the region beyond the region of foregoing circuit is removed.

In the another embodiment using the manufacture method of the printing distributing board of the invention of semi-additive process, comprising：It is accurate The step of Copper foil with carrier and insulated substrate of the standby present invention；Above-mentioned Copper foil with carrier and insulated substrate are carried out to the step of lamination Suddenly；After the above-mentioned Copper foil with carrier of lamination and insulated substrate, the step of carrier of above-mentioned Copper foil with carrier is peeled off；By using acid The methods such as etching or plasma-based Deng etchant solution, the step of very thin layers of copper peeled off above-mentioned carrier and exposed all is removed；Pin To the surface for the above-mentioned resin that above-mentioned very thin layers of copper is removed and exposed by using etching, the step of electroless plating layer is set； The step of plating resist is set in above-mentioned electroless plating layer；Above-mentioned plating resist is exposed, circuit will be formed thereafter The step of plating resist in region is removed；In the region for forming the foregoing circuit through removing above-mentioned plating resist, electrolysis plating is set The step of layer；The step of above-mentioned plating resist is removed；And by dodging erosion etc., will be present in being formed beyond the region of foregoing circuit Region electroless plating layer and very thin layers of copper the step of remove.

In the present invention, so-called improvement semi-additive process refers to lamination metal foil on the insulating layer, is protected by electroplating resist Inverter circuit forming portion, after the copper facing by being electrolysed plating progress circuit forming portion is thickened, removes resist, utilizes (quick) etching The metal foil beyond foregoing circuit forming portion is removed, the method for thus forming circuit on the insulating layer.

Therefore, in the embodiment using the manufacture method for the printing distributing board of the invention for improving semi-additive process, Comprising：The step of preparing Copper foil with carrier and the insulated substrate of the present invention；Above-mentioned Copper foil with carrier and insulated substrate are accumulated The step of layer；After the above-mentioned Copper foil with carrier of lamination and insulated substrate, the step of carrier of above-mentioned Copper foil with carrier is peeled off；To The step of very thin layers of copper that above-mentioned carrier is peeled off and exposed sets through hole and/or blind hole with insulated substrate；For containing above-mentioned logical The step of hole and/or the region of blind hole carry out removing glue Slag treatment；Set for the region containing above-mentioned through hole and/or blind hole without electricity The step of electrodeposited coating；The step of plating resist is set on the very thin layers of copper surface that above-mentioned carrier is peeled off and exposed；Set above-mentioned Electroplate after resist, by being electrolysed the step of plating forms circuit；The step of above-mentioned plating resist is removed；And lost by dodging, will The step of being removed by the very thin layers of copper for removing above-mentioned plating resist and exposing.

Also, the step of circuit is formed on above-mentioned resin bed also can be following steps, i.e., by another Copper foil with carrier certainly Very thin layers of copper side is fitted on above-mentioned resin bed, and foregoing circuit is formed using the Copper foil with carrier for fitting in above-mentioned resin bed. Also, another Copper foil with carrier fitted on above-mentioned resin bed also can be Copper foil with carrier of the invention.Also, in above-mentioned resin The step of circuit is formed on layer also can be by either one in semi-additive process, subtractive process, part addition process or improvement semi-additive process Method is carried out.Also, the above-mentioned Copper foil with carrier in circuit forming surface also can have base on the surface of the carrier of the Copper foil with carrier Plate or resin bed.

In the another embodiment using the manufacture method for the printing distributing board of the invention for improving semi-additive process, bag Contain：The step of preparing Copper foil with carrier and the insulated substrate of the present invention；Above-mentioned Copper foil with carrier and insulated substrate are subjected to lamination The step of；After the above-mentioned Copper foil with carrier of lamination and insulated substrate, the step of carrier of above-mentioned Copper foil with carrier is peeled off；Will be upper State the step of plating resist is set in the very thin layers of copper that carrier is peeled off and exposed；Above-mentioned plating resist is exposed, thereafter will The step of plating resist for forming the region of circuit is removed；Set in the region for forming the foregoing circuit through removing above-mentioned plating resist The step of putting electrolysis electrodeposited coating；The step of above-mentioned plating resist is removed；And by dodging erosion etc., will be present in forming foregoing circuit Region beyond region electroless plating layer and very thin layers of copper the step of remove.

In the present invention, so-called part addition process refers in the substrate provided with conductor layer, optionally gives a farfetched interpretation and through hole or lead Catalyst core is assigned on the substrate in the hole of through hole, is etched and forms conductor circuit, solder resist or plating resist are optionally set After agent, handled, and on above-mentioned conductor circuit, through hole or via hole etc. are thickened by electroless-plating, thus manufacture print The method of brush distributing board.

Therefore, in the embodiment using the manufacture method of the printing distributing board of the invention of part addition process, bag Contain：The step of preparing Copper foil with carrier and the insulated substrate of the present invention；Above-mentioned Copper foil with carrier and insulated substrate are subjected to lamination The step of；After the above-mentioned Copper foil with carrier of lamination and insulated substrate, the step of carrier of above-mentioned Copper foil with carrier is peeled off；Peeling off The step of above-mentioned carrier and the very thin layers of copper exposed set through hole and/or blind hole with insulated substrate；For containing above-mentioned through hole or/ And blind hole region carry out removing glue Slag treatment the step of；The step of catalyst core is assigned to the region containing above-mentioned through hole and/or blind hole Suddenly；The step of etching resist is set on the very thin layers of copper surface peeled off above-mentioned carrier and exposed；Above-mentioned etching resist is exposed Light, and the step of form circuit pattern；The methods such as etching or plasma-based by using etchant solutions such as acid, by above-mentioned very thin layers of copper And above-mentioned catalyst core is the step of remove and form circuit；The step of above-mentioned etching resist is removed；Corrode by using acid etc. The method such as the etching of solution or plasma-based, the above-mentioned insulated substrate surface that above-mentioned very thin layers of copper and above-mentioned catalyst core are removed and exposed The step of solder resist or plating resist are set；And in the above-mentioned region setting electroless plating layer for being not provided with solder resist or electroplating resist The step of.

In the present invention, so-called subtractive process refers to by etching etc., by should not partly selecting for the copper foil on copper-cover laminated plate Remove to selecting property, and the method for forming conductive pattern.

Therefore, in the embodiment using the manufacture method of the printing distributing board of the invention of subtractive process, comprising：It is accurate The step of Copper foil with carrier and insulated substrate of the standby present invention；Above-mentioned Copper foil with carrier and insulated substrate are carried out to the step of lamination Suddenly；After the above-mentioned Copper foil with carrier of lamination and insulated substrate, the step of carrier of above-mentioned Copper foil with carrier is peeled off；It is above-mentioned peeling off The step of carrier and the very thin layers of copper exposed set through hole and/or blind hole with insulated substrate；For containing above-mentioned through hole and/or blind The step of region in hole carries out removing glue Slag treatment；For the region containing above-mentioned through hole and/or blind hole, electroless plating layer is set Step；The step of electrolysis electrodeposited coating is set on the surface of above-mentioned electroless plating layer；In above-mentioned electrolysis electrodeposited coating and/or above-mentioned very thin The step of surface of layers of copper sets etching resist；The step of being exposed to above-mentioned etching resist, and form circuit pattern；Pass through The methods such as etching or plasma-based using etchant solutions such as acid, by above-mentioned very thin layers of copper and above-mentioned electroless plating layer and above-mentioned electrolysis electricity Coating is removed, and the step of form circuit；And the step of above-mentioned etching resist is removed.

In the another embodiment using the manufacture method of the printing distributing board of the invention of subtractive process, comprising：Prepare The step of Copper foil with carrier and insulated substrate of the present invention；The step of above-mentioned Copper foil with carrier and insulated substrate are subjected to lamination； After the above-mentioned Copper foil with carrier of lamination and insulated substrate, the step of carrier of above-mentioned Copper foil with carrier is peeled off；Peeling off above-mentioned load The step of body and the very thin layers of copper exposed set through hole and/or blind hole with insulated substrate；For containing above-mentioned through hole and/or blind hole Region carry out removing glue Slag treatment the step of；The step of electroless plating layer is set for the region containing above-mentioned through hole and/or blind hole Suddenly；The step of shade being formed on the surface of above-mentioned electroless plating layer；Set on the surface for the above-mentioned electroless plating layer for not forming shade The step of putting electrolysis electrodeposited coating；The step of etching resist is set on the surface of above-mentioned electrolysis electrodeposited coating and/or above-mentioned very thin layers of copper； The step of being exposed to above-mentioned etching resist, and form circuit pattern；Etching or plasma-based by using etchant solutions such as acid The step of etc. method, above-mentioned very thin layers of copper and above-mentioned electroless plating layer are removed, and form circuit；And go above-mentioned etching resist Except the step of.

Through hole is set and/or the step of blind hole and subsequent de-smear step also can be without.

Herein, using accompanying drawing, to the concrete example of the manufacture method of the printing distributing board of the Copper foil with carrier using the present invention It is described in detail.Furthermore, here, carried out by taking the Copper foil with carrier with the very thin layers of copper for being formed with roughening treatment layer as an example Illustrate, but be not limited to it, using the Copper foil with carrier with the very thin layers of copper for not forming roughening treatment layer, also can similarly enter The manufacture method of the following printing distributing board of row.

First, as shown in fig. 5-A, the Copper foil with carrier with the very thin layers of copper that roughening treatment layer is formed with surface is prepared (the 1st layer).

Then, as shown in fig. 5-b, the painting erosion resistant agent on the roughening treatment layer of very thin layers of copper, is exposed, develops, and Resist is etched to given shape.

Then, as shown in fig. 5-c, formed after the plating of circuit, resist is removed, the electricity of given shape is consequently formed Plate circuit.

Then, as shown in Fig. 6-D, in the way of covering plating circuit (in the way of burying plating circuit) in very thin layers of copper Set embedment resin and laminated resin layer, then, another Copper foil with carrier (the 2nd layer) from very thin layers of copper side joint.

Then, as shown in Fig. 6-E, carrier is peeled off from the 2nd layer of Copper foil with carrier.

Then, as shown in Fig. 6-F, progress laser perforate is put in positioning for resin bed, plating circuit is exposed and is formed Blind hole.

Then, as shown in Fig. 7-G, it is embedded to copper to blind hole and forms filling perforation.

Then, as shown in Fig. 7-H, in filling perforation, plating circuit is formed such as above-mentioned Fig. 5-B and Fig. 5-C.

And then, as shown in Fig. 7-I, carrier is peeled off from the 1st layer of Copper foil with carrier.

Then, as shown in Fig. 8-J, the very thin layers of copper on two surfaces is removed by dodging erosion, and makes the plating electricity in resin bed Expose on the surface on road.

Then, as shown in Fig. 8-K, projection is formed on the plating circuit in resin bed, copper pillar is formed on the solder. The printing distributing board of the Copper foil with carrier using the present invention is made in the above described manner.

The Copper foil with carrier of the present invention can be used in above-mentioned (the 2nd layer) of another Copper foil with carrier, and previously attached also can be used Carrier copper foil, and then common copper foil also can be used.Also, also can on the 2nd layer shown in Fig. 7-H of circuit so that formed 1 layer Or multiple layers of circuit, also by semi-additive process, subtractive process, part addition process or it the either method in semi-additive process can be improved enter The circuit of the row grade is formed.

The Copper foil with carrier of the present invention is preferably the aberration on the control pole thin copper layer surface in the way of meeting following (1). " aberration on very thin layers of copper surface " so-called in the present invention is the aberration on the surface for representing very thin layers of copper or is being implemented with roughening treatment Etc. various surface treatments situation when, its be surface-treated layer surface aberration.That is, Copper foil with carrier of the invention is preferably with full It is enough down the aberration on the roughening treatment surface of the mode control pole thin copper layer of (1).Furthermore, in the surface treatment copper foil of the present invention So-called " roughening treatment surface " refers to after roughening treatment, carries out the surface to set refractory layer, antirust coat, weatherable layer etc. During the situation of processing, the surface of the surface treatment copper foil after the surface treatment (very thin layers of copper) is carried out.Also, in surface treatment copper foil For the very thin layers of copper of Copper foil with carrier situation when, so-called " roughening treatment surface " refers to after roughening treatment, carry out to set During the situation for the surface treatment for putting refractory layer, antirust coat, weatherable layer etc., the table of the very thin layers of copper after the surface treatment is carried out Face.

(1) aberration on very thin layers of copper surface is that the aberration Δ E*ab based on JIS Z8730 is more than 45.

Herein, aberration Δ L, Δ a, Δ b are to be utilized respectively colour difference meter to be measured, and be plus black/white/red green/Huang/ Indigo plant, and the overall target being indicated using the L*a*b colour systems based on JIS Z8730, with Δ L：White black, Δ a：It is red Green, Δ b：The mode of champac is indicated.Also, Δ E*ab is the aberration using the grade, represented with following formula.

[mathematical expression 2]

Above-mentioned aberration can become the copper concentration in electroplate liquid by uprising current density during very thin layers of copper formation It is low, the line flow velocity of electroplate liquid is uprised and is adjusted.

Also, above-mentioned aberration also can implement roughening treatment by the surface to very thin layers of copper and set roughening treatment layer and enter Row adjustment., can be by using containing copper and selected from the group being made up of nickel, cobalt, tungsten, molybdenum when setting the situation of roughening treatment layer In more than a kind of element electrolyte, and current density is higher than previous (such as 40~60A/dm²), make processing time short It is adjusted in previous (such as 0.1~1.3 second)., can when the situation of roughening treatment layer is not provided with the surface of very thin layers of copper The adjustment of above-mentioned aberration is accomplished in the following manner, that is, uses and Ni concentration is set to more than 2 times of other elements of plating bath, with Less than previous current density (0.1~1.3A/dm²), and the longer setting processing time (20 seconds~40 seconds), and in very thin layers of copper Or the surface of refractory layer or antirust coat or chromic acid process layer or silane coupling agent process layer carries out plating Ni alloys and (such as plates Ni-W to close Gold, plating Ni-Co-P alloys, plating Ni-Zn alloys) processing.

On the aberration on very thin layers of copper surface, if the aberration Δ E*ab based on JIS Z8730 is more than 45, for example, exist During the very thin layers of copper circuit forming surface of Copper foil with carrier, the contrast of very thin layers of copper and circuit becomes distinct, as a result, visibility Become good, and can precision carry out the position alignment of circuit well.The aberration Δ based on JIS Z8730 on very thin layers of copper surface E*ab is preferably more than 50, and more preferably more than 55, and then more preferably more than 60.

As above during the situation of the aberration on control pole thin copper layer surface, become distinct with the contrast of plating circuit, depending on recognizing Property become good.Therefore, in the manufacturing step for example as shown in fig. 5-c of printing distributing board described above, can precision well In ad-hoc location formation plating circuit.Also, according to the manufacture method of printing distributing board described above, being embedded in as plating circuit The composition of resin bed, thus, for example when etching off depolarization thin copper layer is dodged in the utilization shown in Fig. 8-J, plating circuit is by resin bed Protect, and its shape is maintained, the thus formation of fine circuits becomes easy.Also, plating circuit is protected by resin bed, therefore Resistance to migration is improved, and the conducting of the distribution of suppression circuit well.Therefore, the formation of fine circuits becomes easy.Also, such as scheming By dodging during etching off depolarization thin copper layer as shown in 8-J and Fig. 8-K, the exposed surface of plating circuit turns into the shape being recessed from resin bed Shape, therefore projection is easily formed on the plating circuit, and then copper pillar is easily formed on, and manufacture efficiency is carried It is high.

Furthermore, for embedment resin (RESIN), known resin, prepreg can be used.BT (spans for example can be used Carry out acid imide triazine) resin or as containing be soaked with BT resins glass cloth prepreg, Ajinomoto Fine-Techno shares The ABF films or ABF of Co., Ltd's manufacture.Also, for above-mentioned embedment resin (RESIN), can be used described in this specification Resin bed and/or resin and/or prepreg.

Also, Copper foil with carrier used in above-mentioned first layer also can have substrate or resin on the surface of the Copper foil with carrier Layer.By with the substrate or resin bed, and Copper foil with carrier used in first layer is supported, so that fold becomes to be difficult to produce It is raw, therefore have the advantages that productivity raising.Furthermore, in aforesaid substrate or resin bed, as long as supporting above-mentioned first layer to play The effect person of used Copper foil with carrier, then can be used whole substrates or resin bed.Present specification for example can be used Described carrier, prepreg, resin bed or known carrier, prepreg, resin bed, metallic plate, metal foil, inorganic compound Plate, the paper tinsel of inorganic compound, the plate of organic compound, the paper tinsel of organic compound be used as aforesaid substrate or resin bed.

The surface treatment copper foil of the present invention can be fitted in resin substrate from roughening treatment surface side and manufacture laminate.Resin As long as substrate is with the characteristic that can be applied to printing distributing board etc., is then not particularly limited, for example, it can make in rigid PWB use With paper base material phenol resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth-paper composite base material asphalt mixtures modified by epoxy resin Fat, glass cloth-glass adhesive-bonded fabric composite base material epoxy resin and glass cloth base material epoxy resin etc., can be used poly- in FPC use Ester film or polyimide film, liquid crystal polymer (LCP, liquid crystal polymer) film, Teflon (registration mark) film, Fluororesin film etc..Furthermore, in the situation using liquid crystal polymer (LCP) film or fluororesin film, have and use polyimide film Situation compare, the tendency that the peel strength of the film and surface treatment copper foil diminishes.Therefore, liquid crystal polymer (LCP) is being used During the situation of film or fluororesin film, etch the surface treatment copper foil and formed after copper circuit, the copper circuit is covered using coating, Thus make the film and the copper circuit become to be difficult to peel off, and the film and the copper caused by the reduction of peel strength can be prevented The stripping of circuit.

Furthermore, (dielectric loss tangent is smaller (such as dielectric loss tangent is less than 0.008) for the good resin of dielectric property And/or the resin of relative dielectric constant smaller (such as being less than 3 in the situation that signal frequency is 25GHz)) or low dielectric tree The dielectric absorption of fat (resin of relative dielectric constant smaller (such as being less than 3 in the situation that signal frequency is 25GHz)) compared with It is small.Therefore, at the surface using the good resin of the dielectric property or low dielectric resin or low dielectric absorption resin and the present invention The copper-cover laminated plate, printing distributing board, printed circuit board (PCB) for managing copper foil are adapted to high-frequency circuit (with the electricity of high frequency progress signal transmission Road).Herein, so-called low dielectric absorption resin refers to dielectric absorption less than the polyimides for being previously generally used for copper-cover laminated plate Resin.Also, the surface roughness Rz of the surface treatment copper foil of the present invention is smaller, glossiness is higher, therefore surface is smooth, and is adapted to High-frequency circuit purposes.As the good resin of dielectric property or low dielectric resin or low dielectric absorption resin, for example, it can enumerate：Liquid Crystalline polymer (LCP) film or fluororesin film.

Furthermore, surface treatment copper foil of the invention can be adapted in whole purposes.For example available for printing distributing board or print Printed circuit board, the printing distributing board of high-frequency circuit or printed circuit board (PCB), conductor package substrate, the electricity of 2 primary cells or electric capacity Pole etc..

In rigid PWB situation, the method for laminating can be by preparing prepreg, by copper foil from the opposite side of coating Face be overlapped in prepreg and carry out heating pressurization and carry out, above-mentioned prepreg is to make resin impregnated in base materials such as glass cloth, is made Hardening of resin to semi-hardened state is formed.In FPC situation, via solid or without using solid at high temperature under high pressure Polyimides predecessor then in copper foil or is coated, dried, hardened by the base material such as polyimide film lamination, by This can manufacture laminated plates.

The thickness of polyimide base material resin is not particularly restricted, and can generally be enumerated：25 μm or 50 μm.

The laminate of the present invention can be used for various printing distributing boards (PWB), and there is no particular restriction, such as with regard to conductive pattern For the viewpoint of the number of plies, one side PWB, two sides PWB, multilayer PWB (more than 3 layers) are can be applied to, with regard to the species of dielectric substrate material Viewpoint for, can be applied to rigid PWB, flexibility PWB (FPC), rigid-flex PWB.On the e-machine of the present invention can be used Printing distributing board is stated to be made.

Also, the printing distributing board of the present invention is by insulating resin substrate, with existing from surface treated face side lamination Insulated substrate and it is formed with the surface treatment copper foil of copper circuit and is constituted, and using CCD camera across from by surface treatment The insulating resin substrate of face side lamination when being shot to copper circuit, for by shooting the image obtained, along with institute The vertical direction in direction of the copper circuit extension of observation, the observation place that the brightness to each observation place is measured and made In point-brightness curve, from the end of copper circuit to without copper circuit part produce brightness curve top average value Bt with Bottom average value Bb poor Δ B (Δ B=Bt-Bb) is more than 40.If using such a printing distributing board, can more accurately enter The positioning of row printing distributing board.Thus, it is believed that when a printing distributing board and another printing distributing board are attached, Bad connection is reduced, and yield is improved.Furthermore, it is used as the side for being attached a printing distributing board and another printing distributing board Method, can be used via welding or the connection of anisotropic conducting membrance (Anisotropic Conductive Film, ACF), via different The connection of tropism electrocondution slurry (Anisotropic Conductive Paste, ACP) or via conductive solid Connection etc. known to connection method.

Also, the copper-cover laminated plate of the present invention is by insulating resin substrate, with existing from surface treated face side lamination The surface treatment copper foil of insulated substrate is constituted, and wire is made in the surface treatment copper foil by etching copper-cover laminated plate After surface treatment copper foil, using CCD camera across the insulating resin substrate progress from surface treated face side lamination During shooting, for by shooting the image obtained, being hung down along the direction with observed above-mentioned linear surfaces processing copper foil extension In straight direction, observation place-brightness curve that the brightness to each observation place is measured and made, from linear surfaces Manage top average value Bt and bottom of the end of copper foil to the brightness curve produced by the part that copper foil is handled without above-mentioned linear surfaces Portion average value Bb poor Δ B (Δ B=Bt-Bb) is more than 40.If manufacturing printing distributing board using such a copper-cover laminated plate, The positioning of printing distributing board can more accurately be carried out.Thus, it is believed that by a printing distributing board and another printed wiring When plate is attached, bad connection is reduced, and yield is improved.Furthermore, as by a printing distributing board and another printed wiring The method that plate is attached, can be used via welding or anisotropic conducting membrance (Anisotropic Conductive Film, ACF connection), the connection via anisotropy electrocondution slurry (Anisotropic Conductive Paste, ACP) or via Connection method known to connection of conductive solid etc..

Furthermore, in the present invention, " printing distributing board " is also comprising the printing distributing board and printed base plate for being provided with part.

[laminated plates and the localization method using its printing distributing board]

The localization method of the laminated plates of surface treatment copper foil and resin substrate to the present invention is illustrated.First, prepare The laminated plates of surface treatment copper foil and resin substrate.It is used as the tool of the laminated plates of surface treatment copper foil and resin substrate of the invention Style, can be enumerated：By this structure base board and attached circuit substrate and to being set the electric connection such as this in polyimides etc. An at least surface for fat is formed with the e-machine of the flexible printing substrate of copper wiring composition, exactly by flexible printing substrate Positioned, and be crimped on this structure base board and the wiring end of attached circuit substrate and the laminate that makes.That is, if should Situation, then laminated plates turn into the laminate of the wiring end of flexible printing substrate and this structure base board laminating by crimping or The laminated plates that the wiring end of flexible printing substrate and circuit substrate is fitted by crimping.Laminated plates have by the copper wiring A part or other materials formation mark.On the position of mark, if for using CCD camera etc. shoot means across The position that the resin of the laminated plates can be shot is constituted, then is not particularly limited.Herein, so-called mark refers to detect lamination The position of plate or printing distributing board etc., or positioned, or the mark (mark) for carrying out position alignment and using.

In the laminated plates prepared in the above described manner, if being shot using the means that shoot across resin to above-mentioned mark, The position of above-mentioned mark can be then detected well.Then, the position of above-mentioned mark is detected in the above described manner, and can be based on upper The position for the mark being detected is stated, the positioning of the laminated plates of surface treatment copper foil and resin substrate is carried out well.Also, making During with printing distributing board as laminated plates, also similarly, by above-mentioned localization method, shooting means can detect mark well Position, and can more precisely carry out the positioning of printing distributing board.

Thus, it is believed that when a printing distributing board and another printing distributing board are attached, bad connection subtracts Few, yield is improved.Furthermore, as the method for being attached a printing distributing board and another printing distributing board, can be used Via welding or the connection of anisotropic conducting membrance (Anisotropic Conductive Film, ACF), via anisotropy conduction The connection of slurry (Anisotropic Conductive Paste, ACP) or the connection via conductive solid etc. Known connection method.Furthermore, in the present invention, " printing distributing board " is also comprising printing distributing board and the printing for being provided with part Circuit board and printed base plate.Also, more than 2 printing distributing boards of the invention can be connected, and manufacture and be connected with more than 2 printings The printing distributing board of distributing board, also, can be by printing distributing board at least one of the present invention and another printed wiring of the invention Plate or the printing distributing board of printing distributing board equivalent to the present invention is not attached, also can be used above-mentioned printing distributing board system Make e-machine.Furthermore, in the present invention, " copper circuit " also includes copper wiring.And then, also can be by the printing distributing board of the present invention It is connected with part and manufactures printing distributing board.Also, by the present invention printing distributing board at least one, with another print of the invention Brush distributing board or the printing distributing board of printing distributing board equivalent to the present invention is not attached, and then, by the company of the present invention The printing distributing board and part for being connected to more than 2 printing distributing boards are attached, and thus can also be manufactured and are connected with more than 2 printings The printing distributing board of distributing board.Herein, as " part ", it can enumerate：Connector or LCD (Liquid Cristal Display, Liquid crystal display), for electronic components such as LCD glass substrates, containing IC (Integrated Circuit, IC), LSI (Large scale integrated circuit, extensive IC), VLSI (Very Large scale Integrated circuit, ultra-large type IC), ULSI (Ultra-Large Scale Integration, especially big rule Mould IC) etc. the electronic component (such as IC chips, LSI chips, VLSI chips, ULSI chips) of semiconductor IC, To hide the part of electronic circuit and for part necessary to outer cover etc. is fixed on into printing distributing board etc..

Furthermore, the localization method of embodiment of the present invention also can be comprising making laminated plates (comprising copper foil and resin substrate Laminated plates or printing distributing board) mobile step.In moving step, such as can be by ribbon conveyer or chain-linked conveyer Conveyer moves laminated plates, also can move laminated plates by possessing the mobile device of arm mechanism, also using by using Gas laminated plates is suspended and be allowed to mobile mobile device or mobile means make laminated plates movement, also can be by making substantially cylinder The things such as shape rotate and make the mobile device or mobile means (comprising roller or bearing etc.) of laminated plates movement, using oil pressure as power source Mobile device or mobile means, using air pressure as the mobile device of power source or mobile means, using motor as the movement of power source Device or mobile means, support mobile model linear guides platform, support mobile model air guide rail platform, stack Linear guide rail platform, line Property motor driving platform etc. there is mobile device or mobile means of platform etc. move laminated plates.Also, can also carry out using known The moving step of mobile means.In the above-mentioned step for moving laminated plates, laminated plates can be made to move and carry out position alignment.And And, it is believed that by carrying out position alignment, and a printing distributing board and another printing distributing board or part are connected When connecing, bad connection is reduced, and yield is improved.

Furthermore, the localization method of embodiment of the present invention also can be used for surface mounting apparatus or wafer chip mounter.

Also, in the present invention, the surface treatment copper foil and the laminated plates of resin substrate positioned also can be with resin plate And it is arranged on the printing distributing board of the circuit on above-mentioned resin plate.Also, in the situation, above-mentioned mark also can be foregoing circuit.

In the present invention, so-called " positioning " is included " position of detection mark or thing ".Also, in the present invention, so-called " position Alignment ", which is included, " behind the position of detection mark or thing, based on the above-mentioned position detected, makes the mark or thing to ad-hoc location It is mobile ".

[embodiment]

As embodiment 1~35 and comparative example 1~14, prepare the various copper foils described in table 2, and using described in table 1 Condition, to a surface carry out electroplating processes be used as roughening treatment.

Also, on embodiment 31~35, preparing the various carriers described in table 2, under the following conditions, on the surface of carrier Intermediate layer is formed, and very thin layers of copper is formed on the surface in intermediate layer.Then, under conditions of table 1 is described, to very thin layers of copper Surface carries out the plating as roughening treatment.

Embodiment 31

＜ intermediate layers ＞

(1) Ni layers (plating Ni)

For carrier, under the following conditions, electroplated using the continuous electroplating producing line of roll-to-roll type, be consequently formed 1000 μg/dm²Adhesion amount Ni layers.Specific plating conditions are recorded in following.

Nickel sulfate：270~280g/L

Nickel chloride：35~45g/L

Nickel acetate：10~20g/L

Boric acid：30~40g/L

Polishing material：Saccharin, butynediols etc.

Lauryl sodium sulfate：55~75ppm

PH value：4~6

Bath temperature：55~65 DEG C

Current density：10A/dm²

(2) Cr layers (processing of electrolysis chromic acid)

Then, for the Ni layer surfaces formed in (1) washed and pickling after, then in the continuous electroplating of roll-to-roll type On line, electrolysis chromic acid processing is carried out on Ni layers under the following conditions, thus makes 11 μ g/dm²The Cr layers of adhesion amount are attached to On Ni layers.

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

PH value：7~10

Liquid temperature：40~60 DEG C

Current density：2A/dm²

The very thin layers of copper ＞ of ＜

Then, for the Cr layer surfaces formed in (2) washed and pickling after, then in the continuous electroplating of roll-to-roll type On line, electroplated under the following conditions on Cr layers, be consequently formed the very thin layers of copper of 1.5 μm of thickness, and make appendix body Ultrathin copper foil.

Copper concentration：90~110g/L

Sulfuric acid concentration：90~110g/L

Chloride ion concentration：50~90ppm

Leveling agent 1 (double (three sulfopropyls) disulphide)：10~30ppm

Leveling agent 2 (amines)：10~30ppm

Furthermore, leveling agent 2 is used as using following amines.

Electrolyte temperature：50~80 DEG C

Current density：100A/dm²

Electrolyte linear speed：1.5~5m/sec

The TD on very thin layers of copper surface surface roughness is 0.55 μm, and MD 60 degree of glossiness are 519%.

Embodiment 32

＜ intermediate layers ＞

(1) Ni-Mo layers (plating nickel-molybdenum alloy)

For carrier, electroplated under the following conditions using the continuous electroplating line of roll-to-roll type, be consequently formed 3000 μ g/ dm²The Ni-Mo layers of adhesion amount.Specific plating conditions are recorded in following.

(liquid composition) sulfuric acid Ni hexahydrates：50g/dm³, sodium molybdate dihydrate：60g/dm³, sodium citrate：90g/dm³

30 DEG C of (liquid temperature)

(current density) 1~4A/dm²

(conduction time) 3~25 seconds

The very thin layers of copper ＞ of ＜

Very thin layers of copper is formed on the Ni-Mo layers formed in (1).The thickness of very thin layers of copper is set to 3 μm, in addition, Very thin layers of copper is being formed under the same conditions with embodiment 31.The TD on very thin layers of copper surface surface roughness is 0.26 μm, MD 60 degree of glossiness be 770%.

Embodiment 33,34

＜ intermediate layers ＞

(1) Ni layers (plating Ni)

Ni layers are being formed under the same conditions with embodiment 31.

(2) organic matter layer (organic matter layer formation processing)

Then, for the Ni layer surfaces formed in (1) washed and pickling after, then under the conditions of following, for Ni Layer surface, 20 are carried out by the aqueous solution of 40 DEG C of the liquid temperature of the carboxyl benzotriazole (CBTA) containing 1~30g/L of concentration and pH value 5 ~120 seconds spray washings, are consequently formed organic matter layer.

The very thin layers of copper ＞ of ＜

Very thin layers of copper is formed on the organic matter layer formed in (2).The thickness of very thin layers of copper is set to 2 μm, in addition, Very thin layers of copper is being formed under the same conditions with embodiment 31.The TD on very thin layers of copper surface surface roughness is 0.40 μm, MD 60 degree of glossiness be 528%.

Embodiment 35

＜ intermediate layers ＞

(1) Co-Mo layers (plating cobalt molybdenum alloy)

For carrier, electroplated under the following conditions using the continuous electroplating line of roll-to-roll type, be consequently formed 4000 μ g/ dm²Adhesion amount Co-Mo layers.Specific plating conditions are recorded in following.

(liquid composition) sulfuric acid Co：50g/dm³, sodium molybdate dihydrate：60g/dm³, sodium citrate：90g/dm³

30 DEG C of (liquid temperature)

(current density) 1~4A/dm²

(conduction time) 3~25 seconds

The very thin layers of copper ＞ of ＜

Very thin layers of copper is formed on the Co-Mo layers formed in (1).The thickness of very thin layers of copper is set to 8 μm, in addition, Very thin layers of copper is being formed with the identical condition of embodiment 31.The TD on very thin layers of copper surface surface roughness is 0.75 μm, MD's 60 degree of glossiness are 453%.

Carry out after above-mentioned roughening plating processing, for embodiment 1~10,12~27,32~35, comparative example 3,4,6,9 ~14, carry out the electroplating processes to ensuing refractory layer and antirust coat formation.

The formation condition of refractory layer 1 is shown in following.

Liquid is constituted：5~20g/L of nickel, 1~8g/L of cobalt

PH value：2~3

Liquid temperature：40~60 DEG C

Current density：5~20A/dm²

Coulomb amount：10~20As/dm²

It is being provided with formation refractory layer 2 on the copper foil of above-mentioned refractory layer 1.On comparative example 5,7,8, roughening plating is not being carried out The refractory layer 2 is directly formed on the copper foil for applying processing and preparing.The formation condition of refractory layer 2 is shown in following.

Liquid is constituted：2~30g/L of nickel, 2~30g/L of zinc

PH value：3~4

Liquid temperature：30~50 DEG C

Current density：1~2A/dm²

Coulomb amount：1~2As/dm²

It is being provided with the copper foil of above-mentioned refractory layer 1 and 2, and then is forming antirust coat.The formation condition of antirust coat is shown in Below.

Liquid is constituted：1~10g/L of potassium bichromate, 0~5g/L of zinc

PH value：3~4

Liquid temperature：50~60 DEG C

Current density：0~2A/dm²(to impregnate chromic acid processing)

Coulomb amount：0~2As/dm²(to impregnate chromic acid processing)

On the copper foil for being provided with above-mentioned refractory layer 1,2 and antirust coat, and then form weatherable layer.Formation condition is shown in Below.

It is (real using N-2- (amido ethyl) -3- aminocarbonyl propyl trimethoxy silanes as the silane coupling agent with amido Apply example 17,24~27), N-2- (amido ethyl) -3- aminocarbonyl propyl triethoxysilanes (embodiment 1~16,32~35), N-2- (amido ethyl) -3- aminocarbonyl propyls methyl dimethoxysilane (embodiment 18,28,29,30), 3- aminocarbonyl propyl trimethoxy silicon Alkane (embodiment 19), 3- aminocarbonyl propyl triethoxysilanes (embodiment 20,21), 3- triethoxy silicon substrate-N- (1,3- diformazans Base-butylidene) propyl group amine (embodiment 22), N- phenyl -3- aminocarbonyl propyl trimethoxy silanes (embodiment 23) be coated, do It is dry, and form weatherable layer.Also the grade silane coupling agent can be used in the way of combination of more than two kinds.Similarly comparing In example 1~14, it is coated, dried with N-2- (amido ethyl) -3- aminocarbonyl propyl trimethoxy silanes, and forms weatherability Layer.

Furthermore, rolled copper foil is to be manufactured in the following manner.The copper ingot of the composition shown in table 2 is made, heat is carried out cold rolling Afterwards, be repeated 300~800 DEG C continuous annealing line annealing with it is cold rolling, and obtain the thick calendering plates of 1~2mm.This is rolled Plate is annealed in 300~800 DEG C of continuous annealing line, recrystallizes it, carries out final cold rolling up to the thickness of table 2, and Obtain copper foil." refined copper " on " species " column of table 2 is to represent the refined copper using JISH3100C1100 as standard, and " oxygen-free copper " is table Show the oxygen-free copper using JIS H3100C1020 as standard.Also, " refined copper+Ag：100ppm " means to be added with 100 mass in refined copper Ppm Ag.

Electrolytic copper foil is in addition to embodiment 35, the electrolytic copper foil HLP paper tinsels manufactured using Mining days stone metal companies of JX.On reality Example 35 is applied, the electrolytic copper foil JTC paper tinsels manufactured using Mining days stone metal companies of JX are used as electrolytic copper foil.Carry out electrolytic polishing or During the situation of chemical grinding, the thickness of slab after electrolytic polishing or chemical grinding is recorded.

Furthermore, the main points of the making step of copper foil or carrier before surface treatment are recorded in table 2." high glaze calendering " anticipates The value for the oil film equivalent for referring to record carries out final cold rolling (cold rolling after final recrystallization annealing)." generally calendering " means Final cold rolling (cold rolling after final recrystallization annealing) is carried out with the value of the oil film equivalent of record." chemical grinding ", " electrolysis Grinding " means to carry out under the following conditions.

" chemical grinding " is to use H₂SO₄For 1~3 mass %, H₂O₂For 0.05~0.15 mass %, the erosion that the remnants of defeated troops are water Liquid is carved, and milling time is set to 1 hour.

" electrolytic polishing " is under conditions of phosphoric acid 67%+ sulfuric acid 10%+ water 23%, with voltage 10V/cm², table 2 remembered The time (if carrying out the electrolytic polishing of 10 seconds, amount of grinding is 1~2 μm) of load is carried out.

For the embodiment and each sample of comparative example made in the above described manner, various evaluate is carried out as following.

(1) measure of surface roughness (Rz)；

The contact roughmeter Surfcorder SE-3C manufactured using limited company of little Ban research institutes, foundation 10 mean roughness, for roughening face, are measured by JISB0601-1994.Determine datum length 0.8mm, evaluate length Spend under conditions of 4mm, cutoff 0.25mm, transporting velocity 0.1mm/sec, with perpendicular to rolling direction (i.e. TD, in electrolytic copper foil Situation when, perpendicular to the direction of advance of copper foil) mode change and locate, carry out 10 measure, and obtain the survey of 10 times The value fixed.

Furthermore, for the copper foil before surface treatment, surface roughness (Rz) is also obtained in an identical manner in advance.

Also, the surface and the surface of very thin layers of copper of the side for the setting intermediate layer of carrier, also in an identical manner in advance Obtain surface roughness (Rz).

Furthermore, it is resistance in order to set after roughening treatment is carried out to copper foil surface, or in the case of without roughening treatment Thermosphere, antirust coat, weatherable layer etc. and during the situation being surface-treated, for this through refractory layer, antirust coat, weatherable layer etc. The surface of surface treatment copper foil after surface treatment, carries out above-mentioned measure.In the pole that surface treatment copper foil is Copper foil with carrier During the situation of thin copper layer, above-mentioned measure is carried out for the roughening treatment surface of very thin layers of copper.

(2) the area ratio (A/B) of particle；

The surface area of roughening particle is to use the determination method using laser microscopes.Use KEYENCE limited companies The laser microscopes VK8500 of manufacture, determine roughening treatment face equivalent to 100 × 100 μm under 2000 times of multiplying power area B ( It is 9982.52 μm in real data²) in three-dimensional table area A, and by being set to three-dimensional table area A ÷ bivariate table area B=faces Method of the product than (A/B) is set.

(3) glossiness；

The Grossmeters Handy gloss manufactured using the Japanese electricity Se Industries, Incs according to JIS Z8741 Meter-PG-1, with rolling direction (i.e. MD, in the situation of electrolytic copper foil, is the direction of advance of copper foil) and perpendicular to calendering side To direction (i.e. TD, in the situation of electrolytic copper foil, is the direction of the direction of advance perpendicular to copper foil) respective incidence angle 60 degree are measured to roughening face.

Furthermore, for the copper foil before surface treatment, glossiness is also obtained in an identical manner in advance.

Also, the progress for the copper foil before surface treatment has the side in the surface of surface treatment side and the setting intermediate layer of carrier Surface and very thin layers of copper surface, also obtain glossiness in an identical manner in advance.

(4) slope of brightness curve

Surface treatment copper foil is fitted in into polyimide film (Kaneka from the roughening treatment face side of the surface treatment copper foil Manufacture 25 μm or 50 μm of thickness or Dong Li Du Ponts manufacture 50 μm of thickness) two sides, utilize etching (ferric chloride in aqueous solution) remove Copper foil and make sample film.Furthermore, for the copper foil of roughened processing, the roughened process face of copper foil is fitted in into above-mentioned gather Acid imide film is to be made above-mentioned sample film.Also, after roughening treatment is carried out to copper foil surface, or without roughening treatment In the case of in order to refractory layer, antirust coat, weatherable layer etc. are set and are surface-treated situation when, by this through refractory layer, anti- Surface treatment copper foil after the surface treatment such as rusty scale, weatherable layer fits in polyimide film from the surface treated surface side Two sides, using etching (ferric chloride in aqueous solution) remove surface treatment copper foil and be made sample film.It is attached in surface treatment copper foil During the situation of the very thin layers of copper of carrier copper foil, Copper foil with carrier is fitted in into polyamides Asia from the roughening treatment face side of very thin layers of copper The two sides of amine film, thereafter, after carrier is peeled off, removes very thin layers of copper using etching (ferric chloride in aqueous solution) and makes sample Film.Then, the printed article pad of density bullet of wire will be printed with the lower section of sample film, CCD camera (8192 pixels are utilized Line array CCD video camera), printed article is shot across sample film, for by shoot obtain image, along with institute The wire of observation marks the vertical direction in the direction of extension, the observation place that the brightness to each observation place is measured and made In point-brightness curve, Δ B and t1, t2, Sv are determined according to brightness curve.To represent the composition of camera that now uses and The schematic diagram of the assay method of brightness curve is in Fig. 3.

Also, Δ B and t1, t2, Sv be as shown in Figure 2 as be measured using following cameras.

Above-mentioned " being printed with the printed article of the density bullet of wire " is used on the white glossy paper of glossiness 43.0 ± 2 It is loaded with JIS P8208 (1998) (Fig. 1 inclusions measure the duplication of chart) and JIS P8145 (2011) (annex JA (regulation) mesh Compare the duplication that figure figure JA.1- visual method foreign matters compare figure depending on method foreign matter) be printed with using hyaline membrane i.e. shown in Fig. 9 it is various The inclusion (field trash) of line etc. (Chaoyang can limited company's manufacture name of an article：" inclusion determines chart-full sheet width paper " compiles Number：JQA160-20151-1 (manufactured by Nat Printing Bureau Inc. Admini)).

The glossiness of above-mentioned glossy paper is to use to manufacture according to JIS Z8741 Japanese electricity Se Industries, Incs Grossmeters Handy gloss meter-PG-1, with incidence angle, 60 degree are measured.

Camera possesses：CCD camera, the platform across the polyimide substrate that the paper that affix is remembered is provided with lower section (white), the electric consumption on lighting source to the shoot part irradiation light of polyimide substrate, the paper of the mark of attached reference object is placed in down The transporter (not shown) that the evaluation of side is transported with polyimide substrate on platform.The main specifications of the camera is shown In following：

Camera：The sheet material detection apparatus Mujiken of Nireco limited companies manufacture

Line array CCD video camera：8192 pixels (160MHz), 1024 GTG numerical digits (10bit)

Electric consumption on lighting source：High frequency mains lighting supply (power supply module × 2)

Illumination：Fluorescent lamp (30W, model：FPL27EX-D, double fluorescent lamp)

The line of Sv measure is to use 0.7mm²Fig. 9 the arrow drawn of field trash shown in line.The width of the line For 0.3mm.Also, the line array CCD video camera ken is set to the configuration of Fig. 9 dotted line.

In the shooting using line array CCD video camera, using the GTG confirmation signal of full scale 256, measure object not every , (will be above-mentioned transparent with the non-existent position of the density bullet of printed article in the state of polyimide film (polyimide substrate) Film is placed on above-mentioned white glossy paper, using CCD camera, and self-induced transparency film side is to the position that is printed on outside the mark of field trash The situation being measured) crest grayscale signal close at 230 ± 5 mode and adjust lens iris.Video camera sweep time (takes the photograph The time that the shutter of shadow machine is opened, take in the time of light) it is to be fixed as 250 μ seconds, and adjusted in the way of closing within above-mentioned GTG Whole lens iris.

Furthermore, for printing distributing board and copper-cover laminated plate, Δ B and Sv are surveyed by mark of the copper foil of wire During fixed situation, the white glossy paper of glossiness 43.0 ± 2 is applied at the back side for the copper foil for being set to wire, CCD camera is utilized (the line array CCD video cameras of 8192 pixels), are shot across the polyimide film, in the image for being obtained by shooting, Along the direction vertical with the direction of observed copper foil extension, the sight that the brightness to each observation place is measured and made Examine in place-brightness curve, according to the brightness curve that is produced to unmarked part of end from mark, to Δ B and t1, t2, Sv is measured, in addition, is set to being carried out using above-mentioned " printed article for being printed with wire density bullet " to Δ B and Sv The condition of measure is identical.

Furthermore, mean " black " on the brightness shown in Fig. 3,0, brightness 255 means " white ", will be from the grey of " black " to " white " Degree (white black deep or light, gray scale) is divided into 256 GTGs to be indicated.

(5) visibility (resin transparency)；

The surface of the surface treated side of surface treatment copper foil is fitted in into polyimide film, and (Kaneka manufactures 25 μm or 50 μm, or Dong Li Du Ponts manufacture 50 μm of thickness) two sides, using etching (ferric chloride in aqueous solution) remove copper foil and sample is made Film.Furthermore, on carrying out having the copper foil of roughening treatment, the roughened process face of copper foil is fitted in into above-mentioned polyimide film and Above-mentioned sample film is made.Also, to copper foil surface carry out roughening treatment after, or in the case of without roughening treatment in order to During the situation for setting refractory layer, antirust coat, weatherable layer etc. and being surface-treated, by this through refractory layer, antirust coat, weatherability Surface treatment copper foil after the surface treatment such as layer fits in the two sides of polyimide film from the surface treated surface side, utilizes erosion (ferric chloride in aqueous solution) is carved to remove surface treatment copper foil and make sample film.It is the very thin of Copper foil with carrier in surface treatment copper foil During the situation of layers of copper, Copper foil with carrier is fitted in the two sides of polyimide film from the roughening treatment face side of very thin layers of copper, its Afterwards after carrier is peeled off, remove very thin layers of copper using etching (ferric chloride in aqueous solution) and sample film is made.In the resin of acquisition The one side of layer attaches printed article (circle of diameter 6cm black), judges the visibility of printed article across resin bed from opposing face.Will The profile of the circle of the black of printed article person of understanding in more than the 90% of circumference length is evaluated as " ◎ ", by the wheel of the circle of black It is wide circumference more than 80% and be not evaluated as "○" (qualified above) up to the person of understanding in 90% length, by the wheel of the circle of black Exterior feature is not evaluated as "×" (unqualified) in circumference up to the person of understanding in 0~80% length and profile collapse person.

(6) peel strength (Bonding strength)；

By the surface area layer of the surface treated side of surface treatment copper foil, in polyimide film, (Kaneka manufactures 25 μm or 50 μm, or Dong Li Du Ponts 50 μm of thickness of manufacture) after, it is normal using 100 couples of cupping machine Autograph according to IPC-TM-650 State peel strength is measured, and is that more than 0.7N/mm is set to can be used for laminated substrate purposes by above-mentioned normality peel strength.Again Person, on embodiment 31~35, by the surface area layer of the surface treated side of surface treatment copper foil in polyimide film (Kaneka Manufacture 25 μm or 50 μm, or Dong Li Du Ponts manufacture 50 μm of thickness) after, carrier is peeled off, with above-mentioned polyimide film lamination Very thin layers of copper thickness turn into 12 μ m-thicks mode carry out copper facing, peel strength is determined afterwards.Furthermore, enter to copper foil surface After row roughening treatment, or carry out to set refractory layer, antirust coat, weatherable layer etc. in the case of without roughening treatment During the situation of surface treatment, to the surface of the surface treatment copper foil after being surface-treated through refractory layer, antirust coat, weatherable layer etc. Carry out above-mentioned measure.In situation of the surface treatment copper foil for the very thin layers of copper of Copper foil with carrier, the roughening to very thin layers of copper Handle surface and carry out above-mentioned measure.

(7) solder heat resistance evaluation；

The surface of the surface treated side of surface treatment copper foil is fitted in into polyimide film, and (Kaneka manufactures 25 μm or 50 μm, or Dong Li Du Ponts manufacture 50 μm of thickness) two sides.Furthermore, it is for the copper foil for carrying out having roughening treatment, the warp of copper foil is thick Change process face and fit in above-mentioned polyimide film.For the two sides laminated plates of acquisition, the attached body examination according to JIS C6471 is made Piece.By the test coupon of making in after 85 DEG C, 85%RH hot and humid lower exposure 48 hours, making its solder bath at 300 DEG C Middle floating, and evaluate solder heat resistance characteristic.After solder heat resistance experiment, in roughening of copper foil process face and polyimide resin commissure Interface in, by more than 5% area of the copper foil area in test coupon, due to expansion, interface discoloration person is evaluated as × (unqualified), the situation by area not up to 5% expansion discoloration is evaluated as zero, all will not produce expansion discoloration person and is evaluated as ◎。

Furthermore, it is resistance in order to set after roughening treatment is carried out to copper foil surface, or in the case of without roughening treatment Thermosphere, antirust coat, weatherable layer etc. and during the situation being surface-treated, to this through tables such as refractory layer, antirust coat, weatherable layers The surface of surface treatment copper foil after the processing of face carries out above-mentioned measure.In the very thin copper that surface treatment copper foil is Copper foil with carrier During the situation of layer, above-mentioned measure is carried out to the roughening treatment surface of very thin layers of copper.

(8) yield

The surface of the surface treated side of surface treatment copper foil is fitted in into polyimide film, and (Kaneka manufactures 25 μm or 50 μm, or Dong Li Du Ponts 50 μm of thickness of manufacture) two sides, copper foil is etched (ferric chloride in aqueous solution), and be made L/S for 30 μm/FPC of 30 μm of circuit width.Furthermore, for the copper foil for carrying out having roughening treatment, the progress of copper foil is had into roughening treatment Face fits in above-mentioned polyimide film.Thereafter, attempt to utilize CCD camera, see across polyimides 20 μm of 20 μ m of detection The mark of side.More than 9 times detectable situations in 10 times are set to " ◎ ", 7~8 detectable situations are set to 6 detectable situations are set to " △ " by "○", and less than 5 times detectable situations are set into "×".

(9) circuitry shapes (fine pattern characteristic) of etching are utilized

The surface of the surface treated side of surface treatment copper foil is fitted in the polyamides of attached lamination thermosetting solid The two sides of imines film (Kaneka manufactures 25 μm or 50 μm, or Dong Li Du Ponts 50 μm of thickness of manufacture).In order to fine pattern electricity Road formative is evaluated, it is necessary to make copper thickness identical, herein, on the basis of 12 μm of copper thicknesses.That is, 12 are thicker than in thickness μm situation when, carry out subtracting thick until 12 μ m-thicks by electrolytic polishing.On the other hand, when thickness is thinner than 12 μm of situation, lead to Copper plating treatment is crossed thicken until 12 μ m-thicks.For the single-face side of the two sides laminated plates of acquisition, applied by photonasty resist Cloth and step of exposure, and in the copper foil gloss surface side printed with fine pattern circuit of laminated plates, under the following conditions to copper foil not Partly to be etched, and be formed as turned into L/S=20/20 μm of fine pattern circuit.Herein, circuit width is with electricity The mode that the minimum width of road section turns into 20 μm is set.

(etching condition)

Device：The small-sized Etaching device of injecting type

Injection pressure：0.2MPa

Etching solution：Ferric chloride in aqueous solution (Baume of proportion 40)

Liquid temperature degree：50℃

After fine pattern circuit is formed, it is impregnated in 45 DEG C of the NaOH aqueous solution 1 minute, peels off photonasty resist Film.

(10) etching factor (Ef) is calculated

The fine pattern circuit sample of above-mentioned middle acquisition is directed to, the scan-type electricity manufactured using high and new technology company of Hitachi Sub- microphotograph S4700, is observed with 2000 times of multiplying power from circuit top, determines the highest width (Wa) on circuit top With the minimum width (Wb) of circuit bottom.Copper thickness (T) is set to 12 μm.Etching factor (Ef) is calculated by following formula.

Etching factor (Ef)=(2 × T)/(Wb-Wa)

(11) measure of transmission loss

For each sample, the face of the surface treated side of surface treatment copper foil is fitted in into commercially available liquid crystal polymer resin After (the Vecstar CTZ-50 μm of Kuraray (stock) manufactures), using etching, form micro- in the way of characteristic impedance turns into 50 Ω Ripple transmission belt circuit, the network analyzer-HP8720C manufactured using Hewlett-Packard Corporation is determined by coefficient, and is obtained in frequency Transmission loss under 20GHz and frequency 40GHz.Furthermore, in order that appreciation condition is as consistent as possible, by surface treatment copper foil and liquid After the laminating of crystalline polymer resin, copper thickness is set to 18 μm.That is, when the thickness of copper foil is thicker than 18 μm of situation, electricity is passed through Solution grinding progress subtracts thick until 18 μ m-thicks.On the other hand, when thickness is thinner than 18 μm of situation, thickened by copper plating treatment Until 18 μ m-thicks.As the evaluation of the transmission loss under frequency 20GHz, ◎ will not be set to up to 3.7dB/10cm, will be More than 3.7dB/10cm and zero is not set to up to 4.1dB/10cm, will be set to for more than 4.1dB/10cm and up to 5.0dB/10cm △, will be set to for more than 5.0dB/10cm ×.

Furthermore, can be by making tree in printing distributing board or copper-cover laminated plate or surface treatment copper foil with resin bed Liposoluble solution is simultaneously removed, and determines above-mentioned (1) surface roughness (Rz), the area of (2) particle for copper circuit or copper foil surface Than (A/B), (3) glossiness, (4) brightness curve slope (Δ B and t1, t2, Sv).

The above-mentioned condition respectively tested and evaluation are shown in table 1~5.

Table 1

Table 2

※ embodiments 31~35 represent the carrier of Copper foil with carrier.

Table 3

Table 4

Table 5

(evaluation result)

The equal visibility of embodiment 1~35, peel strength, solder heat resistance evaluation and yield are good.Also, embodiment 1~35 is equal Etching factor is larger, and transmission loss is smaller, is good.

The Δ B values of comparative example 1~4,6,9~14 are not up to 40, therefore visibility is bad.

The visibility of comparative example 5,7,8 is excellent, but substrate adaptation is bad.Also, the solder heat resistance evaluation of comparative example 1~14 It is bad.

Furthermore, for the surface treatment copper foil of embodiment 10~12,14,32,35, the μ of coating thickness 1 on roughening treatment surface M acrylic resin, and carry out above-mentioned evaluation.As a result the surface treatment copper foil phase with embodiment 10~12,14,32,35 is turned into Same evaluation result.

Represent that (a) comparative example 1 when above-mentioned Rz is evaluated, (b) comparative example 3, (c) comparative example 5, (d) compare respectively in Fig. 4 Example 6, (e) embodiment 1, the SEM observation photos of the copper foil surface of (f) embodiment 2.

Also, in above-described embodiment 1~35, the width of mark is changed into 0.16mm (certainly close to field trash from 0.3mm Piece area 0.5mm²0.5 record start the 3rd mark (the signified mark of Figure 10 arrow)), carry out identical Δ B values and The measure of Sv values, but Δ B values and Sv values turn into the situation identical value with the width of mark to be set to 0.3mm.

And then, in above-described embodiment 1~35, on " the top average value Bt " of brightness curve is by distance mark The position of 50 μm of the end position of both sides is changed to be set to the position of 100 μm of distance, the position of 300 μm of distance, 500 μm of distance Position, from above-mentioned position respectively with the average value of the brightness at 30 μm of measuring spaces 5 when (both sides add up at 10), carries out identical The measure of Δ B values and Sv values, but Δ B values and Sv values turn into the position of 50 μm of the end position of the both sides with will be marked from distance The average value of brightness during with 30 μm of measuring spaces 5 (at both sides total 10) is set to " the top average value Bt's " of brightness curve The Δ B values and Sv value identical values of situation.

Claims

1. it is that roughening particle in an at least surface is formed with by roughening treatment a kind of surface treatment copper foil, and

The TD on above-mentioned roughening treatment surface 10 mean roughness Rz are 0.20~0.80 μm, and above-mentioned TD is and rolling direction hangs down Straight direction or the direction vertical with copper foil direction of advance,

After above-mentioned copper foil is fitted in into the two sides of polyimide resin substrate, the copper foil on above-mentioned two sides is removed using etching,

The printed article for being printed with wire mark is layed in the lower section of the above-mentioned polyimide substrate exposed, CCD camera is utilized When above-mentioned polyimide substrate is shot to above-mentioned printed article,

In the image for being obtained by above-mentioned shooting, along the side vertical with the direction of observed above-mentioned wire mark extension To, in observation place-brightness curve that the brightness to each observation place is measured and made,

The top average value Bt of the brightness curve produced from the end of above-mentioned mark to the part without above-mentioned mark is averaged with bottom Value Bb poor Δ B (Δ B=Bt-Bb) is more than 40.

2. surface treatment copper foil according to claim 1, wherein, from the end of above-mentioned mark to the part without above-mentioned mark The top average value Bt and bottom average value Bb of produced brightness curve poor Δ B (Δ B=Bt-Bb) are more than 50.

3. surface treatment copper foil according to claim 2, wherein, from the end of above-mentioned mark to the part without above-mentioned mark The top average value Bt and bottom average value Bb of produced brightness curve poor Δ B (Δ B=Bt-Bb) are more than 60.

4. surface treatment copper foil according to claim 1, wherein, it is in above-mentioned observation place-brightness curve, brightness is bent Represent to mark the value of the position of intersection point to be set to t1 closest to above-mentioned wire in line and Bt intersection point, will be bent from brightness on the basis of Bt Line and Bt intersection point are represented closest to above-mentioned wire mark into 0.1 Δ B depth bounds in brightness curve and 0.1 Δ B intersection point When the value of the position of the intersection point of note is set to t2, Sv defined in following (1) formulas is more than 3.5,

Sv=(Δ B × 0.1)/(t1-t2) (1).

5. the surface treatment copper foil according to Claims 2 or 3, wherein, will be bright in above-mentioned observation place-brightness curve The interior value represented closest to the position of above-mentioned wire mark intersection point of the intersection point of line and Bt of writing music is set to t1, will be on the basis of Bt from bright Write music line and Bt intersection point into 0.1 Δ B depth bounds, represented in brightness curve and 0.1 Δ B intersection point closest to above-mentioned line When the value of the position of the intersection point of shape mark is set to t2, Sv defined in following (1) formulas is more than 3.5,

Sv=(Δ B × 0.1)/(t1-t2) (1).

6. surface treatment copper foil according to claim 4, wherein, Sv defined in (1) formula is 3.9 in above-mentioned brightness curve More than.

7. surface treatment copper foil according to claim 5, wherein, Sv defined in (1) formula is 3.9 in above-mentioned brightness curve More than.

8. surface treatment copper foil according to claim 6, wherein, Sv defined in (1) formula is 5.0 in above-mentioned brightness curve More than.

9. surface treatment copper foil according to claim 7, wherein, Sv defined in (1) formula is 5.0 in above-mentioned brightness curve More than.

10. surface treatment copper foil according to claim 1, wherein, the MD on above-mentioned roughening treatment surface 60 degree of glossiness For 76~350%, above-mentioned MD is rolling direction or copper foil direction of advance,

The surface area A of above-mentioned roughening particle, with overlooking above-mentioned roughening particle from above-mentioned copper foil surface side when the ratio between the area B that obtains A/B is 1.90~2.40.

11. the surface treatment copper foil according to any one of claim 2 to 4,6,8, wherein, above-mentioned roughening treatment surface MD 60 degree of glossiness be 76~350%, above-mentioned MD be rolling direction or copper foil direction of advance,

12. surface treatment copper foil according to claim 10, wherein, above-mentioned MD 60 degree of glossiness are 90~250%.

13. surface treatment copper foil according to claim 10, wherein, above-mentioned TD mean roughness Rz is 0.30~0.60 μm。

14. surface treatment copper foil according to claim 10, wherein, above-mentioned A/B is 2.00~2.20.

15. surface treatment copper foil according to claim 10, wherein, the MD on roughening treatment surface 60 degree of glossiness and TD 60 degree of glossiness ratio C (C=(MD 60 degree of glossiness)/(TD 60 degree of glossiness)) be 0.80~1.40.

16. surface treatment copper foil according to claim 11, wherein, the MD on roughening treatment surface 60 degree of glossiness and TD 60 degree of glossiness ratio C (C=(MD 60 degree of glossiness)/(TD 60 degree of glossiness)) be 0.80~1.40.

17. surface treatment copper foil according to claim 15, wherein, the MD on roughening treatment surface 60 degree of glossiness and TD 60 degree of glossiness ratio C (C=(MD 60 degree of glossiness)/(TD 60 degree of glossiness)) be 0.90~1.35.

18. it is that roughening particle in an at least surface is formed with by roughening treatment a kind of surface treatment copper foil, and

The top average value Bt of the brightness curve produced from the end of above-mentioned mark to the part without above-mentioned mark is averaged with bottom Value Bb poor Δ B (Δ B=Bt-Bb) is more than 40,

Surface treatment copper foil meets the condition of at least more than one in following (i)~(iv)：

(i) in above-mentioned observation place-brightness curve, it will represent to mark closest to above-mentioned wire in brightness curve and Bt intersection point The value of the position of intersection point is set to t1, bright by the intersection point on the basis of Bt from brightness curve and Bt into 0.1 Δ B depth bounds When the value of the position of the interior intersection point for representing to mark closest to above-mentioned wire of the intersection point of line and 0.1 Δ B of writing music is set to t2, following (1) Sv defined in formula is more than 3.5,

Sv=(Δ B × 0.1)/(t1-t2) (1)

(ii) MD on roughening treatment surface 60 degree of glossiness are 76~350%,

(iii) the surface area A of above-mentioned roughening particle, with overlooking above-mentioned roughening particle from above-mentioned copper foil surface side when the area that obtains The ratio between B A/B are 1.90~2.40,

(iv) ratio C (C=(MD 60 degree of gloss of the MD on roughening treatment surface 60 degree of glossiness and TD 60 degree of glossiness Degree)/(TD 60 degree of glossiness)) it is 0.90~1.35；

Also, above-mentioned MD is rolling direction or copper foil direction of advance.

19. the surface treatment copper foil according to any one of Claims 1-4,6,8,10,12 to 15,17,18, wherein, Above-mentioned roughening treatment surface possesses resin bed.

20. surface treatment copper foil according to claim 19, wherein, above-mentioned resin bed contains dielectric substance.

21. a kind of Copper foil with carrier, sequentially with carrier, intermediate layer, very thin layers of copper, and above-mentioned very thin layers of copper is claim 1 To the surface treatment copper foil any one of 4,6,8,10,12 to 15,17 to 20.

22. it is lamination Claims 1-4, at the surface any one of 6,8,10,12 to 15,17 to 20 a kind of laminated plates Reason copper foil and resin substrate and constitute.

23. a kind of printing distributing board, the table any one of its usage right requirement 1 to 4,6,8,10,12 to 15,17 to 20 Face handles copper foil.

24. a kind of laminated plates, are that the Copper foil with carrier described in lamination claim 21 is constituted with resin substrate.

25. a kind of printing distributing board, the Copper foil with carrier described in its usage right requirement 21.

26. a kind of e-machine, the printing distributing board described in its usage right requirement 23 or 25.

27. a kind of printing distributing board, is constituted by insulating resin substrate, with surface treatment copper foil, the surface treatment copper foil is certainly Surface treated face side is laminated on above-mentioned insulated substrate and is formed with copper circuit, and

Using CCD camera across the above-mentioned insulating resin substrate from surface treated face side lamination, to above-mentioned copper electricity When road is shot,

In the image for being obtained by above-mentioned shooting, along the side vertical with the direction of observed above-mentioned copper circuit extension To, in observation place-brightness curve that the brightness to each observation place is measured and made,

The top average value Bt of the brightness curve produced from the end of above-mentioned copper circuit to the part without above-mentioned copper circuit and bottom Average value Bb poor Δ B (Δ B=Bt-Bb) is more than 40.

28. a kind of copper-cover laminated plate, is laminated on above-mentioned insulation base by insulating resin substrate and from surface treated face side The surface treatment copper foil of plate is constituted, and

By etching, the above-mentioned surface treatment copper foil of above-mentioned copper-cover laminated plate is made after the surface treatment copper foil of wire, profit With CCD camera when being shot from the above-mentioned insulating resin substrate of surface treated face side lamination,

In the image for being obtained by above-mentioned shooting, along the direction with observed above-mentioned linear surfaces processing copper foil extension In vertical direction, observation place-brightness curve that the brightness to each observation place is measured and made,

The brightness curve that the end for handling copper foil from above-mentioned linear surfaces is produced to the part that copper foil is handled without above-mentioned linear surfaces Top average value Bt and bottom average value Bb poor Δ B (Δ B=Bt-Bb) be more than 40.

29. a kind of printing distributing board, the copper-cover laminated plate described in its usage right requirement 28.

30. a kind of e-machine, the printing distributing board described in its usage right requirement 27 or 29.

31. a kind of manufacture method for manufacturing the printing distributing board for being connected with more than 2 printing distributing boards, is as weighed by more than 2 Profit requires the printing distributing board connection described in 23 and manufactured.

32. a kind of manufacture method for manufacturing the printing distributing board for being connected with more than 2 printing distributing boards, it is included at least one Printing distributing board as claimed in claim 23, with another printing distributing board as claimed in claim 23 or not equivalent to The step of printing distributing board of printing distributing board as claimed in claim 23 is connected.

33. a kind of manufacture method for manufacturing the printing distributing board for being connected with more than 2 printing distributing boards, it is included at least one Printing distributing board as claimed in claim 25, with another printing distributing board as claimed in claim 25 or not equivalent to The step of printing distributing board of printing distributing board as claimed in claim 25 is connected.

34. a kind of e-machine, it is connected with 2 using 1 above by what manufacture method as claimed in claim 32 was made The printing distributing board or printing distributing board as claimed in claim 23 of individual above printing distributing board.

35. a kind of manufacture method of printing distributing board, it, which is comprised at least, will pass through manufacturer's legal system as claimed in claim 32 Into the printing distributing board for being connected with more than 2 printing distributing boards or such as printing distributing board according to claim 23, with The step of part is connected.

36. a kind of manufacture method for manufacturing the printing distributing board for being connected with more than 2 printing distributing boards, it is comprised at least：

By at least one printing distributing board as claimed in claim 23 and another printed wiring as claimed in claim 23 Plate or the step of the printing distributing board equivalent to printing distributing board as claimed in claim 23 is not connected；And

The printing distributing board for being connected with more than 2 printing distributing boards that will be made up of manufacture method as claimed in claim 32 Or printing distributing board as claimed in claim 23, the step of be connected with part.

37. a kind of manufacture method for manufacturing the printing distributing board for being connected with more than 2 printing distributing boards, is as weighed by more than 2 Profit requires the printing distributing board connection described in 27 and manufactured.

38. a kind of manufacture method for manufacturing the printing distributing board for being connected with more than 2 printing distributing boards, it is included at least one Printing distributing board as claimed in claim 27, with another printing distributing board as claimed in claim 27 or not equivalent to The step of printing distributing board of printing distributing board as claimed in claim 27 is connected.

39. a kind of e-machine, it is connected with 2 using 1 above by what manufacture method as claimed in claim 38 was made The printing distributing board or printing distributing board as claimed in claim 27 of individual above printing distributing board.

40. a kind of manufacture method of printing distributing board, it, which is comprised at least, will pass through manufacturer's legal system as claimed in claim 38 Into the printing distributing board or printing distributing board as claimed in claim 27 and part that are connected with more than 2 printing distributing boards The step of being connected.

41. a kind of manufacture method for manufacturing the printing distributing board for being connected with more than 2 printing distributing boards, it is comprised at least：

By at least one printing distributing board as claimed in claim 27 and another printed wiring as claimed in claim 27 Plate or the step of the printing distributing board equivalent to printing distributing board as claimed in claim 27 is not connected；And

The printing distributing board for being connected with more than 2 printing distributing boards that will be made up of manufacture method as claimed in claim 38 Or printing distributing board as claimed in claim 27, the step of be connected with part.

42. a kind of manufacture method of printing distributing board, it is included：

The step of preparing Copper foil with carrier and the insulated substrate described in claim 21；

By after above-mentioned Copper foil with carrier and insulated substrate lamination, formed the step of carrier by peeling off above-mentioned Copper foil with carrier Copper-cover laminated plate,

Thereafter, circuit is formed by the either method in semi-additive process, subtractive process, part addition process or improvement semi-additive process Step.

43. a kind of manufacture method of printing distributing board, it is included：

The step of circuit being formed in the above-mentioned very thin layers of copper side surface of the Copper foil with carrier described in claim 21；

The step of resin bed being formed in the way of burying foregoing circuit in the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier；

The step of circuit being formed on above-mentioned resin bed；

Peel off after above-mentioned carrier, by the way that above-mentioned very thin layers of copper is removed, and make to form burying in above-mentioned very thin layers of copper side surface The step of the circuit of above-mentioned resin bed exposes.