CN108588766A - Copper foil with carrier - Google Patents

Abstract

The present invention relates to Copper foil with carrier.The present invention provides a kind of Copper foil with carrier suitably forming thin space.The Copper foil with carrier is had foil carriers, the peeling layer on foil carriers and the very thin layers of copper on peeling layer, the Rz of the very thin roughened processing of layers of copper, very thin layers of copper surface and is measured as 1.6 μm or less with contactless roughmeter.

Description

Copper foil with carrier

The application is application No. is 201380046519.7, and the applying date is September in 2013 11, 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 generally goes through following step and manufactures：It is then made copper-cover laminated with copper foil making insulating substrate After plate, conductive pattern is formed in copper-clad surface by etching.With the miniaturization of e-machine in recent years, high performance demand Increase and expand carry part high density structure dressization or signal high frequency, thus to printing distributing board requirement have conductor figure The miniaturization (thin space) of case or high frequency answer equity.

It is corresponding with thin spaceization, require recently thickness 9 μm or less, even thickness is in 5 μm of copper foils below, so And this its mechanical strength of very thin copper foil is low, it is easily rupturable in the manufacture of printing distributing board or generate fold, therefore develop Metal foil with thickness is used as carrier and across peeling layer by appendix body copper made of very thin layers of copper electro-deposition thereon Foil.After the surface of very thin layers of copper is fitted in insulating substrate and is thermally compressed, carrier is removed via peeling layer and is removed. In the very thin layers of copper exposed after resist forms circuit pattern, etched using Sulfuric-acid-hydrogen-peroxide system etching solution Very thin layers of copper is removed, this gimmick (MSAP is passed through：Modified-Semi-Additive-Process fine circuits are formed).

Herein, for the very thin copper of surface major requirement of the very thin layers of copper of the Copper foil with carrier as the commissure with resin The peel strength of layer and resin base material is sufficient, and this peel strength is in high-temperature heating, wet processed, welding, Chemical treatment Abundance is also remained Deng after.The method for improving the peel strength between very thin layers of copper and resin base material, it is however generally that be with following Method is representative：In very thin layers of copper after making a large amount of roughening particle be attached to profile (the concave-convex, coarse) increase on surface.

However, even in printing distributing board, if in partly leading with the needs for forming especially fine circuit pattern Body package substrate can then remain unwanted copper using the big very thin layers of copper of this profile (concave-convex, coarse) in circuit etch Particle, the problems such as will produce the defective insulation between circuit pattern.

Therefore, it has attempted not apply on the surface of very thin layers of copper using in No. WO2004/005588 (patent document 1) thick Change the Copper foil with carrier of processing as the Copper foil with carrier for fine circuits headed by conductor package substrate.Since its is low Adaptation (the stripping of the influence of profile (bumps, roughness, coarse), this very thin layers of copper for not applying roughening treatment and resin Intensity) compared with general copper foil for printed wiring board have the tendency that reduction.Therefore, it is necessary to further improve Copper foil with carrier.

Therefore, in Japanese Unexamined Patent Publication 2007-007937 bulletins (patent document 2) and Japanese Unexamined Patent Publication 2010-006071 public affairs It records in report (patent document 3) and is arranged in the face of appendix body ultrathin copper foil contacted with polyimides system resins substrate (then) Ni layers and/or Ni alloy-layers, setting chromate coating, Cr layers of setting and/or Cr alloy-layers, setting Ni layers and chromate coating, setting Ni layers and Cr layers.By the way that such surface-treated layer is arranged, polyimides system resins substrate is closely sealed strong with appendix body ultrathin copper foil Degree can be obtained required Bonding strength without the degree (miniaturization) of roughening treatment or reduction roughening treatment.In addition, also It records and antirust treatment is surface-treated or applied using 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

In the exploitation of Copper foil with carrier, ensure that the peel strength of very thin layers of copper and resin base material is considered as weight up to now Point.Therefore, thin spaceization is not inquired into fully yet, still there is improved space.Therefore the purpose of the present invention is to provide one Kind suitably forms the Copper foil with carrier of thin space.Specifically, the purpose of the present invention is to provide a kind of Copper foil with carrier, it can It is formed than being considered as using MSAP up to now and L/S=20 μm/20 μm finer wirings of the limit that can be formed.

In order to achieve the above objectives, present inventor etc. repeats to concentrate on studies, as a result, it has been found that, by making very thin copper Layer surface low roughness simultaneously forms fine roughening particle in very thin layers of copper, can form uniform and low roughness roughening treatment Face.Also, it was found that the Copper foil with carrier forms very effective fruit for thin space.

The present invention be based on above-mentioned opinion and complete winner is in one aspect a kind of Copper foil with carrier, have copper foil load Body, the peeling layer on foil carriers and the very thin layers of copper on peeling layer, the very thin roughened processing of layers of copper, pole The Rz on thin copper layer surface is measured with contactless roughmeter as 1.6 μm or less.

The present invention is a kind of Copper foil with carrier in another aspect, has foil carriers, on foil carriers Peeling layer and the very thin layers of copper on peeling layer, the very thin roughened processing of layers of copper, the Ra on very thin layers of copper surface is with non-contact It is 0.3 μm or less that formula roughmeter, which is measured,.

The present invention is a kind of Copper foil with carrier in another further aspect, has foil carriers, on foil carriers Peeling layer and the very thin layers of copper on peeling layer, very thin layers of copper is roughened processing, and the Rt on very thin layers of copper surface is connect with non- It is 2.3 μm or less that touch roughmeter, which is measured,.

In an embodiment of the Copper foil with carrier of the present invention, the Rz on very thin layers of copper surface is with contactless roughmeter Be measured is 1.4 μm or less.

In the another embodiment of the Copper foil with carrier of the present invention, the Ra on very thin layers of copper surface is with contactless roughness It is 0.25 μm or less that meter, which is measured,.

In the yet another embodiment of the Copper foil with carrier of the present invention, the Rt on very thin layers of copper surface is with contactless coarse It is 1.8 μm or less that degree meter, which is measured,.

In the yet another embodiment of the Copper foil with carrier of the present invention, very thin its Ssk of layers of copper surface is -0.3~0.3.

In the yet another embodiment of the Copper foil with carrier of the present invention, very thin its Sku of layers of copper surface is 2.7~3.3.

In the yet another embodiment of the Copper foil with carrier of the present invention, it is a kind of Copper foil with carrier, has copper foil load Body, the peeling layer on foil carriers and the very thin layers of copper on peeling layer, the very thin roughened processing of layers of copper, pole The surface area ratio on thin copper layer surface is 1.05~1.5.

In the yet another embodiment of the Copper foil with carrier of the present invention, the surface area ratio on very thin layers of copper surface is 1.05~ 1.5。

In the yet another embodiment of the Copper foil with carrier of the present invention, every 66524 μm of very thin layers of copper surface²Area Volume is 300000 μm³More than.

The present invention is a kind of copper-cover laminated plate in yet another aspect, is manufactured using the Copper foil with carrier of the present invention And winner.

The present invention is a kind of printing distributing board in yet another aspect, is manufactured using the Copper foil with carrier of the present invention And winner.

The present invention is a kind of printed circuit board in yet another aspect, is using the Copper foil with carrier person of being fabricated.

The present invention is a kind of manufacturing method of printing distributing board, it includes following step in yet another aspect：

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；And

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

Thereafter, semi-additive process (Modified Semi are improved by semi-additive process, subtractive process, part addition process or improvement Additive the step of either method in) forms circuit.

The present invention Copper foil with carrier formed suitable for thin space, such as can be formed than be considered as can using MSAP steps The finer wiring in L/S=20 μm of the limit of formation/20 μm, such as L/S=15 μm/15 μm of fine wiring.

Description of the drawings

Fig. 1：The SEM photograph in the faces very thin layers of copper M in embodiment 1 and embodiment 2.

Fig. 2：A~C is the specific embodiment of the manufacturing method for the printing distributing board for having used the Copper foil with carrier of the present invention From circuit plating-until removing photoresist the step of in distributing board section schematic diagram.

Fig. 3：D~F is the specific embodiment of the manufacturing method for the printing distributing board for having used the Copper foil with carrier of the present invention Until the laminated resin and the 2nd layer of Copper foil with carrier to laser trepanning the step of in distributing board section schematic diagram.

Fig. 4：G~I is the specific embodiment of the manufacturing method for the printing distributing board for having used the Copper foil with carrier of the present invention Self-forming through-hole filler until removing the 1st layer of carrier the step of in distributing board section schematic diagram.

Fig. 5：J~K is the specific embodiment of the manufacturing method for the printing distributing board for having used the Copper foil with carrier of the present invention From fast-etching until forming convex block-copper post the step of in distributing board section schematic diagram.

Specific implementation mode

1. carrier ＞ of ＜

Using copper foil as carrier for use in the present invention.For typical case, carrier is with rolled copper foil or electrolytic copper foil Form provides.It manufactures, presses on the rotating cylinder of titanium or stainless steel in general, electrolytic copper foil system makes copper be precipitated from copper sulfate bath electrolysis Prolong copper foil system to repeat to manufacture using the plastic processing and heat treatment of stack.As the material of copper foil, in addition to refined copper or Other than the copper of the high-purities such as oxygen-free copper, also can be used such as mix Sn copper, mix Ag copper, added with Cr, Zr or Mg copper alloy, add The copper alloy of the inferior series copper alloy of card added with Ni and Si etc. etc.Furthermore term " copper foil " in the present specification, is used alone When, also include the meaning of copper alloy 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 on the basis of effect, such as 12 μm or more can be set as.If however, blocked up, produce Cost improves, so generally preferable is set as 70 μm or less.Therefore, the thickness of carrier is typically 12~70 μm, more typically 18 ~35 μm.

2. peeling layer ＞ of ＜

Peeling layer is set on carrier.Can be well known to those skilled in the art in Copper foil with carrier as peeling layer Arbitrary peeling layer.Such as peeling layer be preferably by containing Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al or its etc. alloy, Or its etc. water and object or its etc. oxide or any one of organic matter more than layer formed.Peeling layer also can structure As multilayer.

In embodiments of the invention, peeling layer is constituted from carrier side by following layers, the layer be by Cr, Ni, Co, Any one of groups of elements of Fe, Mo, Ti, W, P, Cu, Al element constitute single metal layer or by be selected from Cr, Ni, Co, Fe, The alloy-layer that the elements of more than one in the groups of elements of Mo, Ti, W, P, Cu, Al is constituted, with lamination thereon by be selected from Cr, The layer that the water and object or oxide of the element of more than one in the groups of elements of Ni, Co, Fe, Mo, Ti, W, P, Cu, Al are constituted.

Peeling layer is preferably constituted with this 2 layers of Ni and Cr.When in this respect, carried respectively with copper foil with Ni layers and Cr layers The interface of body and the mode that connects with the interface of very thin layers of copper carry out lamination.

Peeling layer can for example, 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.To be preferably electroplated for the viewpoint of cost.

3. very thin layers of copper ＞ of ＜

Very thin layers of copper is set on peeling layer.Preferably very thin layers of copper can be by using copper sulphate, cupric pyrophosphate, amido The plating of the electrobath of sulfonic acid copper, copper cyanider etc. and formed, just can shape at higher current densities using common electrolytic copper foil For the aspect of copper foil, preferably copper sulphate is bathed.There is no particular restriction for the thickness of very thin layers of copper, usually thinner than carrier, such as It is 12 μm or less.It is typically 0.5~12 μm, more typically 2~5 μm.

The surface treatment ＞ of 4. roughening treatments of ＜ etc.

The surface of very thin layers of copper for example, by order to make the adaptation with insulating substrate become it is well equal applied it is thick Change processing and roughening treatment layer is set.Roughening treatment can for example, by forming roughening particle by copper or copper alloy in a manner of come into Row.For forming the viewpoint of thin space, roughening treatment layer is preferably by fine particle institute constitutor.It is roughened grain about being formed The plating conditions of the period of the day from 11 p.m. to 1 a.m, have if the copper concentration improved in current density, reduction plating solution or particle can be micro- if increasing coulomb amount The tendency of refinement.

Roughening treatment layer can be made of following electro-deposition grains, the electro-deposition grain be by be selected from by copper, nickel, phosphorus, tungsten, arsenic, molybdenum, The simple substance of any one of the group that chromium, cobalt and zinc are constituted contains any above alloy institute constitutor.

Again, after roughening treatment, offspring or three times particle are formed using nickel, cobalt, copper, the simple substance of zinc or alloy etc. And/or antirust coat and/or refractory layer, also further its surface can be applied at the surfaces such as chromic acid salt treatment, silane coupling processing Reason.That is, can be formed selected from by antirust coat, refractory layer, chromating layer and silane coupling processing on the surface of roughening treatment layer The layer of one or more of the group that layer is constituted.

For example, can have refractory layer and/or antirust coat on roughening treatment layer, on above-mentioned refractory layer and/or antirust coat Have chromating layer, can also have silane coupling process layer on above-mentioned chromating layer.Furthermore it does not limit and is formed The mutual sequence of above-mentioned refractory layer, antirust coat, chromating layer, silane coupling process layer, also can be in roughening treatment layer On form its equal layer in any order.

Grant the surface (be also known as " roughening treatment face ") of the very thin layers of copper after the various surface treatments of roughening treatment etc. in When being measured using contactless roughmeter, Rz (10 mean roughness) is set as 1.6 μm or less and is forming thin space Viewpoint on it is extremely advantageous.Rz is preferably 1.5 μm or less, more preferably 1.4 μm or less, still more preferably from 1.35 μm or less, again More preferably 1.3 μm or less, still more preferably from 1.2 μm or less, still more preferably from 1.0 μm or less, still more preferably from 0.8 μm with Under, still more preferably from 0.6 μm or less.However, if Rz becomes too small, can be reduced with the closing force of resin, so preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably from 0.2 μm or more.

Grant the surface (be also known as " roughening treatment face ") of the very thin layers of copper after the various surface treatments of roughening treatment etc. in When being measured using contactless roughmeter, Ra (arithmetic average roughness) is set as 0.30 μm or less and is forming thin space Viewpoint on it is extremely advantageous.Ra is preferably 0.27 μm or less, more preferably 0.26 μm or less, is more preferably 0.25 μm or less, more Preferably 0.24 μm or less, more preferably 0.23 μm or less, still more preferably from 0.20 μm or less, still more preferably from 0.18 μm with Under, still more preferably from 0.16 μm or less, still more preferably from 0.15 μm or less, still more preferably from 0.13 μm or less.However, if Ra becomes Must be too small, then it can be reduced with the closing force of resin, so preferably 0.005 μm or more, more preferably 0.009 μm or more, 0.01 μ M or more, 0.02 μm or more, more preferably 0.05 μm or more, be more preferably 0.10 μm or more.

Grant the surface (be also known as " roughening treatment face ") of the very thin layers of copper after the various surface treatments of roughening treatment etc. in When being measured using contactless roughmeter, by Rt be set as 2.3 μm or less formed thin space viewpoint on it is extremely advantageous. Rt is preferably 2.2 μm or less, preferably 2.1 μm or less, preferably 2.07 μm or less, more preferably 2.0 μm or less, is more preferably 1.9 μm or less, more preferably 1.8 μm or less, still more preferably from 1.5 μm or less, still more preferably from 1.2 μm or less, even more preferably It is 1.0 μm or less.However, if Rt becomes too small, can be reduced with the closing force of resin, so preferably 0.01 μm or more, more Preferably 0.1 μm or more, more preferably 0.3 μm or more, more preferably 0.5 μm or more.

Again, the surface for granting the very thin layers of copper after the various surface treatments of roughening treatment etc. is contactless coarse in utilizing Degree meter is when being measured, and Ssk (degree of skewness) is set as -0.3~0.3 in the viewpoint for forming thin space preferably.The lower limit of Ssk is excellent Be selected as -0.2 or more, more preferably -0.1 or more, more preferably -0.070 or more, more preferably -0.065 or more, more preferably - 0.060 or more, it is more preferably -0.058 or more, still more preferably from 0 or more.The upper limit of Ssk is preferably 0.2 or less.

Again, the surface for granting the very thin layers of copper after the various surface treatments of roughening treatment etc. is contactless coarse in utilizing Degree meter is when being measured, and Sku (kurtosis) is set as 2.7~3.3 in the viewpoint for forming thin space preferably.The lower limit of Sku is preferred It is 2.8 or more, more preferably 2.9 or more, more preferably 3.0 or more.The upper limit of Sku is preferably 3.2 or less.

In the present invention, the roughness parameter about Rz, the Ra on very thin layers of copper surface is according to JIS B0601-1994 profits It is measured with contactless roughmeter, about the roughness parameter of Rt, is connect using non-according to JIS B0601-2001 Touch roughmeter is measured, and is according to ISO25178draft using non-contact about the roughness parameter of Ssk, Sku Formula roughmeter is measured.

Furthermore the insulating substrate of the resins such as printing distributing board or copper-cover laminated plate etc. and the situation of very thin layers of copper surface then When, it can be removed by dissolving insulating substrate, and above-mentioned surface roughness (Ra, Rt, Rz) is measured to copper circuit or copper foil surface.

In order to form thin space, the volume for controlling roughening treatment face is also important on the etch quantity for reducing roughening particle layer. Volume herein refers to the value being measured using laser microscopes, for the body of the roughening particle present in evaluation roughening treatment face Long-pending index.In the bulky situation in roughening treatment face, have the tendency that the closing force of very thin layers of copper and resin is got higher.And And have the tendency that resistance to migration improves if the closing force if very thin layers of copper and resin is got higher.Specifically, utilizing laser microscopes It is measured, preferably every 66524 μm of roughening treatment face²Area volume is 300000 μm³More than, more preferably 350000 μm³With On.However, etch quantity increases if volume becomes too much, thin space can not be formed, therefore volume is preferably set as 500000 μm³With Under, more preferably it is set as 450000 μm³Below.

Further, in order to form thin space, the surface area ratio in roughening treatment face is controlled caused by ensuring fine roughening particle The adaptation with resin on it is also important.Surface area ratio herein refers to the value being measured using laser microscopes, and refers to The value of real area/area when measuring area and real area.Area refers to measuring reference area, and real area refers to surveying Determine the surface area in reference area.If surface area ratio becomes too much, dhering strength increases, but etch quantity can increase thus can not Thin space is formed, on the other hand, if surface area ratio becomes too small, is unable to ensure dhering strength, therefore preferably 1.05~ 1.5, preferably 1.07~1.47, it is preferably 1.09~1.4, more preferably 1.1~1.3.

5. resin layer ＞ of ＜

In the Copper foil with carrier of the present invention, very thin layers of copper that also can be after granting the various surface treatments of roughening treatment etc. Surface be further equipped with resin layer.For example, also can be in roughening treatment layer, refractory layer, antirust coat, chromating layer or silicon Has resin layer in alkane coupling process layer.Above-mentioned resin layer also can be insulating 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.So-called semi-hardened state (B-stage state), including following state：Even if touching its surface also without glutinous with finger Sense, can overlappingly take care of the insulating resin layer can cause sclerous reaction if further being heated.

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

Also, its 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, poly- Maleimide compound, Maleimide system resin, aromatic series Maleimide resin, polyethylene acetaldehyde tree Fat, amine ester resin (urethane resin), polyether sulfone (be also known as polyethersulphone, polyethersulfone), Polyether sulfone (being also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic series Polyamide resin lipopolymer, rubbery resin, polyamine, aromatic polyamine, polyamide-imide resin, rubber modified asphalt mixtures modified by epoxy resin Fat, phenoxy resin, carboxyl modification acrylonitrile-butadiene resin, polyphenylene oxide, double Maleimides three mouthfuls of well resins, thermmohardenings Property polyphenylene oxide resin, cyanate ester system resin, the acid anhydrides of carboxylic acid, the acid anhydrides of polybasic carboxylic acid, the line with crosslinkable functional group Bis- (the 4- cyanato-s phenyl) propane of shaped polymer, polyphenylene oxide resin, 2,2-, phosphorous phenolic compounds, manganese naphthenate, 2,2- are bis- (4- glycidyl phenyls) propane, polyphenylene oxide-cyanate ester based resin, siloxanes modification polyamide-imide resin, hydrocyanic ester tree Fat, phosphine nitrence system resin, rubber modified polyamide-imide resin, isoprene, hydrogenation type polybutadiene, polyvinyl butyral, Phenoxy group, macromolecule epoxy resin, aromatic polyamide, fluororesin, bis-phenol, block copolymerized polyimide resin and hydrocyanic ester tree Fat.

Also, above-mentioned epoxy resin, which is intramolecular, has 2 or more epoxy group persons, as long as and to can be used for electrically-electronics material Expect purposes person, then can especially use without problems.It shrinks also, above-mentioned epoxy resin preferably has 2 or more using intramolecular Glyceryl compound carries out epoxy resin made of epoxidation.It is selected from also, can be used in mixed way：Bisphenol A type epoxy resin, bis-phenol F types epoxy resin, bisphenol-s epoxy resin, bisphenol-A D-ring oxygen resin, phenolic resin varnish type epoxy resin, cresol novolak Type epoxy resin, alicyclic epoxy resin, bromination (brominated) epoxy resin, phenol 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 type epoxy tree Fat, glycidyl amine type epoxy resin, isocyanuric acid three-glycidyl ester, N, the glycidyl amines such as N- diglycidylanilines The epihydric alcohol ester compounds such as compound, tetrahydrophthalic acid 2-glycidyl ester, phosphorous epoxy resin, biphenyl type epoxy The group of resin, biphenyl phenolic resin varnish type epoxy resin, trihydroxy benzene methylmethane type epoxy resin, tetraphenyl ethane type epoxy resin In it is one kind or two or more, or the hydrogenation body or halogenation body of above-mentioned epoxy resin can be used.

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 epoxy resin that the form of the derivative of object obtains.

The epoxy obtained in the form of the derivative from the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies Resin is that the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies is made to be reacted with naphthoquinones or hydroquinone and followingization is made After compound represented by formula 1 (HCA-NQ) or chemical formula 2 (HCA-HQ), make the part of its OH base reacted with epoxy resin and Phosphorous epoxy resin is made and winner.

[chemical formula 1]

[chemical formula 2]

Using above compound as above-mentioned E ingredients obtained by raw material, that is, phosphorous epoxy resin is preferably used in mixed way a kind Or 2 kinds of following compounds, the compound have the knot represented by any one of 3~chemical formula of chemical formula 5 as shown below Structure formula.Its reason is the excellent in stability of the resin quality under semi-hardened state, while flame retardancy effect is high.

[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 Following brominated epoxy resins of the above epoxy group, the brominated epoxy resin are that have with the shape of the derivative from tetrabromobisphenol A Formula obtain chemical formula 6 represented by structural formula brominated epoxy resin and have represented by chemical formula 7 as shown below The brominated epoxy resin of structural formula.

[chemical formula 6]

[chemical formula 7]

As above-mentioned Maleimide system resin or aromatic series Maleimide resin or Maleimide compound or gather Well known Maleimide system resin or aromatic series Maleimide resin or Malaya's acyl can be used in Maleimide compound Amine compounds or poly- Maleimide compound.For example, as Maleimide system resin or aromatic series Maleimide resin Or Maleimide compound or poly- Maleimide compound, it can be used：The double Maleimides of 4,4'- diphenyl methanes gather Phenylmethane Maleimide stretches the double Maleimides of phenyl, bisphenol-A diphenyl ether double Maleimide, 3,3'- dimethyl- 5,5'- diethyl -4,4'- diphenyl methanes double Maleimide, 4- methyl-1s, 3- stretch phenyl double Maleimide, 4,4'- bis- The double Maleimides of phenylate, 4,4'- diphenyl sulfones double Maleimide, bis- (the 3- Maleimides phenoxy group) benzene of 1,3-, 1,3- Bis- (4- Maleimides phenoxy group) benzene and to make above compound and above compound or other compounds be polymerized poly- Close object etc..Also, above-mentioned Maleimide system resin can be the aromatic series Malaya that intramolecular has 2 or more Maleimide bases Amide resin also can be to make intramolecular with the aromatic series Maleimide resin and polyamine of 2 or more Maleimide bases 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 by bis-phenol and divalent epoxy resin winner is closed by reaction.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, The quinones such as 4,4' dihydroxy diphenyl, HCA (miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies) and hydroquinone, naphthoquinones The bis-phenol etc. that the form of the addition product of class 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 The organic solvent for the temperature that solution is 50 DEG C~200 DEG C in boiling point.If specifically illustrating the so-called threadiness with functional group herein Polymer 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 amine ester system resin can be used As crosslinking agent.

Well known rubbery resin can be used in above-mentioned rubbery resin.For example, above-mentioned rubbery resin 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 Glue, isoprene rubber etc..Further, 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, amine ester rubber etc. have heat resistance is also useful.About such rubbery resin, in order to Aromatic polyamide resin or polyamide-imide resin react and manufacture copolymer, and more satisfactory is to have various officials in two ends It can base person.In particular, the use of CTBN (carboxyl terminal butadiene- nitrile) being useful.If also, being also among acrylonitrile butadiene rubber Carboxyl modifies body, then can get epoxy resin and cross-linked structure, and improves the pliability of the resin layer after hardening.Change as carboxyl Carboxyl terminal nitrile rubber (CTBN), carboxyl terminal butadiene rubber (CTB), carboxyl modification nitrile rubber (C- can be used in plastid NBR)。

As above-mentioned polyamide-imide resin, well known polyimide amide resin can be used.Also, as above-mentioned polyamides Imines amide resin can be used for example：By in N- methyl -2- Pyrrolizidines ketone and/or DMAC N,N' dimethyl acetamide equal solvent Trimellitic anhydride, benzophenone tetracarboxylic anhydride and 3 are heated, 3- dimethyl -4,4- biphenyl diisocyanate and the resin that obtains, Or by heating trimellitic anhydride, diphenyl in N- methyl -2- Pyrrolizidines ketone and/or DMAC N,N' dimethyl acetamide equal solvent Methane diisocyanate and carboxyl terminal acrylonitrile-butadiene rubber and winner.

It is denaturalized polyamide-imide resin as above-mentioned rubber, well known rubber modified polyamidoimide tree can be used Fat.Rubber modified polyamide-imide resin is to make polyamide-imide resin and rubbery resin reaction and obtain 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 nitrence system resin, well known phosphine nitrence system resin can be used.Phosphine nitrence system's resin system is with phosphorus and nitrogen For the resin containing phosphine nitrence with double bond of constitution element.Phosphine nitrence system resin can cooperateing with by nitrogen in molecule and phosphorus Effect, and flame retardant property is improved tremendously.Also, not with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative Together, steadily exist in resin, and obtain the effect for the generation for preventing electron transfer.

As above-mentioned fluororesin, well known fluororesin can be used.Also, as fluororesin, can be used for example 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 heat among (polychlorotrifluoroethylene (borontrifluoride)), polyarylsulfone (PAS), aromatic polysulphides and aromatic polyether The fluororesin etc. that plastic resin is constituted with fluororesin.

Also, above-mentioned resin layer can also contain hardening of resin agent.As hardening of resin agent, well known hardening of resin can be used Agent.For example, as hardening of resin agent, it can be used amines, bisphenol-A, the brominations such as dicyanodiamide, imidazoles, aromatic amine double The acid anhydrides such as novolaks class, the phthalate anhydrides such as the phenols such as phenol A, phenol system novolac resin and cresol novolac resin, connection Benzene-type phenol resin, phenol aralkyl type phenol resin etc..Also, above-mentioned resin layer can also contain one kind or two or more above-mentioned hardening of resin Agent.Such curing agent is especially effective to 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- undecylimidazoles, 2- heptadecylimidazoles, 2- ethyls- 4-methylimidazole, 2- phenyl -4-methylimidazole, 1- cyano ethyl -2- undecylimidazoles, 1- cyano ethyl -2- ethyl -4- methyl Imidazoles, 1- cyano ethyl -2- phenylimidazoles, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethyls Imidazoles etc. can be used alone or as a mixture.

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 improve the resistance to hygroscopicity of the resin layer of semi-hardened state, make length in which can dramatically Phase excellent storage stability.The reason is that imidazoles are the performance catalytic action persons in the hardening of epoxy resin, hardening The initial stage of reaction plays 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 also 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 also contain catalysts.As catalysts, well known catalysts can be used.Example Such as, as catalysts, Crushing of Ultrafine silica, antimony trioxide etc. can be used.

The acid anhydrides of above-mentioned polybasic carboxylic acid is preferably the ingredient to play a role as the curing agent of epoxy resin.Also, above-mentioned The acid anhydrides of polybasic carboxylic acid is preferably phthalate anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, tetrahydroxy benzene two Formic anhydride, hexahydroxybenzene dicarboxylic acid anhydride, methyl hexahydroxybenzene dicarboxylic acid anhydride, resistance to ground acid, the resistance to ground acid of methyl.

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.It is formed also, above-mentioned polyethylene acetaldehyde resin can be its intramolecular importing carboxyl, amido or unsaturated double-bond Person.

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 is using 4,4'- two aminodiphenylmethanes, bis- amido diphenyl sulfones of 3,3'-, isophthalic diformazan Amine, 3,3'- diaminodiphenyl ethers etc..Also, dicarboxylic acids is using phthalic acid, isophthalic acid, terephthalic acid (TPA), fumaric acid Deng.

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 in be processed into the copper foil after copper-cover laminated plate be etched plus Working hour is not damaged and user due to 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) The resin layer of layer (so-called " hard resin-layer " means the resin layer of hardened mistake) and semi-hardened resin layer.Above-mentioned hardening resin Polyimide resin that layer also can be 0ppm/ DEG C~25ppm/ DEG C by coefficient of thermal expansion, such is answered at polyamide-imide resin Any resin component in 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 also can be 40ppm/ DEG C or less.The glass transition temperature of above-mentioned hard resin-layer also can be 300 DEG C or more.Also, above-mentioned semihard It can be former using Maleimide system resin or aromatic series Maleimide resin to change resin layer.To form above-mentioned half The resin combination of hard resin-layer is preferably comprising Maleimide system resin, epoxy resin, with crosslinkable functional group Linear polymer.Epoxy resin recorded in well known epoxy resin or this specification can be used in epoxy resin.Also, conduct Public affairs can be used in Maleimide system resin, aromatic series Maleimide resin, the linear polymer with crosslinkable functional group Maleimide system resin, aromatic series Maleimide resin, the linear polymer with crosslinkable functional group known, or on State Maleimide system resin, aromatic series Maleimide resin, the linear polymer with crosslinkable functional group.

Also, in a kind of Copper foil with carrier with resin layer manufacturing purposes suitable for stereo shaping printing distributing board of offer When situation, above-mentioned hard resin-layer is preferably hardened with flexible high polymer layer.Above-mentioned high molecular polymerization Nitride layer is preferably made of the resin of the glass transition temperature with 150 DEG C or more for tolerable firmly solder installation steps Person.Above-mentioned high polymer layer is preferably by polyamide, polyethersulfone resin, Nomex resin, phenoxy resin, gathers 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 system resin, phenol resin, amine Appointing in ester resin is one kind or two or more.Also, the asphalt mixtures modified by epoxy resin that it is 10 μm~50 μm by thickness that above-mentioned semi-hardened resin layer, which is preferably, Fat composition 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 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 nitrence system resin or mixing it is such made of resin contain The nonflammable resin of phosphorus.

D ingredients：By have be dissolvable in water boiling point be 50 DEG C~200 DEG C range solvent in property liquid rubber at Divide rubber modified polyamide-imide resin made of denaturation.

E ingredients：Hardening of resin agent.

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

As the phosphorous epoxy resin of C ingredients, above-mentioned phosphorous epoxy resin can be used.Also, the phosphine nitrogen as C ingredients Above-mentioned phosphine nitrence system resin can be used in alkene system resin.

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.

Solvent is added in resin combination illustrated above and is used as resin varnish, and forms thermosetting resin layer conduct The following layer of printing distributing board.The resin varnish lies in above-mentioned resin combination and adds solvent, by resin solid content component amount It is prepared as the range of 30wt%~70wt%, when being measured according to the MIL-P-13949G in MIL standards, resin stream can be formed The semi-hardened resin film for the range that momentum is 5%~35%.Well known solvent or above-mentioned solvent can be used in solvent.

Above-mentioned resin series of strata sequentially have the 1st thermosetting resin layer from copper foil side and are located 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 use be mixed with any one of polyimide resin, polyether sulfone, polyphenylene oxide or Two or more resin component and former.Above-mentioned 2nd thermosetting resin layer can be former using epoxy resin ingredient. The thickness t1 (μm) of above-mentioned 1st thermosetting resin layer by the roughening surface roughness of Copper foil with carrier preferably in being set as Rz (μ When the thickness of the 2nd thermosetting resin layer m), being set as t2 (μm), t1 meets the thickness of the condition of Rz ＜ t1 ＜ t2.

Above-mentioned resin layer can be in framework material containing the prepreg for being soaked with resin.The tree being impregnated in above-mentioned framework material Fat is 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 aromatic polyamide fibre or glass fibre or Wholly aromatic polyester fiber.Above-mentioned skeleton material Material is preferably the nonwoven fabric or woven fabric of aromatic polyamide fibre or glass fibre or Wholly aromatic polyester fiber.Also, above-mentioned full virtue Fragrant adoption ester fiber is preferably the Wholly aromatic polyester fiber that fusing point is 300 DEG C or more.So-called above-mentioned fusing point is 300 DEG C or more Wholly aromatic polyester fiber refers to using fiber made of the referred to as resin manufacture of so-called liquid crystal polymer, and the polymerizable mesogenic Object is using 2- hydroxyl -6- naphthoic acids and to the polymer of Para Hydroxy Benzoic Acid as principal component.The Wholly aromatic polyester fiber has Low-k, low dielectric loss tangent, therefore there is excellent performance as the constituent material of electrical insulation layer, it can be with glass Fiber and aromatic polyamide fibre are used in the same manner.

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 to use the silicon such as well known amido system, epoxy Alkane coupling agent or above-mentioned silane coupling agent.

Also, above-mentioned prepreg can be using nominal thickness be 70 μm of aromatic polyamide fibres or glass fibre below not Woven fabric or nominal thickness are to be presoaked made of impregnation thermosetting resin in the framework material that 30 μm of glass cloth below are constituted Body.

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

Above-mentioned resin layer can also 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) also can be powdery.When dielectric substance (dielectric substance filler) is the situation of powdery, Jie It is 0.01 μm~3.0 μm that the powder characteristics of electric body (dielectric substance filler), which must be grain size first, preferably 0.02 μm~2.0 μm Range.So-called grain size herein refers to being dissipated according to laser diffraction since powder forms 2 times certain state of aggregations each other The measured value for penetrating formula determination of particle size distribution or BET method etc. speculates in the indirect determination of average grain diameter etc nothing due to precision is poor Method uses, so dielectric substance (dielectric substance filler) is directly observed using scanning electron microscope (SEM), by the sem photomicrograph picture The average grain diameter of parsing and acquisition.In this part specification, grain size at this time is expressed as DIA.Furthermore make in this part specification The image analysis of the powder for the dielectric substance (dielectric substance filler) observed with scanning electron microscope (SEM) is to use Asahi The IP-1000PC of Engineering limited liability companies manufacture, is set as roundness threshold 10, overlapping degree 20 and carries out round particle Parsing, and find out average grain diameter DIA.

Pass through the scheme of above-mentioned implementation, it is possible to provide the inner layer core material can be improved in a kind of following Copper foil with carrier The adaptation on internal layer circuit surface and the resin layer containing dielectric substance has low dielectric loss tangent with containing to be formed The resin layer of the dielectric substance of capacitor circuit 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 Methyl ether, dimethylformamide, dimethylacetylamide, cyclohexanone, ethyl Sai Lusu, N- methyl -2- Pyrrolizidines ketone, N, N- dimethyl Resin liquid (resin varnish) is made in acetamide, n,N-Dimethylformamide equal solvent, for example, by print roll coating method by its 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 coupling agent On layer, then optionally it is thermally dried removal solvent and becomes B-stage state.As long as drying is 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 flow when being measured according to the MIL-P-13949G in MIL standards For the semi-hardened resin film of 5%~35% range.

In present specification, so-called resin flow means according to the MIL-P-13949G in MIL standards, will set certainly The copper foil with resin that fat thickness is set as 55 μm takes 4 10cm square samples, in the state (product that 4 samples overlap Layer body) under, in 171 DEG C of press temperature, pressing pressure 14kgf/cm², be bonded under conditions of 10 minutes pressing times, according to The resin of measurement at this time flows out obtained by weight as a result, the value calculated based on number 1.

[mathematical expression 1]

Copper foil with carrier (Copper foil with carrier for the having resin) system for having above-mentioned resin layer is used with following aspect：It will Overall thermal is crimped after overlapping with base material and makes the resin layer thermmohardening by the 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 set 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 preimpregnation material is not used completely, Also copper-cover laminated plate can be manufactured.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：Adhesion reduces, in the feelings for being not inserted into preimpregnation material When this being had the Copper foil with carrier of resin laminated on the base material for having inner layer material under condition, it is difficult to ensure the electricity with inner layer material Layer insulation between road.On the other hand, if the thickness of resin layer has following situation than 120 μ m-thicks：It is difficult to be coated at 1 time The resin layer of target thickness is formed in step, and needs extra fee of material and number of steps, therefore economically becomes unfavorable.

Furthermore in being used for the Copper foil with carrier with resin layer to manufacture situation in very thin multi-layer printed circuit board When, it, can when the thickness of above-mentioned resin layer is set as 0.1 μm~5 μm, more preferably 0.5 μm~5 μm, more preferably 1 μm~5 μm The thickness of multi-layer printed circuit board is reduced, so preferably.

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, semi-hardened resin layer is preferably 0.1 μm~120 μm, preferably 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 μ M~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 μm, 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, it is difficult to The case where manufacturing very thin multi-layer printed circuit board, if not having following situation up to 5 μm：Though being easy to form very thin multilayer print Brush distributing board, but will produce the insulating layer i.e. resin layer between the circuit of internal layer and become too thin, and make the insulation between the circuit of internal layer The unstable tendency of property.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 Situation.Conversely, if hardening resin layer thickness is more than 20 μm, there is the effect that the resin layer by hardened mistake is brought not carry especially High situation, total thickness of insulating layer 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, be arranged preferably on very thin layers of copper refractory layer and/or antirust coat and/or chromating layer and/ Or after silane coupling process layer, tree is formed on the refractory layer or antirust coat or chromating layer or silane coupling process layer Lipid layer.

Furthermore the thickness of above-mentioned resin layer refers to by observing being averaged for the thickness measured by section in arbitrary 10 points Value.

Further, another product form of the Copper foil with carrier as this with resin, also can be coating above-mentioned with resin layer In very thin layers of copper or above-mentioned refractory layer, antirust coat or above-mentioned chromating layer or above-mentioned silane coupling process layer on simultaneously After being made for semi-hardened state, then carrier is removed, and is made in the form of the copper foil with resin there is no carrier It makes.

6. Copper foil with carrier ＞ of ＜

In this way, manufacture has foil carriers, the peeling layer on foil carriers, the very thin copper on peeling layer The Copper foil with carrier of layer and arbitrary resin layer.The application method of Copper foil with carrier itself is well known to dealer, such as can be by pole The surface of thin copper layer fits in paper base material phenol resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth- Paper composite base material epoxy resin, glass cloth-glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester Insulating substrates such as film, polyimide film and after being thermally compressed, remove carrier and form copper-cover laminated plate, will be then in insulation base The very thin layers of copper of plate is etched to target conductor pattern, finally manufactures printing distributing board.Further, by being carried in printing distributing board Electronic component class, and complete printed circuit board.Hereinafter, indicating several printing distributing boards using the Copper foil with carrier for having the present invention Manufacturing step embodiment.

In one of the manufacturing method of printing distributing board of present invention embodiment, including following step：Prepare the present invention Copper foil with carrier and the step of insulating substrate；The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；So that very thin copper The mode of layer side and insulating substrate opposite direction by above-mentioned Copper foil with carrier with after insulating substrate lamination, through by above-mentioned Copper foil with carrier Carrier remove the step of and form copper-cover laminated plate, thereafter, pass through semi-additive process, improve improve semi-additive process, part addition process And any one of subtractive process forms the step of circuit.Insulating substrate can also be set as internal layer circuit entrance.

In the present invention, so-called semi-additive process refers in carrying out relatively thin electroless plating on insulating substrate or copper foil seed layer It applies, after forming pattern, using plating and etches the method for forming conductive pattern.

Therefore, in the embodiment using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including Following 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；

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；

In the insulating substrate exposed by using the above-mentioned very thin layers of copper of etching removal or there are resins when resin layer The step of layer setting through-hole and/or blind hole；

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

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

The step of plating resist is set on above-mentioned electroless plating coating；

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

There is the step of electroplated layer is arranged in the region of foregoing circuit in the formation for eliminating above-mentioned plating resist；

The step of removing above-mentioned plating resist；And

The step of electroless plating coating in the region other than the region of foregoing circuit is formed with by removals such as fast-etchings.

In the another embodiment using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including following 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；

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；

In the insulating substrate exposed by using the above-mentioned very thin layers of copper of etching removal or there are resins when resin layer The step of electroless plating coating is arranged in layer surface；

The step of plating resist is set on above-mentioned electroless plating coating；

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

There is the step of electroplated layer is arranged in the region of foregoing circuit in the formation for eliminating above-mentioned plating resist；

The step of removing above-mentioned plating resist；And

The electroless plating coating in the region other than the region of foregoing circuit and very thin is formed with by removals such as fast-etchings The step of layers of copper.

In the present invention, so-called improvement improves semi-additive process, refers to lamination metal foil on the insulating layer, is protected by plating resist Inverter circuit forming portion is protected, after the layers of copper that circuit forming portion is thickened by plating, removes photoresist, is utilized in (quick) etching removal The metal foil other than circuit forming portion is stated, thus in the method for forming circuit on insulating layer.

Therefore, in an embodiment of the manufacturing method of the printing distributing board using the present invention for improving semi-additive process In, including following 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 through-hole and/or blind hole is arranged with insulating substrate in the very thin layers of copper removed above-mentioned carrier and exposed；

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

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

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

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

The step of removing above-mentioned plating resist；And

The step of very thin layers of copper exposed by removing above-mentioned plating resist using fast-etching removal.

In the another embodiment using the manufacturing method of the printing distributing board for the present invention for improving semi-additive process, Including following 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；

The step of plating resist is set on the very thin layers of copper that the above-mentioned carrier of stripping exposes；

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

There is the step of electroplated layer is arranged in the region of foregoing circuit in the formation for eliminating above-mentioned plating resist；

The step of removing above-mentioned plating resist；And

The step of very thin layers of copper in the region other than the region of foregoing circuit is formed with by removals such as fast-etchings.

In the present invention, so-called part addition process refers to the substrate made of conductor layer is arranged, optionally passes through through-hole or auxiliary It helps on substrate made of the hole of hole (via hole) and assigns catalyst core, be etched and form conductor circuit, optionally set After setting solder resist or plating resist, is handled by electroless plating on above-mentioned conductor circuit and through-hole or via hole etc. are increased Thickness, the method for thus manufacturing printing distributing board.

Therefore, in the embodiment using the manufacturing method of the printing distributing board of the present invention of part addition process, packet Containing following 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 through-hole and/or blind hole is arranged with insulating substrate in the very thin layers of copper removed above-mentioned carrier and exposed；

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

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

In the step of very thin layers of copper surface setting removed above-mentioned carrier and exposed etches resist；

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

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

The step of removing above-mentioned etching resist；

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 Agent core and the above-mentioned insulating substrate surface exposed, the step of solder resist or plating resist are set；And

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

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

Therefore, in using one of the manufacturing method of printing distributing board of the present invention of subtractive process embodiment, including under State 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 through-hole and/or blind hole is arranged with insulating substrate in the very thin layers of copper removed above-mentioned carrier and exposed；

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

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

In the step of electroplated layer is arranged in the surface of above-mentioned electroless plating coating；

In the step of etching resist is arranged in the surface of above-mentioned electroplated layer and/or above-mentioned very thin layers of copper；

The step of above-mentioned etching resist 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 electroplated layer, and the step of forming circuit；And

The step of removing above-mentioned etching resist.

In the another embodiment using the manufacturing method of the printing distributing board of the present invention of subtractive process, including following steps 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 through-hole and/or blind hole is arranged with insulating substrate in the very thin layers of copper removed above-mentioned carrier and exposed；

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

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

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

In the step of electroplated layer is arranged in the surface for the above-mentioned electroless plating coating for not forming shade；

In the step of etching resist is arranged in the surface of above-mentioned electroplated layer and/or above-mentioned very thin layers of copper；

The step of above-mentioned etching resist 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 etching resist.

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 of the Copper foil with carrier using the present invention is explained in detail using schema Specific embodiment.Furthermore it herein, is said by taking the Copper foil with carrier with the very thin layers of copper for being formed with roughening treatment layer as an example Bright, 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 The manufacturing method of following printing distributing boards.

First, as shown in Fig. 2-A, preparing surface has the Copper foil with carrier for the very thin layers of copper for being formed with roughening treatment layer (the 1st layer).

Secondly, as shown in fig. 2-b, it is coated with photoresist on the roughening treatment layer of very thin layers of copper, is exposed, develops, it will Photoresist is etched to set shape.

Then, as shown in Fig. 2-C, after forming circuit plating, photoresist is removed, by the way that specific shape is consequently formed Circuit coating.

Then, as shown in Fig. 3-D, in very thin layers of copper (in a manner of burying circuit coating) in a manner of coating circuit coating Upper setting is embedded to resin 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 Fig. 3-E, carrier is removed from the 2nd layer of Copper foil with carrier.

Then, as shown in Fig. 3-F, laser trepanning is carried out in the commitment positions of resin layer, circuit coating is made to expose and be formed Blind hole.

Then, as shown in Fig. 4-G, the through-hole filler of embedment copper is formed in blind hole.

Then, as shown in Fig. 4-H, on through-hole filler, circuit coating is formed in a manner of above-mentioned Fig. 2-B and Fig. 2-C.

Then, as shown in Fig. 4-I, carrier is removed from the 1st layer of Copper foil with carrier.

Then, as shown in Fig. 5-J, the very thin layers of copper on two surfaces is removed by fast-etching, the circuit in resin layer is made to plate Expose on the surface of layer.

Then, as shown in Fig. 5-K, convex block is formed on the circuit coating in resin layer, copper post is formed on the solder.Such as This makes 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, 1 layer is further formed on the 2nd layer of circuit that can be represented by Fig. 4-H Or multilayer circuit, the either method in semi-additive process can be improved by semi-additive process, subtractive process, part addition process or improvement and formed Such circuit.

Also, Copper foil with carrier used in above-mentioned first layer also can have base in the carrier side surface of the Copper foil with carrier Plate.By having the substrate or resin layer, it is supported and becomes difficult to generate fold using the Copper foil with carrier in first layer, therefore Has the advantages that productivity raising.Furthermore as long as aforesaid substrate is with Copper foil with carrier used in the above-mentioned first layer of support Effect person, then whole substrates all can be used.For example, as aforesaid substrate, can be used recorded in present specification Carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metallic plate, metal foil, the plate of inorganic compound, nothing The foil of the foil of machine compound, the plate of organic compound, organic compound.

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 the step of above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier forms resin layer before, more preferably It is formed the step of above-mentioned very thin layers of copper side surface of Copper foil with carrier forms circuit before.

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).This In 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 implementing roughening treatment etc. Indicate that it is surface-treated the aberration of layer surface when the situation of various surface treatments.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 the aberration Δ E ﹡ ab based on JISZ8730 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, and are made The overall target indicated with the L ﹡ a ﹡ b colour systems based on JIS Z8730, 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.

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 that copper and nickel, cobalt, tungsten, molybdenum are formed when the situation of roughening treatment layer is arranged The electric field liquid of more than one elements, 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 the situation of roughening treatment layer is not arranged in the surface of very thin layers of copper, can pass through Using the plating bath of the 2 times or more for a concentration of other elements for making Ni, at very thin layers of copper or refractory layer or antirust coat or chromate The surface for managing layer or silane coupling process layer, to be set lower than existing current density (0.1~1.3A/dm²) and increase processing The mode of time (20 seconds~40 seconds) to plating Ni alloys (such as plating Ni-W alloys, plating Ni-Co-P alloys, plating Ni-Zn alloys) into Row handles and reaches.

If the aberration Δ E ﹡ ab based on JISZ8730 on very thin layers of copper surface are 45 or more, in such as Copper foil with carrier When very thin layers of copper circuit forming surface, the contrast of very thin layers of copper and circuit is clear, and as a result visibility becomes good, can precision it is good The position alignment of circuit is carried out well.The aberration Δ E ﹡ ab based on JISZ8730 on very thin layers of copper surface are preferably 50 or more, more Preferably 55 or more, still more preferably from 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 When the situation of the aberration on the surface of silane coupled layer, it is apparent from the contrast of circuit coating, visibility is good.Therefore, exist It, can be precisely in set position shape in manufacturing step represented by such as Fig. 2-C of printing distributing board as described above At circuit coating.Also, according to the manufacturing method of printing distributing board as described above, formation makes circuit coating be embedded in resin layer Constitute, thus represented by such as Fig. 5-J when removing very thin layers of copper by fast-etching, pass through resin layer protect circuit plating Layer, and its shape is kept, thus it is easy to form fine circuits.Also, in order to protect circuit coating by resin layer, and improve resistance to move Shifting property, the well conducting of the wiring of suppression circuit.Therefore, it is easy to form fine circuits.Also, in such as Fig. 5-J and Fig. 5-K institutes table When removing very thin layers of copper by fast-etching as showing, the exposed surface of circuit coating is formed as the shape being recessed from resin layer, therefore It is easy respectively at forming convex block on the circuit coating, and then forms copper post thereon, and improve manufacture efficiency.

Furthermore it is embedded to resin (Resin) and well known resin, prepreg can be used.Such as BT (double Maleimides can be used Three mouthfuls of wells) 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, the present invention is described in more detail in embodiment through the invention, but the present invention is not by such embodiment Any restriction.

1. the manufacture of Copper foil with carrier

1 ＞ of ＜ embodiments

The electrolytic copper foil (JTC of JX days mine days stone metal company manufacture) for preparing the strip of 35 μm of thickness is carried as copper foil Body.To the glassy surface of the copper foil, it is electroplated under the following conditions using the continuous plating wiring of roll-to-roll type, is consequently formed 4000 μg/dm²Adhesion amount Ni layers.

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：4~6

Bath temperature：50~70 DEG C

Current density：3~15A/dm²

After washing and pickling, then, on the continuous plating wiring of roll-to-roll type, by 11 μ g/dm²Adhesion amount Cr layers It carries out electrolytic chromate processing under the following conditions and it is made to be attached on Ni layers.

Electrolytic chromate processing

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

pH：3~4

Liquid temperature：50~60 DEG C

Current density：0.1~2.6A/dm²

Coulomb amount：0.5~30As/dm²

Then, it continuously plates on wiring in roll-to-roll type, is electroplated using the following conditions, formed on Cr layers therefrom thick 3 μm of very thin layers of copper manufactures Copper foil with carrier.Furthermore the thickness for also manufacturing very thin layers of copper in the present embodiment is formed as 2,5, 10 μm of Copper foil with carrier, and carried out evaluation identical with the embodiment that the thickness of very thin layers of copper is 3 μm.As a result no matter thick it is It is identical to spend its evaluation.

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, roughening treatment 1 below, roughening treatment 2, antirust treatment, chromate are sequentially carried out to very thin layers of copper surface Processing and silane coupling processing.

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(Na₂Cr₂O₇Or CrO₃)：2~10g/L

NaOH or KOH：10~50g/L

ZnOH or ZnSO₄·7H₂O：0.05~10g/L

pH：7~13

Bath temperature：20~80 DEG C

Current density：0.05~5A/dm²

Time：5~30 seconds

Silicon alkane coupling is handled

After the 3- glycidoxypropyltrimewasxysilane aqueous solutions for spraying 0.1vol%~0.3vol%, 100 It is dried-heats in~200 DEG C of air 0.1~10 second.

2 ＞ of ＜ embodiments

With condition same as Example 1 after forming very thin layers of copper on foil carriers, sequentially carry out at roughening below Reason 1, roughening treatment 2, antirust treatment, chromic acid salt treatment and silane coupling processing.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：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：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：3~4

Liquid temperature：50~60 DEG C

Current density：0~2A/dm²(due to for impregnate chromic acid salt treatment, therefore can also implement electroless)

Coulomb amount：0~2As/dm²(due to for impregnate chromic acid salt treatment, therefore can also implement electroless)

Silicon alkane coupling is handled

Coating (the two amido silicon alkane concentration of two amido silicon alkane aqueous solutions：0.1~0.5wt%)

3 ＞ of ＜ embodiments

With condition same as Example 1 after forming very thin layers of copper on foil carriers, then, very thin layers of copper surface according to Sequence carries out roughening treatment 1, roughening treatment 2, antirust treatment, chromic acid salt treatment and silane coupling processing below.Furthermore it is very thin The thickness of copper foil is set as 3 μm.

Roughening treatment 1

(liquid composition 1)

Cu：10~30g/L

H₂SO₄：10~150g/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(Na₂Cr₂O₇Or CrO₃)：2~10g/L

NaOH or KOH：10~50g/L

ZnOH or ZnSO₄·7H₂O：0.05~10g/L

pH：7~13

Bath temperature：20~80 DEG C

Current density：0.05~5A/dm²

Time：5~30 seconds

Silicon alkane coupling is handled

After the 3- glycidoxypropyltrimewasxysilane aqueous solutions for spraying 0.1vol%~0.3vol%, 100 ~200 DEG C of air drying-heating 0.1~10 second.

4 ＞ of ＜ embodiments

With condition same as Example 1 after forming Ni layers and Cr layers on foil carriers, in the continuous plating of roll-to-roll type On wiring, 3 μm of very thin layers of copper of thickness is electroplated under the following conditions, thus forms it on Cr layers, manufactures appendix body Copper foil.Furthermore the thickness for also manufacturing very thin layers of copper in this present embodiment is formed as 2,5,10 μm of Copper foil with carrier, and carries out Evaluation identical with the embodiment that the thickness of very thin layers of copper is 3 μm.As a result it is no matter thickness its evaluation is almost the same.

Very thin layers of copper

Copper concentration：30~120g/L

H₂SO₄Concentration：20~120g/L

Bis- (3 sulfopropyl) disulphide concentration：10~100ppm

3 grades of amine compounds：10~100ppm

Chlorine：10~100ppm

Electrolyte temperature：20~80 DEG C

Current density：10~100A/dm²

Furthermore it can be used following compound as above-mentioned 3 grades of amine compounds.

[chemical formula 11]

(in above-mentioned chemical formula, R₁And R₂To select free hydroxyl alkyl, ether, aryl, the alkyl replaced through aromatic series, unsaturation Person in the group that alkyl, alkyl are formed.Herein, R₁And R₂All it is set as methyl.)

Above compound for example can by the Denacol Ex-314 that manufacture NagaseChemtex limited liability companies with Dimethyl amine is mixed with given amount, and reaction in 3 hours is carried out in 60 DEG C and is obtained.

After forming very thin layers of copper on foil carriers, roughening treatment 1 below, roughening treatment 2 are sequentially carried out, at antirust Reason, chromic acid salt treatment and silane coupling processing.

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：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：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：3~4

Liquid temperature：50~60 DEG C

Current density：0~2A/dm²(due to for impregnate chromic acid salt treatment, therefore can also implement electroless)

Coulomb amount：0~2As/dm²(due to for impregnate chromic acid salt treatment, therefore can also implement electroless)

Silicon alkane coupling is handled

Coating (the two amido silicon alkane concentration of two amido silicon alkane aqueous solutions：0.1~0.5wt%)

5 ＞ of ＜ embodiments

With condition same as Example 1 after forming Ni layers and Cr layers on foil carriers, in the continuous plating of roll-to-roll type On wiring, 3 μm of very thin layers of copper of thickness is electroplated under the following conditions, thus forms it on Cr layers, manufactures appendix body Copper foil.Furthermore the thickness for also manufacturing very thin layers of copper in the present embodiment is formed as 2,5,10 μm of Copper foil with carrier, and carries out Evaluation identical with the embodiment that the thickness of very thin layers of copper is 3 μm.As a result it is no matter to spend its evaluation afterwards almost the same.

Very thin layers of copper

Copper concentration：30~120g/L

H₂SO₄Concentration：20~120g/L

Bis- (3 sulfopropyl) disulphide concentration：10~100ppm

3 grades of amine compounds：10~100ppm

Chlorine：10~100ppm

Electrolyte temperature：20~80 DEG C

Current density：10~100A/dm²

Furthermore it can be used following compound as above-mentioned 3 grades of amine compounds.

[chemical formula 12]

(in above-mentioned chemical formula, R₁And R₂To select free hydroxyl alkyl, ether, aryl, the alkyl replaced through aromatic series, unsaturation Person in the group that alkyl, alkyl are formed.Herein, R₁And R₂All it is set as methyl.)

Above compound for example can by the Denacol Ex-314 that manufacture NagaseChemtex limited liability companies with Dimethyl amine is mixed with given amount, and reaction in 3 hours is carried out in 60 DEG C and is obtained.

After forming very thin layers of copper on foil carriers, roughening treatment 1 below, roughening treatment 2 are sequentially carried out, at antirust Reason, chromic acid salt treatment and silane coupling processing.

Roughening treatment 1

(Ye Ti Group are at 1)

Cu：10~30g/L

H₂SO₄：10~150g/L

W：0.1~50mg/L

Lauryl sodium sulfate：0.1~50mg/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(Na₂Cr₂O₇Or CrO₃)：2~10g/L

NaOH or KOH：10~50g/L

ZnOH or ZnSO₄·7H₂O：0.05~10g/L

pH：7~13

Bath temperature：20~80 DEG C

Current density：0.05~5A/dm²

Time：5~30 seconds

Silicon alkane coupling is handled

After the 3- glycidoxypropyltrimewasxysilane aqueous solutions for spraying 0.1vol%~0.3vol%, in 100 ~200 DEG C of air drying-heating 0.1~10 second.

1 ＞ of ＜ comparative examples

After forming Ni layers and Cr layers on foil carriers with condition same as Example 1, in the continuous plating of roll-to-roll type On wiring, 3 μm of very thin layers of copper of thickness is electroplated under the following conditions, thus forms it on Cr layers, manufactures appendix body Copper foil.

Very thin layers of copper

Copper concentration：30~120g/L

H₂SO₄Concentration：20~120g/L

Electrolyte temperature：20~80 DEG C

Current density：5~9A/dm²

Roughening treatment 1

(liquid composition 1)

Cu：10~30g/L

H₂SO₄：10~150g/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(Na₂Cr₂O₇Or CrO₃)：2~10g/L NaOH or KOH：10~50g/L

ZnOH or ZnSO₄·7H₂O：0.05~10g/L pH：7~13

Bath temperature：20~80 DEG C

Current density：0.05~5A/dm²

Time：5~30 seconds

Silicon alkane coupling is handled

After the 3- glycidoxypropyltrimewasxysilane aqueous solutions for spraying 0.1vol%~0.3vol%, in 100 ~200 DEG C of air drying-heating 0.1~10 second.

2 ＞ of ＜ comparative examples

After forming Ni layers and Cr layers on foil carriers with condition same as Example 1, in the continuous plating of roll-to-roll type On wiring, 3 μm of very thin layers of copper of thickness is electroplated under the following conditions, thus forms it on Cr layers, manufactures appendix body Copper foil.

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

Roughening treatment 1

(Ye Ti Group are at 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：40 seconds

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：80 seconds

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(Na₂Cr₂O₇Or CrO₃)：2~10g/L

NaOH or KOH：10~50g/L

ZnOH or ZnSO₄·7H₂O：0.05~10g/L

pH：7~13

Bath temperature：20~80 DEG C

Current density：0.05~5A/dm²

Time：5~30 seconds

Silicon alkane coupling is handled

After the 3- glycidoxypropyltrimewasxysilane aqueous solutions for spraying 0.1vol%~0.3vol%, in 100 ~200 DEG C of air drying-heating 0.1~10 second.

2. the evaluating characteristics of Copper foil with carrier

To the Copper foil with carrier obtained in the above described manner, implement evaluating characteristics using following methods.Show the result in table 1.

(surface roughness)

Using contactless roughness measuring machine the LEXT OLS 4000 of manufacture (Olympus), for Ra, Rz according to JIS B0601-1994, for Rt according to JIS B0601-2001 and for Ssk, Sku according to ISO25178draft and with Under determination condition the surface roughness (Ra, Rt, Rz, Ssk, Sku) of very thin layers of copper is measured.

＜ determination conditions ＞

It blocks：Nothing

Datum length：257.9μm

Reference area：66524μm²

Determination of the environment temperature：23~25 DEG C

Also, in order to compare, using contact roughness measuring machine, (contact of limited liability company of little Ban research institutes manufacture is thick Roughnessmeter Surfcorder SE-3C), according to JIS B0601-1994 (Ra, Rz) and JIS B0601-2001 (Rt) and with following Determination condition measures the surface roughness (Ra, Rt, Rz) of very thin layers of copper.

＜ determination conditions ＞

It blocks：0.25mm

Datum length：0.8mm

Determination of the environment temperature：23~25 DEG C

(surface area ratio)

Come with following determination condition using contactless roughness measuring machine (the LEXT OLS 4000 of Olympus manufacture) It is measured.Surface area ratio is to measure area and real area, and the value of real area/area is set as surface area ratio.Herein, Area refers to measuring reference area, and real area refers to the surface area measured in reference area.

＜ determination conditions ＞

It blocks：Nothing

Datum length：257.9μm

Reference area：66524μm²

Determination of the environment temperature：23~25 DEG C

(volume in roughening treatment face)

Using contactless roughness measuring machine (laser microscopes, the LEXT OLS 4000 of Olympus manufacture), utilize Determination condition below is measured.Furthermore the volume in roughening treatment face is to be measured as follows.

(1) make the focusing height of laser microscopes cooperation specimen surface.

(2) brightness is adjusted, whole illumination is adjusted to about the 80% of saturation point.

(3) make laser microscopes close to sample, the place that picture illumination completely disappears is set as zero.

(4) make laser microscopes far from sample, the place that picture illumination completely disappears is set as limit level.

(5) it is highly the zero supreme volume for being limited to roughening treatment face only to measure certainly.

＜ determination conditions ＞

It blocks：Nothing

Datum length：257.9μm

Reference area：66524μm²

Determination of the environment temperature：23~25 DEG C

(migration)

Each Copper foil with carrier is set then, then, to remove removal carrier foils with bismuth system resin.Make the pole of exposing by soft etching The thickness of thin copper layer is formed as 1.5 μm.Later, it cleaned, dried, then, in very thin layers of copper upper layer extrusion cloth DF (Hitachis The trade name RY-3625 of Cheng companies manufacture).With 15mJ/cm²Condition be exposed, using developer solution (sodium carbonate) in 38 DEG C Liquid injection and the shake for carrying out 1 minute form corrosion-resisting pattern with various spacing recorded in table 1.Then, using copper sulphate Plating (CUBRITE21 of Ren Yuanyou Gilat manufacture) removes DF in 15 μm of plated UP using stripper (sodium hydroxide). Later, very thin layers of copper is removed to form various spacing recorded in table 1 using the etching solution etching of Sulfuric-acid-hydrogen-peroxide system Wiring.

Recorded spacing is equivalent to the aggregate value at line and interval in table.

Obtained wiring is evaluated using migration measuring machine (MIG-9000 of IMV manufactures) under determination condition below Whether there is or not the insulation degradations between Wiring pattern.

＜ determination conditions ＞

Threshold value：Lower than initial stage resistance 60%

Minute：1000h

Voltage：60V

Temperature：85℃

Relative humidity：85%RH

Table 1-1

Table 1-2

Claims (16)

1. a kind of Copper foil with carrier has foil carriers, the peeling layer on foil carriers and on peeling layer Very thin layers of copper, the very thin roughened processing of layers of copper, the surface area ratio on very thin layers of copper surface is 1.05~1.5, very thin layers of copper surface Every 66524 μm²The volume of area measured using laser microscopes is 300000 μm³More than；Wherein, so-called surface area ratio is The value of real area/area when using laser microscopes measurement area and real area；Area refers to measuring reference area, real Interphase product refers to the surface area measured in reference area.

2. a kind of Copper foil with carrier has foil carriers, the peeling layer on foil carriers and on peeling layer Very thin layers of copper, the very thin roughened processing of layers of copper, the surface area ratio on very thin layers of copper surface is 1.05~1.5, very thin layers of copper surface Its S s k is -0.058~0.3；Wherein, so-called surface area ratio is when measuring area and real area using laser microscopes The value of real area/area；Area refers to measuring reference area, and real area refers to the surface area measured in reference area.

3. a kind of Copper foil with carrier has foil carriers, the peeling layer on foil carriers and on peeling layer Very thin layers of copper, the very thin roughened processing of layers of copper, the surface area ratio on very thin layers of copper surface is 1.05~1.5, very thin layers of copper surface Its Sku is 2.8~3.3；Wherein, so-called surface area ratio is reality when measuring area and real area using laser microscopes The value of area/area；Area refers to measuring reference area, and real area refers to the surface area measured in reference area.

4. Copper foil with carrier according to any one of claim 1 to 3, wherein the surface area ratio on very thin layers of copper surface is 1.1~1.3.

5. Copper foil with carrier according to any one of claim 1 to 3, wherein every 66524 μm of very thin layers of copper surface²Face The long-pending volume measured using laser microscopes is 350000 μm³More than.

6. Copper foil with carrier according to any one of claim 1 to 3, wherein very thin its Ssk of layers of copper surface is -0.058 ~0.3.

7. Copper foil with carrier according to claim 4, wherein very thin its Ssk of layers of copper surface is -0.058~0.3.

8. Copper foil with carrier according to any one of claim 1 to 3, wherein very thin its Sku of layers of copper surface be 2.8~ 3.3。

9. Copper foil with carrier according to claim 4, wherein very thin its Sku of layers of copper surface is 2.8~3.3.

10. Copper foil with carrier according to claim 5, wherein very thin its Sku of layers of copper surface is 2.8~3.3.

11. Copper foil with carrier according to claim 6, wherein very thin its Sku of layers of copper surface is 2.8~3.3.

12. Copper foil with carrier according to claim 7, wherein very thin its Sku of layers of copper surface is 2.8~3.3.

13. a kind of copper-cover laminated plate is manufactured using the Copper foil with carrier described in any one of claim 1 to 12.

14. a kind of printing distributing board is made using Copper foil with carrier according to any one of claim 1 to 12 It makes.

15. a kind of printed circuit board is made using Copper foil with carrier according to any one of claim 1 to 12 It makes.

16. a kind of manufacturing method of printing distributing board, including following step：

The step of preparing Copper foil with carrier according to any one of claim 1 to 12 and insulating substrate；

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

After by above-mentioned Copper foil with carrier and insulating substrate lamination, the shape through the step of removing the carrier of above-mentioned Copper foil with carrier At copper-cover laminated plate,

Thereafter, pass through semi-additive process, subtractive process, part addition process or the step for improving the either method formation circuit in semi-additive process Suddenly.