KR20110021707A - Copper foil for printed wiring board - Google Patents

Copper foil for printed wiring board Download PDF

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KR20110021707A
KR20110021707A KR1020107017993A KR20107017993A KR20110021707A KR 20110021707 A KR20110021707 A KR 20110021707A KR 1020107017993 A KR1020107017993 A KR 1020107017993A KR 20107017993 A KR20107017993 A KR 20107017993A KR 20110021707 A KR20110021707 A KR 20110021707A
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copper foil
atomic concentration
printed wiring
layer
copper
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KR101086656B1 (en
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미사토 주간지
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제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤
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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
    • 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
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

The copper foil for printed wiring boards which is excellent in both adhesiveness with an insulated substrate, and etching property, is suitable for fine pitch formation, and is low in manufacturing cost. The copper foil for printed wiring boards is equipped with the copper foil base material and the coating layer which coat | covers at least one part of the copper foil base material surface, The coating layer contains Ni-Sn alloy layer containing Ni and Sn which were laminated | stacked in order from the copper foil base material surface, and It consists of a Cr layer, Cr is 18-180 microgram / dm <2>, and the Ni-Sn alloy layer has a total amount of Ni and Sn in a coating amount of 18-450 microgram / dm <2>, respectively.

Description

Copper foil for printed wiring board {COPPER FOIL FOR PRINTED WIRING BOARD}

This invention relates to the copper foil for printed wiring boards, and especially relates to the copper foil for flexible printed wiring boards.

Printed wiring boards have made great strides in the last half century, and nowadays are used in almost all electronic devices. With the recent increase in the demand for miniaturization and high performance of electronic devices, high-density mounting of high-frequency components and high frequency of signals have been advanced, and finer conductor patterns (fine pitch) and higher frequency response are required for printed wiring boards.

A printed wiring board is generally manufactured by adhering an insulated substrate to copper foil, making it a copper clad laminated board, and forming a conductor pattern on the copper foil surface by etching. Therefore, adhesiveness and etching property with an insulated substrate are calculated | required by the copper foil for printed wiring boards.

As a technique of improving the adhesiveness with an insulated substrate, it is generally performed to perform the surface treatment which forms an unevenness | corrugation on the copper foil surface called a roughening process. For example, using the copper sulfate acid plating bath on the M surface (rough surface) of an electrolytic copper foil, many copper is electrodeposited by resin or a small spherical form, and fine unevenness | corrugation is formed, (Iii) There is a method of improving the adhesiveness by the effect. After the roughening treatment, a chromate treatment, a treatment with a silane coupling agent, or the like is generally performed in order to further improve the adhesive properties.

The method of forming metal layers or alloy layers, such as tin, chromium, copper, iron, cobalt, zinc, and nickel, on the copper foil surface is also known.

However, the method of improving adhesiveness by roughening process is disadvantageous for fine line formation. That is, when the conductor spacing is narrowed by fine pitching, the roughening treatment part remains on the insulating substrate after the circuit formation by etching, and there is a fear of causing insulation deterioration. In order to prevent this, the etching of all of the roughened surfaces requires a long etching time, so that the predetermined wiring width cannot be maintained.

In the method of forming a Ni layer and a Ni-Cr alloy layer, for example on the copper foil surface, there is much room for improvement in the basic characteristic of adhesiveness with an insulating substrate. In the method of forming a Cr layer on the copper foil surface, for example, relatively high adhesiveness is obtained, but the etching property is inferior, and after etching treatment for conductor pattern formation, Cr remains on the insulating substrate surface. There is a problem that is likely to occur.

Therefore, in recent years, a first metal layer is formed on the surface of a copper foil, and as the second metal layer, a Cr layer having good adhesion to an insulating substrate is thinly formed to a good degree of etching property on the first metal layer. A technique for obtaining good adhesion and good etching property at the same time has been researched and developed.

As such a technique, for example, Patent Document 1 discloses Cr on a Ni layer or / and Ni alloy layer containing 0.03 to 3.0 mg / dm 2 in an amount of Ni in the surface-treated copper foil for a polyimide-based flexible copper clad laminate. By forming a Cr layer or / and Cr alloy layer containing 0.03 to 1.0 mg / dm 2 as a surface treatment layer as a surface treatment layer, it has a high peel strength between the polyimide-based resin layer, and when forming insulation reliability, wiring pattern It is described that the copper foil for polyimide-type flexible copper clad laminated boards which is excellent in the etching characteristic and the bending characteristic of is obtained.

Japanese Laid-Open Patent Publication 2006-222185

However, when carrying out the coating layer of the copper foil surface described by patent document 1 by electroplating, since the Cr layer with favorable adhesiveness with an insulating substrate cannot be formed in high density | concentration, although etching property is favorable, adhesiveness with an insulating substrate There is room for improvement. Moreover, when forming the coating layer containing much Ni by sputtering, there exists also a problem that sputtering efficiency per target sheet | seat becomes low by the influence of the magnetism of Ni, and it is disadvantageous in cost.

Then, this invention makes it a subject to provide the copper foil for printed wiring boards which are excellent in both the adhesiveness with an insulating substrate, and etching property, and are low in manufacturing cost. Moreover, this invention makes it another subject to provide the manufacturing method of such copper foil for printed wiring boards.

Conventionally, it was understood that by forming the Ni layer and the Cr layer on the surface of the copper foil base material in an extremely thin thickness, it is possible to obtain good adhesiveness with the insulating substrate and at the same time obtain good etching properties. On the other hand, the inventors of the present invention further studied to provide a copper foil for a printed wiring board with high adhesion and etching property with an insulating substrate, and as a result, the Ni-Sn alloy layer and Cr layer were sequentially applied to the copper foil substrate surface. When it formed uniformly at the thickness of the ultra-thin of an order, it discovered that the coating layer of copper foil which has the adhesiveness with the more excellent insulating substrate, and the outstanding etching property is obtained.

Moreover, in that case, it was found that the heat resistance which can endure long-term use becomes favorable.

In addition, by adjusting the components of the respective metal elements in the Ni-Sn alloy layer, it was also found that the use efficiency of the target was increased and the manufacturing cost was lowered.

The present invention completed based on the above findings, in one aspect, is a copper foil for a printed wiring board provided with a copper foil base material and a coating layer covering at least a part of the copper foil base material surface, the coating layer being laminated sequentially from the copper foil base material surface. Ni-Sn alloy layer and Cr layer containing Ni and Sn, and Cr is 18-180 µg / dm 2 in the Cr layer, and the total Ni and Sn is 18-450 in the Ni-Sn alloy layer. Each with a coating amount of μg / dm 2.

In one embodiment of the copper foil for printed wiring boards which concerns on this invention, Cr is 30-150 microgram / dm <2> in the said Cr layer, and Ni and Sn are 36-360 microgram / dm <2> in total of Ni and Sn. Each is present in a coating amount.

In one Embodiment of the copper foil for printed wiring boards which concerns on this invention, Cr is 30-90 microgram / dm <2> in the said Cr layer, and Ni and Sn are 50-360 microgram / dm <2> in total of Ni and Sn in the said Ni-Sn alloy layer. Each is present in a coating amount.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, Cr is 36-75 microgram / dm <2>, and the Ni-Sn alloy layer has 75-270 microgram / dm <2> in total of Ni and Sn. Are each present in a coating amount of.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, 3-70 weight% Sn exists in the said Ni-Sn alloy layer.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, when the cross section of a coating layer is observed with a transmission electron microscope, the maximum thickness is 0.5-7.5 nm, and the minimum thickness is 80% or more of the maximum thickness. to be.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is set to f (x). The atomic concentration (%) of the metal chromium is f 1 (x), the atomic concentration (%) of the oxide chromium (chromium in the chromium oxide) is f 2 (x), and (f (x) = f 1 ( x) + f 2 (x)), the atomic concentration (%) of oxygen is g (x), the atomic concentration (%) of copper is h (x), and the total atomic concentration (%) of nickel is i When (x) is set, the atomic concentration (%) of tin is j (x), the atomic concentration (%) of carbon is k (x), and the sum of the other atomic concentrations is l (x). In the interval [0, 1.0], ∫f (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) satisfies 20-50%, and ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h ( x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx ) Is 1.0% or less, 0

Figure pct00001
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00002
1.0 is satisfied, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 10 to 70%, 0.1
Figure pct00003
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00004
1.0.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, when the heat processing equivalent to polyimide hardening is performed, the chromium of the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is carried out. Atomic concentration (%) is f (x), Atomic concentration (%) of metal chromium is f 1 (x), Atomic concentration (%) of oxide chromium is set to f 2 (x) (f (x) ) = f 1 (x) + f 2 (x)), the atomic concentration of oxygen (%) is g (x), the atomic concentration of copper (%) is h (x), and the total atomic concentration of nickel Let (%) be i (x), tin's atomic concentration (%) be j (x), carbon's atomic concentration (%) be k (x), and the sum of the other atomic concentrations being l ( x), ∫f (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + in the interval [0, 1.0] ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) satisfies 20-50%, and ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫ j (x) dx + ∫k (x) dx + ∫l (x) dx) is 1.0% or less, 0

Figure pct00005
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00006
1.0 is satisfied, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) becomes 10 to 70%, 0.1
Figure pct00007
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00008
Is 1.0.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, it is copper foil to which heat processing corresponded to polyimide hardening, and it is chrome of the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS. Let atomic concentration (%) of be f (x), atomic concentration (%) of metal chromium be f 1 (x), atomic concentration (%) of oxide chromium be f 2 (x) (f ( x) = f 1 (x) + f 2 (x)), the atomic concentration (%) of oxygen is g (x), the atomic concentration (%) of copper is h (x), and the total atoms of nickel Let concentration (%) be i (x), tin atom concentration (%) be j (x), carbon atom concentration (%) be k (x), and sum total of other atomic concentrations (x), ∫f (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx in the interval [0, 1.0] + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) satisfies 20 to 50%, and ∫h (x) dx / (∫f (x) dx + ∫g (x ) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 1.0% or less, 0

Figure pct00009
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00010
1.0 is satisfied, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 10 to 70%, 0.1
Figure pct00011
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00012
1.0.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, when the surface of the coating layer after peeling an insulating substrate from the coating layer was analyzed about the copper foil for printed wiring boards which stuck the coating layer to the insulating substrate, The atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface is set to f (x), the atomic concentration (%) of metal chromium is set to f 1 (x), and the oxide The atomic concentration (%) of chromium is f 2 (x) (f (x) = f 1 (x) + f 2 (x)), the atomic concentration (%) of oxygen is g (x), and copper Let atomic concentration (%) of h be (x), total atomic concentration (%) of nickel be i (x), atomic concentration (%) of tin be j (x), atomic concentration of carbon ( When%) is k (x) and the sum of the other atomic concentrations is l (x), the distance from the surface layer where the concentration of metal chromium is maximum is F 1 , and the interval [0, F 1 ], where ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 5.0% or less, 0.1

Figure pct00013
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00014
Satisfies 1.0

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, a copper foil base material is a rolled copper foil.

In another embodiment of the copper foil for printed wiring boards which concerns on this invention, a printed wiring board is a flexible printed wiring board.

In another aspect, the present invention provides a printed wiring board comprising coating at least a part of the surface of a copper foil base material with a Ni—Sn alloy layer having a thickness of 0.25 to 5.0 nm and a Cr layer having a thickness of 0.25 to 2.5 nm by a sputtering method. It is a manufacturing method of molten copper foil.

This invention is another one side. WHEREIN: The copper clad laminated board provided with the copper foil which concerns on this invention.

In one embodiment of the copper clad laminate according to the present invention, the copper foil has a structure bonded to the polyimide.

In yet another aspect, the present invention is a printed wiring board made of a copper clad laminate according to the present invention.

Copper foil for printed wiring boards which are excellent in both adhesiveness with an insulated substrate, and etching property, are suitable for fine pitch formation, and are low in manufacturing cost. Moreover, this invention is applicable also to the technique of laminating | stacking resin, such as polyimide or polyamide, on a metal strip for an electromagnetic shield, a high frequency shield, and insulation.

1 is a TEM photograph (cross section) of a copper foil (sputter rise) of Example No. 4.
2 is a TEM photograph (cross section) of the copper foil (after heat treatment equivalent to polyimide varnish curing) of Example No. 4.
3 is a depth profile by XPS of the copper foil (sputter rise) of Example No. 4;
It is a depth profile by XPS of the copper foil (after heat processing equivalent to polyimide varnish hardening) of Example No.4.
5 is a depth profile by XPS when chromium of the copper foil (sputter rise) of Example No. 4 is separated into metal chromium and chromium oxide.
6 is a depth profile by XPS when chromium of copper foil (after heat treatment equivalent to polyimide varnish curing) of Example No. 4 was separated into metallic chromium and chromium oxide.

DETAILED DESCRIPTION OF THE INVENTION

(Copper foil mention)

Although there is no restriction | limiting in particular in the form of the copper foil base material which can be used for this invention, It can typically be used in the form of a rolled copper foil and an electrolytic copper foil. Generally, an electrolytic copper foil is manufactured by electrolytically depositing copper on a drum of titanium or stainless steel from a copper sulfate plating bath, and a rolled copper foil is manufactured by repeating plastic working and heat processing by a rolling roll. Rolled copper foil is often applied to the application which requires flexibility.

Examples of the copper foil-based material include copper alloys containing Sn-containing copper, Ag-containing copper, Cr, Zr or Mg, in addition to high-purity copper such as tough pitch copper or oxygen-free copper, which are usually used as a conductor pattern of a printed wiring board, Copper alloys, such as a Corson-type copper alloy which added Ni, Si, etc. can also be used. In addition, when the term "copper foil" is used alone in this specification, a copper alloy foil shall also be included.

There is no restriction | limiting in particular also about the thickness of the copper foil base material which can be used for this invention, What is necessary is just to adjust suitably to the thickness suitable for printed wiring boards. For example, it can be about 5-100 micrometers. However, when it aims at formation of a fine pattern, it is 30 micrometers or less, Preferably it is 20 micrometers or less, and is typically about 5-20 micrometers.

It is preferable not to perform a roughening process to the copper foil base material used for this invention. Conventionally, the case which forms the unevenness | corrugation of a micrometer order on the surface by special plating, performs surface roughening process, and has adhesiveness with resin by the physical anchor effect was common. On the other hand, the fine pitch and the high frequency electrical characteristics are considered to be a smooth foil, and act in an unfavorable direction in the roughened foil. Moreover, since a roughening process process is abbreviate | omitted, there exists also an effect of economical efficiency and productivity. Therefore, foil used by this invention is foil which does not give a roughening process in particular.

(Coating layer)

At least a part of the surface of the copper foil base material is coated with the Ni—Sn alloy layer and the Cr layer in order. The Ni—Sn alloy layer and the Cr layer constitute a coating layer. Although there is no restriction | limiting in particular in the point to coat | cover, It is common to set it as the point where adhesion | attachment with an insulating substrate is intended. The presence of the coating layer improves the adhesion to the insulating substrate. In general, the adhesive force between the copper foil and the insulating substrate tends to decrease when placed in a high temperature environment, which is believed to occur by copper thermally diffusing to the surface and reacting with the insulating substrate. In this invention, thermal diffusion of copper can be prevented by forming the Ni-Sn alloy layer excellent in copper diffusion prevention on a copper foil base material beforehand. Moreover, by forming the Cr layer which is excellent in adhesiveness with an insulating substrate rather than a Ni-Sn alloy layer on a Ni-Sn alloy layer, adhesiveness with an insulating substrate can be improved further. Since the thickness of the Cr layer can be made thin due to the presence of the Ni-Sn alloy layer, the adverse effect on the etching property can be reduced. In addition, in addition to the adhesiveness in a normal state, the adhesiveness in this invention refers to the adhesiveness (heat resistance) after putting under high temperature, and the adhesiveness (moisture resistance) after putting under high humidity.

In the copper foil for printed wiring boards which concerns on this invention, a coating layer is extremely thin, uniform thickness, and completely covers the copper foil base material surface. The reason why the adhesiveness to the insulating substrate is improved by such a configuration is that after forming the Cr single layer film having excellent adhesion to the resin as the outermost surface on the Ni-Sn alloy coating, the high temperature thermal history at the time of imidization is achieved. It is supposed that it is because it maintains the single-layered film structure which has high adhesiveness also in (about 30 minutes-several hours at about 350 degreeC). Moreover, it is thought that etching property improved by making the coating layer into ultra-thin and reducing the usage-amount of Cr by making into a two layer structure of Ni-Sn alloy and Cr.

Specifically, the coating layer which concerns on this invention has the following structures.

(1) Identification of Cr, Ni-Sn Alloy Coating Layer

In this invention, at least one part of the surface of copper foil raw material is coat | covered in order of Ni-Sn alloy layer and Cr layer. Identification of these coating layers can be carried out by argon sputtering from the surface layer by a surface analysis apparatus such as XPS or AES, conducting chemical analysis in the depth direction, and identifying the Ni-Sn alloy layer and Cr layer by the presence of the respective detection peaks. have. Moreover, the order which coat | covered from the position of each detection peak can be confirmed.

(2) adhesion amount

On the other hand, since these Ni-Sn alloy layers and Cr layers are very thin, evaluation of exact thickness is difficult in XPS and AES. Therefore, in this invention, the thickness of the Ni-Sn alloy layer and Cr layer was evaluated by the weight of the coating metal per unit area. In the Cr layer according to the present invention, Cr is 18 to 180 µg / dm 2, and the Ni-Sn alloy layer is present in a coating amount of 18 to 450 µg / dm 2. If Cr is less than 18 microgram / dm <2>, sufficient peeling strength will not be obtained, and if Cr exceeds 180 microgram / dm <2>, there exists a tendency for etching property to fall significantly. If the sum of Ni and Sn is less than 18 µg / dm 2, sufficient peel strength is not obtained. If the sum of Ni and Sn exceeds 450 µg / dm 2, the etching property tends to be significantly lowered. The coating amount of Cr is preferably 30 to 150 µg / dm 2, more preferably 30 to 90 µg / dm 2, more preferably 36 to 75 µg / dm 2, and the total coating amount of Ni and Sn is Preferably it is 36-360 microgram / dm <2>, More preferably, it is 50-360 microgram / dm <2>, More preferably, it is 75-270 microgram / dm <2>.

When sputtering a pure Ni layer, pure Ni is used as a target, but this pure Ni target is magnetically strong, and when sputtering by magnetron sputtering etc. becomes low, the use efficiency per target sheet is low, and it is disadvantageous in terms of cost. On the other hand, the Ni-Sn alloy layer which concerns on this invention contains 3 to 70 weight% of Sn. If Sn in Ni-Sn alloy layer is less than 3 weight%, since magnetic is strong, sputtering efficiency is bad. When Sn in Ni-Sn alloy layer exceeds 70 weight%, the amount of Ni which is excellent in the diffusion prevention effect of the base material copper will become small, and sufficient adhesiveness with resin will not be obtained. Sn in Ni-Sn alloy layer becomes like this. Preferably it is 5-30 weight%.

(3) Observation by transmission electron microscope (TEM)

When the cross section of the coating layer which concerns on this invention is observed with the transmission electron microscope, the maximum thickness is 0.5-7.5 nm, Preferably it is 0.8-6.0 nm, and the minimum thickness is 80% or more of the maximum thickness, Preferably it is 85% or more. This is a very low coating layer. This is because, in the heat resistance test and the moisture resistance test, when the coating layer thickness is less than 0.5 nm, the deterioration of the peel strength is large, and when the thickness exceeds 7.5 nm, the etching property is lowered. When the minimum value of the thickness is 80% or more of the maximum value, the thickness of this coating layer is very stable and hardly changes even after the heat resistance test. In the observation by TEM, the clear boundary between the Ni-Sn alloy layer and the Cr layer in the coating layer is hard to find and looks like a single layer (see FIGS. 1 and 2). According to the examination result of this inventor, the coating layer discovered by TEM observation is considered to be the layer which mainly has Cr, and Ni-Sn alloy layer is also considered to exist in the copper foil base material side. Therefore, in this invention, the thickness of the coating layer in the case of TEM observation is defined as the thickness of the coating layer which looks like a single | mono layer. However, depending on the observation point, there may be a place where the boundary of the coating layer is unclear, and such a point is excluded from the measurement point of the thickness.

Since the diffusion of Cu is suppressed by the structure of this invention, it is considered to have a stable thickness. The copper foil of this invention adhere | attaches a polyimide film, and even after peeling resin after passing through heat resistance test (168 hours left in a high-temperature environment in air atmosphere at the temperature of 150 degreeC), the thickness of a coating layer hardly changes, and is the largest The thickness is 0.5 to 8.0 nm, and even at the minimum thickness, 60% or more, preferably 70%, of the maximum thickness can be maintained.

(4) Film structure after film formation

It is preferable that internal copper is not diffused on the outermost surface of the coating layer (range of 0 to 1.0 nm from the surface) in order to increase the adhesive strength. Therefore, in the copper foil for printed wiring boards which concerns on this invention, the atomic concentration (%) of chromium of the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is set to f (x), Atomic concentration (%) is set to f 1 (x), Atomic concentration (%) of chromium oxide is set to f 2 (x) (f (x) = f 1 (x) + f 2 (x)), oxygen Let the atomic concentration (%) of g be (x), the atomic concentration (%) of copper be h (x), the total atomic concentration (%) of nickel be i (x), and the atomic concentration of tin ( When%) is j (x), the atomic concentration of carbon (%) is k (x), and the sum of the other atomic concentrations is l (x), in the interval [0, 1.0], ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l It is preferable that (x) dx) is 1.0% or less.

Moreover, it is preferable that Cr layer which is excellent in adhesiveness with an insulating substrate exists in the coating layer outermost surface (range of 0-1.0 nm from the surface) after film-forming at high density | concentration. In the inside of the coating layer (range of 1.0 to 2.5 nm from the surface), it is preferable that the Ni-Sn alloy layer excellent in copper diffusion prevention is present at a high concentration. However, too high a concentration of any of the layers may cause deterioration of the etching property. Therefore, in the copper foil for printed wiring boards which concerns on this invention, in the section [0, 1.0] of the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS, ∫f (x) dx / (∫ f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) Satisfies -50%, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g (x) dx + ∫h (x It is preferable that dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 10 to 70%.

On the outermost surface of the coating layer (range of 0 to 1.0 nm from the surface), both chromium and chromium oxide are present in chromium. From the viewpoint of preventing diffusion of copper inside and securing adhesion, metal chromium is preferable. However, chromium oxide is preferable in obtaining good etching property. At a depth of 1.0-2.5 nm just below the outermost surface of the coating layer, it is preferable that the oxygen concentration is small and chromium is present in the metal state. This is because chromium has a higher ability to prevent copper diffusion inside the metal state than the oxidized state and can improve heat resistance. Therefore, in achieving both the etching property and the adhesive force, the atomic concentration (%) in the depth direction (x: unit nm) of the metal chromium and chromium oxide obtained in the depth direction analysis from the surface by XPS is respectively determined by f 1 ( x), f 2 (x) is 0 in the interval [0, 1.0]

Figure pct00015
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00016
1.0 is satisfied and 0.1 in the interval [1.0, 2.5]
Figure pct00017
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00018
It is preferable that it is 1.0.

(5) Film structure after heat processing equivalent to polyimide hardening

After heat treatment equivalent to polyimide hardening (nitrogen atmosphere, 350 ° C., heating for 30 minutes to several hours), internal copper diffuses to the surface by thermal history on the outermost surface of the coating layer (range of 0 to 1.0 nm from the surface). The thing which is not is preferable in raising adhesive strength. Therefore, in the copper foil for printed wiring boards which concerns on this invention, after the heat processing equivalent of polyimide hardening, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is set to f ( x), the atomic concentration (%) of metal chromium is f 1 (x), and the atomic concentration (%) of oxide chromium is f 2 (x) (f (x) = f 1 (x) + f 2 (x)), the atomic concentration (%) of oxygen is g (x), the atomic concentration (%) of copper is h (x), and the total atomic concentration (%) of nickel is i (x). If the atomic concentration (%) of tin is j (x), the atomic concentration (%) of carbon is k (x), and the sum of the other atomic concentrations is l (x), the interval [0 , 1.0], where ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫ It is preferable that k (x) dx + ∫l (x) dx) be 1.0% or less.

In addition, a high concentration of Cr layer having excellent adhesion to an insulating substrate is applied to the outermost surface of the coating layer (range of 0 to 1.0 nm from the surface) after heat treatment equivalent to polyimide curing (nitrogen atmosphere, 350 ° C., 30 minutes to several hours heating). It is preferable to exist. In the inside of the coating layer (range of 1.0 to 2.5 nm from the surface), it is preferable that the Ni-Sn alloy layer excellent in copper diffusion prevention is present at a high concentration. However, too high a concentration of any of the layers may cause deterioration of the etching property. Therefore, in the copper foil for printed wiring boards which concerns on this invention, after heat processing equivalent to polyimide hardening, in the section [0, 1.0] of the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS, ∫ f (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫ l (x) dx) satisfies 20-50%, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g ( It is preferable that x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 10 to 70%.

Moreover, in the depth direction analysis from the surface by XPS in the coating surface outermost surface (range of 0-1.0 nm from surface) after heat processing equivalent to polyimide hardening (nitrogen atmosphere, 350 degreeC, heating for 30 minutes-several hours), When the atomic concentration (%) in the depth direction (x: unit nm) of the obtained metal chromium and chromium oxide is f 1 (x) and f 2 (x), respectively, 0 in the interval [0, 1.0].

Figure pct00019
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00020
1.0 is satisfied and 0.1 in the interval [1.0, 2.5]
Figure pct00021
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00022
It is preferable that it is 1.0.

(Film Structure of Insulating Substrate Peeling Surface)

When analyzing the surface of the coating layer after peeling an insulating substrate from the coating layer with respect to the copper foil for printed wiring boards stuck on the insulating substrate through the coating layer, internal copper is in the coating layer outermost surface (range of 0-1.0 nm from the surface). The thing which is not diffused is preferable in raising adhesive strength. The atomic concentration (%) of chromium obtained by the depth direction analysis from the surface by XPS is set to f (x), the atomic concentration of oxygen (%) is set to g (x), and the atomic concentration of copper (%) is h (x), the atomic concentration (%) of nickel is i (x), the atomic concentration (%) of tin is j (x), and the atomic concentration (%) of carbon is k (x). When the sum of the other atomic concentrations is l (x) and the distance from the surface layer where the concentration of the metal chromium is maximum is F 1 , in the interval [0, F 1 ], ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) Is preferably 5.0% or less.

Moreover, when analyzing the surface of the coating layer after peeling an insulating substrate from a coating layer with respect to the copper foil for printed wiring boards stuck on the insulating substrate through the coating layer, the atomic concentration of the metal chromium obtained by the depth direction analysis from the surface by XPS. When (%) is f 1 (x), the atomic concentration (%) of oxide chromium is f 2 (x), and the distance from the surface layer where the concentration of metal chromium is maximum is F 1 , the interval [0] , F 1 ]

Figure pct00023
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00024
It is preferable that it is 1.0.

The chromium concentration and the oxygen concentration are calculated from the peak intensities of the Cr2p orbit and the O1s orbit respectively obtained in the depth direction analysis from the surface by XPS. In addition, the depth direction: the distance (x ㎚ unit), and by a distance calculated from the sputter rate in terms of SiO 2. The chromium concentration is a total value of the chromium oxide concentration and the metal chromium concentration, and can be analyzed separately from the chromium oxide concentration and the metal chromium concentration.

(Manufacturing method of copper foil which concerns on this invention)

The copper foil for printed wiring boards which concerns on this invention can be formed by sputtering method. That is, at least a part of the surface of the copper foil base material by the sputtering method is a Ni-Sn alloy layer having a thickness of 0.25 to 5.0 nm, preferably 0.5 to 4.0 nm, more preferably 1.0 to 3.0 nm, and a thickness of 0.25 to 2.5 nm, preferably Preferably, it can manufacture by covering in order with the Cr layer of 0.3-2.0 nm, More preferably, 0.5-1.0 nm. When such an ultra-thin film is laminated by electroplating, a variation occurs in the thickness, and the peel strength is likely to decrease after the heat / moisture resistance test.

The thickness here is not the thickness determined by the above-mentioned XPS or TEM, but the thickness derived from the film formation rate of sputtering. The film-forming speed | rate under any sputtering conditions can sputter | spatter 0.1 micrometer (100 nm) or more, and can measure it from the relationship between sputter time and sputter | spatter thickness. If the film-forming speed | rate under the said sputtering conditions can be measured, a sputter time is set according to a desired thickness. In addition, sputter | spatter may be performed by either continuous or a batch, and can coat | coat a coating layer uniformly by the thickness prescribed | regulated by this invention. As a sputtering method, a direct current magnetron sputtering method is mentioned.

(Manufacture of a printed wiring board)

The printed wiring board (PWB) can be manufactured according to a conventional method using the copper foil which concerns on this invention. Below, the manufacture example of a printed wiring board is shown.

First, copper foil and an insulated substrate are bonded together and a copper clad laminated board is manufactured. The insulating substrate on which copper foil is laminated is not particularly limited as long as it has a property applicable to a printed wiring board. For example, a paper-based phenol resin, a paper-based epoxy resin, a synthetic fiber cloth-based epoxy resin, a glass cloth, and a paper composite substrate for a rigid PWB. An epoxy resin, a glass cloth, a glass nonwoven fabric composite base material epoxy resin, a glass cloth base material epoxy resin, etc. can be used, and a polyester film, a polyimide film, etc. can be used for FPC.

When the bonding method is for rigid PWB, a resin is impregnated into a substrate such as a glass cloth, and a prepreg obtained by curing the resin to a semi-cured state is prepared. It can carry out by heating and pressing the surface which has a prepreg and the coating layer of copper foil.

In the case of flexible printed wiring boards (FPC), the surface which has a coating layer of a polyimide film or a polyester film and copper foil can be adhere | attached using an epoxy type or an acrylic adhesive (3 layer structure). Moreover, as a method (two-layer structure) which does not use an adhesive agent, the casting method and imide which apply | coat the polyimide varnish (polyamic acid varnish) which is a precursor of a polyimide to the surface which has a coating layer of copper foil, and imide by heating The lamination method which apply | coats a thermoplastic polyimide on a mid film, laminates the surface which has a coating layer of copper foil on it, and heat-presses is mentioned. In the casting method, it is also effective to apply an anchor coat material such as thermoplastic polyimide in advance before applying the polyimide varnish.

The effect of the copper foil which concerns on this invention is remarkable when the FPC is manufactured using the casting method. That is, in order to bond copper foil and resin without using an adhesive agent, the adhesiveness of copper foil to resin is especially required, The copper foil which concerns on this invention is excellent in adhesiveness with resin, especially polyimide, It can be said that it is suitable for manufacture of the copper clad laminated board by this.

The copper clad laminated board which concerns on this invention can be used for various printed wiring boards (PWB), Although it does not restrict | limit especially, For example, it is applicable to single-sided PWB, double-sided PWB, multilayer PWB (3 or more layers) from a viewpoint of the number of layers of a conductor pattern. It can be applied to rigid PWB, flexible PWB (FPC), and rigid flex PWB from the viewpoint of the type of insulating substrate material.

The process of manufacturing a printed wiring board from a copper clad laminated board may use the method well-known to those skilled in the art, For example, an etching resist is apply | coated to the copper foil surface of a copper clad laminated board only to a necessary part as a conductor pattern, and unnecessary copper foil is sprayed by spraying etching liquid on copper foil surface. Can be removed to form a conductor pattern, and then the etching resist can be peeled and removed to expose the conductor pattern.

Example

Examples of the present invention are shown below, which are provided to better understand the present invention and are not intended to limit the present invention.

(Example 1: Examples No. 1 to 11)

As a copper foil base material, the 18 degree-thick-rolled copper foil (Nikko Metal Co., Ltd. C1100) and the non-harmonic process foil of the electrolytic copper foil were prepared. The surface roughness (Rz) of the rolled copper foil and the electrolytic copper foil was 0.7 µm and 1.5 µm, respectively.

About one side of this copper foil, the thin oxide film previously affixed on the copper foil base material surface on the following conditions was removed with the reverse sputter | spatter, and the Ni-Sn alloy layer and Cr layer were formed in order. The thickness of the coating layer was changed by adjusting the film formation time.

Apparatus: Batch-type sputtering apparatus (R.D., type MNS-6000)

Reach vacuum level: 1.0 × 10 -5

Sputtering pressure: 0.2 kPa

Reverse Sputter Power: RF100W

Target:

Ni-Sn alloy layer = Ni-Sn alloy of various target compositions and alloy compositions shown in Table 1 below

The target composition and the coating alloy composition are not necessarily the same because the sputtering speeds vary depending on the constituent elements.

For Cr layer = Cr (purity 3 N)

Sputtering Power: 50 W

Film-forming speed: About 0.2 micrometer film-forming at the output 2.5W / cm <2> with respect to each target, thickness was measured with the three-dimensional measuring instrument, and the sputter rate per unit time was computed.

The polyimide film was adhere | attached on the copper foil which formed the coating layer in the following procedures.

(1) Ube Hung San U- varnish-A (polyimide varnish) was apply | coated so that it might be set to 25 micrometers with a dry body using the applicator with respect to the copper foil of 7 cm * 7 cm.

(2) The copper foil with a resin obtained by (1) is dried by air at 120 degreeC for 30 minutes under air.

(3) In the high temperature heating furnace in which the nitrogen flow rate is set to 10 l / min, heating is performed at 350 ° C. for 30 minutes to cure the resin.

<Measurement of adhesion amount>

50 ㎜ × 50 ㎜ the copper foil a coating layer on the surface was dissolved in a mixed solution of HNO 3 (2 wt%) and HCl (5% by weight), the respective metal concentrations ICP emission spectral analysis of the solution unit (SI child, It was quantified by Nano Technology Co., Ltd. product, SFC-3100), and the metal amount (microgram / dm <2>) per unit area was computed. It measured 5 times about each sample, and made the average value into the adhesion amount.

<Measurement by XPS>

The operating conditions of XPS when the depth profile of the coating layer was created are shown below.

Device: XPS Measuring Device (Albac Paisa, Type 5600 MC)

Reach vacuum level: 3.8 × 10 -7

X-ray: Monochromatic AlKα, X-ray output 300 W, detection area 800 μmΦ, angle between sample and detector 45 °

Ion line: Ion species Ar + , acceleration voltage 3 kW, sweeping area 3 mm x 3 mm, sputtering rate 2.0 nm / min (SiO 2 equivalent)

In the measurement result of XPS, separation of chromium oxide and metal chromium was performed using Alk &lt; K &gt; Analysis software Multi Vk V7.3.1.

After the film formation by sputtering, the heat treatment (350 degreeC x 120 minutes) of severe conditions rather than the polyimide hardening conditions (350 degreeC x 30 minutes) at the time of adhesive strength analysis, and the film after peeling an insulating substrate are analyzed. It was.

<Measurement by TEM>

The measurement conditions of TEM when the coating layer was observed by TEM are shown below. The thickness shown in the table measured the maximum value and minimum value of the thickness of the whole coating layer reflected in the observation visual field between 50 nm with respect to one visual field, and obtained the maximum value and minimum value of 3 visual fields selected arbitrarily, the maximum value, and the maximum value The ratio of the minimum value for was obtained as a percentage. In addition, after TEM observation result of "after a heat test" in a table | surface, after bonding a polyimide film on the coating layer of a test piece by the said procedure, putting a test piece in the following high temperature environment, the polyimide film was 90-degree from the obtained test piece. It is a TEM image after peeling according to the peeling method (JIS C 6471 8.1). 1 and 2 exemplarily show respective observation pictures immediately after the sputtering by TEM and after heat treatment corresponding to polyimide varnish curing.

Device: TEM (Hitachi Corporation, Model H9000NAR)

Acceleration voltage: 300 ㎸

Magnification: 300000 times

Observation Field of View: 60 nm × 60 nm

<Adhesive evaluation>

About the copper foil which laminated | stacked the polyimide as mentioned above, after peeling a peeling strength (normal state) for 168 hours in a high temperature environment in 150 degreeC of air atmosphere (heat resistance) immediately after lamination (heat resistance), temperature 40 degreeC relative humidity 95% After standing for 96 hours in a high humidity environment in an air atmosphere (moisture resistance), it was measured under three conditions. Peel strength was measured according to the 90 ° peeling method (JIS C 6471 8.1).

Etchability Evaluation

The white tape was affixed on this coating layer, and it etched using the etching liquid (copper chloride dihydrate, ammonium chloride, ammonia water, liquid temperature of 50 degreeC). Then, the metal component of the etching residue adhering to the tape after processing was quantified by the ICP emission spectroscopy apparatus, and the following references | standards evaluated.

X: etching residue is 140 µg / dm 2 or more

(Triangle | delta): An etching residue is 70 or more and less than 140 microgram / dm <2>.

(Circle): etching residue is less than 70 microgram / dm <2>.

(Example 2: Comparative Example Nos. A to j)

Sputter time was changed to the single side | surface of the rolled copper foil base material used in Example 1, and the film of the thickness of Table 2 was formed. In addition, in No. b (wet plating / chromate), Ni electroplating and chromate treatment were performed in order on the following conditions.

(1) Ni plating

Plating bath: Nickel sulfamate (110 g / l as Ni 2+ ), H 3 BO 3 (40 g / l)

Current density: 1.0 A / dm

Bath temperature: 55 ℃

Ni content: 220 μg / dm 2 (thickness about 1.1 nm)

(2) chromate treatment

Plating bath: CrO 3 (1 g / ℓ), Zn (powder 0.4 g), Na 3 SO 4 (10 g / ℓ)

Current density: 2.0 A / dm

Bath temperature: 55 ℃

Cr amount: 21 μg / dm 2 (thickness about 0.5 nm)

Then, the polyimide film was stuck by the same procedure as Example 1 with respect to the copper foil which provided the coating layer.

The measurement conditions and the measurement result of the said Example No. 1-11 and Comparative Examples No. a-j are shown to Tables 1-4. In Table, SP / SP shows that Ni-Sn alloy and Cr coat | covered with sputter | spatter.

Figure pct00025

Figure pct00026

Figure pct00027

Figure pct00028

(Evaluation of Example)

As shown in Tables 1 and 2, Examples No. 1 to 11 all had good peel strength and etching properties. 3 and 4 show each depth profile by XPS after the sputtering up of the copper foil of Example No. 4 and heat processing equivalent of polyimide varnish hardening. Moreover, about the copper foil of Example No. 4, each depth profile by XPS when the chromium after sputter | spatter raise and heat processing equivalent to polyimide varnish hardening is separated into metal chromium and chromium oxide is shown to FIG. 5 and 6. FIG.

Moreover, in Examples No. 1 to 11, the use efficiency of the Ni-Sn target was all 30 to 40%.

(Evaluation of comparative example)

In Comparative Example No. a, the use efficiency of the target was low as compared with the examples. This is because the comparative example No.a formed the Ni layer instead of the Ni-Sn alloy layer, and thus the magnetism was strong and adversely affected the use efficiency of the target.

In Comparative Example No. b, the Ni layer and the Cr layer were formed by the wet plating treatment and the chromate treatment, but the peel strength was poor.

Comparative Example No. c did not form a Cr layer, and the peel strength was poor.

Comparative Example No. d did not form a Cr layer, and the peel strength was poor. Moreover, the sum total of Ni and Sn in Ni-Sn alloy layer exceeded 450 microgram / dm <2>, and etching property was unsatisfactory.

In Comparative Example No.e, the Cr strength of the Cr layer was less than 18 µg / dm 2, and the peel strength was poor.

In Comparative Example No. f, Cr of the Cr layer exceeded 180 µg / dm 2, and the etching property was poor.

Comparative Examples No. g and h did not form a Ni—Sn alloy layer, and were poor in etching or peel strength.

In the comparative example No.i, the sum total of Ni and Sn in Ni-Sn alloy layer exceeded 450 microgram / dm <2>, and etching property was unsatisfactory.

In Comparative Example No. j, the Ni-Sn alloy layer was less than 18 µg / dm 2, and the peel strength was poor.

1, 2: thickness of the coating layer at the time of TEM observation

Claims (16)

Copper foil base material and copper foil for printed wiring boards provided with the coating layer which coat | covers at least one part of the said copper foil base material surface, The said coating layer is Ni-Sn alloy layer containing Ni and Sn which laminated sequentially from the copper foil base material surface, and Cr. A copper foil for a printed wiring board comprising a layer, wherein Cr is 18 to 180 µg / dm 2 and a total amount of Ni and Sn is 18 to 450 µg / dm 2, respectively, in the Cr layer. . The method of claim 1,
The copper foil for printed wiring boards which Cr has 30-150 microgram / dm <2>, and the said Ni-Sn alloy layer has a total amount of Ni and Sn in a coating amount of 36-360 microgram / dm <2>, respectively. The method of claim 2,
The copper foil for printed wiring boards which Cr has 30-90 microgram / dm <2>, and the said Ni-Sn alloy layer has a total amount of Ni and Sn in 50-360 microgram / dm <2> respectively. The method of claim 3, wherein
A copper foil for a printed wiring board, wherein Cr is 36 to 75 µg / dm 2, and a total amount of Ni and Sn is present in the Ni-Sn alloy layer at 75 to 270 µg / dm 2. The method according to any one of claims 1 to 4,
Copper foil for printed wiring boards which 3-70 weight% Sn exists in the said Ni-Sn alloy layer. 6. The method according to any one of claims 1 to 5,
When the cross section of a coating layer is observed with a transmission electron microscope, the maximum thickness is 0.5-7.5 nm, and the minimum thickness is 80% or more of the maximum thickness copper foil for printed wiring boards. The method according to any one of claims 1 to 6,
The atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained in the depth direction analysis from the surface by XPS is set to f (x), and the atomic concentration (%) of metal chromium is set to f 1 (x). The atomic concentration (%) of chromium oxide is f 2 (x), (f (x) = f 1 (x) + f 2 (x)), and the atomic concentration (%) of oxygen is g (x). The atomic concentration (%) of copper is h (x), the total atomic concentration (%) of nickel is i (x), the atomic concentration (%) of tin is j (x), and carbon If the atomic concentration (%) is k (x) and the sum of the other atomic concentrations is l (x), in the interval [0, 1.0], ∫f (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) satisfies 20 to 50% , ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 1.0% or less, 0
Figure pct00029
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00030
1.0 is satisfied, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 10 to 70%, 0.1
Figure pct00031
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00032
Copper foil for 1.0 printed wiring board. The method according to any one of claims 1 to 7,
When the heat treatment equivalent to polyimide hardening was performed, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained in the depth direction analysis from the surface by XPS was taken as f (x), and the atom of the metal chromium Let concentration (%) be f 1 (x), atomic concentration (%) of oxide chromium be f 2 (x) (f (x) = f 1 (x) + f 2 (x)), and oxygen Let atomic concentration (%) be g (x), copper atomic concentration (%) be h (x), nickel total atomic concentration (%) be i (x), tin concentration (%) ) Is j (x), the atomic concentration (%) of carbon is k (x), and the sum of the other atomic concentrations is l (x). In the interval [0, 1.0], ∫f ( x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l ( x) dx) satisfies 20-50%, and ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫ j (x) dx + ∫k (x) dx + ∫l (x) dx) is 1.0% or less, 0
Figure pct00033
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00034
1.0 is satisfied, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) becomes 10 to 70%, 0.1
Figure pct00035
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00036
Copper foil for printed wiring boards becoming 1.0. The method according to any one of claims 1 to 8,
Heat treatment equivalent to polyimide hardening is carried out, and the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained by the depth direction analysis from the surface by XPS is defined as f (x), Let atomic concentration (%) be f 1 (x), atomic concentration (%) of oxide chromium be f 2 (x) (f (x) = f 1 (x) + f 2 (x)), oxygen Let the atomic concentration (%) of g be (x), the atomic concentration (%) of copper be h (x), the total atomic concentration (%) of nickel be i (x), and the atomic concentration of tin ( When%) is j (x), the atomic concentration of carbon (%) is k (x), and the sum of the other atomic concentrations is l (x), in the interval [0, 1.0], ∫f (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) satisfies 20-50%, and ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 1.0% or less, 0
Figure pct00037
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00038
1.0 is satisfied, and in [1.0, 2.5], (∫i (x) dx + ∫j (x) dx) / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 10 to 70%, 0.1
Figure pct00039
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00040
Copper foil for 1.0 printed wiring board. The method according to any one of claims 1 to 9,
When the surface of the coating layer after peeling an insulating substrate from the coating layer was analyzed about the copper foil for printed wiring boards which adhered the coating layer to the insulating substrate, the depth direction (x: unit nm) of the depth direction obtained by the depth direction analysis from the surface by XPS. The atomic concentration (%) of chromium is f (x), the atomic concentration (%) of metal chromium is f 1 (x), and the atomic concentration (%) of oxide chromium is f 2 (x) (f (x) = f 1 (x) + f 2 (x)), the atomic concentration (%) of oxygen is g (x), the atomic concentration (%) of copper is h (x), and the sum of nickel The atomic concentration (%) is i (x), the atomic concentration (%) of tin is j (x), the atomic concentration (%) of carbon is k (x), and the sum of the other atomic concentrations is When l (x) is set, the distance from the surface layer where the concentration of the metal chromium is maximized is F 1. In the section [0, F 1 ], ∫h (x) dx / (∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx + ∫l (x) dx) is 5.0% or less, 0.1
Figure pct00041
∫f 1 (x) dx / ∫f 2 (x) dx
Figure pct00042
Copper foil for printed wiring boards satisfying 1.0. The method according to any one of claims 1 to 10,
Copper foil base material is copper foil for printed wiring boards which is rolled copper foil. The method according to any one of claims 1 to 11,
A printed wiring board is copper foil for printed wiring boards which is a flexible printed wiring board. The manufacturing method of the copper foil for printed wiring boards which coats at least one part of the copper foil base material surface by the sputtering method sequentially with the Ni-Sn alloy layer of 0.25-5.0 nm in thickness, and the Cr layer of 0.25-2.5 nm in thickness. The copper clad laminated board provided with the copper foil as described in any one of Claims 1-12. The method of claim 14,
The copper clad laminated board which has a structure by which copper foil is bonded to the polyimide. The printed wiring board which used the copper clad laminated board of Claim 14 or 15 as a material.
KR1020107017993A 2009-06-30 2009-11-25 Copper foil for printed wiring board KR101086656B1 (en)

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PCT/JP2009/069879 WO2011001551A1 (en) 2009-06-30 2009-11-25 Copper foil for printed wiring boards

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JP4659140B2 (en) 2011-03-30
TWI414215B (en) 2013-11-01
KR101086656B1 (en) 2011-11-24
TW201106816A (en) 2011-02-16
CN102150479A (en) 2011-08-10
JPWO2011001551A1 (en) 2012-12-10
WO2011001551A1 (en) 2011-01-06
CN102150479B (en) 2013-03-27

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