CN104943270A - Copper foil with carrier, printed wiring board, laminate, electronic machine and method for manufacturing printed wiring board - Google Patents

Copper foil with carrier, printed wiring board, laminate, electronic machine and method for manufacturing printed wiring board Download PDF

Info

Publication number
CN104943270A
CN104943270A CN201510147943.1A CN201510147943A CN104943270A CN 104943270 A CN104943270 A CN 104943270A CN 201510147943 A CN201510147943 A CN 201510147943A CN 104943270 A CN104943270 A CN 104943270A
Authority
CN
China
Prior art keywords
copper foil
copper
appendix
layer
appendix body
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510147943.1A
Other languages
Chinese (zh)
Other versions
CN104943270B (en
Inventor
宫本宣明
本多美里
石井雅史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Original Assignee
JX Nippon Mining and Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Publication of CN104943270A publication Critical patent/CN104943270A/en
Application granted granted Critical
Publication of CN104943270B publication Critical patent/CN104943270B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

The invention discloses a copper foil with a carrier, a printed wiring board, a laminate, an electronic machine and a method for manufacturing the printed wiring board. Specifically, the invention provides a copper foil with a carrier, and the copper foil has good circuit formability. The copper foil with the carrier sequentially has a carrier, an intermediate layer and an extremely thin copper layer, and when the copper foil with the carrier is heated at a speed of 30 DEG C/min to 500 DEG C, the water content that is less than generated is 160ppm/g.

Description

The manufacture method of the Copper Foil of appendix body, printed wiring board, layered product, e-machine and printed wiring board
Technical field
The present invention relates to the manufacture method of a kind of Copper Foil of appendix body, printed wiring board, layered product, e-machine and printed wiring board.
Background technology
Printed wiring board manufactures through following steps usually: insulated substrate be adhered to Copper Foil and after making copper clad laminate, form conductive pattern by being etched in copper-clad surface.Along with the miniaturization of e-machine in recent years, the growth of high performance demand, carry the high-density installation of part or the high frequency development of signal, the miniaturization (micro-spacing) of conductive pattern is required to printed wiring board or tackles high frequency etc.
Corresponding to micro-spacing, the Copper Foil of nearest required thickness less than 9 μm and then thickness less than 5 μm, but the mechanical strength of this ultrathin copper foil is low, easily break when manufacturing printed wiring board or produce gauffer, so there is the Copper Foil of following appendix body: will have thickness metal forming be used as carrier, and by very thin layers of copper across peel ply electro-deposition in metal forming.The surface of very thin layers of copper is being fitted to insulated substrate and after carrying out thermo-compressed, via peel ply carrier peeled off and remove.After forming circuit pattern by utilizing resist in the very thin layers of copper exposed, utilize the etchant of Sulfuric-acid-hydrogen-peroxide system that the method (MSAP:Modified-Semi-Additive-Process improves half additive process) of very thin layers of copper etching removal is formed fine circuits.
Here, for becoming the surface with the very thin layers of copper of the Copper Foil of the appendix body of the adhesive surface of resin, the peel strength of the very thin layers of copper of major requirement and resin base material is abundant and also fully kept its peel strength after high-temperature heating, wet processed, welding, chemical treatments etc.As the method for the peel strength improved between very thin layers of copper and resin base material, usually representational is the method for adhering to a large amount of alligatoring particle in the very thin layers of copper of the profile (concavo-convex, roughness) increasing surface.
But, if use to the conductor package substrate that especially must form fine circuit pattern in printed wiring board the very thin layers of copper that this profile (concavo-convex, roughness) is large, then can remain unwanted copper particle when circuit etch, produce the problems such as the defective insulation between circuit pattern.
Therefore, in No. WO2004/005588 (patent document 1), as the Copper Foil of appendix body of fine circuits purposes taking conductor package substrate as representative, attempt using the Copper Foil surface of very thin layers of copper being implemented to the appendix body of roughening treatment.Thisly do not implement the impact due to the low profile (concavo-convex, rugosity, roughness) of very thin layers of copper of the very thin layers of copper of roughening treatment and the adaptation (peel strength) of resin, and have the tendency lower than common printed wiring board-use copper-clad.Therefore, require further to improve to the Copper Foil of appendix body.
Thus, in Japanese Patent Laid-Open 2007-007937 publication (patent document 2) and Japanese Patent Laid-Open 2010-006071 publication (patent document 3), describe and Ni layer and/or Ni alloy-layer are set in the face contacting (bonding) with polyimides system resin substrate of the ultrathin copper foil of appendix body, chromate coating is set, Cr layer and/or Cr alloy-layer are set, Ni layer and chromate coating are set, Ni layer and Cr layer are set.By arranging these surface-treated layers, can not carry out roughening treatment or reduce roughening treatment degree (miniaturization) and make the ultrathin copper foil of polyimides system resin substrate and appendix body dhering strength obtain needed for bonding strength.Further, also describe and utilize silane coupler to carry out surface treatment, or implement antirust treatment.
[prior art document]
[patent document]
No. WO2004/005588, [patent document 1];
[patent document 2] Japanese Patent Laid-Open 2007-007937 publication;
[patent document 3] Japanese Patent Laid-Open 2010-006071 publication.
Summary of the invention
[invention institute for solution problem]
In the exploitation of the Copper Foil of appendix body, focus on the peel strength guaranteeing very thin layers of copper and resin base material before this.Therefore, about the circuit formative of very thin layers of copper, also do not study fully, still leave room for improvement.
Can carry out adding thermo-compressed when the Copper Foil of appendix body to be fitted to resin from very thin layers of copper side, but now have the gases such as the steam owing to producing between carrier/very thin layers of copper and produce the situation of bubble (bloating (swelling)).If produce this bloating, then can produce the very thin layers of copper depression for the formation of circuit, dysgenic problem is produced to circuit formative.The invention provides a kind of Copper Foil of appendix body, the number bloated produced during by suppressing to heat under given conditions the Copper Foil of appendix body, and there is good etching.Or, the invention provides a kind of Copper Foil of appendix body, the amount of moisture produced during by suppressing to heat under given conditions the Copper Foil of appendix body, and the generation bloated that suppression is caused by gases such as the steam resulted between carrier/very thin layers of copper, and there is good etching.
[solving the technological means of problem]
The present invention completed based on above opinion is a kind of Copper Foil of appendix body in one aspect, sequentially possesses carrier, intermediate layer and very thin layers of copper, is below 160ppm/g by the Copper Foil of described appendix body with the amount of moisture that 30 DEG C/min produce when being heated to 500 DEG C.
The Copper Foil of appendix body of the present invention in one embodiment, by the Copper Foil of described appendix body with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C for 0 ~ 130ppm/g.
The Copper Foil of appendix body of the present invention in another embodiment, by the Copper Foil of described appendix body with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C for 0 ~ 110ppm/g.
The present invention is a kind of Copper Foil of appendix body in another aspect, and it sequentially possesses carrier, intermediate layer and very thin layers of copper, is 20/dm by the Copper Foil of described appendix body with 220 DEG C of little produced bloating constantly of heating 4 2below.
The Copper Foil of appendix body of the present invention so that another embodiment in, be 0 ~ 15/dm by the Copper Foil of described appendix body with little produced the bloating constantly of 220 DEG C of heating 4 2below.
The Copper Foil of appendix body of the present invention so that another embodiment in, be 0 ~ 60/dm by the Copper Foil of described appendix body with bloating of producing during 400 DEG C of heating 10 minutes 2below.
The Copper Foil of appendix body of the present invention so that another embodiment in, described intermediate layer contain in the group being selected from and being made up of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, organic matter one or more.
The Copper Foil of appendix body of the present invention so that another embodiment in, described intermediate layer when containing Cr, containing 5 μ g/dm 2above 100 μ g/dm 2following Cr, when containing Mo, containing 50 μ g/dm 2above 1000 μ g/dm 2following Mo, when containing Ni, containing 100 μ g/dm 2above 40000 μ g/dm 2following Ni, when containing Co, containing 100 μ g/dm 2above 40000 μ g/dm 2following Co, when containing Zn, containing 1 μ g/dm 2above 120 μ g/dm 2following Zn.
The Copper Foil of appendix body of the present invention so that another embodiment in, organic matter is contained with the thickness of more than 25nm below 80nm in described intermediate layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, described organic matter is by one or more organic matters formed be selected from organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid.
The Copper Foil of appendix body of the present invention so that another embodiment in, any surface on the surface of described very thin layers of copper surface or described carrier or two sides have roughening treatment layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, there is on the surface of described roughening treatment layer more than one the layer in the group being selected from and being made up of refractory layer, antirust coat, chromating layer and silane coupled processing layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, at least one deck of described antirust coat and described refractory layer contains more than one the element be selected from nickel, cobalt, copper, zinc.
The Copper Foil of appendix body of the present invention so that another embodiment in, at least one deck of described antirust coat and described refractory layer is made up of more than one the element be selected from nickel, cobalt, copper, zinc.
The Copper Foil of appendix body of the present invention so that another embodiment in, described roughening treatment layer has described refractory layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, described roughening treatment layer or described refractory layer have described antirust coat.
The Copper Foil of appendix body of the present invention so that another embodiment in, described antirust coat has described chromating layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, described chromating layer has described silane coupled processing layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, there is on the surface of described very thin layers of copper more than one the layer in the group being selected from and being made up of refractory layer, antirust coat, chromating layer and silane coupled processing layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, described very thin layers of copper possesses resin bed.
The Copper Foil of appendix body of the present invention so that another embodiment in, described roughening treatment layer possesses resin bed.
The Copper Foil of appendix body of the present invention so that another embodiment in, possess resin bed being selected from more than one the layer in the group be made up of described refractory layer, antirust coat, chromating layer and silane coupled processing layer.
The Copper Foil of appendix body of the present invention so that another embodiment in, described resin bed contains dielectric medium.
The present invention so that on the other hand in be a kind of printed wiring board, manufactured by the Copper Foil using appendix body of the present invention.
The present invention so that on the other hand in be a kind of e-machine, use manufactured by printed wiring board of the present invention.
The present invention so that on the other hand in be a kind of layered product, manufactured by the Copper Foil using appendix body of the present invention.
The present invention so that on the other hand in be a kind of layered product, the Copper Foil containing appendix body of the present invention and resin, part or all of the end face of the Copper Foil of described appendix body is covered by described resin.
The present invention so that on the other hand in be a kind of layered product, the Copper Foil of appendix body of the present invention for a slice is laminated to the described carrier side of the Copper Foil of another sheet appendix of the present invention body from described carrier side or described very thin layers of copper side or described very thin layers of copper side forms.
Layered product of the present invention in one embodiment, is formed via adhesive contact laminating as required in the described carrier side surface of the Copper Foil of the described carrier side of the Copper Foil of described a slice appendix body surface or described very thin layers of copper side surface and another sheet appendix body described or described very thin layers of copper side surface.
In another embodiment, described carrier or the described pole thin copper layer Even of the described carrier side surface of the Copper Foil of described a slice appendix body or the Copper Foil of described very thin layers of copper side surface and another sheet appendix body described connect layered product of the present invention.
The present invention so that on the other hand in be a kind of manufacture method of printed wiring board, use layered product of the present invention.
The present invention so that on the other hand in be a kind of layered product, part or all of its end face is covered by resin.
The present invention so that on the other hand in be a kind of manufacture method of printed wiring board, this is two-layer to comprise the steps: at least to arrange 1 resin bed and circuit at layered product of the present invention; And at least formed 1 described resin bed and circuit this two-layer after, peel off described very thin layers of copper from the Copper Foil of the appendix body of described layered product.
The present invention so that on the other hand in be a kind of manufacture method of printed wiring board, comprise the steps: the Copper Foil and the insulated substrate that prepare appendix body of the present invention; The Copper Foil of described appendix body and insulated substrate are carried out lamination; And after the Copper Foil of described appendix body and insulated substrate are carried out lamination, forming copper clad laminate through peeling off the step of the foil carriers of the Copper Foil of described appendix body, forming circuit by any one method in semi-additive process, subtractive process, part addition process or improvement semi-additive process thereafter.
The present invention so that on the other hand in be a kind of manufacture method of printed wiring board, comprise the steps: at the described very thin layers of copper side of the Copper Foil of appendix body of the present invention or described carrier side circuit forming surface; Resin bed is formed in the described very thin layers of copper side of the Copper Foil of described appendix body or described carrier side surface in the mode burying described circuit; Described resin bed forms circuit; After described resin bed forms circuit, peel off described carrier or described very thin layers of copper; And after peeling off described carrier or described very thin layers of copper, by removing described very thin layers of copper or described carrier and making the circuit be buried in described resin bed being formed in described very thin layers of copper side surface or described carrier side surface expose.
The manufacture method of printed wiring board of the present invention in one embodiment, the described step forming circuit is on the resin layer fitted in described resin bed by the Copper Foil of other appendix body from very thin layers of copper side or carrier side, uses the Copper Foil being fitted in appendix body on described resin bed and the step forming described circuit.
In another embodiment, the Copper Foil of described laminating other appendix body is on the resin layer the Copper Foil of appendix body of the present invention to the manufacture method of printed wiring board of the present invention.
The manufacture method of printed wiring board of the present invention so that another embodiment in, the described step forming circuit is on the resin layer undertaken by any one method in semi-additive process, subtractive process, part addition process or improvement semi-additive process.
The manufacture method of printed wiring board of the present invention so that another embodiment in, described will have substrate at the Copper Foil of the appendix body of circuit forming surface on the surface of the surface of the carrier side of the Copper Foil of this appendix body or very thin layers of copper side.
The present invention so that on the other hand in be a kind of manufacture method of printed wiring board, comprise the steps: the described very thin layers of copper side surface of the Copper Foil of appendix body of the present invention or described carrier side surface and resin substrate to carry out lamination; Described appendix body Copper Foil and be that the very thin layers of copper side surface of opposition side or described carrier side surface at least arrange 1 resin bed and circuit this is two-layer with the side of resin substrate lamination; And at least formed 1 described resin bed and circuit this two-layer after, peel off described carrier or described very thin layers of copper from the Copper Foil of described appendix body.
The present invention so that on the other hand in be a kind of manufacture method of printed wiring board, comprise the steps: the described carrier side surface of the Copper Foil of appendix body of the present invention and resin substrate to carry out lamination; Described appendix body Copper Foil and 1 resin bed and circuit are at least set with the very thin layers of copper side surface that the side of resin substrate lamination is opposition side this are two-layer; And at least formed 1 described resin bed and circuit this two-layer after, peel off described carrier from the Copper Foil of described appendix body.
[effect of invention]
According to the present invention, the Copper Foil of the appendix body that a kind of circuit formative can be provided good.
Accompanying drawing explanation
In Fig. 1, A ~ C is the schematic diagram of wiring plate section in the step to plating circuit, removal plating resist application of the concrete example of the manufacture method of the printed wiring board of the Copper Foil using appendix body of the present invention.
In Fig. 2, D ~ F is the schematic diagram of wiring plate section the Copper Foil from laminated resin and the 2nd layer of appendix body of the concrete example of the manufacture method of the printed wiring board of the Copper Foil using appendix body of the present invention step to laser beam drilling.
In Fig. 3 G ~ I be the concrete example of the manufacture method of the printed wiring board of the Copper Foil using appendix body of the present invention from the schematic diagram forming wiring plate section filling through hole thing (via-fill) step to stripping the 1st layer of carrier.
In Fig. 4 J ~ K be the concrete example of the manufacture method of the printed wiring board of the Copper Foil using appendix body of the present invention from fast-etching to the step formed projection copper post the schematic diagram of wiring plate section.
Fig. 5 is the schematic diagram of the cross section of the width of circuit pattern in embodiment and uses the outline of computational methods of etching coefficient (EF) of this schematic diagram.
Detailed description of the invention
The Copper Foil > of < appendix body
The Copper Foil of appendix body of the present invention sequentially possesses carrier, intermediate layer and very thin layers of copper.The using method of the Copper Foil of appendix body itself is that dealer is well-known, such as the surface of very thin layers of copper can be fitted 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 non-woven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film, liquid crystalline polymer film, the insulated substrates such as fluororesin film also peel off carrier after carrying out thermo-compressed, the very thin layers of copper being bonded in insulated substrate is etched into the conductive pattern of target, final manufacture printed wiring board.
< carrier >
May be used for carrier of the present invention typical case for metal forming or resin molding, such as, provide with the form of Copper Foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, ferroalloy paper tinsel, stainless steel foil, aluminium foil, alloy foil, insulating resin film, polyimide film, LCD film.
May be used for carrier of the present invention typical case to provide with the form of rolled copper foil or electrolytic copper foil.Usually, electrolytic copper foil makes copper precipitate into titanium or stainless rotating cylinder from copper sulfate bath electrolysis and manufacture, and rolled copper foil repeatedly carries out utilizing the plastic working of stack and heat treatment and manufactures.As the material of Copper Foil, except the high-purity coppers such as smart copper (JIS H3100 alloy numbering C1100) or oxygen-free copper (JIS H3100 alloy numbering C1020 or JIS H3510 alloy numbering C1011), such as, also can use the copper alloy mixed Sn copper, mix Ag copper, with the addition of the copper alloy of Cr, Zr or Mg etc., with the addition of the class of gloomy series copper alloy such as the section of Ni and Si etc.
In addition, as electrolytic copper foil, following electrolyte can be utilized to form and manufacturing condition making.
Manufacture the situation of electrolytic copper foil in following condition, the electrolytic copper foil that Rz 60 degree of glossiness that are little, TD of the TD (direction (width) rectangular with the direct of travel of Copper Foil in the manufacturing equipment of Copper Foil) of copper foil surface are high can be obtained.
< electrolyte composition >
Copper: 90 ~ 110g/L
Sulfuric acid: 90 ~ 110g/L
Chlorine: 50 ~ 100ppm
Levelling agent 1 (two (3-sulfopropyl) disulphide): 10 ~ 30ppm
Levelling agent 2 (amines): 10 ~ 30ppm
Described amines can use the amines of following chemical formula.
In addition, the remainder of the treatment fluid used for electrolysis of the present invention, surface treatment or plating etc. as long as no expressing especially, is then water.
(in described chemical formula, R 1and R 2be selected from the group be made up of hydroxy alkyl, ether, aryl, aromatic series substituted alkyl, unsaturated alkyl, alkyl)
< manufacturing condition >
Current density: 70 ~ 100A/dm 2
Electrolyte temperature: 50 ~ 60 DEG C
Electrolyte linear velocity: 3 ~ 5m/sec
Electrolysis time: 0.5 ~ 10 minute
In addition, when being used alone by term " Copper Foil " in this description, also copper alloy foil is comprised.
Also be not particularly limited about the thickness that may be used for carrier of the present invention, if be suitably adjusted to play as carrier effect in suitable thickness just can, such as can be set to more than 5 μm.If but blocked up, then production cost improves, so be usually preferably set to less than 35 μm.Therefore, the thickness typical case of carrier is 8 ~ 70 μm, and more typical is 12 ~ 70 μm, and more typical is 18 ~ 35 μm.In addition, from the viewpoint reducing cost of material, the thickness of preferred vector is little.Therefore, the thickness typical case of carrier is more than 5 μm less than 35 μm, preferably more than 5 μm less than 18 μm, preferably more than 5 μm less than 12 μm, preferably more than 5 μm less than 11 μm, preferably more than 5 μm less than 10 μm.In addition, when carrier thickness is little, easily produce gauffer when carrier leads to paper tinsel.In order to prevent gauffer, effectively such as make the transport roller of the Copper Foil manufacturing installation of appendix body level and smooth or shorten the distance of transport roller and next transport roller.In addition, the implantation (Enbedded Process) when of the manufacture method as printed wiring board uses the Copper Foil of appendix body, the rigidity of carrier is necessary for height.Therefore, when for implantation, the thickness of carrier is preferably more than 18 μm less than 300 μm, is preferably more than 25 μm less than 150 μm, is preferably more than 35 μm less than 100 μm, is more preferably more than 35 μm less than 70 μm further.
In addition, also can be opposition side with the surface arranging very thin layers of copper side surface arranges roughening treatment layer at carrier.Can use known method that this roughening treatment layer is set, following roughening treatment also can be utilized to arrange.Roughening treatment layer is set with the surface that is opposition side, the surface arranging very thin layers of copper side there is following advantage at carrier: when carrier is laminated to the supporters such as resin substrate from the face side that this has roughening treatment layer, carrier and resin substrate are not easily peeled off.
< intermediate layer >
The single or double of carrier arranges intermediate layer.Between carrier and intermediate layer, also other layer can be set.Intermediate layer used in the present invention is formed as follows: before the copper foil layer of appendix body is pressed onto the step of insulated substrate, very thin layers of copper is not easily peeled off from carrier, on the other hand, after being laminated to the step of insulated substrate, very thin layers of copper can be peeled off from carrier.Such as, the Copper Foil of appendix body of the present invention intermediate layer can containing be selected from the group that is made up of Ni and Cr, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, organic matter one or more.In addition, intermediate layer can be multilayer.
In addition, intermediate layer preferably on carrier sequentially lamination nickel or nickel-containing alloys the layer of any one and containing chromium, evanohm, chromium oxide in more than one layer and form.And, the layer of any one of nickel or nickel-containing alloys and/or containing in more than one the layer in the oxide of chromium, evanohm, chromium preferably containing zinc.Here, nickel-containing alloys refers to the alloy that more than one the element in the group be made up of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium nickel and being selected from is formed.Nickel-containing alloys also can for the alloy be made up of the element of more than 3 kinds.In addition, evanohm refers to the alloy that more than one the element in the group be made up of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium chromium and being selected from is formed.Evanohm also can for the alloy be made up of the element of more than 3 kinds.In addition, also can be chromating layer containing more than one the layer in the oxide of chromium, evanohm, chromium.Here, chromating layer refers to the layer through the liquid handling containing chromate or bichromate.Chromating layer also can contain the metals such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium.In the present invention, the chromating layer through chromic anhybride or potassium dichromate aqueous solution process is called pure chromating layer.In addition, in the present invention, the chromating layer through the treatment fluid process containing acid anhydrides or potassium bichromate and zinc is called zinc chromate processing layer.
In addition, any one layer in any one layer preferably on carrier sequentially in lamination nickel, nickel-kirsite, nickel-phosphor alloy, nickel-cobalt alloy of intermediate layer and zinc chromate processing layer, pure chromating layer, chrome plating and forming, intermediate layer further preferred on carrier sequentially lamination nickel dam or nickel-zinc alloy layer and zinc chromate processing layer and form, or sequentially lamination nickel-zinc alloy layer and pure chromating layer or zinc chromate processing layer and form.Because the bonding force of nickel and copper is higher than the bonding force of chromium and copper, so when peeling off very thin layers of copper, become and peel off on the interface of very thin layers of copper and chromating layer.In addition, expect that the copper component that prevents of the nickel in intermediate layer is diffused into the barriering effect of very thin layers of copper from carrier.In addition, preferably chromating layer is formed but not chrome plating in intermediate layer.Chrome plating is because form fine and close chromium oxide layer on surface, so resistance rises and easily produces pin hole when utilizing plating to form ultrathin copper foil.Define the surface of chromating layer because form the chromium oxide layer not as chrome plating densification, so not easily become the resistance utilizing and electroplate when forming ultrathin copper foil, can pin hole be reduced.Here, by forming zinc chromate processing layer as chromating layer, utilizing resistance during plating formation ultrathin copper foil to become lower than common chromating layer, the generation of pin hole can be suppressed further.
When using electrolytic copper foil as carrier, from the viewpoint reducing pin hole, preferably intermediate layer is set at bright.
Chromating layer in intermediate layer is present in very thin layers of copper interface compared with unfertile land is preferred from obtaining following characteristic aspect: before the step being laminated to insulated substrate, very thin layers of copper can not be peeled off from carrier, on the other hand, very thin layers of copper can be peeled off from carrier after being laminated to the step of insulated substrate.When not arranging nickel dam or nickeliferous alloy-layer (such as nickel-zinc alloy layer) and making chromating layer be present in the border of carrier and very thin layers of copper, fissility improves hardly, when there is no chromating layer and by nickel dam or nickeliferous alloy-layer (such as nickel-zinc alloy layer) and very thin layers of copper contact laminating, according to the nickel amount in nickel dam or nickeliferous alloy-layer (such as nickel-zinc alloy layer), peel strength is crossed strong or excessively weak, cannot obtain suitable peel strength.
In addition, if chromating layer is present in the border of carrier and nickel dam or nickeliferous alloy-layer (such as nickel-zinc alloy layer), then peel off very thin layers of copper time intermediate layer also can with stripping, that is can be peeling between carrier and intermediate layer, thus not preferred.This situation, not only when producing when the interface with carrier arranges chromating layer, even if arrange chromating layer with the interface of very thin layers of copper, if chromium amount is too much, then also may produce.Think that its reason is: due to the easy solid solution of copper and mickel, if so their contacts, then bonding force can be made to improve because of phase counterdiffusion, not easily peel off, on the other hand, due to the not easily solid solution of chromium and copper, not easily produce phase counterdiffusion, so at the interface of chromium and copper, bonding force is weak, easily peels off.In addition, when the nickel quantity not sufficient in intermediate layer, because only there is the chromium of trace between carrier and very thin layers of copper, so both are closely sealed and not easily peel off.
The nickel dam in intermediate layer or nickeliferous alloy-layer (such as nickel-zinc alloy layer) such as can utilize plating, the wet type plating of class of electroless plating and dipping plating or sputter, CVD and PDV the dry type plating of class formed.Preferably electroplate from the viewpoint of cost.In addition, when carrier is resin molding, the wet type plating of the class of the dry type plating of the class of CVD and PDV or electroless plating and dipping plating can be utilized to form intermediate layer.
In addition, chromating layer such as can utilize the formation such as electrolytic chromate or dipping chromate, but utilizes electrolytic chromate to be formed owing to can improve chromium concn, makes very thin layers of copper become good, so preferably from the peel strength of carrier.
In addition, in preferred interlayer, the adhesion amount of nickel is 100 ~ 40000 μ g/dm 2, the adhesion amount of chromium is 5 ~ 100 μ g/dm 2, the adhesion amount of zinc is 1 ~ 70 μ g/dm 2.By controlling the adhesion amount of nickel, chromium, zinc like this, the Copper Foil of appendix body of the present invention can control the Ni amount peeling off the surface of the very thin layers of copper after very thin layers of copper from the Copper Foil of appendix body.In order to so control the Ni amount on the very thin layers of copper surface after peeling off, preferably reduce the Ni adhesion amount in intermediate layer, and make intermediate layer contain the metal species (Cr, Zn) suppressing Ni to spread to very thin layers of copper side.From this viewpoint, the Ni content in intermediate layer is preferably 100 ~ 40000 μ g/dm 2, more preferably 200 μ g/dm 2above 20000 μ g/dm 2below, more preferably 500 μ g/dm 2above 10000 μ g/dm 2below, more preferably 700 μ g/dm 2above 5000 μ g/dm 2below.In addition, Cr is preferably containing 5 ~ 100 μ g/dm 2, more preferably 8 μ g/dm 2above 50 μ g/dm 2below, more preferably 10 μ g/dm 2above 40 μ g/dm 2below, more preferably 12 μ g/dm 2above 30 μ g/dm 2below.Zn is preferably containing 1 ~ 70 μ g/dm 2, more preferably 3 μ g/dm 2above 30 μ g/dm 2below, more preferably 5 μ g/dm 2above 20 μ g/dm 2below.If the Ni controlling to peel off from the Copper Foil of appendix body the very thin layers of copper surface after very thin layers of copper measures, (such as Ni amount is 5 ~ 300 μ g/dm 2), then there are the effects such as the etching of very thin layers of copper (soluble property or circuitry shapes etc.) raising.In addition, the nickel described in cobalt replacement can also be used.Now the adhesion amount of cobalt can be set to identical with the adhesion amount of nickel.
The intermediate layer of the Copper Foil of appendix body of the present invention can on carrier sequentially lamination nickel dam and containing in organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid any one organic matter layer and form, in intermediate layer, the adhesion amount of nickel is 100 ~ 40000 μ g/dm 2.In addition, the intermediate layer of the Copper Foil of appendix body of the present invention also can on carrier sequentially lamination to contain in organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid any one organic matter layer and nickel dam and form, in intermediate layer, the adhesion amount of nickel is 100 ~ 40000 μ g/dm 2.As mentioned above, in the Copper Foil of appendix body of the present invention, after peeling off very thin layers of copper from the Copper Foil of appendix body, the Ni on very thin layers of copper surface measures control, in order to control the Ni amount on the very thin layers of copper surface after peeling off like this, the Ni adhesion amount in preferred minimizing intermediate layer, and the organic matter layer containing in organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid any one intermediate layer being contained suppress Ni spread to very thin layers of copper side.From this viewpoint, the Ni content in intermediate layer is preferably 100 ~ 40000 μ g/dm 2, more preferably 200 μ g/dm 2above 20000 μ g/dm 2below, more preferably 300 μ g/dm 2above 10000 μ g/dm 2below, more preferably 500 μ g/dm 2above 5000 μ g/dm 2below.In addition, cobalt also can be used to replace described nickel.Now the adhesion amount of cobalt can be set to identical with the adhesion amount of nickel.In addition, as the organic matter that this to contain in organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid any one, BTA (BTA), MBT (mercaptobenzothiazoler) etc. can be enumerated.
In addition, as the organic matter contained by intermediate layer, preferably use by one or more organic matters formed be selected from organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid.In organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid, organic compounds containing nitrogen comprises and has substituent organic compounds containing nitrogen.As concrete organic compounds containing nitrogen, be preferably used as and there is 1,2 of substituent triazole compounds, 3-BTA, carboxyl benzotriazole, N ', N '-bis-(BTA ylmethyl) urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole etc.
Organic compounds containing sulfur preferably uses mercaptobenzothiazoler, Vencide, trithiocyanuric acid and 2-benzimidazole mercaptan etc.
As carboxylic acid, particularly preferably use monocarboxylic acid, wherein preferably use oleic acid, linolenic acid and linolenic acid etc.
Described organic matter preferably contains more than 25nm below 80nm with thickness gauge, more preferably containing more than 30nm below 70nm.Multiple (more than one) described organic matter also can be contained in intermediate layer.
In addition, organic thickness can profit be measured with the following methods.
The organic matter thickness G reatT.GreaT.GT in < intermediate layer
After the very thin layers of copper of the Copper Foil of appendix body is peeled off from carrier, with the surface of the side, intermediate layer of the carrier exposed, XPS measuring is carried out to the surface of the side, intermediate layer of the very thin layers of copper exposed, makes depth profile (depth profile).And, the degree of depth that concentration of carbon the surface of the side, intermediate layer from very thin layers of copper can be become at first below 3at% is set to A (nm), the degree of depth that concentration of carbon the surface of the side, intermediate layer from carrier becomes below 3at% is at first set to B (nm), the sum total of A and B is set to the organic thickness (nm) in intermediate layer.
The operating condition of XPS is as follows.
Device: XPS measuring device (ULVAC-PHI company, model 5600MC)
Final vacuum: 3.8 × 10 -7pa
X-ray: monochrome is AlK α or polyenergetic is MgK α, and X-ray exports as 300W, and area of detection is 800 μm of φ, and the angle that sample and detector are formed is 45 °
Ion beam: ionic species is Ar +, accelerating potential is 3kV, and scan area is 3mm × 3mm, and sputtering rate is that 2.8nm/min is (with SiO 2convert)
About the organic using method contained by intermediate layer, below, simultaneously also carry out describing one side to the method forming intermediate layer in carrier foils to be described.Described organic matter can be dissolved in solvent and in this solvent impregnated carrier, or spray, spray-on process are used to the face that will form intermediate layer, drip method and electrodeposition process etc. and be formed on carrier by intermediate layer, the not special necessity adopting the method for restriction.The scope that concentration preferred concentration in described organic matter is whole of now organic system agent in solvent is 0.01g/L ~ 30g/L, liquid temperature is 20 ~ 60 DEG C.Organic concentration is not particularly limited, the high or low original not problem of concentration.In addition, organic concentration is higher, carrier and to dissolve time of contact of described organic solvent longer in addition, then have the tendency that the organic matter thickness in intermediate layer more increases.Further, when the organic matter thickness in intermediate layer is thick, the tendency that the organic effect suppressing Ni to spread to very thin layers of copper side increases is had.
In addition, intermediate layer preferably sequentially lamination nickel and molybdenum or cobalt or molybdenum-cobalt alloy and form on carrier.Because the bonding force of nickel and copper is higher than the bonding force of molybdenum or cobalt and copper, so when peeling off very thin layers of copper, can at the interface peel of very thin layers of copper and molybdenum or cobalt or molybdenum-cobalt alloy.In addition, the barriering effect preventing copper component from spreading from carrier to very thin layers of copper of the nickel in intermediate layer is expected.
In addition, described nickel also can be nickeliferous alloy.Here, nickeliferous alloy refers to the alloy that more than one the element in the group be made up of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium nickel and being selected from is formed.In addition, described molybdenum also can be the alloy containing molybdenum.Here, the alloy that more than one the element in the group be made up of cobalt, iron, chromium, nickel, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium molybdenum and being selected from is formed is referred to containing the alloy of molybdenum.In addition, described cobalt also can be the alloy containing cobalt.Here, the alloy that more than one the element in the group be made up of molybdenum, iron, chromium, nickel, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium cobalt and being selected from is formed is referred to containing the alloy of cobalt.
Molybdenum-cobalt alloy also can contain the element (being such as selected from more than one the element in the group be made up of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium) beyond molybdenum, cobalt.
When using electrolytic copper foil as carrier, from the viewpoint reducing pin hole, preferably intermediate layer is set at bright.
Molybdenum in intermediate layer or cobalt or molybdenum-cobalt alloy layer are present in very thin layers of copper interface compared with unfertile land is preferred from obtaining following characteristic aspect: before the step being laminated to insulated substrate, very thin layers of copper can not be peeled off from carrier, on the other hand, very thin layers of copper can be peeled off from carrier after being laminated to the step of insulated substrate.When making molybdenum or cobalt or molybdenum-cobalt alloy layer be present in the border of carrier and very thin layers of copper when not arranging nickel dam, there is the situation that fissility improves hardly, when there is no molybdenum or cobalt or molybdenum-cobalt alloy layer by nickel dam and very thin layers of copper contact laminating, nickel amount in good grounds nickel dam, peel strength is crossed strong or is crossed weak and cannot obtain the situation of suitable peel strength.
In addition, if molybdenum or cobalt or molybdenum-cobalt alloy layer are present in the border of carrier and nickel dam, then have intermediate layer when peeling off very thin layers of copper also with the situation of stripping, that is have between carrier and intermediate layer and can be peeling thus preferred situation.This situation not only can produce when arrange molybdenum or cobalt or molybdenum-cobalt alloy layer at the interface with carrier, even and if the interface of very thin layers of copper molybdenum or cobalt or molybdenum-cobalt alloy layer are set, if molybdenum amount or cobalt amount too much, then also may produce.Think that its reason is: due to the easy solid solution of copper and mickel, if so their contacts, then bonding force can be improved because of phase counterdiffusion, not easily peel off, on the other hand, due to molybdenum or cobalt and copper not easily solid solution, not easily produce phase counterdiffusion, so on the interface of molybdenum or cobalt or molybdenum-cobalt alloy layer and copper, bonding force is weak, easily peels off.In addition, when the nickel quantity not sufficient in intermediate layer, have because only there is molybdenum or the cobalt of trace between carrier and very thin layers of copper, so both closely sealed and situations that are that not easily peel off.
The nickel in intermediate layer and cobalt or molybdenum-cobalt alloy such as can utilize plating, the wet type plating of class of electroless plating and dipping plating or sputter, CVD and PDV the dry type plating of class formed.In addition, molybdenum can only utilize the dry type plating of the class of CVD and PDV to be formed.Preferably electroplate from the viewpoint of cost.
In intermediate layer, the adhesion amount of preferred nickel is 100 ~ 40000 μ g/dm 2, the adhesion amount of molybdenum is 10 ~ 1000 μ g/dm 2, the adhesion amount of cobalt is 10 ~ 1000 μ g/dm 2.As mentioned above, the Ni amount on the surface of very thin layers of copper after the Copper Foil of appendix body of the present invention controls to peel off very thin layers of copper from the Copper Foil of appendix body, in order to control the Ni amount on the very thin layers of copper surface after peeling off like this, the Ni adhesion amount in preferred minimizing intermediate layer, and make intermediate layer contain the metal species (Co, Mo) suppressing Ni to spread to very thin layers of copper side.From this viewpoint, nickel adhesion amount is preferably set to 100 ~ 40000 μ g/dm 2, be preferably set to 200 ~ 20000 μ g/dm 2, be more preferably set to 300 ~ 15000 μ g/dm 2, be more preferably set to 300 ~ 10000 μ g/dm 2.When molybdenum is contained in intermediate layer, molybdenum adhesion amount is preferably set to 10 ~ 1000 μ g/dm 2, molybdenum adhesion amount is preferably set to 20 ~ 600 μ g/dm 2, be more preferably set to 30 ~ 400 μ g/dm 2.When cobalt is contained in intermediate layer, cobalt adhesion amount is preferably set to 10 ~ 1000 μ g/dm 2, cobalt adhesion amount is preferably set to 20 ~ 600 μ g/dm 2, be more preferably set to 30 ~ 400 μ g/dm 2.
In addition, as mentioned above, intermediate layer on carrier sequentially lamination nickel and molybdenum or cobalt or molybdenum-cobalt alloy, be used for arranging the current density in the plating process of molybdenum or cobalt or molybdenum-cobalt alloy layer if reduced, slow down the travelling speed of carrier, then have the tendency that the density of molybdenum or cobalt or molybdenum-cobalt alloy layer improves.If the density of the layer containing molybdenum and/or cobalt improves, then the nickel of nickel dam not easily spreads, and can control the Ni amount on the very thin layers of copper surface after peeling off.
When only arranging intermediate layer at one side, preferably the antirust coats such as Ni coating are set at the opposing face of carrier.In addition, when utilizing chromate process or zinc chromate process or plating process to arrange intermediate layer, think that a part for the metal having chromium or zinc etc. to adhere to becomes the situation of hydrate or oxide.
The Copper Foil of appendix body of the present invention is controlled as in one aspect and becomes below 160ppm/g with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C.If the Copper Foil of heating appendix body, then have the situation producing bubble (bloating) because of gases such as the steam produced between carrier/very thin layers of copper.If produce this bloating, then can produce the very thin layers of copper depression for the formation of circuit, dysgenic problem is caused to circuit formative.On the other hand, by adopting the Copper Foil of the appendix body of the generation that inhibit moisture after specific heat treatment as mentioned above, can suppress the generation bloated well, the circuit formative of very thin layers of copper becomes good.If by the Copper Foil of appendix body with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C more than 160ppm/g, then the number bloated between carrier/very thin layers of copper becomes 30/dm 2above, be difficult to etch very thin layers of copper and formed than L/S=30 μm the fine wiring of/30 μm of finer wirings, the fine wiring of such as L/S=25 μm/25 μm, the fine wiring of such as L/S=20 μm/20 μm, such as L/S=15 μm/15 μm.
The amount of moisture that the Copper Foil of appendix body of the present invention preferably controls as producing when being heated to 500 DEG C with 30 DEG C/min becomes 0 ~ 130ppm/g, more preferably controlling is 0 ~ 110ppm/g, more preferably controlling further is 0 ~ 90ppm/g, and more preferably controlling further is 0 ~ 70ppm/g.
The Copper Foil of appendix body in another aspect, controls to become 20/dm for heating 4 little produced bloating constantly with 220 DEG C by the Copper Foil of appendix body of the present invention 2below.If the Copper Foil of heating appendix body, then have the situation producing bubble (bloating) because of gases such as the steam produced between carrier/very thin layers of copper.If produce this bloating, then can produce the very thin layers of copper depression for the formation of circuit, dysgenic problem is caused to circuit formative.On the other hand, the Copper Foil of appendix body of the present invention suppresses the generation bloated well, and the circuit formative of very thin layers of copper becomes good.If the Copper Foil of appendix body produced constantly to be bloated more than 20/dm so that 220 DEG C of heating 4 are little 2, be then difficult to etch very thin layers of copper and formed than L/S=30 μm the fine wiring of/30 μm of finer wirings, the fine wiring of such as L/S=25 μm/25 μm, the fine wiring of such as L/S=20 μm/20 μm, such as L/S=15 μm/15 μm.In addition, described " with 220 DEG C of heating 4 hours " represent the typical heating condition when Copper Foil of appendix body being fitted in insulated substrate and carrying out thermo-compressed.
The Copper Foil of appendix body of the present invention preferably controls as becoming 0 ~ 15/dm with little produced the bloating constantly of 220 DEG C of heating 4 2below, more preferably controlling is 0 ~ 12/dm 2, more preferably controlling further is 0 ~ 9/dm 2, more preferably controlling further is 0 ~ 5/dm 2.
In addition, the Copper Foil of appendix body of the present invention more preferably control further for as heating condition harsh further heat 10 minutes with 400 DEG C time produce bloat and become 0 ~ 60/dm 2below, more preferably controlling is 0 ~ 50/dm 2, more preferably controlling further is 0 ~ 40/dm 2, more preferably controlling further is 0 ~ 30/dm 2.
The number being controlled or bloat in order to moisture generation when making heating as above obtains the Copper Foil of the appendix body controlled, control during manufacture importantly as follows.
The plating condition of intermediate layer [be used for formed]
By forming intermediate layer based on following plating condition, the number that moisture generation when can make heating as above is controlled or bloats obtains the Copper Foil of the appendix body controlled.
(1) pre-treatment
By carrying out degreasing and pickling as pre-treatment, can effectively carry out follow-up plating process.
(degreasing)
By degreasing, plated flush coat is cleaned, and surface wettability promotes, so effectively can carry out follow-up pickling.
Basic handling: by carrier impregnation in sodium hydrate aqueous solution (1 ~ 100g/L).
Surfactant: if add proper amount of surfactant in sodium hydrate aqueous solution, then surface tension reduces, more effectively and preferably.
Electrolytic degreasing: and if with following arbitrary electrolysis, then more effectively degreasing can be carried out.
A () only has negative electrode degreasing (10A/dm 2left and right)
B () only has anode degreasing (5A/dm 2left and right)
(c) negative electrode degreasing → anode degreasing
(d) negative electrode degreasing → anode degreasing → negative electrode degreasing
(pickling)
By carrying out pickling after described degreasing, when carrier is Copper Foil, the cupric oxide etc. on surface can be removed, active copper surface can be made to expose.Therefore, effectively follow-up nickel plating can be carried out.
Basic handling: by carrier impregnation in sulfuric acid (50mL/L).
Oxidant: preferably make in sulfuric acid containing the oxidant such as persulfate, hydrogen peroxide.By containing oxidant, slightly can cut down carrier surface and expose active surface.
(2) nickel plating or cobalt plating
After pre-treatment, then carry out nickel plating or cobalt plating.Now, densification, evenly and do not have defective coating is importantly finish-machined to.As nickel plating or cobalt plating, carry out in following condition.
Plating solution
Nickel or cobalt: 20 ~ 200g/L
Boric acid: 5 ~ 60g/L
Liquid temperature: 40 ~ 65 DEG C
PH:1.5 ~ 5.0, preferably 2.0 ~ 3.0.By being arranged by pH lower slightlyly periodically carry out plating process, and producing hydrogen, making cathode surface become reducing environment.Therefore, oxide, hydroxide, hydrate etc. can be suppressed to produce the generation of the reason key element of moisture.
Current density: 0.5 ~ 20A/dm 2, preferably 2 ~ 8A/dm 2.Carry out processing owing to not easily causing plating slightly crisp under low current density, become the few and coating of densification of defect, so preferably.
Stir (liquid internal circulating load)
100 ~ 1000L/ minute.The many meetings of liquid internal circulating load make the air release of the hydrogen of generation become good, and the defects such as pin hole tail off.In addition, there is the effect reducing thickness of diffusion layer, hydroxide etc. can be suppressed to produce the generation of the reason key element of moisture.
Travelling speed
2 ~ 30m/ minute, preferably 5 ~ 10m/ minute.Travelling speed can be formed smoothly and the Ni layer of densification slowly.
Additive
Additive preferably uses with polishing material and secondary polishing material next time.Thus, crystal becomes level and smooth and fine and close.Therefore, the defect that plating produces reduces, and the absorption of moisture reduces.
(polishing material)
It is 1,5-naphthalene disulfonate: 2 ~ 10g/L, 1,3,6-naphthalene trisulfonic acid sodium: 10 ~ 30g/L, para toluene sulfonamide: 0.5 ~ 4g/L, saccharin sodium: any one in 0.5 ~ 5g/L.
(secondary polishing material)
It is formalin: 0.5 ~ 5g/L, gelatin: 0.005 ~ 0.5g/L, thiocarbamide: 0.05 ~ 1.0g/L, propargyl alcohol: 0.01 ~ 0.3g/L, Isosorbide-5-Nitrae-butynediols: 0.05 ~ 0.5g/L, cyanoethanol: any one in 0.05 ~ 0.5g/L.
After carrying out the metal-plated such as nickel plating, then carry out (3) chromate process under the following conditions or carry out (4) under the following conditions utilizing organic process.
(3) chromate process
Treatment fluid
Chromium: 0.5 ~ 6.0g/L
Zinc: 0.1 ~ 2.0g/L
pH：2.5～5.0
Liquid temperature: 25 ~ 60 DEG C
Current density: 0.1 ~ 4A/dm 2
In addition, also other element can be contained in the treatment fluid of chromate process.
(4) organic process is utilized
Treatment fluid
Organic matter: 0.1 ~ 20g/L
pH：2～5
Liquid temperature: 20 ~ 40 DEG C
Dip time: 5 ~ 30 seconds
The preferred described organic matter of organic matter, such as comprise the organic matter of any one in organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid.
[process carried out to forming very thin layers of copper after forming intermediate layer]
Behind formation intermediate layer to the very thin layers of copper of formation, preferably carry out following heating and/or reduction treatment further.By carrying out this process, moisture generation when can make heating as mentioned above obtains the Copper Foil of the appendix body controlled.
(5) heat
In chromate process or after utilizing organic process, remove moisture by carrying out under the following conditions heating before copper facing.
Such as, utilize and line processes with heating about 100 ~ 200 DEG C, preferably 180 DEG C 1 minute.Further, if go back and use the heating using IR heater, then more effective.In addition, if one side passes into the heating of hydrogen one side, then also there is reduction effect, further effectively.
(6) reduction treatment
By using reducing agent to carry out post processing under the following conditions, O (oxygen) can be reduced.
Such as, the formic acid (0.1 ~ 100g/L) of reducing agent is used as to carry out impregnation process.
The very thin layers of copper > of <
Very thin layers of copper is set on the intermediate layer.Also other layer can be set between intermediate layer and very thin layers of copper.Very thin layers of copper can be formed by utilizing the plating of the electrobaths such as copper sulphate, cupric pyrophosphate, sulfamic acid copper, copper cyanider, and from the viewpoint that high current density can be utilized to form layers of copper, preferably sulfuric acid copper is bathed.The thickness of very thin layers of copper is not particularly limited, usually thin than carrier, such as, be less than 12 μm.Typical case is 0.5 ~ 12 μm, and more typical is 1 ~ 5 μm, and more typical is further 1.5 ~ 5 μm, and more typical is further 2 ~ 5 μm.In addition, very thin layers of copper also can be arranged on the two-sided of carrier.
The Copper Foil of appendix body of the present invention can be used to carry out making layer laminate (copper foil covered laminate etc.).As this layered product, it can be such as the formation of sequentially lamination " very thin layers of copper/intermediate layer/carrier/resin or prepreg ", also can be the formation of sequentially lamination " carrier/intermediate layer/very thin layers of copper/resin or prepreg ", also can be the formation of sequentially lamination " very thin layers of copper/intermediate layer/carrier/resin or prepreg/carrier/intermediate layer/very thin layers of copper ", also can be the formation of sequentially lamination " carrier/intermediate layer/very thin layers of copper/resin or prepreg/very thin layers of copper/intermediate layer/carrier ".As long as described resin or the following resin bed of prepreg just can, also can comprise resin, hardening of resin agent, compound, hardening accelerator, dielectric medium, catalysts, crosslinking agent, polymer, prepreg, framework material etc. that following resin bed uses.In addition, the Copper Foil of appendix body also can be less than resin or prepreg when overlooking.
< roughening treatment and other surface treatment >
Such as well etc. can implement roughening treatment to make with the adaptation of insulated substrate by any surface on the surface of very thin layers of copper or the surface of carrier or two sides, thus roughening treatment layer is set.Roughening treatment such as can form alligatoring particle by utilizing copper or copper alloy and carry out.Roughening treatment also can be fine.Roughening treatment layer by the arbitrary simple substance be selected from the group that is made up of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc or can comprise the layer etc. that any one above alloy forms.In addition, after utilizing copper or copper alloy to form alligatoring particle, the simple substance of nickel, cobalt, copper, zinc or alloy etc. can also be utilized further to carry out arranging the roughening treatment of offspring or three particles.Thereafter, the simple substance of nickel, cobalt, copper, zinc or alloy etc. can be utilized to form refractory layer and/or antirust coat, also can implement the process such as chromate process, silane coupled process on its surface further.Or also can not carry out roughening treatment and utilize the simple substance of nickel, cobalt, copper, zinc or alloy etc. to form refractory layer and/or antirust coat, implementing the process such as chromate process, silane coupled process on its surface further.That is, more than one the layer be selected from the group be made up of refractory layer, antirust coat, chromating layer and silane coupled processing layer can be formed on the surface of roughening treatment layer, also can form more than one the layer be selected from the group be made up of refractory layer, antirust coat, chromating layer and silane coupled processing layer on the surface of very thin layers of copper.In addition, described refractory layer, antirust coat, chromating layer, silane coupled processing layer can form multilayer (such as more than 2 layers, 3 layers with first-class) respectively.
Here, chromating layer refers to and utilizes the liquid comprising chromic anhybride, chromic acid, dichromic acid, chromate or bichromate to carry out the layer processed.Chromating layer also can contain the elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium (can be the form arbitrarily such as metal, alloy, oxide, nitride, sulfide).As the concrete example of chromating layer, can enumerate utilize chromic anhybride or potassium dichromate aqueous solution carried out process chromating layer, utilize comprise chromic anhybride or potassium bichromate and zinc treatment fluid carried out process chromating layer etc.
As refractory layer, antirust coat, known refractory layer, antirust coat can be used.Such as, refractory layer and/or antirust coat can be comprise be selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group in the layer of more than one element, also can be the metal level or alloy-layer that are made up of the element of more than one in the group being selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum.In addition, refractory layer and/or antirust coat also can containing comprise be selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group in oxide, nitride, the silicide of more than one element.In addition, refractory layer and/or antirust coat also can be the layers comprising nickel-kirsite.In addition, refractory layer and/or antirust coat also can be nickel-zinc alloy layers.Described nickel-zinc alloy layer, except inevitable impurity, can contain nickel 50wt% ~ 99wt%, zinc 50wt% ~ 1wt%.The zinc of described nickel-zinc alloy layer and the total adhesion amount of nickel can be 5 ~ 1000mg/m 2, preferably 10 ~ 500mg/m 2, preferably 20 ~ 100mg/m 2.In addition, the ratio (adhesion amount of the adhesion amount/zinc of=nickel) comprising the layer of nickel-kirsite or the adhesion amount of nickel of described nickel-zinc alloy layer and the adhesion amount of zinc described in preferably 1.5 ~ 10.In addition, the preferred 0.5mg/m of adhesion amount of the layer of nickel-kirsite or the nickel of described nickel-zinc alloy layer is comprised described in 2~ 500mg/m 2, more preferably 1mg/m 2~ 50mg/m 2.When refractory layer and/or antirust coat are the layer comprising nickel-kirsite, the adaptation of Copper Foil and resin substrate promotes.
Such as, refractory layer and/or antirust coat can be adhesion amounts is 1mg/m 2~ 100mg/m 2, preferred 5mg/m 2~ 50mg/m 2nickel or nickel alloy layer and adhesion amount be 1mg/m 2~ 80mg/m 2, preferred 5mg/m 2~ 40mg/m 2tin layers sequentially lamination form, described nickel alloy layer can be made up of any one in nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt.In addition, the total adhesion amount of refractory layer and/or the preferred nickel of antirust coat or nickel alloy and tin is 2mg/m 2~ 150mg/m 2, more preferably 10mg/m 2~ 70mg/m 2.In addition, refractory layer and/or antirust coat be [the nickel adhesion amount in nickel or nickel alloy]/[tin adhesion amount]=0.25 ~ 10 preferably, and more preferably 0.33 ~ 3.If use this refractory layer and/or antirust coat, then after the Copper Foil of appendix body being processed into printed wiring board, the peel strength of circuit, the chemical-resistant deterioration rate etc. of this peel strength become good.
In addition, known silane coupler can be used for the silane coupler arranging silane coupled processing layer, such as, can use amino system silane coupler or epoxy silane coupler, sulfydryl system silane coupler.In addition, silane coupler can use vinyltrimethoxy silane, ethenylphenyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, 4-glycidyl butyl trimethoxy silane, γ aminopropyltriethoxy silane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-3-(4-(the amino propoxyl group of 3-) butoxy) propyl group-3-TSL 8330, imidizole silane, triazine silane, γ mercaptopropyitrimethoxy silane etc.
Described silane coupled processing layer can use the formation such as silane coupler such as epoxy silane, amino system silane, methacryloxy system silane, sulfydryl system silane.In addition, this silane coupler also can mix two or more use.Wherein, amino system silane coupler or epoxy silane coupler is preferably used to be formed.
Amino system mentioned here silane coupler can be selected from by N-(2-amino-ethyl)-3-TSL 8330, 3-(N-styrylmethyl-2-aminoethylamino) propyl trimethoxy silicane, APTES, two (2-hydroxyethyl)-APTES, TSL 8330, N-dimethylaminopropyl trimethoxy silane, N-phenyl amino propyl trimethoxy silane, N-(3-acryloxy-2-hydroxypropyl)-APTES, 4-ammobutyltriethoxysilane, (aminoethylaminomethyl) phenethyl trimethoxy silane, N-(2-amino-ethyl-3-aminopropyl) trimethoxy silane, N-(2-amino-ethyl-3-aminopropyl) three (2-ethyl hexyl oxy) silane, 6-(aminohexylaminopropyl) trimethoxy silane, aminophenyl trimethoxy silane, 3-(the amino propoxyl group of 1-)-3,3-dimethyl-1-acrylic trimethoxy silanes, 3-aminopropyl three (methoxyethoxyethoxy) silane, APTES, 3-TSL 8330, omega-amino-undecyltrimethoxysilane, 3-(2-N-hexylamino diethylaminobutyyl) trimethoxy silane, two (2-hydroxyethyl)-APTES, (N, N-diethyl-3-aminopropyl) trimethoxy silane, (N, N-dimethyl-3-aminopropyl) trimethoxy silane, N-dimethylaminopropyl trimethoxy silane, N-phenyl amino propyl trimethoxy silane, 3-(N-styrylmethyl-2-aminoethylamino) propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, the group that N-3-(4-(the amino propoxyl group of 3-) butoxy) propyl group-3-TSL 8330 forms.
Silane coupled processing layer it is desirable to convert at 0.05mg/m with silicon atom 2~ 200mg/m 2, preferred 0.15mg/m 2~ 20mg/m 2, preferred 0.3mg/m 2~ 2.0mg/m 2scope in arrange.In described scope, the adaptation of base material and surface treatment copper foil can be improved further.
In addition, the surface treatment described in International Publication numbering WO2008/053878, No. 2008-111169, Japanese Patent Laid-Open, No. 5024930th, Japan Patent, No. 4828427th, International Publication numbering WO2006/028207, Japan Patent, No. 5046927th, International Publication numbering WO2006/134868, Japan Patent, No. 5180815th, International Publication numbering WO2007/105635, Japan Patent, No. 2013-19056, Japanese Patent Laid-Open can be carried out to the surface of very thin layers of copper, roughening treatment floor, refractory layer, antirust coat, silane coupled processing layer or chromating layer.
In addition, the Copper Foil of appendix body of the present invention also can possess resin bed in described very thin layers of copper or on described roughening treatment layer or on described refractory layer, antirust coat or chromating layer or silane coupled processing layer.Described resin bed also can be insulating resin layer.
Described resin bed can be adhesive, also can be the insulating resin layer of the semi-hardened state (B-stage state) of bonding.Semi-hardened state (B-stage state) comprises following state: namely use finger touch insulating resin layer surface also not adhere to sense, by the keeping of this insulating resin ply, if heated further, then can produce sclerous reaction.
In addition, described resin bed can contain thermosetting resin, also can be thermoplastic resin.In addition, described resin bed also can contain thermoplastic resin.Its kind is not particularly limited, as suitable resin, such as can enumerate: comprise epoxy resin, polyimide resin, multi-functional cyanate esters, maleimide compound, polyvinyl acetal resin, polyurethane resin, polyether sulfone, polyethersulfone resin, aromatic polyamide resin, polyamide-imide resin, rubber becomes epoxy resin, phenoxy resin, carboxyl upgrading acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide-triazine resin, thermosetting polyphenylene oxide resin, cyanate ester based resin, the resin of the acid anhydride of polybasic carboxylic acid etc.
Described resin bed also can comprise known resin, hardening of resin agent, compound, hardening accelerator, dielectric medium (can use the dielectric medium arbitrarily such as the dielectric medium comprising inorganic compound and/or organic compound, the dielectric medium comprising metal oxide), catalysts, crosslinking agent, polymer, prepreg, framework material etc.In addition, described resin bed also can use such as No. WO2008/004399, International Publication numbering, International Publication numbering WO2008/053878, International Publication numbering WO2009/084533, No. 11-5828, Japanese Patent Laid-Open, No. 11-140281, Japanese Patent Laid-Open, No. 3184485th, Japan Patent, International Publication numbering WO97/02728, No. 3676375th, Japan Patent, No. 2000-43188, Japanese Patent Laid-Open, No. 3612594th, Japan Patent, No. 2002-179772, Japanese Patent Laid-Open, No. 2002-359444, Japanese Patent Laid-Open, No. 2003-304068, Japanese Patent Laid-Open, Japan Patent the 3992225th, No. 2003-249739, Japanese Patent Laid-Open, No. 4136509th, Japan Patent, No. 2004-82687, Japanese Patent Laid-Open, No. 4025177th, Japan Patent, No. 2004-349654, Japanese Patent Laid-Open, No. 4286060th, Japan Patent, No. 2005-262506, Japanese Patent Laid-Open, No. 4570070th, Japan Patent, No. 2005-53218, Japanese Patent Laid-Open, No. 3949676th, Japan Patent, No. 4178415th, Japan Patent, International Publication numbering WO2004/005588, No. 2006-257153, Japanese Patent Laid-Open, No. 2007-326923, Japanese Patent Laid-Open, No. 2008-111169, Japanese Patent Laid-Open, No. 5024930th, Japan Patent, International Publication numbering WO2006/028207, No. 4828427th, Japan Patent, No. 2009-67029, Japanese Patent Laid-Open, International Publication numbering WO2006/134868, No. 5046927th, Japan Patent, No. 2009-173017, Japanese Patent Laid-Open, International Publication numbering WO2007/105635, No. 5180815th, Japan Patent, International Publication numbering WO2008/114858, International Publication numbering WO2009/008471, No. 2011-14727, Japanese Patent Laid-Open, International Publication numbering WO2009/001850, International Publication numbering WO2009/145179, International Publication numbering WO2011/068157, material (resin described in No. 2013-19056, Japanese Patent Laid-Open, hardening of resin agent, compound, hardening accelerator, dielectric medium, catalysts, crosslinking agent, polymer, prepreg, framework material etc.) and/or the formation method of resin bed, forming apparatus is formed.
These resins are such as dissolved in methyl ethyl ketone (MEK), toluene equal solvent and make resin liquid, rolling method etc. it is such as utilized to be coated in described very thin layers of copper or on described refractory layer, antirust coat or described chromate skin membrane or described silane coupling agent layer, then heat drying and remove solvent as required, makes B-stage state.Use as long as dry such as hot-air drying stove just can, baking temperature is 100 ~ 250 DEG C, preferably 130 ~ 200 DEG C just can.
The Copper Foil (Copper Foil of the appendix body of attached resin) possessing the appendix body of described resin bed uses with following form: after this resin bed and base material overlap, entirety is carried out thermo-compressed and makes this resin bed thermmohardening, then carrier peeled off and expose very thin layers of copper (certainly, what expose is the surface of the side, intermediate layer of this very thin layers of copper), and form specific wiring pattern in very thin layers of copper.
If use the Copper Foil of the appendix body of this attached resin, then can reduce the use sheet number of prepreg material when manufacturing multi-layer printed wiring base plate.And, the thickness of resin bed can be set to the thickness can guaranteeing layer insulation, even if or do not use prepreg material also can manufacture copper clad laminate completely.In addition, now also surperficial flatness can be improved further by primary coat insulating resin on the surface of base material.
In addition, when not using prepreg material, there is following advantage: the material cost of saving prepreg material, and lamination step also becomes simple, so economical advantages, in addition, the lower thickness of the multi-layer printed wiring base plate manufactured with the thickness of prepreg material, the thickness that can manufacture 1 layer is the very thin multi-layer printed wiring base plate of less than 100 μm.
The thickness of this resin bed preferably 0.1 ~ 80 μm.The thickness of if tree lipid layer is thinner than 0.1 μm, then there is following situation: bonding force reduces, be not situated between every prepreg material, the copper foil layer of the appendix body of this attached resin is pressed in the base material possessing inner layer material time, be difficult to guarantee and inner layer material circuit between layer insulation.
On the other hand, be thicker than 80 μm if be set to by the thickness of resin bed, be then difficult to the resin bed utilizing 1 application step formation target thickness, unnecessary fee of material and man-hour can be spent, so unfavorable economically.Further, there is following situation: the flexibility of the resin bed of formation is poor, so easily produce be full of cracks etc. during operation, and too much resin flows can be produced with during inner layer material thermo-compressed, be difficult to successfully lamination.
And, as another product form of the Copper Foil of the appendix body of this attached resin, also can resin bed be utilized to be coated in described very thin layers of copper or on described refractory layer, antirust coat or described chromating layer or described silane coupled processing layer, and after making semi-hardened state, then carrier is peeled off, there is not the form manufacture of the Copper Foil of the attached resin of carrier.
Below, the example that some use the manufacturing step of the printed wiring board of the Copper Foil of appendix body of the present invention is enumerated.
In an embodiment of the manufacture method of printed wiring board of the present invention, comprise the steps: the Copper Foil and the insulated substrate that prepare appendix body of the present invention; The Copper Foil of described appendix body and insulated substrate are carried out lamination; And by the Copper Foil of described appendix body and insulated substrate with after the mode lamination relative with insulated substrate of very thin layers of copper side, forming copper clad laminate through peeling off the step of the carrier of the Copper Foil of described appendix body, forming circuit by any one method in semi-additive process, improvement semi-additive process, part addition process and subtractive process thereafter.Insulated substrate also can be set to the insulated substrate being provided with internal layer circuit.
In the present invention, semi-additive process refers to carries out thin electroless plating on insulated substrate or Copper Foil inculating crystal layer, after forming pattern, uses plating and etching to form the method for conductive pattern.
Therefore, in an embodiment of the manufacture method of the printed wiring board of the present invention of use semi-additive process, comprise the steps:
Prepare Copper Foil and the insulated substrate of appendix body of the present invention;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, peel off the carrier of the Copper Foil of described appendix body;
The very thin layers of copper that the described carrier of stripping exposes being utilized uses acid to wait the methods such as the etching of etchant solution or plasma all to remove;
At the described resin exposed by utilizing etching to remove described very thin layers of copper, through hole and/or blind hole are set;
De-smear process is carried out to the region comprising described through hole and/or blind hole;
In the region comprising described resin and described through hole and/or blind hole, electroless plating is set;
Described electroless plating arranges plating resist application;
Described plating resist application is exposed, removes thereafter the plating resist application in the region formed for circuit;
In the described region for circuit formation eliminating described plating resist application, electro deposition is set;
Remove described plating resist application; And
Fast-etching etc. is utilized to remove described for the electroless plating on the region beyond the region of circuit formation.
In another embodiment of the manufacture method of the printed wiring board of the present invention of use semi-additive process, comprise the steps:
Prepare Copper Foil and the insulated substrate of appendix body of the present invention;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, peel off the carrier of the Copper Foil of described appendix body;
The very thin layers of copper that the described carrier of stripping exposes being utilized uses acid to wait the methods such as the etching of etchant solution or plasma all to remove;
On the surface of the described resin exposed by utilizing etching to remove described very thin layers of copper, electroless plating is set;
Described electroless plating arranges plating resist application;
Described plating resist application is exposed, removes thereafter the plating resist application in the region formed for circuit;
In the described region for circuit formation eliminating described plating resist application, electro deposition is set;
Remove described plating resist application; And
Fast-etching etc. is utilized to remove described for the electroless plating on the region beyond the region of circuit formation and very thin layers of copper.
In the present invention; improvement semi-additive process refers to following method: laminated metal foil on the insulating layer; plating resist application is utilized to protect inverter circuit forming portion; utilize electrolysis plating in the copper facing of circuit forming portion; thereafter plating resist application is removed; utilize the metal forming beyond the described circuit forming portion of (fast) etching removal, form circuit on the insulating layer thus.
Therefore, in the embodiment of manufacture method using the printed wiring board of the present invention improveing semi-additive process, comprise the steps:
Prepare Copper Foil and the insulated substrate of appendix body of the present invention;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, peel off the carrier of the Copper Foil of described appendix body;
The very thin layers of copper exposed peeling off described carrier and insulated substrate arrange through hole and/or blind hole;
De-smear process is carried out to the region comprising described through hole and/or blind hole;
In the region comprising described through hole and/or blind hole, electroless plating is set;
The very thin layers of copper surface of exposing peeling off described carrier arranges plating resist application;
After described plating resist application is set, electrolysis plating is utilized to form circuit;
Remove described plating resist application; And
Fast-etching is utilized to remove the very thin layers of copper exposed by removing described plating resist application.
In another embodiment of manufacture method using the printed wiring board of the present invention improveing semi-additive process, comprise the steps:
Prepare Copper Foil and the insulated substrate of appendix body of the present invention;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, peel off the carrier of the Copper Foil of described appendix body;
The very thin layers of copper that the described carrier of stripping exposes arranges plating resist application;
Described plating resist application is exposed, removes thereafter the plating resist application in the region formed for circuit;
In the described region for circuit formation eliminating described plating resist application, electro deposition is set;
Remove described plating resist application; And
Fast-etching etc. is utilized to remove described for the electroless plating on the region beyond the region of circuit formation and very thin layers of copper.
In the present invention, part addition process refers to following method: arrange conductor layer substrate, as required get through through hole or perforation hole substrate on give catalyst core, carry out etching and forming conductor circuit, after solder resist or plating resist application are set as required, described conductor circuit utilizes electroless plating process to carry out plating to through hole or perforation etc., manufactures printed wiring board thus.
Therefore, in an embodiment of the manufacture method of the printed wiring board of the present invention of use part addition process, comprise the steps:
Prepare Copper Foil and the insulated substrate of appendix body of the present invention;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, peel off the carrier of the Copper Foil of described appendix body;
Peeling off the very thin layers of copper exposed of described carrier and insulated substrate arranges through hole and/or blind hole;
De-smear process is carried out to the region comprising described through hole and/or blind hole;
Catalyst core is given to the region comprising described through hole and/or blind hole;
The very thin layers of copper surface of exposing peeling off described carrier arranges resist;
Described resist is exposed and forms circuit pattern;
Utilize methods such as using the etching of the etchant solutions such as acid or plasma to remove described very thin layers of copper and described catalyst core and form circuit;
Remove described resist;
The described insulated substrate surface of exposing utilizing methods such as using the etching of the etchant solutions such as acid or plasma to remove described very thin layers of copper and described catalyst core arranges solder resist or plating resist application; And
In the region not arranging described solder resist or plating resist application, electroless plating is set.
In the present invention, subtractive process refers to and utilizes etching to wait the unwanted part optionally removing the Copper Foil on copper clad laminate and the method forming conductive pattern.
Therefore, in an embodiment of the manufacture method of the printed wiring board of the present invention of use subtractive process, comprise the steps:
Prepare Copper Foil and the insulated substrate of appendix body of the present invention;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, peel off the carrier of the Copper Foil of described appendix body;
The very thin layers of copper exposed peeling off described carrier and insulated substrate arrange through hole and/or blind hole;
De-smear process is carried out to the region comprising described through hole and/or blind hole;
In the region comprising described through hole and/or blind hole, electroless plating is set;
On the surface of described electroless plating, electro deposition is set;
On the surface of described electro deposition and/or described very thin layers of copper, resist is set;
Described resist is exposed, forms circuit pattern;
Described very thin layers of copper and described electroless plating and described electro deposition utilized the removal such as the method that uses the etching of the etchant solutions such as acid or plasma and form circuit; And
Remove described resist.
In another embodiment of the manufacture method of the printed wiring board of the present invention of use subtractive process, comprise the steps:
Prepare Copper Foil and the insulated substrate of appendix body of the present invention;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, peel off the carrier of the Copper Foil of described appendix body;
Peeling off the very thin layers of copper exposed of described carrier and insulated substrate arranges through hole and/or blind hole;
De-smear process is carried out to the region comprising described through hole and/or blind hole;
In the region comprising described through hole and/or blind hole, electroless plating is set;
Shade is formed on the surface of described electroless plating;
On the surface of the described electroless plating not forming shade, electro deposition is set;
On the surface of described electro deposition and/or described very thin layers of copper, resist is set;
Described resist is exposed and forms circuit pattern;
Utilize methods such as using the etching of the etchant solutions such as acid or plasma to remove described very thin layers of copper and described electroless plating and form circuit; And
Remove described resist.
Also step and subsequent de-smear step that through hole and/or blind hole are set can not be carried out.
Here, the concrete example of the graphic manufacture method to using the printed wiring board of the Copper Foil of appendix body of the present invention is used to be described in detail.In addition, here, be described for the Copper Foil defining the appendix body of roughening treatment layer on very thin layers of copper surface, but also can not form roughening treatment layer.
First, as shown in Fig. 1-A, prepare that there is the Copper Foil (the 1st layer) that surface defines the appendix body of the very thin layers of copper of roughening treatment layer.
Then, as shown if figure 1-b, the roughening treatment layer of very thin layers of copper is coated with plating resist application, and carries out exposing, developing, plating resist application is etched into specific shape.
Then, as shown in Fig. 1-C, after formation circuit coating, remove plating resist application, form the circuit coating of given shape thus.
Then, as depicted in fig. 2-d, in the mode (to bury the mode of circuit coating) covering circuit coating, landfill resin is set in very thin layers of copper and laminated resin layer, then bonds the Copper Foil (the 2nd layer) of another sheet appendix body from very thin layers of copper side.
Then, as shown in Fig. 2-E, carrier is peeled off from the Copper Foil of the 2nd layer of appendix body.
Then, as shown in Fig. 2-F, carry out laser beam drilling at the ad-hoc location of resin bed, expose circuit coating and form blind hole.
Then, as shown in Fig. 3-G, filling through hole thing is formed at blind hole landfill copper.
Then, as shown in Fig. 3-H, filling through hole thing forms circuit coating in the mode of described Fig. 1-B and Fig. 1-C.
Then, as shown in Fig. 3-I, carrier is peeled off from the Copper Foil of the 1st layer of appendix body.
Then, as shown in Fig. 4-J, utilize fast-etching to remove the very thin layers of copper on two surfaces, expose the surface of the circuit coating in resin bed.
Then, as shown in Fig. 4-K, the circuit coating in resin bed forms projection, this solder is formed copper post.Make the printed wiring board of the Copper Foil using appendix body of the present invention in the manner.
The Copper Foil (the 2nd layer) of described other appendix body can use the Copper Foil of appendix body of the present invention, also can use the Copper Foil of appendix body in the past, and then also can use common Copper Foil.In addition, also and then 1 layer or multilayer circuit can be formed on layer circuit of the 2nd shown in Fig. 3-H, also can form these circuit by any one method in semi-additive process, subtractive process, part addition process or improvement semi-additive process.
In addition, the Copper Foil of the described 1st layer of appendix body used also can have substrate on the carrier side surface of the Copper Foil of this appendix body.By having this substrate, the Copper Foil of the 1st layer of appendix body used is supported, and not easily produces gauffer, so the advantage having productivity to promote.In addition, as long as described substrate has the effect of the Copper Foil supporting the described 1st layer of appendix body used, then all substrates can be used.Such as, as described substrate, the carrier described in this case description, prepreg, resin bed or known carrier, prepreg, resin bed, metallic plate, metal forming, the plate of inorganic compound, the paper tinsel of inorganic compound, the plate of organic compound, the paper tinsel of organic compound can be used.
Be not particularly limited about the time point forming substrate on carrier side surface, but must be formed before stripping carrier.Especially be preferable over and formed before the described very thin layers of copper side surface of the Copper Foil of described appendix body forms the step of resin bed, more preferably formed before the described very thin layers of copper side surface of the Copper Foil at appendix body forms the step of circuit.
In addition, landfill resin (resin) can use known resin, prepreg.Such as can use BT (Bismaleimide Triazine) resin or the prepreg of the glass cloth of BT resin, Ajinomoto Fine-Techno limited company manufacture as impregnation ABF film or ABF.In addition, described landfill resin can contain thermosetting resin, also can be thermoplastic resin.In addition, described landfill resin also can contain thermoplastic resin.The kind of described landfill resin is not particularly limited, as suitable resin, such as can enumerate: comprise epoxy resin, polyimide resin, multi-functional cyanate esters, maleimide compound, polyvinyl acetal resin, polyurethane resin, block copolymerization polyimide resin, block copolymerization polyimide resin, polyether sulfone, polyethersulfone resin, aromatic polyamide resin, polyamide-imide resin, rubber becomes epoxy resin, phenoxy resin, carboxyl upgrading acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide-triazine resin, thermosetting polyphenylene oxide resin, cyanate ester based resin, the resin of the acid anhydride of polybasic carboxylic acid etc., or paper base material phenol resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth/paper composite base material epoxy resin, glass cloth/glass non-woven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film, liquid crystalline polymer film, fluororesin film etc.In addition, described landfill resin (resin) can use resin bed described in this description and/or resin and/or prepreg.
Further, by printed wiring board electronic component mounting class of the present invention, thus printed circuit board (PCB) is completed.In the present invention, " printed wiring board " also comprises the printed wiring board and printed circuit board (PCB) and printed base plate that have carried electronic component class like this.
In addition, this printed wiring board can be used to make e-machine, this also can be used to have carried the print circuit plates making e-machine of electronic component class, the printed base plate that this also can be used to have carried electronic component class makes e-machine.
In addition, the manufacture method of printed wiring board of the present invention also can be the manufacture method (called non-sleeve method) of the printed wiring board comprised the steps: by the described very thin layers of copper side surface of the Copper Foil of appendix body of the present invention or described carrier side surface and resin substrate carry out lamination; The surface of the Copper Foil of the appendix body being opposition side on very thin layers of copper side surface or the described carrier side surface with described and resin substrate lamination at least arranges 1 resin bed and circuit, and this is two-layer; And formation described resin bed and circuit this two-layer after, peel off described carrier or described very thin layers of copper from the Copper Foil of described appendix body.About this called non-sleeve method, as concrete example, first, by the very thin layers of copper side surface of the Copper Foil of appendix body of the present invention or carrier side surface and resin substrate carry out lamination.Thereafter, surface forms resin bed with being the Copper Foil of the appendix body of opposition side with the very thin layers of copper side surface of resin substrate lamination or described carrier side surface.Also the Copper Foil of resin bed from carrier side or very thin layers of copper side and then another sheet appendix body of lamination on carrier side surface or very thin layers of copper side surface can be formed at.In the case, become following formation: centered by resin substrate, in two face side of this resin substrate with the order of carrier/intermediate layer/very thin layers of copper or with the Copper Foil of the order lamination appendix body of very thin layers of copper/intermediate layer/carrier.Also the surface can exposed at very thin layers of copper or the carrier at two ends arranges another resin bed, and and then layers of copper or metal level are set, then this layers of copper or metal level are processed, form circuit thus.Also can and then another resin bed be arranged on this circuit in the mode of this circuit of landfill.In addition, also the formation of this circuit and resin bed can be carried out more than 1 time (Layer increasing method).Further, about the layered product formed in the above described manner (hereinafter also referred to layered product B), the very thin layers of copper of the Copper Foil of each appendix body or carrier can be peeled off from carrier or very thin layers of copper and made coreless substrate.In addition, when making described coreless substrate, also the Copper Foil of 2 appendix bodies can be used, the layered product of the layered product making the following layered product with the formation of very thin layers of copper/intermediate layer/carrier/carrier/intermediate layer/very thin layers of copper or the formation with carrier/intermediate layer/very thin layers of copper/very thin layers of copper/intermediate layer/carrier or the formation with carrier/intermediate layer/very thin layers of copper/carrier/intermediate layer/very thin layers of copper, and this layered product is used for center.This is two-layer can to arrange more than 1 time resin bed and circuit in the very thin layers of copper of both sides of these layered products (hereinafter also referred to layered product A) or the surface of carrier, arrange more than 1 time resin bed and circuit this two-layer after, the very thin layers of copper of the Copper Foil of each appendix body or carrier are peeled off from carrier or very thin layers of copper and are made coreless substrate.Described layered product is on the surface of the surface of very thin layers of copper, carrier, also can have other layer between carrier and carrier, between very thin layers of copper and very thin layers of copper, between very thin layers of copper and carrier.In addition, in this description, " surface of very thin layers of copper ", " very thin layers of copper side surface ", " surface of carrier ", " carrier side surface ", " surface of layered product ", when very thin layers of copper, carrier, layered product have other layer at very thin layers of copper surface, carrier surface, laminate surface, are the concepts being set to the surface (most surface) comprising this other layer.In addition, layered product preferably has the formation of very thin layers of copper/intermediate layer/carrier/carrier/intermediate layer/very thin layers of copper.This be due to: when using this layered product to make coreless substrate, because configure very thin layers of copper in coreless substrate side, so easily use improvement semi-additive process to form circuit on coreless substrate.In addition, be due to: because the thickness of very thin layers of copper is thin, so easily remove this very thin layers of copper, after removing very thin layers of copper, easily use semi-additive process to form circuit on coreless substrate.
In addition, in this manual, " layered product " that be not recorded into " layered product A " or " layered product B " especially represents the layered product at least comprising layered product A and layered product B.
In addition, in the manufacture method of described coreless substrate, part or all of the Copper Foil of appendix body or the end face of layered product (layered product A) is covered by utilizing resin, when utilizing Layer increasing method to manufacture printed wiring board, can prevent liquid from penetrating between the Copper Foil of a slice appendix body of intermediate layer or constituting layer laminate and the Copper Foil of another sheet appendix body, being separated or the corrosion of Copper Foil of appendix body of the very thin layers of copper that caused by the infiltration of liquid and carrier can be prevented, can yield be promoted.As used " covering the resin of part or all of the end face of the Copper Foil of appendix body " or " resin of part or all of the end face of cover layer laminate ", the resin that can be used in resin bed can be used here.In addition, in the manufacture method of described coreless substrate, when overlooking the Copper Foil of appendix body or layered product, can being covered by resin or prepreg at least partially of the periphery of the Copper Foil of appendix body or the laminated portion (laminated portion of the Copper Foil of the laminated portion of carrier and very thin layers of copper or the Copper Foil of a slice appendix body and another sheet appendix body) of layered product.In addition, the layered product (layered product A) utilizing the manufacture method of described coreless substrate to be formed also can be make the Copper Foil of a pair appendix body mutually contact in a detachable fashion and form.In addition, when overlooking the Copper Foil of this appendix body, the periphery entirety of the Copper Foil of appendix body or the laminated portion (laminated portion of the Copper Foil of the laminated portion of carrier and very thin layers of copper or the Copper Foil of a slice appendix body and another sheet appendix body) of layered product also can be covered by resin or prepreg.By being set to this formation, when overlooking Copper Foil or the layered product of appendix body, the Copper Foil of appendix body or the laminated portion of layered product are covered by resin or prepreg, other parts can be prevented from this part side direction, namely collide relative to the direction of laminating direction transverse direction, as a result, the Copper Foil stripping each other of carrier and very thin layers of copper or appendix body in operation can be reduced.In addition, by utilizing resin or prepreg to cover in the mode of the periphery of the laminated portion of the Copper Foil or layered product that do not expose appendix body, liquid treatment step herb liquid described above can be prevented to the infiltration at the interface of this laminated portion, corrosion or the erosion of the Copper Foil of appendix body can be prevented.In addition, when the Copper Foil of a pair appendix body from layered product is separated the Copper Foil of a slice appendix body, or when being separated the carrier of Copper Foil and Copper Foil (the very thin layers of copper) of appendix body, must by cutting off the Copper Foil of appendix body or the laminated portion (laminated portion of the Copper Foil of the laminated portion of carrier and very thin layers of copper or the Copper Foil of a slice appendix body and another sheet appendix body) of layered product that wait and remove and utilize resin or prepreg covering.
Also the Copper Foil of appendix body of the present invention can be laminated to the carrier side of the Copper Foil of another sheet appendix of the present invention body or very thin layers of copper side from carrier side or very thin layers of copper side and constituting layer laminate.In addition, can be the layered product that the described carrier side surface of Copper Foil of described a slice appendix body or the described carrier side surface of the Copper Foil of described very thin layers of copper side surface and another sheet appendix body described or described very thin layers of copper side surface obtain via adhesive contact laminating as required.In addition, also the carrier of the Copper Foil of the carrier of the Copper Foil of described a slice appendix body or very thin layers of copper and another sheet appendix body described or pole thin copper layer Even can be connect.Here, Gai “ Even connects " when carrier or very thin layers of copper have surface-treated layer, also comprise the form connect via this surface-treated layer Xiang Hu Even.In addition, also part or all of the end face of this layered product can be covered by resin.
Carrier lamination each other except merely overlap, such as, can utilize following methods to carry out.
A () Ye Jin Even connects method: welding (arc welding, TIG (tungsten inert gas, tungsten-inert gas) welding, MIG (metal inert gas, metal-noble gas) welding, electric resistance welding, seam welding, means of spot welds), crimping (ultrasonic welding, friction stir weld), soldering;
B () Ji Xie Even connects method: ca(u)lk, utilize rivet Even to connect (utilize self-pierce riveting Even to connect, utilize rivet Even to connect), binder;
C () Wu Li Even connects method: adhesive, (two-sided) adhesive tape
Connecing method by part or all with another carrier of part or all of a carrier being used the Even that states to enter row Even and connect, can manufacture a carrier and another carrier lamination, carrier is contacted each other in a detachable fashion and the layered product that forms.If a carrier and another carrier more weak ground Even connect, then, when by a carrier and another carrier lamination, even if the Even not removing a carrier and another carrier meets portion, also a carrier can be separated with another carrier.In addition, when a carrier and another carrier compare Qiang Di Even connect, utilize the removal such as cut-out or chemical grinding (etching etc.), mechanical lapping by a position carrier and another Zai Ti Even connect, a carrier and another carrier can be separated.
In addition, printed wiring board can be made by being implemented as follows step: this is two-layer at least to arrange 1 resin bed and circuit at the layered product formed in the above described manner; And at least formed 1 described resin bed and circuit this two-layer after, peel off described very thin layers of copper or carrier from the Copper Foil of the appendix body of described layered product.In addition, also can arrange resin bed and circuit this is two-layer on of this layered product surface or two surfaces.
[embodiment]
Below, be described based on embodiment and comparative example.In addition, the present embodiment is an example only, is not limited to this example.
1. manufacture the Copper Foil of appendix body
As foil carriers, prepare the rectangular electrolytic copper foil (JTC that JX day ore deposit day stone metal company manufactures) of thickness 35 μm and the rolled copper foil (C1100 that JX day ore deposit day stone metal company manufactures) of thickness 33 μm.The continuous plating line of roller-roll shape is utilized to carry out nickel plating (Ni) or cobalt plating (Co) as after metal-plated under the following conditions to the glassy surface (bright face) of this Copper Foil, carry out BTA process as chromate process or utilize organic process, form intermediate layer thus.In addition, " degreasing ", " pickling " of table 1 represent utilize following condition to carrier respectively the surface of nickel plating or cobalt plating side will carry out the pre-treatment of nickel plating (Ni).Further, " polishing material " of table 1 represents in following nickel plating (Ni) process in the plating solution containing polishing material (polishing material and secondary polishing material).In addition, for embodiment 1,3,5,9,11, heat after chromate process.Heating-up temperature (baking temperature) is now shown in table 1.In addition, sequentially degreasing, pickling processes are carried out to the surface of carrier.This degreasing condition and acid washing conditions are shown in hereafter.
[degreasing]
Use following ungrease treatment liquid, carry out electrolytic degreasing under the following conditions.
Ungrease treatment liquid: sodium hydrate aqueous solution (naoh concentration 70g/L)
Electrolytic degreasing: carry out catholyte degreasing under the following conditions, carries out anode electrolysis degreasing thereafter, again carries out catholyte degreasing thereafter.
Negative electrode (electrolysis) degreasing (current density 10A/dm 2): 20 seconds
Anode (electrolysis) degreasing (current density 5A/dm 2): 20 seconds
Negative electrode (electrolysis) degreasing (current density 10A/dm 2): 20 seconds
[pickling]
Pickling processes liquid: aqueous sulfuric acid (sulfuric acid concentration: 50mL/L)
Dip time: 20 seconds
[nickel plating (Ni)]
Plating solution
Nickel: 20 ~ 200g/L
Boric acid: 5 ~ 60g/L
Liquid temperature: 40 ~ 65 DEG C
pH：1.5～5.0
Current density: 0.5 ~ 20A/dm 2
Conduction time: 1 ~ 20 second
Stir (liquid internal circulating load): 100 ~ 1000L/ minute
Travelling speed: 2 ~ 30m/ minute
Additive: polishing material (saccharin sodium: 0.5 ~ 5g/L), secondary polishing material (thiocarbamide: 0.05 ~ 1g/L) [cobalt plating (Co)]
Plating solution
Cobalt: 20 ~ 200g/L
Boric acid: 5 ~ 60g/L
Liquid temperature: 40 ~ 65 DEG C
pH：1.5～5.0
Current density: 0.5 ~ 20A/dm 2
Conduction time: 1 ~ 20 second
Stir (liquid internal circulating load): 100 ~ 1000L/ minute
Travelling speed: 2 ~ 30m/ minute
Additive: polishing material (saccharin sodium: 0.5 ~ 5g/L), secondary polishing material (thiocarbamide: 0.05 ~ 1g/L) [chromate process]
Treatment fluid
Chromium: 0.5 ~ 6.0g/L
Zinc: 0.1 ~ 2.0g/L
Liquid temperature: 25 ~ 60 DEG C
pH：2.5～5.0
Current density: 0.1 ~ 4A/dm 2
Conduction time: 1 ~ 30 second
[BTA process]
BTA process: the antirust treatment using BTA
Treatment fluid
BTA: 0.1 ~ 20g/L
pH：2～5
Liquid temperature: 20 ~ 40 DEG C
Dip time: 5 ~ 30 seconds
Then, by the continuous plating line of roller-roll shape, carry out under the following conditions electroplating and the very thin layers of copper of thickness on the intermediate layer described in formation table 1, thus make the Copper Foil of appendix body.
Very thin layers of copper
Copper concentration: 90 ~ 120g/L
H 2sO 4concentration: 20 ~ 120g/L
Electrolyte temperature: 20 ~ 80 DEG C
Current density: 10 ~ 70A/dm 2
Plating solution linear flow speed: 1.0m/s
About these embodiments and comparative example, following roughening treatment, antirust treatment, chromate process and silane coupled process are sequentially carried out to the surface of all very thin layers of copper.
Roughening treatment
Cu：10～20g/L
Co：5～15g/L
Ni：5～15g/L
pH：1～4
Temperature: 40 ~ 50 DEG C
Current density Dk:40 ~ 50A/dm 2
Time: 0.5 second ~ 2 seconds
Cu adhesion amount: 15 ~ 40mg/dm 2
Co adhesion amount: 100 ~ 3000 μ g/dm 2
Ni adhesion amount: 100 ~ 1000 μ g/dm 2
Antirust treatment
Zn：0～20g/L
Ni：0～5g/L
pH：3.5
Temperature: 40 DEG C
Current density Dk:0 ~ 1.7A/dm 2
Time: 1 second
Zn adhesion amount: 5 ~ 250 μ g/dm 2
Ni adhesion amount: 5 ~ 300 μ g/dm 2
Antirust treatment
Zn：10g/L
Ni：35g/L
pH：3.5
Temperature: 40 DEG C
Current density Dk:0.5A/dm 2
Time: 46 seconds
Zn adhesion amount: 150 ~ 1500 μ g/dm 2
Ni adhesion amount: 300 ~ 2600 μ g/dm 2
Chromate process
Treatment fluid forms:
K 2Cr 2O 7
(Na 2cr 2o 7or CrO 3): 2 ~ 10g/L
NaOH or KOH:10 ~ 50g/L
ZnO or ZnSO 47H 2o:0.05 ~ 10g/L
pH：7～13
Bath temperature: 20 ~ 80 DEG C
Current density: 0.05 ~ 5A/dm 2
Time: 5 ~ 30 seconds
Cr adhesion amount: 10 ~ 150 μ g/dm 2
Silane coupled process
The VTES aqueous solution
(VTES concentration: 0.1 ~ 1.4wt%)
pH：4～5
Time: 5 ~ 30 seconds
2. the assessment of the Copper Foil of appendix body
Various assessment is carried out to each sample of the embodiment made in the manner and comparative example is as described below.
The metal adhering amount in intermediate layer
Nickel adhesion amount and cobalt adhesion amount are nitric acid dissolves sample being utilized concentration 20 quality %, and the ICP emission spectrographic analysis device (model: SPS3100) using SII company to manufacture utilizes ICP luminesceence analysis to measure, zinc, chromium adhesion amount are the dissolving with hydrochloric acid by sample being utilized concentration 7 quality %, and the atomic absorption spectroscopy photometer (model: AA240FS) using VARIAN company to manufacture utilizes atom light absorption method carry out quantitative analysis and measure.In addition, the measurement of described nickel, cobalt, zinc, chromium adhesion amount is that profit is carried out with the following methods.First, after peeling off very thin layers of copper from the Copper Foil of appendix body, only dissolve the near surface of the side, intermediate layer of very thin layers of copper (when the thickness of very thin layers of copper is more than 1.4 μm, only dissolve 0.5 μm, the surface thickness apart from the side, intermediate layer of very thin layers of copper, when the thickness of very thin layers of copper does not reach 1.4 μm, only dissolve and play 20% of very thin copper layer thickness from the surface of the side, intermediate layer of very thin layers of copper), measure the adhesion amount on the surface of the side, intermediate layer of very thin layers of copper.In addition, after the very thin layers of copper of stripping, only dissolve the near surface (apart from the 0.5 μm of thickness in surface) of the side, intermediate layer of carrier, measure the adhesion amount on the surface of the side, intermediate layer of carrier.Further, the value adhesion amount on the surface of the adhesion amount on the surface of the side, intermediate layer to very thin layers of copper and the side, intermediate layer of carrier being amounted to gained is set to the metal adhering amount in intermediate layer.
Etching
The Copper Foil of appendix body attached to BT resin substrate or FR-4 substrate and carry out adding thermo-compressed in 2 hours with 220 DEG C, carrying out heat treatment in 4 hours with 220 DEG C thereafter.Then, very thin layers of copper is peeled off from foil carriers.Then, after the very thin layers of copper surface coating photonasty plating resist application on substrate, utilize exposure, development step forms the plating resist application pattern of 50 L/S=10 μm/10 μm wide, going down at following spraying etching condition does not need part except layers of copper.
(spraying etching condition)
Etching solution: ferric chloride in aqueous solution (Baume degrees: 40 degree)
Liquid temperature: 60 DEG C
Spraying pressure: 2.0MPa
Continue etching, measuring circuit top width becomes the time of 4 μm, and then the length of side X Di assessment circuit bottom width (now) and etching coefficient.When being etched into fan-shaped (when producing turned-down edge), drop wire is drawn from Copper Foil upper surface when supposing that circuit vertically etches, when the distance of the length of the turned-down edge the intersection point from vertical line and resin substrate is set to a, etching coefficient is the ratio of the thickness b representing this and Copper Foil: b/a, this numerical value is larger, mean that inclination angle is larger, more not residual etch residue, turned-down edge is less.The schematic diagram of the cross section of the width of indication circuit pattern in Figure 5, and the outline representing the computational methods of the etching coefficient using this schematic diagram.This measures by carrying out SEM observation above circuit, calculates etching coefficient (EF=b/a).In addition, b=(X (μm)-4 (μm))/2 is utilized to calculate.By using this etching coefficient, can judge that whether etching is good simply.In the present invention, be that more than 2.5 to be set to etching good by etching coefficient, 2.5 will do not reached and maybe cannot calculate (being included in base part, the situation of short circuit between adjacent circuit) and be judged to be that etching is abnormal, and assess every 1dm 2the abnormal number of etching.
The covering rate of the element beyond copper
The Copper Foil of appendix body is peeled off between carrier/very thin layers of copper, carrier side be impregnated in ammonium sulfide solution.Ammonium sulfide has the character making Cu blackening, only has the part blackening that the coat of metal do not formed by the metal beyond copper by Ni coating or Co coating etc. of copper carrier substrate or the layer such as chromating layer, organic matter layer cover.
Ammonium sulfide solution
Ammonium sulfide: 5 ~ 20vol%
Liquid temperature: 20 ~ 30 DEG C
Dip time: 30 seconds ~ 2 minutes
Thereafter, with scanner scanning carrier peel ply side, its image is processed into black and white with " 2 GTG ".White and black " threshold value " of image is set as the area occupation ratio of white portion (in vain: 0, black: 255), is defined as the covering rate of the element beyond copper by 70.
Moisture generation (amount of moisture by the Copper Foil of appendix body produces when being heated to 500 DEG C with 30 DEG C/min)
In the glove box through argon replaces, the Copper Foil of appendix body is cut into the size of φ 9 ~ 20mm, peel off very thin layers of copper from the carrier of the Copper Foil of appendix body.After stripping, carrier and very thin layers of copper are imported to simultaneously in the chamber of intensification disengaging gas analyzing apparatus (TDS1200) that electronics science limited company manufactures.Vacuum in chamber is now 2.0 × 10 -7below Pa, chamber indoor temperature is 30 ~ 60 DEG C.Then, be warmed up to 500 DEG C with the speed of 30 DEG C/min, measure now produced amount of moisture A (quality (g)).Amount of moisture uses following formula to calculate as moisture generation (quality (g)) (ppm) of the every 1g of Copper Foil of appendix body.
Quality (g) × 10 of the sample of the Copper Foil of the appendix body of moisture generation (amount of moisture by the Copper Foil of appendix body produces when being heated to 500 DEG C with 30 DEG C/min) (ppm/g)=moisture generation A (quality (g))/measured 6
The number bloated
The Copper Foil of appendix body is heated 4 hours in the atmospheric heating furnace of 220 DEG C.After heating, light microscope is utilized to count every 1dm with visual 2the number bloated.In addition, the Copper Foil of appendix body is heated 10 minutes in the atmospheric heating furnace of 400 DEG C.After heating, light microscope is utilized to count every 1dm with visual 2the number bloated.
Described experimental condition and result of the test are shown in table 1.
(assessment result)
Embodiment 1 ~ 12 by the Copper Foil of appendix body with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C all for below 160ppm/g, the generation bloated and etching generation rate all suppressed well.
In addition, the Copper Foil of appendix body is all 20/dm with 220 DEG C of little produced bloating constantly of heating 4 by embodiment 1 ~ 12 2below, moisture generation and etching generation rate all suppressed well.
Comparative example 1 ~ 3 by the Copper Foil of appendix body with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C all more than 160ppm/g, the generation bloated is all many, etching generation rate all bad.
In addition, the Copper Foil of appendix body produced constantly to bloat all more than 20/dm so that 220 DEG C of heating 4 are little by comparative example 1 ~ 3 2, the generation of moisture is all many, and etching generation rate is all bad.

Claims (57)

1. a Copper Foil for appendix body, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
Be below 160ppm/g by the Copper Foil of described appendix body with the amount of moisture that 30 DEG C/min produce when being heated to 500 DEG C.
2. the Copper Foil of appendix body according to claim 1, wherein by the Copper Foil of described appendix body with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C for 0 ~ 130ppm/g.
3. the Copper Foil of appendix body according to claim 2, wherein by the Copper Foil of described appendix body with 30 DEG C/min of amounts of moisture produced when being heated to 500 DEG C for 0 ~ 110ppm/g.
4. the Copper Foil of described appendix body is wherein 20/dm with 220 DEG C of little produced bloating constantly of heating 4 by the Copper Foil of appendix body according to claim 1 2below.
5. the Copper Foil of described appendix body is wherein 20/dm with 220 DEG C of little produced bloating constantly of heating 4 by the Copper Foil of the appendix body according to Claims 2 or 3 2below.
6. the Copper Foil of described appendix body is wherein 0 ~ 15/dm with 220 DEG C of little produced bloating constantly of heating 4 by the Copper Foil of appendix body according to any one of claim 1 to 4 2below.
7. the Copper Foil of described appendix body is wherein 0 ~ 12/dm with 220 DEG C of little produced bloating constantly of heating 4 by the Copper Foil of appendix body according to any one of claim 1 to 4 2below.
8. the Copper Foil of appendix body according to claim 1, bloating of producing when wherein the Copper Foil of described appendix body being heated 10 minutes with 400 DEG C is 0 ~ 60/dm 2below.
9. the Copper Foil of appendix body according to claim 1, bloating of producing when wherein the Copper Foil of described appendix body being heated 10 minutes with 400 DEG C is 0 ~ 30/dm 2below.
10. the Copper Foil of appendix body according to claim 4, bloating of producing when wherein the Copper Foil of described appendix body being heated 10 minutes with 400 DEG C is 0 ~ 60/dm 2below.
The Copper Foil of 11. appendix bodies according to claim 4, bloating of producing when wherein the Copper Foil of described appendix body being heated 10 minutes with 400 DEG C is 0 ~ 30/dm 2below.
The Copper Foil of 12. appendix bodies according to claim 7, bloating of producing when wherein the Copper Foil of described appendix body being heated 10 minutes with 400 DEG C is 0 ~ 60/dm 2below.
The Copper Foil of 13. 1 kinds of appendix bodies, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
Be 20/dm by the Copper Foil of described appendix body with 220 DEG C of little produced bloating constantly of heating 4 2below.
The Copper Foil of described appendix body is wherein 0 ~ 15/dm with 220 DEG C of little produced bloating constantly of heating 4 by the Copper Foil of 14. appendix bodies according to claim 13 2below.
The Copper Foil of described appendix body is wherein 0 ~ 12/dm with 220 DEG C of little produced bloating constantly of heating 4 by the Copper Foil of 15. appendix bodies according to claim 13 2below.
The Copper Foil of 16. appendix bodies according to claim 13, bloating of producing when wherein the Copper Foil of described appendix body being heated 10 minutes with 400 DEG C is 0 ~ 60/dm 2below.
The Copper Foil of described appendix body is wherein 0 ~ 60/dm with bloating of producing during 400 DEG C of heating 10 minutes by the Copper Foil of 17. appendix bodies according to any one of claim 2,3,9,14 to 15 2below.
The Copper Foil of 18. appendix bodies according to claim 15, wherein said intermediate layer when containing Cr, containing 5 μ g/dm 2above 100 μ g/dm 2following Cr, when containing Mo, containing 50 μ g/dm 2above 1000 μ g/dm 2following Mo, when containing Ni, containing 100 μ g/dm 2above 40000 μ g/dm 2following Ni, when containing Co, containing 100 μ g/dm 2above 40000 μ g/dm 2following Co, when containing Zn, containing 1 μ g/dm 2above 120 μ g/dm 2following Zn.
The Copper Foil of 19. appendix bodies according to claim 16, at least one deck of wherein said antirust coat and described refractory layer contains more than one the element be selected from nickel, cobalt, copper, zinc.
The Copper Foil of 20. 1 kinds of appendix bodies, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
Bloating of producing when the Copper Foil of described appendix body is heated 10 minutes with 400 DEG C is 0 ~ 60/dm 2below.
The Copper Foil of 21. 1 kinds of appendix bodies, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
Bloating of producing when the Copper Foil of described appendix body is heated 10 minutes with 400 DEG C is 0 ~ 50/dm 2below.
The Copper Foil of 22. 1 kinds of appendix bodies, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
Bloating of producing when the Copper Foil of described appendix body is heated 10 minutes with 400 DEG C is 0 ~ 40/dm 2below.
The Copper Foil of 23. 1 kinds of appendix bodies, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
Bloating of producing when the Copper Foil of described appendix body is heated 10 minutes with 400 DEG C is 0 ~ 30/dm 2below.
The Copper Foil of 24. appendix bodies according to any one of Claims 1-4,8 to 11,13 to 16,20 to 23, wherein said intermediate layer contain in the group being selected from and being made up of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, organic matter one or more.
The Copper Foil of 25. appendix bodies according to claim 24, organic matter is contained with the thickness of more than 25nm below 80nm in wherein said intermediate layer.
The Copper Foil of 26. appendix bodies according to claim 24, wherein said organic matter is by one or more organic matters formed be selected from organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid.
The Copper Foil of 27. appendix bodies according to any one of Claims 1-4,8 to 11,13 to 16,20 to 23, any surface wherein on the surface of described very thin layers of copper surface or described carrier or two sides have roughening treatment layer.
The Copper Foil of 28. appendix bodies according to claim 27, wherein has more than one the layer in the group being selected from and being made up of refractory layer, antirust coat, chromating layer and silane coupled processing layer on the surface of described roughening treatment layer.
The Copper Foil of 29. appendix bodies according to claim 28, wherein has described refractory layer on described roughening treatment layer.
The Copper Foil of 30. appendix bodies according to claim 28, wherein has described antirust coat on described roughening treatment layer or described refractory layer.
The Copper Foil of 31. appendix bodies according to claim 28, wherein has described chromating layer on described antirust coat.
The Copper Foil of 32. appendix bodies according to claim 28, wherein has described silane coupled processing layer on described chromating layer.
The Copper Foil of 33. appendix bodies according to any one of Claims 1-4,8 to 11,13 to 16,20 to 23, wherein has more than one the layer in the group being selected from and being made up of refractory layer, antirust coat, chromating layer and silane coupled processing layer on the surface of described very thin layers of copper.
The Copper Foil of 34. appendix bodies according to any one of Claims 1-4,8 to 11,13 to 16,20 to 23, wherein possesses resin bed in described very thin layers of copper.
The Copper Foil of 35. appendix bodies according to claim 27, wherein possesses resin bed on described roughening treatment layer.
The Copper Foil of 36. appendix bodies according to claim 28, wherein possesses resin bed being selected from more than one the layer in the group be made up of described refractory layer, antirust coat, chromating layer and silane coupled processing layer.
The Copper Foil of 37. appendix bodies according to claim 34, wherein said resin bed contains dielectric medium.
38. 1 kinds of printed wiring boards, use the Copper Foil of the appendix body according to any one of claim 1 to 37 and manufacture.
39. 1 kinds of copper clad laminates, use the Copper Foil of the appendix body according to any one of claim 1 to 37 and manufacture.
40. 1 kinds of e-machines, use the printed wiring board described in claim 38 and manufacture.
41. 1 kinds of layered products, use the Copper Foil of the appendix body according to any one of claim 1 to 37 and manufacture.
42. 1 kinds of layered products, the Copper Foil containing the appendix body according to any one of claims 1 to 37 and resin, part or all of the end face of the Copper Foil of described appendix body is covered by described resin.
43. 1 kinds of layered products, are laminated to the described carrier side of the Copper Foil of the appendix body according to any one of another sheet claims 1 to 37 by the Copper Foil of the appendix body according to any one of a slice claims 1 to 37 from described carrier side or described very thin layers of copper side or described very thin layers of copper side forms.
44. layered products according to claim 43, are formed via adhesive contact laminating as required by the described carrier side surface of the Copper Foil of the described carrier side of the Copper Foil of described a slice appendix body surface or described very thin layers of copper side surface and another sheet appendix body described or described very thin layers of copper side surface.
45. layered products according to claim 43, described carrier or the described pole thin copper layer Even of the Copper Foil of the described carrier of the Copper Foil of wherein said a slice appendix body or described very thin layers of copper and another sheet appendix body described connect.
The manufacture method of 46. 1 kinds of printed wiring boards, uses the layered product according to any one of claim 41 to 45.
47. layered products according to any one of claim 43 to 45, part or all of the end face of wherein said layered product is covered by resin.
The manufacture method of 48. 1 kinds of printed wiring boards, comprises the steps:
Layered product according to any one of claim 43 to 45 at least arranges 1 resin bed and circuit, and this is two-layer; And
At least formed 1 described resin bed and circuit this two-layer after, peel off described very thin layers of copper or described carrier from the Copper Foil of the appendix body of described layered product.
The manufacture method of 49. 1 kinds of printed wiring boards, comprises the steps:
This is two-layer at least to arrange 1 resin bed and circuit at layered product according to claim 47; And
At least formed 1 described resin bed and circuit this two-layer after, peel off described very thin layers of copper or described carrier from the Copper Foil of the appendix body of described layered product.
The manufacture method of 50. 1 kinds of printed wiring boards, comprises the steps:
Prepare Copper Foil and the insulated substrate of the appendix body according to any one of claims 1 to 37;
The Copper Foil of described appendix body and insulated substrate are carried out lamination;
After the Copper Foil of described appendix body and insulated substrate are carried out lamination, form copper clad laminate through peeling off the step of the foil carriers of the Copper Foil of described appendix body,
Thereafter, circuit is formed by any one method in semi-additive process, subtractive process, part addition process or improvement semi-additive process.
The manufacture method of 51. 1 kinds of printed wiring boards, comprises the steps:
The described very thin layers of copper side of the Copper Foil of the appendix body according to any one of claims 1 to 37 or described carrier side circuit forming surface;
Resin bed is formed at the described very thin layers of copper side surface of the Copper Foil of described appendix body or described carrier side in the mode burying described circuit;
Described resin bed forms circuit;
After described resin bed forms circuit, peel off described carrier or described very thin layers of copper; And
After peeling off described carrier or described very thin layers of copper, by removing described very thin layers of copper or described carrier, and the circuit be buried in described resin bed being formed in described very thin layers of copper side surface or described carrier side surface is exposed.
The manufacture method of 52. printed wiring boards according to claim 51, the wherein said step forming circuit is on the resin layer fitted in described resin bed by the Copper Foil of other appendix body from very thin layers of copper side or carrier side, uses the Copper Foil that is fitted in the appendix body of described resin bed and form the step of described circuit.
The manufacture method of 53. printed wiring boards according to claim 52, the Copper Foil of wherein said laminating other appendix body is on the resin layer the Copper Foil of the appendix body according to any one of claims 1 to 37.
The manufacture method of 54. printed wiring boards according to claim 51, the wherein said step forming circuit on the resin layer can be undertaken by any one method in semi-additive process, subtractive process, part addition process or improvement semi-additive process.
The manufacture method of 55. printed wiring boards according to claim 51, wherein said will have substrate at the Copper Foil of the appendix body of circuit forming surface on the surface of the surface of the carrier side of the Copper Foil of this appendix body or very thin layers of copper side.
The manufacture method of 56. 1 kinds of printed wiring boards, comprises the steps:
By the described very thin layers of copper side surface of the Copper Foil of the appendix body according to any one of claims 1 to 37 or described carrier side surface and resin substrate carry out lamination;
Described appendix body Copper Foil and be that the very thin layers of copper side surface of opposition side or described carrier side surface at least arrange 1 resin bed and circuit this is two-layer with the side of resin substrate lamination; And
At least formed 1 described resin bed and circuit this two-layer after, peel off described carrier or described very thin layers of copper from the Copper Foil of described appendix body.
The manufacture method of 57. 1 kinds of printed wiring boards, comprises the steps:
Lamination is carried out on the described carrier side surface of the Copper Foil of the appendix body according to any one of claims 1 to 37 and resin substrate;
Described appendix body Copper Foil and 1 resin bed and circuit are at least set with the very thin layers of copper side surface that the side of resin substrate lamination is opposition side this are two-layer; And
At least formed 1 described resin bed and circuit this two-layer after, peel off described carrier from the Copper Foil of described appendix body.
CN201510147943.1A 2014-03-31 2015-03-31 The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board Active CN104943270B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014073870 2014-03-31
JP2014073841 2014-03-31
JP2014-073870 2014-03-31
JP2014-073841 2014-03-31

Publications (2)

Publication Number Publication Date
CN104943270A true CN104943270A (en) 2015-09-30
CN104943270B CN104943270B (en) 2017-10-31

Family

ID=54158578

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510147943.1A Active CN104943270B (en) 2014-03-31 2015-03-31 The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board

Country Status (4)

Country Link
JP (1) JP6342356B2 (en)
KR (1) KR101705969B1 (en)
CN (1) CN104943270B (en)
TW (1) TWI613940B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105704948A (en) * 2016-03-28 2016-06-22 上海美维电子有限公司 Manufacturing method of ultra-thin printed circuit board and ultra-thin printed circuit board
CN107623990A (en) * 2017-07-26 2018-01-23 珠海亚泰电子科技有限公司 Thickened copper substrate and preparation process
CN108093572A (en) * 2017-12-15 2018-05-29 上海美维科技有限公司 A kind of production method of the printed circuit board with no porose disc blind hole structure
CN110293712A (en) * 2018-03-23 2019-10-01 三井金属矿业株式会社 Band carrier copper foil, copper clad laminate and printed circuit board
CN111690957A (en) * 2019-08-12 2020-09-22 长春石油化学股份有限公司 Surface-treated copper foil
CN112423982A (en) * 2018-07-18 2021-02-26 昭和电工材料株式会社 Copper-clad laminate, printed wiring board, semiconductor package, and method for manufacturing copper-clad laminate
CN113677519A (en) * 2019-05-09 2021-11-19 纳美仕有限公司 Laminate

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6570430B2 (en) * 2015-11-12 2019-09-04 Ｊｘ金属株式会社 Method for producing copper foil with carrier, method for producing printed wiring board, and method for producing electronic device
JP2017124533A (en) * 2016-01-13 2017-07-20 Ｊｘ金属株式会社 Copper foil with carrier, laminate, method for manufacturing copper foil with carrier, method for manufacturing printed wiring board, and method for manufacturing electric equipment
JP2017177611A (en) * 2016-03-30 2017-10-05 Ｊｘ金属株式会社 Copper foil with carrier, laminate, manufacturing method of printed wiring board and manufacturing method of electronic device
JP2017177610A (en) * 2016-03-30 2017-10-05 Ｊｘ金属株式会社 Copper foil with carrier, laminate, manufacturing method of printed wiring board and manufacturing method of electronic device
JP6391621B2 (en) * 2016-03-31 2018-09-19 Ｊｘ金属株式会社 Titanium copper foil, copper products, electronic equipment parts and autofocus camera module
KR101881287B1 (en) 2017-01-16 2018-07-27 일진머티리얼즈 주식회사 Copper foil attached to the carrier foil

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0373338A (en) * 1989-05-17 1991-03-28 Fukuda Metal Foil & Powder Co Ltd Composite foil and manufacture thereof
CN1383705A (en) * 2000-07-07 2002-12-04 三井金属鉱业株式会社 Carrier-field copper foil circuit, printed circuit board mfg. method using circuit, and printed circuit board
JP2006045493A (en) * 2004-07-09 2006-02-16 Toyota Industries Corp Slide member for compressor
CN103392028A (en) * 2011-08-31 2013-11-13 Jx日矿日石金属株式会社 Copper foil with carrier
WO2014017606A1 (en) * 2012-07-25 2014-01-30 Jx日鉱日石金属株式会社 Copper foil with carrier

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4160131B2 (en) * 1994-12-26 2008-10-01 日立化成工業株式会社 Method for producing metal foil for printed wiring board
JP2001127429A (en) * 1999-10-25 2001-05-11 Hitachi Chem Co Ltd Method for producing multilayer printed wiring board
WO2004005588A1 (en) 2002-07-04 2004-01-15 Mitsui Mining & Smelting Co.,Ltd. Electrolytic copper foil with carrier foil
JP4429979B2 (en) 2005-06-29 2010-03-10 古河電気工業株式会社 Ultra-thin copper foil with carrier and method for producing ultra-thin copper foil with carrier
JP4927503B2 (en) * 2005-12-15 2012-05-09 古河電気工業株式会社 Ultra-thin copper foil with carrier and printed wiring board
CN101449633B (en) * 2006-03-24 2011-10-26 宇部兴产株式会社 Process for producing copper wiring polyimide film, and copper wiring polyimide film
JP2010006071A (en) 2009-08-21 2010-01-14 Furukawa Electric Co Ltd:The Surface treatment copper foil, extremely thin copper foil with carrier, flexible copper clad laminate, and polyimide based flexible printed wiring board
US8329315B2 (en) * 2011-01-31 2012-12-11 Nan Ya Plastics Corporation Ultra thin copper foil with very low profile copper foil as carrier and its manufacturing method
KR101510366B1 (en) * 2011-03-30 2015-04-07 미쓰이금속광업주식회사 Multilayer printed wiring board manufacturing method
JP2013001993A (en) * 2011-06-21 2013-01-07 Meltex Inc Ultrathin copper foil with carrier foil and method of manufacturing the same
JP5413693B2 (en) * 2012-02-06 2014-02-12 日立化成株式会社 Circuit forming support substrate and method of manufacturing semiconductor device mounting package substrate
KR101391811B1 (en) * 2012-08-17 2014-05-07 일진머티리얼즈 주식회사 Copper foil attached to the carrier foil, copper-clad laminate and printed circuit board using the same
JP5481577B1 (en) * 2012-09-11 2014-04-23 Ｊｘ日鉱日石金属株式会社 Copper foil with carrier
JP5521099B1 (en) * 2013-09-02 2014-06-11 Ｊｘ日鉱日石金属株式会社 Copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and printed wiring board manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0373338A (en) * 1989-05-17 1991-03-28 Fukuda Metal Foil & Powder Co Ltd Composite foil and manufacture thereof
CN1383705A (en) * 2000-07-07 2002-12-04 三井金属鉱业株式会社 Carrier-field copper foil circuit, printed circuit board mfg. method using circuit, and printed circuit board
JP2006045493A (en) * 2004-07-09 2006-02-16 Toyota Industries Corp Slide member for compressor
CN103392028A (en) * 2011-08-31 2013-11-13 Jx日矿日石金属株式会社 Copper foil with carrier
WO2014017606A1 (en) * 2012-07-25 2014-01-30 Jx日鉱日石金属株式会社 Copper foil with carrier

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105704948A (en) * 2016-03-28 2016-06-22 上海美维电子有限公司 Manufacturing method of ultra-thin printed circuit board and ultra-thin printed circuit board
CN105704948B (en) * 2016-03-28 2018-05-29 上海美维电子有限公司 The production method of ultra-thin printed circuit board and ultra-thin printed circuit board
CN107623990A (en) * 2017-07-26 2018-01-23 珠海亚泰电子科技有限公司 Thickened copper substrate and preparation process
CN108093572A (en) * 2017-12-15 2018-05-29 上海美维科技有限公司 A kind of production method of the printed circuit board with no porose disc blind hole structure
CN110293712A (en) * 2018-03-23 2019-10-01 三井金属矿业株式会社 Band carrier copper foil, copper clad laminate and printed circuit board
CN112423982A (en) * 2018-07-18 2021-02-26 昭和电工材料株式会社 Copper-clad laminate, printed wiring board, semiconductor package, and method for manufacturing copper-clad laminate
CN113677519A (en) * 2019-05-09 2021-11-19 纳美仕有限公司 Laminate
CN111690957A (en) * 2019-08-12 2020-09-22 长春石油化学股份有限公司 Surface-treated copper foil

Also Published As

Publication number Publication date
KR101705969B1 (en) 2017-02-10
TWI613940B (en) 2018-02-01
CN104943270B (en) 2017-10-31
TW201542047A (en) 2015-11-01
JP6342356B2 (en) 2018-06-13
JP2015199355A (en) 2015-11-12
KR20150113901A (en) 2015-10-08

Similar Documents

Publication Publication Date Title
CN104943270B (en) The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board
CN106455341B (en) The manufacturing method of Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine
CN104717831B (en) Surface treatment copper foil, laminate, printed wiring board, e-machine, the manufacture method of Copper foil with carrier and printed wiring board
CN106455342B (en) The manufacturing method of Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine
TWI527687B (en) Production method of copper foil, copper clad laminate, printed wiring board, electronic machine, and printed wiring board
CN106358377B (en) Copper foil with carrier, laminate, the manufacturing method of laminate, the manufacturing method of the manufacturing method of printing distributing board and e-machine
JP5228130B1 (en) Copper foil with carrier
CN106455310A (en) Carrier-attached copper foil, laminate, method for producing printed wiring board, and method for producing electronic device
TW201800242A (en) Surface-treated copper foil and copper-clad laminate produced using same
CN105408524A (en) Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed circuit board, copper-clad laminate, and method for manufacturing printed circuit board
CN105142897A (en) Copper foil with carrier, printed circuit board, copper clad laminated sheet, electronic device, and printed circuit board fabrication method
EP2821528B1 (en) Copper foil with attached carrier foil, method for manufacturing copper foil with attached carrier foil, and method for manufacturing copper clad laminate board for laser beam drilling obtained by using copper foil with attached carrier foil
CN105007687A (en) Copper foil with carrier, printed wiring board, laminated body, electronic machine and method for manufacturing printed wiring board
JP2023123687A (en) Surface treated copper foil, surface treated copper foil with resin layer, copper foil with carrier, laminate, method for producing printed circuit board, and method for producing electronic device
CN105101627A (en) Carrier-attached copper foil and manufacturing method thereof, printed circuit board and manufacturing method thereof, laminate, and electronic machine
JP6140480B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP5386652B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP5449596B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP5298252B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP6140481B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP6842232B2 (en) Manufacturing method of metal foil with carrier, laminate, printed wiring board, electronic device, metal foil with carrier and manufacturing method of printed wiring board
JP6271134B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP6176948B2 (en) Copper foil with carrier, method for producing copper foil with carrier, method for producing printed circuit board, method for producing copper-clad laminate, and method for producing printed wiring board
JP6329727B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP6329731B2 (en) Copper foil with carrier, method for producing copper-clad laminate, and method for producing printed wiring board

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP02 Change in the address of a patent holder

Address after: No.4, 10-fan, erdingmu, huzhimen, Tokyo, Japan

Patentee after: JX Nippon Mining & Metals Corp.

Address before: Tokyo, Japan

Patentee before: JX Nippon Mining & Metals Corp.

CP02 Change in the address of a patent holder