CN108697006A - The manufacturing method of surface treatment copper foil, Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine - Google Patents

The manufacturing method of surface treatment copper foil, Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine Download PDF

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Publication number
CN108697006A
CN108697006A CN201810292331.5A CN201810292331A CN108697006A CN 108697006 A CN108697006 A CN 108697006A CN 201810292331 A CN201810292331 A CN 201810292331A CN 108697006 A CN108697006 A CN 108697006A
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China
Prior art keywords
copper foil
less
carrier
surface treatment
roughness
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CN201810292331.5A
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CN108697006B (en
Inventor
大理友希
新井英太
三木敦史
福地亮
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to surface treatment copper foil, the manufacturing methods of Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine.A kind of surface treatment copper foil is provided, inhibits falling off for the roughening particle being arranged in the roughening particle layer of copper foil surface well, and inhibits the case where generating gauffer, striped when being bonded with insulating substrate well.The surface treatment copper foil of the present invention is to be provided with roughening treatment layer on a surface of copper foil and/or two surfaces, and the roughness Ra of roughening treatment layer side surface is 0.08 μm or more and 0.20 μm hereinafter, the glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil is 70% or less.

Description

The manufacturing method of surface treatment copper foil, Copper foil with carrier, laminate, printing distributing board And the manufacturing method of e-machine
Technical field
The present invention relates to a kind of surface treatment copper foil, the surface treatment copper foil with resin layer, Copper foil with carrier, laminations The manufacturing method of body, the manufacturing method of printing distributing board and e-machine.
Background technology
Since nearly half a century, printing distributing board realizes rapid progress, is almost used for all e-machines.In recent years Come, with the miniaturization of e-machine, the increase of high performance demand, the high-density installation for carrying part continues to develop, right Printing distributing board requires the miniaturization (micro- spacing) of conductive pattern.
Printing distributing board is formed into first by copper foil and based on glass epoxy substrate, BT resins, polyimide film etc. Copper-cover laminated body made of insulating substrate fitting.Fitting, which may be used, pressurizes heating after insulating substrate and copper foil overlapping and is carried out Method (laminating method) or carried out after face of the copper foil with coating is coated with as the varnish of dielectric substrate material precursor The method (curtain coating (キ ャ ス テ ィ Application グ) method) of heating, hardening.
The processing of following printed wiring copper foil is disclosed for the project of micro- spacing, such as in patent document 1 Method, it is characterised in that:After carrying out roughening treatment in the coating surface of copper foil copper-cobalt-nickel alloy, forms cobalt-nickel and close Gold plate, and then form zinc-nickel alloy coating.And describe, by this micro- spacing for being configured to realize conductive pattern Change.
[Xian Youjishuwenxian ]
[Zhuan Liwenxian ]
[Patent document 1]No. 2849059 bulletins of Japanese Patent No.
Invention content
[Fa Mingyaoxiejuewenti ]
In the manufacturing method of printing distributing board as described above, need sometimes using special device etc. remove copper foil surface or Foreign matter on the surface of printing distributing board.It is used for promoting the roughening treatment with the adhesion of insulating resin to what copper foil surface assigned Layer becomes fine to cope with wiring miniaturization as described above.Therefore, when removing the foreign matter, roughening treatment layer is constituted Roughening particle can fall off (also referred to as powder falling) from the surface of copper foil and be transferred as foreign conducting matter, be attached to copper foil or print and match The carrying device of line plate.The foreign conducting matter for being so attached to the surface of the carrying device of copper foil or printing distributing board is possible to again It is secondary to be transferred to copper foil or printed wiring plate surface.Such case can cause when forming circuit using the copper foil or the printing is matched Short circuit occurs for circuit in line plate.
But inhibit the falling off of roughening particle (powder falling) in the surface treatment copper foil with roughening treatment layer well The correlative study of technology is still insufficient, still stays that there is room for improvement.In addition, manufacturing printing distributing board etc. using surface treatment copper foil When, surface treatment copper foil and resin are bonded sometimes and make laminate, but is insulated base by surface treatment copper foil and resin etc. Plate be bonded when, there are when will produce gauffer or striped the problem of.Moreover, the problem of when the fitting of this and insulating substrate, also waits changing It is kind.Therefore, falling off the issue of the present invention is to provide a kind of roughening particle being arranged in the roughening particle layer of copper foil surface Gauffer is generated when well being inhibited the phenomenon that and being bonded with insulating substrate, the surface treatment copper that striped is also well inhibited Foil.
[The Shou Duan &#93 solved the problems, such as;
In order to reach the purpose, present inventor et al. passes through the research of effort repeatedly, as a result, it has been found that, for roughening treatment Copper foil surface is set as specified roughness by the roughening particle of layer, and by the roughening treatment layer side table of surface treatment copper foil The glossiness control of the TD in face is designated value hereinafter, thus to solve the problem.
The present invention is completed based on above-mentioned opinion, is on the one hand a kind of surface treatment copper foil, with copper foil, With the roughening treatment layer positioned at least one surface of the copper foil or two surfaces, roughening treatment layer side surface it is coarse Ra is spent for 0.08 μm or more and 0.20 μm hereinafter, the gloss of the TD of the roughening treatment layer side surface of the surface treatment copper foil Degree is 70% or less.
The present invention is a kind of surface treatment copper foil on the other hand, with copper foil and positioned at least the one of the copper foil The roughness Rz of the roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface is 1.00 μm or more and 2.00 μm hereinafter, the TD of the roughening treatment layer side surface of the surface treatment copper foil glossiness be 70% or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughness Sq of the roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface is 0.16 μm or more and 0.30 μm hereinafter, the TD of the roughening treatment layer side surface of the surface treatment copper foil glossiness be 70% or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughness Ssk of the roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface is -0.6 or more and -0.35 Hereinafter, the glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughness Sa of the roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface is 0.12 μm or more and 0.23 μm hereinafter, the TD of the roughening treatment layer side surface of the surface treatment copper foil glossiness be 70% or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughness Sz of the roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface is 2.20 μm or more and 3.50 μm hereinafter, the TD of the roughening treatment layer side surface of the surface treatment copper foil glossiness be 70% or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughness Sku of the roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface is 3.75 or more and 4.50 Hereinafter, the glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughening treatment layer on a surface or two surfaces, the roughness Spk of roughening treatment layer side surface be 0.13 μm or more and 0.27 μm hereinafter, the glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
About the surface treatment copper foil of the present invention, at the roughening of the surface treatment copper foil described in yet another aspect Manage the aberration Δ E based on JIS Z8730 of layer side surface*Ab is 65 or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface meet selected from following (10-1)~(10-8) Arbitrary two or more in group,
(10-1) roughness Ra be 0.08 μm or more and 0.20 μm or less,
(10-2) roughness Rz be 1.00 μm or more and 2.00 μm or less,
(10-3) roughness Sq be 0.16 μm or more and 0.30 μm or less,
(10-4) roughness Ssk be -0.6 or more and -0.35 or less,
(10-5) roughness Sa be 0.12 μm or more and 0.23 μm or less,
(10-6) roughness Sz be 2.20 μm or more and 3.50 μm or less,
(10-7) roughness Sku be 3.75 or more and 4.50 or less,
(10-8) roughness Spk be 0.13 μm or more and 0.27 μm hereinafter,
The glossiness of the TD of roughening treatment layer side surface is 70% or less.
The present invention is a kind of surface treatment copper foil at another aspect, with copper foil and positioned at least the one of the copper foil The roughening treatment layer on a surface or two surfaces, roughening treatment layer side surface meet selected from following (11-1)~(11-8) Arbitrary two or more in group,
(11-1) roughness Ra be 0.08 μm or more and 0.20 μm or less,
(11-2) roughness Rz be 1.00 μm or more and 2.00 μm or less,
(11-3) roughness Sq be 0.16 μm or more and 0.30 μm or less,
(11-4) roughness Ssk be -0.6 or more and -0.35 or less,
(11-5) roughness Sa be 0.12 μm or more and 0.23 μm or less,
(11-6) roughness Sz be 2.20 μm or more and 3.50 μm or less,
(11-7) roughness Sku be 3.75 or more and 4.50 or less,
(11-8) roughness Spk be 0.13 μm or more and 0.27 μm hereinafter,
The aberration Δ E based on JIS Z8730 of roughening treatment layer side surface*Ab is 65 hereinafter, the roughening treatment The glossiness of the TD of layer side surface is 70% or less.
About the present invention surface treatment copper foil, the roughening treatment layer side surface described in another implementation form based on The aberration Δ E of JISZ8730*Ab is 45 or more and 65 or less.
About the surface treatment copper foil of the present invention, there is choosing on the surface of the roughening treatment layer in yet another aspect The layer of one or more of the group that free refractory layer, antirust coat, chromating layer and silane coupled process layer are formed.
It is for radiating in yet another aspect about the surface treatment copper foil of the present invention.
The present invention is a kind of surface treatment copper foil with resin layer at another aspect, in the surface treatment copper of the present invention The roughening treatment layer side surface of foil has resin layer.
About the surface treatment copper foil with resin layer of the present invention, the resin layer described in an implementation form is that bonding is used The resin of resin and/or semi-hardened state.
The present invention is a kind of Copper foil with carrier at another aspect, described very thin with carrier, middle layer, very thin layers of copper Layers of copper is the surface treatment copper foil of the present invention or the surface treatment copper foil with resin layer of the present invention.
The present invention is a kind of laminate at another aspect, has the surface treatment copper foil of the present invention or having for the present invention The surface treatment copper foil of resin layer.
The present invention is a kind of laminate at another aspect, has the Copper foil with carrier of the present invention.
The present invention is a kind of laminate at another aspect, contains the Copper foil with carrier and resin of the present invention, the appendix Part or all of the end face of body copper foil is covered by the resin.
The present invention is a kind of laminate, the Copper foil with carrier with the two panels present invention at another aspect.
The present invention is a kind of manufacturing method of printing distributing board at another aspect, uses the surface treatment copper foil of the present invention Or the Copper foil with carrier of the surface treatment copper foil or the present invention with resin layer of the present invention.
The present invention is a kind of manufacturing method of printing distributing board at another aspect comprising following steps:
Prepare the surface treatment copper foil of the present invention or the surface treatment copper foil with resin layer of the present invention or of the invention Copper foil with carrier and insulating substrate;
Copper-cover laminated plate is formed, which includes the either step in following (24-1)~(24-3),
The surface treatment copper foil and the insulating substrate are subject to lamination by (24-1)
The surface treatment copper foil with resin layer and the insulating substrate are subject to lamination by (24-2)
The Copper foil with carrier and the insulating substrate are subject to remove the load of the Copper foil with carrier after lamination by (24-3) Body;And
Pass through semi-additive process (セ ミ ア デ ィ テ ィ Block method), subtractive process (サ Block ト ラ Network テ ィ Block method), part addition process (パ ー ト リ ー ア デ ィ テ ィ Block method) or improve either method in semi-additive process (モ デ ィ Off ァ イ De セ ミ ア デ ィ テ ィ Block method), Circuit is formed using the copper-cover laminated plate.
The present invention is a kind of manufacturing method of printing distributing board at another aspect comprising following steps:The present invention's The roughening treatment layer side surface of surface treatment copper foil forms circuit, or in the described very thin of Copper foil with carrier of the invention Layers of copper side surface or the carrier side circuit forming surface;In a manner of burying the circuit into resin layer, in the table The roughening treatment layer side surface of surface treatment copper foil or the very thin layers of copper side surface or described of the Copper foil with carrier Carrier side surface forms the resin layer;Circuit is formed on the resin layer;And lead to after formation circuit on the resin layer It crosses and removes the surface treatment copper foil, or by the way that the very thin layers of copper will be removed after the carrier or the very thin layers of copper stripping Or the carrier, and the circuit being buried in the resin layer is made to expose.
The present invention is a kind of manufacturing method of printing distributing board at another aspect comprising following steps:By the present invention's The Copper foil with carrier and resin substrate of surface treatment copper foil or the surface treatment copper foil or the present invention with resin layer of the present invention It is subject to lamination;In the surface treatment copper foil or the surface treatment copper foil with resin layer or the Copper foil with carrier and tree Resin layer and circuit at least once is arranged in the opposite side surfaces of the side of aliphatic radical plate lamination;Forming the resin layer and circuit Afterwards, the resin substrate and the surface treatment copper foil are removed, or the removal resin substrate and described with resin layer The surface treatment copper foil of surface treatment copper foil, or remove the carrier or the very thin layers of copper from the Copper foil with carrier.
The present invention is a kind of manufacturing method of printing distributing board at another aspect comprising following steps:The present invention's Resin layer at least once and circuit are set on laminate;And after forming the resin layer and circuit, from the composition laminate Copper foil with carrier remove the carrier or the very thin layers of copper.
The present invention is a kind of manufacturing method of e-machine at another aspect, manufactured by method through the invention Printing distributing board.
[Fa Mingxiaoguo ]
According to the present invention, it is possible to provide a kind of roughening particle being arranged in the roughening particle layer of copper foil surface falls off to obtain The surface treatment copper foil that the case where generating gauffer, striped when well inhibiting, and being bonded with insulating substrate is also well inhibited.
Description of the drawings
Figure 1A~C is to arrive plating in the concrete example using the manufacturing method of the printing distributing board of the Copper foil with carrier of the present invention The schematic diagram of distributing board section in the step of covering until circuit-removal resist (レ ジ ス ト).
Fig. 2 D~F are the slave products in the concrete example using the manufacturing method of the printing distributing board of the Copper foil with carrier of the present invention The schematic diagram of distributing board section in the step of until layer resin and the 2nd layer of Copper foil with carrier to laser boring.
Fig. 3 G~I are the slave shapes in the concrete example using the manufacturing method of the printing distributing board of the Copper foil with carrier of the present invention The schematic diagram of distributing board section in the step of at filling perforation (ビ ア Off ィ Le) until removing the 1st layer of carrier.
Fig. 4 J~K are in the concrete example using the manufacturing method of the printing distributing board of the Copper foil with carrier of the present invention from fast The schematic diagram of distributing board section in the step of speed etching (Off ラ ッ シ ュ エ ッ チ Application グ) is until forming convex block, copper post.
Specific implementation mode
< surface treatment copper foils >
The surface treatment copper foil of the present invention is set on a surface and/or two surfaces on a surface of copper foil, i.e. copper foil It is equipped with roughening treatment layer.In the present invention, one " surface " and/or two " surfaces " of so-called copper foil, on the surface of copper foil by surface The case where handling (in the bottom plating etc. of copper foil surface copper facing etc.) (such as the sequence according to copper foil/surface treatment/roughening treatment The surface treatment copper foil handled) under, refer to the surface (most surface) after carrying out the surface treatment.It is bonded on insulating substrate The surface treatment copper foil of the present invention and after manufacturing laminate (copper-cover laminated plate), surface treatment copper foil etching is become into target conductor Pattern can finally manufacture printing distributing board.The surface treatment copper foil of the present invention is also used as example receiving next spontaneous The heat of thermal part and the heat transmission surface treatment copper foil or heat sink disengaged well.
< copper foils >
There is no particular restriction for the form for the copper foil that can be used in the present invention, for typical, the copper foil that is used in the present invention Can be any of electrolytic copper foil or rolled copper foil.In general, electrolytic copper foil is to make to be electrolysed from copper sulfate bath to be precipitated Copper deposit on titanium or stainless steel rotating cylinder and manufacture, rolled copper foil is plastic processing and the heat being repeated using stack It handles and manufactures.It is required that bendability is rolled copper foil with what is applied mostly on the way.
As copper foil material, in addition to the conductive pattern of printing distributing board usually used refined copper (JIS H3100, alloy Number C1100) or oxygen-free copper (JIS H3100, alloy number C1020;Or JIS H3510, alloy number C1011) or phosphorus deoxidation Other than the high-purity coppers such as copper (JIS H3100 alloys numbers C1201, C1220 or C1221) or cathode copper, it can also use for example Stanniferous (Sn) copper, argentiferous (Ag) copper, the copper alloy added with chromium (Cr), zirconium (Zr) or magnesium (Mg) etc. are added with nickel (Ni) and silicon (Si) copper alloy of inferior (the U Le ソ Application) series copper alloy of card etc such as.In addition, in this specification, " copper foil " word individually makes Used time is also including copper alloy foil.
In addition, the plate thickness of copper foil is without being particularly limited to, for example, 1 μm or more and 1000 μm hereinafter, or be 1 μm or more and 500 μm hereinafter, or for 1 μm or more and 300 μm hereinafter, or be 3 μm or more and 100 μm hereinafter, or be 5 μm or more and 70 μm with Under, or for 6 μm or more and 35 μm hereinafter, or being 9 μm or more and 18 μm or less.
In addition, the present invention is a kind of Copper foil with carrier on the other hand, sequentially there is carrier, middle layer, very thin layers of copper, The very thin layers of copper is the surface treatment copper foil of the present invention.In the present invention, using Copper foil with carrier, in very thin copper The surface-treated layers such as following roughening treatment layers are arranged in layer surface.In addition, another implementation form of Copper foil with carrier also can be in hereafter It illustrates.
< roughening treatment layers >
Typically for the face for waiting for being bonded with resin base material of copper foil, i.e. roughening face, in order to promote the stripping of the copper foil after lamination From intensity, and the surface of the copper foil after degreasing implements to carry out the roughening treatment of " furuncle tumor " shape plating.Electrolytic copper foil is when manufacture Just there are bumps, the protrusion of electrolytic copper foil is enhanced by roughening treatment by makes concave-convex bigger.Sometimes as pretreatment before roughening And carry out common copper facing etc., also common copper facing can be carried out as processing eventually etc. after roughening to prevent electronplate de- sometimes It falls.In the present invention, above pretreatment and eventually processing are referred to as " roughening treatment ".
The roughness of the roughening treatment layer side surface of the surface treatment copper foil of present invention Ra (number equal roughness) on the one hand It is 0.08 μm or more and 0.20 μm or less.Since the roughness Ra of the roughening treatment layer side surface of surface treatment copper foil is 0.08 μm Above and 0.20 μm hereinafter, so can ensure the adhesion of surface treatment copper foil surface and insulating resin, and control well Powder falling processed.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, preferably 0.1 μm or more of the Ra, It is preferred that 0.09 μm or more, preferably 0.10 μm or more, preferably 0.11 μm or more, preferably 0.12 μm or more, preferably 0.13 μm or more, excellent Select 0.14 μm or more, more preferable 0.15 μm or more.
For the viewpoint that powder falling is well controllled, preferably 0.18 μm of the Ra hereinafter, it is preferred that 0.17 μm hereinafter, it is preferred that 0.16 μm hereinafter, it is preferred that 0.15 μm hereinafter, it is preferred that 0.14 μm hereinafter, it is preferred that 0.13 μm hereinafter, it is preferred that 0.12 μm hereinafter, it is preferred that 0.11 μm Below.
Roughness Rz (10 average roughness on the one hand of the roughening treatment layer side surface of the surface treatment copper foil of the present invention Degree) it is 1.00 μm or more and 2.00 μm or less.Since the roughness Rz of the roughening treatment layer side surface of surface treatment copper foil is 1.00 μm or more and 2.00 μm hereinafter, so can ensure the adhesion of surface treatment copper foil surface and insulating resin, Er Qieliang Control powder falling well.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, preferably 1.10 μm of the Rz with On, preferably 1.20 μm or more, preferably 1.3 μm or more, preferably 1.30 μm or more, preferably 1.4 μm or more, preferably 1.40 μm or more, It is preferred that 1.50 μm or more, more preferable 1.60 μm or more.
For the viewpoint that powder falling is well controllled, the preferred 1.90m of Rz hereinafter, it is preferred that 1.80m hereinafter, it is preferred that 1.7m with Under, preferably 1.70m is hereinafter, it is preferred that 1.60m is hereinafter, it is preferred that 1.50m is hereinafter, it is preferred that 1.40m is hereinafter, more preferably 1.30m or less.
(root mean square is high by Sq on the other hand for the roughness of the roughening treatment layer side surface of the surface treatment copper foil of the present invention Degree) it is 0.16 μm or more and 0.30 μm or less.Since the roughness Sq of the roughening treatment layer side surface of surface treatment copper foil is 0.16 μm or more and 0.30 μm hereinafter, so can ensure the adhesion of copper foil surface and insulating resin, and is well controllled Powder falling.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, preferably 0.17 μm of the Sq with On, preferably 0.18 μm or more, preferably 0.19 μm or more, more preferable 0.20 μm or more, more preferable 0.21 μm or more, more preferable 0.22 μm or more.
For the viewpoint that powder falling is well controllled, preferably 0.29 μm of the Sq hereinafter, it is preferred that 0.28 μm hereinafter, it is preferred that 0.27 μm hereinafter, more preferable 0.26 μm hereinafter, more preferable 0.25 μm hereinafter, more preferable 0.24 μm hereinafter, more preferable 0.23 μm hereinafter, more It is preferred that 0.22 μm hereinafter, more preferable 0.21 μm or less.
Roughness Ssk (degree of skewness (the ス on the other hand of the roughening treatment layer side surface of the surface treatment copper foil of the present invention キ ュ ー ネ ス)) it is -0.6 or more and -0.35 or less.Due to the roughness of the roughening treatment layer side surface of surface treatment copper foil Ssk is -0.6 or more and -0.35 hereinafter, so can ensure the adhesion of copper foil surface and insulating resin, and is controlled well Powder falling processed.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, the Ssk preferably -0.60 with On, preferably -0.59 or more, preferably -0.58 or more, more preferably -0.55 or more, more preferably -0.53 or more, more preferably -0.51 with On, more preferably -0.49 or more, more preferably -0.47 or more, more preferably -0.45 or more, more preferably -0.43 or more.
For the viewpoint that powder falling is well controllled, the Ssk preferably -0.37 is hereinafter, it is preferred that -0.4 hereinafter, it is preferred that -0.40 Hereinafter, it is preferred that -0.42 hereinafter, it is preferred that -0.44 hereinafter, more preferably -0.45 hereinafter, more preferably -0.47 hereinafter, more preferably -0.49 Below.
The roughness of the roughening treatment layer side surface of the surface treatment copper foil of present invention Sa (number height) on the other hand It is 0.12 μm or more and 0.23 μm or less.Since the roughness Sa of the roughening treatment layer side surface of surface treatment copper foil is 0.12 μm Above and 0.23 μm hereinafter, so can ensure the adhesion of copper foil surface and insulating resin, and powder falling is well controllled.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, preferably 0.125 μm of the Sa with On, more preferable 0.13 μm or more, more preferable 0.14 μm or more, more preferable 0.15 μm or more, more preferable 0.16 μm or more, more preferably 0.17 μm or more.
For the viewpoint that powder falling is well controllled, preferably 0.22 μm of the Sa hereinafter, it is preferred that 0.21 μm hereinafter, it is preferred that 0.20 μm hereinafter, more preferable 0.19 μm hereinafter, it is preferred that 0.18 μm hereinafter, more preferable 0.17 μm hereinafter, more preferable 0.16 μm hereinafter, more excellent Select 0.15 μm or less.
Roughness Sz (maximum height) on the other hand of the roughening treatment layer side surface of the surface treatment copper foil of the present invention It is 2.20 μm or more and 3.50 μm or less.Since the roughness Sz of the roughening treatment layer side surface of surface treatment copper foil is 2.20 μm Above and 3.50 μm hereinafter, so can ensure the adhesion of copper foil surface and insulating resin, and powder falling is well controllled.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, preferably 2.2 μm or more of the Sz, It is preferred that 2.25 μm or more, preferably 2.30 μm or more, more preferable 2.4 μm or more, more preferable 2.40 μm or more, more preferable 2.50 μm with On, more preferable 2.60 μm or more, more preferable 2.80 μm or more, more preferable 3.00 μm or more.
For the viewpoint that powder falling is well controllled, preferably 3.4 μm of the Sz hereinafter, it is preferred that 3.40 μm hereinafter, it is preferred that 3.30 μ M hereinafter, it is preferred that 3.20 μm hereinafter, it is preferred that 3.10 μm hereinafter, more preferable 3.0 μm hereinafter, more preferable 3.00 μm hereinafter, more preferably 2.90 μm hereinafter, it is preferred that 2.80 μm or less.
Roughness Sku (steepness (the Network on the other hand of the roughening treatment layer side surface of the surface treatment copper foil of the present invention Le ト シ ス)) it is 3.75 or more and 4.50 or less.Since the roughness Sku of the roughening treatment layer side surface of surface treatment copper foil is 3.75 or more and 4.50 hereinafter, so can ensure the adhesion of copper foil surface and insulating resin, and powder falling is well controllled.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, the Sku preferably 4.45 hereinafter, It is preferred that 4.4 hereinafter, it is preferred that 4.40 hereinafter, more preferable 4.3 hereinafter, more preferable 4.30 hereinafter, more preferable 4.20 hereinafter, more preferably 4.10 hereinafter, more preferable 4.00 hereinafter, more preferable 3.90 or less.
For the viewpoint that powder falling is well controllled, the Sku preferably 3.8 or more, preferably 3.80 or more, more preferable 3.9 with On, more preferable 3.90 or more, more preferable 4.00 or more, more preferable 4.10 or more.
Spk (protrudes mountain portion to the roughness of the roughening treatment layer side surface of the surface treatment copper foil of the present invention on the other hand Highly) it is 0.13 μm or more and 0.27 μm or less.Since the roughness Spk of the roughening treatment layer side surface of surface treatment copper foil is 0.13 μm or more and 0.27 μm hereinafter, so can ensure the adhesion of copper foil surface and insulating resin, and is well controllled Powder falling.
For the viewpoint for ensuring the adhesion of surface treatment copper foil surface and insulating resin, preferably 0.14 μm of the Spk with On, preferably 0.15 μm or more, more preferable 0.16 μm or more, more preferable 0.17 μm or more, more preferable 0.18 μm or more, more preferably 0.19 μm or more, more preferable 0.20 μm or more.
For the viewpoint that powder falling is well controllled, preferably 0.26 μm of the Spk hereinafter, it is preferred that 0.25 μm hereinafter, it is preferred that 0.24 μm hereinafter, it is preferred that 0.23 μm hereinafter, it is preferred that 0.22 μm hereinafter, it is preferred that 0.21 μm hereinafter, more preferable 0.20 μm hereinafter, more excellent Select 0.19 μm or less.
The roughness of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can lead to as described below Treatment conditions i.e. current density and/or Plating times, and/or plating liquid temperature when crossing control setting roughening treatment layer and/or Copper concentration in plating liquid and controlled.
The roughness Ra (the equal roughness of number) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can pass through The temperature of plating liquid when controlling current density and/or Plating times and/or carrying out plating and/or the copper concentration in plating liquid and It is controlled.
It can be by improving current density, and increase Ra.It can be by reducing current density, and reduce Ra.It can pass through Extend Plating times, and increases Ra.Can be by shortening Plating times, and reduce Ra.Can by reduce plating liquid temperature, And increase Ra.It can be by improving the temperature of plating liquid, and reduce Ra.Furthermore it is possible to by improving the copper concentration in plating liquid, And reduce Ra.Furthermore it is possible to by reducing the copper concentration in plating liquid, and increase Ra.
The roughness Rz (10 mean roughness) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can be with The temperature of plating liquid when controlling current density and/or Plating times and/or carrying out plating by, is controlled.
It can be by improving current density, and increase Rz.It can be by reducing current density, and reduce Rz.It can pass through Extend Plating times, and increases Rz.Can be by shortening Plating times, and reduce Rz.Can by reduce plating liquid temperature, And increase Rz.It can be by improving the temperature of plating liquid, and reduce Rz.
The roughness Sq (root-mean-square height) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can pass through Control current density and/or Plating times and/or carry out plating when plating liquid temperature and controlled.
It can be by improving current density, and increase Sq.It can be by reducing current density, and reduce Sq.It can pass through Extend Plating times, and increases Sq.Can be by shortening Plating times, and reduce Sq.Can by reduce plating liquid temperature, And increase Sq.It can be by improving the temperature of plating liquid, and reduce Sq.
The roughness Ssk (degree of skewness) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can pass through control The temperature of plating liquid when current density and/or Plating times and/or progress plating and/or the copper foil before formation roughening treatment layer Surface the directions TD Rz (10 mean roughness) and controlled.
It can be by improving current density, and increase Ssk.It can be by reducing current density, and reduce Ssk.It can lead to Extension Plating times are crossed, and increase Ssk.Can be by shortening Plating times, and reduce Ssk.It can be by reducing plating liquid Temperature, and increase Ssk.It can be by improving the temperature of plating liquid, and reduce Ssk.Roughening treatment layer can be formed by increasing The Rz (10 mean roughness) in the directions TD on the surface of preceding copper foil, and increase Ssk.Roughening treatment can be formed by reducing The Rz (10 mean roughness) in the directions TD on the surface of the copper foil before layer, and reduce Ssk.
The roughness Sa (number height) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can pass through control Current density processed and/or Plating times and/or carry out plating when the temperature of plating liquid and/or the copper concentration in plating liquid and into Row control.
It can be by improving current density, and increase Sa.It can be by reducing current density, and reduce Sa.It can pass through Extend Plating times, and increases Sa.Can be by shortening Plating times, and reduce Sa.Can by reduce plating liquid temperature, And increase Sa.It can be by improving the temperature of plating liquid, and reduce Sa.Furthermore it is possible to by improving the copper concentration in plating liquid, And reduce Sa.Furthermore it is possible to by reducing the copper concentration in plating liquid, and increase Sa.
The roughness Sz (maximum height) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can pass through control Current density processed and/or Plating times and/or carry out plating when plating liquid temperature and controlled.
It can be by improving current density, and increase Sz.It can be by reducing current density, and reduce Sz.It can pass through Extend Plating times, and increases Sz.Can be by shortening Plating times, and reduce Sz.Can by reduce plating liquid temperature, And increase Sz.It can be by improving the temperature of plating liquid, and reduce Sz.
The roughness Sku (steepness) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can pass through control Current density and/or Plating times and/or carry out plating when the temperature of plating liquid and/or the copper concentration in plating liquid and carry out Control.
It can be by improving current density, and reduce Sku.It can be by reducing current density, and increase Sku.It can lead to Extension Plating times are crossed, and reduce Sku.Can be by shortening Plating times, and increase Sku.It can be by reducing plating liquid Temperature, and reduce Sku.It can be by improving the temperature of plating liquid, and increase Sku.Furthermore it is possible to by improving in plating liquid Copper concentration, and increase Sku.Furthermore it is possible to by reducing the copper concentration in plating liquid, and reduce Sku.
The roughness Spk (prominent mountain portion height) of the roughening treatment layer side surface of the surface treatment copper foil of the present invention can lead to It crosses the temperature of plating liquid when controlling current density and/or Plating times and/or carrying out plating and is controlled.
It can be by improving current density, and increase Spk.It can be by reducing current density, and reduce Spk.It can lead to Extension Plating times are crossed, and increase Spk.Can be by shortening Plating times, and reduce Spk.It can be by reducing plating liquid Temperature, and increase Spk.It can be by improving the temperature of plating liquid, and reduce Spk.
The present invention surface treatment copper foil preferably by roughening treatment layer side surface with white board (using D65 light sources, 10 degree When the visual field, the X of the white board10Y10Z10The tristimulus values of color system (JIS Z8701 1999) are X10=80.7, Y10= 85.6,Z10=91.5, L*a*b*The object color of the white board under color system is L*=94.14, a*=-0.90, b*=0.24) Object color as aberration, the i.e. aberration Δ E based on JIS Z8730 in the case of reference colours*Ab controls are 65 or less.Pass through This composition can further decrease and be likely to result in aberration Δ E*The presence of the laminate for the coarse roughening particle that ab becomes larger Frequency can control powder falling better.The present invention surface treatment copper foil roughening treatment layer side surface based on JIS The aberration Δ E of Z8730*Ab preferably 62 is hereinafter, more preferable 60 hereinafter, more preferable 57 hereinafter, more preferable 50 or less.
In addition, about aberration Δ E*The lower limiting value of ab if controlling it as 42 or more, such as has following situation: In printed wiring board manufacturing process, when copper foil surface forms circuit, the contrast of copper foil and circuit becomes distinct, therefore electricity The visual recognition on road is good, can be accurately proceed circuit positioning.In addition, in order to improve the integrated circuit of printing distributing board Density, it is general using the method for forming laser hole and connecting internal layer and outer layer by the hole, at this point, if by surface treatment copper foil Roughening treatment layer side surface aberration Δ E*Ab controls are 42 or more, then in the lamination for carrying out multi-layer FPC using CCD camera When positioning, it is necessary to confirm the copper foil circuit position on the white microscope carrier through PI (polyimides), therefore the precision improvement positioned. In addition, copper is extremely low for the absorptivity of the laser in the wavelength region of the far infrareds such as carbon dioxide gas volumetric laser~infrared ray, Therefore, by making Δ E*Ab is 42 or more, also there is the case where absorptivity improvement.The aberration Δ E*Ab preferably 45 or more, it is more excellent Select 47 or more, more preferable 49 or more, more preferable 50 or more, more preferable 51 or more, more preferable 52 or more.In addition, can because having The case where advanced optimizing the adhesion of copper foil surface and insulating resin, it is advantageous to make the aberration Δ E*ab become 49.1 with On.
It is so-called " roughening treatment layer side surface " in the present invention, the surface of roughening treatment layer is provided with refractory layer, antirust Refer to the surface treatment layer surface in the case of the various surface-treated layers such as layer, chromating layer or silane coupled process layer (most surface).
For example, in the present invention, so-called " the aberration Δ E based on JIS Z8730 of roughening treatment layer side surface*Ab ", thick The surface for changing process layer is provided with the various surface treatments such as refractory layer, antirust coat, chromating layer or silane coupled process layer Refer to the aberration Δ E based on JIS Z8730 of the surface treatment layer surface (most surface) in the case of layer*ab.The table of the present invention The aberration Δ E based on JIS Z8730 of the roughening treatment layer side surface of surface treatment copper foil*Ab more preferable 52 or more, more preferable 54 More than.
Herein, the aberration Δ E*Ab is indicated with following formula.Aberration Δ L, Δ a, Δ b in following formula are to use respectively Color difference meter is measured, in addition black/white/red green/yellow blue, L is used based on JIS Z8730 (2009)*a*b*Color system table The overall target shown, Δ L characterize black and white, and Δ a characterizations are red green, and Δ b characterizes champac.(Δ L, Δ a, Δ b) can be used the aberration The color difference meter MiniScan XE Plus of HunterLab companies manufacture are measured.In addition, aberration Δ L, Δ a, Δ b are respectively The aberration of JIS Z8730 (2009) is based in the case of using the object color of the white board as reference colours, Δ L is JIS L specified in Z8729 (2004)*a*b*The CIE luminance L of two object colors under color system*Difference, Δ a, Δ b are JIS L specified in Z8729 (2004)*a*b*The chromaticity coordinates a of two object colors under color system*Or b*Difference.
The aberration can be controlled by the formation condition of roughening treatment layer.Specifically, forming roughening treatment layer When, use one comprising multiple element, for example in the group being made of copper, nickel, cobalt, tungsten, molybdenum, phosphorus, zinc, tin, chromium and iron Kind or more element electrolyte, and control current density, processing time and treatment fluid temperature, thus, it is possible to control the aberration. In order to easily control the roughness and/or aberration of roughening particle, roughening treatment layer preferably comprises the alloy of copper.By carrying High current density can increase aberration.By reducing current density, aberration can be reduced.By extending Plating times, Neng Gouzeng Big aberration.By shortening Plating times, aberration can be reduced.By reducing bath temperature, aberration can be increased.It is plated by improving Liquid temperature can reduce aberration.
In addition, the metal as roughening treatment liquid forms, by reducing copper concentration and improving the metal concentration other than copper, Aberration can be increased.
The surface treatment copper foil of the present invention controls the glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil It is 70% or less.If the glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil is more than 70%, have by table Surface treatment copper foil and resin generate the worry of gauffer or striped when being bonded.The TD of the roughening treatment layer side surface of surface treatment copper foil Glossiness preferably 69% hereinafter, more preferable 68% hereinafter, more preferable 68% hereinafter, more preferable 67% hereinafter, more preferable 66% Hereinafter, in turn more preferable 65% hereinafter, in turn more preferable 60% hereinafter, in turn more preferable 55% hereinafter, in turn more preferable 50% Hereinafter, in turn more preferable 45% hereinafter, in turn more preferable 25% hereinafter, in turn more preferable 20% hereinafter, in turn more preferable 10% Hereinafter, in turn more preferable 5% or less.In addition, the lower limit of the glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil Without being particularly limited to, for typical, for example, 0.01% or more, for example, 0.1 or more, for example, 0.3 or more, for example, 0.5% or more.
The glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil can by copper foil before surface treatment or The glossiness, and/or current density and/or Plating times of the TD of carrier and/or bath temperature when carrying out plating control.It is logical The glossiness for crossing the TD of copper foil or carrier before reducing surface treatment, can reduce the roughening treatment layer side table of surface treatment copper foil The glossiness of the TD in face.By improving the glossiness of the TD of copper foil or carrier before being surface-treated, surface treatment copper can be improved The glossiness of the TD of the roughening treatment layer side surface of foil.By improving current density, the roughening of surface treatment copper foil can be reduced The glossiness of the TD of process layer side surface.By reducing current density, the roughening treatment layer side of surface treatment copper foil can be improved The glossiness of the TD on surface.By extending Plating times, the TD of the roughening treatment layer side surface of surface treatment copper foil can be reduced Glossiness.By shortening Plating times, the glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil can be improved. By reducing bath temperature, the glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil can be reduced.Pass through raising The temperature of plating solution can improve the glossiness of the TD of the roughening treatment layer side surface of surface treatment copper foil.
Roughening treatment layer in the surface treatment copper foil of the present invention can make under the following conditions.
(roughening treatment layer plating conditions)
If enumerating to be formed an example of the plating conditions of roughening treatment layer, as follows.
Liquid forms:Copper 10g/L or more and 25g/L or less, cobalt 7g/L or more and 10g/L or less, nickel 7g/L or more and 10g/L Below
PH value:2.0 or more and 3.0 or less
Liquid temperature:40 DEG C or more and 60 DEG C or less
Current density:10A/dm2Above and 60A/dm2Below
Plating times:0.2 second or more and 1.6 seconds or less
Coulomb amount:0.6As/dm2Above and 100As/dm2Below
In the case that with a high current density, bath temperature need to be set as to the range and/or shorten Plating times.In electric current In the case of low density, the high value that bath temperature need to be set as in the range and/or extend Plating times to a certain extent.
Liquid composition to form roughening treatment layer can also be using any of following (A)~(E).Other conditions can be with Using the condition.
(A) 10~20g/L of copper, 3~10g/L of nickel, 0.1~2.0g/L of phosphorus
(B) 3~10g/L of copper, 10~20g/L of cobalt, 10~20g/L of nickel
(C) 3~10g/L of copper, 10~20g/L of cobalt, 10~20g/L of nickel, 0.001~5g/L of tungsten
(D) 5~15g/L of copper, 5~15g/L of nickel, 0.1~10g/L of molybdenum
(E) 5~15g/L of copper, 5~15g/L of nickel, 0.1~10g/L of molybdenum, 0.1~2.0g/L of phosphorus
The treatment fluid to form roughening treatment layer can include to be selected from nickel, cobalt, tungsten, molybdenum, phosphorus, zinc, tin, chromium and iron One or more of element.
In addition, as described above, the roughening treatment layer can be formed in the present invention surface treatment copper foil a surface, Two surfaces can also be formed in.
< Copper foil with carrier >
Copper foil with carrier as another implementation form of the present invention sequentially has middle layer, pole in the one or both sides of carrier Thin copper layer.Also, the very thin layers of copper is the surface treatment copper foil as an implementation form of the invention.
< carriers >
It is metal foil or resin film for the carrier typical case that can be used in the present invention, such as with copper foil, copper alloy foil, nickel Foil, nickel alloy foil, iron foil, ferroalloy foil, stainless steel foil, aluminium foil, alloy foil, insulating resin film, polyimide film, LCP (liquid Crystalline polymer) film, fluororesin film, PET (polyethylene terephthalate) film, PP (polypropylene) film, PA membrane, polyamide acyl The form of imines film provides.
It is to be provided in the form of rolled copper foil or electrolytic copper foil for the carrier typical case that can be used in the present invention.It is general and Speech, electrolytic copper foil is to make to deposit on titanium or stainless steel rotating cylinder and manufacture from the copper for being electrolysed precipitation in copper sulfate bath, calendering Copper foil is to be repeated using the plastic processing and heat treatment of stack and manufacture.As the material of copper foil, in addition to refined copper (JISH3100, alloy number C1100) or oxygen-free copper (JIS H3100, alloy number C1020;Or JIS H3510, alloy number ) etc. C1011 other than high-purity coppers, for example stanniferous (Sn) copper, argentiferous (Ag) copper can also be used, added with chromium (Cr), zirconium (Zr) Or the copper alloy of magnesium (Mg) etc., the copper alloy of inferior series copper alloy of card added with nickel (Ni) and silicon (Si) etc. etc.In addition, this theory In bright book, " copper foil " word is when being used alone also including copper alloy foil.
The thickness for the carrier that can be used in the present invention is also not particularly limited, as long as in the base for playing the effect as carrier It is suitably adjusted to suitable thickness on plinth, such as 5 μm or more can be set as.But production cost is got higher if blocked up, So being generally preferably set as 35 μm or less.Therefore, for the thickness typical case of carrier for 8 μm or more and 70 μm hereinafter, it is more typical and Speech is for 12 μm or more and 70 μm hereinafter, being 18 μm or more and 35 μm or less for more typical.In addition, just reducing the sight of cost of material For point, the thickness of carrier is preferably smaller.Therefore, for the thickness typical case of carrier for 5 μm or more and 35 μm hereinafter, it is preferred that 5 μm Above and 18 μm hereinafter, it is preferred that 5 μm or more and 12 μm hereinafter, it is preferred that 5 μm or more and 11 μm hereinafter, it is preferred that 5 μm or more and 10 μm Below.In addition, if the thickness of carrier is small, then folding, gauffer are easy tod produce when carrier leads to foil.In order to prevent generate fold, Gauffer, such as effectively keep carrying roller smooth of Copper foil with carrier manufacturing device or shorten a carrying roller and next remove Send the distance of roller.In addition, Copper foil with carrier to be used for the implantation (embedding inlay technique as one of printed wiring board fabrication method (Enbedded Process)) in the case of, it is high rigidity to need carrier.Therefore, for implantation, carrier Preferably 18 μm or more of thickness and 300 μm hereinafter, it is preferred that 25 μm or more and 150 μm hereinafter, it is preferred that 35 μm or more and 100 μm hereinafter, And then more preferable 35 μm or more and 70 μm or less.
In addition it is also possible to which roughening treatment is arranged to the surface of the side opposite with the very thin surface of layers of copper side is arranged of carrier Layer.The roughening treatment layer may be used known method and be configured, and can also be configured by following roughening treatments.To carrier The surface setting roughening treatment layer of the side opposite with the very thin surface of layers of copper side is arranged have the following advantages that:By carrier to have There is the surface side lamination of the roughening treatment layer when on the supporters such as resin substrate, carrier and resin substrate are not easily stripped.
Use electrolytic copper foil as an example of the manufacturing condition in the case of carrier hereinafter, illustrating.
< electrolyte forms >
Copper:90g/L or more and 110g/L or less
Sulfuric acid:90g/L or more and 110g/L or less
Chlorine:50ppm or more and 100ppm or less
Levelling agent 1 (bis- (3- sulfopropyls) disulfides):10ppm or more and 30ppm or less
Levelling agent 2 (amine compounds):10ppm or more and 30ppm or less
The amine compounds can use the amine compounds of following below formula.
As long as in addition, the remainder of the treatment fluid used in electrolysis of the present invention, surface treatment or plating etc. It is water to be not specifically noted.
&#91;Change 1&#93;
(in the chemical formula, R1And R2Selected from by hydroxy alkyl, ether, aryl, aromatic series substitution alkyl, unsaturated hydrocarbons The group that base, alkyl are formed)
< manufacturing conditions >
Current density:70A/dm2Above and 100A/dm2Below
Electrolyte temperature:50 DEG C or more and 60 DEG C or less
Electrolyte linear velocity:3m/sec or more and 5m/sec or less
Electrolysis time:0.5 minute or more and 10 minutes or less
< middle layers >
Middle layer is set on carrier.Other layers can also be set between carrier and middle layer.It is used in the present invention As long as middle layer is that very thin layers of copper is made to be not easy to remove from carrier before layering steps of the Copper foil with carrier to insulating substrate, another party Face enables composition of the very thin layers of copper from carrier after the layering steps to insulating substrate, then is not particularly limited.For example, this hair The middle layer of bright Copper foil with carrier can include selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these metals One or more of the group that alloy, the hydrate of these metals, the oxide of these metals, organic matter are formed.Separately Outside, middle layer can be multilayer.
In addition, middle layer can be constituted in the following way, for example, formed from carrier side by be selected from Cr, Ni, Co, Fe, The single metal layer that is formed of a kind of element in the groups of elements that Mo, Ti, W, P, Cu, Al, Zn are constituted, or formed by be selected from Cr, The alloy-layer that one or more of the groups of elements that Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn are constituted element is formed, It is formed on one or more of the groups of elements by being constituted selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn The layer that the hydrate or oxide or organic matter of element are formed, or formed by be selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, The single metal layer that is formed of a kind of element in the groups of elements that Al, Zn are constituted, or formed by be selected from Cr, Ni, Co, Fe, Mo, The alloy-layer that one or more of the groups of elements that Ti, W, P, Cu, Al, Zn are constituted element is formed.
When middle layer only being set to single side, the antirust coats such as nickel plating (Ni) layer preferably are arranged to the opposing face of carrier.In addition, recognizing When middle layer is arranged by chromic acid salt treatment or zinc chromate processing or plating, to there is the metal accompanying by chromium or zinc etc. A part becomes the case where hydrate or oxide.
In addition, middle layer can for example pass through sequentially lamination nickel, nickel-phosphor alloy or nickel-cobalt alloy and by chromium on carrier It constitutes.The bonding force of nickel and copper is higher than the bonding force of chromium and copper, so when removing very thin layers of copper, at the interface of very thin layers of copper and chromium It is peeling-off.In addition, it can be expected that the nickel of middle layer, which has, prevents the barrier effect that copper component is spread from carrier to very thin layers of copper.In The adhesion amount of nickel in interbed preferably 100 μ g/dm2Above and 40000 μ g/dm2Hereinafter, more preferable 100 μ g/dm2Above and 4000 μg/dm2Hereinafter, more preferable 100 μ g/dm2Above and 2500 μ g/dm2Hereinafter, more preferable 100 μ g/dm2Above and not up to 1000 μ g/dm2, the adhesion amount preferably 5 μ g/dm of the chromium in middle layer2Above and 100 μ g/dm2Below.
The very thin layers of copper > of <
Very thin layers of copper is set on the intermediate layer.Other layers can also be set between middle layer and very thin layers of copper.Very thin copper Layer can be electroplated by using the electrobath of copper sulphate, pyrophosphoric acid, sulfamic acid copper, copper cyanider etc. and be formed, and preferably can It is enough to be copper sulphate bath used in general electrolytic copper foil with high current density formation copper foil.The thickness of very thin layers of copper has no spy It does not limit, it is however generally that be thinner than carrier, for example, 12 μm or less.For typical case for 0.5 μm or more and 12 μm hereinafter, it is more typical and Speech for 1 μm or more and 5 μm hereinafter, be 1.5 μm or more and 5 μm for typical in turn hereinafter, be for typical case in turn 2 μm or more and 5 μm or less.In addition it is also possible to which very thin layers of copper is arranged on the two sides of carrier.
So manufacture has the attached of the very thin layers of copper of the middle layer and lamination of carrier, lamination on carrier on the intermediate layer Carrier copper foil.
The application method of Copper foil with carrier itself is that dealer is known, such as can the surface of very thin layers of copper be fitted in paper substrate Material phenol resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth paper composite base material epoxy resin, Glass cloth glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film etc. are exhausted On edge substrate and after being thermally compressed, removes carrier and form copper-cover laminated plate, the very thin layers of copper that will be bonded on insulating substrate Etching becomes target conductor pattern, is finally made printing distributing board.
< other surfaces handle >
After roughening treatment, can also by Ni, Co, Cu, Zn elemental metals or Ni alloys, Co alloys, Cu alloys, Zn alloys or Including alloy of the element selected from one or more of Ni, Co, Cu, Zn etc. forms refractory layer or antirust coat, it can also be right in turn Implement the processing such as chromic acid salt treatment, silane coupled processing in its surface.I.e., it is possible to be formed selected from by resistance on the surface of roughening treatment layer The layer of one or more of the group that thermosphere, antirust coat, chromating layer and silane coupled process layer are formed.In addition, described resistance to Thermosphere, antirust coat, chromating layer, silane coupled process layer can be formed (such as 2 layers or more, 3 layers or more by multilayer respectively Deng).
In this specification, so-called chromating layer refers to using comprising chromic anhybride, chromic acid, two chromic acid, chromate or two The layer that the solution of chromate is handled.Chromating layer can also include Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, The elements such as Sn, As and Ti (forms such as metal, alloy, oxide, nitride, sulfide).As chromating layer Concrete example can be enumerated:The chromating layer that is handled using chromic anhybride or two chromic acid aqueous solutions of potassium or using comprising The chromating layer etc. that chromic anhybride or the treatment fluid of two potassium chromates and zinc are handled.
As refractory layer, antirust coat, well known refractory layer, antirust coat can be used.For example, refractory layer and/or antirust coat Can be to include the group selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, Silver, platinum family element, iron, tantalum One or more of element layer, or by be selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, Jin, Silver, platinum family element, iron, tantalum one or more of group the element metal layer or alloy-layer that are constituted.In addition, refractory layer And/or antirust coat can also contain the oxide comprising the element, nitride, silicide.In addition, refractory layer and/or antirust Layer or the layer for including nickel-zinc alloy.In addition, refractory layer and/or antirust coat may be nickel-zinc alloy-layer.The nickel- In zinc alloy layer other than inevitable impurity, can contain nickel 50wt% or more and 99wt% or less, zinc 50wt% with Upper and 1wt% or less.Total adhesion amount of zinc and nickel in the nickel-zinc alloy-layer can be 5mg/m2Above and 1000mg/m2 Hereinafter, it is preferred that 10mg/m2Above and 500mg/m2Hereinafter, it is preferred that 20mg/m2Above and 100mg/m2Below.In addition, described include In the layer of nickel-zinc alloy or the nickel-zinc alloy-layer, the ratio (=nickel adhesion amount/amount of zinc adhesion) of nickel adhesion amount and amount of zinc adhesion It is preferred that 1.5 or more and 10 or less.In addition, the nickel adhesion amount in the layer comprising nickel-zinc alloy or the nickel-zinc alloy-layer is excellent Select 0.5mg/m2Above and 500mg/m2Hereinafter, more preferable 1mg/m2Above and 50mg/m2Below.In refractory layer and/or antirust coat In the case of for the layer comprising nickel-zinc alloy, when the inner wall part of through-hole or guide hole etc. and removing glue slag liquid contact, copper foil and resin The interface of substrate is not easy by de-smear corrosion, the adhesion promotion of copper foil and resin substrate.
Silane coupled process layer can be formed using well known silane coupling agent, can also use epoxy silane, ammonia Base system silane, methacryloxy system silane, sulfydryl system silane, ethylene base system silane, imidazoles system silane, triazine system silane etc. Silane coupling agent etc. and formed.Furthermore, it is possible to which two or more in these silane coupling agents is used in mixed way.Wherein, it is preferable to use Amino system silane coupling agent or epoxy silane coupling agent and the silane coupled process layer formed.
Furthermore it is possible to copper foil, very thin layers of copper, roughening treatment layer, refractory layer, antirust coat, silane coupled process layer or chromium The surface of hydrochlorate process layer carries out international publication number WO2008/053878, Japanese Patent Laid-Open 2008-111169, Japan specially Profit the 5024930th, international publication number WO2006/028207, Japanese Patent No. 4828427, international publication number WO2006/ 134868, Japanese Patent No. 5046927, international publication number WO2007/105635, Japanese Patent No. 5180815, Japan are special Recorded surface treatment in sharp special open 2013-19056.Or it can be to copper foil, very thin layers of copper, roughening treatment layer, heat-resisting The well known surface treatment of surface progress of layer, antirust coat, silane coupled process layer or chromating layer.
< resin layers >
Surface treatment copper foil can have resin layer in roughening treatment layer side surface.The resin layer can be bonding agent, Or the insulating resin layer of the semi-hardened state (B-stage) of bonding.So-called semi-hardened state (B-stage) includes using finger It touches its surface also to feel without adhesion and the insulating resin layer can be overlapped and be taken care of, and then when heated processing can then occur firmly Change the state of reaction.
In addition, the resin layer can include thermosetting resin, or thermoplastic resin.In addition, the resin Layer can also include thermoplastic resin.Resin types are not particularly limited, for example, can be preferably listed comprising selected from asphalt mixtures modified by epoxy resin Fat, polyimide resin, multi-functional cyanate esters, maleimide compound, polymaleimide compounds, Malaysia Imide series resin, aromatic series maleimide resin, polyvinyl acetal resin, urethane resin, polyether sulfone, polyether sulfone tree Fat, aromatic polyamide resin, aromatic polyamide resin polymer, rubbery resin, polyamines, aromatic polyamine, polyamide Imide resin, rubber modified epoxy resin, phenoxy resin, carboxy-modified acrylonitrile-butadiene resin, polyphenylene oxide, span Carry out acid imide cyanate resin, thermosetting polyphenylene oxide resin, cyanate ester based resin, carboxylic acid anhydrides, polybasic acid anhydride, have and can hand over Bis- (the 4- cyanic acid bases phenyl) propane of linear polymer, polyphenylene oxide resin, 2,2- of the functional group of connection, phosphorous phenol system compound, Bis- (4- glycidyl phenyls) propane of manganese naphthenate, 2,2-, polyphenylene oxide-cyanate ester based resin, silicone-modified polyamide acyl Imide resin, phosphine nitrile system resin, rubber modified polyamide-imide resin, isoprene, hydrogenation type polybutadiene, polyvinyl alcohol Butyral, phenoxy group, macromolecule epoxy resin, aromatic polyamide, fluororesin, bis-phenol, block copolymerized polyimide resin and The resin of one or more of the group of cyano ester resin.
As long as in addition, the epoxy resin intramolecular has 2 or more epoxy groups, and can be used in electrical, electronics material Expect purposes, so that it may to be used without special problem.In addition, it is preferable to use the contractings that intramolecular has 2 or more for the epoxy resin The glyceryl compound of water carries out the epoxy resin obtained by epoxidation.It is selected from bisphenol type epoxy tree alternatively, it is also possible to be used in mixed way Fat, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A D-ring oxygen resin, phenol aldehyde type epoxy resin, cresol novolak type Epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolak type epoxy, naphthalene type epoxy resin, brominated bisphenol A types epoxy resin, o-cresol phenol aldehyde type epoxy resin, modified rubber bisphenol A type epoxy resin, glycidyl amine epoxy tree Fat, isocyanuric acid three-glycidyl ester, N, the glycidols amine compounds such as N- 2-glycidyl aniline, tetrahydrophthalic acid two The epihydric alcohol ester compounds such as ethylene oxidic ester, phosphorous epoxy resin, biphenyl type epoxy resin, biphenyl phenolic epoxy tree Fat, trihydroxy benzene methylmethane type epoxy resin, tetraphenyl ethane type epoxy resin group in it is one kind or two or more, or can make With the hydride or halide of the epoxy resin.
As the phosphorous epoxy resin, the well known epoxy resin containing phosphorus can be used.In addition, described phosphorous 9,10- dihydro-9-oxy miscellaneous -10- phospha of the epoxy resin preferably for example as the epoxy group for having 2 or more from intramolecular The derivative of phenanthrene -10- oxides and the epoxy resin obtained.
The resin layer can include that well known resin, hardening of resin agent, compound, hardening accelerator, dielectric medium (can be with Use the arbitrary dielectrics such as the dielectric medium comprising inorganic compound and/or organic compound, the dielectric medium comprising metal oxide Matter), catalysts, crosslinking agent, polymer, prepreg, skeleton material etc..In addition, the resin layer can use such as world Publication number WO2008/004399, international publication number WO2008/053878, international publication number WO2009/084533, Japan Patent Unexamined Patent 11-5828, Japanese Patent Laid-Open 11-140281, Japanese Patent No. 3184485, international publication number WO97/ 02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open 2000-43188, Japanese Patent No. 3612594, Japan are special Sharp special open 2002-179772, Japanese Patent Laid-Open 2002-359444, Japanese Patent Laid-Open 2003-304068, Japan Patent the 3992225th, Japanese Patent Laid-Open 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open 2004-349654, Japanese Patent No. 4286060 Number, Japanese Patent Laid-Open 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, day This patent the 3949676th, Japanese Patent No. 4178415, international publication number WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open 2007-326923, Japanese Patent Laid-Open 2008-111169, Japanese Patent No. No. 5024930, international publication number WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open 2009-67029 Number, it is international publication number WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open 2009-173017, international Publication number WO2007/105635, Japanese Patent No. 5180815, international publication number WO2008/114858, international publication number WO2009/008471, Japanese Patent Laid-Open 2011-14727, international publication number WO2009/001850, international publication number Recorded substance in WO2009/145179, international publication number WO2011/068157, Japanese Patent Laid-Open 2013-19056 (resin, hardening of resin agent, compound, hardening accelerator, dielectric medium, catalysts, crosslinking agent, polymer, prepreg, bone Frame material etc.) and/or resin layer forming method, forming apparatus and formed.In addition, the resin layer can also use well known tree Forming method, the forming apparatus of lipid layer and formed.
So that these described resins is dissolved in such as MEK (methyl ethyl ketone), toluene equal solvent and resin liquid is made, passes through example As described in made resin liquid is coated on by print roll coating method in very thin layers of copper or the refractory layer, antirust coat or described It on chromate skin membrane or the silane coupling agent layer, is then optionally thermally dried, removes solvent and make B Stage condition.For example using hot-air drying stove, drying temperature is 100 DEG C or more and 250 DEG C or less, preferably 130 DEG C for drying Above and 200 DEG C or less.
The Copper foil with carrier (Copper foil with carrier for having resin) for having the resin layer is used in the form of following:It should After resin layer is overlapped in base material, which is made to the whole thermo-compression bonding that carries out, then carrier is removed and makes very thin layers of copper Expose (certainly, exposing be the very thin layers of copper middle layer side surface), specified Wiring pattern is formed in exposed surface.
If having the Copper foil with carrier of resin using this, preimpregnation when manufacture multilayer printed wiring board can be reduced Expect the use the piece number of material.Moreover, the thickness of resin layer can be made to become the thickness etc. for being enough to ensure that layer insulation, even if completely not Copper-cover laminated plate can be also manufactured using prepreg material.In addition, at this moment can also base material surface primary coat insulating resin and into One step improves the flatness on surface.
In addition, without using prepreg material, have the following advantages:The material cost of prepreg material is saved, separately It is outer to also simplify layering steps, therefore economical advantages, also, the thickness of prepreg material is thinning and correspondingly make manufactured more The thickness of layer printed wiring board is thinning, is 100 μm of very thin multi-sheet printed wirings below so as to manufacture thickness in monolayer Substrate.
Preferably 0.1 μm or more and 80 μm or less of the thickness of the resin layer.If the thickness of resin layer is less than 0.1 μm, glue Relay can reduce, be not interposed prepreg material and by the Copper foil with carrier with resin laminated on the base material for having internal layer material When, there is the case where layer insulation being difficult to ensure between the circuit of internal layer material.
On the other hand, it if the thickness of resin layer is more than 80 μm, is difficult to form target thickness by 1 application step Resin layer can expend extra fee of material and working hour, therefore economically disadvantageous.In turn, it is flexible poor to be formed by resin layer, therefore Slight crack etc. is easy tod produce in processing, in addition, there is the resin superfluous when being thermally compressed with internal layer material that flowing occurs and is difficult to Successfully the case where lamination.
In turn, another product form of the Copper foil with carrier as this with resin, can also be in the very thin layers of copper It is carried out with resin layer in the upper or described refractory layer, antirust coat or the chromating layer or the silane coupled process layer It is coating, and make semi-hardened state, then remove carrier, and the system in the form of the copper foil with resin there is no carrier It makes.
By completing printed circuit board to printing distributing board electronic component mounting class.In the present invention, " printing distributing board " Printing distributing board, printed circuit board and printed base plate including so carrying electronic component class.
Further, it is possible to use the printing distributing board and make e-machine, electronic component class can also using the carrying Printed circuit board and make e-machine, electronic machine can also be made using the printed base plate equipped with electronic component class Device.Hereinafter, illustrating several examples using the manufacturing step of the printing distributing board of the Copper foil with carrier of the present invention.In addition, will The surface treatment copper foil of the present invention is used as similarly manufacturing printing distributing board when the very thin layers of copper of Copper foil with carrier.
In an embodiment of the manufacturing method of the printing distributing board of the present invention, include the following steps:Prepare the present invention Copper foil with carrier and insulating substrate;The Copper foil with carrier and insulating substrate are subject to lamination;By the Copper foil with carrier and Insulating substrate after lamination, removes the carrier of the Copper foil with carrier, through this in such a way that very thin layers of copper side and insulating substrate are opposite Step forms copper-cover laminated plate, then passes through either one in semi-additive process, improvement semi-additive process, part addition process and subtractive process Method forms circuit.Insulating substrate can be provided with internal layer circuit.
In the present invention, semi-additive process refers to following method:On insulating substrate or copper foil seed crystal (シ ー De) layer carry out compared with After forming pattern, conductive pattern is formed using plating and etching for thin electroless plating.
Therefore, in the embodiment using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including Following steps:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
The carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin Layers of copper all removes;
In the resin setting through-hole or/and blind hole for removing the very thin layers of copper by using etching and exposing;
De-smear (デ ス ミ ア) is carried out to the region comprising the through-hole or/and blind hole to handle;
In the resin and comprising the region of the through-hole or/and blind hole, electroless coating is set;
Reserve (め っ I レ ジ ス ト) is set on the electroless coating;
The reserve is exposed, the reserve of circuit region to be formed is then removed;
In the circuit region to be formed for having removed the reserve, electro deposition is set;
Remove the reserve;
Electroless coating present in the region other than the circuit region to be formed is removed by fast-etching etc..
In another embodiment using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including it is as follows Step:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
In the stripping carrier, through-hole or/and blind hole is arranged in the very thin layers of copper exposed and the insulating resin substrate;
Removing glue Slag treatment is carried out to the region comprising the through-hole or/and blind hole;
The carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin Layers of copper all removes;
In the resin exposed by using the removal very thin layers of copper such as etching and include the through-hole or/and blind Electroless coating is arranged in the region in hole;
Reserve is set on the electroless coating;
The reserve is exposed, the reserve of circuit region to be formed is then removed;
In the circuit region to be formed for having removed the reserve, electro deposition is set;
Remove the reserve;
Electroless coating present in the region other than the circuit region to be formed is removed by fast-etching etc..
In another embodiment using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including it is as follows Step:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
In the stripping carrier, through-hole or/and blind hole is arranged in the very thin layers of copper exposed and the insulating resin substrate;
The carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin Layers of copper all removes;
Removing glue Slag treatment is carried out to the region comprising the through-hole or/and blind hole;
In the resin exposed by using the removal very thin layers of copper such as etching and include the through-hole or/and blind Electroless coating is arranged in the region in hole;
Reserve is set on the electroless coating;
The reserve is exposed, the reserve of circuit region to be formed is then removed;
In the circuit region to be formed for having removed the reserve, electro deposition is set;
Remove the reserve;
Electroless coating present in the region other than the circuit region to be formed is removed by fast-etching etc..
In another embodiment using the manufacturing method of the printing distributing board of the present invention of semi-additive process, including it is as follows Step:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
The carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin Layers of copper all removes;
On the surface of the resin exposed by using the etching removal very thin layers of copper, electroless coating is set;
Reserve is set on the electroless coating;
The reserve is exposed, the reserve of circuit region to be formed is then removed;
In the circuit region to be formed for having removed the reserve, electro deposition is set;
Remove the reserve;
Electroless coating and pole present in the region other than the circuit region to be formed are removed by fast-etching etc. Thin copper layer.
In the present invention, it refers to following method to improve semi-additive process:Lamination metal foil on the insulating layer is protected using reserve Inverter circuit forming portion after thickening the copper of circuit forming portion by electrolytic coating, removes resist, passes through (quick (Off ラ ッ シ ュ)) etching removes the metal foil other than the circuit forming portion, thus forms circuit on the insulating layer.
Therefore, in the embodiment using the manufacturing method of the printing distributing board for the present invention for improving semi-additive process, Include the following steps:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
In very thin layers of copper and insulating substrate the setting through-hole or/and blind hole removed the carrier and exposed;
Removing glue Slag treatment is carried out to the region comprising the through-hole or/and blind hole;
In the region comprising the through-hole or/and blind hole, electroless coating is set;
On the very thin layers of copper surface removed the carrier and exposed, reserve is set;
After the reserve is set, circuit is formed by electrolytic coating,
Remove the reserve;
The very thin layers of copper by exposing by removing the reserve is removed by fast-etching.
In another embodiment using the manufacturing method of the printing distributing board for the present invention for improving semi-additive process, including Following steps:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
Reserve is set in the very thin layers of copper that the stripping carrier exposes;
The reserve is exposed, the reserve of circuit region to be formed is then removed;
In the circuit region to be formed for having removed the reserve, electro deposition is set;
Remove the reserve;
Electroless coating and pole present in the region other than the circuit region to be formed are removed by fast-etching etc. Thin copper layer.
In the present invention, part addition process refers to following method:To substrate made of setting conductor layer, optionally open up through-hole Or catalysis core is assigned on substrate made of guide hole hole, etching forms conductor circuit, and solder resist (ソ Le ダ レ ジ are optionally arranged ス ト) or reserve after, by electroless plating by the conductor circuit, through-hole (ス Le ー ホ ー Le) or guide hole (バ イ ア ホ ー Le) etc. thickenings, thus manufacture printing distributing board.
Therefore, in the embodiment using the manufacturing method of the printing distributing board of the present invention of part addition process, packet Include following steps:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
In very thin layers of copper and insulating substrate the setting through-hole or/and blind hole removed the carrier and exposed;
Removing glue Slag treatment is carried out to the region comprising the through-hole or/and blind hole;
Catalysis core is assigned to the region comprising the through-hole or/and blind hole;
On the very thin layers of copper surface removed the carrier and exposed, resist is set;
The resist is exposed, circuit pattern is formed;
The very thin layers of copper and the catalysis are removed by using the methods of the etching of the etchant solutions such as acid or plasma Core forms circuit;
Remove the resist;
By using etchant solutions such as acid etching or the methods of the plasma removal very thin layers of copper and described urge Solder resist or reserve is arranged in the insulating substrate surface changed core and exposed;
In the region that the solder resist or reserve are not arranged, electroless coating is set.
In the present invention, subtractive process refers to following method:The copper foil being optionally removed by etching etc. on copper-cover laminated plate Unnecessary portion, and form conductive pattern.
Therefore, in the embodiment using the manufacturing method of the printing distributing board of the present invention of subtractive process, including such as Lower step:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
In very thin layers of copper and insulating substrate the setting through-hole or/and blind hole removed the carrier and exposed;
Removing glue Slag treatment is carried out to the region comprising the through-hole or/and blind hole;
In the region comprising the through-hole or/and blind hole, electroless coating is set;
On the surface of the electroless coating, electro deposition is set;
In the surface of the electro deposition or/and very thin layers of copper setting resist (エ ッ チ Application グ レ ジ ス ト);
The resist is exposed, circuit pattern is formed;
The very thin layers of copper and the no electricity are removed by using the methods of the etching of the etchant solutions such as acid or plasma Coating and the electro deposition are solved, circuit is formed;
Remove the resist.
In another embodiment using the manufacturing method of the printing distributing board of the present invention of subtractive process, including walk as follows Suddenly:
Prepare the Copper foil with carrier and insulating substrate of the present invention;
The Copper foil with carrier and insulating substrate are subject to lamination;
After the Copper foil with carrier and insulating substrate lamination, the carrier of the Copper foil with carrier is removed;
In very thin layers of copper and insulating substrate the setting through-hole or/and blind hole removed the carrier and exposed;
Removing glue Slag treatment is carried out to the region comprising the through-hole or/and blind hole;
In the region comprising the through-hole or/and blind hole, electroless coating is set;
Mask is formed on the surface of the electroless coating;
On the surface for the electroless coating for not forming mask, electro deposition is set;
On the surface of the electro deposition or/and the very thin layers of copper, resist is set;
The resist is exposed, circuit pattern is formed;
The very thin layers of copper and the no electricity are removed by using the methods of the etching of the etchant solutions such as acid or plasma Coating is solved, circuit is formed;
Remove the resist.
The step of through-hole or/and blind hole can not also be configured and de-smear step later.
Herein, with reference to schema, the concrete example of the manufacturing method of the printing distributing board of the Copper foil with carrier to using the present invention It is described in detail.
First, as shown in Fig. 1-A, prepare the Copper foil with carrier (first layer) with very thin layers of copper, the very thin layers of copper is in table Face is formed with roughening treatment layer.
Then, as shown if figure 1-b, it is coated with resist on the roughening treatment layer of very thin layers of copper, is exposed, develops, will hindered Agent etching becomes designated shape.
Then, as shown in Fig. 1-C, after forming circuit coating, resist is removed, the circuit plating of designated shape is consequently formed Layer.
Then, as depicted in fig. 2-d, in a manner of covering circuit coating (by bury bury circuit coating in a manner of) very thin In layers of copper setting embedment resin and laminated resin layer, so that another Copper foil with carrier (second layer) is existed with very thin layers of copper side bonds On the resin layer.
Then, as shown in Fig. 2-E, carrier is removed from the Copper foil with carrier of the second layer.
Then, as shown in Fig. 2-F, laser opening is carried out in the designated position of resin layer, circuit coating is made to expose and be formed Blind hole.
Then, it as shown in Fig. 3-G, is embedded to copper into blind hole (Block ラ イ Application De ビ ア) and forms filling perforation (ビ ア Off ィ Le).
Then, as shown in Fig. 3-H, circuit coating is formed as shown in Fig. 1-B and Fig. 1-C in filling perforation.
Then, as shown in Fig. 3-I, carrier is removed from the Copper foil with carrier of first layer.
Then, as shown in Fig. 4-J, the very thin layers of copper on two surfaces is removed by fast-etching, and makes the electricity in resin layer Expose on the surface of road coating.
Then, as shown in Fig. 4-K, convex block is formed on the circuit coating in resin layer, copper post is formed on the solder.Through It crosses above step and makes the printing distributing board using Copper foil with carrier of the invention.
In addition, in the manufacturing method of the printing distributing board, " very thin layers of copper " can also be changed into carrier, " carrier " is changed Poling thin copper layer buries circuit in the carrier side circuit forming surface of Copper foil with carrier using resin, and manufactures printing and match Line plate.
Another Copper foil with carrier (second layer) can use the Copper foil with carrier of the present invention, can also use existing Copper foil with carrier can also use common copper foil.Alternatively, it is also possible to further shape on the circuit of the second layer shown in Fig. 3-H At 1 layer or multilayer circuit, these circuits can be by semi-additive process, subtractive process, part addition process or improvement semi-additive process Either method is formed.
By the manufacturing method of printing distributing board as described above, become structure circuit coating being embedded in resin layer At, therefore when removing very thin layers of copper by fast-etching shown in such as Fig. 4-J, circuit coating is protected and protected by resin layer Its shape is held, fine circuits are formed to become easy.In addition, circuit coating is by resin layer because protected, resistance to migration Property promoted, the conducting of suppression circuit wiring well.Therefore, it is easy to form fine circuits.In addition, such as Fig. 4-J and Fig. 4-K institutes Show, when removing very thin layers of copper by fast-etching, the exposed surface of circuit coating becomes the shape being recessed from resin layer, therefore holds Convex block easily is formed on the circuit coating, is easy to be formed on copper post in addition, manufacture efficiency is promoted.
In addition, embedment resin can use well known resin, prepreg.BT (ビ ス マ レ イ ミ De ト リ can be used for example ア ジ Application, Bismaleimide Triazine) resin or as the prepreg containing the glass cloth for being soaked with BT resins, aginomoto fine chemistry industry The ABF films or ABF of (Ajinomoto Fine-Techno) limited liability company manufacture.In addition, the embedment resin can use Resin layer and/or resin recorded in this specification and/or prepreg.
In addition, Copper foil with carrier used in the first layer can also the surface of the Copper foil with carrier have substrate or Resin layer.So that Copper foil with carrier used in first layer is supported by there is the substrate or resin layer, is not likely to produce wrinkle Pleat, therefore have the advantages that productivity promotion.In addition, as long as various substrates or resin layer play and the first layer are supported to be used Copper foil with carrier effect, then can be employed as the substrate or resin layer.It, can be with for example, as the substrate or resin layer Use carrier recorded in present specification, prepreg, resin layer or well known carrier, prepreg, resin layer, gold The foil of category plate, metal foil, the plate of inorganic compound, the foil of inorganic compound, the plate of organic compound, organic compound.
In addition, the manufacturing method of the printing distributing board of the present invention may be the system of the printing distributing board included the following steps Make method (centreless (U ア レ ス) method):By the very thin layers of copper side surface of the Copper foil with carrier of the present invention or the carrier side Surface and resin substrate are subject to lamination;With the resin substrate layer very thin layers of copper side surface or the carrier side surface Resin layer and circuit at least once is arranged in the surface of the Copper foil with carrier of opposite side;And after forming the resin layer and circuit, from The Copper foil with carrier removes the carrier or the very thin layers of copper.It, first will be of the invention as concrete example about the called non-sleeve method Copper foil with carrier very thin layers of copper side surface or carrier side surface and resin substrate be subject to lamination and manufacture laminate (also referred to as Copper-cover laminated plate, copper-cover laminated body).Then, the very thin layers of copper side surface of lamination or the carrier side are being carried out with resin substrate The surface of the Copper foil with carrier of the opposite side on surface forms resin layer.It can also be to being formed in carrier side surface or very thin layers of copper side The resin layer and then another Copper foil with carrier of lamination on surface, another Copper foil with carrier are carried out with carrier side or very thin layers of copper side Lamination.Alternatively, it is also possible to have centered on resin substrate or resin or prepreg, in the resin substrate or resin or preimpregnation Two surface sides of material, according to the sequence of carrier/middle layer/very thin layers of copper or the sequential lamination of very thin layers of copper/middle layer/carrier The laminate of the composition of Copper foil with carrier has according to " carrier/middle layer/very thin layers of copper/resin substrate or resin or preimpregnation The laminate of the composition of the sequential lamination of material/carrier/middle layer/very thin layers of copper " has according to " carrier/middle layer/very thin The laminate of the composition of the sequential lamination of layers of copper/resin substrate/carrier/middle layer/very thin layers of copper " has according to " very thin copper The laminate of the composition of the sequential lamination of layer/middle layer/carrier/resin substrate/carrier/middle layer/very thin layers of copper " is for described The manufacturing method (called non-sleeve method) of printing distributing board.It is then possible to which the very thin layers of copper or carrier at the both ends of the laminate are exposed Surface another resin layer is set, and then after layers of copper or metal layer are set, the layers of copper or metal layer are processed, are consequently formed Circuit.In turn, can also on the circuit by by the circuit embedment it is therein in a manner of another resin layer is set.Furthermore it is possible into The formation (increasing layer (ビ Le De ア ッ プ) method) of the primary above this circuit and resin layer of row.Then, to so product of formation Layer body (hereinafter also referred to laminate B) removes the very thin layers of copper of each Copper foil with carrier or carrier from carrier or very thin layers of copper, And coreless substrate can be made.In addition, the making of the coreless substrate can also use 2 Copper foil with carrier, following tools are made Have the composition of very thin layers of copper/middle layer/carrier/carrier/middle layer/very thin layers of copper laminate or with carrier/middle layer/ The laminate of the composition of very thin layers of copper/very thin layers of copper/middle layer/carrier or with carrier/middle layer/very thin layers of copper/carrier/ The laminate is used for center by the laminate of the composition of middle layer/very thin layers of copper.Can these laminates (hereinafter also referred to Laminate A) both sides very thin layers of copper or carrier the primary above resin layer and circuit of surface setting, be arranged primary above After resin layer and circuit, the very thin layers of copper of each Copper foil with carrier or carrier are removed from carrier or very thin layers of copper, and can made Make coreless substrate.The laminate can also be between the surface of very thin layers of copper, the surface of carrier, carrier and carrier, very thin copper Between layer and very thin layers of copper, there are other layers between very thin layers of copper and carrier.Other layers can be resin substrate or resin layer.This Outside, in the present specification, " surface of very thin layers of copper ", " very thin layers of copper side surface ", " very thin layers of copper surface ", " table of carrier Face ", " carrier side surface ", " carrier surface ", " surface of laminate ", " laminate surface " are in very thin layers of copper, carrier, laminate In the case that very thin layers of copper surface, carrier surface, laminate surface have other layers, it is set as including the surface of other layers Concept including (most surface).In addition, laminate preferably has very thin layers of copper/middle layer/carrier/carrier/middle layer/very thin copper The composition of layer.The reason is that when making coreless substrate using the laminate, very thin layers of copper is configured in coreless substrate side, So being easy to form circuit on coreless substrate using semi-additive process is improved.In addition, reason also resides in the thickness of very thin layers of copper It is thin, so the very thin layers of copper easily removes, it is easy to form electricity on coreless substrate using semi-additive process after removing very thin layers of copper Road.
In addition, in the present specification, " laminate " for not being recorded as " laminate A " or " laminate B " especially indicates at least Including the laminate of laminate A and laminate B.
In addition, in the manufacturing method of the coreless substrate, Copper foil with carrier or the lamination are covered by using resin Part or all of the end face of body (include laminate A), and when manufacturing printing distributing board with Layer increasing method, chemical drugs can be prevented Liquid is penetrated between middle layer or a piece of Copper foil with carrier and another Copper foil with carrier of composition laminate, so as to prevent Cause very thin layers of copper and carrier generation separation or Copper foil with carrier to be corroded because penetrating into chemical liquid, yield can be promoted. As " some or all of resin of the end face of covering Copper foil with carrier " used herein or " cover the end face of laminate Some or all of resin " can use and can be used for the resin of resin layer or well known resin.In addition, in the centreless base In the manufacturing method of plate, in overlook observation Copper foil with carrier or laminate, the lamination part of Copper foil with carrier or laminate (carries The lamination part of the lamination part or a piece of Copper foil with carrier and another Copper foil with carrier of body and very thin layers of copper) periphery At least part can be covered by resin or prepreg.In addition, the laminate formed by the manufacturing method of the coreless substrate (laminate A) can also be to make a pair of of Copper foil with carrier that can contact and constitute separated from each other.In addition, in the overlook observation appendix When body copper foil, lamination part (the lamination part or a piece of appendix body copper of carrier and very thin layers of copper of Copper foil with carrier or laminate The lamination part of foil and another Copper foil with carrier) periphery entirety or lamination part whole face can be covered by resin or prepreg Lid.Additionally, it is preferred that resin or prepreg are more than the lamination part of Copper foil with carrier or laminate or laminate when looking down, preferably It is made with the laminate constituted as follows:In Copper foil with carrier or the two sides lamination of the laminate resin or prepreg, and utilize Copper foil with carrier or laminate are carried out envelope (package) by resin or prepreg.It is attached in overlook observation by sampling this composition When carrier copper foil or laminate, the lamination part of Copper foil with carrier or laminate is covered by resin or prepreg, can prevent and Other component has collision on the side direction of the part, the horizontal direction namely relative to lamination direction, as a result can mitigate Carrier and very thin layers of copper or Copper foil with carrier peeling-off situation each other in processing.In addition, by using resin or preimpregnation Body covers the periphery of the lamination part of Copper foil with carrier or laminate so as not to expose, and can prevent in chemistry as described above Chemical solution penetrates into the interface of the lamination part in solution treatment steps, can prevent Copper foil with carrier from being corroded or being invaded Erosion.In addition, when detaching a piece of Copper foil with carrier from a pair of of Copper foil with carrier of laminate or separation Copper foil with carrier carrier When with copper foil (very thin layers of copper), if the lamination part (carrier of the Copper foil with carrier or laminate covered by resin or prepreg With the lamination part of the lamination part of very thin layers of copper or a piece of Copper foil with carrier and another Copper foil with carrier) by resin or pre- Leaching body etc. touches securely, then sometimes for by cutting off removals such as the lamination parts etc..
The laminate of the present invention can have 2 Copper foil with carrier of the invention.Specifically, can be by the attached of the present invention Carrier side or very thin layers of copper side of the carrier copper foil with carrier side or very thin layers of copper side lamination in the Copper foil with carrier of another present invention And constitute laminate.Alternatively, it is also possible to being by the carrier side surface of a piece of Copper foil with carrier or the very thin layers of copper The carrier side surface or the very thin layers of copper side surface of side surface and another Copper foil with carrier are optionally via viscous The laminate for connecing the direct lamination of agent and obtaining.Alternatively, it is also possible to by the carrier of a piece of Copper foil with carrier or very thin layers of copper and The carrier of another Copper foil with carrier or very thin layers of copper are engaged.Herein, it is somebody's turn to do " engagement " and is also included within carrier or very thin The form that layers of copper is interconnected in the case of having surface-treated layer across the surface-treated layer.Alternatively, it is also possible to utilize tree Fat covers part or all of the end face of the laminate.
Carrier each other, very thin layers of copper each other, the mutual lamination of the copper foil of carrier and very thin layers of copper, appendix body is in addition to simple Other than overlapping, such as it can also carry out by the following method.
(a) metallurgical, bond method:Melting welding (arc-welding, TIG (タ Application グ ス テ Application イ ナ ー ト ガ ス, tungsten-indifferent gas Body) welding, MIG (メ タ Le イ ナ ー ト ガ ス, metal-noble gas) welding, electric resistance welding, seam weld, spot welding), crimping (ultrasonic welding, friction stir weld), soldering;
(b) mechanical interface method:Ca(u)lk, riveted joint (self-punching rivet (セ Le Off ピ ア ッ シ Application グ リ ベ ッ ト) engagement, riveting Nail joint close), order conjunction (ス テ ッ チ ャ ー);
(c) physical engagement method:Bonding agent, (two-sided) adhesive tape
By using the joint method by part or all and another carrier of a carrier part or all or Part or all of the very thin layers of copper of person is engaged, and makes a carrier and another carrier or very thin layers of copper lamination, so as to The laminate that manufacture makes carrier each other or carrier and very thin layers of copper separably contact and constitutes.By a carrier and another carrier Or in the case that very thin layers of copper weaker engages and makes a carrier and another carrier or very thin layers of copper lamination, even if not removing a load The joint portion of body and another carrier or very thin layers of copper can also detach a carrier and another carrier or very thin layers of copper.In addition, In the case that one carrier and another carrier or very thin layers of copper more securely engage, pass through cut-out or chemical grinding (etching etc.), machine The junction of removal one carrier and another carrier or very thin layers of copper such as tool grinding, thus, it is possible to by a carrier and another carrier or Very thin layers of copper separation.
In addition, to resin layer at least once and circuit are arranged on thus configured laminate, and forming institute at least once After stating resin layer and circuit, the very thin layers of copper or carrier are removed from the Copper foil with carrier of the laminate, more than implementation Step and the printing distributing board that centreless can be made.Furthermore, it is possible in a surface of the laminate or two surface setting trees Lipid layer and circuit.
Resin substrate, resin layer, resin, prepreg used in the laminate can be recorded in this specification Resin layer can also include resin, hardening of resin agent, compound, hardening used in resin layer recorded in this specification Accelerating agent, dielectric medium, catalysts, crosslinking agent, polymer, prepreg, skeleton material etc..In addition, the Copper foil with carrier or Laminate can be less than resin or prepreg or resin substrate or resin layer when looking down.Furthermore, it is possible to by described or following trees Aliphatic radical plate, resin layer, resin, prepreg and the present invention surface treatment copper foil carry out lamination and manufacture copper-cover laminated plate.In turn, The surface treatment copper foil of the copper-cover laminated plate is processed into copper wiring by etching etc., thus, it is possible to manufacture printing distributing board.
In addition, resin substrate is as long as with the characteristic that can be applied to printing distributing board etc., there is no particular restriction, for example, Rigid PWB (printing distributing board) used times can use 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 etc., FPC (flexible printing patch panel) used times can use polyester film or polyimide film, LCP (liquid crystal Polymer) film, fluororesin film, low dielectric coefficient polyimide resin film, COP (cyclic olefin polymer) film etc..In addition, and using Polyimide film is compared, and has the stripping of the film and surface treatment copper foil strong when using LCP (liquid crystal polymer) films or fluororesin film Spend the tendency to become smaller.Therefore, it using LCP (liquid crystal polymer) films or fluororesin film, after forming copper circuit, utilizes Coating covers copper circuit, thus enables that the film and copper circuit are not easily stripped, prevents the reduction because of peel strength from leading to the film It is peeling-off with copper circuit.
In addition, LCP (liquid crystal polymer) films or fluororesin film or low dielectric coefficient polyimide resin film or COP (cyclenes Hydrocarbon polymer) resin film dielectric loss angle tangent it is small, therefore use LCP (liquid crystal polymer) films or fluororesin film or low dielectric Constant polyimide resin film or COP (cyclic olefin polymer) resin films and the surface treatment copper foil of the present invention it is copper-cover laminated Plate, printing distributing board, printed circuit board are suitable for high-frequency circuit (circuit that signal is transmitted using high frequency) purposes.In addition, this hair Bright surface treatment copper foil is since the aspect ratio of roughening particle is controlled as designated shape, so being also applied for high-frequency circuit use On the way.In addition, in the present specification, it is normal that the value of dielectric loss angle tangent is that 0.01 polyimide resin below is known as low dielectric Number polyimide resin.Dielectric loss angle tangent can pass through the meeting of general civic organization's Japan Electronics circuit industry"Printing is matched Line plate copper-cover laminated plate test method relative dielectric constant and dielectric loss angle tangent"It is recorded in JPCA-TM001-2007 Three tablet resonator methods be measured.It is formed alternatively, it is also possible to be bonded copper foil and insulating substrate using bonding agent and covers copper Laminated plates.The bonding agent can use well known bonding agent.In addition, it is preferable to use low-k bondings for the bonding agent Agent.In the present specification, it is that 3.5 bonding agents below are known as low-k bonding agent by dielectric constant.In addition, in this explanation In book, the dielectric constant dielectric constant of substrate dielectric constant, resin (substrate dielectric constant) and dielectric loss angle tangent (base material Dielectric loss angle tangent, substrate dielectric loss angle tangent, the dielectric loss angle tangent of resin) value refer under signal frequency 1GHz Dielectric constant and dielectric loss angle tangent value.
In addition, the surface treatment copper foil or Copper foil with carrier of the present invention are also applied for the secondary cells such as lithium rechargeable battery The battery materials such as negative electrode collector.The surface treatment copper foil or Copper foil with carrier of the present invention is due to by the aspect ratio of roughening particle And glossiness is controlled in specified range, so and the surface treatment copper foil without being controlled as described or appendix body Copper foil is compared and is had the following advantages.The surface treatment copper foil or Copper foil with carrier and the adhesion of active material of the present invention is excellent. In addition, being fallen off since roughening particle is less, so can mitigate on the surface to surface treatment copper foil or Copper foil with carrier Pollution of the roughening particle to manufacturing equipment in the step of upper setting active material etc..In addition, the table of the present invention can be used for example Surface treatment copper foil or Copper foil with carrier manage copper foil or Copper foil with carrier at the surface as battery or the collector of secondary cell On formed active material film and make electrode.Also, it can finally manufacture using the electrode as electrode (positive or negative pole ) battery or secondary cell.The method for forming active material film on the current collector is not particularly limited, such as can be arranged It lifts:CVD method, vapour deposition method, plasma spraying, is subject to dry side after liquid of the coating comprising active material at sputtering method on the current collector Method or plating method etc..Among these film forming methods, CVD method, sputtering method and vapour deposition method are particularly preferably used.In addition, also may be used To form middle layer on the current collector, and active material film is formed in the middle layer.The present invention surface treatment copper foil or Copper foil with carrier can be used for well known electrode, well known collector, well known battery.As well known battery, such as can arrange It lifts:Lithium rechargeable battery, all solid state secondary battery, air cell (lithium-air battery, zinc-air battery etc.), sodium ion electricity Pond, Magnesium ion battery, multivalent ion battery, anode are lived using secondary cell, the anode of sulphur system substance using display redox Secondary cell, nickel-cadmium cell, manganese cell (dry cell), alkaline battery (dry cell), the lithium battery (dry cell) of the organic matter of property Deng.As well known electrode, well known collector, the electrode for the known batteries, collector can be enumerated.
&#91;Shi Shili &#93;
Hereinafter, being illustrated based on Examples and Comparative Examples.In addition, the present embodiment only as an example of, the present invention simultaneously not only limits Due to the example.That is, the present invention also includes other forms or deformation.
Examples 1 to 34, comparative example 1~13,15, reference example 14
Prepare the various copper foils made under conditions of table 1 is recorded, to a surface under conditions of table 2 and table 3 are recorded Carry out the plating as roughening treatment.In addition, about reference example 14, such as the record of table 2 and table 3, sequentially carry out processing 1 and Processing 2.Processing 1 be carry out processing 1-1 current density and Plating times processing after, then carry out processing 1-2 electric current it is close The processing of degree and Plating times.
In addition, about embodiment 19~23, prepare the metal foil recorded in table 2 and table 3 as various carriers, at following Under part, middle layer is formed on the surface of carrier, very thin layers of copper is formed on the surface of middle layer.Also, it is recorded in table 2 and table 3 Under the conditions of plating as roughening treatment is carried out to the surface of very thin layers of copper.
Embodiment 19
< middle layers >
(1) Ni layers (plating Ni)
For carrier, by under the following conditions in the continuous plating overgrowth of roll-to-roll (ロ ー Le ト ウ ロ ー Le) type It is electroplated in producing line and forms 1000 μ g/dm2Adhesion amount Ni layers.Plating conditions are specific as follows.
Nickel sulfate:270g/L or more and 280g/L or less
Nickel chloride:35g/L or more and 45g/L or less
Nickel acetate:10g/L or more and 20g/L or less
Boric acid:30g/L or more and 40g/L or less
Gloss agent:Saccharin, butynediols etc.
Lauryl sodium sulfate:55ppm or more and 75ppm or less
PH value:4 or more and 6 or less
Liquid temperature:55 DEG C or more and 65 DEG C or less
Current density:10A/dm2
(2) Cr layers (electrolytic chromate processing)
Then, after carrying out washing and pickling to the Ni layer surfaces formed in (1), continue the continuous plating overgrowth in roll-to-roll type In producing line, adhere to 11 μ g/dm on Ni layers by carrying out electrolytic chromate processing under the following conditions2Adhesion amount Cr Layer.
Potassium bichromate 1g/L or more and 10g/L or less, zinc 0g/L
PH value:7 or more and 10 or less
Liquid temperature:40 DEG C or more and 60 DEG C or less
Current density:2A/dm2
The very thin layers of copper > of <
Then, after carrying out washing and pickling to the Cr layer surfaces formed in (2), continue the continuous plating overgrowth in roll-to-roll type In producing line, the very thin layers of copper of 3 μm of thickness is formed on Cr layers by being electroplated under the following conditions, is made with carrier Ultrathin copper foil.
Copper concentration:90g/L or more and 110g/L or less
Sulfuric acid concentration:90g/L or more and 110g/L or less or less
Chloride ion concentration:50ppm or more and 90ppm or less
Levelling agent 1 (bis- (3- sulfopropyls) disulfides):10ppm or more and 30ppm or less
Levelling agent 2 (amine compounds):10ppm or more and 30ppm or less
In addition, using following amine compounds as levelling agent 2.
&#91;Change 2&#93;
(in the chemical formula, R1And R2Selected from by hydroxy alkyl, ether, aryl, aromatic series substitution alkyl, unsaturated hydrocarbons The group that base, alkyl are formed)
Electrolyte temperature:50 DEG C or more and 80 DEG C or less
Current density:100A/dm2
Electrolyte linear velocity:1.5m/sec or more and 5m/sec or less
Embodiment 20
< middle layers >
(1) Ni-Mo layers (plating nickel-molybdenum alloys)
For carrier, formed by being electroplated on the continuous plating lines of roll-to-roll type under the following conditions 3000μg/dm2Adhesion amount Ni-Mo layers.Plating conditions are specific as follows.
(liquid composition) nickel sulfate hexahydrate closes object:50g/dm3, sodium molybdate dihydrate:60g/dm3, sodium citrate:90g/dm3
30 DEG C of (liquid temperature)
(current density) 1A/dm2Above and 4A/dm2Below
(conduction time) 3 seconds or more and 25 seconds or less
The very thin layers of copper > of <
Very thin layers of copper is formed on the Ni-Mo layers formed in (1).The thickness of very thin layers of copper is set as 1.5 μm, in addition to this, Very thin layers of copper is being formed under the same conditions with embodiment 19.
Embodiment 21
< middle layers >
(1) Ni layers (plating Ni)
Ni layers are being formed under the same conditions with embodiment 19.
(2) organic matter layer (organic matter layer formation processing)
Then, after carrying out washing and pickling to the Ni layer surfaces formed in (1), then, under the following conditions to Ni layers of table Liquid temperature 40 DEG C of the face spray comprising concentration 1g/L or more and 30g/L CBTA below (carboxyl benzotriazole), pH value 5 it is water-soluble Liquid, spraying 20 seconds or more and 120 seconds are hereinafter, be consequently formed organic matter layer.
The very thin layers of copper > of <
Very thin layers of copper is formed on the organic matter layer formed in (2).The thickness of very thin layers of copper is set as 5 μm, in addition to this, Very thin layers of copper is formed under the same conditions with embodiment 19.
Embodiment 22,23
< middle layers >
(1) Co-Mo layers (plating cobalt molybdenum alloys)
For carrier, formed by being electroplated on the continuous plating lines of roll-to-roll type under the following conditions 4000μg/dm2Adhesion amount Co-Mo layers.Plating conditions are specific as follows.
(liquid composition) cobaltous sulfate:50g/dm3, sodium molybdate dihydrate:60g/dm3, sodium citrate:90g/dm3
30 DEG C of (liquid temperature)
(current density) 1A/dm2Above and 4A/dm2Below
(conduction time) 3 seconds or more and 25 seconds or less
The very thin layers of copper > of <
Very thin layers of copper is formed on the Co-Mo layers formed in (1).The thickness of the very thin layers of copper of embodiment 22 is set as 3 μm, in fact The thickness for applying the very thin layers of copper of example 23 is set as 1 μm, in addition to this, very thin layers of copper is being formed under the same conditions with embodiment 19.
After carrying out the plating (being documented in table 2 and table 3) as roughening treatment, such as the record of table 6, for implementation Example 1~18,24~34, comparative example 9~12,15, carry out to formed following refractory layers and/or antirust coat plating and/ Or silane coupled processing.In addition, " Ni-Co ", " Ni-Co (2) ", " Ni-Co (3) ", " Ni-P ", " Ni- recorded in table 6 Zn ", " Ni-Zn (2) ", " Ni-Zn (3) ", " Ni-W ", " chromate ", " silane coupled processing " refer to following surface treatments.
The formation condition of refractory layer 1 is as follows.
Refractory layer 1
&#91;Ni-Co&#93;:Plate nickel-cobalt alloy
Liquid forms:Nickel 5g/L or more and 20g/L or less, cobalt 1g/L or more and 8g/L or less
PH value:2 or more and 3 or less
Liquid temperature:40 DEG C or more and 60 DEG C or less
Current density:5A/dm2Above and 20A/dm2Below
Coulomb amount:10As/dm2Above and 20As/dm2Below
&#91;Ni-Co(2)&#93;:Plate nickel-cobalt alloy
Liquid forms:Nickel 5g/L or more and 20g/L or less, cobalt 1g/L or more and 8g/L or less
PH value:2 or more and 3 or less
Liquid temperature:40 DEG C or more and 60 DEG C or less
Current density:5A/dm2Above and 20A/dm2Below
Coulomb amount:35As/dm2Above and 50As/dm2Below
&#91;Ni-Co(3)&#93;:Plate nickel-cobalt alloy
Liquid forms:Nickel 5g/L or more and 20g/L or less, cobalt 1g/L or more and 8g/L or less
PH value:2 or more and 3 or less
Liquid temperature:40 DEG C or more and 60 DEG C or less
Current density:5A/dm2Above and 20A/dm2Below
Coulomb amount:25As/dm2Above and 35As/dm2Below
&#91;Ni-P&#93;:Ni-P
Liquid forms:Nickel 5g/L or more and 20g/L or less, phosphorus 2g/L or more and 8g/L or less
PH value:2 or more and 3 or less
Liquid temperature:40 DEG C or more and 60 DEG C or less
Current density:5A/dm2Above and 20A/dm2Below
Coulomb amount:10As/dm2Above and 20As/dm2Below
Refractory layer 2
&#91;Ni-Zn&#93;:Nickel-zinc alloy electropalting
For embodiment on the books in 2 one column of refractory layer of table 6, comparative example, in the copper foil that the refractory layer 1 has been arranged Upper formation refractory layer 2.In addition, for comparative example 9~12, it is not provided with refractory layer 1 and forms refractory layer 2.The formation item of refractory layer 2 Part is as follows.
Liquid forms:Nickel 2g/L or more and 30g/L or less, zinc 2g/L or more and 30g/L or less
PH value:3 or more and 4 or less
Liquid temperature:30 DEG C or more and 50 DEG C or less
Current density:1A/dm2Above and 2A/dm2Below
Coulomb amount:1As/dm2Above and 2As/dm2Below
&#91;Ni-Zn(2)&#93;:Nickel-zinc alloy electropalting
Liquid forms:Nickel 2g/L or more and 30g/L or less, zinc 2g/L or more and 30g/L or less
PH value:3 or more and 4 or less
Liquid temperature:30 DEG C or more and 50 DEG C or less
Current density:1A/dm2Above and 2A/dm2Below
Coulomb amount:3As/dm2Above and 4As/dm2Below
&#91;Ni-Zn(3)&#93;:Nickel-zinc alloy electropalting
Liquid forms:Nickel 2g/L or more and 30g/L or less, zinc 2g/L or more and 30g/L or less
PH value:3 or more and 4 or less
Liquid temperature:30 DEG C or more and 50 DEG C or less
Current density:1A/dm2Above and 2A/dm2Below
Coulomb amount:2As/dm2Above and 3As/dm2Below
&#91;Ni-W&#93;:Plate nickel-tungsten
Liquid forms:Nickel 2g/L or more and 30g/L or less, tungsten 0.5g/L or more and 20g/L or less
PH value:3 or more and 4 or less
Liquid temperature:30 DEG C or more and 50 DEG C or less
Current density:1A/dm2Above and 2A/dm2Below
Coulomb amount:1As/dm2Above and 2As/dm2Below
Antirust coat
&#91;Ge Suanyan &#93;:Chromic acid salt treatment
It is not arranged on the copper foil that the refractory layer 1 and/or 2 have been set or on the copper foil of the refractory layer, to implementing Copper foil other than example 23 is further formed antirust coat.The formation condition of antirust coat is as follows.
Liquid forms:Potassium bichromate 1g/L or more and 10g/L or less, zinc 0g/L or more and 5g/L or less
PH value:3 or more and 4 or less
Liquid temperature:50 DEG C or more and 60 DEG C or less
Current density:0A/dm2Above and 2A/dm2Below (for carrying out dipping chromic acid salt treatment)
Coulomb amount:0As/dm2Above and 2As/dm2Below (for carrying out dipping chromic acid salt treatment)
Weatherable layer
It is further formed weatherable layer on the copper foil that the refractory layer 1,2 and antirust coat have been set.Formation condition is as follows.
It is coated with N-2- (amino-ethyl) -3- TSL 8330s as the silane coupling agent with amino (Examples 1 to 5,12~17,19~21,23~26, comparative example 1~13, reference example 14), N-2- (amino-ethyl) -3- amino Propyl-triethoxysilicane (embodiment 6~10), N-2- (amino-ethyl) -3- aminopropylmethyldimethoxysilanes (are implemented Example 11), 3- triethoxy silicon substrates-N- (1,3- dimethyl-butylidene) propyl amine (embodiment 18), be subject to drying, and formed resistance to Time property layer.Two or more in these silane coupling agents can also be applied in combination.Similarly, about comparative example 1~12, coating N-2- (amino-ethyl) -3- TSL 8330s, are subject to drying, and form weatherable layer.
In addition, rolled copper foil is to manufacture in the following way.The copper ingot formed shown in manufacture table 1, after hot rolling, instead The annealing and cold rolling of 300 DEG C or more and 800 DEG C of continuous annealing assembly lines below are carried out again, and obtain thickness 1mm or more and 2mm Calendering plate below.The calendering plate is annealed on 300 DEG C or more and 800 DEG C continuous annealing assembly lines below and is allowed to Recrystallization carries out final cold rolling until it becomes the thickness of table 1 under conditions of table 1 is recorded, and obtains copper foil." type " of table 1 In one column, " refined copper " indicates that the refined copper of JIS H3100 C1100 defineds, " oxygen-free copper " indicate that JIS H3100 C1020 are advised Fixed oxygen-free copper.In addition, " refined copper+Ag:100ppm " refers to the Ag that 100 mass ppm are added to refined copper.
The electrolytic copper foil HLP foils that electrolytic copper foil is manufactured using JX metal companies.In addition, being directed to embodiment 19~23, analysing It appears surface treatment that (when electrolytic copper foil manufactures with the face of the opposite side in face for the side for contact electrolysis rotating cylinder) formation specifies Or middle layer, very thin layers of copper.In addition, also describing the surface roughness Rz and glossiness of the precipitation surface side of electrolytic copper foil in table 1.
In addition, also describing the key point of the copper foil making step before surface treatment in table 1." high glaze calendering " refers to root Final cold rolling (cold rolling after final recrystallization annealing) is carried out according to the value of recorded oil film equivalent." usually calendering " refers to Final cold rolling (cold rolling after final recrystallization annealing) is carried out according to the value of recorded oil film equivalent.
For each sample of the Examples and Comparative Examples made in the above manner, following various evaluations are carried out.
The measurement of surface roughness (Rz):
The contact roughmeter Surfcorder SE-3C manufactured using limited liability company of little Ban research institutes, foundation JIS B0601-1982, to measuring 10 mean roughness comprising the copper foil surface before the processing of roughening treatment inner surface. Datum length 0.8mm, evaluation length 4mm, critical value 0.25mm, screen are measured under conditions of 0.1mm/ seconds, edge and calendering The vertical direction in direction (directions TD are the direction, that is, width direction vertical with logical foil direction in the case of electrolytic copper foil) changes It locates, carries out 10 measurement, take value of the average value of 10 measured values as surface roughness (Rz).
Glossiness:
According to JIS Z8741, hand-held Grossmeters (the Ha Application デ manufactured using Japanese electricity Se Industries, Incs ィ ー グ ロ ス メ ー タ ー) PG-1, to including roughening treatment inner surface processing before copper foil surface and including roughening treatment Inner surface treated copper foil surface, respectively with incidence angle 60 degree measure and the rectangular direction of rolling direction (TD, electrolysis In the case of copper foil, Copper foil with carrier for the direction rectangular with logical foil direction (MD), width direction) glossiness.Change and surveys Positioning is set, and the measurement of 10 glossiness is carried out, and takes 10 average value as the value of the glossiness of TD.
Visual recognition:
The surface of the surface treated side of surface treatment copper foil is fitted in polyimide film, and (Kaneka is manufactured, 25 μ of thickness M (PIXEO (polyimide types:FRS), the polyimide film with adhesive linkage of copper-cover laminated plate, PMDA (Pyromellitic Acids Acid anhydride) it is polyimide film (PMDA-ODA (4,4'Diamino-diphenyl ether) be polyimide film)) two sides, pass through etching (three Ferric chloride in aqueous solution) it removes surface treatment copper foil and sample film is made.In addition, for the copper foil for carrying out roughening treatment, by copper The face of the roughened processing of foil is fitted on the polyimide film and makes the sample film.The one of the resin layer obtained The attached printed article of face paste (circle of the black of diameter 6cm), the visual recognition of printed article is judged from opposing face through resin layer. The black for accounting for printed article in 60% or more length range of circumference is circular clear-cut, then is evaluated as " ◎ ";Accounting for circle Perimeter 50% or more and it is circular not clear-cut up to black in 60% length range, then it is (above to close to be evaluated as "○" Lattice);It is accounting for the 0% of circumference and black is not circular clear-cut and profile deformation in the length range up to 50%, is then evaluating For " △ " (unqualified).In addition, to after copper foil surface progress roughening treatment or when not carrying out roughening treatment, it is heat-resisting in order to be arranged Layer, antirust coat, weatherable layer etc. and be surface-treated, in the case, to by the refractory layer, antirust coat, weatherable layer Surface Deng the surface treatment copper foil after surface treatment carries out the measurement.It is the very thin of Copper foil with carrier in surface treatment copper foil In the case of layers of copper, the measurement is carried out to the roughening treatment surface of very thin layers of copper.
Aberration:
The color difference meter MiniScan XE Plus manufactured using HunterLab companies are measured copper and dissipated according to JIS Z8730 Hot material surface with white board (using D65 light sources, 10 degree of visuals field when, the X of the white board10Y10Z10Color system (JIS Z8701 1999) tristimulus values are X10=80.7, Y10=85.6, Z10=91.5, L*a*b*The object of the white board under color system Body colour is L*=94.14, a*=-0.90, b*=0.24) object color is as the aberration in the case of reference colours.In addition, for The measured value of the aberration of white board is set as Δ E by the color difference meter*Ab=0 will use black bag (ligh trap (light trap)) The measured value of aberration when overlay measurement hole is measured is set as Δ E*ab=94.14, and correcting chromatic aberration.Herein, aberration Δ E* Ab is that the white board is set as 0 and black is set as 94.14 and is defined.In addition, the tiny areas such as copper circuit surface based on The aberration Δ E of JIS Z8730*Ab can use the small face of such as electricity Se Industries, Incs of Japan manufacture to be divided aberration Instrument (pattern:VSS400 etc.) or must congratulate testing machine (ス ガ Try Omen Machine) limited liability company manufacture small face spectral photometric colour measuring meter (pattern:SC-50 μ etc.) etc. known in measurement device be measured.
Powder falling:
About powder falling, transparent invisible tape (メ Application デ ィ are attached on the surface of the surface treated side of surface treatment copper foil Application グ テ ー プ), according to the adhesive tape discoloration situation caused by the particle that falls off adhered on adhesive tape bonding face when removing the adhesive tape, and Evaluate powder falling.The taint-free situation of adhesive tape is denoted as ◎, changes colour and is denoted as zero for the case where grey, change colour and be denoted as the case where black ×。
Peel strength (adhesive strength):
By the surface area layer of the surface treated side of surface treatment copper foil in polyimide film (25 μm of thickness, the emerging production in space portion The Upilex of manufacture) { Upilex (registered trademark)-VT, BPDA (biphenyltetracarboxylic dianhydride) system (BPDA-PDA (p-phenylenediamine) System) polyimide resin substrate on after, according to IPC-TM-650, cupping machine Autograph 100 is used to measure normality stripping From intensity.In turn, it is set as the surface treatment copper foil that the normality peel strength is 0.5N/mm or more can be used in laminated substrate The surface treatment copper foil of purposes.
In addition, the lamination condition of surface treatment copper foil and polyimide film is recommended using the polyimide film manufacturer Condition.In addition, about embodiment 19~23, by the surface area layer of the surface treated side of surface treatment copper foil in polyimides Film (25 μm of thickness, the Upilex of the emerging production manufacture in space portion) { Upilex (registered trademark)-VT, BPDA (biphenyltetracarboxylic dianhydride) system (BPDA-PDA (p-phenylenediamine) system) polyimide resin substrate } on after, remove carrier, with the polyimide film lamination After the thickness of very thin layers of copper carries out copper facing as 12 μm of mode, peel strength is measured.In addition, being carried out at roughening to copper foil surface After reason or when not carrying out roughening treatment, it is surface-treated in order to which refractory layer, antirust coat, weatherable layer etc. is arranged, in this feelings Under condition, the survey is carried out to the surface of the surface treatment copper foil after the surface treatments such as the refractory layer, antirust coat, weatherable layer It is fixed.In the case where surface treatment copper foil is the very thin layers of copper of Copper foil with carrier, the roughening treatment surface of very thin layers of copper is carried out The measurement.
The roughness of copper foil surface:
The line roughness Rz of copper foil, the line roughness Ra of roughening treatment layer side surface, Rz and face before surface treatment is coarse Degree Sq, Ssk, Sa, Sz, Sku, Spk are the laser microscope (testing machines manufactured using Olympus Corp:OLYMPUS LEXT OLS 4000, resolution ratio:XY-0.12 μm, Z-0.0 μm, cut-off:Nothing) it is measured.In addition, the measurement area in portion of observing is set It is 66524 μm2.In addition, evaluation length is set as 257.9 μm.Determination of the environment temperature is set as 23~25 DEG C.Surface roughness Sq, Ssk, Sa, Sz, Sku, Spk are measured according to ISO25178.In addition, at the line roughness Rz of copper foil, roughening before surface treatment Line roughness Ra, the Rz for managing layer side surface are measured along the direction parallel with TD.In addition, the copper foil before surface treatment Line roughness Rz, roughening treatment layer side surface line roughness Ra, Rz be to be measured according to JIS B0601 1994.
At measure the surface treatment copper foil for being set as 10cm × 10cm square of counting arbitrary 5, and these average value is set For the roughness of each surface treatment.
Productivity:
Roughening particle its rugosity in the roughening coating of surface treatment is thinner and height is higher, then is got over when being under pressure It easily snaps off, the roller when being transported on the strip production line (ス リ ッ ト ラ イ Application) for cutting off copper foil width direction both ends is removed During sending, roughening particle, which is easy to happen, to fall off.The roughening particle being attached to after falling off on roller etc. is consolidated with the conveyance of copper foil The defects of determining, transported copper foil caused to generate impression or dent.
Therefore, in the strip production line for cutting off the edge of copper foil, the conveyance of copper foil is mostly often transported copper foil with roller It is just cleaned after thousands of rice primary.So evaluating productivity according to the pollutional condition of the carrying roller of the strip production line.If that is, mistake Pollution level is light, then can reduce the cleaning frequency of carrying roller, therefore productivity is promoted.After carrying roller is cleaned up, observation It is played from conveyance copper foil is started by the surface state of the roller after copper foil conveyance 5000m.And judged according to following benchmark.
◎:Roller surface is nearly no roughening particle attachment, the substantially unpolluted state of carrying roller for conveyance
○:The visible state for having a small amount of roughening particle attachment of conveyance roller surface
×:Transport the visible state for thering is roughening particle to adhere to of almost entire surface of roller surface
The evaluation of copper foil gauffer etc. caused by lamination process:
By the surface treatment copper foil of each embodiment or each comparative example respectively with the surface side lamination with roughening treatment layer in thickness (Kaneka (カ ネ カ) manufactures (PIXEO (polyimide types to the polyimide resin of 25 μm of degree:FRS), copper-cover laminated plate Polyimide film with adhesive linkage, PMDA (pyromellitic dianhydride) are polyimide film (PMDA-ODA (4,4'Diamino two Phenyl ether) be polyimide film)) two surfaces, in turn, in each surface treatment copper foil the and described polyimide resin lamination Side opposite side face on 125 μm of lamination thickness protective film (polyimides system), in this case, i.e. protective film/table Under 5 layer states of surface treatment copper foil/polyimide resin/surface treatment copper foil/protective film, protected on one side from two panels using laminating roll The outside of cuticula applies heat and carries out being bonded processing (lamination process) on one side with pressure, and is bonded table on the two sides of polyimide resin Surface treatment copper foil.Then, after the protective film for removing two surfaces, visual observation surface treatment copper foil the and described polyimides tree The surface of the opposite side of the side of fat lamination, confirmation have non-wrinkled or striped, ◎ are evaluated as when not generating gauffer or striped completely, It is evaluated as zero when 5m long only observes at 1 gauffer or striped on copper foil, can be observed more than at 2 every 5m long on copper foil Be evaluated as when gauffer or striped ×.
The evaluation of etching:
By surface treatment copper foil with surface treated surface side be fitted in lamination with thermosetting adhesive linkage Polyimide film (25 μm of thickness, the Upilex of the emerging production manufacture in space portion) { Upilex (registered trademark)-VT, BPDA (biphenyltetracarboxyacid acid Dianhydride) system (BPDA-PDA (p-phenylenediamine) system) polyimide resin substrate two sides.In order to form fine circuit pattern, copper Foil thickness need to be consistent, be set as benchmark copper thickness by 12 μm herein.That is, in the case where thickness is more than 12 μm, pass through electrolysis Grinding is by reduced down in thickness to 12 μm.On the other hand, in the case where thickness is less than 12 μm, thickness is thickened by copper plating treatment 12μm.In the case where surface treatment copper foil is the very thin layers of copper of Copper foil with carrier, Copper foil with carrier is pasted with very thin layers of copper side It closes behind the two sides of the polyimide film with thermosetting adhesive linkage of the lamination, then stripping carrier passes through copper facing Processing thicken until the aggregate thickness of very thin layers of copper and copper coating reaches 12 μm.For the list of the two sides laminated plates obtained Surface side, by being bonded dry film resist and step of exposure, and in the copper foil gloss surface side printed with fine circuit pattern of laminated plates, to copper The unnecessary portion of foil carries out the etching process of following conditions, forms the fine circuit pattern such as L/S=30/30 μm.Herein, electric Degree of having a lot of social connections is the width for making the bottom width of circuit section become 30 μm.
(etching condition)
Device:Small-sized etaching device of atomizing
Atomisation pressure:0.2MPa
Etching solution:Ferric chloride aqueous solutions (40 Baume (ボ ー メ of proportion))
Liquid temperature:50℃
After forming fine circuit pattern, is impregnated 1 minute in 45 DEG C of NaOH aqueous solutions and remove photonasty resist film.
For fine pattern circuit sample achieved above, high and new technology company of Hitachi (Hitachi Ha イ テ Network ノ ロ are used ジ ー ズ societies) manufacture scanning electron microscope photo S4700, circuit bottom is observed under 5000 times of multiplying power, is seen at 10 Examine respectively be in position circuit bottom without etch residue when be denoted as ◎, when having visible etch residue at 1 in look-out station at 10 It is denoted as zero, △ is denoted as when having visible above etch residue at 2 in look-out station at 10.
In addition, to after the very thin layers of copper surface progress roughening treatment of copper foil surface or Copper foil with carrier or not carrying out at roughening It when reason, is surface-treated in order to which refractory layer, antirust coat, weatherable layer etc. is arranged, in the case, to heat-resisting by this The surface of surface treatment copper foil after the surface treatments such as layer, antirust coat, weatherable layer carries out the measurement.
Embodiment, the manufacturing condition of comparative example and evaluation result etc. are shown in table 1~6.
&#91;Table 1&#93;
Embodiment 19~23 indicates the carrier of Copper foil with carrier.
&#91;Table 2&#93;
&#91;Table 3&#93;
&#91;Table 6&#93;
(evaluation result)
In Examples 1 to 34, the roughness Ra of roughening treatment layer side surface is 0.08 μm or more and 0.20 μm hereinafter, Rz Be 1.00 μm or more and 2.00 μm hereinafter, Sq be 0.16 μm or more and 0.30 μm hereinafter, Ssk be -0.6 or more and - 0.35 hereinafter, Sa is 0.12 μm or more and 0.23 μm hereinafter, Sz is 2.20 μm or more and 3.50 μm hereinafter, Sku is 3.75 or more and 4.50 hereinafter, or Spk be 0.13 μm or more and 0.27 μm hereinafter, surface treatment copper foil roughening treatment layer side The glossiness of the TD on surface is 70% or less.
As a result, Examples 1 to 34 respectively inhibit well be arranged it is thick in the roughening particle layer of copper foil surface Change the case where generating gauffer, striped when falling off and being bonded with resin of particle.
Comparative example 1~7,15 is unsatisfactory for the defined any one of the roughness of roughening treatment layer side surface, so falling Mealiness is bad.
In comparative example 8~13, glossiness is more than 70%, and gauffer, striped are generated when failing to inhibit to be bonded with resin well The case where.
In addition, this application claims based on the Japanese patent application filed an application on March 31st, 2017 the 2017-73216th Priority, the full content of the Japanese patent application is quoted into the application.

Claims (28)

1. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Ra of the roughening treatment layer side surface of the surface treatment copper foil be 0.08 μm or more and 0.20 μm hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
2. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Rz of the roughening treatment layer side surface of the surface treatment copper foil be 1.00 μm or more and 2.00 μm hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
3. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Sq of the roughening treatment layer side surface of the surface treatment copper foil be 0.16 μm or more and 0.30 μm hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
4. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Ssk of the roughening treatment layer side surface of the surface treatment copper foil be -0.6 or more and -0.35 hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
5. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Sa of the roughening treatment layer side surface of the surface treatment copper foil be 0.12 μm or more and 0.23 μm hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
6. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Sz of the roughening treatment layer side surface of the surface treatment copper foil be 2.20 μm or more and 3.50 μm hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
7. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Sku of the roughening treatment layer side surface of the surface treatment copper foil be 3.75 or more and 4.50 hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
8. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughness Spk of the roughening treatment layer side surface of the surface treatment copper foil be 0.13 μm or more and 0.27 μm with Under,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
9. surface treatment copper foil according to any one of claim 1 to 8, wherein the surface treatment copper foil it is described The aberration Δ E based on JIS Z8730 of roughening treatment layer side surface*Ab is 65 or less.
10. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughening treatment layer side surface of the surface treatment copper foil meets in the group selected from following (10-1)~(10-8) Arbitrary two or more,
(10-1) roughness Ra be 0.08 μm or more and 0.20 μm or less,
(10-2) roughness Rz be 1.00 μm or more and 2.00 μm or less,
(10-3) roughness Sq be 0.16 μm or more and 0.30 μm or less,
(10-4) roughness Ssk be -0.6 or more and -0.35 or less,
(10-5) roughness Sa be 0.12 μm or more and 0.23 μm or less,
(10-6) roughness Sz be 2.20 μm or more and 3.50 μm or less,
(10-7) roughness Sku be 3.75 or more and 4.50 or less,
(10-8) roughness Spk be 0.13 μm or more and 0.27 μm hereinafter,
The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
11. a kind of surface treatment copper foil, has
Copper foil and
Roughening treatment layer positioned at least one surface of the copper foil or two surfaces,
The roughening treatment layer side surface of the surface treatment copper foil meets in the group selected from following (11-1)~(11-8) Arbitrary two or more,
(11-1) roughness Ra be 0.08 μm or more and 0.20 μm or less,
(11-2) roughness Rz be 1.00 μm or more and 2.00 μm or less,
(11-3) roughness Sq be 0.16 μm or more and 0.30 μm or less,
(11-4) roughness Ssk be -0.6 or more and -0.35 or less,
(11-5) roughness Sa be 0.12 μm or more and 0.23 μm or less,
(11-6) roughness Sz be 2.20 μm or more and 3.50 μm or less,
(11-7) roughness Sku be 3.75 or more and 4.50 or less,
(11-8) roughness Spk be 0.13 μm or more and 0.27 μm hereinafter,
The aberration Δ E based on JIS Z8730 of the roughening treatment layer side surface of the surface treatment copper foil*Ab be 65 hereinafter, The glossiness of the TD of the roughening treatment layer side surface of the surface treatment copper foil is 70% or less.
12. according to the surface treatment copper foil described in claim 1 to 8,10, any one of 11, wherein the surface treatment copper foil Roughening treatment layer side surface meet selected from following (12-1)~(12-8) group in any one, two, three, four , five, six, seven or eight,
(12-1) roughness Ra meets following (12-1-1) and any one in (12-1-2) or two
(12-1-1) roughness Ra meets any one of below
0.18 μm or less
0.17 μm or less
0.16 μm or less
0.15 μm or less
0.14 μm or less
0.13 μm or less
(12-1-2) roughness Ra meets any one of below
0.09 μm or more
0.10 μm or more
0.11 μm or more
0.12 μm or more
(12-2) roughness Rz meets following (12-2-1) and any one in (12-2-2) or two
(12-2-1) roughness Rz meets any one of below
1.90m following
1.80m following
1.70m following
1.60m following
1.50m following
1.40m following
1.30m following
(12-2-2) roughness Rz meets any one of below
1.10 μm or more
1.20 μm or more
(12-3) roughness Sq meets following (12-3-1) and any one in (12-3-2) or two
(12-3-1) roughness Sq meets any one of below
0.29 μm or less
0.28 μm or less
0.27 μm or less
0.26 μm or less
0.25 μm or less
0.24 μm or less
0.23 μm or less
0.22 μm or less
0.21 μm or less
(12-3-2) roughness Sq meets any one of below
0.17 μm or more
0.18 μm or more
0.19 μm or more
0.20 μm or more
(12-4) roughness Ssk meets following (12-4-1) and any one in (12-4-2) or two
(12-4-1) roughness Ssk meets any one of below
- 0.37 or less
- 0.40 or less
- 0.42 or less
- 0.44 or less
- 0.45 or less
- 0.47 or less
- 0.49 or less
(12-4-2) roughness Ssk meets any one of below
- 0.59 or more
- 0.58 or more
- 0.55 or more
- 0.53 or more
- 0.51 or more
(12-5) roughness Sa meets following (12-5-1) and any one in (12-5-2) or two
(12-5-1) roughness Sa meets any one of below
0.22 μm or less
0.21 μm or less
0.20 μm or less
0.19 μm or less
0.18 μm or less
0.17 μm or less
0.16 μm or less
0.15 μm or less
(12-5-2) roughness Sa meets any one of below
0.125 μm or more
0.13 μm or more
0.14 μm or more
(12-6) roughness Sz meets following (12-6-1) and any one in (12-6-2) or two
(12-6-1) roughness Sz meets any one of below
3.40 μm or less
3.30 μm or less
3.20 μm or less
3.10 μm or less
3.00 μm or less
2.90 μm or less
2.80 μm or less
(12-6-2) roughness Sz meets any one of below
2.25 μm or more
2.30 μm or more
2.40 μm or more
2.50 μm or more
2.60 μm or more
(12-7) roughness Sku meets following (12-7-1) and any one in (12-7-2) or two
(12-7-1) roughness Sku meets any one of below
4.45 following
4.40 following
4.30 following
4.20 following
4.10 following
4.00 following
3.90 following
(12-7-2) roughness Sku meets any one of below
More than 3.80
More than 3.90
More than 4.00
More than 4.10
(12-8) roughness Spk meets following (12-8-1) and any one in (12-8-2) or two
(12-8-1) roughness Spk meets any one of below
0.26 μm or less
0.25 μm or less
0.24 μm or less
0.23 μm or less
0.22 μm or less
0.21 μm or less
0.20 μm or less
0.19 μm or less
0.18 μm or less
0.17 μm or less
(12-8-2) roughness Spk meets any one of below
0.14 μm or more
0.15 μm or more
0.16 μm or more.
13. according to the surface treatment copper foil described in claim 1 to 8,10, any one of 11, wherein the surface treatment copper foil Roughening treatment layer side surface the aberration Δ E based on JIS Z8730*Ab is 45 or more and 65 or less.
14. according to the surface treatment copper foil described in claim 1 to 8,10, any one of 11, wherein in the roughening treatment layer Surface have a kind in the group being made of refractory layer, antirust coat, chromating layer and silane coupled process layer with On layer.
15. it is for radiating according to the surface treatment copper foil described in claim 1 to 8,10, any one of 11.
16. a kind of surface treatment copper foil with resin layer, at the surface according to any one of claim 1 to 15 The roughening treatment layer side surface of reason copper foil has resin layer.
17. the surface treatment copper foil according to claim 16 with resin layer, wherein the resin layer is bonding tree The resin of fat and/or semi-hardened state.
18. a kind of Copper foil with carrier, in the one or both sides of carrier there is middle layer, very thin layers of copper, the very thin layers of copper to be Surface treatment copper foil according to any one of claim 1 to 15 or according to described in any one of claim 16 or 17 The surface treatment copper foil with resin layer.
19. a kind of laminate, there is surface treatment copper foil according to any one of claim 1 to 15 or according to power Profit requires the surface treatment copper foil with resin layer described in any one of 16 or 17.
20. a kind of laminate, with Copper foil with carrier according to claim 18.
21. a kind of laminate, it includes Copper foil with carrier according to claim 18 and resin,
Part or all of the end face of the Copper foil with carrier is covered by the resin.
22. a kind of laminate, with two panels Copper foil with carrier according to claim 18.
23. a kind of manufacturing method of printing distributing board uses the surface treatment according to any one of claim 1 to 15 Copper foil either according to any one of claim 16 or 17 with the surface treatment copper foil of resin layer or according to right It is required that the Copper foil with carrier described in 18.
24. a kind of manufacturing method of printing distributing board comprising following steps:
Prepare the surface treatment copper foil according to any one of claim 1 to 15 or appoints according in claim 16 or 17 Surface treatment copper foil with resin layer or Copper foil with carrier according to claim 18 described in one and insulation base Plate;
Copper-cover laminated plate is formed, which includes the either step in following (24-1)~(24-3),
The surface treatment copper foil and the insulating substrate are subject to lamination by (24-1)
The surface treatment copper foil with resin layer and the insulating substrate are subject to lamination by (24-2)
The Copper foil with carrier and the insulating substrate are subject to remove the carrier of the Copper foil with carrier after lamination by (24-3);And
Pass through semi-additive process (セ ミ ア デ ィ テ ィ Block method), subtractive process (サ Block ト ラ Network テ ィ Block method), part addition process (パ ー ト リ ー ア デ ィ テ ィ Block method) or either method in semi-additive process (モ デ ィ Off ァ イ De セ ミ ア デ ィ テ ィ Block method) is improved, it uses The copper-cover laminated plate and form circuit.
25. a kind of manufacturing method of printing distributing board comprising following steps:
Electricity is formed in the roughening treatment layer side surface of the surface treatment copper foil according to any one of claim 1 to 15 Road, or in the very thin layers of copper side surface of Copper foil with carrier according to claim 18 or carrier side surface shape At circuit;
In a manner of burying the circuit into resin layer, in the roughening treatment layer side surface of the surface treatment copper foil Or the Copper foil with carrier the very thin layers of copper side surface or the carrier side surface form the resin layer;
Circuit is formed on the resin layer;And
After forming circuit on the resin layer, by removing the surface treatment copper foil, or by by the carrier or institute The very thin layers of copper or the carrier are removed after stating very thin layers of copper stripping, and the circuit being buried in the resin layer is made to expose.
26. a kind of manufacturing method of printing distributing board comprising following steps:
By according to any one of claim 1 to 15 surface treatment copper foil or according to any in claim 16 or 17 Surface treatment copper foil with resin layer or Copper foil with carrier according to claim 18 described in and resin substrate It is subject to lamination;
The surface treatment copper foil or the surface treatment copper foil with resin layer or the Copper foil with carrier and resin Resin layer and circuit at least once is arranged in the opposite side surfaces of the side of substrate lamination;And
After forming the resin layer and circuit, the resin substrate and the surface treatment copper foil are removed, or described in removal The surface treatment copper foil of resin substrate and the surface treatment copper foil with resin layer, or removed from the Copper foil with carrier The carrier or the very thin layers of copper.
27. a kind of manufacturing method of printing distributing board comprising following steps:
Resin layer at least once and circuit are set on the laminate according to any one of claim 19 to 22;And
After forming the resin layer and circuit, the carrier or the pole are removed from the Copper foil with carrier for constituting the laminate Thin copper layer.
28. a kind of manufacturing method of e-machine uses and passes through the method according to any one of claim 23 to 27 Manufactured printing distributing board.
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