WO2016158775A1 - Roughened copper foil, copper foil provided with carrier, copper-clad laminated sheet, and printed wiring board - Google Patents

Roughened copper foil, copper foil provided with carrier, copper-clad laminated sheet, and printed wiring board Download PDF

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Publication number
WO2016158775A1
WO2016158775A1 PCT/JP2016/059671 JP2016059671W WO2016158775A1 WO 2016158775 A1 WO2016158775 A1 WO 2016158775A1 JP 2016059671 W JP2016059671 W JP 2016059671W WO 2016158775 A1 WO2016158775 A1 WO 2016158775A1
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Prior art keywords
copper foil
roughened
substantially spherical
ave
carrier
Prior art date
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PCT/JP2016/059671
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French (fr)
Japanese (ja)
Inventor
浩人 飯田
光由 松田
吉川　和広
信之 河合
翼 加藤
Original Assignee
三井金属鉱業株式会社
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Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to CN201680020446.8A priority Critical patent/CN107429417B/en
Priority to JP2017509918A priority patent/JP6293365B2/en
Priority to MYPI2017703411A priority patent/MY186266A/en
Priority to KR1020177016424A priority patent/KR102273442B1/en
Publication of WO2016158775A1 publication Critical patent/WO2016158775A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • 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
    • 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
    • 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
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0723—Electroplating, e.g. finish plating
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating

Definitions

  • the present invention relates to a roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed wiring board.
  • the SAP method is a method suitable for forming an extremely fine circuit, and as an example, it is performed using a roughened copper foil with a carrier.
  • a roughened copper foil with a carrier For example, as shown in FIGS. 1 and 2, an ultrathin copper foil 10 having a roughened surface is used, and a prepreg 12 and a primer layer 13 are used on an insulating resin substrate 11 having a base substrate 11a and a lower layer circuit 11b. Then, the carrier foil (not shown) is peeled off, and then a via hole 14 is formed by laser drilling as necessary (step (b)).
  • the ultrathin copper foil is removed by etching to expose the primer layer 13 provided with the roughened surface profile (step (c)).
  • the electroless copper plating 15 is applied to the roughened surface (step (d))
  • it is masked with a predetermined pattern by exposure and development using the dry film 16 (step (e))
  • the electrolytic copper plating 17 is applied.
  • Step (f) After removing the dry film 16 to form the wiring portion 17a (step (g)), unnecessary electroless copper plating 15 between the adjacent wiring portions 17a and 17a is removed by etching (step (h)).
  • a wiring 18 formed in a predetermined pattern is obtained.
  • the roughened copper foil itself is removed by etching after laser drilling (step (c)). And since the uneven
  • the MSAP (Modified Semi-Additive Process) method that does not perform the copper foil removal step corresponding to step (c) is also widely used, but copper is used in the etching step (corresponding to step (h)) after development. Since the two layers of the foil layer and the electroless copper plating layer must be removed by etching, it is necessary to perform the etching deeper than the SAP method which only requires etching removal of one electroless copper plating layer. Therefore, it is necessary to make the circuit space somewhat narrower in consideration of a larger amount of etching, so that the MSAP method can be said to be somewhat inferior to the SAP method in terms of fine circuit formation. That is, the SAP method is more advantageous for the purpose of forming a finer circuit.
  • a roughened copper foil with a carrier in which the shape of the roughened particles is controlled is known.
  • Patent Document 1 Japanese Patent Laid-Open No. 2013-199082
  • the average diameter D1 of the particle root at a position of 10% of the particle length is 0.2 ⁇ m to 1.0 ⁇ m on the surface of the ultrathin copper layer
  • a copper foil with a carrier characterized by having a roughened layer having a ratio L1 / D1 of the particle length L1 and the average diameter D1 of the particle root of 15 or less is disclosed.
  • the ratio D2 / D1 of the average diameter D2 of the center of the particle at the position of 50% of the particle length to the average diameter D1 of the particle root is 1 to 4 on the surface of the ultrathin copper layer, and the particle The ratio D2 / D3 of the average diameter D2 at the center and the particle tip D3 at a position of 90% of the particle length is preferably 0.8 to 1.0. Moreover, it is disclosed by the Example of patent document 1 that the length of a roughening particle
  • the roughened copper foil itself is removed by etching after laser drilling (step (c)). And since the uneven
  • the present inventors recently set the average height of the substantially spherical protrusions to 2.60 ⁇ m or less, and substantially When the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusions to the average neck diameter a ave of the spherical protrusions is 1.2 or more, only excellent plating circuit adhesion is obtained when used in the SAP method.
  • a roughened copper foil can be provided that can impart a surface profile excellent in etching property to electroless copper plating to the laminate.
  • the knowledge that extremely fine dry film resolution was realizable was also acquired in the dry film image development process in SAP method by using the said roughening process copper foil.
  • the object of the present invention is to provide a laminate with a surface profile that is excellent not only in plating circuit adhesion but also in etching performance for electroless copper plating and dry film resolution when used in the SAP method. Another object is to provide a roughened copper foil. Moreover, the other object of this invention is to provide the copper foil with a carrier provided with such a roughening process copper foil.
  • a roughened copper foil having a roughened surface on at least one side, the roughened surface comprising a plurality of substantially spherical protrusions made of copper particles,
  • the average height of the substantially spherical protrusions is 2.60 ⁇ m or less, and the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusions to the average neck diameter a ave of the substantially spherical protrusions is 1.2 or more.
  • a roughened copper foil is provided.
  • a carrier foil a release layer provided on the carrier foil, and the roughening treatment of the above aspect provided on the release layer with the roughening treatment surface facing outward.
  • a copper foil with a carrier comprising a copper foil.
  • a copper clad laminate obtained using the roughened copper foil of the above aspect or the copper foil with a carrier of the above aspect.
  • a printed wiring board obtained using the roughened copper foil of the above aspect or the copper foil with a carrier of the above aspect.
  • FIG. 4B is an enlarged cross-sectional view of a portion surrounded by a frame in FIG. 4A, for explaining the definition of highly inclined substantially spherical particles. It is a photograph which shows an example of the dry film pattern in which resolution was performed favorably in the SAP method. It is a photograph which shows an example of the dry film pattern in which resolution was not performed favorably in SAP method.
  • the “substantially spherical protrusion” is a protrusion having a substantially spherical round shape, and is distinguished from an anisotropic shape protrusion or particle such as a needle shape, a columnar shape, and an elongated shape. is there.
  • the substantially spherical protrusion 32 is connected to the copper foil surface 30 by the constricted root portion 34 connected to the copper foil surface 30, and thus cannot be a perfect sphere.
  • parts other than the root part 32 should just be substantially spherical. Therefore, as long as the substantially spherical protrusion has a substantially spherical round shape, the presence of some unevenness or deformation is allowed.
  • the said protrusion may only be called a spherical protrusion, since it cannot become a perfect sphere as mentioned above, it should be understood as meaning the substantially spherical protrusion mentioned above.
  • the “neck diameter a of the substantially spherical protrusion” is the diameter of the narrow base portion 34 connected to the copper foil surface 30 in the substantially spherical protrusion 32, as schematically shown in FIG. It means the shortest distance between the constrictions.
  • the “average neck diameter a ave of the substantially spherical protrusion” is a surface profile of a rough replica-processed copper foil having a substantially spherical protrusion made of resin, and the surface of the obtained resin replica (for example, 435 ⁇ m 2).
  • the average value of the neck diameters a 1 , a 2 ,..., A N of N substantially spherical protrusions (that is, the value of (a 1 + a 2 +... + A N ) / N). ).
  • the production of the resin replica may be performed in accordance with various conditions described in the examples of the present specification.
  • the “maximum diameter b of the substantially spherical protrusion” is the maximum diameter of the substantially spherical protrusion 32 measured in a direction parallel to the copper foil surface 30 as schematically shown in FIG.
  • the “average maximum diameter b ave of approximately spherical protrusions” is the maximum diameter b 1 , b 2 ,... Of N approximately spherical protrusions measured on the surface of the roughened copper foil (for example, a region of 435 ⁇ m 2 ). .., an average value of b N (that is, a value of (b 1 + b 2 +... + B N ) / N).
  • the “substantially spherical protrusion height c” is based on the root portion 34 of the substantially spherical protrusion 32 measured in the direction perpendicular to the copper foil surface 30 as schematically shown in FIG. Height.
  • the “average height c ave of substantially spherical protrusions” is the heights c 1 and c 2 of N substantially spherical protrusions measured in the cross-sectional profile of the roughened copper foil (for example, a reference length of 25 ⁇ m).
  • C N is an average value (that is, a value of (c 1 + c 2 +... + C N ) / N).
  • the “separate root d of substantially spherical protrusions” means a separation distance at the level of the root of adjacent substantially granular particles 30, that is, the roots of substantially granular particles 30, as schematically shown in FIG. 3. This is the shortest distance between the constriction of the portion 34 and the constriction of the root portion 34 of the adjacent substantially spherical particle 32.
  • the “average root separation distance d ave of approximately spherical protrusions” means that a replica shape of a surface profile provided with approximately spherical protrusions of a roughened copper foil is made of a resin, and a resin replica surface obtained (for example, 435 ⁇ m) 2 ), the average value of root separation distances d 1 , d 2 ,..., D N ⁇ 1 between N substantially spherical projections (ie, (d 1 + d 2 +... + D N ⁇ 1 ) / (N-1)).
  • the production of the resin replica may be performed in accordance with various conditions described in the examples of the present specification.
  • the “highly inclined substantially spherical protrusion” means a root boundary line of the substantially spherical protrusion 32 (boundary line of the root portion 34) among the substantially spherical protrusions 32 as schematically shown in FIGS. 4A and 4B.
  • the line L VC connecting the midpoint C and the vertex V of substantially spherical projections 32, acute ⁇ is 85 ° forming roughened surface of the roughened copper foil and the opposite face parallel to the reference line L B is Refers to the following:
  • the "ratio of the high-tilt substantially spherical protrusions occupying the total number of substantially spherical projections" were measured in the cross-section profile of the roughened copper foil (e.g. 10 ⁇ m standard length), to the total number N A substantially spherical projection
  • the ratio of the number of highly inclined substantially spherical protrusions N H that is, 100 ⁇ N H / N A (%).
  • the neck diameter “a”, the maximum diameter “b”, and the root separation distance “d” of the substantially spherical protrusion are measured by subjecting an image acquired by SEM observation to image processing such as binarization processing using a commercially available image analysis device and software. be able to.
  • image processing such as binarization processing using a commercially available image analysis device and software.
  • image analysis apparatus there is LUZEX AP manufactured by Nireco Corporation.
  • the image processing may be performed according to various conditions described in the examples of the present specification.
  • the “average distance between surface peaks (Peak spacing)” refers to a peak after removing a high-frequency swell component from information on unevenness of a sample surface obtained using a three-dimensional surface structure analysis microscope. The average distance between peaks in data extracted by filtering waveform data.
  • maximum waviness difference means that waveform data relating to waviness is extracted from information relating to unevenness of the sample surface obtained using a three-dimensional surface structure analysis microscope using a filter.
  • the maximum value of the height difference of the waveform data (the sum of the maximum peak height of the waveform and the maximum valley depth).
  • the average distance between peak peaks (Peak spacing) and the maximum difference in waviness (Wmax) are both commercially available three-dimensional surface structure analysis microscopes (for example, zygo New View 5032 (manufactured by Zygo)) and commercially available analysis software. (For example, Metro Pro Ver. 8.0.2) can be used with a low frequency filter set to 11 ⁇ m for measurement. At this time, the surface to be measured of the foil is fixed in close contact with the sample stage, and 6 fields of 108 ⁇ m ⁇ 144 ⁇ m are selected and measured within the 1 cm square range of the sample piece, and obtained from the 6 measurement points. The average value of the measured values obtained is preferably adopted as the representative value.
  • the “electrode surface” of the carrier foil refers to the surface on the side in contact with the cathode when the carrier foil was produced.
  • the “deposition surface” of the carrier foil refers to the surface on the side where electrolytic copper is deposited when the carrier foil is produced, that is, the surface not in contact with the cathode.
  • the copper foil according to the present invention is a roughened copper foil.
  • This roughened copper foil has a roughened surface on at least one side.
  • the roughened surface is provided with a plurality of substantially spherical protrusions 32 made of copper particles, as schematically shown in FIG.
  • the average height c ave of these substantially spherical protrusions 32 is 2.60 ⁇ m or less.
  • the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusion to the average neck diameter a ave of the substantially spherical protrusion is 1.2 or more.
  • the average height c ave of the substantially spherical protrusions is 2.60 ⁇ m or less, and the substantially spherical protrusions
  • the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusion to the average neck diameter a ave is 1.2 or more, not only excellent plating circuit adhesion but also when used in the SAP method. It is possible to provide a roughened copper foil capable of imparting a surface profile excellent in etching property to electroless copper plating to a laminate.
  • extremely fine dry film resolution can be realized in the dry film development step in the SAP method.
  • Plating circuit adhesion and etchability for electroless copper plating are inherently difficult to achieve at the same time, but according to the present invention, they can both be achieved unexpectedly. That is, as described above, since the surface profile suitable for improving the adhesion to the plating circuit tends to be rough unevenness, the etching property of the electroless copper plating is lowered in the step (h) of FIG. It's easy to do. That is, as the electroless copper plating bites into rough irregularities, more etching is required to eliminate residual copper. However, according to the roughened copper foil of the present invention, excellent plating circuit adhesion can be secured while realizing such a reduction in the etching amount.
  • the average height c ave of the substantially spherical protrusions is set to be as low as 2.60 ⁇ m or less, thereby avoiding the above-described decrease in etching property due to the rough unevenness, while the average height c ave of the substantially spherical protrusions is reduced.
  • the adhesiveness with the plating circuit which is concerned with the decrease, can be improved by setting the ratio b ave / a ave to 1.2 or more.
  • the larger the ratio b ave / a ave the more the substantially spherical protrusion 32 is constricted at the root portion 34 connected to the copper foil surface 30.
  • an anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be exhibited, and an excellent plating circuit and It is considered that the adhesion of the material can be realized. And it is thought that very fine dry film resolution can be realized in the dry film development process in the SAP method by satisfying both such excellent adhesion and excellent etching property for electroless copper plating. . Therefore, it is preferable that the roughened copper foil of this invention is used for preparation of the printed wiring board by a semi-additive method (SAP). In other words, it can be said that the roughened copper foil of the present invention is preferably used for transferring the concavo-convex shape to the insulating resin layer for the printed wiring board.
  • SAP semi-additive method
  • the roughened copper foil of the present invention has a roughened surface on at least one side. That is, the roughened copper foil may have a roughened surface on both sides, or may have a roughened surface only on one side. When both sides have roughened surfaces, the surface on the laser irradiation side (the surface opposite to the surface to be in close contact with the insulating resin) is also roughened when used in the SAP method. As a result, the laser drillability can be improved.
  • the roughened surface is provided with a plurality of substantially spherical protrusions 32, and the plurality of substantially spherical protrusions 32 are made of copper particles. That is, each substantially spherical protrusion 32 is basically composed of a single copper particle.
  • the copper particles may be made of metallic copper, or may be made of a copper alloy. However, when the copper particles are a copper alloy, the solubility in the copper etching solution may decrease, or the life of the etching solution may decrease due to the alloy components mixed in the copper etching solution. Preferably it consists of.
  • the average height c ave of the substantially spherical protrusion 32 is 2.60 ⁇ m or less, preferably 1.5 ⁇ m or less, more preferably 1.0 ⁇ m or less, and even more preferably 0.6 ⁇ m or less. Within these ranges, the etching property for electroless copper plating is significantly improved. Although the lower limit of the average height c ave is is not particularly limited, the average height c ave is preferably 0.2 ⁇ m or more, and more preferably 0.4 ⁇ m or more.
  • the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusion 32 to the average neck diameter a ave of the approximately spherical protrusion 32 is 1.2 or more, preferably 1.2 to 5.0, more preferably 1 .3 to 3.0, more preferably 1.3 to 2.0, particularly preferably 1.4 to 1.7. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved.
  • the average neck diameter a ave of the substantially spherical protrusion 32 is preferably 0.1 to 2.0 ⁇ m, more preferably 0.2 to 1.0 ⁇ m, and still more preferably 0.3 to 0.6 ⁇ m.
  • the average maximum diameter b ave of the substantially spherical protrusion 32 is preferably 2.5 ⁇ m or less, more preferably 0.2 to 2.5 ⁇ m, still more preferably 0.3 to 1.5 ⁇ m, and particularly preferably 0.4 to 1.2 ⁇ m, most preferably 0.4 to 0.8 ⁇ m. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved.
  • the ratio of the substantially spherical protrusion 32 in which the ratio b / a of the maximum diameter b of the substantially spherical protrusion 32 to the neck diameter a of the approximately spherical protrusion 32 occupies in the substantially spherical protrusion 32 existing on the roughened surface is 1.2 or more. It is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more on the number basis. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved.
  • the average root separation distance d of the substantially spherical protrusions 32 is preferably 0.10 to 0.30 ⁇ m, more preferably 0.15 to 0.25 ⁇ m. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved. .
  • the approximately spherical protrusions 32 are preferably present at an area density of 1 to 10 / ⁇ m 2 , more preferably 2 to 5 / ⁇ m 2 , and further preferably 3 to 5 / ⁇ m 2 . Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved. .
  • the roughened surface generally has waviness, and the substantially spherical protrusion 32 can be inclined due to this waviness.
  • the ratio of the highly inclined substantially spherical protrusions to the total number of substantially spherical protrusions 32 is preferably 30 to 60%, more preferably. It is 35 to 57%, more preferably 40 to 57%.
  • the line L VC connecting the vertex V of substantially spherical midpoint C of the root boundary projections 32 and substantially spherical projection 32, the roughened surface of the roughened copper foil acute ⁇ formed by the other side of the plane parallel to the reference line L B is substantially spherical protrusions is 85 ° or less.
  • the ratio of the highly inclined substantially spherical protrusions is 60% or less, the roughened copper foil is etched away by the SAP method, and the unevenness derived from the roughened surface is given to the unevenness at the time of exposure.
  • the resulting diffused reflection of light can be reduced and the dry film can be cured more advantageously, and as a result, the resolution of the dry film resist is further improved.
  • the adhesiveness with respect to a base material further improves that the ratio of a high inclination substantially spherical protrusion is 30% or more. Therefore, by setting the ratio of the highly inclined substantially spherical protrusions to 30 to 60%, it is possible to provide a roughened copper foil that is superior in achieving both dry film resolution and adhesion to the substrate.
  • the thickness of the roughened copper foil of the present invention is not particularly limited, but is preferably 0.1 to 18 ⁇ m, more preferably 0.5 to 10 ⁇ m, still more preferably 0.5 to 7 ⁇ m, and particularly preferably 0.5 to 5 ⁇ m, most preferably 0.5 to 3 ⁇ m.
  • the roughened copper foil of the present invention is not limited to the one obtained by subjecting the surface of the normal copper foil to the roughening treatment, but may be one obtained by subjecting the copper foil surface of the copper foil with carrier to the roughening treatment. Good.
  • the roughened copper foil according to the present invention is not limited to the method described below, and the roughened copper foil according to the present invention is used. It may be manufactured by any method as long as the surface profile of the treated copper foil can be realized.
  • the thickness of the copper foil is not particularly limited, but is preferably 0.1 to 18 ⁇ m, more preferably 0.5 to 10 ⁇ m, still more preferably 0.5 to 7 ⁇ m, particularly preferably 0.5 to 5 ⁇ m, and most preferably 0. .5-3 ⁇ m.
  • the copper foil is prepared in the form of a copper foil with a carrier, the copper foil is prepared by a wet film formation method such as an electroless copper plating method and an electrolytic copper plating method, a dry film formation method such as sputtering and chemical vapor deposition, or It may be formed by a combination thereof.
  • the surface to be subjected to the roughening treatment of the copper foil before the roughening treatment is not particularly limited, but the maximum height difference (Wmax) of the waviness is preferably 6.0 ⁇ m or less, more preferably 0.8 ⁇ m. It is preferably 1 to 2.0 ⁇ m, more preferably 0.2 to 1.3 ⁇ m, and the average distance (Peak spacing) between surface peaks is preferably 100 ⁇ m or less, more preferably 3 to 70 ⁇ m, still more preferably 5 to 30 ⁇ m.
  • the ratio of highly inclined substantially spherical protrusions to the total number of substantially spherical protrusions after the subsequent roughening treatment is preferably 30 to 60%, more preferably 35 to 57. %, More preferably 40 to 57%, can be conveniently formed.
  • the realization of low peak spacing and Wmax within the above range is that the surface of the rotating cathode used when electrolytically forming the carrier foil is a baffle of a predetermined count. The surface roughness can be adjusted by polishing.
  • the surface profile of the rotating cathode thus adjusted is transferred to the electrode surface of the carrier foil, and the copper foil is formed on the electrode surface of the carrier foil thus provided with the desired surface profile via the release layer.
  • the surface profile described above can be applied to the surface on which the foil is roughened (that is, the side opposite to the release layer).
  • a preferred buff count is greater than # 1000 and less than # 3000, more preferably # 1500 to # 2500, and particularly preferably # 2000.
  • the undulation of the surface of the copper foil can be controlled, and the ratio of the highly inclined substantially spherical particles can be controlled as intended.
  • Roughening treatment At least one surface of the copper foil is roughened using copper particles.
  • This roughening is performed by electrolysis using a copper electrolytic solution for roughening treatment.
  • This electrolysis is preferably performed through a two-step plating process.
  • a copper sulfate solution containing a copper concentration of 8 to 12 g / L and a sulfuric acid concentration of 200 to 280 g / L is used, the liquid temperature is 20 to 40 ° C., the current density is 15 to 35 A / dm 2 , and the time is 5
  • Electrodeposition is preferably performed under plating conditions of ⁇ 25 seconds.
  • a copper sulfate solution containing a copper concentration of 65 to 80 g / L and a sulfuric acid concentration of 200 to 280 g / L is used, the liquid temperature is 45 to 55 ° C., the current density is 5 to 30 A / dm 2 , and the time is 5 Electrodeposition is preferably performed under plating conditions of ⁇ 25 seconds.
  • the amount of electricity in each stage is such that the ratio (Q 1 / Q 2 ) of the amount of electricity Q 1 in the first stage plating process to the amount of electricity Q 2 in the second stage plating process is 1.5 to 2.5. It is preferable to set to.
  • the ratio Q 1 / Q 2 When the ratio Q 1 / Q 2 is less than 1.5, the constriction of the substantially spherical protrusion becomes small (that is, the ratio b / a becomes small), and the plating circuit adhesion can be lowered. On the other hand, when the ratio Q 1 / Q 2 exceeds 2.5, the constriction of the substantially spherical protrusion is increased (that is, the ratio b / a is increased), and the roughened particles are likely to fall off.
  • the copper foil after the roughening treatment may be subjected to a rust prevention treatment.
  • the rust prevention treatment preferably includes a plating treatment using zinc.
  • the plating treatment using zinc may be either a zinc plating treatment or a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a zinc-nickel alloy treatment.
  • the zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, and Co.
  • the Ni / Zn adhesion ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and still more preferably 2.7 to 4 in terms of mass ratio.
  • the rust prevention treatment preferably further includes a chromate treatment, and this chromate treatment is more preferably performed on the surface of the plating containing zinc after the plating treatment using zinc.
  • rust prevention property can further be improved.
  • a particularly preferable antirust treatment is a combination of a zinc-nickel alloy plating treatment and a subsequent chromate treatment.
  • the copper foil may be treated with a silane coupling agent to form a silane coupling agent layer.
  • a silane coupling agent layer can be formed by appropriately diluting and applying a silane coupling agent and drying.
  • silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, or ⁇ -aminopropyltriethoxysilane, N- ⁇ (amino Amino functions such as ethyl) ⁇ -aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane Silane coupling agent, or mercapto functional silane coupling agent such as ⁇ -mercaptopropyltrimethoxysilane, or olefin functional silane coupling agent such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, or ⁇ -methacryloxypropyl Trimetoki Acrylic-functional silane coupling
  • the roughened copper foil of the present invention can be provided in the form of a copper foil with carrier.
  • the carrier-attached copper foil includes a carrier foil, a release layer provided on the carrier foil, and the roughened copper foil of the present invention provided on the release layer with the roughened surface facing outside. It is equipped with.
  • a known layer structure can be adopted as the carrier-attached copper foil except that the roughened copper foil of the present invention is used.
  • the carrier foil is a foil for supporting the roughened copper foil and improving its handleability.
  • the carrier foil include an aluminum foil, a copper foil, a resin film whose surface is metal-coated, and the like, and preferably a copper foil.
  • the copper foil may be a rolled copper foil or an electrolytic copper foil.
  • the thickness of the carrier foil is typically 200 ⁇ m or less, preferably 12 ⁇ m to 35 ⁇ m.
  • the surface on the release layer side of the carrier foil preferably has a 10-point surface roughness Rzjis of 0.5 to 1.5 ⁇ m, more preferably 0.6 to 1.0 ⁇ m.
  • Rzjis can be determined according to JIS B 0601: 2001.
  • the release layer is a layer having a function of weakening the peeling strength of the carrier foil, ensuring the stability of the strength, and further suppressing interdiffusion that may occur between the carrier foil and the copper foil during press molding at a high temperature. It is.
  • the release layer is generally formed on one side of the carrier foil, but may be formed on both sides.
  • the release layer may be either an organic release layer or an inorganic release layer. Examples of organic components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids and the like. Examples of nitrogen-containing organic compounds include triazole compounds, imidazole compounds, and the like. Among these, triazole compounds are preferred in terms of easy release stability.
  • triazole compounds examples include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1,2,4-triazole and 3-amino- And 1H-1,2,4-triazole.
  • sulfur-containing organic compound examples include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol and the like.
  • carboxylic acid examples include monocarboxylic acid and dicarboxylic acid.
  • examples of inorganic components used in the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, and a chromate-treated film.
  • the release layer may be formed by bringing a release layer component-containing solution into contact with at least one surface of the carrier foil and fixing the release layer component to the surface of the carrier foil.
  • the contact of the carrier foil with the release layer component-containing solution may be performed by immersion in the release layer component-containing solution, spraying of the release layer component-containing solution, flowing down of the release layer component-containing solution, or the like.
  • the release layer component may be fixed to the surface of the carrier foil by adsorption or drying of the release layer component-containing solution, electrodeposition of the release layer component in the release layer component-containing solution, or the like.
  • the thickness of the release layer is typically 1 nm to 1 ⁇ m, preferably 5 nm to 500 nm.
  • the roughened copper foil of the present invention described above is used as the roughened copper foil.
  • the roughening treatment of the present invention is performed by roughening using copper particles.
  • a copper layer is formed as a copper foil on the surface of the release layer, and then at least roughening is performed. . Details of the roughening are as described above.
  • copper foil is comprised with the form of an ultra-thin copper foil in order to utilize the advantage as copper foil with a carrier.
  • a preferable thickness of the ultrathin copper foil is 0.1 ⁇ m to 7 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m, and still more preferably 0.5 ⁇ m to 3 ⁇ m.
  • auxiliary metal layer is preferably made of nickel and / or cobalt.
  • the thickness of the auxiliary metal layer is preferably 0.001 to 3 ⁇ m.
  • the roughened copper foil or carrier-attached copper foil of the present invention is preferably used for the production of a copper-clad laminate for printed wiring boards. That is, according to the preferable aspect of this invention, the copper clad laminated board obtained using the said roughening copper foil or the said copper foil with a carrier is provided.
  • a copper clad laminate particularly suitable for the SAP method can be provided.
  • This copper-clad laminate comprises the carrier-attached copper foil of the present invention and a resin layer provided in close contact with the roughened surface.
  • the copper foil with a carrier may be provided on one side of the resin layer or may be provided on both sides.
  • the resin layer comprises a resin, preferably an insulating resin.
  • the resin layer is preferably a prepreg and / or a resin sheet.
  • the prepreg is a general term for composite materials in which a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass nonwoven fabric, and paper is impregnated with a synthetic resin.
  • Preferable examples of the insulating resin include an epoxy resin, a cyanate resin, a bismaleimide triazine resin (BT resin), a polyphenylene ether resin, and a phenol resin.
  • the insulating resin that constitutes the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins.
  • the filler particle etc. which consist of various inorganic particles, such as a silica and an alumina, may contain in the resin layer from a viewpoint of improving insulation.
  • the thickness of the resin layer is not particularly limited, but is preferably 1 to 1000 ⁇ m, more preferably 2 to 400 ⁇ m, and still more preferably 3 to 200 ⁇ m.
  • the resin layer may be composed of a plurality of layers.
  • a resin layer such as a prepreg and / or a resin sheet may be provided on the ultrathin copper foil with a carrier via a primer resin layer previously applied to the surface of the copper foil.
  • the roughened copper foil or carrier-attached copper foil of the present invention is preferably used for the production of a printed wiring board, particularly preferably for the production of a printed wiring board by a semi-additive method (SAP). That is, according to the preferable aspect of this invention, the printed wiring board obtained using the roughening process copper foil mentioned above or the said copper foil with a carrier is provided.
  • SAP semi-additive method
  • the printed wiring board according to this aspect includes a layer configuration in which a resin layer and a copper layer are laminated in this order.
  • the roughened copper foil of the present invention is removed in the step (c) of FIG. 1, and therefore the printed wiring board produced by the SAP method no longer contains the roughened copper foil of the present invention. Only the surface profile transferred from the roughened surface of the roughened copper foil remains.
  • the resin layer is as described above for the copper-clad laminate. In any case, a known layer structure can be adopted for the printed wiring board.
  • the printed wiring board examples include a single-sided or double-sided printed wiring board formed with a circuit on the laminated body obtained by bonding the ultrathin copper foil of the present invention to one side or both sides of the prepreg, and a multilayer in which these are multilayered.
  • a printed wiring board etc. are mentioned.
  • Other specific examples include a flexible printed wiring board, a COF, a TAB tape, and the like that form a circuit by forming the ultrathin copper foil of the present invention on a resin film.
  • examples thereof include an electronic material for glass, and an electromagnetic wave shielding film obtained by applying a conductive adhesive to the ultrathin copper foil of the present invention.
  • the ultrathin copper foil with a carrier of the present invention is suitable for the SAP method.
  • a configuration as shown in FIGS. 1 and 2 can be employed.
  • carrier foil A copper sulfate solution having the composition shown below as a copper electrolyte, and a rotating electrode made of titanium having an arithmetic average surface roughness Ra (based on JIS B 0601: 2001) of 0.20 ⁇ m as a cathode.
  • a DSA dimensional stability anode
  • electrolysis was performed at a solution temperature of 45 ° C. and a current density of 55 A / dm 2 , thereby obtaining an electrolytic copper foil having a thickness of 12 ⁇ m as a carrier foil.
  • an electrode whose surface roughness was adjusted by polishing with a # 1000 buff was used as the rotating cathode.
  • auxiliary metal layer Formation of auxiliary metal layer
  • the carrier copper foil on which the organic release layer is formed is immersed in a solution having a nickel concentration of 20 g / L prepared using nickel sulfate, and the liquid temperature is 45 ° C., pH 3, and the current density.
  • nickel with a deposition amount corresponding to a thickness of 0.001 ⁇ m was deposited on the organic release layer.
  • a nickel layer was formed as an auxiliary metal layer on the organic release layer.
  • Example 1 zygo New View 5032 (manufactured by Zygo) was used as the measuring instrument, and Metro Pro Ver. 8.0.2, using a low frequency filter under the condition of 11 ⁇ m, the maximum height difference (Wmax) of the waviness on the deposition surface (surface opposite to the auxiliary metal layer and the release layer) of the ultrathin copper foil ) And the average distance (Peak spacing) between the surface peaks.
  • Wmax maximum height difference
  • the ultra-thin copper foil was fixed in close contact with the sample stage, and measured by selecting 6 fields of 108 ⁇ m ⁇ 144 ⁇ m within the 1 cm square range of the sample piece, and obtained from 6 measurement points. The average value of the measured values was adopted as the representative value.
  • the deposition surface (surface opposite to the release layer) of the ultrathin copper foil had a Wmax of 1.38 ⁇ m and a peak spacing of 21.37 ⁇ m.
  • the roughening process was performed with respect to the precipitation surface of the above-mentioned ultra-thin copper foil.
  • This roughening treatment was performed by the following two-stage plating.
  • a copper sulfate solution containing a copper concentration of 10.0 to 11.5 g / L and a sulfuric acid concentration of 230 to 250 g / L is used, the liquid temperature is 20 to 40 ° C., and the current density is 10 to 25 A / dm.
  • Electrodeposition was performed under the plating conditions of 2 .
  • a copper sulfate solution containing a copper concentration of 65 to 75 g / L and a sulfuric acid concentration of 230 to 250 g / L is used, and the plating temperature is 50 to 55 ° C. and the current density is 5 to 15 A / dm 2 . I electrodeposited.
  • the amount of electricity at each stage is 2.1 (Example 1) in which the ratio (Q 1 / Q 2 ) of the amount of electricity Q 1 in the first stage plating process to the amount of electricity Q 2 in the second stage plating process is 2.1 (Example 1).
  • Example 8 (Example 2), 2.4 (Example 3), 1.9 (Example 4), 1.7 (Example 5), 1.6 (Example 6) or 1.2 (Example 7) did.
  • Six types of roughened copper foils of Examples 1 to 6 were prepared by appropriately varying the conditions within the above range.
  • Rust prevention treatment comprising inorganic rust prevention treatment and chromate treatment was performed on both surfaces of the ultrathin copper foil with carrier foil after the roughening treatment.
  • inorganic rust prevention treatment using a pyrophosphate bath, potassium pyrophosphate concentration 80 g / L, zinc concentration 0.2 g / L, nickel concentration 2 g / L, liquid temperature 40 ° C., current density 0.5 A / dm 2 Zinc-nickel alloy rust prevention treatment was performed.
  • a chromate treatment a chromate layer was further formed on the zinc-nickel alloy rust preventive treatment. This chromate treatment was performed at a chromic acid concentration of 1 g / L, pH 11, a solution temperature of 25 ° C., and a current density of 1 A / dm 2 .
  • Silane coupling agent treatment The copper foil that has been subjected to the above rust prevention treatment is washed with water and then immediately treated with a silane coupling agent to adsorb the silane coupling agent on the rust prevention treatment layer of the roughened surface. It was.
  • this silane coupling agent treatment pure water is used as a solvent, a solution having a 3-aminopropyltrimethoxysilane concentration of 3 g / L is used, and this solution is sprayed onto the roughened surface by showering to perform an adsorption treatment. went. After adsorption of the silane coupling agent, moisture was finally diffused by an electric heater to obtain a copper foil with a carrier having a roughened copper foil having a thickness of 3 ⁇ m.
  • ⁇ Measurement of neck diameter a and root separation distance d> The surface profile of the roughened copper foil having a substantially spherical protrusion is made of a resin, and the surface profile of the obtained resin replica is observed with an SEM, and image analysis is performed. And the average root separation distance d were measured.
  • the specific procedure is as follows. First, a copper foil with a carrier and a prepreg (manufactured by Mitsubishi Gas Chemical Company, Inc., GHPL-830NSF, thickness 0.1 mm) were thermocompression bonded to produce a copper-clad laminate. Then, after peeling off the carrier of the copper foil with a carrier, the roughened copper foil was removed by etching.
  • the surface on which the surface profile of the cured prepreg (that is, resin replica) thus transferred was transferred was subjected to SEM observation (5000 times), and image analysis was performed using an image analyzer (LUZEX AP, manufactured by Nireco Corporation). For the region of 435 ⁇ m 2, the neck diameter a and the root separation distance d were measured, and the average values thereof (that is, the average neck diameter a ave and the average root separation distance d ave ) were obtained.
  • the specific image analysis procedure was as follows. First, an image photographed by SEM was binarized (threshold value 0 to 110) by image processing software. In order to separate the bonded particles in the binarized image thus obtained, a circular cut-out process was performed using a logical filter. Next, after removing the noise of the outline by the smoothing process, the minute particles as noise were removed by the logic filter. Thereafter, the neck diameter a and the root separation distance d were calculated for each detected particle.
  • the conditions adopted in each treatment were as follows. -Binarization processing: Threshold value 0 to 110 (The binarization threshold value that can be set in the image processing software is 0 to 255. 0 corresponds to perfect black, and 255 corresponds to complete white.) -Logical filter circular cutout: 6 (degree) -Logical particle size cut: 0.03 ⁇ m 2 or less
  • ⁇ Measurement of maximum diameter b> The surface profile of the roughened copper foil with substantially spherical protrusions was observed with an SEM (5000 magnifications) and image analysis was performed using an image analyzer (LUZEX_AP, manufactured by Nireco Corporation). For the region of 435 ⁇ m 2 , the maximum diameter b of the substantially spherical protrusions was measured, and the average value thereof (that is, average maximum diameter b ave ) was determined.
  • the specific image analysis procedure was as follows. First, an image photographed by SEM was subjected to spatial filter processing by image processing software. This spatial filter processing was performed by enhancing the contour line with a Laplacian filter after reducing the noise of the original image by averaging. Next, the image was binarized (threshold values 64 to 165). The contour line of the binarized image thus obtained was expanded so that one approximately spherical protrusion was recognized as one particle. And in order to isolate
  • threshold value 64 to 145 (the binarization threshold value that can be set in the image processing software is 0 to 255. 0 corresponds to perfect black, and 255 corresponds to complete white.)
  • Example 1 ⁇ Measurement of tilt angle of substantially spherical particles>
  • the roughened copper foil was pressed and bonded to a prepreg (manufactured by Mitsubishi Gas Chemical Company, Inc., GHPL-830NSF, thickness 0.1 mm) on the roughened surface side.
  • a cross section is produced from the surface of the roughened copper foil by CP (cross section polisher) processing, the cross section is observed with an SEM, and the reference length is 10 ⁇ m in the foil surface direction (direction perpendicular to the thickness direction).
  • the inclination angle of each of the substantially spherical protrusions was measured. Specifically, first, as shown in FIG.
  • the reference line L B in the low magnification can be drawn as a straight line.
  • a copper-clad laminate was produced using an ultrathin copper foil with a carrier.
  • an ultrathin copper foil with a carrier is laminated on the surface of the inner layer substrate via a prepreg (manufactured by Mitsubishi Gas Chemical Co., Ltd., GHPL-830NSF, thickness 0.1 mm), and a pressure of 4.0 MPa, After thermocompression bonding at a temperature of 220 ° C. for 90 minutes, the carrier foil was peeled off to produce a copper clad laminate.
  • ⁇ Plating circuit adhesion (peel strength)> A dry film was laminated to the laminate for SAP evaluation, and exposure and development were performed. After depositing a copper layer having a thickness of 19 ⁇ m by pattern plating on the laminate masked with the developed dry film, the dry film was peeled off. The electroless copper plating exposed by the sulfuric acid / hydrogen peroxide etching solution was removed, and a sample for measuring peel strength having a height of 20 ⁇ m and a width of 10 mm was prepared. In accordance with JIS C 6481 (1996), the peel strength when the copper foil was peeled from the sample for evaluation was measured.
  • ⁇ Etching property> The laminate for SAP evaluation was etched by 0.1 ⁇ m with a sulfuric acid / hydrogen peroxide etching solution, and the amount (depth) until copper on the surface was completely removed was measured. The measuring method was confirmed with an optical microscope (500 times). More specifically, each time 0.1 ⁇ m etching was performed, the operation of checking with or without copper was repeated with an optical microscope, and the value ( ⁇ m) obtained by (number of etchings) ⁇ 0.1 ⁇ m was used as an index of etching property.
  • ⁇ Dry film resolution (minimum L / S)>
  • a dry film having a thickness of 25 ⁇ m was laminated on the surface of the laminate for SAP evaluation, and exposure and development were performed using a mask in which a line / space (L / S) pattern of 2 ⁇ m / 2 ⁇ m to 15 ⁇ m / 15 ⁇ m was formed. .
  • the exposure amount at this time was set to 125 mJ.
  • the surface of the sample after development was observed with an optical microscope (500 times), and the smallest (that is, the finest) L / S in the L / S that could be developed without any problem was adopted as an index for the resolution of the dry film.
  • L / S 15 ⁇ m / 15 ⁇ m to 10 ⁇ m / 10 ⁇ m.
  • Example 7 (Comparison) Other than the ratio (Q 1 / Q 2 ) of the amount of electricity Q 1 in the first step plating step to the amount of electricity Q 2 in the second step plating step (Q 1 / Q 2 ) in the roughening treatment.
  • Example 8 Comparable Roughened copper with carrier in the same manner as described with respect to Examples 1 to 6 except that the roughening treatment was performed according to the following procedure according to Example 2 of Patent Document 1 (Japanese Patent Laid-Open No. 2013-199082). Preparation and evaluation of foil were performed.
  • Roughening treatment Roughening was performed by performing roughening plating using a plating solution having the following liquid composition. At this time, the ratio of the limiting current density during the formation of roughened particles was 3.10, and the electroplating temperature was 50 ° C.
  • Example 9 A roughened copper foil with a carrier was prepared and evaluated in the same manner as in Example 1 except that an electrode whose surface was polished by adjusting the surface with a # 2000 buff was used as the rotating cathode.
  • Wmax was 1.00 micrometer
  • Peak spacing was 20.28 micrometers.
  • Example 10 Preparation and evaluation of the roughened copper foil with carrier were performed in the same manner as in Example 1 except that the organic release layer was formed on the deposition surface side of the carrier copper foil.
  • the precipitation surface of the ultrathin copper foil before the roughening treatment had a Wmax of 0.71 ⁇ m and a peak spacing of 52.13 ⁇ m.
  • Example 1 As shown in Table 1, all of Examples 1 to 6 were good in plating circuit adhesion, etching property, and dry film resolution.
  • Example 7 which is out of the scope of the present invention because the a ave / b ave ratio is low, the adhesion of the plating circuit is poor and the dry film resolution is also poor. there were.
  • Example 8 which is outside the scope of the present invention because of the high average height c ave , the etching property was inferior.
  • Example 9 in which the ratio of the highly inclined substantially spherical protrusions is in the range of 30 to 60% is superior to Examples 1 and 10 outside the above range in terms of both dry film resolution and plating circuit adhesion. It was a thing.

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Abstract

Provided is a roughened copper foil which, when used in the SAP method, can endow a laminate with a surface profile excellent not only in plated circuit adhesion but also in etching performance for electroless copper plating and dry film resolution. This roughened copper foil has a roughened surface on at least one side, wherein: the roughened surface is provided with a plurality of substantially spherical projections composed of copper particles; the mean height of the substantially spherical projections is 2.60 μm or less; and the ratio bave/aave of the mean maximum diameter bave of the substantially spherical projections to the mean neck diameter aave of the substantially spherical projections is 1.2 or higher.

Description

粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board
　本発明は、粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板に関するものである。 The present invention relates to a roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed wiring board.
　近年、回路の微細化に適したプリント配線板の製造工法として、ＳＡＰ（セミ・アディティブ・プロセス）法が広く採用されている。ＳＡＰ法は、極めて微細な回路を形成するのに適した手法であり、その一例としてキャリア付粗化処理銅箔を用いて行われている。例えば、図１及び２に示されるように、粗化表面を備えた極薄銅箔１０を、下地基材１１ａに下層回路１１ｂを備えた絶縁樹脂基板１１上にプリプレグ１２とプライマー層１３を用いてプレスして密着させ（工程（ａ））、キャリア箔（図示せず）を引き剥がした後、必要に応じてレーザー穿孔によりビアホール１４を形成する（工程（ｂ））。次いで、極薄銅箔をエッチングにより除去して、粗化表面プロファイルが付与されたプライマー層１３を露出させる（工程（ｃ））。この粗化表面に無電解銅めっき１５を施した（工程（ｄ））後に、ドライフィルム１６を用いた露光及び現像により所定のパターンでマスキングし（工程（ｅ））、電気銅めっき１７を施す（工程（ｆ））。ドライフィルム１６を除去して配線部分１７ａを形成した（工程（ｇ））後、隣り合う配線部分１７ａ，１７ａ間の不要な無電解銅めっき１５をエッチングにより除去して（工程（ｈ））、所定のパターンで形成された配線１８を得る。 In recent years, the SAP (semi-additive process) method has been widely adopted as a method for manufacturing a printed wiring board suitable for circuit miniaturization. The SAP method is a method suitable for forming an extremely fine circuit, and as an example, it is performed using a roughened copper foil with a carrier. For example, as shown in FIGS. 1 and 2, an ultrathin copper foil 10 having a roughened surface is used, and a prepreg 12 and a primer layer 13 are used on an insulating resin substrate 11 having a base substrate 11a and a lower layer circuit 11b. Then, the carrier foil (not shown) is peeled off, and then a via hole 14 is formed by laser drilling as necessary (step (b)). Next, the ultrathin copper foil is removed by etching to expose the primer layer 13 provided with the roughened surface profile (step (c)). After the electroless copper plating 15 is applied to the roughened surface (step (d)), it is masked with a predetermined pattern by exposure and development using the dry film 16 (step (e)), and the electrolytic copper plating 17 is applied. (Step (f)). After removing the dry film 16 to form the wiring portion 17a (step (g)), unnecessary electroless copper plating 15 between the adjacent wiring portions 17a and 17a is removed by etching (step (h)). A wiring 18 formed in a predetermined pattern is obtained.
　このように粗化処理銅箔を用いたＳＡＰ法は、粗化処理銅箔自体はレーザー穿孔後にエッチングにより除去されることになる（工程（ｃ））。そして、粗化処理銅箔が除去された積層体表面には粗化処理銅箔の粗化処理面の凹凸形状が転写されているので、その後の工程において絶縁層（例えばプライマー層１３又はそれが無い場合にはプリプレグ１２）とめっき回路（例えば配線１８）との密着性を確保することができる。なお、工程（ｃ）に相当する銅箔除去工程を行わないＭＳＡＰ（モディファイド・セミ・アディティブ・プロセス）法も広く採用されているが、現像後のエッチング工程（工程（ｈ）に相当）で銅箔層と無電解銅めっき層の２つの層をエッチングで除去しなければならないため、無電解銅めっき層１層のエッチング除去で済むＳＡＰ法よりもエッチングを深く行う必要がある。そのため、より多くのエッチング量を勘案して回路スペースを幾分狭くする必要が生じることから、ＭＳＡＰ法は微細回路形成性においてＳＡＰ法よりは幾分劣るといえる。すなわち、更なる微細な回路形成という目的においてはＳＡＰ法の方が有利である。 Thus, in the SAP method using the roughened copper foil, the roughened copper foil itself is removed by etching after laser drilling (step (c)). And since the uneven | corrugated shape of the roughening process surface of roughening process copper foil is transcribe | transferred to the laminated body surface from which the roughening process copper foil was removed, an insulating layer (for example, primer layer 13 or it is the same) in the subsequent process. In the absence, adhesion between the prepreg 12) and the plating circuit (for example, the wiring 18) can be secured. Note that the MSAP (Modified Semi-Additive Process) method that does not perform the copper foil removal step corresponding to step (c) is also widely used, but copper is used in the etching step (corresponding to step (h)) after development. Since the two layers of the foil layer and the electroless copper plating layer must be removed by etching, it is necessary to perform the etching deeper than the SAP method which only requires etching removal of one electroless copper plating layer. Therefore, it is necessary to make the circuit space somewhat narrower in consideration of a larger amount of etching, so that the MSAP method can be said to be somewhat inferior to the SAP method in terms of fine circuit formation. That is, the SAP method is more advantageous for the purpose of forming a finer circuit.
　一方、粗化粒子の形状を制御したキャリア付き粗化処理銅箔が知られている。例えば、特許文献１（特開２０１３－１９９０８２号公報）には、極薄銅層表面に、粒子長さの１０％の位置の粒子根元の平均直径Ｄ１が０．２μｍ～１．０μｍであり、粒子長さＬ１と粒子根元の平均直径Ｄ１との比Ｌ１／Ｄ１が１５以下の粗化処理層を有することを特徴とするキャリア付銅箔が開示されている。この特許文献１では、極薄銅層表面に、粒子長さの５０％の位置の粒子中央の平均直径Ｄ２と粒子根元の平均直径Ｄ１の比Ｄ２／Ｄ１が１～４であり、かつ、粒子中央の平均直径Ｄ２と粒子長さの９０％の位置の粒子先端Ｄ３の比Ｄ２／Ｄ３が０．８～１．０であることが好ましいとされている。また、特許文献１の実施例には粗化粒子の長さが２．６８μｍ以上であることが開示されている。 Meanwhile, a roughened copper foil with a carrier in which the shape of the roughened particles is controlled is known. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2013-199082), the average diameter D1 of the particle root at a position of 10% of the particle length is 0.2 μm to 1.0 μm on the surface of the ultrathin copper layer, A copper foil with a carrier characterized by having a roughened layer having a ratio L1 / D1 of the particle length L1 and the average diameter D1 of the particle root of 15 or less is disclosed. In Patent Document 1, the ratio D2 / D1 of the average diameter D2 of the center of the particle at the position of 50% of the particle length to the average diameter D1 of the particle root is 1 to 4 on the surface of the ultrathin copper layer, and the particle The ratio D2 / D3 of the average diameter D2 at the center and the particle tip D3 at a position of 90% of the particle length is preferably 0.8 to 1.0. Moreover, it is disclosed by the Example of patent document 1 that the length of a roughening particle | grain is 2.68 micrometers or more.
特開２０１３－１９９０８２号公報JP 2013-199082 A
　前述のように粗化処理銅箔を用いたＳＡＰ法は、粗化処理銅箔自体はレーザー穿孔後にエッチングにより除去されることになる（工程（ｃ））。そして、粗化処理銅箔が除去された積層体表面には粗化処理銅箔の粗化処理面の凹凸形状が転写されているので、その後の工程において絶縁層（例えばプライマー層１３又はそれが無い場合にはプリプレグ１２）とめっき回路（例えば配線１８）との密着性を確保することができる。しかしながら、めっき回路との密着性を上げるのに適した表面プロファイルは、概して粗い凹凸となる傾向があるため、工程（ｈ）において無電解銅めっきに対するエッチング性が低下しやすい。すなわち、無電解銅めっきが粗い凹凸に食い込んでいる分、残留銅を無くすためにより多くのエッチングを要してしまう。 As described above, in the SAP method using the roughened copper foil, the roughened copper foil itself is removed by etching after laser drilling (step (c)). And since the uneven | corrugated shape of the roughening process surface of roughening process copper foil is transcribe | transferred to the laminated body surface from which the roughening process copper foil was removed, an insulating layer (for example, primer layer 13 or it is the same) in the subsequent process. In the absence, adhesion between the prepreg 12) and the plating circuit (for example, the wiring 18) can be secured. However, since the surface profile suitable for improving the adhesion to the plating circuit tends to be rough unevenness in general, the etching property for the electroless copper plating tends to be lowered in the step (h). That is, as the electroless copper plating bites into rough irregularities, more etching is required to eliminate residual copper.
　本発明者らは、今般、銅粒子からなる複数の略球状突起を備えた粗化処理面を有する粗化処理銅箔において、略球状突起の平均高さを２．６０μｍ以下とし、かつ、略球状突起の平均ネック径ａａｖｅに対する略球状突起の平均最大径ｂａｖｅの比ｂａｖｅ／ａａｖｅを１．２以上とすることにより、ＳＡＰ法に用いた場合に、優れためっき回路密着性のみならず、無電解銅めっきに対するエッチング性にも優れた表面プロファイルを積層体に付与可能な、粗化処理銅箔を提供できるとの知見を得た。また、上記粗化処理銅箔を用いることで、ＳＡＰ法におけるドライフィルム現像工程において、極めて微細なドライフィルム解像性を実現できるとの知見も得た。 In the roughened copper foil having a roughened surface provided with a plurality of substantially spherical protrusions made of copper particles, the present inventors recently set the average height of the substantially spherical protrusions to 2.60 μm or less, and substantially When the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusions to the average neck diameter a ave of the spherical protrusions is 1.2 or more, only excellent plating circuit adhesion is obtained when used in the SAP method. In addition, they obtained knowledge that a roughened copper foil can be provided that can impart a surface profile excellent in etching property to electroless copper plating to the laminate. Moreover, the knowledge that extremely fine dry film resolution was realizable was also acquired in the dry film image development process in SAP method by using the said roughening process copper foil.
　したがって、本発明の目的は、ＳＡＰ法に用いた場合に、めっき回路密着性のみならず、無電解銅めっきに対するエッチング性、及びドライフィルム解像性にも優れた表面プロファイルを積層体に付与可能な、粗化処理銅箔を提供することにある。また、本発明の他の目的は、そのような粗化処理銅箔を備えたキャリア付銅箔を提供することにある。 Therefore, the object of the present invention is to provide a laminate with a surface profile that is excellent not only in plating circuit adhesion but also in etching performance for electroless copper plating and dry film resolution when used in the SAP method. Another object is to provide a roughened copper foil. Moreover, the other object of this invention is to provide the copper foil with a carrier provided with such a roughening process copper foil.
　本発明の一態様によれば、少なくとも一方の側に粗化処理面を有する粗化処理銅箔であって、前記粗化処理面が銅粒子からなる複数の略球状突起を備えてなり、前記略球状突起の平均高さが２．６０μｍ以下であり、かつ、前記略球状突起の平均ネック径ａａｖｅに対する前記略球状突起の平均最大径ｂａｖｅの比ｂａｖｅ／ａａｖｅが１．２以上である、粗化処理銅箔が提供される。 According to one aspect of the present invention, a roughened copper foil having a roughened surface on at least one side, the roughened surface comprising a plurality of substantially spherical protrusions made of copper particles, The average height of the substantially spherical protrusions is 2.60 μm or less, and the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusions to the average neck diameter a ave of the substantially spherical protrusions is 1.2 or more. A roughened copper foil is provided.
　本発明の他の一態様によれば、キャリア箔と、該キャリア箔上に設けられた剥離層と、該剥離層上に前記粗化処理面を外側にして設けられた上記態様の粗化処理銅箔とを備えた、キャリア付銅箔が提供される。 According to another aspect of the present invention, a carrier foil, a release layer provided on the carrier foil, and the roughening treatment of the above aspect provided on the release layer with the roughening treatment surface facing outward. Provided is a copper foil with a carrier comprising a copper foil.
　本発明の他の一態様によれば、上記態様の粗化処理銅箔又は上記態様のキャリア付銅箔を用いて得られた銅張積層板が提供される。 According to another aspect of the present invention, there is provided a copper clad laminate obtained using the roughened copper foil of the above aspect or the copper foil with a carrier of the above aspect.
　本発明の他の一態様によれば、上記態様の粗化処理銅箔又は上記態様のキャリア付銅箔を用いて得られたプリント配線板が提供される。 According to another aspect of the present invention, there is provided a printed wiring board obtained using the roughened copper foil of the above aspect or the copper foil with a carrier of the above aspect.
ＳＡＰ法を説明するための工程流れ図であり、前半の工程（工程（ａ）～（ｄ））を示す図である。It is a process flow chart for explaining the SAP method, and is a diagram showing the first half steps (steps (a) to (d)). ＳＡＰ法を説明するための工程流れ図であり、後半の工程（工程（ｅ）～（ｈ））を示す図である。It is a process flow chart for explaining the SAP method, and shows the latter half of the process (processes (e) to (h)). 本発明の粗化処理銅箔における略球状粒子を示す模式断面図である。It is a schematic cross section which shows the substantially spherical particle in the roughening copper foil of this invention. 高傾斜略球状粒子を含むうねりのある表面を有する粗化処理銅箔の模式断面図である。It is a schematic cross section of the roughening copper foil which has the surface with the wave | undulation containing a high inclination substantially spherical particle. 図４Ａにおいて枠で囲った部分の拡大断面図であり、高傾斜略球状粒子の定義を説明するための図である。FIG. 4B is an enlarged cross-sectional view of a portion surrounded by a frame in FIG. 4A, for explaining the definition of highly inclined substantially spherical particles. ＳＡＰ法において解像が良好に行われたドライフィルムパターンの一例を示す写真である。It is a photograph which shows an example of the dry film pattern in which resolution was performed favorably in the SAP method. ＳＡＰ法において解像が良好に行われなかったドライフィルムパターンの一例を示す写真である。It is a photograph which shows an example of the dry film pattern in which resolution was not performed favorably in SAP method.
　定義
　本発明を特定するために用いられる用語ないしパラメータの定義を以下に示す。 Definitions The definitions of terms and parameters used to specify the present invention are shown below.
　本明細書において「略球状突起」とは、略球状の丸みを帯びた概形を有する突起であり、針状、柱状、細長い形状等の異方形状の突起ないし粒子とは区別されるものである。図３２に模式的に示されるように、略球状突起３２は、銅箔表面３０と連結されるくびれた根元部分３４で銅箔表面３０と連結しているため、完全なる球体にはなり得ないが、根元部分３２以外の部分が概ね球状であればよい。したがって、略球状突起は、略球状の丸みを帯びた概形が保持されているかぎり、多少の凹凸や変形等の存在は許容される。なお、上記突起を単に球状突起と称してもよいが、上述のとおり完全なる球体にはなり得ないため、上述した略球状突起を意味するものとして解されるべきである。 In the present specification, the “substantially spherical protrusion” is a protrusion having a substantially spherical round shape, and is distinguished from an anisotropic shape protrusion or particle such as a needle shape, a columnar shape, and an elongated shape. is there. As schematically shown in FIG. 32, the substantially spherical protrusion 32 is connected to the copper foil surface 30 by the constricted root portion 34 connected to the copper foil surface 30, and thus cannot be a perfect sphere. However, parts other than the root part 32 should just be substantially spherical. Therefore, as long as the substantially spherical protrusion has a substantially spherical round shape, the presence of some unevenness or deformation is allowed. In addition, although the said protrusion may only be called a spherical protrusion, since it cannot become a perfect sphere as mentioned above, it should be understood as meaning the substantially spherical protrusion mentioned above.
　本明細書において「略球状突起のネック径ａ」は、図３に模式的に示されるように、略球状突起３２において銅箔表面３０と連結されるくびれた根元部分３４における径、すなわち対向するくびれ間の最短距離を意味する。また、「略球状突起の平均ネック径ａａｖｅ」は、粗化処理銅箔の略球状突起を備えた表面プロファイルのレプリカ形状を樹脂で作製し、得られた樹脂製レプリカの表面（例えば４３５μｍ２の領域）において測定された、Ｎ個の略球状突起のネック径ａ１、ａ２、・・・、ａＮの平均値（すなわち（ａ１＋ａ２＋・・・＋ａＮ）／Ｎの値）である。樹脂製レプリカの作製については本明細書の実施例に記載される諸条件に従って行えばよい。 In the present specification, the “neck diameter a of the substantially spherical protrusion” is the diameter of the narrow base portion 34 connected to the copper foil surface 30 in the substantially spherical protrusion 32, as schematically shown in FIG. It means the shortest distance between the constrictions. In addition, the “average neck diameter a ave of the substantially spherical protrusion” is a surface profile of a rough replica-processed copper foil having a substantially spherical protrusion made of resin, and the surface of the obtained resin replica (for example, 435 μm 2). ), The average value of the neck diameters a 1 , a 2 ,..., A N of N substantially spherical protrusions (that is, the value of (a 1 + a 2 +... + A N ) / N). ). The production of the resin replica may be performed in accordance with various conditions described in the examples of the present specification.
　本明細書において「略球状突起の最大径ｂ」は、図３に模式的に示されるように、銅箔表面３０と平行方向に測定される略球状突起３２の最大径である。また、「略球状突起の平均最大径ｂａｖｅ」は、粗化処理銅箔の表面（例えば４３５μｍ２の領域）において測定された、Ｎ個の略球状突起の最大径ｂ１、ｂ２、・・・、ｂＮの平均値（すなわち（ｂ１＋ｂ２＋・・・＋ｂＮ）／Ｎの値）である。 In this specification, the “maximum diameter b of the substantially spherical protrusion” is the maximum diameter of the substantially spherical protrusion 32 measured in a direction parallel to the copper foil surface 30 as schematically shown in FIG. Further, the “average maximum diameter b ave of approximately spherical protrusions” is the maximum diameter b 1 , b 2 ,... Of N approximately spherical protrusions measured on the surface of the roughened copper foil (for example, a region of 435 μm 2 ). .., an average value of b N (that is, a value of (b 1 + b 2 +... + B N ) / N).
　本明細書において「略球状突起の高さｃ」は、図３に模式的に示されるように、銅箔表面３０に対して垂直方向に測定される略球状突起３２の根元部分３４を基準とした高さである。また、「略球状突起の平均高さｃａｖｅ」は、粗化処理銅箔の断面プロファイル（例えば２５μｍの基準長さ）において測定された、Ｎ個の略球状突起の高さｃ１、ｃ２、・・・、ｃＮの平均値（すなわち（ｃ１＋ｃ２＋・・・＋ｃＮ）／Ｎの値）である。 In this specification, the “substantially spherical protrusion height c” is based on the root portion 34 of the substantially spherical protrusion 32 measured in the direction perpendicular to the copper foil surface 30 as schematically shown in FIG. Height. The “average height c ave of substantially spherical protrusions” is the heights c 1 and c 2 of N substantially spherical protrusions measured in the cross-sectional profile of the roughened copper foil (for example, a reference length of 25 μm). ,..., C N is an average value (that is, a value of (c 1 + c 2 +... + C N ) / N).
　本明細書において「略球状突起の根元離間距離ｄ」とは、図３に模式的に示されるように、隣り合う略粒状粒子３０の根元部分レベルでの離間距離、すなわち略粒状粒子３０の根元部分３４のくびれと隣りの略球状粒子３２の根元部分３４のくびれとの最短距離である。また、「略球状突起の平均根元離間距離ｄａｖｅ」とは、粗化処理銅箔の略球状突起を備えた表面プロファイルのレプリカ形状を樹脂で作製し、得られた樹脂製レプリカ表面（例えば４３５μｍ２）において測定された、Ｎ個の略球状突起の間の根元離間距離ｄ１、ｄ２、・・・、ｄＮ－１の平均値（すなわち（ｄ１＋ｄ２＋・・・＋ｄＮ－１）／（Ｎ－１）の値）である。樹脂製レプリカの作製については本明細書の実施例に記載される諸条件に従って行えばよい。 In this specification, the “separate root d of substantially spherical protrusions” means a separation distance at the level of the root of adjacent substantially granular particles 30, that is, the roots of substantially granular particles 30, as schematically shown in FIG. 3. This is the shortest distance between the constriction of the portion 34 and the constriction of the root portion 34 of the adjacent substantially spherical particle 32. Further, the “average root separation distance d ave of approximately spherical protrusions” means that a replica shape of a surface profile provided with approximately spherical protrusions of a roughened copper foil is made of a resin, and a resin replica surface obtained (for example, 435 μm) 2 ), the average value of root separation distances d 1 , d 2 ,..., D N−1 between N substantially spherical projections (ie, (d 1 + d 2 +... + D N− 1 ) / (N-1)). The production of the resin replica may be performed in accordance with various conditions described in the examples of the present specification.
　本明細書において「高傾斜略球状突起」とは、図４Ａ及び４Ｂに模式的に示されるように、略球状突起３２のうち、略球状突起３２の根元境界線（根元部分３４の境界線）の中点Ｃと略球状突起３２の頂点Ｖを結んだ線ＬＶＣと、粗化処理銅箔の粗化処理面と反対側の面と平行な基準線ＬＢとがなす鋭角θが８５°以下であるものを指す。また、「略球状突起の総数に占める高傾斜略球状突起の割合」とは、粗化処理銅箔の断面プロファイル（例えば１０μｍの基準長さ）において測定された、略球状突起の総数ＮＡに対する高傾斜略球状突起の数ＮＨの割合、すなわち１００×ＮＨ／ＮＡ（％）である。 In the present specification, the “highly inclined substantially spherical protrusion” means a root boundary line of the substantially spherical protrusion 32 (boundary line of the root portion 34) among the substantially spherical protrusions 32 as schematically shown in FIGS. 4A and 4B. the line L VC connecting the midpoint C and the vertex V of substantially spherical projections 32, acute θ is 85 ° forming roughened surface of the roughened copper foil and the opposite face parallel to the reference line L B is Refers to the following: In addition, the "ratio of the high-tilt substantially spherical protrusions occupying the total number of substantially spherical projections" were measured in the cross-section profile of the roughened copper foil (e.g. 10μm standard length), to the total number N A substantially spherical projection The ratio of the number of highly inclined substantially spherical protrusions N H , that is, 100 × N H / N A (%).
　略球状突起のネック径ａ、最大径ｂ及び根元離間距離ｄは、ＳＥＭ観察により取得した画像を市販の画像解析装置とソフトウェアを用いて二値化処理等の画像処理を施すことにより、測定することができる。そのような画像解析装置の例としては、株式会社ニレコ製のＬＵＺＥＸ　ＡＰが挙げられる。画像処理については本明細書の実施例に記載される諸条件に従って行えばよい。 The neck diameter “a”, the maximum diameter “b”, and the root separation distance “d” of the substantially spherical protrusion are measured by subjecting an image acquired by SEM observation to image processing such as binarization processing using a commercially available image analysis device and software. be able to. As an example of such an image analysis apparatus, there is LUZEX AP manufactured by Nireco Corporation. The image processing may be performed according to various conditions described in the examples of the present specification.
　本明細書において「表面ピーク間の平均距離（Ｐｅａｋ　ｓｐａｃｉｎｇ）」とは、三次元表面構造解析顕微鏡を用いて得られる試料表面の凹凸に関する情報から、高周波のうねり成分を除去したのち、ピークに係る波形データをフィルタリングして抽出したデータにおける、ピーク間の平均距離をいう。 In this specification, the “average distance between surface peaks (Peak spacing)” refers to a peak after removing a high-frequency swell component from information on unevenness of a sample surface obtained using a three-dimensional surface structure analysis microscope. The average distance between peaks in data extracted by filtering waveform data.
　本明細書において「うねりの最大高低差（Ｗｍａｘ）」とは、三次元表面構造解析顕微鏡を用いて得られる試料表面の凹凸に係る情報から、うねりに係る波形データをフィルタを用いて抽出したときの波形データの高低差の最大値（波形の最大ピーク高さと最大バレー深さの和）をいう。 In this specification, “maximum waviness difference (Wmax)” means that waveform data relating to waviness is extracted from information relating to unevenness of the sample surface obtained using a three-dimensional surface structure analysis microscope using a filter. The maximum value of the height difference of the waveform data (the sum of the maximum peak height of the waveform and the maximum valley depth).
　表面ピーク間の平均距離（Ｐｅａｋ　ｓｐａｃｉｎｇ）及びうねりの最大高低差（Ｗｍａｘ）は、いずれも、市販の三次元表面構造解析顕微鏡（例えば、ｚｙｇｏ　Ｎｅｗ　Ｖｉｅｗ　５０３２（Ｚｙｇｏ社製））と市販の解析ソフト（例えばＭｅｔｒｏ　Ｐｒｏ　Ｖｅｒ．８．０．２）を用い、低周波フィルタを１１μｍの条件に設定して測定することができる。このとき、箔の被測定面を試料台に密着させて固定し、試料片の１ｃｍ角の範囲内の中で１０８μｍ×１４４μｍの視野を６点選択して測定し、６箇所の測定点から得られた測定値の平均値を代表値として採用するのが好ましい。 The average distance between peak peaks (Peak spacing) and the maximum difference in waviness (Wmax) are both commercially available three-dimensional surface structure analysis microscopes (for example, zygo New View 5032 (manufactured by Zygo)) and commercially available analysis software. (For example, Metro Pro Ver. 8.0.2) can be used with a low frequency filter set to 11 μm for measurement. At this time, the surface to be measured of the foil is fixed in close contact with the sample stage, and 6 fields of 108 μm × 144 μm are selected and measured within the 1 cm square range of the sample piece, and obtained from the 6 measurement points. The average value of the measured values obtained is preferably adopted as the representative value.
　本明細書において、キャリア箔の「電極面」とはキャリア箔作製時に陰極と接していた側の面を指す。 In this specification, the “electrode surface” of the carrier foil refers to the surface on the side in contact with the cathode when the carrier foil was produced.
　本明細書において、キャリア箔の「析出面」とはキャリア箔作製時に電解銅が析出されていく側の面、すなわち陰極と接していない側の面を指す。 In this specification, the “deposition surface” of the carrier foil refers to the surface on the side where electrolytic copper is deposited when the carrier foil is produced, that is, the surface not in contact with the cathode.
　粗化処理銅箔
　本発明による銅箔は粗化処理銅箔である。この粗化処理銅箔は、少なくとも一方の側に粗化処理面を有する。粗化処理面は、図３に模式的に示されるように、銅粒子からなる複数の略球状突起３２を備えてなる。これら略球状突起３２の平均高さｃａｖｅは２．６０μｍ以下である。また、略球状突起の平均ネック径ａａｖｅに対する略球状突起の平均最大径ｂａｖｅの比ｂａｖｅ／ａａｖｅが１．２以上である。このように、銅粒子からなる複数の略球状突起を備えた粗化処理面を有する粗化処理銅箔において、略球状突起の平均高さｃａｖｅを２．６０μｍ以下とし、かつ、略球状突起の平均ネック径ａａｖｅに対する略球状突起の平均最大径ｂａｖｅの比ｂａｖｅ／ａａｖｅを１．２以上とすることにより、ＳＡＰ法に用いた場合に、優れためっき回路密着性のみならず、無電解銅めっきに対するエッチング性にも優れた表面プロファイルを積層体に付与可能な、粗化処理銅箔を提供することができる。また、上記粗化処理銅箔を用いることで、ＳＡＰ法におけるドライフィルム現像工程において、極めて微細なドライフィルム解像性を実現することができる。 Roughened copper foil The copper foil according to the present invention is a roughened copper foil. This roughened copper foil has a roughened surface on at least one side. The roughened surface is provided with a plurality of substantially spherical protrusions 32 made of copper particles, as schematically shown in FIG. The average height c ave of these substantially spherical protrusions 32 is 2.60 μm or less. Further, the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusion to the average neck diameter a ave of the substantially spherical protrusion is 1.2 or more. Thus, in the roughened copper foil having a roughened surface provided with a plurality of substantially spherical protrusions made of copper particles, the average height c ave of the substantially spherical protrusions is 2.60 μm or less, and the substantially spherical protrusions When the ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusion to the average neck diameter a ave is 1.2 or more, not only excellent plating circuit adhesion but also when used in the SAP method It is possible to provide a roughened copper foil capable of imparting a surface profile excellent in etching property to electroless copper plating to a laminate. In addition, by using the roughened copper foil, extremely fine dry film resolution can be realized in the dry film development step in the SAP method.
　めっき回路密着性と、無電解銅めっきに対するエッチング性は本来的には両立し難いものであるが、本発明によれば予想外にもそれらが両立可能となる。すなわち、前述したように、めっき回路との密着性を上げるのに適した表面プロファイルは、概して粗い凹凸となる傾向があるため、図２の工程（ｈ）において無電解銅めっきのエッチング性が低下しやすい。すなわち、無電解銅めっきが粗い凹凸に食い込んでいる分、残留銅を無くすためにより多くのエッチングを要してしまう。しかしながら、本発明の粗化処理銅箔によればそのようなエッチング量の低減を実現しながら、優れためっき回路密着性を確保できる。これは、略球状突起の平均高さｃａｖｅを２．６０μｍ以下と低めに設定することで上記粗い凹凸に起因する上記エッチング性の低下を回避する一方、略球状突起の平均高さｃａｖｅの低下に伴い懸念されるめっき回路との密着性を上記比ｂａｖｅ／ａａｖｅを１．２以上とすることで向上できるためと考えられる。これは、図３から理解されるように、上記比ｂａｖｅ／ａａｖｅが大きいほど、略球状突起３２が銅箔表面３０と連結される根元部分３４においてより大きくくびれていることになるため、かかる形状が転写された絶縁層（例えばプライマー層１３又はそれが無い場合にはプリプレグ１２）において、略球状突起３２に由来するくびれ形状に基づくアンカー効果を発揮させることができ、優れためっき回路との密着性を実現可能にするものと考えられる。そして、そのように優れた密着性と無電解銅めっきに対する優れたエッチング性を両立できたことによって、ＳＡＰ法におけるドライフィルム現像工程において、極めて微細なドライフィルム解像性を実現できるものと考えられる。したがって、本発明の粗化処理銅箔は、セミアディティブ法（ＳＡＰ）によるプリント配線板の作製に用いられるのが好ましい。別の表現をすれば、本発明の粗化処理銅箔は、プリント配線板用の絶縁樹脂層に凹凸形状を転写するために用いられるのが好ましいともいえる。 Plating circuit adhesion and etchability for electroless copper plating are inherently difficult to achieve at the same time, but according to the present invention, they can both be achieved unexpectedly. That is, as described above, since the surface profile suitable for improving the adhesion to the plating circuit tends to be rough unevenness, the etching property of the electroless copper plating is lowered in the step (h) of FIG. It's easy to do. That is, as the electroless copper plating bites into rough irregularities, more etching is required to eliminate residual copper. However, according to the roughened copper foil of the present invention, excellent plating circuit adhesion can be secured while realizing such a reduction in the etching amount. This is because the average height c ave of the substantially spherical protrusions is set to be as low as 2.60 μm or less, thereby avoiding the above-described decrease in etching property due to the rough unevenness, while the average height c ave of the substantially spherical protrusions is reduced. This is considered to be because the adhesiveness with the plating circuit, which is concerned with the decrease, can be improved by setting the ratio b ave / a ave to 1.2 or more. As can be understood from FIG. 3, the larger the ratio b ave / a ave , the more the substantially spherical protrusion 32 is constricted at the root portion 34 connected to the copper foil surface 30. In an insulating layer to which such a shape is transferred (for example, the primer layer 13 or the prepreg 12 when there is no such layer), an anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be exhibited, and an excellent plating circuit and It is considered that the adhesion of the material can be realized. And it is thought that very fine dry film resolution can be realized in the dry film development process in the SAP method by satisfying both such excellent adhesion and excellent etching property for electroless copper plating. . Therefore, it is preferable that the roughened copper foil of this invention is used for preparation of the printed wiring board by a semi-additive method (SAP). In other words, it can be said that the roughened copper foil of the present invention is preferably used for transferring the concavo-convex shape to the insulating resin layer for the printed wiring board.
　本発明の粗化処理銅箔は、少なくとも一方の側に粗化処理面を有する。すなわち、粗化処理銅箔は両側に粗化処理面を有するものであってもよいし、一方の側にのみ粗化処理面を有するものであってもよい。両側に粗化処理面を有する場合は、ＳＡＰ法に用いた場合にレーザー照射側の面（絶縁樹脂に密着させる面と反対側の面）も粗化されていることになるので、レーザー吸収性が高まる結果、レーザー穿孔性をも向上させることができる。 The roughened copper foil of the present invention has a roughened surface on at least one side. That is, the roughened copper foil may have a roughened surface on both sides, or may have a roughened surface only on one side. When both sides have roughened surfaces, the surface on the laser irradiation side (the surface opposite to the surface to be in close contact with the insulating resin) is also roughened when used in the SAP method. As a result, the laser drillability can be improved.
　粗化処理面は、複数の略球状突起３２を備えてなり、これら複数の略球状突起３２は銅粒子からなる。すなわち、個々の略球状突起３２は基本的に１個の銅粒子で構成される。銅粒子は金属銅からなるものであってもよいし、銅合金からなるものであってもよい。しかしながら、銅粒子が銅合金の場合、銅エッチング液に対する溶解性が低下したり、或いは銅エッチング液への合金成分混入によりエッチング液の寿命が低下したりすることがあるため、銅粒子は金属銅からなることが好ましい。 The roughened surface is provided with a plurality of substantially spherical protrusions 32, and the plurality of substantially spherical protrusions 32 are made of copper particles. That is, each substantially spherical protrusion 32 is basically composed of a single copper particle. The copper particles may be made of metallic copper, or may be made of a copper alloy. However, when the copper particles are a copper alloy, the solubility in the copper etching solution may decrease, or the life of the etching solution may decrease due to the alloy components mixed in the copper etching solution. Preferably it consists of.
　略球状突起３２の平均高さｃａｖｅが２．６０μｍ以下であり、好ましくは１．５μｍ以下、より好ましくは１．０μｍ以下、さらに好ましくは０．６μｍ以下である。これらの範囲内であると無電解銅めっきに対するエッチング性が有意に向上する。平均高さｃａｖｅがの下限値は特に限定されないが、平均高さｃａｖｅは好ましくは０．２μｍ以上、より好ましくは０．４μｍ以上である。 The average height c ave of the substantially spherical protrusion 32 is 2.60 μm or less, preferably 1.5 μm or less, more preferably 1.0 μm or less, and even more preferably 0.6 μm or less. Within these ranges, the etching property for electroless copper plating is significantly improved. Although the lower limit of the average height c ave is is not particularly limited, the average height c ave is preferably 0.2μm or more, and more preferably 0.4μm or more.
　略球状突起３２の平均ネック径ａａｖｅに対する略球状突起３２の平均最大径ｂａｖｅの比ｂａｖｅ／ａａｖｅは１．２以上であり、好ましくは１．２～５．０、より好ましくは１．３～３．０、さらに好ましくは１．３～２．０、特に好ましくは１．４～１．７である。これらの範囲内であると略球状突起３２に由来するくびれ形状に基づくアンカー効果を十分に発揮させることができ、めっき回路密着性及びドライフィルム解像性が向上する。 The ratio b ave / a ave of the average maximum diameter b ave of the substantially spherical protrusion 32 to the average neck diameter a ave of the approximately spherical protrusion 32 is 1.2 or more, preferably 1.2 to 5.0, more preferably 1 .3 to 3.0, more preferably 1.3 to 2.0, particularly preferably 1.4 to 1.7. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved.
　略球状突起３２の平均ネック径ａａｖｅは０．１～２．０μｍが好ましく、より好ましくは０．２～１．０μｍ、さらに好ましくは０．３～０．６μｍである。平均ネック径ａａｖｅが２．０μｍ以下であると、ライン／スペース（Ｌ／Ｓ）＝５μｍ／５μｍの微細回路パターンにおいても、ライン幅内に２個以上の略球状突起を存在させることができるので、めっき回路密着性及びドライフィルム解像性が向上する。 The average neck diameter a ave of the substantially spherical protrusion 32 is preferably 0.1 to 2.0 μm, more preferably 0.2 to 1.0 μm, and still more preferably 0.3 to 0.6 μm. When the average neck diameter a ave is 2.0 μm or less, two or more substantially spherical protrusions can exist in the line width even in a fine circuit pattern of line / space (L / S) = 5 μm / 5 μm. Therefore, plating circuit adhesion and dry film resolution are improved.
　略球状突起３２の平均最大径ｂａｖｅは２．５μｍ以下であるのが好ましく、より好ましくは０．２～２．５μｍ、さらに好ましくは０．３～１．５μｍ、特に好ましくは０．４～１．２μｍ、最も好ましくは０．４～０．８μｍである。これらの範囲内であると略球状突起３２に由来するくびれ形状に基づくアンカー効果を十分に発揮させることができ、めっき回路密着性及びドライフィルム解像性が向上する。 The average maximum diameter b ave of the substantially spherical protrusion 32 is preferably 2.5 μm or less, more preferably 0.2 to 2.5 μm, still more preferably 0.3 to 1.5 μm, and particularly preferably 0.4 to 1.2 μm, most preferably 0.4 to 0.8 μm. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved.
　粗化処理面に存在する略球状突起３２に占める、略球状突起３２のネック径ａに対する略球状突起３２の最大径ｂの比ｂ／ａが１．２以上である略球状突起３２の割合が個数基準で６０％以上であるのが好ましく、より好ましくは７０％以上、さらに好ましくは８０％以上、特に好ましくは９０％以上である。これらの範囲内であると、略球状突起３２に由来するくびれ形状に基づくアンカー効果を十分に発揮させることができ、めっき回路密着性及びドライフィルム解像性が向上する。 The ratio of the substantially spherical protrusion 32 in which the ratio b / a of the maximum diameter b of the substantially spherical protrusion 32 to the neck diameter a of the approximately spherical protrusion 32 occupies in the substantially spherical protrusion 32 existing on the roughened surface is 1.2 or more. It is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more on the number basis. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved.
　略球状突起３２の平均根元離間距離ｄは０．１０～０．３０μｍであるのが好ましく、より好ましくは０．１５～０．２５μｍである。これらの範囲内であるとこれらの範囲内であると、略球状突起３２に由来するくびれ形状に基づくアンカー効果を十分に発揮させることができ、めっき回路密着性及びドライフィルム解像性が向上する。 The average root separation distance d of the substantially spherical protrusions 32 is preferably 0.10 to 0.30 μm, more preferably 0.15 to 0.25 μm. Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved. .
　略球状突起３２が１～１０個／μｍ２の面密度で存在するのが好ましく、より好ましくは２～５個／μｍ２、さらに好ましくは３～５個／μｍ２である。これらの範囲内であるとこれらの範囲内であると、略球状突起３２に由来するくびれ形状に基づくアンカー効果を十分に発揮させることができ、めっき回路密着性及びドライフィルム解像性が向上する。 The approximately spherical protrusions 32 are preferably present at an area density of 1 to 10 / μm 2 , more preferably 2 to 5 / μm 2 , and further preferably 3 to 5 / μm 2 . Within these ranges, the anchor effect based on the constricted shape derived from the substantially spherical protrusion 32 can be sufficiently exhibited, and the plating circuit adhesion and the dry film resolution are improved. .
　粗化処理面は一般的にうねりを有しており、このうねりに起因して略球状突起３２は傾斜しうる。特に、粗化処理銅箔が一方の側にのみ粗化処理面を有する場合、略球状突起３２の総数に占める高傾斜略球状突起の割合が３０～６０％であるのが好ましく、より好ましくは３５～５７％、さらに好ましくは４０～５７％である。高傾斜略球状突起は、前述のとおり、略球状突起３２の根元境界線の中点Ｃと略球状突起３２の頂点Ｖを結んだ線ＬＶＣと、粗化処理銅箔の粗化処理面と反対側の面と平行な基準線ＬＢとがなす鋭角θが８５°以下である略球状突起である。高傾斜略球状突起の割合が６０％以下であると、ＳＡＰ法において粗化処理銅箔をエッチング除去して粗化処理面由来の凹凸形状が付与された基材表面において、露光時における凹凸に起因する光の乱反射を低減してドライフィルムの硬化をより有利に行うことができ、その結果、ドライフィルムレジストの解像性がさらに改善する。また、高傾斜略球状突起の割合が３０％以上であると基材に対する密着性がさらに改善する。したがって、高傾斜略球状突起の割合を３０～６０％とすることで、ドライフィルム解像性と基材との密着性との両立により優れた粗化処理銅箔を提供することができる。 The roughened surface generally has waviness, and the substantially spherical protrusion 32 can be inclined due to this waviness. In particular, when the roughened copper foil has a roughened surface only on one side, the ratio of the highly inclined substantially spherical protrusions to the total number of substantially spherical protrusions 32 is preferably 30 to 60%, more preferably. It is 35 to 57%, more preferably 40 to 57%. High gradient substantially spherical protrusions, as described above, the line L VC connecting the vertex V of substantially spherical midpoint C of the root boundary projections 32 and substantially spherical projection 32, the roughened surface of the roughened copper foil acute θ formed by the other side of the plane parallel to the reference line L B is substantially spherical protrusions is 85 ° or less. When the ratio of the highly inclined substantially spherical protrusions is 60% or less, the roughened copper foil is etched away by the SAP method, and the unevenness derived from the roughened surface is given to the unevenness at the time of exposure. The resulting diffused reflection of light can be reduced and the dry film can be cured more advantageously, and as a result, the resolution of the dry film resist is further improved. Moreover, the adhesiveness with respect to a base material further improves that the ratio of a high inclination substantially spherical protrusion is 30% or more. Therefore, by setting the ratio of the highly inclined substantially spherical protrusions to 30 to 60%, it is possible to provide a roughened copper foil that is superior in achieving both dry film resolution and adhesion to the substrate.
　本発明の粗化処理銅箔の厚さは特に限定されないが、０．１～１８μｍが好ましく、より好ましくは０．５～１０μｍ、さらに好ましくは０．５～７μｍ、特に好ましくは０．５～５μｍ、最も好ましくは０．５～３μｍである。なお、本発明の粗化処理銅箔は、通常の銅箔の表面に粗化処理を行ったものに限らず、キャリア付銅箔の銅箔表面の粗化処理を行ったものであってもよい。 The thickness of the roughened copper foil of the present invention is not particularly limited, but is preferably 0.1 to 18 μm, more preferably 0.5 to 10 μm, still more preferably 0.5 to 7 μm, and particularly preferably 0.5 to 5 μm, most preferably 0.5 to 3 μm. Note that the roughened copper foil of the present invention is not limited to the one obtained by subjecting the surface of the normal copper foil to the roughening treatment, but may be one obtained by subjecting the copper foil surface of the copper foil with carrier to the roughening treatment. Good.
　粗化処理銅箔の製造方法
　本発明による粗化処理銅箔の好ましい製造方法の一例を説明するが、本発明による粗化処理銅箔は以下に説明する方法に限らず、本発明の粗化処理銅箔の表面プロファイルを実現できるかぎり、あらゆる方法によって製造されたものであってよい。 Method for Producing Roughened Copper Foil An example of a preferred method for producing a roughened copper foil according to the present invention will be described. However, the roughened copper foil according to the present invention is not limited to the method described below, and the roughened copper foil according to the present invention is used. It may be manufactured by any method as long as the surface profile of the treated copper foil can be realized.
（１）銅箔の準備
　粗化処理銅箔の製造に使用する銅箔として、電解銅箔及び圧延銅箔の双方の使用が可能である。銅箔の厚さは特に限定されないが、０．１～１８μｍが好ましく、より好ましくは０．５～１０μｍ、さらに好ましくは０．５～７μｍ、特に好ましくは０．５～５μｍ、最も好ましくは０．５～３μｍである。銅箔がキャリア付銅箔の形態で準備される場合には、銅箔は、無電解銅めっき法及び電解銅めっき法等の湿式成膜法、スパッタリング及び化学蒸着等の乾式成膜法、又はそれらの組合せにより形成したものであってよい。 (1) Preparation of copper foil As copper foil used for manufacture of roughening processing copper foil, use of both electrolytic copper foil and rolled copper foil is possible. The thickness of the copper foil is not particularly limited, but is preferably 0.1 to 18 μm, more preferably 0.5 to 10 μm, still more preferably 0.5 to 7 μm, particularly preferably 0.5 to 5 μm, and most preferably 0. .5-3 μm. When the copper foil is prepared in the form of a copper foil with a carrier, the copper foil is prepared by a wet film formation method such as an electroless copper plating method and an electrolytic copper plating method, a dry film formation method such as sputtering and chemical vapor deposition, or It may be formed by a combination thereof.
　粗化処理前の銅箔の粗化処理が施されることになる面は、特に限定されないが、うねりの最大高低差（Ｗｍａｘ）が６．０μｍ以下であるのが好ましく、より好ましくは０．１～２．０μｍ、さらに好ましくは０．２～１．３μｍであり、かつ、表面ピーク間の平均距離（Ｐｅａｋ　ｓｐａｃｉｎｇ）が１００μｍ以下であるのが好ましく、より好ましくは３～７０μｍ、さらに好ましくは５～３０μｍである。このような範囲内のＷｍａｘ及びＰｅａｋ　ｓｐａｃｉｎｇであると、後続の粗化処理を経て、略球状突起の総数に占める高傾斜略球状突起の割合が好ましくは３０～６０％、より好ましくは３５～５７％、さらに好ましくは４０～５７％である粗化処理面を好都合に形成することができる。例えば、銅箔がキャリア付銅箔の形態で準備される場合、上記範囲内の低いＰｅａｋ　ｓｐａｃｉｎｇとＷｍａｘの実現は、キャリア箔を電解製箔する際に用いる回転陰極の表面を所定の番手のバフで研磨して表面粗さを調整することにより行うことができる。すなわち、こうして調整された回転陰極の表面プロファイルがキャリア箔の電極面に転写され、こうして望ましい表面プロファイルが付与されたキャリア箔の電極面上に剥離層を介して銅箔を形成することで、銅箔の粗化処理が施される側（すなわち剥離層と反対側）の面に上述した表面プロファイルを付与することができる。好ましいバフの番手は＃１０００より大きく＃３０００未満であり、より好ましくは＃１５００～＃２５００であり、特に好ましくは＃２０００である。このようにバフの番手を上記範囲内で適宜選択することにより、銅箔表面のうねりを制御して、高傾斜略球状粒子の割合を狙いどおりに制御することができる。 The surface to be subjected to the roughening treatment of the copper foil before the roughening treatment is not particularly limited, but the maximum height difference (Wmax) of the waviness is preferably 6.0 μm or less, more preferably 0.8 μm. It is preferably 1 to 2.0 μm, more preferably 0.2 to 1.3 μm, and the average distance (Peak spacing) between surface peaks is preferably 100 μm or less, more preferably 3 to 70 μm, still more preferably 5 to 30 μm. In the case of Wmax and Peak spacing within such a range, the ratio of highly inclined substantially spherical protrusions to the total number of substantially spherical protrusions after the subsequent roughening treatment is preferably 30 to 60%, more preferably 35 to 57. %, More preferably 40 to 57%, can be conveniently formed. For example, when the copper foil is prepared in the form of a copper foil with a carrier, the realization of low peak spacing and Wmax within the above range is that the surface of the rotating cathode used when electrolytically forming the carrier foil is a baffle of a predetermined count. The surface roughness can be adjusted by polishing. That is, the surface profile of the rotating cathode thus adjusted is transferred to the electrode surface of the carrier foil, and the copper foil is formed on the electrode surface of the carrier foil thus provided with the desired surface profile via the release layer. The surface profile described above can be applied to the surface on which the foil is roughened (that is, the side opposite to the release layer). A preferred buff count is greater than # 1000 and less than # 3000, more preferably # 1500 to # 2500, and particularly preferably # 2000. Thus, by appropriately selecting the buff count within the above range, the undulation of the surface of the copper foil can be controlled, and the ratio of the highly inclined substantially spherical particles can be controlled as intended.
（２）粗化処理
　銅粒子を用いて銅箔の少なくとも一方の表面を粗化する。この粗化は、粗化処理用銅電解溶液を用いた電解により行われる。この電解は２段階のめっき工程を経て行われるのが好ましい。１段階目のめっき工程では、銅濃度８～１２ｇ／Ｌ及び硫酸濃度２００～２８０ｇ／Ｌを含む硫酸銅溶液を用いて、液温２０～４０℃、電流密度１５～３５Ａ／ｄｍ２、時間５～２５秒のめっき条件で電着を行うのが好ましい。２段階目のめっき工程では、銅濃度６５～８０ｇ／Ｌ及び硫酸濃度２００～２８０ｇ／Ｌを含む硫酸銅溶液を用いて、液温４５～５５℃及び電流密度５～３０Ａ／ｄｍ２、時間５～２５秒のめっき条件で電着を行うのが好ましい。各段階における電気量は、１段階目のめっき工程における電気量Ｑ１の２段階目のめっき工程における電気量Ｑ２に対する比（Ｑ１／Ｑ２）は１．５～２．５となるように設定するのが好ましい。比Ｑ１／Ｑ２が１．５を下回る場合には略球状突起のくびれが小さくなり（すなわち比ｂ／ａが小さくなり）めっき回路密着性の低下を招きうる。一方、比Ｑ１／Ｑ２が２．５を超える場合には略球状突起のくびれが大きくなり（すなわち比ｂ／ａが大きくなり）粗化粒子が脱落しやすくなる。 (2) Roughening treatment At least one surface of the copper foil is roughened using copper particles. This roughening is performed by electrolysis using a copper electrolytic solution for roughening treatment. This electrolysis is preferably performed through a two-step plating process. In the first plating process, a copper sulfate solution containing a copper concentration of 8 to 12 g / L and a sulfuric acid concentration of 200 to 280 g / L is used, the liquid temperature is 20 to 40 ° C., the current density is 15 to 35 A / dm 2 , and the time is 5 Electrodeposition is preferably performed under plating conditions of ˜25 seconds. In the second plating step, a copper sulfate solution containing a copper concentration of 65 to 80 g / L and a sulfuric acid concentration of 200 to 280 g / L is used, the liquid temperature is 45 to 55 ° C., the current density is 5 to 30 A / dm 2 , and the time is 5 Electrodeposition is preferably performed under plating conditions of ˜25 seconds. The amount of electricity in each stage is such that the ratio (Q 1 / Q 2 ) of the amount of electricity Q 1 in the first stage plating process to the amount of electricity Q 2 in the second stage plating process is 1.5 to 2.5. It is preferable to set to. When the ratio Q 1 / Q 2 is less than 1.5, the constriction of the substantially spherical protrusion becomes small (that is, the ratio b / a becomes small), and the plating circuit adhesion can be lowered. On the other hand, when the ratio Q 1 / Q 2 exceeds 2.5, the constriction of the substantially spherical protrusion is increased (that is, the ratio b / a is increased), and the roughened particles are likely to fall off.
（３）防錆処理
　所望により、粗化処理後の銅箔に防錆処理を施してもよい。防錆処理は、亜鉛を用いためっき処理を含むのが好ましい。亜鉛を用いためっき処理は、亜鉛めっき処理及び亜鉛合金めっき処理のいずれであってもよく、亜鉛合金めっき処理は亜鉛－ニッケル合金処理が特に好ましい。亜鉛－ニッケル合金処理は少なくともＮｉ及びＺｎを含むめっき処理であればよく、Ｓｎ、Ｃｒ、Ｃｏ等の他の元素をさらに含んでいてもよい。亜鉛－ニッケル合金めっきにおけるＮｉ／Ｚｎ付着比率は、質量比で、１．２～１０が好ましく、より好ましくは２～７、さらに好ましくは２．７～４である。また、防錆処理はクロメート処理をさらに含むのが好ましく、このクロメート処理は亜鉛を用いためっき処理の後に、亜鉛を含むめっきの表面に行われるのがより好ましい。こうすることで防錆性をさらに向上させることができる。特に好ましい防錆処理は、亜鉛－ニッケル合金めっき処理とその後のクロメート処理との組合せである。 (3) Rust prevention treatment If desired, the copper foil after the roughening treatment may be subjected to a rust prevention treatment. The rust prevention treatment preferably includes a plating treatment using zinc. The plating treatment using zinc may be either a zinc plating treatment or a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a zinc-nickel alloy treatment. The zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, and Co. The Ni / Zn adhesion ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and still more preferably 2.7 to 4 in terms of mass ratio. The rust prevention treatment preferably further includes a chromate treatment, and this chromate treatment is more preferably performed on the surface of the plating containing zinc after the plating treatment using zinc. By carrying out like this, rust prevention property can further be improved. A particularly preferable antirust treatment is a combination of a zinc-nickel alloy plating treatment and a subsequent chromate treatment.
（４）シランカップリング剤処理
　所望により、銅箔にシランカップリング剤処理を施し、シランカップリング剤層を形成してもよい。これにより耐湿性、耐薬品性及び接着剤等との密着性等を向上することができる。シランカップリング剤層は、シランカップリング剤を適宜希釈して塗布し、乾燥させることにより形成することができる。シランカップリング剤の例としては、４－グリシジルブチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン等のエポキシ官能性シランカップリング剤、又はγ－アミノプロピルトリエトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルトリメトキシシラン、Ｎ－３－（４－（３－アミノプロポキシ）ブトキシ）プロピル－３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ官能性シランカップリング剤、又はγ－メルカプトプロピルトリメトキシシラン等のメルカプト官能性シランカップリング剤又はビニルトリメトキシシラン、ビニルフェニルトリメトキシシラン等のオレフィン官能性シランカップリング剤、又はγ－メタクリロキシプロピルトリメトキシシラン等のアクリル官能性シランカップリング剤、又はイミダゾールシラン等のイミダゾール官能性シランカップリング剤、又はトリアジンシラン等のトリアジン官能性シランカップリング剤等が挙げられる。 (4) Silane coupling agent treatment If desired, the copper foil may be treated with a silane coupling agent to form a silane coupling agent layer. Thereby, moisture resistance, chemical resistance, adhesiveness with an adhesive agent, etc. can be improved. The silane coupling agent layer can be formed by appropriately diluting and applying a silane coupling agent and drying. Examples of silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane, or γ-aminopropyltriethoxysilane, N-β (amino Amino functions such as ethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Silane coupling agent, or mercapto functional silane coupling agent such as γ-mercaptopropyltrimethoxysilane, or olefin functional silane coupling agent such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, or γ-methacryloxypropyl Trimetoki Acrylic-functional silane coupling agent such as a silane, or imidazole functional silane coupling agent such as imidazole silane, or triazine functional silane coupling agents such as triazine silane.
　キャリア付銅箔
　本発明の粗化処理銅箔は、キャリア付銅箔の形態で提供することができる。この場合、キャリア付銅箔は、キャリア箔と、このキャリア箔上に設けられた剥離層と、この剥離層上に粗化処理面を外側にして設けられた本発明の粗化処理銅箔とを備えてなる。もっとも、キャリア付銅箔は、本発明の粗化処理銅箔を用いること以外は、公知の層構成が採用可能である。 Copper foil with carrier The roughened copper foil of the present invention can be provided in the form of a copper foil with carrier. In this case, the carrier-attached copper foil includes a carrier foil, a release layer provided on the carrier foil, and the roughened copper foil of the present invention provided on the release layer with the roughened surface facing outside. It is equipped with. However, a known layer structure can be adopted as the carrier-attached copper foil except that the roughened copper foil of the present invention is used.
　キャリア箔は、粗化処理銅箔を支持してそのハンドリング性を向上させるための箔である。キャリア箔の例としては、アルミニウム箔、銅箔、表面をメタルコーティングした樹脂フィルム等が挙げられ、好ましくは銅箔である。銅箔は圧延銅箔及び電解銅箔のいずれであってもよい。キャリア箔の厚さは典型的には２００μｍ以下であり、好ましくは１２μｍ～３５μｍである。 The carrier foil is a foil for supporting the roughened copper foil and improving its handleability. Examples of the carrier foil include an aluminum foil, a copper foil, a resin film whose surface is metal-coated, and the like, and preferably a copper foil. The copper foil may be a rolled copper foil or an electrolytic copper foil. The thickness of the carrier foil is typically 200 μm or less, preferably 12 μm to 35 μm.
　キャリア箔の剥離層側の面は、０．５～１．５μｍの十点表面粗さＲｚｊｉｓを有するのが好ましく、より好ましくは０．６～１．０μｍである。ＲｚｊｉｓはＪＩＳ　Ｂ　０６０１：２００１に準拠して決定することができる。このような十点表面粗さＲｚｊｉｓをキャリア箔の剥離層側の面に付与しておくことで、その上に剥離層を介して作製される本発明の粗化処理銅箔に望ましい表面プロファイルを付与しやすくすることができる。 The surface on the release layer side of the carrier foil preferably has a 10-point surface roughness Rzjis of 0.5 to 1.5 μm, more preferably 0.6 to 1.0 μm. Rzjis can be determined according to JIS B 0601: 2001. By giving such a ten-point surface roughness Rzjis to the surface of the carrier foil on the release layer side, a surface profile desirable for the roughened copper foil of the present invention produced via the release layer on the carrier foil is obtained. It can be made easier to apply.
　剥離層は、キャリア箔の引き剥がし強度を弱くし、該強度の安定性を担保し、さらには高温でのプレス成形時にキャリア箔と銅箔の間で起こりうる相互拡散を抑制する機能を有する層である。剥離層は、キャリア箔の一方の面に形成されるのが一般的であるが、両面に形成されてもよい。剥離層は、有機剥離層及び無機剥離層のいずれであってもよい。有機剥離層に用いられる有機成分の例としては、窒素含有有機化合物、硫黄含有有機化合物、カルボン酸等が挙げられる。窒素含有有機化合物の例としては、トリアゾール化合物、イミダゾール化合物等が挙げられ、中でもトリアゾール化合物は剥離性が安定し易い点で好ましい。トリアゾール化合物の例としては、１，２，３－ベンゾトリアゾール、カルボキシベンゾトリアゾール、Ｎ’，Ｎ’－ビス（ベンゾトリアゾリルメチル）ユリア、１Ｈ－１，２，４－トリアゾール及び３－アミノ－１Ｈ－１，２，４－トリアゾール等が挙げられる。硫黄含有有機化合物の例としては、メルカプトベンゾチアゾール、チオシアヌル酸、２－ベンズイミダゾールチオール等が挙げられる。カルボン酸の例としては、モノカルボン酸、ジカルボン酸等が挙げられる。一方、無機剥離層に用いられる無機成分の例としては、Ｎｉ、Ｍｏ、Ｃｏ、Ｃｒ、Ｆｅ、Ｔｉ、Ｗ、Ｐ、Ｚｎ、クロメート処理膜等が挙げられる。なお、剥離層の形成はキャリア箔の少なくとも一方の表面に剥離層成分含有溶液を接触させ、剥離層成分をキャリア箔の表面に固定されること等により行えばよい。キャリア箔の剥離層成分含有溶液への接触は、剥離層成分含有溶液への浸漬、剥離層成分含有溶液の噴霧、剥離層成分含有溶液の流下等により行えばよい。また、剥離層成分のキャリア箔表面への固定は、剥離層成分含有溶液の吸着や乾燥、剥離層成分含有溶液中の剥離層成分の電着等により行えばよい。剥離層の厚さは、典型的には１ｎｍ～１μｍであり、好ましくは５ｎｍ～５００ｎｍである。 The release layer is a layer having a function of weakening the peeling strength of the carrier foil, ensuring the stability of the strength, and further suppressing interdiffusion that may occur between the carrier foil and the copper foil during press molding at a high temperature. It is. The release layer is generally formed on one side of the carrier foil, but may be formed on both sides. The release layer may be either an organic release layer or an inorganic release layer. Examples of organic components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids and the like. Examples of nitrogen-containing organic compounds include triazole compounds, imidazole compounds, and the like. Among these, triazole compounds are preferred in terms of easy release stability. Examples of triazole compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1,2,4-triazole and 3-amino- And 1H-1,2,4-triazole. Examples of the sulfur-containing organic compound include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol and the like. Examples of the carboxylic acid include monocarboxylic acid and dicarboxylic acid. On the other hand, examples of inorganic components used in the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, and a chromate-treated film. The release layer may be formed by bringing a release layer component-containing solution into contact with at least one surface of the carrier foil and fixing the release layer component to the surface of the carrier foil. The contact of the carrier foil with the release layer component-containing solution may be performed by immersion in the release layer component-containing solution, spraying of the release layer component-containing solution, flowing down of the release layer component-containing solution, or the like. The release layer component may be fixed to the surface of the carrier foil by adsorption or drying of the release layer component-containing solution, electrodeposition of the release layer component in the release layer component-containing solution, or the like. The thickness of the release layer is typically 1 nm to 1 μm, preferably 5 nm to 500 nm.
　粗化処理銅箔としては、上述した本発明の粗化処理銅箔を用いる。本発明の粗化処理は銅粒子を用いた粗化が施されたものであるが、手順としては、先ず剥離層の表面に銅層を銅箔として形成し、その後少なくとも粗化を行えばよい。粗化の詳細については前述したとおりである。なお、銅箔はキャリア付銅箔としての利点を活かすべく、極薄銅箔の形態で構成されるのが好ましい。極薄銅箔としての好ましい厚さは０．１μｍ～７μｍであり、より好ましくは０．５μｍ～５μｍ、さらに好ましくは０．５μｍ～３μｍである。 The roughened copper foil of the present invention described above is used as the roughened copper foil. The roughening treatment of the present invention is performed by roughening using copper particles. As a procedure, first, a copper layer is formed as a copper foil on the surface of the release layer, and then at least roughening is performed. . Details of the roughening are as described above. In addition, it is preferable that copper foil is comprised with the form of an ultra-thin copper foil in order to utilize the advantage as copper foil with a carrier. A preferable thickness of the ultrathin copper foil is 0.1 μm to 7 μm, more preferably 0.5 μm to 5 μm, and still more preferably 0.5 μm to 3 μm.
　剥離層と銅箔の間に他の機能層を設けてもよい。そのような他の機能層の例としては補助金属層が挙げられる。補助金属層はニッケル及び／又はコバルトからなるのが好ましい。補助金属層の厚さは、０．００１～３μｍとするのが好ましい。 Other functional layers may be provided between the release layer and the copper foil. An example of such another functional layer is an auxiliary metal layer. The auxiliary metal layer is preferably made of nickel and / or cobalt. The thickness of the auxiliary metal layer is preferably 0.001 to 3 μm.
　銅張積層板
　本発明の粗化処理銅箔ないしキャリア付銅箔はプリント配線板用銅張積層板の作製に用いられるのが好ましい。すなわち、本発明の好ましい態様によれば、上記粗化処理銅箔又は上記キャリア付銅箔を用いて得られた銅張積層板が提供される。本発明の粗化処理銅箔ないしキャリア付銅箔を用いることで、ＳＡＰ法に特に適した銅張積層板を提供することができる。この銅張積層板は、本発明のキャリア付銅箔と、該粗化処理面に密着して設けられる樹脂層とを備えてなる。キャリア付銅箔は樹脂層の片面に設けられてもよいし、両面に設けられてもよい。樹脂層は、樹脂、好ましくは絶縁性樹脂を含んでなる。樹脂層はプリプレグ及び／又は樹脂シートであるのが好ましい。プリプレグとは、合成樹脂板、ガラス板、ガラス織布、ガラス不織布、紙等の基材に合成樹脂を含浸させた複合材料の総称である。絶縁性樹脂の好ましい例としては、エポキシ樹脂、シアネート樹脂、ビスマレイミドトリアジン樹脂（ＢＴ樹脂）、ポリフェニレンエーテル樹脂、フェノール樹脂等が挙げられる。また、樹脂シートを構成する絶縁性樹脂の例としては、エポキシ樹脂、ポリイミド樹脂、ポリエステル樹脂等の絶縁樹脂が挙げられる。また、樹脂層には絶縁性を向上する等の観点からシリカ、アルミナ等の各種無機粒子からなるフィラー粒子等が含有されていてもよい。樹脂層の厚さは特に限定されないが、１～１０００μｍが好ましく、より好ましくは２～４００μｍであり、さらに好ましくは３～２００μｍである。樹脂層は複数の層で構成されていてよい。プリプレグ及び／又は樹脂シート等の樹脂層は予め銅箔表面に塗布されるプライマー樹脂層を介してキャリア付極薄銅箔に設けられていてもよい。 Copper- clad laminate The roughened copper foil or carrier-attached copper foil of the present invention is preferably used for the production of a copper-clad laminate for printed wiring boards. That is, according to the preferable aspect of this invention, the copper clad laminated board obtained using the said roughening copper foil or the said copper foil with a carrier is provided. By using the roughened copper foil or the copper foil with carrier of the present invention, a copper clad laminate particularly suitable for the SAP method can be provided. This copper-clad laminate comprises the carrier-attached copper foil of the present invention and a resin layer provided in close contact with the roughened surface. The copper foil with a carrier may be provided on one side of the resin layer or may be provided on both sides. The resin layer comprises a resin, preferably an insulating resin. The resin layer is preferably a prepreg and / or a resin sheet. The prepreg is a general term for composite materials in which a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass nonwoven fabric, and paper is impregnated with a synthetic resin. Preferable examples of the insulating resin include an epoxy resin, a cyanate resin, a bismaleimide triazine resin (BT resin), a polyphenylene ether resin, and a phenol resin. Examples of the insulating resin that constitutes the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins. Moreover, the filler particle etc. which consist of various inorganic particles, such as a silica and an alumina, may contain in the resin layer from a viewpoint of improving insulation. The thickness of the resin layer is not particularly limited, but is preferably 1 to 1000 μm, more preferably 2 to 400 μm, and still more preferably 3 to 200 μm. The resin layer may be composed of a plurality of layers. A resin layer such as a prepreg and / or a resin sheet may be provided on the ultrathin copper foil with a carrier via a primer resin layer previously applied to the surface of the copper foil.
　プリント配線板
　本発明の粗化処理銅箔ないしキャリア付銅箔はプリント配線板の作製に用いられるのが好ましく、特に好ましくはセミアディティブ法（ＳＡＰ）によるプリント配線板の作製に用いられる。すなわち、本発明の好ましい態様によれば、前述した粗化処理銅箔又は上記キャリア付銅箔を用いて得られたプリント配線板が提供される。本発明の粗化処理銅箔ないしキャリア付銅箔を用いることで、プリント配線板の製造において、優れためっき回路密着性のみならず、無電解銅めっきに対するエッチング性にも優れた表面プロファイルを積層体に付与可能な、粗化処理銅箔を提供することができる。また、上記粗化処理銅箔を用いることで、ＳＡＰ法におけるドライフィルム現像工程において、極めて微細なドライフィルム解像性を実現することができる。したがって、極めて微細な回路形成が施されたプリント配線板を提供することができる。本態様によるプリント配線板は、樹脂層と、銅層とがこの順に積層された層構成を含んでなる。ＳＡＰ法の場合には本発明の粗化処理銅箔は図１の工程（ｃ）において除去されるため、ＳＡＰ法により作製されたプリント配線板は本発明の粗化処理銅箔をもはや含まず、粗化処理銅箔の粗化処理面から転写された表面プロファイルが残存するのみである。また、樹脂層については銅張積層板に関して上述したとおりである。いずれにしても、プリント配線板は公知の層構成が採用可能である。プリント配線板に関する具体例としては、プリプレグの片面又は両面に本発明の極薄銅箔を接着させ硬化した積層体とした上で回路形成した片面又は両面プリント配線板や、これらを多層化した多層プリント配線板等が挙げられる。また、他の具体例としては、樹脂フィルム上に本発明の極薄銅箔を形成して回路を形成するフレキシブルプリント配線板、ＣＯＦ、ＴＡＢテープ等も挙げられる。さらに他の具体例としては、本発明の極薄銅箔に上述の樹脂層を塗布した樹脂付銅箔（ＲＣＣ）を形成し、樹脂層を絶縁接着材層として上述のプリント基板に積層した後、極薄銅箔を配線層の全部又は一部としてモディファイド・セミアディティブ（ＭＳＡＰ）法、サブトラクティブ法等の手法で回路を形成したビルドアップ配線板や、極薄銅箔を除去してセミアディティブ（ＳＡＰ）法で回路を形成したビルドアップ配線板、半導体集積回路上へ樹脂付銅箔の積層と回路形成を交互に繰りかえすダイレクト・ビルドアップ・オン・ウェハー等が挙げられる。より発展的な具体例として、上記樹脂付銅箔を基材に積層し回路形成したアンテナ素子、接着剤層を介してガラスや樹脂フィルムに積層しパターンを形成したパネル・ディスプレイ用電子材料や窓ガラス用電子材料、本発明の極薄銅箔に導電性接着剤を塗布した電磁波シールド・フィルム等も挙げられる。特に、本発明のキャリア付極薄銅箔はＳＡＰ法に適している。例えば、ＳＡＰ法により回路形成した場合には図１及び２に示されるような構成が採用可能である。 Printed wiring board The roughened copper foil or carrier-attached copper foil of the present invention is preferably used for the production of a printed wiring board, particularly preferably for the production of a printed wiring board by a semi-additive method (SAP). That is, according to the preferable aspect of this invention, the printed wiring board obtained using the roughening process copper foil mentioned above or the said copper foil with a carrier is provided. By using the roughened copper foil or the copper foil with carrier according to the present invention, in the production of printed wiring boards, not only excellent plating circuit adhesion but also surface profile excellent in etching property for electroless copper plating is laminated. A roughened copper foil that can be applied to a body can be provided. In addition, by using the roughened copper foil, extremely fine dry film resolution can be realized in the dry film development step in the SAP method. Therefore, it is possible to provide a printed wiring board on which an extremely fine circuit is formed. The printed wiring board according to this aspect includes a layer configuration in which a resin layer and a copper layer are laminated in this order. In the case of the SAP method, the roughened copper foil of the present invention is removed in the step (c) of FIG. 1, and therefore the printed wiring board produced by the SAP method no longer contains the roughened copper foil of the present invention. Only the surface profile transferred from the roughened surface of the roughened copper foil remains. The resin layer is as described above for the copper-clad laminate. In any case, a known layer structure can be adopted for the printed wiring board. Specific examples of the printed wiring board include a single-sided or double-sided printed wiring board formed with a circuit on the laminated body obtained by bonding the ultrathin copper foil of the present invention to one side or both sides of the prepreg, and a multilayer in which these are multilayered. A printed wiring board etc. are mentioned. Other specific examples include a flexible printed wiring board, a COF, a TAB tape, and the like that form a circuit by forming the ultrathin copper foil of the present invention on a resin film. As another specific example, after forming the resin-coated copper foil (RCC) obtained by applying the above resin layer to the ultrathin copper foil of the present invention, and laminating the resin layer as an insulating adhesive layer on the above printed board , Build-up wiring board with ultra-thin copper foil as a whole or part of the wiring layer, modified semi-additive (MSAP) method, subtractive method, etc. Examples thereof include a build-up wiring board in which a circuit is formed by the (SAP) method, a direct build-up-on-wafer that alternately repeats the lamination of a copper foil with resin on a semiconductor integrated circuit and the circuit formation. As a more specific example, antenna elements formed by laminating the above resin-coated copper foil on a substrate to form a circuit, panels and electronic materials for panels and displays formed on a glass or resin film via an adhesive layer, and windows Examples thereof include an electronic material for glass, and an electromagnetic wave shielding film obtained by applying a conductive adhesive to the ultrathin copper foil of the present invention. In particular, the ultrathin copper foil with a carrier of the present invention is suitable for the SAP method. For example, when a circuit is formed by the SAP method, a configuration as shown in FIGS. 1 and 2 can be employed.
　本発明を以下の例によってさらに具体的に説明する。 The present invention will be described more specifically by the following examples.
　例１～６
　キャリア箔付粗化処理銅箔の作製及び評価を以下のようにして行った。 Examples 1-6
Production and evaluation of the roughened copper foil with carrier foil were performed as follows.
（１）キャリア箔の作製
　銅電解液として以下に示される組成の硫酸銅溶液を用い、陰極に算術平均表面粗さＲａ（ＪＩＳ　Ｂ　０６０１：２００１に準拠）が０．２０μｍのチタン製の回転電極を用い、陽極にはＤＳＡ（寸法安定性陽極）を用いて、溶液温度４５℃、電流密度５５Ａ／ｄｍ２で電解し、厚さ１２μｍの電解銅箔をキャリア箔として得た。このとき、回転陰極として、表面を＃１０００のバフで研磨して表面粗さを整えた電極を用いた。得られたキャリア箔の電極側の面の十点平均粗さＲｚｊｉｓをＪＩＳ　Ｂ　０６０１：２００１に準拠して測定したところ、０．９μｍであった。また、得られたキャリア箔の析出側の面の十点平均粗さＲｚｊｉｓは０．６μｍであった。
＜硫酸銅溶液の組成＞
‐　銅濃度：８０ｇ／Ｌ
‐　硫酸濃度：２６０ｇ／Ｌ
‐　ビス（３－スルホプロピル）ジスルフィド濃度：３０ｍｇ／Ｌ
‐　ジアリルジメチルアンモニウムクロライド重合体濃度：５０ｍｇ／Ｌ
‐　塩素濃度：４０ｍｇ／Ｌ (1) Production of carrier foil A copper sulfate solution having the composition shown below as a copper electrolyte, and a rotating electrode made of titanium having an arithmetic average surface roughness Ra (based on JIS B 0601: 2001) of 0.20 μm as a cathode. Was used, and a DSA (dimensional stability anode) was used as an anode, and electrolysis was performed at a solution temperature of 45 ° C. and a current density of 55 A / dm 2 , thereby obtaining an electrolytic copper foil having a thickness of 12 μm as a carrier foil. At this time, an electrode whose surface roughness was adjusted by polishing with a # 1000 buff was used as the rotating cathode. When the ten-point average roughness Rzjis of the surface of the obtained carrier foil on the electrode side was measured in accordance with JIS B 0601: 2001, it was 0.9 μm. Further, the ten-point average roughness Rzjis of the surface on the deposition side of the obtained carrier foil was 0.6 μm.
<Composition of copper sulfate solution>
-Copper concentration: 80 g / L
-Sulfuric acid concentration: 260 g / L
-Bis (3-sulfopropyl) disulfide concentration: 30 mg / L
-Diallyldimethylammonium chloride polymer concentration: 50 mg / L
-Chlorine concentration: 40 mg / L
（２）剥離層の形成
　酸洗処理されたキャリア用銅箔の電極面側を、ＣＢＴＡ（カルボキシベンゾトリアゾール）濃度１ｇ／Ｌ、硫酸濃度１５０ｇ／Ｌ及び銅濃度１０ｇ／ＬのＣＢＴＡ水溶液に、液温３０℃で３０秒間浸漬し、ＣＢＴＡ成分をキャリア箔の電極面に吸着させた。こうして、キャリア用銅箔の電極面の表面にＣＢＴＡ層を有機剥離層として形成した。 (2) Formation of release layer The electrode surface side of the pickled copper foil for carrier was liquidized in a CBTA aqueous solution having a CBTA (carboxybenzotriazole) concentration of 1 g / L, a sulfuric acid concentration of 150 g / L, and a copper concentration of 10 g / L. It was immersed for 30 seconds at a temperature of 30 ° C., and the CBTA component was adsorbed on the electrode surface of the carrier foil. Thus, a CBTA layer was formed as an organic release layer on the surface of the electrode surface of the carrier copper foil.
（３）補助金属層の形成
　有機剥離層が形成されたキャリア用銅箔を、硫酸ニッケルを用いて作製されたニッケル濃度２０ｇ／Ｌの溶液に浸漬して、液温４５℃、ｐＨ３、電流密度５Ａ／ｄｍ２の条件で、厚さ０．００１μｍ相当の付着量のニッケルを有機剥離層上に付着させた。こうして有機剥離層上にニッケル層を補助金属層として形成した。 (3) Formation of auxiliary metal layer The carrier copper foil on which the organic release layer is formed is immersed in a solution having a nickel concentration of 20 g / L prepared using nickel sulfate, and the liquid temperature is 45 ° C., pH 3, and the current density. Under the condition of 5 A / dm 2 , nickel with a deposition amount corresponding to a thickness of 0.001 μm was deposited on the organic release layer. Thus, a nickel layer was formed as an auxiliary metal layer on the organic release layer.
（４）極薄銅箔形成
　補助金属層が形成されたキャリア用銅箔を、以下に示される組成の硫酸銅溶液に浸漬して、溶液温度５０℃、電流密度５～３０Ａ／ｄｍ２で電解し、厚さ３μｍの極薄銅箔を補助金属層上に形成した。
＜溶液の組成＞
‐　銅濃度：６０ｇ／Ｌ
‐　硫酸濃度：２００ｇ／Ｌ (4) Ultra-thin copper foil formation A copper foil for carriers on which an auxiliary metal layer is formed is immersed in a copper sulfate solution having the composition shown below, and electrolysis is performed at a solution temperature of 50 ° C. and a current density of 5 to 30 A / dm 2 . Then, an ultrathin copper foil having a thickness of 3 μm was formed on the auxiliary metal layer.
<Composition of solution>
-Copper concentration: 60 g / L
-Sulfuric acid concentration: 200 g / L
　例１においては、測定機器としてｚｙｇｏ　Ｎｅｗ　Ｖｉｅｗ　５０３２（Ｚｙｇｏ社製）を用い、解析ソフトとしてＭｅｔｒｏ　Ｐｒｏ　Ｖｅｒ．８．０．２を用いて、低周波フィルタを１１μｍの条件を採用して、極薄銅箔の析出面（補助金属層及び剥離層と反対側の面）について、うねりの最大高低差（Ｗｍａｘ）及び表面ピーク間の平均距離（Ｐｅａｋ　ｓｐａｃｉｎｇ）の測定を行った。このとき、極薄銅箔を試料台に密着させて固定し、試料片の１ｃｍ角の範囲内の中で１０８μｍ×１４４μｍの視野を６点選択して測定し、６箇所の測定点から得られた測定値の平均値を代表値として採用した。その結果、極薄銅箔の析出面（剥離層と反対側の面）は、Ｗｍａｘが１．３８μｍ、Ｐｅａｋ　ｓｐａｃｉｎｇが２１．３７μｍであった。 In Example 1, zygo New View 5032 (manufactured by Zygo) was used as the measuring instrument, and Metro Pro Ver. 8.0.2, using a low frequency filter under the condition of 11 μm, the maximum height difference (Wmax) of the waviness on the deposition surface (surface opposite to the auxiliary metal layer and the release layer) of the ultrathin copper foil ) And the average distance (Peak spacing) between the surface peaks. At this time, the ultra-thin copper foil was fixed in close contact with the sample stage, and measured by selecting 6 fields of 108 μm × 144 μm within the 1 cm square range of the sample piece, and obtained from 6 measurement points. The average value of the measured values was adopted as the representative value. As a result, the deposition surface (surface opposite to the release layer) of the ultrathin copper foil had a Wmax of 1.38 μm and a peak spacing of 21.37 μm.
（５）粗化処理
　上述の極薄銅箔の析出面に対して粗化処理を行った。この粗化処理は、以下の２段階めっきにより行った。１段階目のめっき工程では、銅濃度１０．０～１１．５ｇ／Ｌ及び硫酸濃度２３０～２５０ｇ／Ｌを含む硫酸銅溶液を用いて、液温２０～４０℃、電流密度１０～２５Ａ／ｄｍ２のめっき条件で電着を行った。２段階目のめっき工程では、銅濃度６５～７５ｇ／Ｌ及び硫酸濃度２３０～２５０ｇ／Ｌを含む硫酸銅溶液を用いて、液温５０～５５℃及び電流密度５～１５Ａ／ｄｍ２のめっき条件で電着を行った。各段階における電気量は、１段階目のめっき工程における電気量Ｑ１の２段階目のめっき工程における電気量Ｑ２に対する比（Ｑ１／Ｑ２）は２．１（例１）、１．８（例２）、２．４（例３）、１．９（例４）、１．７（例５）、１．６（例６）又は１．２（例７）となるように設定した。上記条件の範囲内で適宜変動させることにより例１～６の６種類の粗化処理銅箔を作製した。 (5) Roughening process The roughening process was performed with respect to the precipitation surface of the above-mentioned ultra-thin copper foil. This roughening treatment was performed by the following two-stage plating. In the first plating process, a copper sulfate solution containing a copper concentration of 10.0 to 11.5 g / L and a sulfuric acid concentration of 230 to 250 g / L is used, the liquid temperature is 20 to 40 ° C., and the current density is 10 to 25 A / dm. Electrodeposition was performed under the plating conditions of 2 . In the second plating step, a copper sulfate solution containing a copper concentration of 65 to 75 g / L and a sulfuric acid concentration of 230 to 250 g / L is used, and the plating temperature is 50 to 55 ° C. and the current density is 5 to 15 A / dm 2 . I electrodeposited. The amount of electricity at each stage is 2.1 (Example 1) in which the ratio (Q 1 / Q 2 ) of the amount of electricity Q 1 in the first stage plating process to the amount of electricity Q 2 in the second stage plating process is 2.1 (Example 1). 8 (Example 2), 2.4 (Example 3), 1.9 (Example 4), 1.7 (Example 5), 1.6 (Example 6) or 1.2 (Example 7) did. Six types of roughened copper foils of Examples 1 to 6 were prepared by appropriately varying the conditions within the above range.
（６）防錆処理
　粗化処理後のキャリア箔付極薄銅箔の両面に、無機防錆処理及びクロメート処理からなる防錆処理を行った。まず、無機防錆処理として、ピロリン酸浴を用い、ピロリン酸カリウム濃度８０ｇ／Ｌ、亜鉛濃度０．２ｇ／Ｌ、ニッケル濃度２ｇ／Ｌ、液温４０℃、電流密度０．５Ａ／ｄｍ２で亜鉛－ニッケル合金防錆処理を行った。次いで、クロメート処理として、亜鉛－ニッケル合金防錆処理の上に、更にクロメート層を形成した。このクロメート処理は、クロム酸濃度が１ｇ／Ｌ、ｐＨ１１、溶液温度２５℃、電流密度１Ａ／ｄｍ２で行った。 (6) Rust prevention treatment Rust prevention treatment comprising inorganic rust prevention treatment and chromate treatment was performed on both surfaces of the ultrathin copper foil with carrier foil after the roughening treatment. First, as an inorganic rust prevention treatment, using a pyrophosphate bath, potassium pyrophosphate concentration 80 g / L, zinc concentration 0.2 g / L, nickel concentration 2 g / L, liquid temperature 40 ° C., current density 0.5 A / dm 2 Zinc-nickel alloy rust prevention treatment was performed. Next, as a chromate treatment, a chromate layer was further formed on the zinc-nickel alloy rust preventive treatment. This chromate treatment was performed at a chromic acid concentration of 1 g / L, pH 11, a solution temperature of 25 ° C., and a current density of 1 A / dm 2 .
（７）シランカップリング剤処理
　上記防錆処理が施された銅箔を水洗し、その後直ちにシランカップリング剤処理を行い、粗化処理面の防錆処理層上にシランカップリング剤を吸着させた。このシランカップリング剤処理は、純水を溶媒とし、３－アミノプロピルトリメトキシシラン濃度が３ｇ／Ｌの溶液を用い、この溶液をシャワーリングにて粗化処理面に吹き付けて吸着処理することにより行った。シランカップリング剤の吸着後、最終的に電熱器により水分を気散させ、厚さ３μｍの粗化処理銅箔を備えた、キャリア付銅箔を得た。 (7) Silane coupling agent treatment The copper foil that has been subjected to the above rust prevention treatment is washed with water and then immediately treated with a silane coupling agent to adsorb the silane coupling agent on the rust prevention treatment layer of the roughened surface. It was. In this silane coupling agent treatment, pure water is used as a solvent, a solution having a 3-aminopropyltrimethoxysilane concentration of 3 g / L is used, and this solution is sprayed onto the roughened surface by showering to perform an adsorption treatment. went. After adsorption of the silane coupling agent, moisture was finally diffused by an electric heater to obtain a copper foil with a carrier having a roughened copper foil having a thickness of 3 μm.
（８）粗化処理銅箔の評価
　得られた粗化処理銅箔について、略球状突起を含む表面プロファイルの諸特性を以下のとおり行った。 (8) Evaluation of roughened copper foil About the obtained roughened copper foil, the various characteristics of the surface profile containing a substantially spherical protrusion were performed as follows.
＜ネック径ａと根元離間距離ｄの測定＞
　粗化処理銅箔の略球状突起を備えた表面プロファイルのレプリカ形状を樹脂で作製し、得られた樹脂製レプリカの表面プロファイルをＳＥＭ観察し、画像解析することにより、略球状突起のネック径ａと平均根元離間距離ｄの測定を行った。具体的な手順は以下のとおりである。まず、キャリア付銅箔とプリプレグ（三菱瓦斯化学株式会社製、ＧＨＰＬ－８３０ＮＳＦ、厚さ０．１ｍｍ）とを熱圧着して銅張積層板を作製した。その後、当該キャリア付銅箔のキャリアを引き剥がした後、粗化処理銅箔をエッチング除去した。こうして残った硬化後のプリプレグ（すなわち樹脂製レプリカ）の表面プロファイルが転写された表面をＳＥＭ観察（５０００倍）し、画像解析装置（株式会社ニレコ製、ＬＵＺＥＸ　ＡＰ）により画像解析した。４３５μｍ２の領域についてネック径ａと根元離間距離ｄと測定し、それらの平均値（すなわち平均ネック径ａａｖｅと平均根元離間距離ｄａｖｅ）を求めた。 <Measurement of neck diameter a and root separation distance d>
The surface profile of the roughened copper foil having a substantially spherical protrusion is made of a resin, and the surface profile of the obtained resin replica is observed with an SEM, and image analysis is performed. And the average root separation distance d were measured. The specific procedure is as follows. First, a copper foil with a carrier and a prepreg (manufactured by Mitsubishi Gas Chemical Company, Inc., GHPL-830NSF, thickness 0.1 mm) were thermocompression bonded to produce a copper-clad laminate. Then, after peeling off the carrier of the copper foil with a carrier, the roughened copper foil was removed by etching. The surface on which the surface profile of the cured prepreg (that is, resin replica) thus transferred was transferred was subjected to SEM observation (5000 times), and image analysis was performed using an image analyzer (LUZEX AP, manufactured by Nireco Corporation). For the region of 435 μm 2, the neck diameter a and the root separation distance d were measured, and the average values thereof (that is, the average neck diameter a ave and the average root separation distance d ave ) were obtained.
　具体的な画像解析の手順は以下のとおりとした。まず、ＳＥＭによって撮影した画像を、画像処理ソフトにより二値化処理（閾値０～１１０）した。こうして得た二値化画像において結合している粒子同士を分離するため、論理フィルタにより円形切り出し処理を行った。次に、平滑化処理により輪郭のノイズを除去した後、ノイズである微小な粒子を論理フィルタにより除去した。その後、検出された個々の粒子に対してネック径ａと根元離間距離ｄを算出した。各処理において採用した条件は以下のとおりとした。
‐　二値化処理：閾値０～１１０（画像処理ソフトにおいて設定可能な二値化の閾値は０～２５５である。０が完全な黒に対応し、２５５が完全な白に対応する。）
‐　論理フィルタ円形切り出し：６（度合い）
‐　論理フィルタ指定サイズ粒子のカット：０．０３μｍ２以下の粒子をカット The specific image analysis procedure was as follows. First, an image photographed by SEM was binarized (threshold value 0 to 110) by image processing software. In order to separate the bonded particles in the binarized image thus obtained, a circular cut-out process was performed using a logical filter. Next, after removing the noise of the outline by the smoothing process, the minute particles as noise were removed by the logic filter. Thereafter, the neck diameter a and the root separation distance d were calculated for each detected particle. The conditions adopted in each treatment were as follows.
-Binarization processing: Threshold value 0 to 110 (The binarization threshold value that can be set in the image processing software is 0 to 255. 0 corresponds to perfect black, and 255 corresponds to complete white.)
-Logical filter circular cutout: 6 (degree)
-Logical particle size cut: 0.03μm 2 or less
＜最大径ｂの測定＞
　粗化処理銅箔の略球状突起を備えた表面プロファイルをＳＥＭ観察（５０００倍）して画像解析装置（株式会社ニレコ製、ＬＵＺＥＸ_ＡＰ）により画像解析した。４３５μｍ２の領域について略球状突起の最大径ｂを測定し、それらの平均値（すなわち平均最大径ｂａｖｅ）を求めた。 <Measurement of maximum diameter b>
The surface profile of the roughened copper foil with substantially spherical protrusions was observed with an SEM (5000 magnifications) and image analysis was performed using an image analyzer (LUZEX_AP, manufactured by Nireco Corporation). For the region of 435 μm 2 , the maximum diameter b of the substantially spherical protrusions was measured, and the average value thereof (that is, average maximum diameter b ave ) was determined.
　具体的な画像解析の手順は以下のとおりとした。まず、ＳＥＭによって撮影した画像を、画像処理ソフトにより空間フィルタ処理を行った。この空間フィルタ処理は、平均化により元画像のノイズを低減した後、ラプラシアンフィルタにより輪郭線を強調することにより行った。次に、画像を二値化処理（閾値６４～１６５）した。こうして得た二値化画像の輪郭線を拡張し、略球状突起一つが一つの粒子として認識されるようにした。そして、粒子同士を分離するため論理フィルタにより円形切り出し処理を実施した。次に、平滑化処理により輪郭のノイズを除去した後、ノイズである微小な粒子を論理フィルタにより除去した。その後、検出された個々の粒子に対して平均最大径ｂを算出した。各処理において採用した条件は以下のとおりとした。
‐　二値化処理：閾値６４～１４５（画像処理ソフトにおいて設定可能な二値化の閾値は０～２５５である。０が完全な黒に対応し、２５５が完全な白に対応する。）
‐　論理フィルタ指定サイズ粒子除去：０．０５μｍ２
‐　論理フィルタ円形切り出し：１０（度合い）
‐　論理フィルタ指定サイズ粒子除去：０．０５μｍ２ The specific image analysis procedure was as follows. First, an image photographed by SEM was subjected to spatial filter processing by image processing software. This spatial filter processing was performed by enhancing the contour line with a Laplacian filter after reducing the noise of the original image by averaging. Next, the image was binarized (threshold values 64 to 165). The contour line of the binarized image thus obtained was expanded so that one approximately spherical protrusion was recognized as one particle. And in order to isolate | separate particles, the circular cut-out process was implemented with the logic filter. Next, after removing the noise of the outline by the smoothing process, the minute particles as noise were removed by the logic filter. Thereafter, the average maximum diameter b was calculated for each detected particle. The conditions adopted in each treatment were as follows.
-Binarization processing: threshold value 64 to 145 (the binarization threshold value that can be set in the image processing software is 0 to 255. 0 corresponds to perfect black, and 255 corresponds to complete white.)
-Logic filter specified size particle removal: 0.05μm 2
-Logical filter circular segmentation: 10 (degree)
-Logic filter specified size particle removal: 0.05μm 2
＜高さｃの測定＞
　粗化処理銅箔の表面からＦＩＢ（Ｆｏｃｕｓｅｄ　Ｉｏｎ　Ｂｅａｍ）加工にて断面を作製し、その断面をＳＥＭ観察（５０００倍）し、箔面方向（厚さ方向に対して垂直な方向）で基準長さ２５μｍの範囲にある個々の略球状突起の高さを測定した。 <Measurement of height c>
A cross section is prepared from the surface of the roughened copper foil by FIB (Focused Ion Beam) processing, the cross section is observed with SEM (5000 times), and the reference length in the foil surface direction (direction perpendicular to the thickness direction) The height of each substantially spherical protrusion in the range of 25 μm was measured.
＜略球状粒子の傾斜角の測定＞
　例１においては、粗化処理銅箔を粗化処理面側でプリプレグ（三菱瓦斯化学株式会社製、ＧＨＰＬ－８３０ＮＳＦ、厚さ０．１ｍｍ）にプレスして張り合わせた。粗化処理銅箔の表面からＣＰ（クロスセクションポリッシャ）加工にて断面を作製し、その断面をＳＥＭ観察し、箔面方向（厚さ方向に対して垂直な方向）で基準長さ１０μｍの範囲にある個々の略球状突起の傾斜角を測定した。具体的には、まず、図４Ａに示されるように、銅箔全体が視野に入るように低倍率（例えば５０００倍）でＳＥＭ観察した断面ＳＥＭ像において、銅箔の粗化処理面と反対側の面と平行に基準線ＬＢを引いた。粗化処理面と反対側の面は粗化処理がなされていない比較的平坦な面であるため、上記低倍率では基準線ＬＢは直線として引くことができる。次に、図４Ｂに示されるように、ＳＥＭの倍率を１０，０００倍に拡大し、拡大した断面ＳＥＭ像の基準線ＬＢの基準長さ１０μｍの範囲において、略球状突起の根元境界線の中点Ｃと略球状突起の頂点Ｖを結んだ線ＬＶＣを引き、線ＬＶＣと基準線ＬＢとがなす鋭角が８５°以下である略球状突起の、略球状突起の総数に占める割合Ａを算出した。同様にして粗化処理面の他の２つの視野においても上記割合Ａを算出し、合計３視野で算出された割合Ａの平均値を採用した。 <Measurement of tilt angle of substantially spherical particles>
In Example 1, the roughened copper foil was pressed and bonded to a prepreg (manufactured by Mitsubishi Gas Chemical Company, Inc., GHPL-830NSF, thickness 0.1 mm) on the roughened surface side. A cross section is produced from the surface of the roughened copper foil by CP (cross section polisher) processing, the cross section is observed with an SEM, and the reference length is 10 μm in the foil surface direction (direction perpendicular to the thickness direction). The inclination angle of each of the substantially spherical protrusions was measured. Specifically, first, as shown in FIG. 4A, in the cross-sectional SEM image observed by SEM at a low magnification (for example, 5000 times) so that the entire copper foil enters the field of view, the side opposite to the roughened surface of the copper foil minus the reference line L B parallel to the surface. Because the surface of the roughened surface opposite to a relatively flat surface roughening treatment is not performed, the reference line L B in the low magnification can be drawn as a straight line. Next, as shown in FIG. 4B, enlarged magnification SEM 10,000 times, the reference length range of 10μm baseline L B of enlarged cross-sectional SEM image, the root boundary substantially spherical projections draw a line L VC connecting the midpoint C and the vertex V of the substantially spherical protrusions, substantially spherical projections acute angle and the line L VC and the reference line L B is 85 ° or less, a percentage of the total number of substantially spherical projections A was calculated. Similarly, the ratio A was calculated for the other two visual fields of the roughened surface, and the average value of the ratios A calculated for a total of three visual fields was adopted.
（９）銅張積層板の作製
　キャリア付極薄銅箔を用いて銅張積層板を作製した。まず、内層基板の表面に、プリプレグ（三菱瓦斯化学株式会社製、ＧＨＰＬ－８３０ＮＳＦ、厚さ０．１ｍｍ）を介してキャリア付極薄銅箔の極薄銅箔を積層し、圧力４．０ＭＰａ、温度２２０℃で９０分間熱圧着した後、キャリア箔を剥離し、銅張積層板を作製した。 (9) Production of copper-clad laminate A copper-clad laminate was produced using an ultrathin copper foil with a carrier. First, an ultrathin copper foil with a carrier is laminated on the surface of the inner layer substrate via a prepreg (manufactured by Mitsubishi Gas Chemical Co., Ltd., GHPL-830NSF, thickness 0.1 mm), and a pressure of 4.0 MPa, After thermocompression bonding at a temperature of 220 ° C. for 90 minutes, the carrier foil was peeled off to produce a copper clad laminate.
（１０）ＳＡＰ評価用積層体の作製
　次いで、硫酸・過酸化水素系エッチング液で銅張積層板表面の銅箔をすべて除去した後、脱脂、Ｐｄ系触媒付与、及び活性化処理を行った。こうして活性化された表面に無電解銅めっき（厚さ：１μｍ）を行い、ＳＡＰ法においてドライフィルムが張り合わせられる直前の積層体（以下、ＳＡＰ評価用積層体という）を得た。これらの工程はＳＡＰ法の公知の条件に従って行った。 (10) Production of Laminated Body for SAP Evaluation Next, all the copper foil on the surface of the copper-clad laminate was removed with a sulfuric acid / hydrogen peroxide-based etching solution, and then degreasing, Pd-based catalyst application, and activation treatment were performed. The surface thus activated was subjected to electroless copper plating (thickness: 1 μm) to obtain a laminate (hereinafter referred to as “SAP evaluation laminate”) immediately before the dry film was laminated by the SAP method. These steps were performed according to known conditions of the SAP method.
（１１）ＳＡＰ評価用積層体の評価
　上記得られたＳＡＰ評価用積層体について、各種特性の評価を以下のとおり行った。 (11) Evaluation of Laminated Body for SAP Evaluation Various characteristics of the obtained laminated body for SAP evaluation were evaluated as follows.
＜めっき回路密着性（剥離強度）＞
　ＳＡＰ評価用積層体にドライフィルムを張り合わせ、露光及び現像を行った。現像されたドライフィルムでマスキングされた積層体にパターンめっきで厚さ１９μｍの銅層を析出させた後、ドライフィルムを剥離した。硫酸・過酸化水素系エッチング液で表出している無電解銅めっきを除去し、高さ２０μｍ、幅１０ｍｍの剥離強度測定用サンプルを作成した。ＪＩＳ　Ｃ　６４８１（１９９６）に準拠して、評価用サンプルから銅箔を剥離する際の、剥離強度を測定した。 <Plating circuit adhesion (peel strength)>
A dry film was laminated to the laminate for SAP evaluation, and exposure and development were performed. After depositing a copper layer having a thickness of 19 μm by pattern plating on the laminate masked with the developed dry film, the dry film was peeled off. The electroless copper plating exposed by the sulfuric acid / hydrogen peroxide etching solution was removed, and a sample for measuring peel strength having a height of 20 μm and a width of 10 mm was prepared. In accordance with JIS C 6481 (1996), the peel strength when the copper foil was peeled from the sample for evaluation was measured.
＜エッチング性＞
　ＳＡＰ評価用積層体に対して硫酸・過酸化水素系エッチング液で０．１μｍずつエッチングを行い、表面の銅が完全になくなるまでの量（深さ）を計測した。計測方法は、光学顕微鏡（５００倍）で確認した。より詳しくは、０．１μｍエッチングする毎に光学顕微鏡で銅の有無で確認する作業を繰り返し、（エッチングの回数）×０．１μｍにより得られた値（μｍ）をエッチング性の指標として用いた。例えば、エッチング性が１．２μｍということは、０．１μｍのエッチングを１２回行ったところで、光学顕微鏡で残存銅が検出されなくなったことを意味する（すなわち０．１μｍ×１２回＝１．２μｍ）。すなわち、この値が小さいほど少ない回数のエッチングで表面の銅を除去できることを意味する。すなわちこの値が小さいほどエッチング性が良好であることを意味する。 <Etching property>
The laminate for SAP evaluation was etched by 0.1 μm with a sulfuric acid / hydrogen peroxide etching solution, and the amount (depth) until copper on the surface was completely removed was measured. The measuring method was confirmed with an optical microscope (500 times). More specifically, each time 0.1 μm etching was performed, the operation of checking with or without copper was repeated with an optical microscope, and the value (μm) obtained by (number of etchings) × 0.1 μm was used as an index of etching property. For example, an etching property of 1.2 μm means that residual copper is no longer detected by an optical microscope after performing 0.1 μm etching 12 times (that is, 0.1 μm × 12 times = 1.2 μm). ). That is, as this value is smaller, it means that copper on the surface can be removed by a smaller number of etchings. That is, the smaller this value, the better the etching property.
＜ドライフィルム解像性（最小Ｌ／Ｓ）＞
　ＳＡＰ評価用積層体の表面に厚さ２５μｍのドライフィルムを張り合わせ、ライン／スペース（Ｌ／Ｓ）が２μｍ／２μｍから１５μｍ／１５μｍまでのパターンが形成されたマスクを用いて露光及び現像を行った。このときの露光量は１２５ｍＪとした。現像後のサンプルの表面を光学顕微鏡（５００倍）で観察し、問題なく現像が行えたＬ／Ｓにおける最小の（すなわち最も微細な）Ｌ／Ｓをドライフィルム解像性の指標として採用した。例えば、ドライフィルム解像性評価の指標である最小Ｌ／Ｓ＝１０μｍ／１０μｍということは、Ｌ／Ｓ＝１５μｍ／１５μｍから１０μｍ／１０μｍまでは問題無く解像できたことを意味する。例えば、問題無く解像できた場合は図５に示されるようにドライフィルムパターン間で鮮明なコントラストが観察されるのに対し、解像が良好に行われなかった場合には図６に示されるようにドライフィルムパターン間に黒ずんだ部分が観察され鮮明なコントラストが観察されない。 <Dry film resolution (minimum L / S)>
A dry film having a thickness of 25 μm was laminated on the surface of the laminate for SAP evaluation, and exposure and development were performed using a mask in which a line / space (L / S) pattern of 2 μm / 2 μm to 15 μm / 15 μm was formed. . The exposure amount at this time was set to 125 mJ. The surface of the sample after development was observed with an optical microscope (500 times), and the smallest (that is, the finest) L / S in the L / S that could be developed without any problem was adopted as an index for the resolution of the dry film. For example, the minimum L / S = 10 μm / 10 μm, which is an index for evaluating the dry film resolution, means that the resolution could be achieved without any problem from L / S = 15 μm / 15 μm to 10 μm / 10 μm. For example, when the resolution can be performed without any problem, a clear contrast is observed between the dry film patterns as shown in FIG. 5, whereas when the resolution is not performed well, the resolution is shown in FIG. Thus, a darkened portion is observed between the dry film patterns, and no clear contrast is observed.
　例７（比較）
　粗化処理における、１段階目のめっき工程における電気量Ｑ１の２段階目のめっき工程における電気量Ｑ２に対する比（Ｑ１／Ｑ２）を１．５未満となるように設定したこと以外は例１～６に関して述べた手順と同様にしてキャリア付粗化処理銅箔の作製及び評価を行った。 Example 7 (Comparison)
Other than the ratio (Q 1 / Q 2 ) of the amount of electricity Q 1 in the first step plating step to the amount of electricity Q 2 in the second step plating step (Q 1 / Q 2 ) in the roughening treatment. Prepared and evaluated roughened copper foil with carrier in the same manner as described in Examples 1-6.
　例８（比較）
　特許文献１（特開２０１３－１９９０８２号公報）の実施例２に記載に従い以下の手順で粗化処理を行ったこと以外は例１～６に関して述べた手順と同様にしてキャリア付粗化処理銅箔の作製及び評価を行った。 Example 8 (Comparison)
Roughened copper with carrier in the same manner as described with respect to Examples 1 to 6 except that the roughening treatment was performed according to the following procedure according to Example 2 of Patent Document 1 (Japanese Patent Laid-Open No. 2013-199082). Preparation and evaluation of foil were performed.
（粗化処理）
　以下の液組成のめっき液を用いて粗化めっきを施すことにより粗化処理を行った。このとき粗化粒子形成時の対限界電流密度比は３．１０とし、電気めっき温度は５０℃とした。＜粗化処理用めっき液の組成＞
-　Ｃｕ：１５ｇ／Ｌ
-　Ｈ２ＳＯ４：１００ｇ／Ｌ
-　Ｗ：３ｍｇ／Ｌ
-　ドデシル硫酸ナトリウム添加量：１０ｐｐｍ (Roughening treatment)
Roughening was performed by performing roughening plating using a plating solution having the following liquid composition. At this time, the ratio of the limiting current density during the formation of roughened particles was 3.10, and the electroplating temperature was 50 ° C. <Composition of plating solution for roughening treatment>
-Cu: 15 g / L
-H 2 SO 4 : 100 g / L
-W: 3mg / L
-Sodium dodecyl sulfate addition amount: 10ppm
　例９
　回転陰極として、表面を＃２０００のバフで研磨して表面粗さを整えた電極を用いたこと以外は例１と同様にして、キャリア付粗化処理銅箔の作製及び評価を行った。なお、粗化処理前の極薄銅箔の析出面は、Ｗｍａｘが１．００μｍ、Ｐｅａｋ　ｓｐａｃｉｎｇが２０．２８μｍであった。 Example 9
A roughened copper foil with a carrier was prepared and evaluated in the same manner as in Example 1 except that an electrode whose surface was polished by adjusting the surface with a # 2000 buff was used as the rotating cathode. In addition, as for the precipitation surface of the ultra-thin copper foil before a roughening process, Wmax was 1.00 micrometer and Peak spacing was 20.28 micrometers.
　例１０
　有機剥離層の形成をキャリア用銅箔の析出面側に行ったこと以外は例１と同様にして、キャリア付粗化処理銅箔の作製及び評価を行った。粗化処理前の極薄銅箔の析出面は、Ｗｍａｘが０．７１μｍ、Ｐｅａｋ　ｓｐａｃｉｎｇが５２．１３μｍであった。 Example 10
Preparation and evaluation of the roughened copper foil with carrier were performed in the same manner as in Example 1 except that the organic release layer was formed on the deposition surface side of the carrier copper foil. The precipitation surface of the ultrathin copper foil before the roughening treatment had a Wmax of 0.71 μm and a peak spacing of 52.13 μm.
　結果
　例１～１０において得られた評価結果は表１及び２に示されるとおりであった。 Results The evaluation results obtained in Examples 1 to 10 were as shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１に示されるように、例１～６においてはいずれも、めっき回路密着性、エッチング性及びドライフィルム解像性のいずれにも良好であった。一方、表２に示されるように、ａａｖｅ／ｂａｖｅ比が低いが故に本発明の範囲外である例７（比較）においてはめっき回路密着性が悪く、ドライフィルム解像性も劣るものであった。また、平均高さｃａｖｅが高いが故に本発明の範囲外である例８（比較）においてはエッチング性に劣るものであった。また、高傾斜略球状突起の割合が３０～６０％の範囲内の例９は、上記範囲外の例１及び１０と比較して、ドライフィルム解像性とめっき回路密着性との両立により優れるものであった。

  As shown in Table 1, all of Examples 1 to 6 were good in plating circuit adhesion, etching property, and dry film resolution. On the other hand, as shown in Table 2, in Example 7 (comparison), which is out of the scope of the present invention because the a ave / b ave ratio is low, the adhesion of the plating circuit is poor and the dry film resolution is also poor. there were. Moreover, in Example 8 (comparison) which is outside the scope of the present invention because of the high average height c ave , the etching property was inferior. In addition, Example 9 in which the ratio of the highly inclined substantially spherical protrusions is in the range of 30 to 60% is superior to Examples 1 and 10 outside the above range in terms of both dry film resolution and plating circuit adhesion. It was a thing.

Claims (14)

  1. 　少なくとも一方の側に粗化処理面を有する粗化処理銅箔であって、前記粗化処理面が銅粒子からなる複数の略球状突起を備えてなり、前記略球状突起の平均高さが２．６０μｍ以下であり、かつ、前記略球状突起の平均ネック径ａａｖｅに対する前記略球状突起の平均最大径ｂａｖｅの比ｂａｖｅ／ａａｖｅが１．２以上である、粗化処理銅箔。 A roughened copper foil having a roughened surface on at least one side, wherein the roughened surface comprises a plurality of substantially spherical protrusions made of copper particles, and the average height of the substantially spherical protrusions is 2 A roughened copper foil having a ratio b ave / a ave of not more than 60 μm and a ratio of the average maximum diameter b ave of the substantially spherical protrusions to the average neck diameter a ave of the substantially spherical protrusions being 1.2 or more.
  2. 　前記比ｂａｖｅ／ａａｖｅが５．０以下である、請求項１に記載の粗化処理銅箔。 The roughened copper foil according to claim 1, wherein the ratio b ave / a ave is 5.0 or less.
  3. 　前記比ｂａｖｅ／ａａｖｅが１．３～２．０である、請求項１又は２に記載の粗化処理銅箔。 The roughened copper foil according to claim 1 or 2, wherein the ratio b ave / a ave is 1.3 to 2.0.
  4. 　前記略球状突起の平均最大径ｂａｖｅが２．５μｍ以下である、請求項１～３のいずれか一項に記載の粗化処理銅箔。 The roughened copper foil according to any one of claims 1 to 3, wherein an average maximum diameter b ave of the substantially spherical protrusion is 2.5 µm or less.
  5. 　前記粗化処理面に存在する略球状突起に占める、略球状突起のネック径ａに対する前記略球状突起の最大径ｂの比ｂ／ａが１．２以上である略球状突起の割合が６０％以上である、請求項１～４のいずれか一項に記載の粗化処理銅箔。 The ratio of the substantially spherical protrusions in which the ratio b / a of the maximum diameter b of the substantially spherical protrusions to the neck diameter a of the substantially spherical protrusions occupies in the substantially spherical protrusions existing on the roughened surface is 60% or more. The roughened copper foil according to any one of claims 1 to 4, which is as described above.
  6. 　前記略球状突起の平均根元離間距離が０．１～０．３μｍである、請求項１～５のいずれか一項に記載の粗化処理銅箔。 The roughened copper foil according to any one of claims 1 to 5, wherein an average root separation distance of the substantially spherical protrusions is 0.1 to 0.3 µm.
  7. 　前記略球状突起が１～１０個／μｍ２の面密度で存在する、請求項１～６のいずれか一項に記載の粗化処理銅箔。 The roughened copper foil according to any one of claims 1 to 6, wherein the substantially spherical protrusions are present at a surface density of 1 to 10 pieces / μm 2 .
  8. 　前記粗化処理銅箔が一方の側にのみ前記粗化処理面を有し、かつ、前記略球状突起の総数に占める高傾斜略球状突起の割合が３０～６０％であり、前記高傾斜略球状突起は、略球状突起の根元境界線の中点と前記略球状突起の頂点を結んだ線と、前記粗化処理銅箔の前記粗化処理面と反対側の面と平行な基準線とがなす鋭角が８５°以下である略球状突起である、請求項１～７のいずれか一項に記載の粗化処理銅箔。 The roughened copper foil has the roughened surface only on one side, and the ratio of the highly inclined substantially spherical protrusions to the total number of the approximately spherical protrusions is 30 to 60%, and the high inclined substantially The spherical protrusion is a line connecting the midpoint of the base boundary line of the substantially spherical protrusion and the apex of the substantially spherical protrusion, and a reference line parallel to the surface opposite to the roughened surface of the roughened copper foil. The roughened copper foil according to any one of claims 1 to 7, which is a substantially spherical protrusion having an acute angle of 85 ° or less.
  9. 　前記粗化処理銅箔が０．５～５μｍの厚さを有する、請求項１～８のいずれか一項に記載の粗化処理銅箔。 The roughened copper foil according to any one of claims 1 to 8, wherein the roughened copper foil has a thickness of 0.5 to 5 µm.
  10. 　プリント配線板用の絶縁樹脂層に凹凸形状を転写するために用いられる、請求項１～９のいずれか一項に記載の粗化処理銅箔。 The roughened copper foil according to any one of claims 1 to 9, which is used for transferring an uneven shape to an insulating resin layer for a printed wiring board.
  11. 　セミアディティブ法（ＳＡＰ）によるプリント配線板の作製に用いられる、請求項１～１０のいずれか一項に記載の粗化処理銅箔。 The roughened copper foil according to any one of claims 1 to 10, which is used for production of a printed wiring board by a semi-additive method (SAP).
  12. 　キャリア箔と、該キャリア箔上に設けられた剥離層と、該剥離層上に前記粗化処理面を外側にして設けられた請求項１～１１のいずれか一項に記載の粗化処理銅箔とを備えた、キャリア付銅箔。 A roughened copper according to any one of claims 1 to 11, provided with a carrier foil, a release layer provided on the carrier foil, and the release surface with the roughened surface facing outside. A copper foil with a carrier provided with a foil.
  13. 　請求項１～１１のいずれか一項に記載の粗化処理銅箔又は請求項１２に記載のキャリア付銅箔を用いて得られた銅張積層板。 A copper-clad laminate obtained using the roughened copper foil according to any one of claims 1 to 11 or the copper foil with a carrier according to claim 12.
  14. 　請求項１～１１のいずれか一項に記載の粗化処理銅箔又は請求項１２に記載のキャリア付銅箔を用いて得られたプリント配線板。

          A printed wiring board obtained using the roughened copper foil according to any one of claims 1 to 11 or the copper foil with carrier according to claim 12.

PCT/JP2016/059671 2015-03-31 2016-03-25 Roughened copper foil, copper foil provided with carrier, copper-clad laminated sheet, and printed wiring board WO2016158775A1 (en)

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