WO2016158775A1 - Feuille de cuivre rugosifiée, feuille de cuivre pourvue d'un support, plaque stratifiée cuivrée, et carte de circuit imprimé - Google Patents

Feuille de cuivre rugosifiée, feuille de cuivre pourvue d'un support, plaque stratifiée cuivrée, et carte de circuit imprimé 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
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PCT/JP2016/059671
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English (en)
Japanese (ja)
Inventor
浩人 飯田
光由 松田
吉川 和広
信之 河合
翼 加藤
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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/zh
Priority to MYPI2017703411A priority patent/MY186266A/en
Priority to KR1020177016424A priority patent/KR102273442B1/ko
Priority to JP2017509918A priority patent/JP6293365B2/ja
Publication of WO2016158775A1 publication Critical patent/WO2016158775A1/fr

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/605Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus 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
    • H05K3/18Apparatus 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
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03Metal processing
    • H05K2203/0307Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703Plating
    • H05K2203/0723Electroplating, e.g. finish plating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus 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
    • H05K3/18Apparatus 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
    • H05K3/188Apparatus 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

L'invention concerne une plaque de cuivre rugosifiée qui, lorsqu'elle est utilisée dans le procédé SAP, peut doter un stratifié d'un profil de surface excellent non seulement en termes d'adhérence de circuit plaqué, mais également en termes de qualité de gravure pour un cuivrage chimique autocatalytique et une résolution de film sec. Cette feuille de cuivre rugosifiée présente une surface rugosifiée sur au moins un côté, la surface rugosifiée étant pourvue d'une pluralité de saillies sensiblement sphériques composées de particules de cuivre; la hauteur moyenne des saillies sensiblement sphériques est inférieure ou égale à 2,60 μm; et le rapport bave/aave du diamètre maximal moyen bave des saillies sensiblement sphériques au diamètre de col moyen aave des saillies sensiblement sphériques est égal ou supérieur à 1,2.
PCT/JP2016/059671 2015-03-31 2016-03-25 Feuille de cuivre rugosifiée, feuille de cuivre pourvue d'un support, plaque stratifiée cuivrée, et carte de circuit imprimé WO2016158775A1 (fr)

Priority Applications (4)

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CN201680020446.8A CN107429417B (zh) 2015-03-31 2016-03-25 粗糙化处理铜箔、带载体铜箔、覆铜层叠板及印刷电路板
MYPI2017703411A MY186266A (en) 2015-03-31 2016-03-25 Roughened copper foil, copper foil provided with carrier, copper-clad laminated sheet, and printed wiring board
KR1020177016424A KR102273442B1 (ko) 2015-03-31 2016-03-25 조화 처리 동박, 캐리어 부착 동박, 동장 적층판 및 프린트 배선판
JP2017509918A JP6293365B2 (ja) 2015-03-31 2016-03-25 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

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018211951A1 (fr) * 2017-05-19 2018-11-22 三井金属鉱業株式会社 Feuille de cuivre rugosifiée, feuille de cuivre fixée à un support, stratifié plaqué cuivre et carte de circuits imprimés
WO2019111914A1 (fr) * 2017-12-05 2019-06-13 古河電気工業株式会社 Feuille de cuivre traitée en surface et stratifié cuivré et carte de circuit imprimé utilisant chacun celle-ci
WO2019188712A1 (fr) * 2018-03-27 2019-10-03 三井金属鉱業株式会社 Feuille de cuivre rugueuse, feuille de cuivre pourvue d'un support, plaque multicouche cuivrée et carte de circuit imprimé
WO2020093729A1 (fr) * 2018-11-09 2020-05-14 广州方邦电子股份有限公司 Connecteur flexible et son procédé de fabrication
WO2020196106A1 (fr) * 2019-03-26 2020-10-01 三井金属鉱業株式会社 Procédé de fabrication d'une carte de circuit imprimé
WO2020196105A1 (fr) * 2019-03-26 2020-10-01 三井金属鉱業株式会社 Procédé de fabrication de carte de circuit imprimé
JP2020158832A (ja) * 2019-03-26 2020-10-01 古河電気工業株式会社 表面処理銅箔、並びにこれを用いた銅張積層板及びプリント配線板
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KR20200135303A (ko) 2018-03-27 2020-12-02 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어를 구비한 구리박, 동장 적층판 및 프린트 배선판
JPWO2019188712A1 (ja) * 2018-03-27 2021-04-22 三井金属鉱業株式会社 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
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JPWO2020196106A1 (ja) * 2019-03-26 2021-10-14 三井金属鉱業株式会社 プリント配線板の製造方法
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WO2020196106A1 (fr) * 2019-03-26 2020-10-01 三井金属鉱業株式会社 Procédé de fabrication d'une carte de circuit imprimé
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JP7410128B2 (ja) 2019-03-26 2024-01-09 三井金属鉱業株式会社 プリント配線板の製造方法
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