CN108277509A - Copper foil with carrier - Google Patents

Abstract

The invention discloses Copper foil with carrier.Specifically, the present invention provides a kind of Copper foil with carrier suitably forming thin space.The Copper foil with carrier of the present invention sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, and the average value of the Rz on very thin layers of copper surface is to be measured according to JIS B0601 1982 using contact roughmeter and be 1.5 μm hereinafter, and the standard deviation of Rz is 0.1 μm or less.

Description

Copper foil with carrier

The application is application No. is 201380060497.X, and the applying date is on November 20th, 2013, entitled " appendix The divisional application of the Chinese patent application of body copper foil ".

Technical field

The present invention relates to a kind of Copper foil with carrier.More specifically, the present invention relates to a kind of materials as printing distributing board The Copper foil with carrier of material.

Background technology

Printing distributing board is typically then and after copper-cover laminated plate is made, to be etched by passing through by copper foil and insulating substrate It is manufactured in the step of copper-clad surface forms conductive pattern.With the miniaturization of e-machine in recent years, the increasing of high performance demand Greatly, the high-density installation of part or the high frequency progress of signal are carried, the fine of conductive pattern is required for printing distributing board Change (thin space (fine pitch) change) or in response to high frequency etc..

In response to fine-pitch, 5 μm of copper foils below of 9 μm of thickness or less and then thickness, but such very thin copper are required recently Foil is easy damaged when manufacturing printing distributing board or generates gauffer since mechanical strength is relatively low, so occur using with thickness Copper foil with carrier made of very thin layers of copper is electroplated across peeling layer as carrier, to it in the metal foil of degree.By the table of very thin layers of copper After face is fitted in insulating substrate and is thermally compressed, carrier is removed via peeling layer and is removed.Pass through the very thin layers of copper in exposing After the upper formation circuit pattern using resist, very thin layers of copper is etched by the method removed with Sulfuric-acid-hydrogen-peroxide system etchant (MSAP：Modified-Semi-Additive-Process improves half addition manufacturing method) and form fine circuits.

Herein, to the very thin layers of copper of surface major requirement of the very thin layers of copper of the Copper foil with carrier as the commissure with resin It is sufficient with the peel strength of resin base material, and also can be fully after high-temperature heating, wet processed, welding, chemical treatment etc. Keep its peel strength.As the method for improving the peel strength between very thin layers of copper and resin base material, typically representing property is Adhere to the method for a large amount of roughening particles in the very thin layers of copper for increasing surface profile (concave-convex, roughness).

If however, the conductor package substrate for necessarily especially being formed fine circuit pattern in printing distributing board uses The larger very thin layers of copper of such profile (concave-convex, roughness), then can remain unwanted copper particle in circuit etch, generate electricity The problems such as defective insulation between the pattern of road.

Therefore, it in No. WO2004/005588 (patent document 1), attempts to implement the surface of very thin layers of copper using not thick Change the Copper foil with carrier of processing as using conductor package substrate as the Copper foil with carrier of the fine circuits purposes of representative.It is such not Implement the very thin layers of copper of roughening treatment and the adaptation (peel strength) of resin because of its low profile (bumps, rugosity, roughness) It influences and there is the tendency reduced compared with common copper foil for printed wiring board.Therefore, Copper foil with carrier is required further Improvement.

Therefore, in Japanese Unexamined Patent Publication 2007-007937 bulletins (patent document 2) and Japanese Unexamined Patent Publication 2010-006071 public affairs It reports in (patent document 3), records and set in the face of appendix body ultrathin copper foil contacted with polyimides system resins substrate (then) Set Ni layers and/or Ni alloy-layers, setting chromate coating, Cr layer of setting and/or Cr alloy-layers, Ni layers of setting and chromate coating and Ni layers and Cr layers of setting.By the way that such surface-treated layer is arranged, for polyimides system resins substrate and appendix body ultrathin copper foil Dhering strength, can without roughening treatment or reduce roughening treatment degree (miniaturization) and obtain needed for Bonding strength. In turn, it also records and antirust treatment is surface-treated or implemented with silane coupling agent.

[patent document 1] No. WO2004/005588 number

[patent document 2] Japanese Unexamined Patent Publication 2007-007937 bulletins

[patent document 3] Japanese Unexamined Patent Publication 2010-006071 bulletins.

Invention content

[the problem of invention is to be solved]

So far, being placed in center of gravity in the exploitation of Copper foil with carrier ensures that the stripping of very thin layers of copper and resin base material is strong Degree.It accordingly, with respect to fine-pitch, is not yet adequately studied, still there are rooms for improvement.Therefore, project of the invention exists In a kind of Copper foil with carrier suitably forming thin space of offer.Specifically, project is that providing one kind can form and be considered It so far can be with L/S=20 μm/20 μm Copper foil with carrier for comparing finer wiring of the MSAP limit formed.

[technical means to solve problem]

To reach above-mentioned purpose, effort research is repeated in the inventors of the present invention, as a result, it has been found that can be by by very thin layers of copper The low roughness in surface and so that fine roughening particle is formed uniformly in face in very thin layers of copper, and forms uniform and low rugosity Roughening treatment face.Also, it was found that the Copper foil with carrier is to forming the very effective fruit of thin space.

The present invention is completed based on above-mentioned opinion, is a kind of Copper foil with carrier in one aspect, sequentially has load Body, peeling layer, very thin layers of copper and arbitrary resin layer person, and the average value of the Rz on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 1.5 μm hereinafter, and the standard deviation of Rz is 0.1 μm or less.

The present invention is a kind of Copper foil with carrier in another aspect, sequentially have carrier, peeling layer, very thin layers of copper and Arbitrary resin layer person, and the average value of the Rt on very thin layers of copper surface is to utilize contact roughmeter foundation JIS B0601- 2001 are measured and are 2.0 μm hereinafter, and the standard deviation of Rt is 0.1 μm or less.

The present invention is a kind of Copper foil with carrier in another aspect in turn, sequentially has carrier, peeling layer, very thin copper Layer and arbitrary resin layer person, and the average value of the Ra on very thin layers of copper surface is to utilize contact roughmeter foundation JIS B0601-1982 is measured and is 0.2 μm hereinafter, and the standard deviation of Ra is 0.03 μm or less.

In an embodiment of the Copper foil with carrier of the present invention, the very thin roughened processing of layers of copper.

The present invention is a kind of printing distributing board in another aspect in turn, is made using the Copper foil with carrier of the present invention At.

The present invention is a kind of printed circuit board in another aspect in turn, is made using the Copper foil with carrier of the present invention At.

The present invention is a kind of copper-cover laminated plate in another aspect in turn, is made using the Copper foil with carrier of the present invention At.

[The effect of invention]

The Copper foil with carrier of the present invention suitably forms thin space, is relatively considered to be formed with MSAP steps for example, can be formed The limit L/S=20 μm/20 μm finer wirings, such as L/S=15 μm/15 μm of fine wiring.Especially at this In invention, the inner evenness of the surface roughness of very thin layers of copper is higher, and the thus sudden strain of a muscle when forming circuit using MSAP methods is lost In, inner evenness becomes good, therefore it can be expected that improves yield.

Description of the drawings

Fig. 1 is the schematic diagram for indicating the fortune foil mode using rotating cylinder.

Fig. 2 is the schematic diagram indicated in the way of the fortune foil of bending (zigzag folding).

Fig. 3 is the step A of the concrete example of the manufacturing method for the printing distributing board for indicating the Copper foil with carrier using the present invention To C.

Fig. 4 is the step D of the concrete example of the manufacturing method for the printing distributing board for indicating the Copper foil with carrier using the present invention To F.

Fig. 5 is the step G of the concrete example of the manufacturing method for the printing distributing board for indicating the Copper foil with carrier using the present invention To I.

Fig. 6 is the step J of the concrete example of the manufacturing method for the printing distributing board for indicating the Copper foil with carrier using the present invention To K.

Specific implementation mode

1. carrier ＞ of ＜

The carrier that can be used in the present invention is typically metal foil or resin film, e.g. with copper foil, copper alloy foil, nickel Foil, nickel alloy foil, iron foil, ferroalloy foil, stainless steel foil, aluminium foil, alloy foil, insulating resin film (such as polyimide film, liquid Crystalline polymer (LCP) film, polyethylene terephthalate (PET) film, PA membrane, polyester film, fluororesin film etc.) form carry For.

As the carrier that can be used in the present invention, it is preferable to use copper foil.For typical case, carrier be with rolled copper foil or The form of electrolytic copper foil provides.In general, electrolytic copper foil is to be electrolysed copper from copper sulfate bath on the rotating cylinder of titanium or stainless steel It is precipitated and manufactures, rolled copper foil is to repeat to manufacture using the plastic processing and heat treatment of stack.Material as copper foil Material also can be used other than the high-purity coppers such as refined copper or oxygen-free copper such as mixing Sn copper, mix Ag copper, added with Cr, Zr or Mg Copper alloy, inferior series copper alloy of card added with Ni and Si etc. etc copper alloy.Furthermore it in the present specification, is used alone Also include copper alloy foil when term " copper foil ".

About the thickness for the carrier that can be used in the present invention, also there is no particular restriction, as long as reaching as carrier It is suitably adjusted to suitable thickness in function and effect, such as 12 μm or more can be set as.But if blocked up, production cost It improves, 70 μm or less is set as so being preferably generally.Therefore, the thickness of carrier is typically 12~70 μm, more typically 18~35 μ m。

2. peeling layer ＞ of ＜

Peeling layer is set on carrier.Other layers can be also set between foil carriers and peeling layer.It is attached as peeling layer The arbitrary peeling layer known to dealer can be arranged in carrier copper foil.For example, peeling layer preferably by comprising Cr, Ni, Co, Fe, Mo, Ti, W, more than any in P, Cu, Al, Zn or such alloy or such hydrate or such oxide or organic matter Layer formed.Peeling layer can be also made of multiple layers.Furthermore peeling layer can have the function of non-proliferation.Herein, so-called non-proliferation work( Can, it is to have the function of preventing the extremely thin copper layer side of the elements diffusion from base material.

In the embodiment of the present invention, peeling layer is to be made of from carrier side such as lower layer：By Cr, Ni, Co, Fe, Single metal layer that any element in the groups of elements of Mo, Ti, W, P, Cu, Al, Zn is constituted or by be selected from Cr, Ni, Co, The alloy-layer that one or more of groups of elements of Fe, Mo, Ti, W, P, Cu, Al, Zn element is constituted is (such to have non-proliferation work( Can), lamination on it by one or more of groups of elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn element Hydrate or the layer that is constituted of oxide or organic matter.

Also, for example peeling layer can be made of from carrier side such as lower layer：By Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn Groups of elements in the single metal layer that is constituted of any element or by be selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, The alloy-layer that one or more of groups of elements of Zn element is constituted, secondly, by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Single metal layer that any element in the groups of elements of Zn is constituted or by be selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, The alloy-layer that one or more of groups of elements of Al, Zn element is constituted.Furthermore total adhesion amount of each element can be for example set as 1~6000 μ g/dm².Also, can also be constituted in the layer that other layer of use can be used as peeling layer and use.

Peeling layer is preferably made of 2 layers of Ni and Cr.When in this respect, be respectively Ni layers with contact with foil carriers Interface mode lamination, and Cr layers to contact the lamination in a manner of with the interface of very thin layers of copper.

Peeling layer for example can by plating, the wet type plating of electroless plating and dipping plating etc or sputter, CVD and The dry type plating of PDV etc and obtain.For the viewpoint of cost, preferably it is electroplated.

Also, for example, peeling layer can on carrier sequentially lamination nickel, nickel-phosphor alloy or nickel-cobalt alloy and chromium and constitute.Nickel Be higher than the adhesion of chromium and copper with the adhesion of copper, therefore when remove very thin layers of copper, be the interface of very thin layers of copper and chromium into Row stripping.Also, expecting to prevent copper component from diffusing to from carrier the barrier effect of very thin layers of copper in the nickel of peeling layer.In peeling layer Nickel adhesion amount is preferably 100 μ g/dm²Above and 40000 μ g/dm²Hereinafter, more preferably 100 μ g/dm²Above and 4000 μ g/dm² Hereinafter, 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 chromium adhesion amount in peeling layer is preferably 5 μ g/dm²Above and 100 μ g/dm²Below.Peeling layer only is being set in single side When situation, preferably in antirust coats such as face setting platings Ni layer opposite with carrier.

Furthermore peeling layer also may be provided at the two sides of carrier.

3. very thin layers of copper ＞ of ＜

Very thin layers of copper is set on peeling layer.Other layers can be also set between peeling layer and very thin layers of copper.Very thin layers of copper It can be formed by using the plating for the electrobath for having copper sulphate, cupric pyrophosphate, amine sulfonic acid copper, copper cyanider etc., just using usual Electrolytic copper foil and can be formed at higher current densities for the aspect of copper foil, preferably copper sulphate bathe.The thickness of very thin layers of copper There is no particular restriction, is usually thinner than carrier, for example, 12 μm or less.It is typically 0.5~12 μm, more typically 2~5 μm.Furthermore Very thin layers of copper also may be provided at the two sides of carrier.Also, can also be constituted in the layer that other layer of use can be used as peeling layer and use.

4. roughening treatment ＞ of ＜

It is good etc. with the adaptation of insulating substrate in order to for example make for the surface of very thin layers of copper, it also can be thick by implementing Change processing and roughening treatment layer is set.Roughening treatment for example can form roughening particle by using copper or copper alloy and be formed.Just It is formed for the viewpoint of thin space, roughening treatment layer is preferably made of fine particle.Electricity when about formation roughening particle Plating condition has particle to carry out inclining for miniaturization if improving current density, reducing the copper concentration in plating solution or increasing coulomb amount To.

Roughening treatment layer can be constituted by grain is electroplated as follows：By being selected from by copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc institute group At any one of group monomer or constituted containing wantonly a kind or more of alloy.

In terms of the inner evenness of the surface roughness in the surface treatment face of raising, fixedly roughening treatment layer is kept to be formed When anode-cathode between distance it is more effective.And be not limited, for industrial viewpoint, by regarding rotating cylinder etc. as branch It holds the fortune foil mode of medium and ensures that the method for fixed interpolar distance is more effective.Fig. 1 is the signal for indicating the fortune foil mode Figure.It utilizes rotating cylinder to support the carrier copper foil transported with carrying roller on one side, is formed on one side on very thin layers of copper surface by being electrolysed plating Roughening particle layer.The process face for the carrier copper foil supported using rotating cylinder has both cathode, in the rotating cylinder and with the side with rotating cylinder opposite direction Each electrolysis plating is carried out in plating solution between the anode of formula setting.On the other hand, it is recorded in Fig. 2 and indicates to utilize existing type The schematic diagram of the fortune foil mode of bending.Which exists because of the influence such as electrolyte and fortune foil tension to be difficult to make anode and cathode Distance fix problem.Furthermore when fixedly keeping the formation of roughening treatment layer for the fortune foil mode by using bending Anode-cathode between distance, more improve to transport the tension of foil compared with those existing, the distance that shortens between carrying roller it is more effective.

As shown in Figure 1, cannot be only used for roughening treatment in the way of the fortune foil of rotating cylinder, also can be used for peeling layer formation and The formation of very thin layers of copper.Its reason is can be by using in a manner of the fortune foil by rotating cylinder, and improves peeling layer or very thin layers of copper Thickness and precision.Furthermore when peeling layer or very thin layers of copper fixedly being kept to be formed for the fortune foil mode by using bending It is more effective more to improve the distance transported the tension of foil, shortened between carrying roller compared with those existing for distance between anode-cathode.

Interpolar distance is simultaneously not limited, if long, increased production cost, on the other hand, uneven in face to be easy if too short Become larger, therefore preferably generally 3~100mm, more preferably 5~80mm.

Also, offspring or three times particle can be formed by nickel, cobalt, copper, the monomer of zinc or alloy etc. after roughened processing And/or antirust coat, and then the processing such as chromic acid salt treatment, silane coupling processing are implemented to its surface.That is, can be in roughening treatment layer Surface is formed selected from one or more of the group being made of antirust coat, chromating layer and silane coupling process layer layer, also may be used It is formed selected from by antirust coat, chromating layer and silane coupling process layer without roughening treatment on the surface of very thin layers of copper One or more of group formed layer.Furthermore such surface treatment is on the surface roughness of very thin layers of copper almost without influence.

Very thin layers of copper surface (refers to very thin after being surface-treated when implementing the situation of the various surface treatments such as roughening treatment The surface (being also known as in " surface treatment face ") of layers of copper) it is to be surveyed according to JIS B0601-1982 using contact roughmeter Periodically, the average value of Rz (10 mean roughness) is set as 1.5 μm hereinafter, situation pole for the viewpoint for forming thin space It is advantageous.The average value of Rz be preferably 1.4 μm hereinafter, more preferably 1.3 μm hereinafter, more preferably 1.2 μm hereinafter, more preferably 1.0 μm hereinafter, more preferably 0.8 μm or less.But if the average value of Rz is too small, reduced with the closing force of resin, with regard to this side For face, preferably 0.01 μm or more, more preferably 0.1 μm or more, and then more preferably 0.3 μm or more, most preferably 0.5 μm More than.

In the present invention, the average value of Rz is obtained using the standard deviation interval for finding out Rz by method described below The average value of each Rz.In the present invention, in turn, the standard deviation of the Rz on very thin layers of copper surface can be set as 0.1 μm hereinafter, it is preferred that For 0.05 μm can be set as hereinafter, can for example be set as 0.01~0.7 μm.The standard deviation of the Rz on very thin layers of copper surface is according in face 100 measurement datas and find out.Furthermore in face 100 points of measurement data be by by 550mm square sheet material in longitudinal direction, cross 10 parts are divided on direction respectively, and measures each central portion in 100 partial segmentation regions and obtains.The application be in order to It keeps inner evenness and uses this method, but verification method does not limit herein.Even if for example, by usually used 550mm The sample of the sizes such as × 440mm~400mm × 200mm is divided into 100 parts (being divided into 10 parts in length and breadth) in face, also Identical data can be taken.

Also, for the viewpoint that thin space is formed, very thin layers of copper surface is preferably utilizing contact roughmeter foundation When JIS B0601-2001 are measured, by the average value of Rt (maximum section height) be set as 2.0 μm or less, be preferably 1.8 μm or less, Preferably 1.5 μm or less, preferably 1.3 μm or less, preferably 1.1 μm or less.But if the average value of Rt becomes too small, It is reduced with the closing force of resin, in this connection, preferably 0.5 μm or more, more preferably 0.6 μm or more, and then more preferably It is 0.8 μm or more.In the present invention, the average value of Rt is obtained using the standard deviation interval for finding out Rt by method described below The average value of each Rt obtained.

In the present invention, in turn, the standard deviation of the Rt on very thin layers of copper surface can be set as to 0.1 μm hereinafter, preferably can 0.05 μm is set as hereinafter, can for example be set as 0.01~0.6 μm.The Rt standard deviations on very thin layers of copper surface be with Rz likewise by 100 points of measurement data in face and find out.

Also, for the viewpoint that thin space is formed, very thin layers of copper surface is preferably utilizing contact roughmeter foundation When JIS B0601-1982 are measured, the average value of Ra (arithmetic average roughness) is set as 0.2 μm hereinafter, being more preferably set as 0.18 μm hereinafter, being preferably set to 0.15 μm or less.But if the average value of Ra is too small, reduced with the closing force of resin, just in this respect For, preferably 0.01 μm or more, more preferably 0.05 μm or more, and then more preferably 0.12 μm or more, most preferably 0.13 μ M or more.In the present invention, the average value of Ra is using each of the standard deviation interval acquisition for finding out Ra by method described below The average value of Ra.

In the present invention, in turn, the Ra standard deviations on very thin layers of copper surface can be set as to 0.03 μm hereinafter, can preferably set For 0.02 μm hereinafter, can for example be set as 0.001~0.03 μm.The standard deviation of the Ra on very thin layers of copper surface is the root in the same manner as Rz It is found out according to 100 points of measurement data in face.

Furthermore by the insulating substrates such as resin or resin layer then in the Copper foil with carrier with resin layer, printed wiring Plate or copper-cover laminated plate etc., very thin layers of copper surface situation when, by insulating substrate melt and remove, thus can be to copper circuit or copper The above-mentioned surface roughness of foil surface measurements (Ra, Rt, Rz).

5. other surfaces of ＜ handle ＞

After roughened processing, refractory layer or antirust coat are formed using nickel, cobalt, copper, the monomer of zinc or alloy etc., in turn The processing such as chromic acid salt treatment, silane coupling processing are implemented to its surface.Alternatively, also can without roughening treatment and utilize nickel, cobalt, Copper, the monomer of zinc or alloy etc. form refractory layer or antirust coat, and then implement chromic acid salt treatment, silane coupling processing to its surface Deng processing.That is, can be formed selected from by the coupling of refractory layer, antirust coat, chromating layer and silane on the surface of roughening treatment layer The layer of one or more of the group that process layer is formed, also can the surface of very thin layers of copper formed selected from by refractory layer, antirust coat, The layer of one or more of the group that chromating layer and silane coupling process layer are formed.Furthermore above-mentioned refractory layer, antirust coat, Chromating layer, silane coupling process layer can be formed by such as 2 layers or more, 3 layers with first-class multiple layers respectively.

As refractory layer, antirust coat, well known refractory layer, antirust coat can be used.For example, refractory layer and/or antirust coat can For containing selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group in The layer of a kind or more element also can be by being selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family The metal layer or alloy-layer that one or more of the group of element, iron, tantalum element is constituted.Also, refractory layer and/or antirust coat also may be used Including containing selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group in 1 kind or more element oxide, nitride, silicide.Also, refractory layer and/or antirust coat 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 can be in addition to inevitably miscellaneous Other than matter, contain nickel 50wt%~99wt% and zinc 50wt%~1wt% person.The zinc of above-mentioned nickel-zinc alloy-layer and adding up to for nickel Adhesion amount can be 5~1000mg/m², preferably 10~500mg/m², preferably 20~100mg/m².Also, above-mentioned includes nickel-zinc The ratio (adhesion amount of adhesion amount/zinc of=nickel) of the nickel adhesion amount and amount of zinc adhesion of the layer of alloy or above-mentioned nickel-zinc alloy-layer is excellent It is selected as 1.5~10.Also, the nickel adhesion amount of the above-mentioned layer comprising 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 comprising nickel-zinc alloy, When the inner wall part of through-hole or guide hole (viahole) etc. and removing glue slag liquid being made to contact, the interface of copper foil and resin substrate be not easy by except The adaptation of glue residue corrosion, copper foil and resin substrate improves.

Such as refractory layer and/or antirust coat can be that sequentially lamination adhesion amount is 1mg/m²~100mg/m², preferably 5mg/m² ~50mg/m²Nickel or nickel alloy layer, with adhesion amount be 1mg/m²~80mg/m², preferably 5mg/m²~40mg/m²Tin layers and Winner, above-mentioned nickel alloy layer can be made of any one of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt.Also, refractory layer and/or antirust coat Preferably total adhesion amount of nickel or nickel alloy and tin is 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, it is more excellent It is selected as 0.33~3.If using the refractory layer and/or antirust coat, Copper foil with carrier is processed into printing distributing board, later electricity The peel strength on road, chemical-resistant deterioration rate of the peel strength etc. can become good.

Furthermore well known silane coupling agent can be used in the silane coupling agent for silane coupling processing, also can be used for example Amido system silane coupling agent or epoxy silane coupling agent, sulfydryl system silane coupling agent.Also, ethylene also can be used in silane coupling agent Base trimethoxy silane, ethenylphenyl trimethoxy silane, γ-metacryloxy propyl trimethoxy silicane, γ-shrink Glycerine oxygroup propyl trimethoxy silicane, 4- glycidyls butyl trimethoxy silane, γ-aminocarbonyl propyl triethoxysilicane Alkane, N- β-(amido ethyl)-γ-aminocarbonyl propyl trimethoxy silanes, N-3- (4- (3- amidos propoxyl group) butoxy) propyl -3- Aminocarbonyl propyl trimethoxy silane, imidizole silane, triazine silane, γ mercaptopropyitrimethoxy silane etc..

Epoxy silane, amido system silane, metacryloxy system silane, sulfydryl can be used in above-mentioned silane coupling process layer It is silane coupling agents such as silane etc. and is formed.Furthermore such silane coupling agent can be also mixed with two or more.Wherein, preferably The former using amido system silane coupling agent or epoxy silane coupling agent.

So-called amido system silane coupling agent herein can be selected from by N- (2- amidos ethyl) -3- aminocarbonyl propyl trimethoxies Silane, 3- (N- styrylmethyl -2- amido ethyls amido) propyl trimethoxy silicane, 3- aminocarbonyl propyl triethoxysilicanes Alkane, bis- (2- hydroxyethyls) -3- aminocarbonyl propyl triethoxysilanes, aminocarbonyl propyl trimethoxy silane, N- methylamino propyl Trimethoxy silane, N- phenyl aminocarbonyl propyl trimethoxy silane, N- (3- propenyloxy group -2- hydroxypropyls) -3- aminocarbonyl propyls Triethoxysilane, 4- amido butyl triethoxysilane, (amido ethyl aminomethyl) phenethyl trimethoxy silane, N- (2- amido 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- dimethyl -1- acrylic trimethoxy silanes, 3- aminocarbonyl propyls three (methoxyethoxyethoxy) silane, 3- amidos third Ethyl triethoxy silicane alkane, 3- aminocarbonyl propyl trimethoxy silanes, ω-amido undecyltrimethoxysilane, 3- (2-N- benzyls Amido ethyl aminocarbonyl propyl) trimethoxy silane, bis- (2- hydroxyethyls) -3- aminocarbonyl propyl triethoxysilanes, (N, N- diethyl Base -3- aminocarbonyl propyls) trimethoxy silane, (N, N- dimethyl -3- aminocarbonyl propyls) trimethoxy silane, N- methylamino propyl Trimethoxy silane, N- phenyl aminocarbonyl propyl trimethoxy silane, 3- (N- styrylmethyl -2- amido ethyls amido) propyl Trimethoxy silane, γ-aminocarbonyl propyl triethoxysilane, N- β-(amido ethyl)-γ-aminocarbonyl propyl trimethoxy silanes, Person in the group that N-3- (4- (3- amidos propoxyl group) butoxy) propyl -3- aminocarbonyl propyl trimethoxy silanes are formed.

Silane coupling process layer is preferably set as 0.05mg/m with silicon atom conversion²~200mg/m², preferably 0.15mg/m²~20mg/m², preferably 0.3mg/m²~2.0mg/m²Range.It, can be further in the situation of above range Improve the adaptation of substrate resin and surface treatment copper foil.

Also, can be to very thin layers of copper, roughening treatment layer, refractory layer, antirust coat, silane coupling process layer or chromating layer Surface carry out International Publication number WO2008/053878, Japanese Unexamined Patent Publication 2008-111169, Japanese Patent No. 5024930 Number, International Publication number WO2006/028207, Japanese Patent No. 4828427, International Publication number WO2006/134868, day This patent the 5046927th, International Publication number WO2007/105635, Japanese Patent No. 5180815 or Japanese Unexamined Patent Publication Recorded surface treatment in No. 2013-19056.

[resin layer in very thin layers of copper]

Can (when in the situation being surface-treated to very thin layers of copper, be in the very thin layers of copper of the Copper foil with carrier of the present invention Refer to the surface-treated layer that is formed in very thin layers of copper by the surface treatment) on have resin layer.Above-mentioned resin layer also can be exhausted Edge resin layer.

Above-mentioned resin layer can be then to use resin, i.e. solid, also can be then to use semi-hardened state (B-stage state) Insulating resin layer.Semi-hardened state (B-stage state) includes following state：Even if touching its surface with finger also to feel without adhesion, The insulating resin layer can overlappingly be taken care of can cause sclerous reaction if being heated in turn.

Also, above-mentioned resin layer can contain thermosetting resin, also can be thermoplastic resin.Also, above-mentioned resin layer can also contain There is thermoplastic resin.Above-mentioned resin layer can contain well known resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, Catalysts, crosslinking agent, polymer, prepreg, framework material etc..Also, above-mentioned resin layer for example can be used in following document Recorded substance (resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, catalysts, crosslinking agent, polymerization Object, prepreg, framework material etc.) and/or resin layer forming method, forming apparatus and formed：International Publication number WO2008/ No. 004399, International Publication number WO2008/053878, International Publication number WO2009/084533, Japanese Unexamined Patent Publication 11- No. 5828, Japanese Unexamined Patent Publication 11-140281, Japanese Patent No. 3184485, International Publication number WO97/02728, Japan Patent the 3676375th, Japanese Unexamined Patent Publication 2000-43188, Japanese Patent No. 3612594, Japanese Unexamined Patent Publication 2002-179772 Number, Japanese Unexamined Patent Publication 2002-359444, Japanese Unexamined Patent Publication 2003-304068, Japanese Patent No. 3992225, Japanese Unexamined Patent Publication No. 2003-249739, Japanese Patent No. 4136509, Japanese Unexamined Patent Publication 2004-82687, Japanese Patent No. No. 4025177, day This special open 2004-349654, Japanese Patent No. 4286060, Japanese Unexamined Patent Publication 2005-262506, Japanese Patent No. No. 4570070, it is Japanese Unexamined Patent Publication 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, international public The number of beginning the compilation of WO2004/005588, Japanese Unexamined Patent Publication 2006-257153, Japanese Unexamined Patent Publication 2007-326923, Japanese Unexamined Patent Publication 2008- No. 111169, Japanese Patent No. 5024930, International Publication number WO2006/028207, Japanese Patent No. No. 4828427, day This special open 2009-67029, International Publication number WO2006/134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication No. 2009-173017, International Publication number WO2007/105635, Japanese Patent No. 5180815, International Publication number WO2008/114858, International Publication number WO2009/008471, Japanese Unexamined Patent Publication 2011-14727, International Publication number WO2009/001850, International Publication number WO2009/145179, International Publication number WO2011/068157, Japanese Unexamined Patent Publication No. 2013-19056.

Also, the type of above-mentioned resin layer is not particularly limited, as preferred person, such as can enumerate containing selected from following ingredient One or more of group resin：Epoxy resin, polyimide resin, multi-functional cyanate esters, maleimide Compound, polymaleimide compounds, maleimide amine system resin, aromatic series maleimide resin, polyethylene acetaldehyde tree Fat, amido formate resin, polyether sulfone (being also known as polyethersulphone, polyethersulfone), polyether sulfone are (also Referred to as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin Polymer, rubbery resin, polyamine, aromatic polyamine, polyamide-imide resin, rubber modified epoxy resin, phenoxy group tree Fat, carboxyl modification acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide-triazine resin, thermosetting polyphenylene oxide resin, Cyanate ester system resin, the acid anhydrides of carboxylic acid, the acid anhydrides of polybasic carboxylic acid, the linear polymer with crosslinkable functional group, polyphenyl Bis- (4- cyanatephenyls) propane of ether resin, 2,2-, phosphorous phenolic compounds, manganese naphthenate, bis- (the 4- glycidyls of 2,2- Phenyl) propane, polyphenylene oxide-cyanate ester based resin, siloxanes modification polyamide-imide resin, hydrocyanic ester resin, phosphine nitrile system resin, Rubber modified polyamide-imide resin, isoprene, hydrogenation type polybutadiene, polyvinyl butyral, phenoxy group, high-molecular-weight epoxy Resin, aromatic polyamide, fluororesin, bis-phenol, block copolymerized polyimide resin and hydrocyanic ester resin.

Also, above-mentioned epoxy resin, which is intramolecular, has 2 or more epoxy group persons, as long as and to can be used for electrical, electronics Material applications person can then use without problems completely.It shrinks also, above-mentioned epoxy resin preferably has 2 or more using intramolecular Glyceryl compound carries out epoxy resin made of epoxidation.Also, can be by a kind in the group being made of following ingredient Or two or more mixes and uses：Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A D types Epoxy resin, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, bromination (brominated) epoxy resin, phenol system phenolic resin varnish type epoxy resin, naphthalene type epoxy resin, brominated bisphenol a type epoxy resin, O-cresol phenolic epoxy varnish, rubber modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin, isocyanide urine Sour three-glycidyl ester, N, the glycidols such as N- diglycidylanilines amine compounds, tetrahydrophthalic acid two are shunk sweet The epihydric alcohol ester compounds such as grease, phosphorous epoxy resin, biphenyl type epoxy resin, biphenyl phenolic resin varnish type epoxy resin, Trihydroxy benzene methylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, or the hydrogenation body of above-mentioned epoxy resin can be used Or halogenation body.

Contain the epoxy resin of phosphorus as above-mentioned phosphorous epoxy resin well known to can be used.Also, above-mentioned phosphorous epoxy Resin be preferably such as intramolecular have 2 or more epoxy groups to be aoxidized from the miscellaneous -10- phospho hetero phenanthrenes -10- of 9,10- dihydro-9-oxies The ring that the form of the derivative of object (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) obtains Oxygen resin.

The asphalt mixtures modified by epoxy resin obtained in the form of the derivative from the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies Fat is so that 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is reacted with naphthoquinones or hydroquinone and following chemistry is made After compound represented by formula 1 (HCA-NQ) or chemical formula 2 (HCA-HQ), the part of its OH base is made to react and make with epoxy resin At phosphorous epoxy resin.

[chemical formula 1]

[chemical formula 2]

Above-mentioned E ingredients, that is, phosphorous epoxy resin that above compound is obtained as raw material is preferably used in mixed way a kind or 2 Kind has the compound of the structural formula represented by any one of following represented 3~chemical formula of chemical formula 5.Its reason is The excellent in stability of resin quality under semi-hardened state, while flame retardancy effect is higher.

[chemical formula 3]

[chemical formula 4]

[chemical formula 5]

Also, as above-mentioned bromination (brominated) epoxy resin, can be used well known through bromination (brominated) Epoxy resin.For example, above-mentioned bromination (brominated) epoxy resin is preferably used in mixed way a kind or 2 kinds of intramoleculars have 2 The bromination for having the structural formula represented by the chemical formula 6 obtained in the form of the derivative from tetrabromobisphenol A of the above epoxy group Epoxy resin and the brominated epoxy resin for having the structural formula represented by chemical formula 7 as shown below.

[chemical formula 6]

[chemical formula 7]

As above-mentioned maleimide amine system resin or aromatic series maleimide resin or maleimide compound or gather Well known maleimide amine system resin or aromatic series maleimide resin or maleimide can be used in maleimide compound Amine compounds or polymaleimide compounds.For example, as maleimide amine system resin or aromatic series maleimide resin Or maleimide compound or polymaleimide compounds, it can be used：4,4'- diphenyl methanes bismaleimide is gathered Phenylmethane maleimide stretches phenyl-bismaleimide, bisphenol-A Diphenyl Ether Bismaleimide, 3,3'- dimethyl- 5,5'- diethyl -4,4'- diphenyl methanes bismaleimide, 4- methyl-1s, 3- stretch phenyl-bismaleimide, 4,4'- bis- Bis- (3- maleimidephenoxies) benzene of phenylate bismaleimide, 4,4'- diphenyl sulfones bismaleimide, 1,3-, 1,3- Bis- (4- maleimidephenoxies) benzene and to make above compound and above compound or other compounds be polymerized poly- Close object etc..Also, above-mentioned maleimide amine system resin can be the aromatic series Malaysia acyl that intramolecular has 2 or more dimaleoyl iminos Imide resin, also can be make intramolecular have 2 or more dimaleoyl iminos aromatic series maleimide resin and polyamine or The polymer adduct that aromatic polyamine is polymerized.

As above-mentioned polyamine or aromatic polyamine, well known polyamine or aromatic polyamine can be used.For example, as polyamine or Aromatic polyamine can be used：M-phenylene diamine (MPD), p-phenylenediamine, bis- amido dicyclohexyl methyl hydrides of 4,4'-, 1,4- diamines butylcyclohexane, Bis- (4- aminocarbonyl phenyls) propane of 2,6- diamino pyridines, 4,4'- two aminodiphenylmethanes, 2,2-, bis- amido hexichol of 4,4'- Ether, bis- amido -3- methyl diphenyl ethers of 4,4'-, bis- amido diphenyl sulfides of 4,4'-, bis- aminobenzophenones of 4,4'-, 4,4'- diamines Base diphenyl sulfone, bis- (4- aminocarbonyl phenyls) phenyl amines, m-xylene diamine, p dimethylamine, bis- [the 4- amidos phenoxy group] benzene of 1,3-, 3- methyl -4,4'- two aminodiphenylmethanes, 3,3'- diethyl -4,4'- two aminodiphenylmethanes, 3,3'- bis- chloro- 4, 4'- two aminodiphenylmethanes, 2,2', the bis- (3- methyl -4- amidos of tetra- chloro- 4,4'- two aminodiphenylmethanes of 5,5'-, 2,2- Phenyl) propane, bis- (3- ethyl -4- aminocarbonyl phenyls) propane of 2,2-, bis- (bis- chloro- 4- aminocarbonyl phenyls of the 2,3-) propane of 2,2-, it is bis- (2, 3- dimethyl -4- aminocarbonyl phenyls) diphenylphosphino ethane, ethylenediamine and hexamethylene diamine, bis- (4- (the 4- amidos phenoxy group) phenyl) propane of 2,2-, And the polymer etc. for making above compound be polymerized with above compound or other compounds.Also, one kind or two can be used Kind polyamine above known and/or aromatic polyamine or above-mentioned polyamine or aromatic polyamine.

As above-mentioned phenoxy resin, well known phenoxy resin can be used.Also, as above-mentioned phenoxy resin, can make With passing through person synthesized by the reacting of bis-phenol and divalent epoxy resin.As epoxy resin, can be used well known epoxy resin and/or Above-mentioned epoxy resin.

As above-mentioned bis-phenol, well known bis-phenol can be used, in addition, can be used with bisphenol-A, Bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4' dihydroxy diphenyl, HCA (9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide) and hydrogen The bis-phenol etc. that the form of the addition product of the quinones such as quinone, naphthoquinones obtains.

As the above-mentioned linear polymer with crosslinkable functional group, can be used well known with crosslinkable functional group Linear polymer.It is helped for example, the above-mentioned linear polymer with crosslinkable functional group preferably has hydroxyl, carboxyl etc. In the functional group of the sclerous reaction of epoxy resin.Also, there should be the linear polymer of crosslinkable functional group preferably solvable Solution is in the organic solvent that boiling point is 50 DEG C~200 DEG C temperature.If specifically illustrating the so-called linear polymerization with functional group herein Object is then polyethylene acetaldehyde resin, phenoxy resin, polyethersulfone resin, polyamide-imide resin etc..

Above-mentioned resin layer can contain crosslinking agent.Well known crosslinking agent can be used in crosslinking agent.Such as amido formate can be used It is resin as crosslinking agent.

Well known rubbery resin can be used in above-mentioned rubbery resin.For example, above-mentioned rubbery resin system be recorded as include Concept including natural rubber and synthetic rubber, have in the synthetic rubber of the latter SBR styrene butadiene rubbers, butadiene rubber, Butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, acrylic rubber (acrylate copolymer), polybutadiene Rubber, isoprene rubber etc..In turn, in the heat resistance for ensuring to be formed by resin layer, selection uses nitrile rubber, neoprene two The synthetic rubber that alkene rubber, silicon rubber, amido formate rubber etc. have heat resistance is also useful.About such rubbery resin, Copolymer is manufactured in order to be reacted with aromatic polyamide resin or polyamide-imide resin, more satisfactory is to have in two ends Various functional groups.In particular, more useful using CTBN (carboxyl terminal butadiene- nitrile).If also, acrylonitrile butadiene rubber it In be also that carboxyl modifies body, then can get epoxy resin and cross-linked structure, and improve the pliability of the resin layer after hardening.As Carboxyl modifies body, and carboxyl terminal nitrile rubber (CTBN), carboxyl terminal butadiene rubber (CTB), carboxyl can be used to modify butyronitrile Rubber (C-NBR).

As above-mentioned polyamide-imide resin, well known polyimide amide resin can be used.Also, as above-mentioned polyamides Imines amide resin, such as can be used：By in N- methyl -2- Pyrrolizidines ketone and/or DMAC N,N' dimethyl acetamide equal solvent To trihemellitic acid acid anhydride, benzophenone tetracarboxylic anhydride and stretch ditolyl diisocyanate (bitolylene diisocyanate) into The resin of row heating and acquisition, or by right in N- methyl -2- Pyrrolizidines ketone and/or n,N-dimethylacetamide equal solvent Trihemellitic acid acid anhydride, methyl diphenylene diisocyanate and carboxyl terminal acrylonitrile-butadiene rubber are heated and winner.

Polyamide-imide resin is modified as above-mentioned rubber, and well known rubber modified polyamidoimide tree can be used Fat.Rubber modified polyamide-imide resin system makes polyamide-imide resin and rubbery resin reaction and obtains person.Make polyamides Amine imide resin and rubbery resin reaction and using the case where be to improve the softness of polyamide-imide resin itself Property and carry out.That is, making polyamide-imide resin and rubbery resin reaction, by the sour component (ring of polyamide-imide resin Hexane dicarboxylic acid etc.) a part be substituted by rubber constituent.Well known polyamidoimide can be used in polyamide-imide resin Resin.Also, well known rubbery resin or above-mentioned rubbery resin can be used in rubbery resin.Make rubber modified polyamide acyl When imide resin polymerize, the solvent for dissolving polyamide-imide resin and rubbery resin is preferably used in mixed way a kind or 2 Kind or more dimethylformamide, dimethylacetylamide, N- methyl -2- Pyrrolizidines ketone, dimethyl sulfoxide (DMSO), nitromethane, nitro second Alkane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, gamma-butyrolacton etc..

As above-mentioned phosphine nitrile system resin, well known phosphine nitrile system resin can be used.Phosphine nitrile system resin is containing being with phosphorus and nitrogen The resin of the phosphine nitrile with double bond of constitution element.Phosphine nitrile system resin can be by the synergy of nitrogen and phosphorus in molecule, and flies Improve flame retardant property to jump property.Also, it is different from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, it can get Steadily it is present in resin and prevents the effect migrated.

As above-mentioned fluororesin, well known fluororesin can be used.Also, as fluororesin, such as can be used by being selected from PTFE (polytetrafluoroethylene (PTFE) (tetrafluoride)), PFA (tetrafluoroethylene-perfluoro alkyl vinyl ether copolymer), FEP (hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)s Copolymer (four, lithium)), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (bifluoride)), PCTFE Arbitrary at least one kind of thermoplastic in (polychlorotrifluoroethylene (borontrifluoride)), polyarylsulfone (PAS), aromatic polysulphides and aromatic polyether Property the fluororesin etc. that is constituted of resin and fluororesin.

Also, above-mentioned resin layer can contain hardening of resin agent.As hardening of resin agent, well known hardening of resin agent can be used. For example, as hardening of resin agent, amines, bisphenol-A, the brominated bisphenol A such as dicyanodiamide, imidazoles, aromatic amine can be used Acid anhydrides, the biphenyl types such as novolaks class, the phthalate anhydrides such as equal phenols, phenol system novolac resin and cresol novolac resin Phenol resin, phenol aralkyl type phenol resin etc..Also, above-mentioned resin layer is also hard containing one kind or two or more above-mentioned resin Agent.Such curing agent is particularly effective epoxy resin.

By the particular instantiation of above-mentioned biphenyl type phenol resin in chemical formula 8.

[chemical formula 8]

Also, by the particular instantiation of above-mentioned phenol aralkyl type phenol resin in chemical formula 9.

[chemical formula 9]

As imidazoles, known person can be used, such as can enumerate：2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- second Base -4-methylimidazole, 2- phenyl -4-methylimidazole, 1- cyano ethyl -2- undecyl imidazoles, 1- cyano ethyl -2- ethyls - 4-methylimidazole, 1- cyano ethyl -2- phenylimidazoles, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxyls Ylmethyl imidazoles etc. can be used alone or as a mixture such.

Also, wherein, it is preferable to use have the imidazoles of the structural formula represented by chemical formula 10 below.By using this The imidazoles of structural formula represented by chemical formula 10 can significantly increase the resistance to hygroscopicity of the resin layer of semi-hardened state, make length Phase excellent storage stability.The reason is that imidazoles play catalytic effect when tying up to the hardening of epoxy resin, hardening The initial stage of reaction is played a role as the reaction initiator for causing the auto polymerization of epoxy resin to be reacted.

[chemical formula 10]

As the hardening of resin agent of above-mentioned amine, well known amine can be used.Also, the hardening of resin as above-mentioned amine Agent, such as above-mentioned polyamine or aromatic polyamine can be used, in addition, also can be used selected from aromatic polyamine, polyamide-based and make such It polymerize with epoxy resin or polybasic carboxylic acid or is condensed and one kind or two or more in the group of amine additives that obtains.Also, as upper State the hardening of resin agent of amine, it is preferable to use 4,4'- bis- amidos two stretch phenylsulfone, 3,3'-, bis- amidos two stretch phenylsulfone, 4,4- It is any in bis- [4- (the 4- amidos phenoxy group) phenyl] propane of benzidine, 2,2- or bis- [4- (4- amidos phenoxy group) phenyl] sulfones Kind or more.

Above-mentioned resin layer can contain hardening accelerator.As hardening accelerator, well known hardening accelerator can be used.Example Such as, as hardening accelerator, tertiary amine, imidazoles, urea system hardening accelerator etc. can be used.

Above-mentioned resin layer can contain catalysts.As catalysts, well known catalysts can be used.Example Such as, Crushing of Ultrafine silica, antimony trioxide etc. can be used to be used as catalysts.

The ingredient that the acid anhydrides of above-mentioned polybasic carboxylic acid plays a role preferably as the curing agent of epoxy resin.Also, above-mentioned polynary The acid anhydrides of carboxylic acid be preferably phthalate anhydride, maleic anhydride, trihemellitic acid acid anhydride, pyromellitic dianhydride, tetrahydroxy benzene dicarboxylic acid anhydride, Hexahydroxybenzene dicarboxylic acid anhydride, methyl hexahydroxybenzene dicarboxylic acid anhydride, nadic acid (nadic acid), methyl nadic acid.

Above-mentioned thermoplastic resin can be with can be with the thermoplasticity of the functional group other than the alcohol hydroxyl group of polymerization of epoxy resins Resin.

Above-mentioned polyethylene acetaldehyde resin can with other than hydroxyl and hydroxyl can be with epoxy resin or maleimide chemical combination The functional group of object polymerization.Also, above-mentioned polyethylene acetaldehyde resin can be its intramolecular import carboxyl, amido or unsaturated double-bond and Winner.

As above-mentioned aromatic polyamide resin polymer, can enumerate keeps aromatic polyamide resin and rubbery resin anti- It answers and winner.Herein, so-called aromatic polyamide resin refers to being synthesized with the condensation polymerization of dicarboxylic acids by aromatic diamine Person.Aromatic diamine at this time using 4,4'- two aminodiphenylmethanes, bis- amido diphenyl sulfones of 3,3'-, m-xylene diamine, 3,3'- diaminodiphenyl ethers etc..Also, dicarboxylic acids uses phthalic acid, isophthalic acid, terephthalic acid (TPA), fumaric acid etc..

Well known rubbery tree can be used in the so-called above-mentioned rubbery resin that can be reacted with above-mentioned aromatic polyamide resin Fat or above-mentioned rubbery resin.

The aromatic polyamide resin polymer be in order to be processed into the copper foil after copper-cover laminated plate be etched plus Working hour will not be damaged due to user because of etching solution by caused by end eclipse.

Also, above-mentioned resin layer can be to have sequentially formed hardening resin from copper foil side (i.e. the very thin layers of copper side of Copper foil with carrier) Layer (so-called " hard resin-layer " is the resin layer for indicating hardening and completing), the resin layer with semi-hardened resin layer.Above-mentioned hardening tree It is polyimide resin that lipid layer also can be 0ppm/ DEG C~25ppm/ DEG C by coefficient of thermal expansion, polyamide-imide resin, such Any resin component in compound resin is constituted.

Also, the coefficient of thermal expansion that can be arranged on above-mentioned hard resin-layer after hardening is the half of 0ppm/ DEG C~50ppm/ DEG C Hard resin-layer.Also, the thermal expansion system of the resin layer entirety after making above-mentioned hard resin-layer be hardened with above-mentioned semi-hardened resin layer Number can be 40ppm/ DEG C or less.The glass transition temperature of above-mentioned hard resin-layer can be 300 DEG C or more.Also, above-mentioned semi-harden tree Lipid layer also can be former using maleimide amine system resin or aromatic series maleimide resin.To form above-mentioned semihard Change the resin combination of resin layer preferably comprising maleimide amine system resin, epoxy resin, with crosslinkable functional group's Linear polymer.Epoxy resin recorded in well known epoxy resin or this specification can be used in epoxy resin.Also, as horse Come imide series resin, aromatic series maleimide resin, the linear polymer with crosslinkable functional group, can be used known Maleimide amine system resin, aromatic series maleimide resin, the linear polymer with crosslinkable functional group or above-mentioned Maleimide amine system resin, aromatic series maleimide resin, the linear polymer with crosslinkable functional group.

Also, providing a kind of Copper foil with carrier with resin layer manufacturing purposes suitable for stereo shaping printing distributing board When, above-mentioned hard resin-layer is preferably hardened with flexible high polymer layer.Above-mentioned high polymer layer In order to bear solder installation steps, preferably by the resin institute constitutor of the glass transition temperature with 150 DEG C or more.On High polymer layer is stated preferably by polyamide, polyethersulfone resin, aromatic polyamide resin, phenoxy resin, polyamides One kind or two or more hybrid resin is appointed to constitute in imide resin, polyethylene acetaldehyde resin, polyamide-imide resin.Also, The thickness of above-mentioned high polymer layer is preferably 3 μm~10 μm.

Also, above-mentioned high polymer layer is preferably containing epoxy resin, maleimide amine system resin, phenol resin, amine Appointing in carbamate resin is one kind or two or more.Also, it is 10 μm~50 μm that above-mentioned semi-hardened resin layer, which is preferably by thickness, Epoxy resin component is constituted.

Also, above-mentioned epoxy resin component is preferably each ingredient person containing following A ingredients~E ingredients.

A ingredients：Epoxide equivalent is 200 or less and by selected from bisphenol A type epoxy resin, the bisphenol-f type for being at room temperature liquid One kind or two or more constituted epoxy resin in the group of epoxy resin and bisphenol-A D-ring oxygen resin.

B component：High-fire resistance epoxy resin.

C ingredients：Wantonly a kind in phosphorous epoxy system resin, phosphine nitrile system resin or mixing it is such made of resin, that is, phosphorous Nonflammable resin.

D ingredients：By having the liquid rubber constituent that may be dissolved in the property in the solvent that boiling point is 50 DEG C~200 DEG C ranges Rubber modified polyamide-imide resin made of modification.

E ingredients：Hardening of resin agent.

B component is so-called glass transition temperature Tg higher " high-fire resistance epoxy resin "." high-fire resistance epoxy so-called herein Resin " be preferably phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, phenol system phenolic resin varnish type epoxy resin, The polyfunctional epoxy resins such as naphthalene type epoxy resin.

As the phosphorous epoxy resin of C ingredients, above-mentioned phosphorous epoxy resin can be used.Also, the phosphine nitrile as C ingredients It is resin, above-mentioned phosphine nitrile system resin can be used.

As the rubber modified polyamide-imide resin of D ingredients, above-mentioned rubber modified polyamidoimide tree can be used Fat.As the hardening of resin agent of E ingredients, above-mentioned hardening of resin agent can be used.

It adds solvent in resin combination indicated above to use as resin varnish, as printing distributing board Following layer forms thermosetting resin layer.The resin varnish is to add solvent in above-mentioned resin combination, by resin solid content Component amount is adjusted to the range of 30wt%~70wt%, when being measured according to the MIL-P-13949G in MIL standards, can be formed The semi-hardened resin film for the range that resin spillway discharge (resin flow) is 5%~35%.Solvent can be used well known solvent or Above-mentioned solvent.

Above-mentioned resin layer is that sequentially have the 1st thermosetting resin layer from copper foil side and positioned at the 1st thermosetting resin The resin layer of the 2nd thermosetting resin layer on the surface of layer, the 1st thermosetting resin layer also can be by not dissolving in distributing board manufacture The resin component institute former of chemicals when removing glue Slag treatment in manufacturing method, the 2nd thermosetting resin layer also can be It is formed using the resin of chemicals and clean removal when dissolving in the removing glue Slag treatment in distributing board manufacture manufacturing method Person.Above-mentioned 1st thermosetting resin layer can be using wantonly a kind or 2 be mixed in polyimide resin, polyether sulfone, polyphenylene oxide Kind or more resin component and former.Above-mentioned 2nd thermosetting resin layer can be former using epoxy resin ingredient.On State the 1st thermosetting resin layer thickness t1 (μm) preferably by the roughening surface roughness of Copper foil with carrier be set as Rz (μm), When the thickness of 2nd thermosetting resin layer is set as t2 (μm), t1 meets the thickness of Rz ＜ t1 ＜ t2 conditions.

Above-mentioned resin layer can be in framework material containing the prepreg for being soaked with resin.The resin being impregnated in above-mentioned framework material Preferably thermosetting resin.Above-mentioned prepreg also can be the preimpregnation used in well known prepreg or printing distributing board manufacture Body.

Above-mentioned framework material can contain aramid fibre or glass fibre or Wholly aromatic polyester fiber.Above-mentioned skeleton Material is preferably the nonwoven fabric or woven fabric of aramid fibre or glass fibre or Wholly aromatic polyester fiber.Also, above-mentioned Wholly aromatic polyester fiber is preferably the Wholly aromatic polyester fiber that fusing point is 300 DEG C or more.So-called above-mentioned fusing point be 300 DEG C with On Wholly aromatic polyester fiber, refer to using being known as fiber made of the resin manufacture of so-called liquid crystal polymer, and the liquid crystal Polymer is using 2- hydroxyl -6- naphthoic acids and to the polymer of Para Hydroxy Benzoic Acid as principal component.The Wholly aromatic polyester fiber There is excellent performance with low-k, lower Dielectric loss tangent, therefore as the constituent material of electrical insulation layer, It can be used in the same manner with glass fibre and aramid fibre.

Furthermore constitute the fiber of above-mentioned nonwoven fabric and woven fabric in order to improve the wetability with the resin on its surface, preferably Implement silane coupling agent processing.Silane coupling agent at this time can be according to using purpose and use well known amido system, epoxy etc. Silane coupling agent or above-mentioned silane coupling agent.

Also, above-mentioned prepreg can be 70 μm of aramid fibres or glass fibre below to have nominal thickness in use Nonwoven fabric or nominal thickness be pre- made of impregnation thermosetting resin in the framework material that 30 μm of glass cloth below are constituted Soak body.

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

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

When containing the situation of dielectric substance (dielectric substance filler) in any of the above-described resin layer or resin combination, it can be used for shape At the purposes of capacitor layer, and increase the capacitance of capacitor circuit.The dielectric substance (dielectric substance filler) is to use BaTiO₃、 SrTiO₃、Pb(Zr-Ti)O₃(common name PZT), PbLaTiO₃- PbLaZrO (common name PLZT), SrBi₂Ta₂O₉Tools such as (common name SBT) There is the dielectric substance powder of the composite oxides of perovskite structure.

Dielectric substance (dielectric substance filler) can be powdery.When dielectric substance (dielectric substance filler) is the situation of powdery, the dielectric The powder characteristics of body (dielectric substance filler) must make grain size be 0.01 μm~3.0 μm first, preferably 0.02 μm~2.0 μm of model It encloses.So-called grain size herein refers to since powder forms 2 times certain state of aggregations each other, so according to laser diffraction scattering The measured value of formula determination of particle size distribution or BET method etc. speculate in the indirect determination of average grain diameter etc because precision is poor can not It uses, and scanning electron microscope (SEM) is utilized directly to observe dielectric substance (dielectric substance filler), image is carried out to the SEM pictures The average grain diameter of parsing and acquisition.In the specification of the present application, grain size at this time is expressed as DIA.Furthermore present specification In the image analysis of the powder of dielectric substance (dielectric substance filler) observed using scanning electron microscope (SEM) be to use The IP-1000PC of Asahi Engineering limited liability companies manufacture, makes roundness threshold be 10, overlapping degree is 20 and carries out Round particle parses, and finds out average grain diameter DIA.

Pass through the embodiment above, it is possible to provide the interior of the inner layer core material can be improved in a kind of following Copper foil with carrier The adaptation of layer circuit surface and the resin layer containing dielectric substance has lower Dielectric loss tangent with containing to be formed Capacitor circuit layer dielectric substance resin layer.

Resin and/or resin combination and/or compound contained in above-mentioned resin layer is set to be dissolved in such as Methylethyl Ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetylamide, N- methylpyrrole pyridines ketone, toluene, methanol, ethyl alcohol, propylene glycol Monomethyl ether, dimethylformamide, dimethylacetylamide, cyclohexanone, ethyl Cellosolve, N- methyl -2- Pyrrolizidines ketone, N, N- bis- Resin liquid (resin varnish) is made in methylacetamide, n,N-Dimethylformamide equal solvent, for example, by print roll coating method It is coated in above-mentioned very thin layers of copper or above-mentioned refractory layer, antirust coat or above-mentioned chromating layer or above-mentioned silane is even In mixture layer, then optionally it is thermally dried removal solvent and becomes B-stage state.As long as dry for example using hot air drying Dry stove, as long as drying temperature is 100~250 DEG C, preferably 130~200 DEG C.Above-mentioned resin layer is dissolved using solvent Constituent, can be made into resin solid content ingredient be 3wt%~70wt%, preferably 3wt%~60wt%, preferably 10wt% The resin liquid of~40wt%, more preferably 25wt%~40wt%.Furthermore for the viewpoint of environment, it is most preferably at this stage It is dissolved using the mixed solvent of methyl ethyl ketone and cyclopentanone.Furthermore solvent is preferably 50 DEG C~200 DEG C using boiling point Range solvent.

Also, above-mentioned resin layer is preferably resin spillway discharge when being measured according to the MIL-P-13949G in MIL standards For the semi-hardened resin film of 5%~35% range.

In the specification of the present application, so-called resin spillway discharge refers to certainly will according to the MIL-P-13949G in MIL standards The copper foil with resin that resin thickness is set as 55 μm takes 4 10cm square samples, in the state that 4 samples overlap Under (laminate), in 171 DEG C of press temperature, pressing pressure 14kgf/cm², be bonded under conditions of 10 minutes pressing times, It is flowed out according to the resin measured at this time obtained by weight as a result, the value calculated based on mathematical expression 1.

[mathematical expression 1]

The Copper foil with carrier (Copper foil with carrier for having resin) for having above-mentioned resin layer is to use as follows：It should Overall thermal is crimped after overlapping with base material and makes the resin layer thermmohardening by resin layer, is then removed carrier and is exposed very thin layers of copper (expose certainly be the very thin layers of copper middle layer side surface), be formed on specific Wiring pattern.

If having the Copper foil with carrier of resin using this, preimpregnation material when manufacture multilayer printed wiring board can be reduced Use the piece number.Moreover, the thickness of resin layer is set as to can ensure that the thickness of layer insulation, or prepreg is not used completely Material, can also manufacture copper-cover laminated plate.Also, at this point, insulating resin priming paint to be coated on to the surface of base material, it can also improve surface in turn Flatness.

Furthermore when without using the situation of preimpregnation material, the material cost of preimpregnation material can be saved, in addition, layering steps are also Become simple, therefore economically advantageously, moreover, having the following advantages：The only multilayer of the thickness degree of manufacture preimpregnation material The thickness of printed wiring board is thinning, and the thickness that can manufacture 1 layer is 100 μm of very thin multilayer printed wiring boards below.

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

If the thickness of resin layer is thinner than 0.1 μm, there is following situation：Do not make adhesion reduce and be inserted into preimpregnation material In the case of, by the Copper foil with carrier lamination with resin when on the base material for have inner layer material, it is difficult to ensure with internal layer material Layer insulation between the circuit of material.On the other hand, if the thickness of resin layer is thicker than 120 μm, there is following situation：It is difficult at 1 time The resin layer of target thickness is formed in application step, and needs extra fee of material and number of steps, therefore is economically become not Profit.

Furthermore it, will be upper when the Copper foil with carrier with resin layer to be used to manufacture in very thin multi-layer printed circuit board State resin layer thickness be set as 0.1 μm~5 μm, more preferably 0.5 μm~5 μm, more preferably 1 μm~5 μm when, multilayer can be reduced The thickness of printing distributing board, so it is preferred that.

Also, when resin layer contains the situation of dielectric substance, the thickness of resin layer is preferably 0.1~50 μm, preferably 0.5 μm ~25 μm, more preferably 1.0 μm~15 μm.

Also, the resin layer overall thickness of above-mentioned hard resin-layer and semi-hardened resin layer is preferably 0.1 μm~120 μm, preferably It is 5 μm~120 μm, preferably 10 μm~120 μm, more preferably 10 μm~60 μm.Also, the thickness of hard resin-layer is preferably 2 μm~30 μm, preferably 3 μm~30 μm, more preferably 5~20 μm.Also, the thickness of semi-hardened resin layer is preferably 3 μm~55 μ M, preferably 7 μm~55 μm, be more preferably 15~115 μm.If its reason is that resin layer overall thickness is more than 120 μm, in distress The case where to manufacture very thin multi-layer printed circuit board, if not having following situation up to 5 μm：Though being easy to form very thin multilayer Printing distributing board, but will produce the insulating layer i.e. resin layer between the circuit of internal layer and become too thin, and it is exhausted between making the circuit of internal layer The unstable tendency of edge.Also, if hardening resin layer thickness has the surface roughness that must take into consideration roughening of copper foil face not up to 2 μm The case where.Conversely, if hardening resin layer thickness is more than 20 μm, there is the effect that the resin layer completed by hardening is brought not special The case where raising, insulating layer overall thickness can thicken.

Furthermore when the thickness of above-mentioned resin layer to be set as to 0.1 μm~5 μm of situation, in order to improve resin layer and appendix The adaptation of body copper foil, preferably be arranged in very thin layers of copper refractory layer and/or antirust coat and/or chromating layer and/ Or after silane coupling process layer, resin is formed on the refractory layer or antirust coat or chromating layer or silane coupling process layer Layer.

Furthermore the thickness of above-mentioned resin layer refers to the average value by observing the thickness that section measures at arbitrary 10 points.

In turn, as this with resin Copper foil with carrier another product form, also can coated with resin layer in above-mentioned pole On thin copper layer or in above-mentioned refractory layer, antirust coat or above-mentioned chromating layer or above-mentioned silane coupling process layer, become half After hardening state, carrier is then removed, is manufactured in the form of the copper foil with resin there is no carrier.

6. printing distributing board ＞ of ＜

Hereinafter, indicating that the manufacture of the printing distributing board of several surface treatment copper foils or Copper foil with carrier using the present invention walks Rapid example.Also, by the electronic component mounting class on printing distributing board, and complete printed circuit board.

Via above-mentioned manufacturing method, manufacture sequentially has the Copper foil with carrier of foil carriers, peeling layer and very thin layers of copper. The application method of Copper foil with carrier itself is that such as the surface of very thin layers of copper can be fitted in paper base material phenol system tree well known to dealer Fat, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth-paper composite base material epoxy resin, glass cloth-glass On the insulating substrates such as glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film simultaneously After being thermally compressed, the very thin layers of copper then in insulating substrate is etched by stripping carrier thus after forming copper-cover laminated plate Target conductor pattern, finally manufactures printing distributing board.

The Copper foil with carrier of the present invention suitably forms the printing distributing board of thin space.For example, can be by using the present invention's Copper foil with carrier manufactures following printing distributing board：The printing distributing board has insulating substrate and is arranged on above-mentioned insulating substrate Copper circuit, and the circuit width of above-mentioned copper circuit, not up to 20 μm, the gap width between adjacent copper circuit is not up to 20 μm.Into And the circuit width that also can manufacture above-mentioned copper circuit is 17 μm hereinafter, the gap width between the copper circuit of adjoining is 17 μm or less Printing distributing board.In turn, the circuit width that can also manufacture above-mentioned copper circuit is 15 μm hereinafter, gap between adjacent copper circuit Width is 15 μm of printing distributing boards below.In turn, the circuit width that can also manufacture above-mentioned copper circuit is 5~10 μm, adjacent The printing distributing board that gap width between copper circuit is 5~10 μm.

In turn, by the electronic component mounting class on printing distributing board, and printed circuit board is completed.By using the present invention Copper foil with carrier, for example, following printed circuit board can be manufactured：The printed circuit board has insulating substrate and setting above-mentioned exhausted Copper circuit on edge substrate, and the circuit width of above-mentioned copper circuit, not up to 20 μm, the gap width between adjacent copper circuit does not reach 20μm.In turn, the circuit width that also can manufacture above-mentioned copper circuit is 17 μm hereinafter, the gap width between the copper circuit of adjoining is 17 μm printed circuit board below.In turn, the circuit width that can also manufacture above-mentioned copper circuit is 17 μm hereinafter, between the copper circuit of adjoining Gap width be 17 μm of printing distributing boards below.In turn, can also manufacture above-mentioned copper circuit circuit width be 15 μm hereinafter, Gap width between adjacent copper circuit is 15 μm of printed circuit boards below.In turn, the circuit of above-mentioned copper circuit can also be manufactured Width is 5~10 μm, preferably 5~9 μm, more preferably 5~8 μm, the gap width between adjacent copper circuit is 5~10 μm, Preferably 5~9 μm, more preferably 5~8 μm of printed circuit board.Also, the spacing in line and gap is not preferably up to 40 μm, it is more excellent Be selected as 34 μm hereinafter, more preferably 30 μm hereinafter, more preferably 20 μm hereinafter, more preferably 15 μm or less.Furthermore line and gap Lower limit without particularly providing, for example, 6 μm or more or 8 μm or more or 10 μm or more.

Furthermore the spacing of so-called line and gap refers to from the center of copper circuit width to the copper circuit width abutted The distance in center.

Hereinafter, indicating the example of the manufacturing step of several printing distributing boards using the Copper foil with carrier for having the present invention.

One embodiment of the manufacturing method of the printing distributing board of the present invention comprises the following steps：Prepare the appendix of the present invention The step of body copper foil and insulating substrate；The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；And so that very thin layers of copper side With the mode of insulating substrate opposite direction by after above-mentioned Copper foil with carrier and insulating substrate lamination, by by the load of above-mentioned Copper foil with carrier The step of body is removed and form copper-cover laminated plate, thereafter, by semi-additive process (semi additive method), improve half plus At method (modified semi additive method), part addition process (partly additive method) and subtract into Any one of method (subtractive method) method forms the step of circuit.Insulating substrate can also be set as internal layer circuit and enter Mouthful.

In the present invention, so-called semi-additive process refers to being carried out on insulating substrate or copper foil seed layer (seed layer) Relatively thin electroless plating after forming pattern, using plating and etches the method for forming conductive pattern.

Therefore, a use of embodiment of the manufacturing method of the printing distributing board of the present invention of semi-additive process include following step Suddenly：

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

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the step of the carrier of above-mentioned Copper foil with carrier is removed；

The very thin copper that will be removed above-mentioned carrier by using the methods of the etching or plasma-based that have the etchant solutions such as acid and expose The step of layer completely removes；

Remove above-mentioned very thin layers of copper by using etching and on the resin layer and insulating substrate that expose setting through-hole and/or The step of blind hole (blind via)；

The step of removing glue Slag treatment is carried out to the region comprising above-mentioned through-hole and/or blind hole；

Above-mentioned resin and comprising the region of above-mentioned through-hole and/or blind hole be arranged electroless plating coating the step of；

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

Above-mentioned plating resist application is exposed, thereafter, remove be formed with circuit region plating resist application the step of；

There is the step of region setting electrolysis plating layer of foregoing circuit in the formation for having removed above-mentioned plating resist application；

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

By dodging the step of removals such as erosion are formed with the electroless plating coating in the region other than the region of foregoing circuit.

It is comprised the following steps using the another embodiment of the manufacturing method of the printing distributing board of the present invention of semi-additive process：

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

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the step of the carrier of above-mentioned Copper foil with carrier is removed；

The very thin copper that will be removed above-mentioned carrier by using the methods of the etching or plasma-based that have the etchant solutions such as acid and expose The step of layer completely removes；

On the surface of the resin layer exposed by using the above-mentioned very thin layers of copper of etching removal, electroless plating coating is set Step；

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

Above-mentioned plating resist application is exposed, thereafter, remove be formed with circuit region plating resist application the step of；

There is the step of region setting electrolysis plating layer of foregoing circuit in the formation for having removed above-mentioned plating resist application；

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

By dodging the step of removals such as erosion are formed with the electroless plating coating in the region other than the region of foregoing circuit.

In the present invention, so-called improvement semi-additive process refers to lamination metal foil on the insulating layer, is protected by plating resist application Inverter circuit forming portion removes resist after the layers of copper for thickening circuit forming portion is electroplated, and utilizes (quick) etching to remove above-mentioned Metal foil other than circuit forming portion, the method for thus forming circuit on the insulating layer.

Therefore, a use of embodiment of the manufacturing method of the printing distributing board for the present invention for improving semi-additive process include such as Lower step：

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

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the step of the carrier of above-mentioned Copper foil with carrier is removed；

In the step of very thin layers of copper that the above-mentioned carrier of stripping exposes is with setting through-hole on insulating substrate and/or blind hole；

The step of removing glue Slag treatment is carried out to the region comprising above-mentioned through-hole and/or blind hole；

In the step of electroless plating coating is arranged in the region comprising above-mentioned through-hole and/or blind hole；

In the step of plating resist application is arranged in the very thin layers of copper surface removed above-mentioned carrier and exposed；

After above-mentioned plating resist application is arranged, by the way that the step of forming circuit is electroplated；

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

The step of very thin layers of copper exposed by removing above-mentioned plating resist agent being removed using sudden strain of a muscle etching off.

Another embodiment using the manufacturing method of the printing distributing board for the present invention for improving semi-additive process includes as follows Step：

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

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the step of the carrier of above-mentioned Copper foil with carrier is removed；

In the step of plating resist application is arranged in the very thin layers of copper that the above-mentioned carrier of stripping exposes；

Above-mentioned plating resist application is exposed, thereafter, remove be formed with circuit region plating resist application the step of；

There is the step of region setting electrolysis plating layer of foregoing circuit in the formation for having removed above-mentioned plating resist application；

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

By dodging the step of removals such as erosion are formed with the very thin layers of copper in the region other than the region of foregoing circuit.

In the present invention, so-called part addition process, refer to the substrate made of conductor layer is set, optionally pass through through-hole or Catalysis core is assigned on substrate made of the hole of guide hole, is etched to form conductor circuit, and solder resist or plating resist are optionally set After application, is handled by electroless plating on above-mentioned conductor circuit and through-hole or guide hole etc. are thickened, thus manufacture printing The method of distributing board.

Therefore, a use of embodiment of the manufacturing method of the printing distributing board of the present invention of part addition process include as follows Step：

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

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the step of the carrier of above-mentioned Copper foil with carrier is removed；

In the step of very thin layers of copper that the above-mentioned carrier of stripping exposes is with setting through-hole on insulating substrate and/or blind hole；

The step of removing glue Slag treatment is carried out to the region comprising above-mentioned through-hole and/or blind hole；

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

In the step of very thin layers of copper surface removed above-mentioned carrier and exposed is arranged anti-etching dose；

The step of above-mentioned anti-etching dose is exposed, circuit pattern is formed；

Above-mentioned very thin layers of copper and above-mentioned catalysis core are removed by using the methods of etching or plasma-based for there are the etchant solutions such as acid, The step of forming circuit；

The step of removing above-mentioned anti-etching dose；

Above-mentioned very thin layers of copper and above-mentioned catalysis are being removed by using the methods of etching or plasma-based for there are the etchant solutions such as acid Core and the above-mentioned insulating substrate surface exposed, the step of solder resist or plating resist application are set；And

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

In the present invention, so-called subtractive process refers to the copper foil being optionally removed by etching etc. on copper-cover laminated plate Unwanted part, and the method for forming conductive pattern.

Therefore, a use of embodiment of the manufacturing method of the printing distributing board of the present invention of subtractive process include following step Suddenly：

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

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the step of the carrier of above-mentioned Copper foil with carrier is removed；

In the step of very thin layers of copper that the above-mentioned carrier of stripping exposes is with setting through-hole on insulating substrate and/or blind hole；

The step of removing glue Slag treatment is carried out to the region comprising above-mentioned through-hole and/or blind hole；

In the step of electroless plating coating is arranged in the region comprising above-mentioned through-hole and/or blind hole；

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

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

The step of above-mentioned anti-etching dose is exposed, circuit pattern is formed；

Above-mentioned very thin layers of copper and above-mentioned electroless is removed by using the methods of etching or plasma-based for there are the etchant solutions such as acid Plating layer and above-mentioned electrolysis plating layer, and the step of forming circuit；And

The step of removing above-mentioned anti-etching dose.

It is comprised the following steps using the another embodiment of the manufacturing method of the printing distributing board of the present invention of subtractive process：

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

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the step of the carrier of above-mentioned Copper foil with carrier is removed；

In the step of very thin layers of copper that the above-mentioned carrier of stripping exposes is with setting through-hole on insulating substrate and/or blind hole；

The step of removing glue Slag treatment is carried out to the region comprising above-mentioned through-hole and/or blind hole；

In the step of electroless plating coating is arranged in the region comprising above-mentioned through-hole and/or blind hole；

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

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

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

The step of above-mentioned anti-etching dose is exposed, circuit pattern is formed；

Above-mentioned very thin layers of copper and above-mentioned electroless is removed by using the methods of etching or plasma-based for there are the etchant solutions such as acid Plating layer, and the step of forming circuit；And

The step of removing above-mentioned anti-etching dose.

Also can be without setting through-hole and/or blind hole the step of and subsequent de-smear step.

Herein, the manufacturing method of the printing distributing board using the Copper foil with carrier for having the present invention is explained in detail using attached drawing Concrete example.Furthermore herein, illustrated by taking the Copper foil with carrier with the very thin layers of copper for being formed with roughening treatment layer as an example, But it is not limited to this, using the Copper foil with carrier with the very thin layers of copper for not forming roughening treatment layer, can also be carried out similarly down State the manufacturing method of printing distributing board.

First, as shown in A in Fig. 3, prepare the Copper foil with carrier of very thin layers of copper that there is surface to be formed with roughening treatment layer (the 1st layer).

Secondly, as shown in B in Fig. 3, it is coated with resist on the roughening treatment layer of very thin layers of copper, is exposed, develops, it will Resist is etched to specific shape.

Then, as shown in C in Fig. 3, after forming circuit plating, resist is removed, specific shape is consequently formed Circuit plating.

Then, as shown in D in Fig. 4, in very thin copper (in a manner of burying circuit plating) in a manner of coating circuit plating Setting embedment resin on layer and laminated resin layer, then, from very thin layers of copper side then another Copper foil with carrier (the 2nd layer).

Then, as shown in E in Fig. 4, carrier is removed from the 2nd layer of Copper foil with carrier.

Then, as shown in F in Fig. 4, laser trepanning is carried out in the specific position of resin layer, exposes circuit plating and is formed blind Hole.

Then, as shown in G in Fig. 5, the filling perforation of embedment copper is formed in blind hole.

Then, as shown in H in Fig. 5, in filling perforation, circuit plating is formed in a manner of C in B and Fig. 3 in above-mentioned Fig. 3.

Then, as shown in I in Fig. 5, carrier is removed from the 1st layer of Copper foil with carrier.

Then, as shown in J in Fig. 6, the very thin layers of copper on two surfaces is removed by dodging etching off, makes the circuit plating in resin layer Expose on surface.

Then, as shown in K in Fig. 6, the circuit plating in resin layer applies to form convex block, and copper post is formed on the solder. So make the printing distributing board of the Copper foil with carrier using the present invention.

(the 2nd layer) Copper foil with carrier that the present invention can be used of above-mentioned another Copper foil with carrier, also can be used existing appendix Body copper foil, and then common copper foil also can be used.Also, can in Figure 5 on the 2nd layer of circuit represented by H so that formed 1 layer or Multiple layers of circuit, can be formed by any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process method should Equal circuits.

Also, can have substrate in the carrier side surface of the Copper foil with carrier for above-mentioned 1st layer of Copper foil with carrier.Pass through It with the substrate or resin layer, and supports the Copper foil with carrier for the 1st layer, becomes to be not likely to produce gauffer, therefore be improved life The advantages of production property.Furthermore it as long as aforesaid substrate has the effect of supporting the above-mentioned Copper foil with carrier for being used in the 1st layer, may be used All substrates.For example, the carrier described in present specification, prepreg, resin layer or well known carrier, preimpregnation can be used Body, resin layer, metallic plate, metal foil, the plate of inorganic compound, the foil of inorganic compound, the plate of organic compound, organic compound The foil of object is as aforesaid substrate.

At the time point that carrier side surface forms substrate, there is no particular restriction, but must be formed before removing carrier.Especially It is preferably to be formed before the step of above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier forms resin layer, more preferably To be formed before the step of forming circuit in the above-mentioned very thin layers of copper side surface of Copper foil with carrier.

The Copper foil with carrier of the present invention is preferably the aberration on the control pole thin copper layer surface in a manner of meeting following (1). In the present invention, so-called " aberration on very thin layers of copper surface " is the aberration on the surface for indicating very thin layers of copper, or is being implemented at roughening It is surface-treated the aberration of layer surface when the situations of various surface treatments such as reason.That is, the present invention Copper foil with carrier preferably with The mode control pole thin copper layer or roughening treatment layer or refractory layer or antirust coat or chromating layer or silane of (1) below meeting The aberration on the surface of coupled layer.

(1) very thin layers of copper or roughening treatment layer or refractory layer or antirust coat or chromating layer or silane are coupled process layer Surface base JISZ 8730 aberration Δ E ﹡ ab be 45 or more.

Herein, aberration Δ L, Δ a, Δ b are to be measured respectively with colour difference meter, take black/white/red green/yellow blue, are used L ﹡ a ﹡ b colour systems based on JIS Z8730 and the overall target indicated, and it is expressed as Δ L：White black, Δ a：Red green, Δ b：It is yellow It is blue.Also, Δ E ﹡ ab are indicated with following formula using such aberration.

[mathematical expression 2]

Current density when above-mentioned aberration can be formed by improving very thin layers of copper, the copper concentration in reduction plating solution, raising The line flow velocity of plating solution and be adjusted.

Also, above-mentioned aberration can also be carried out by by roughening treatment is implemented on the surface of very thin layers of copper and roughening treatment layer is arranged Adjustment.It, can be by using containing in the group being made of copper and nickel, cobalt, tungsten, molybdenum when the situation of roughening treatment layer is arranged More than one elements electrolyte, it is more existing to further increase current density (such as 40~60A/dm²), shorten processing time (such as 0.1~1.3 second) and be adjusted.When not the surface of very thin layers of copper be arranged roughening treatment layer situation when, can pass through Reach such as under type：Using the plating bath of the 2 times or more for a concentration of other elements for making Ni, to very thin layers of copper or refractory layer or prevent The surface of rusty scale or chromating layer or silane coupling process layer, so that Ni alloy plateds (such as Ni-W alloy plateds, Ni- Co-P alloy plateds, Ni-Zn alloy plateds) it is less than existing current density (0.1~1.3A/dm²) and the setting processing of longer ground The time mode of (20 seconds~40 seconds) is handled.

If the aberration Δ E ﹡ ab based on JIS Z8730 on very thin layers of copper surface are 45 or more, such as in Copper foil with carrier Very thin layers of copper circuit forming surface when, the contrast of very thin layers of copper and circuit is apparent from, and as a result visibility becomes good, can Precisely carry out the position alignment of circuit.The aberration Δ E ﹡ ab based on JIS Z8730 on very thin layers of copper surface are preferably 50 More than, more preferably 55 or more, and then more preferably 60 or more.

As described above as control pole thin copper layer or roughening treatment layer or refractory layer or antirust coat or chromating layer or It when the situation of the aberration on the surface of silane coupled layer, is apparent from the contrast of circuit plating, visibility becomes good.Cause This can be precisely specific in manufacturing step in such as Fig. 3 of printing distributing board as described above represented by C Position forms circuit plating.Also, according to the manufacturing method of printing distributing board as described above, formation makes circuit plating be embedded to resin Layer composition, therefore in such as Fig. 6 represented by J by dodge etching off depolarization thin copper layer when, pass through resin layer protect circuit plating It applies, and keeps its shape, thus be easy to form fine circuits.Also, due to protecting circuit plating by resin layer, so resistance to migration Property improve, can favorably inhibit the conducting of the wiring of circuit.Therefore, it is easy to form fine circuits.Also, the J and Fig. 6 in such as Fig. 6 When as middle K is represented by dodging etching off depolarization thin copper layer, the exposed surface of circuit plating becomes the shape being recessed from resin layer, therefore It is easy to apply to form convex block in circuit plating respectively, and then is formed on copper post, manufacture efficiency improves.

Furthermore it is embedded to resin (Resin) and well known resin, prepreg can be used.Such as BT (bismaleimide can be used Triazine) resin or be impregnated with BT resins glass cloth, that is, prepreg, Ajinomoto Fine-Techno limited liability companies manufacture ABF films or ABF.Also, above-mentioned embedment resin (Resin) can be used resin layer recorded in this specification and/or resin and/or Prepreg.

[embodiment]

Hereinafter, embodiment through the invention illustrates the present invention in further detail, but the present invention is not by such implementation Any restriction of example.

1. the manufacture of Copper foil with carrier

1 ＞ of ＜ embodiments

As foil carriers, prepare the strip electrolytic copper foil (JTC of JX days mine days stone metal company manufacture) of 35 μm of thickness. Under the following conditions, continuously to plate wiring by roll-to-roll type (roll to roll) right (in the way of using the bending represented by Fig. 2) Glassy surface (the Rz of the copper foil：1.2~1.4 μm) it is electroplated, 4000 μ g/dm are consequently formed²The Ni layers of adhesion amount.

Ni layers

Nickel sulfate：250~300g/L

Nickel chloride：35~45g/L

Nickel acetate：10~20g/L

Trisodium citrate：15~30g/L

Gloss agent：Saccharin, butynediols etc.

Lauryl sodium sulfate：30~100ppm

PH value：4~6

Bath temperature：50~70 DEG C

Current density：3~15A/dm²

After washing and pickling, then, by continuously plating wiring in roll-to-roll type (using the bending mode represented by Fig. 2) On, under the following conditions to 11 μ g/dm²The Cr layers of adhesion amount carry out electrolytic chromate processing and are allowed to be attached on Ni layers.

Electrolytic chromate processing

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

PH value：3~4

Liquid temperature：50~60 DEG C

Current density：0.1~2.6A/dm²

Coulomb amount：0.5~30As/dm²

Then, by continuously being plated on wiring in roll-to-roll type (using the rotating cylinder mode represented by Fig. 1), under the following conditions 3 μm of very thin layers of copper of thickness is electroplated and is allowed to be formed on Cr layers, to manufacture Copper foil with carrier.Furthermore this implementation Also manufacture makes the Copper foil with carrier that the thickness of very thin layers of copper is 1,2,5,10 μm to example, the implementation that the thickness to very thin layers of copper is 3 μm Example carries out identical evaluation.As a result unrelated with thickness and be identical.

Very thin layers of copper

Copper concentration：30~120g/L

H₂SO₄Concentration：20~120g/L

Electrolyte temperature：20~80 DEG C

Current density：10~100A/dm²

Then, sequentially to very thin layers of copper surface progress roughening treatment 1 below, roughening treatment 2, antirust treatment, chromate Processing and silane coupling processing.Roughening treatment 1 and roughening treatment 2 are using the fortune foil mode (interpolar using rotating cylinder represented by Fig. 1 Distance is 50mm), antirust treatment, chromic acid salt treatment and silane coupling processing are using the bending mode represented by Fig. 2.

Roughening treatment 1

(liquid composition 1)

Cu：10~30g/L

H₂SO₄：10~150g/L

W：0~50mg/L

Lauryl sodium sulfate：0~50mg/L

As：0~200mg/L

(plating conditions 1)

Temperature：30~70 DEG C

Current density：25~110A/dm²

It is roughened coulomb amount：50~500As/dm²

Plating time：0.5~20 second

Roughening treatment 2

(liquid composition 2)

Cu：20~80g/L

H₂SO₄：50~200g/L

(plating conditions 2)

Temperature：30~70 DEG C

Current density：5~50A/dm²

It is roughened coulomb amount：50~300As/dm²

Plating time：1~60 second

Antirust treatment

(liquid composition)

NaOH：40~200g/L

NaCN：70~250g/L

CuCN：50~200g/L

Zn(CN)₂：2~100g/L

As₂O₃：0.01~1g/L

(liquid temperature)

40~90 DEG C

(current condition)

Current density：1~50A/dm²

Plating time：1~20 second

Chromic acid salt treatment

K₂Cr₂O₇(N₂Cr₂O₇Or CrO₃)：2~10g/L

NaOH or KOH：10~50g/L

ZnOH or ZnSO₄·7H₂O：0.05~10g/L

PH value：7~13

Bath temperature：20~80 DEG C

Current density：0.05~5A/dm²

Time：5~30 seconds

Silane coupling is handled

After the 3- glycidoxypropyltrimewasxysilane aqueous solution spraying coatings of 0.1vol%~0.3vol%, Drying, heating in 0.1~10 second are carried out in 100~200 DEG C of air.

After above-mentioned surface treatment, the resin layer of following " A " is formed in very thin layers of copper side.

2 ＞ of ＜ embodiments

After forming very thin layers of copper on foil carriers under the same conditions as example 1, roughening below is sequentially carried out Processing 1, roughening treatment 2, antirust treatment, chromic acid salt treatment and silane coupling processing.Roughening treatment 1 and roughening treatment 2 use Fig. 1 The represented fortune foil mode (interpolar distance is 50mm) using rotating cylinder, antirust treatment, chromic acid salt treatment and silane coupling processing Using the bending mode represented by Fig. 2.Furthermore the thickness of ultrathin copper foil is set as 3 μm.

Roughening treatment 1

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

Liquid temperature：25~50 DEG C

Current density：1~58A/dm²

Coulomb amount：4~81As/dm²

Roughening treatment 2

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

PH value：2~3

Liquid temperature：30~50 DEG C

Current density：24~50A/dm²

Coulomb amount：34~48As/dm²

Antirust treatment

Liquid forms：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

Chromic acid salt treatment

Liquid forms：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(in order to carry out dipping chromic acid salt treatment, also can be in electroless lower implementation)

Coulomb amount：0~2As/dm²(in order to carry out dipping chromic acid salt treatment, also can be in electroless lower implementation)

Silane coupling is handled

Coating (the two amino containing silane concentration of two amino containing silane aqueous solutions：0.1~0.5wt%)

After above-mentioned surface treatment, the resin layer of following " B " is formed in very thin layers of copper side.

3 ＞ of ＜ embodiments

As foil carriers, prepare the strip electrolytic copper foil (HLP of JX days mine days stone metal company manufacture) of 35 μm of thickness, To the glassy surface (Rz of the copper foil：0.1~0.3 μm), with sequentially built Copper foil with carrier same as Example 1.Wherein, resin Series of strata are formed following " C ".

4 ＞ of ＜ embodiments

As foil carriers, prepare the strip electrolytic copper foil (HLP of JX days mine days stone metal company manufacture) of 35 μm of thickness, To the glassy surface (Rz of the copper foil：0.1~0.3 μm), with sequentially built Copper foil with carrier same as Example 2.Wherein, resin Series of strata are formed following " D ".

5 ＞ of ＜ embodiments

As foil carriers, prepare the strip electrolytic copper foil (HLP of JX days mine days stone metal company manufacture) of 35 μm of thickness. Under the same conditions as example 1, glassy surface (Rz of the wiring to the copper foil is continuously plated using roll-to-roll type：0.1~0.3 μm) It is electroplated, 4000 μ g/dm is consequently formed²The Ni layers of adhesion amount then sequentially form very thin copper with same as Example 1 After layer, does not implement roughening treatment and implement following antirust treatments (using bending mode).

Antirust treatment

Liquid forms：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

After above-mentioned surface treatment, the resin layer of following " E " is formed in very thin layers of copper side.

1 ＞ of ＜ comparative examples

After forming very thin layers of copper on foil carriers under the same conditions as example 1, then, sequentially to very thin layers of copper Surface carries out roughening treatment 1, roughening treatment 2, antirust treatment, chromic acid salt treatment and silane coupling processing below.Roughening treatment 1 And roughening treatment 2 uses the fortune foil mode (interpolar distance is 50mm) using rotating cylinder represented by Fig. 1, antirust treatment, chromate Processing and silane coupling processing are using the bending mode represented by Fig. 2.Furthermore the thickness of ultrathin copper foil is set as 3 μm.

Roughening treatment 1

(liquid composition 1)

Cu：31~45g/L

H₂SO₄：10~150g/L

As：0.1~200mg/L

(plating conditions 1)

Temperature：30~70 DEG C

Current density：25~110A/dm²

It is roughened coulomb amount：50~500As/dm²

Plating time：0.5~20 second

Roughening treatment 2

(liquid composition 2)

Cu：20~80g/L

H₂SO₄：50~200g/L

(plating conditions 2)

Temperature：30~70 DEG C

Current density：5~50A/dm²

It is roughened coulomb amount：50~300As/dm²

Plating time：1~60 second

Antirust treatment

(liquid composition)

NaOH：40~200g/L

NaCN：70~250g/L

CuCN：50~200g/L

Zn(CN)₂：2~100g/L

As₂O₃：0.01~1g/L

(liquid temperature)

40~90 DEG C

(current condition)

Current density：1~50A/dm²

Plating time：1~20 second

Chromic acid salt treatment

K₂Cr₂O₇(N₂Cr₂O₇Or CrO₃)：2~10g/L

NaOH or KOH：10~50g/L

ZnOH or ZnSO₄·7H₂O：0.05~10g/L

PH value：7~13

Bath temperature：20~80 DEG C

Current density：0.05~5A/dm²

Time：5~30 seconds

Silane coupling is handled

After the 3- glycidoxypropyltrimewasxysilane aqueous solution spraying coatings of 0.1vol%~0.3vol%, Drying, heating in 0.1~10 second are carried out in 100~200 DEG C of air.

After above-mentioned surface treatment, resin layer is not formed.

2 ＞ of ＜ comparative examples

Roughening treatment 1 and roughening treatment 2 using represented by Fig. 2 using the fortune foil bent in the way of, in addition to this, with reality Apply 1 identical sequentially built Copper foil with carrier of example.But resin layer is not formed.

3 ＞ of ＜ comparative examples

Roughening treatment 1 and roughening treatment 2 using represented by Fig. 2 using the fortune foil bent in the way of, in addition to this, with reality Apply 2 identical sequentially built Copper foil with carrier of example.But resin layer is not formed.

4 ＞ of ＜ comparative examples

Following resin layers " A " are formed in the very thin layers of copper side of the Copper foil with carrier of comparative example 1.

5 ＞ of ＜ comparative examples

Following resin layers " B " are formed in the very thin layers of copper side of the Copper foil with carrier of comparative example 2.

6 ＞ of ＜ comparative examples

Following resin layers " C " are formed in the very thin layers of copper side of the Copper foil with carrier of comparative example 3.

6 ＞ of ＜ embodiments

Resin layer is not formed, in addition to this, with sequentially built Copper foil with carrier same as Example 1.

7 ＞ of ＜ embodiments

Resin layer is not formed, in addition to this, with sequentially built Copper foil with carrier same as Example 2.

8 ＞ of ＜ embodiments

Resin layer is not formed, in addition to this, with sequentially built Copper foil with carrier same as Example 3.

9 ＞ of ＜ embodiments

Resin layer is not formed, in addition to this, with sequentially built Copper foil with carrier same as Example 4.

10 ＞ of ＜ embodiments

Resin layer is not formed, in addition to this, with sequentially built Copper foil with carrier same as Example 5.

The formation ＞ of ＜ resin layers

The formation of resin layer is to proceed as follows.

·“A”

(resins synthesis example)

Attached spherical condensation tube is installed on the trap for having stainless steel heavy stone used as an anchor type stirring rod, nitrogen ingress pipe and stop cock Reflux cooler 2 liters of three-necked flask in, addition 3,4/3', 4'- biphenyltetracarboxylic dianhydrides 117.68g (400mmol), 1, Bis- (3- amidos phenoxy group) the benzene 87.7g (300mmol) of 3-, gamma-valerolactone 4.0g (40mmol), pyridine 4.8g (60mmol), N- Methyl -2- Pyrrolizidines ketone (being denoted as NMP below) 300g and toluene 20g are cooled to room temperature attached after being heated 1 hour at 180 DEG C Closely, bis- { 4- (the 4- amidos phenoxy group) benzene of 3,4/3'4'- biphenyltetracarboxylic dianhydrides 29.42g (100mmol), 2,2- are added thereafter Base } propane 82.12g (200mmol), NMP 200g and toluene 40g, at room temperature mix 1 hour after, heat 3 at 180 DEG C Hour, obtain the block copolymerization polyimides of solid content ingredient 38%.It is following represented in the block copolymerization polyimides General formula (1)：General formula (2)=3：2, number average molecular weight：70000, weight average molecular weight：150000.

The block copolymerization polyimide solution obtained in synthesis example is further diluted using NMP, and solid content ingredient is made 10% block copolymerization polyimide solution.With bis- (4- maleimide benzene in the block copolymerization polyimide solution Base) the solid content Ingredients Weight ratio 35 of methane (BMI-H, K-I Chemical Industry), block copolymerization polyimides Solid content Ingredients Weight ratio 65 (that is, (4- maleimide phenyls) methane solid content ingredients bis- contained in resin solution Weight：Block copolymerization polyimides solid content Ingredients Weight=35 contained in resin solution：65) form at 60 DEG C into Row dissolving in 20 minutes mixes and resin solution is made.Thereafter, above-mentioned resin solution is set coated on setting using reverse roll coating machine The very thin layers of copper side surface of Copper foil with carrier before lipid layer is dried 3 minutes, in 160 at 120 DEG C in a nitrogen environment It after being dried 3 minutes at DEG C, finally carries out heating for 2 minutes at 300 DEG C, and makes Copper foil with carrier.Furthermore resin The thickness of layer is set as 2 μm.

·“B”

B be prepare 69 parts by weight of epoxy resin, 11 parts by weight of curing agent, 0.25 parts by weight of hardening accelerator, polymer at Divide the resin combination of 15 parts by weight, 3 parts by weight of crosslinking agent, 3 parts by weight of rubbery resin.

Specifically, indicating as follows.

[composition of resin combination]

Constituent/specific constituent/specific chemical the name of an article (manufacturing company)/composition (parts by weight)

Epoxy resin/bisphenol A-type/YD-907 (Dongdu chemical conversion manufacture)/15

Epoxy resin/bisphenol A-type/YD-011 (Dongdu chemical conversion manufacture)/54

Bis- amido diphenyl sulfones of curing agent/aromatic amine/4,41- (Wakayama refine manufacture)/12

Hardening accelerator/imidazoles/2E4MZ (four countries' chemical conversion manufacture)/0.4

Component of polymer/polyvinyl acetal resin/5000A (electrochemically industry manufacture)/15

Crosslinking agent/amido formate resin/AP-Stable (Nippon Polyurethane manufactures)/3

Rubber constituent/hud typed nitrile rubber/XER-91 (manufacture of JSR companies)/3

Then, to above-mentioned represented resin combination, using methyl ethyl ketone and dimethylacetylamide by resin solid Object composition adjustment is 30 weight %, is thus made to form the resin combination solution of resin layer.Then, using intaglio plate coating The very thin layers of copper of Copper foil with carrier of the resin combination solution coating that this is formed resin layer by machine before resin layer is set The face of side.Then, carry out 5 minutes air-dry, thereafter, drying process in 3 minutes is carried out in 140 DEG C of heating environment, formation The semi-hardened resin layer (following layer) of 1.5 μ m-thicks of semi-hardened state, and manufacture Copper foil with carrier.What is obtained at this time is semi-harden The measurement of the resin spillway discharge of resin layer (following layer) is that the resin combination solution with above-mentioned to form resin layer manufactures 18 μ The single side of the copper foil of m thickness is provided with the semi-hardened resin layer person of 40 μ m-thicks, and is set to resin spillway discharge measurement sample.So Afterwards, 4 10cm square samples are taken by the resin spillway discharge measurement sample, carrying out resin according to above-mentioned MIL-P-13949G overflows The measurement of flow.Bearing-age tree seborrhea flow is 1.5%.

·“C”

Manufacture constitutes the resin solution of resin layer.When manufacturing the resin solution, epoxy resin (Japanese chemical drug share is used Co., Ltd manufacture EPPN-502), polyethersulfone resin (Sumitomo Chemical limited liability company manufacture Sumikaexcel PES- 5003P) it is used as raw material.Then, as the imidazoles system 2E4MZ of hardening accelerator, (four countries' chemical conversion industry share has for addition wherein Limit company manufactures) and resin combination is made.

Resin combination：50 parts by weight of epoxy resin

50 parts by weight of polyethersulfone resin

1 parts by weight of hardening accelerator

It is 30wt% by resin solid content composition adjustment to the resin combination, and then using dimethylformamide, thus Resin solution is made.The resin solution manufactured in the above-described manner is coated on to the appendix before setting resin layer using gravure coater The face of the very thin layers of copper side of body copper foil.Also, drying process in 3 minutes is carried out in 140 DEG C of heating environment thereafter, forms half The resin layer of 1.5 μ m-thicks of hardening state, and obtain the Copper foil with carrier of the present application.Furthermore on the other hand, in order to measure Bottom coating resin layer is set as attached resin copper foil (18 μm of copper thickness) (hereinafter referred to as " resin of 40 μ m-thicks by resin spillway discharge, manufacture Spillway discharge measurement sample ").Then, 4 10cm square samples are taken by the resin spillway discharge measurement sample, according to above-mentioned MIL-P-13949G, carry out resin spillway discharge measurement.Bearing-age tree seborrhea flow is 1.4%.

·“D”

The very thin layers of copper side surface of Copper foil with carrier before resin layer is arranged is formed sub- as the polyamides of hard resin-layer Amine resin layer, the formation of semi-hardened resin layer are the examples using the Copper foil with carrier for having maleimide amine system resin.

The preparation of polyamide acid varnish：To gathering to form hard resin-layer by the tape casting (casting method) Amic acid varnish illustrates.Bis- amido diphenyl ether 1mol of pyromellitic acid anhydride 1mol and 4,4'- is dissolved in as molten In the N- methylpyrrole pyridine ketone of agent, and mixed.Reaction temperature at this time is 25 DEG C, is reacted 10 hours.Then, resin is obtained Solid content component amount is the polyamide acid varnish of 20 mass %.

The formation of hard resin-layer：Then, obtained polyamide acid varnish is used, hardening resin is formed using the tape casting Layer.By Multi Coater, (Hirano Tecseed companies manufacture：M-400), polyamide acid varnish is coated on setting tree The very thin layers of copper side surface of Copper foil with carrier before lipid layer carries out in air drier under conditions of 110 DEG C × 6 minutes It is dry.The resin thickness of hard resin-layer after drying is set as 35 μm, and the solvent survival rate in the stage is relative to the total of resin layer Amount is 32wt%.The complex of the electrolytic copper foil for being coated with polyamide acid varnish is positioned over to the hot-air oven replaced through nitrogen In, 15 minutes are lasted from room temperature to 400 DEG C, thereafter, after being kept for 8 minutes at 400 DEG C, are cooled down.As a result, from coating Residual solvents are removed in the complex for having the Copper foil with carrier of polyamic acid, it is sub- by the acyl for carrying out dehydration closed-loop to polyamic acid Amine reacts, and the very thin layers of copper side surface lamination for being formed in Copper foil with carrier has the copper-clad polyimide of the state of hard resin-layer Resin base material.The solvent survival rate by the copper-clad polyimide resin base material that final heat treatment obtains is opposite to be adhered to It is 0.5wt% in the resin total amount of Copper foil with carrier.

Then, the Copper foil with carrier (copper-clad polyimide resin base material) of hard resin-layer carries out at corona lamination Reason, carries out the surfaction of the hard resin-layer.Sided corona treatment be in an atmosphere, electric power 210W, speed 2m/min, discharge capacity 300W·min/m², self-electrode irradiation distance 1.5mm under conditions of carry out.Also, in order to which the heat for measuring hard resin-layer is swollen Swollen coefficient, by Copper foil with carrier from surfaction treated lamination has hard resin-layer (sided corona treatment complete cover copper Polyimide resin base material) Copper foil with carrier is removed and etched and is removed.As a result the hardening for removing Copper foil with carrier and obtaining The resin thickness of resin layer (polyimide film) is 27 μm, and coefficient of thermal expansion is 25ppm/ DEG C.

The formation of semi-hardened resin layer：Herein, the hardening tree for the copper-clad polyimide resin base material completed in sided corona treatment Semi-hardened resin layer is formed in lipid layer.First, using N, N'- dimethylacetylamides make following represented resin group as solvent Dissolved at object, by make resin solid content ingredient as 30wt% resin varnish in a manner of prepared.

[resin combination for forming semi-hardened resin layer]

Maleimide resin：4,4'- diphenyl methane bismaleimide (trade names：BMI-1000, big and chemical conversion work Industry company manufactures)/30 parts by weight

Aromatic polyamine resin：Bis- [the 4- amidos phenoxy group] benzene (trade names of 1,3-：TPE-R, Wakayama are refined industrial group Manufacture)/35 parts by weight

Epoxy resin：Bisphenol A type epoxy resin (trade name：EPICLON 850S, ink chemical industrial company of big Japan system Make)/20 parts by weight

Linear polymer with crosslinkable functional group：Polyvinyl acetal resin (trade name：Denka Butyral 5000A, Denki Kagaku Kogyo kabushiki's manufacture)/15 parts by weight

Above-mentioned resin varnish is coated on to the polyimide resin of the copper-clad polyimide resin base material of sided corona treatment completion Face, at room temperature carry out 5 minutes air-dry, be thermally dried under conditions of 160 DEG C × 5 minutes, lamination forms semi-harden Resin layer.The resin thickness of semi-hardened resin layer at this time is set as 20 μm.

It, will using method same as described above also, in order to measure the coefficient of thermal expansion of semi-hardened resin layer after curing The above-mentioned resin varnish for being used to form semi-hardened resin layer is coated on fluorine system heat-resistant film, at room temperature carry out 5 minutes air-dry, Heat drying under conditions of 160 DEG C × 5 minutes carries out hardening heating in 200 DEG C × 2 hours and 20 μm of thickness is made in turn Experiment hard resin-layer.That is, the experiment is equivalent to the semi-harden of the Copper foil with carrier for making the present application with hard resin-layer The case where resin layer hardens.The coefficient of thermal expansion of experiment hard resin-layer is 45ppm/ DEG C.

The thickness of the resin layer entirety of the Copper foil with carrier obtained in the above-described manner is 47 μm.Also, by following methods, Copper foil is etched from the attached resin copper foil and is removed, using the resin layer being made of hard resin-layer and semi-hardened resin layer, to it The hardening heating for carrying out 200 DEG C × 2 hours, measures the thermal expansion system of the resin layer entirety after making the semi-hardened resin layer harden Number.As a result coefficient of thermal expansion is 35ppm/ DEG C.Also, peel strength is 1.0kgf/cm.

·“E”

Initially manufactured the 1st resin combination for constituting resin layer.When manufacturing 1 resin combination, o-cresol is used Phenolic resin varnish type epoxy resin (YDCN-704 of Dongdu chemical conversion limited liability company manufacture), the aromatic series polyamides for being soluble in solvent It polyimide resin polymer and is manufactured using the mixing varnish with the cyclopentanone as solvent and commercially available NIPPON PHARMACEUTICAL CO., LTD BP3225-50P as raw material.Also, big Japanese ink limited liability company is added in the phenol resin as curing agent The VH-4170 of the manufacture and 2E4MZ that limited liability company's manufacture is melted into as the four countries of hardening accelerator, and in the mixing varnish In the 1st resin combination with following represented allotment ratio is made.

To the 1st resin combination and then methyl ethyl ketone is used, is 30 weight % by resin solid content composition adjustment, by Resin solution is made in this.

The very thin layers of copper side surface of Copper foil with carrier before resin layer is formed is (be surface-treated very thin layers of copper It is the surface treated surface when situation) it is immersed in following solution：In ion exchange in a manner of the concentration as 5g/l Solution made of γ-glycidoxypropyltrimewasxysilane is added in water, and carries out sorption processing.Then, 4 seconds are lasted It is being adjusted to discharge moisture in the stove of 180 DEG C of environment using electric heater, is carrying out the condensation reaction of silane coupling agent and form silane It is coupled oxidant layer.

The resin solution manufactured in the above-described manner is coated on to the silane for being formed with Copper foil with carrier using gravure coater It is coupled the face of oxidant layer.Then, carry out 5 minutes air-dry, thereafter, carried out in 140 DEG C of heating environment at drying in 3 minutes Reason, forms the resin layer of 1.5 μ m-thicks of semi-hardened state, obtains the Copper foil with carrier of the present application.Furthermore resin spillway discharge Measurement be manufacture make bottom coating resin layer be 40 μ m thicks attached resin copper foil (hereinafter referred to as " and resin spillway discharge measurements examination Sample ").

Also, 4 10cm square samples are taken from the resin spillway discharge measurement sample, according to above-mentioned MIL-P- 13949G carries out the measurement of resin spillway discharge.Bearing-age tree seborrhea flow is 1.5%.

2. the evaluating characteristics of Copper foil with carrier

Evaluating characteristics are implemented to the Copper foil with carrier obtained in the above-described manner using following methods.Show the result in table 1.Again " 3.91E-16 " of person, " Ra " on " standard deviation (μm) column " of table 1 are to indicate 3.91 × 10^-16(μm), " 1.30E-02 " are tables Show 1.30 × 10^-2(μm)。

(surface roughness)

Each Copper foil with carrier (square of 550mm × 550mm) before self-forming resin layer is with 55mm spacing vertically and horizontally On draw straight line, distribute each 55mm × 55mm square 100, region position.Each region is surveyed using contact roughness Machine (the contact roughmeter Surfcorder SE-3C of limited liability company of little Ban research institutes manufacture) is determined, according to JIS B0601- 1982 (Ra, Rz) and JIS B0601-2001 (Rt), measured under following determination condition very thin layers of copper surface roughness (Ra, Rt, Rz), measure its average value and standard deviation.

＜ determination conditions ＞

Cut off：0.25mm

Datum length：0.8mm

Determination of the environment temperature：23~25 DEG C

(migration)

Each Copper foil with carrier (square of 550mm × 550mm) before resin layer will be formed then in bismuth system resin, It is secondary, carrier foils are removed and are removed.The thickness for the very thin layers of copper for making to be exposed by soft etching becomes 1.5 μm.Thereafter, it is washed After Net, drying, DF (Hitachi is melted into company's manufacture, trade name RY-3625) lamination is coated in very thin layers of copper.In 15mJ/cm² Under conditions of be exposed, liquid injection oscillation in 1 minute is carried out at 38 DEG C using developer solution (sodium carbonate), with line and gap (L/ )=15 μm S/15 μm of formation photoresist patterns.Then, copper sulphate plating (CUBRITE21 of Ebara-Udylite manufactures) plating is utilized After high 15 μm, DF is removed with stripper (sodium hydroxide).Thereafter, very thin layers of copper is etched with Sulfuric-acid-hydrogen-peroxide system etchant Removal forms L/S=15 μm/15 μm of wiring.Match from what is obtained in the region of size according to above-mentioned each 55mm × 55mm Line substrate cuts out 100 wiring substrates.

To each wiring substrate obtained, using migration measuring machine (MIG-9000 of IMV manufactures), in following determination condition Under whether there is or not insulation degradations to evaluate between Wiring pattern.About 100 wiring substrates, carried out to generating the number of substrate of migration Evaluation.

Furthermore about embodiment 2, in turn, the spacing for forming line and gap is 20 μm of (L/S=8 μm/12 μm, L/S=10 μ M/10 μm, L/S=12 μm/8 μm) wiring and carry out the evaluation of above-mentioned migration.Also, about embodiment 3, in turn, formed line with The spacing in gap is that the spacing of 20 μm (L/S=8 μm/12 μm, L/S=10 μm/10 μm, L/S=12 μm/8 μm), line and gap is The wiring of 15 μm (L/S=5 μm/10 μm, L/S=8 μm/7 μm) and the evaluation for carrying out above-mentioned migration.Furthermore online with gap When the situation that spacing is 15 μm, high thickness will be plated and be set as 10 μm.As a result, being formed in the Copper foil with carrier using embodiment 2 L/S=8 μm/12 μm, L/S=10 μm/10 μm, the situation of L/S=12 μm/8 μm of wiring when, migration generation rate difference in face It is 2/100,2/100,3/100.Also, using embodiment 3 Copper foil with carrier formed L/S=8 μm/12 μm, L/S=10 μm/ 10 μm, L/S=12 μm/8 μm, L/S=5 μm/10 μm, the situation of L/S=8 μm/7 μm of wiring when, migration generation rate point in face It Wei 1/100,1/100,2/100,1/100,3/100.

＜ determination conditions ＞

Threshold value：Initial stage resistance declines 60%

Minute：1000h

Voltage：60V

Temperature：85℃

Relative humidity：85%RH

(peel strength)

For the made appendix body with resin layer (wherein, having no resin layer when not forming the situation of resin layer) Copper foil, to being measured from the peel strength of resin base material for very thin layers of copper.Use BT base materials (Bismaleimide Triazine tree Fat, the GHPL-830MBT of gas chemistry limited liability company of Mitsubishi manufacture) it is used as resin base material, by its lamination in appendix body copper The resin layer side of foil carries out heating crimping under the conditions of the recommendation of gas chemistry limited liability company of Mitsubishi and makes copper-cover laminated Plate.Thereafter, after removing carrier, the circuit of width 10mm is made by wet etching, 10 surveys are respectively prepared in embodiment/comparative example Random sample product.Thereafter, the very thin layers of copper for forming circuit is removed, 90 degree of peel strengths is measured to 10 samples, find out peel strength Average value, maximum value, minimum value, the unevenness of peel strength ((maximum value-minimum value)/average value × 100 (%)).BT bases Material is representative conductor package substrate base material.Peel strength from the very thin layers of copper of BT base materials when BT base material laminations is excellent It is selected as 0.70kN/m or more, more preferably 0.85kN/m or more.

Claims (30)

1. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, and very thin copper The average value of the Rt of layer surface be using contact roughmeter according to JIS B0601-2001 be measured and be 2.0 μm with Under, and the standard deviation of Rt is 0.1 μm or less.

2. Copper foil with carrier according to claim 1, wherein the average value of the Rz on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 1.5 μm hereinafter, and the standard deviation of Rz is 0.1 μm or less.

3. Copper foil with carrier according to claim 1, wherein the average value of the Ra on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 0.2 μm hereinafter, and the standard deviation of Ra is 0.03 μm or less.

4. Copper foil with carrier according to claim 2, wherein the average value of the Ra on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 0.2 μm hereinafter, and the standard deviation of Ra is 0.03 μm or less.

5. Copper foil with carrier according to any one of claim 1 to 4, wherein the average value of the Rt on very thin layers of copper surface It is 1.0 μm or less.

6. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, very thin layers of copper table The average value of the Rt in face be using contact roughmeter according to JIS B0601-2001 be measured and be 2.0 μm hereinafter, and The standard deviation of Rt is 0.1 μm hereinafter, and meeting following A)~L) in one, binomial, three, four, five, six, Seven, eight, nine, ten, 11 or ten binomials,

A) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.5 μm hereinafter,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.4 μm hereinafter,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.3 μm hereinafter,

4:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.2 μm hereinafter,

5:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.0 μm hereinafter,

6:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.8 μm hereinafter,

7:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.5 μm hereinafter,

B) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.1 μm or more,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.3 μm or more,

C) 1 in the group being made of project below：

1:The standard deviation of the Rz on very thin layers of copper surface be 0.1 μm hereinafter,

2:The standard deviation of the Rz on very thin layers of copper surface be 0.068 μm hereinafter,

3:The standard deviation of the Rz on very thin layers of copper surface be 0.05 μm hereinafter,

D):The standard deviation of the Rz on very thin layers of copper surface is 0.01 μm or more,

E) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.8 μm hereinafter,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.5 μm hereinafter,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.3 μm hereinafter,

4:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.1 μm hereinafter,

5:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.0 μm hereinafter,

F) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.5 μm or more,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.6 μm or more,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.8 μm or more,

G) 1 in the group being made of project below：

1:The standard deviation of the Rt on very thin layers of copper surface be 0.060 μm hereinafter,

2:The standard deviation of the Rt on very thin layers of copper surface be 0.05 μm hereinafter,

H):The standard deviation of the Rt on very thin layers of copper surface is 0.01 μm or more,

I) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.2 μm hereinafter,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.18 μm hereinafter,

3:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.15 μm hereinafter,

J) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.05 μm or more,

3:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.12 μm or more,

4:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.13 μm or more,

K) 1 in the group being made of project below：

1:The standard deviation of the Ra on very thin layers of copper surface be 0.03 μm hereinafter,

2:The standard deviation of the Ra on very thin layers of copper surface be 0.026 μm hereinafter,

3:The standard deviation of the Ra on very thin layers of copper surface be 0.02 μm hereinafter,

L):The standard deviation of the Ra on very thin layers of copper surface is 0.001 μm or more.

7. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer person, and very thin The average value of the Ra on layers of copper surface be using contact roughmeter according to JIS B0601-1982 be measured and be 0.2 μm with Under, and the standard deviation of Ra is 0.03 μm or less.

8. Copper foil with carrier according to claim 7, wherein the average value of the Rz on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 1.5 μm hereinafter, and the standard deviation of Rz is 0.1 μm or less.

9. Copper foil with carrier according to claim 7, wherein the average value of the Rt on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-2001 and is 2.0 μm hereinafter, and the standard deviation of Rt is 0.1 μm or less.

10. Copper foil with carrier according to claim 8, wherein the average value of the Rt on very thin layers of copper surface is to utilize contact Formula roughmeter is measured according to JIS B0601-2001 and is 2.0 μm hereinafter, and the standard deviation of Rt is 0.1 μm or less.

11. Copper foil with carrier according to any one of claims 7 to 10, wherein the Ra's on very thin layers of copper surface is averaged Value is 0.15 μm or less.

12. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, very thin layers of copper The average value of the Ra on surface be using contact roughmeter according to JIS B0601-1982 be measured and be 0.2 μm hereinafter, And the standard deviation of Ra is 0.03 μm hereinafter, and meeting following A)~L) in one, binomial, three, four, five, six Item, seven, eight, nine, ten, 11 or ten binomials,

A) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.5 μm hereinafter,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.4 μm hereinafter,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.3 μm hereinafter,

4:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.2 μm hereinafter,

5:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.0 μm hereinafter,

6:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.8 μm hereinafter,

7:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.5 μm hereinafter,

B) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.1 μm or more,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.3 μm or more,

C) 1 in the group being made of project below：

1:The standard deviation of the Rz on very thin layers of copper surface be 0.1 μm hereinafter,

2:The standard deviation of the Rz on very thin layers of copper surface be 0.068 μm hereinafter,

3:The standard deviation of the Rz on very thin layers of copper surface be 0.05 μm hereinafter,

D):The standard deviation of the Rz on very thin layers of copper surface is 0.01 μm or more,

E) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 2.0 μm hereinafter,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.8 μm hereinafter,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.5 μm hereinafter,

4:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.3 μm hereinafter,

5:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.1 μm hereinafter,

6:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.0 μm hereinafter,

F) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.5 μm or more,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.6 μm or more,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.8 μm or more,

G) 1 in the group being made of project below：

1:The standard deviation of the Rt on very thin layers of copper surface be 0.1 μm hereinafter,

2:The standard deviation of the Rt on very thin layers of copper surface be 0.060 μm hereinafter,

3:The standard deviation of the Rt on very thin layers of copper surface be 0.05 μm hereinafter,

H):The standard deviation of the Rt on very thin layers of copper surface is 0.01 μm or more,

I) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.18 μm hereinafter,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.15 μm hereinafter,

J) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.05 μm or more,

3:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.12 μm or more,

4:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.13 μm or more,

K) 1 in the group being made of project below：

1:The standard deviation of the Ra on very thin layers of copper surface be 0.026 μm hereinafter,

2:The standard deviation of the Ra on very thin layers of copper surface be 0.02 μm hereinafter,

L):The standard deviation of the Ra on very thin layers of copper surface is 0.001 μm or more.

13. according to the Copper foil with carrier described in Claims 1-4,6 to 10, any one of 12, wherein very thin layers of copper is by thick Change is handled.

14. a kind of printing distributing board is made using the Copper foil with carrier described in any one of claim 1 to 13.

15. printing distributing board according to claim 14, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is not up to 20 μm, and the gap width between adjacent copper circuit is not up to 20 μm.

16. printing distributing board according to claim 14, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is 17 μm hereinafter, the gap width between the copper circuit of adjoining is 17 μm or less.

17. printing distributing board according to claim 14, wherein the spacing in line and gap is not up to 40 μm.

18. printing distributing board according to claim 14, wherein the spacing in line and gap is 34 μm or less.

19. a kind of printed circuit board is made using the Copper foil with carrier described in any one of claim 1 to 13.

20. printed circuit board according to claim 19, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is not up to 20 μm, and the gap width between adjacent copper circuit is not up to 20 μm.

21. printed circuit board according to claim 19, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is 17 μm hereinafter, the gap width between the copper circuit of adjoining is 17 μm or less.

22. printed circuit board according to claim 19, wherein the spacing in line and gap is not up to 40 μm.

23. printed circuit board according to claim 19, wherein the spacing in line and gap is 34 μm or less.

24. a kind of copper-cover laminated plate is manufactured using the Copper foil with carrier described in any one of claim 1 to 13.

25. a kind of manufacturing method of printing distributing board, it includes following steps：

The step of preparing the Copper foil with carrier and insulating substrate described in any one of claim 1 to 13；

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, by the step of carrier of above-mentioned Copper foil with carrier is removed Copper-cover laminated plate is formed,

Thereafter, circuit is formed by any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process method Step.

26. a kind of manufacturing method of printing distributing board, it includes following steps：

The above-mentioned very thin layers of copper side surface of Copper foil with carrier described in any one of claim 1 to 13 forms the step of circuit Suddenly；

In a manner of burying foregoing circuit the step of the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier forms resin layer；

In the step of forming circuit on above-mentioned resin layer；

After forming circuit on above-mentioned resin layer, above-mentioned carrier is removed；And

By removing above-mentioned very thin layers of copper after removing above-mentioned carrier, and make to be formed in being buried in for above-mentioned very thin layers of copper side surface The step of circuit of above-mentioned resin layer exposes.

27. the manufacturing method of printing distributing board according to claim 26, wherein form circuit on above-mentioned resin layer Step is to be fitted in another Copper foil with carrier on above-mentioned resin layer from very thin layers of copper side, using being fitted in the attached of above-mentioned resin layer Carrier copper foil forms the step of foregoing circuit.

28. the manufacturing method of printing distributing board according to claim 27, wherein be fitted in another on above-mentioned resin layer Copper foil with carrier is the Copper foil with carrier described in any one of claim 1 to 13.

29. the manufacturing method of the printing distributing board according to any one of claim 26 to 28, wherein in above-mentioned resin layer The step of upper formation circuit is by semi-additive process, subtractive process, part addition process or to improve any one of semi-additive process method It carries out.

30. the manufacturing method of the printing distributing board according to any one of claim 26 to 28 is further contained in stripping Before carrier, in the step of carrier side surface of Copper foil with carrier forms substrate.