TW202134053A - Composite copper member having voids - Google Patents

Composite copper member having voids Download PDF

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TW202134053A
TW202134053A TW110105957A TW110105957A TW202134053A TW 202134053 A TW202134053 A TW 202134053A TW 110105957 A TW110105957 A TW 110105957A TW 110105957 A TW110105957 A TW 110105957A TW 202134053 A TW202134053 A TW 202134053A
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copper
composite
composite copper
copper component
copper oxide
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小畠直貴
小鍛冶快允
佐藤牧子
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日商納美仕有限公司
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B32B38/004—Heat treatment by physically contacting the layers, e.g. by the use of heated platens or rollers
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • H05K1/03—Use of materials for the substrate
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

Provided is a composite copper member in which a copper-oxide-containing layer is formed on at least part of the surface of a copper member, the composite copper member being such that voids are present in the copper-oxide-containing layer.

Description

具有空隙之複合銅構件Composite copper components with voids

本發明係關於一種具有空隙之複合銅構件。The present invention relates to a composite copper component with voids.

用於印刷佈線板之銅箔需要與絕緣性樹脂基材之密著性。為了提升此密著性，已有藉由蝕刻等將銅箔表面粗化處理，即藉由所謂的錨定效應（anchor effect）以提升機械性黏著力的方法。另一方面，由印刷佈線板之高密度化或在高頻帶之傳輸損失的觀點而言，銅箔表面需要平坦化。為了滿足上述相反的要求，已開發出進行氧化步驟及還原步驟等之銅表面處理方法（國際公開第2014/126193號公報）。該方法中，係將銅箔前處理，浸漬於含有氧化劑之藥水，使銅箔表面氧化以形成氧化銅之凹凸後，浸漬於含有還原劑之藥水以使氧化銅還原，藉此調整表面的凹凸以調整表面粗度。此外，另開發有在氧化步驟中添加界面活性分子的方法作為利用氧化、還原之銅箔處理的密著性改善方法（日本特表第2013-534054號公報）、在還原步驟後使用胺基噻唑系化合物等在銅箔表面形成保護皮膜的方法（日本特開平8-97559號公報）。The copper foil used for the printed wiring board needs adhesion to the insulating resin substrate. In order to improve the adhesion, there has been a method of roughening the surface of the copper foil by etching or the like, that is, by using the so-called anchor effect to improve the mechanical adhesion. On the other hand, from the viewpoint of increased density of printed wiring boards or transmission loss in high frequency bands, the surface of the copper foil needs to be flattened. In order to meet the above-mentioned opposite requirements, a copper surface treatment method that performs an oxidation step and a reduction step has been developed (International Publication No. 2014/126193). In this method, the copper foil is pre-treated and immersed in a potion containing an oxidizing agent to oxidize the surface of the copper foil to form copper oxide bumps, and then immersed in a potion containing a reducing agent to reduce the copper oxide, thereby adjusting the surface bumps To adjust the surface roughness. In addition, a method of adding interfacial active molecules in the oxidation step has also been developed as a method for improving the adhesion of copper foil treatment by oxidation and reduction (Japanese Patent Application No. 2013-534054), and the use of aminothiazole after the reduction step A method of forming a protective film on the surface of a copper foil with a compound or the like (Japanese Patent Application Laid-Open No. 8-97559).

一般而言，樹脂與金屬之間的黏著，除了機械性黏著力以外，亦與1）樹脂與金屬之間的分子間作用力產生的物理性鍵結力或2）樹脂的官能基與金屬之共價鍵等產生的化學性鍵結力有關。高頻電路用之絕緣性樹脂為了達到低電容率、低耗散因子，係減少OH基（氫氧基）的比例，但樹脂的OH基對於與金屬之鍵結有關，故導致與銅箔之化學性鍵結力變弱（國際公開第2017/150043號公報）。因此，高頻電路用之絕緣性樹脂與銅箔之黏著需要更強的機械性黏著力。Generally speaking, in addition to mechanical adhesion, the adhesion between resin and metal is also related to 1) the physical bonding force generated by the intermolecular force between the resin and the metal or 2) the functional group of the resin and the metal. It is related to the chemical bonding force produced by covalent bonds. In order to achieve low permittivity and low dissipation factor, the insulating resin used in high-frequency circuits reduces the proportion of OH groups (hydroxy groups). The chemical bonding force becomes weaker (International Publication No. 2017/150043). Therefore, the adhesion of insulating resin and copper foil for high-frequency circuits requires stronger mechanical adhesion.

本案發明人等亦開發了一種複合銅箔，係對經粗化處理之銅箔以電鍍鍍敷鎳，且密著性優異（國際公開第2019/093494號公報）。The inventors of this case have also developed a composite copper foil, which is electroplated with nickel on the roughened copper foil, and has excellent adhesion (International Publication No. 2019/093494).

本發明提供一種新穎的複合銅構件及使用其之印刷佈線板、以及銅構件作為載體作用且被金屬鍍敷之銅構件。The present invention provides a novel composite copper component, a printed wiring board using the same, and a copper component that functions as a carrier and is metal-plated.

本發明人等致力研究的結果，發現藉由使以粗化處理生成的包含銅氧化物之層產生空隙，不使形成凹凸的包含銅氧化物之層的強度提升，反而使其降低，藉此可製作適用於形成印刷佈線板及半導體封裝基板之電路，特別是適用於半加成法（Semi-Additive Process）（SAP法）或M-SAP（Modified Semi-Additive Process）（MSAP法）的複合銅構件。As a result of intensive research, the inventors found that by creating voids in the copper oxide-containing layer formed by the roughening treatment, the strength of the copper oxide-containing layer forming the unevenness is not increased, but is reduced, thereby Can be used to make circuits suitable for forming printed wiring boards and semiconductor packaging substrates, especially suitable for semi-additive process (SAP method) or M-SAP (Modified Semi-Additive Process) (MSAP method) Copper components.

本發明具有以下的實施態樣： ［1］一種複合銅構件，係於銅構件的表面的至少一部分形成有包含銅氧化物之層，該包含銅氧化物之層具有數個空隙。 ［2］如［1］之複合銅構件，其中，該數個空隙中，至少一部分的空隙存在於該包含銅氧化物之層與該銅構件的表面之界面。 ［3］如［1］或［2］之複合銅構件，其中，該包含銅氧化物之層與該銅構件的表面之間的剝離強度為0.001kgf/cm以上且0.30kgf/cm以下。 ［4］如［1］～［3］中任一項之複合銅構件，其中，取得掃描式電子顯微鏡之截面的拍攝影像，將該拍攝影像二值化時，在與該包含銅氧化物之層平行的方向測量時，任意每3.8μm中偵測到之該空隙的數量為30個以上。 ［5］如［1］～［4］中任一項之複合銅構件，其中，將該複合銅構件的該包含銅氧化物之層的表面以規定條件熱壓接於樹脂基材，形成積層體，取得該積層體的掃描式電子顯微鏡之截面的拍攝影像，將該拍攝影像二值化時，在與被積層之面平行的方向測量時，任意每3.8μm中偵測到之該空隙的數量為30個以上。 ［6］如［4］或［5］之複合銅構件，其中，該二值化之截面的拍攝影像中，該空隙間的平均距離為100nm以下。 ［7］如［4］或［5］之複合銅構件，其中，該二值化之截面的拍攝影像中，該空隙間的距離為50nm以下的比例占空隙間整體的40%以上。 ［8］如［5］～［7］中任一項之複合銅構件，其中，該樹脂基材含有選自由聚苯醚、環氧樹脂、聚氧二甲苯、聚苯噁唑、聚四氟乙烯、液晶聚合物、亞磷酸三苯酯、氟樹脂、聚醚醯亞胺、聚醚醚酮、聚環烯烴、雙馬來醯亞胺樹脂、低電容率聚醯亞胺及氰酸樹脂所組成之群組中的至少一種絕緣性樹脂。 ［9］如［5］～［8］中任一項之複合銅構件，其中，該熱壓接的規定條件係於50℃～400℃之溫度、0～20MPa之壓力及1分鐘～5小時之時間的範圍內。 ［10］如［5］～［9］中任一項之複合銅構件，其中，形成有該包含銅氧化物之層的表面的Ra為0.04μm以上，相對於該Ra，由該樹脂基材剝離之該銅構件的表面的Ra之比例為未滿100%。 ［11］如［5］～［10］中任一項之複合銅構件，其中，熱壓接後由該樹脂基材剝離之該銅構件的表面積相對於形成有該包含銅氧化物之層的表面之表面積的比例為未滿100%。 ［12］如［1］～［11］中任一項之複合銅構件，其中，該包含銅氧化物之層包含銅以外之金屬。 ［13］如［12］之複合銅構件，其中，該銅以外之金屬為鎳。 ［14］如［1］～［11］中任一項之複合銅構件，其中，該包含銅氧化物之層包含銅鍍層。 ［15］一種附載體金屬箔，包含如［12］～［14］中任一項之複合銅構件，該包含銅氧化物之層作為金屬箔使用，該銅構件作為相對於該金屬箔之載體使用。 ［16］一種積層體，係於如［1］～［14］中任一項之複合銅構件的該包含銅氧化物之層的至少一部分表面積層有樹脂基材。 ［17］如［16］之積層體，其中，該樹脂基材含有選自由聚苯醚、環氧樹脂、聚氧二甲苯、聚苯噁唑、聚四氟乙烯、液晶聚合物、亞磷酸三苯酯、氟樹脂、聚醚醯亞胺、聚醚醚酮、聚環烯烴、雙馬來醯亞胺樹脂、低電容率聚醯亞胺及氰酸樹脂所組成之群組中的至少一種絕緣性樹脂。 ［18］如［1］～［14］中任一項之複合銅構件，係用於製作印刷佈線板。 ［19］如［18］之複合銅構件，係用於以半加成法或M-SAP法製作印刷佈線板。The present invention has the following implementation aspects: [1] A composite copper component in which a layer containing copper oxide is formed on at least a part of the surface of the copper component, and the layer containing copper oxide has several voids. [2] The composite copper component according to [1], wherein, among the plurality of voids, at least a part of the voids exists at the interface between the copper oxide-containing layer and the surface of the copper component. [3] The composite copper member according to [1] or [2], wherein the peel strength between the copper oxide-containing layer and the surface of the copper member is 0.001 kgf/cm or more and 0.30 kgf/cm or less. [4] The composite copper member as described in any one of [1] to [3], in which a cross-sectional image of the scanning electron microscope is taken, and when the captured image is binarized, it is compared with the copper oxide containing When the layers are measured in the direction parallel to each other, the number of the gaps detected in any 3.8 μm is more than 30. [5] The composite copper component according to any one of [1] to [4], wherein the surface of the copper oxide-containing layer of the composite copper component is thermocompression bonded to the resin substrate under predetermined conditions to form a laminate When measuring in a direction parallel to the layered surface, when the captured image is binarized by the scanning electron microscope cross-section of the laminated body, the amount of the gap detected in any 3.8μm The number is more than 30. [6] The composite copper member as in [4] or [5], wherein the average distance between the voids in the captured image of the binarized cross-section is 100 nm or less. [7] The composite copper member as in [4] or [5], wherein in the captured image of the binarized cross-section, the ratio of the distance between the voids of 50 nm or less accounts for more than 40% of the entire void. [8] The composite copper component as described in any one of [5] to [7], wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, and polytetrafluoroethylene Ethylene, liquid crystal polymer, triphenyl phosphite, fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin At least one insulating resin in the composition group. [9] The composite copper component as described in any one of [5] to [8], wherein the prescribed conditions for the thermal compression bonding are at a temperature of 50°C to 400°C, a pressure of 0 to 20 MPa, and 1 minute to 5 hours Within the range of time. [10] The composite copper member according to any one of [5] to [9], wherein the Ra of the surface on which the copper oxide-containing layer is formed is 0.04 μm or more, and the resin base material The ratio of Ra on the surface of the peeled copper member is less than 100%. [11] The composite copper member according to any one of [5] to [10], wherein the surface area of the copper member peeled from the resin substrate after thermocompression bonding is relative to the surface area of the copper oxide-containing layer The ratio of the surface area of the surface is less than 100%. [12] The composite copper component according to any one of [1] to [11], wherein the layer containing copper oxide contains a metal other than copper. [13] The composite copper component as in [12], wherein the metal other than copper is nickel. [14] The composite copper component according to any one of [1] to [11], wherein the layer containing copper oxide includes a copper plating layer. [15] A metal foil with a carrier, comprising the composite copper member as described in any one of [12] to [14], the layer containing copper oxide is used as a metal foil, and the copper member is used as a carrier relative to the metal foil use. [16] A laminate in which at least a part of the surface area of the copper oxide-containing layer of the composite copper member according to any one of [1] to [14] is layered with a resin substrate. [17] The laminated body as in [16], wherein the resin base material contains three selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer, and phosphorous acid. At least one insulation from the group consisting of phenyl ester, fluororesin, polyether imide, polyether ether ketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin性resin. [18] The composite copper component as in any one of [1] to [14] is used to make printed wiring boards. [19] The composite copper components such as [18] are used to make printed wiring boards by the semi-additive method or the M-SAP method.

［20］一種印刷佈線板的製造方法，係使用如［1］～［14］中任一項之複合銅構件的印刷佈線板的製造方法，包含： 1）在該複合銅構件的該包含銅氧化物之層上將樹脂基材以規定條件熱壓接的步驟； 2）由該樹脂基材以規定條件將該銅構件剝離，得到具有形成該包含銅氧化物之層的金屬之一部分或全部之樹脂基材的步驟；及 3）在具有形成該包含銅氧化物之層的金屬之一部分或全部之樹脂基材的表面進行銅鍍處理的步驟。 ［21］一種具有金屬之樹脂基材的製造方法，包含： 1）在如［1］～［14］中任一項之複合銅構件的該包含銅氧化物之層上將樹脂基材以規定條件熱壓接的步驟；及 2）由該樹脂基材以規定條件將該銅構件剝離，得到具有形成該包含銅氧化物之層的金屬之一部分或全部之樹脂基材的步驟。 ［22］一種複合銅構件的製造方法，係如［1］～［11］中任一項之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之表面作部分塗覆的步驟；及 2）將該被部分塗覆之該表面氧化處理的步驟。 ［23］一種複合銅構件的製造方法，係如［1］～［11］中任一項之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之表面作部分塗覆的步驟； 2）將該被部分塗覆之該表面氧化處理的步驟；及 3）將所形成之包含銅氧化物之層的表面以修飾劑處理的步驟，在此，該修飾劑包含選自由氯化鎳、氯化鋅、氯化鐵、氯化鉻、檸檬酸銨、氯化銨、氯化鉀、硫酸銨、硫酸鎳銨、乙二胺四乙酸、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉及葡萄糖酸鈉所組成之群組的化合物。 ［24］一種複合銅構件的製造方法，係如［12］之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之表面作部分塗覆的步驟； 2）將該被部分塗覆之該表面氧化處理的步驟；及 3）在經氧化處理之該表面形成包含銅以外之金屬的層的步驟。 ［25］一種複合銅構件的製造方法，係如［12］之複合銅構件的製造方法，包含： 1）將該銅構件之該表面氧化處理的步驟； 2）將經該氧化處理之該表面以修飾劑處理的步驟；及 3）在經該修飾劑處理之該表面，形成包含銅以外之金屬的層的步驟，在此，該修飾劑包含選自由氯化鎳、氯化鋅、氯化鐵、氯化鉻、檸檬酸銨、氯化銨、氯化鉀、硫酸銨、硫酸鎳銨、乙二胺四乙酸、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉及葡萄糖酸鈉所組成之群組的化合物。 ［26］一種複合銅構件的製造方法，係如［12］之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之該表面作部分塗覆的步驟； 2）將該被部分塗覆之該表面氧化處理的步驟； 3）將經該氧化處理之該表面以修飾劑處理的步驟，及 4）在經該修飾劑處理之該表面，形成包含銅以外之金屬的層的步驟，在此，該修飾劑包含選自由氯化鎳、氯化鋅、氯化鐵、氯化鉻、檸檬酸銨、氯化銨、氯化鉀、硫酸銨、硫酸鎳銨、乙二胺四乙酸、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉及葡萄糖酸鈉所組成之群組的化合物。[20] A method for manufacturing a printed wiring board, which is a method for manufacturing a printed wiring board using a composite copper member as described in any one of [1] to [14], including: 1) A step of thermocompression bonding a resin substrate under specified conditions on the copper oxide-containing layer of the composite copper component; 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having part or all of the metal forming the copper oxide-containing layer; and 3) A step of performing copper plating treatment on the surface of a resin substrate having part or all of the metal forming the copper oxide-containing layer. [21] A method for manufacturing a resin substrate with metal, including: 1) A step of thermocompression bonding a resin base material under prescribed conditions on the copper oxide-containing layer of the composite copper component as in any one of [1] to [14]; and 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having a part or all of the metal forming the copper oxide-containing layer. [22] A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in any one of [1] to [11], including: 1) The step of partially coating the surface of the copper component with silane coupling agent; and 2) The step of oxidizing the partially coated surface. [23] A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in any one of [1] to [11], including: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) The step of treating the surface of the formed copper oxide-containing layer with a modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, Ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinate Acid, 3-hydroxy-2,2'-imino sodium disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl)imino A compound of the group consisting of disodium diacetate and sodium gluconate. [24] A method of manufacturing composite copper components, such as the method of manufacturing composite copper components in [12], including: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) A step of forming a layer containing a metal other than copper on the surface that has been oxidized. [25] A method for manufacturing composite copper components, such as the method for manufacturing composite copper components in [12], including: 1) The step of oxidizing the surface of the copper component; 2) The step of treating the surface after the oxidation treatment with a modifier; and 3) A step of forming a layer containing metals other than copper on the surface treated with the modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate. [26] A method of manufacturing composite copper components, such as the method of manufacturing composite copper components in [12], including: 1) The step of partially coating the surface of the copper component with a silane coupling agent; 2) The step of oxidizing the partially coated surface; 3) The step of treating the surface after the oxidation treatment with a modifier, and 4) A step of forming a layer containing metals other than copper on the surface treated with the modifier. Here, the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate.

以下使用附加圖式詳細地說明本發明的較佳實施形態，但不限定於此。又，根據本說明書的記載，發明所屬技術領域中具有通常知識者係明瞭本發明的目的、特徵、優點及其構思，發明所屬技術領域中具有通常知識者可容易地根據本說明書的記載重現本發明。以下記載之發明的實施形態及具體實施例等，係表示本發明的較佳實施態樣，用於例示及說明，不用以限定本發明。發明所屬技術領域中具有通常知識者係明瞭，在本說明書所揭示之本發明的意圖及範圍內，可基於本說明書的記載進行各種修飾。The preferred embodiments of the present invention will be described in detail below using additional drawings, but it is not limited thereto. In addition, based on the description of this specification, a person with ordinary knowledge in the technical field of the invention can understand the purpose, features, advantages, and concept of the present invention, and a person with ordinary knowledge in the technical field of the invention can easily reproduce it from the description of this specification. this invention. The embodiments and specific examples of the invention described below represent preferred embodiments of the invention, and are used for illustration and description, and do not limit the invention. Those having ordinary knowledge in the technical field to which the invention pertains will understand that various modifications can be made based on the description of this specification within the intent and scope of the invention disclosed in this specification.

複合銅構件：本發明之一實施態樣為複合銅構件，係於銅構件的至少一部分之表面形成包含銅氧化物之層。銅構件係包含銅作為主成分而形成構造的一部分。銅構件具體而言包含電解銅箔、壓延銅箔及附載體銅箔等銅箔、銅線、銅板、銅製導線架、銅粉等，但不限定於該等。銅構件較佳為可電鍍者。銅構件較佳為銅純度99.9質量%以上之純銅形成之材料，更佳為以韌煉銅、去氧銅、無氧銅形成，又較佳為以含氧量0.001質量%～0.0005質量%之無氧銅形成。Composite copper component: One embodiment of the present invention is a composite copper component. A layer containing copper oxide is formed on at least a part of the surface of the copper component. The copper member system contains copper as a main component and forms a part of the structure. The copper member specifically includes copper foil such as electrolytic copper foil, rolled copper foil, and copper foil with a carrier, copper wire, copper plate, copper lead frame, copper powder, etc., but is not limited to these. The copper member is preferably one that can be electroplated. The copper member is preferably a material made of pure copper with a copper purity of 99.9% by mass or more, more preferably made of toughened copper, deoxidized copper, and oxygen-free copper, and preferably has an oxygen content of 0.001% to 0.0005% by mass Oxygen-free copper is formed.

銅構件為銅箔的情況下，其厚度不特別限定，較佳為0.1μm以上且100μm以下，更佳為0.5μm以上且50μm以下。銅構件為銅板的情況下，其厚度較佳超過100μm。雖未特別限定，較佳為1mm以上、2mm以上或10mm以上，又較佳為10cm以下、5cm以下或2.5cm以下。When the copper member is a copper foil, the thickness is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 50 μm or less. When the copper member is a copper plate, the thickness thereof preferably exceeds 100 μm. Although not particularly limited, it is preferably 1 mm or more, 2 mm or more, or 10 mm or more, and more preferably 10 cm or less, 5 cm or less, or 2.5 cm or less.

包含銅氧化物之層係形成於銅構件的表面，包含氧化銅（CuO）及／或氧化亞銅（Cu2 O）。此包含銅氧化物之層可藉由將銅構件表面氧化處理來形成。藉由此氧化處理，銅構件表面被粗化。對於包含銅氧化物之層，可用溶解劑調整經氧化後之銅構件表面的凸部之形狀。又，可將此包含銅氧化物之層的表面藉由還原劑作還原處理，純銅的電阻率為1.7×10-8 （Ωm），相較於此，氧化銅的電阻率為1～10（Ωm），氧化亞銅的電阻率為1×106 ～1×107 （Ωm），故包含銅氧化物之層的導電性低，即使轉移至樹脂基材的包含銅氧化物之層的量較多，使用複合銅構件形成印刷佈線板或半導體封裝基板的電路時，亦難以產生集膚效應導致的傳輸損失。The layer containing copper oxide is formed on the surface of the copper member, and contains copper oxide (CuO) and/or cuprous oxide (Cu 2 O). The layer containing copper oxide can be formed by oxidizing the surface of the copper member. With this oxidation treatment, the surface of the copper member is roughened. For the layer containing copper oxide, a dissolving agent can be used to adjust the shape of the convex portion on the surface of the oxidized copper member. In addition, the surface of the copper oxide-containing layer can be reduced by a reducing agent. The resistivity of pure copper is 1.7×10 -8 (Ωm). In contrast, the resistivity of copper oxide is 1-10 ( Ωm), the resistivity of cuprous oxide is 1×10 6 ～1×10 7 (Ωm), so the conductivity of the copper oxide-containing layer is low, even if the amount of the copper oxide-containing layer transferred to the resin substrate In many cases, when a composite copper component is used to form a printed wiring board or a circuit of a semiconductor package substrate, it is difficult to produce transmission loss caused by the skin effect.

包含銅氧化物之層具有數個空隙。空隙可與外界連接亦可封閉。較佳係即使在包含銅氧化物之層上熱壓接樹脂基材，樹脂基材亦不進入空隙而可維持空隙。空隙可在複合銅構件的SEM截面影像中偵測到。空隙存在於包含銅氧化物之層，較佳亦包括存在於包含銅氧化物之層與銅構件表面之間的界面者。例如，此界面可藉由SEM截面影像中因組成所造成的濃淡差異，或構成銅構件之銅結晶構造的有無所造成的濃淡差異等來判別（第3圖）。較佳係空隙數量的50%以上、60%以上、70%以上、80%以上、90%以上、95%以上或100%存在於包含銅氧化物之層與銅構件表面之間的界面，但不特別限定。The layer containing copper oxide has several voids. The gap can be connected to the outside world or closed. Preferably, even if the resin substrate is thermally compressed on the layer containing copper oxide, the resin substrate does not enter the void and can maintain the void. The voids can be detected in the SEM cross-sectional image of the composite copper component. The voids are present in the layer containing copper oxide, and preferably also include those present at the interface between the layer containing copper oxide and the surface of the copper member. For example, this interface can be distinguished by the difference in density caused by the composition in the SEM cross-sectional image, or the difference in density caused by the presence or absence of the copper crystal structure that constitutes the copper component (Figure 3). Preferably, 50% or more, 60% or more, 70% or more, 80% or more, 90%, 95% or 100% of the number of voids are present at the interface between the copper oxide-containing layer and the surface of the copper member, but It is not particularly limited.

具體而言，空隙係可藉由例如以下步驟由複合銅構件的截面SEM影像來確定。 1）取得SEM截面影像，使影像中銅氧化物層在上，銅構件在下。 2）畫面上存在於最靠近銅構件側之銅及銅氧化物所包圍的區域；或者通過銅氧化物所包圍的區域之頂點且與包含銅氧化物之層平行的直線、及通過包含銅氧化物之層的最高凸部之頂點且與包含銅氧化物之層平行的直線所包圍的區域作為測量範圍。 3）進行調整測量範圍之影像的對比後，進行反相處理，使影像的明亮部分及暗部分互換。 4）進行自動二值化，選擇銅及銅氧化物所包圍的區域或銅氧化物所包圍的區域。 5）將邊長1像素者視為雜訊刪除。 6）將影像的左上方作為原點，影像中往下之方向作為X軸，往右之方向作為Y軸。以自動二值化選擇的存在於X=最大、Y=最小之區域（1）作為起點，在Y軸方向位於最近距離之區域作為區域（2）。在Y軸方向上距離最靠近區域（2）的區域作為區域（3），之後以相同步驟決定區域（4）～（N）至測量範圍中Y=最大為止。在此所決定之各區域（1）～（N）為空隙。或者，空隙亦可藉由相同步驟由積層樹脂基材後之複合銅構件的截面SEM影像來確定。二值化係藉由將影像的濃淡以規定之閾值分割，閾值以上者為1，未滿閾值者為0來處理影像。二值化係可藉由OTSU法（判別分析法）、Sauvola法、Goto法等來進行二值化。Specifically, the void system can be determined from the cross-sectional SEM image of the composite copper member by, for example, the following steps. 1) Obtain a SEM cross-sectional image, so that the copper oxide layer is on the top and the copper component is on the bottom in the image. 2) The area surrounded by copper and copper oxide that exists on the side closest to the copper member on the screen; or a straight line passing through the apex of the area surrounded by copper oxide and parallel to the layer containing copper oxide, and passing through the copper oxide The area surrounded by the apex of the highest protrusion of the layer of objects and a straight line parallel to the layer containing copper oxide is used as the measurement range. 3) After adjusting the contrast of the image in the measurement range, perform inversion processing to exchange the bright part and dark part of the image. 4) For automatic binarization, select the area surrounded by copper and copper oxide or the area surrounded by copper oxide. 5) The one with a side length of 1 pixel is regarded as noise and deleted. 6) Use the top left of the image as the origin, the downward direction in the image as the X axis, and the right direction as the Y axis. Take the area (1) with X=maximum and Y=minimum selected by automatic binarization as the starting point, and the area with the closest distance in the Y-axis direction as the area (2). The area closest to the area (2) in the Y-axis direction is taken as area (3), and then the same steps are used to determine areas (4) to (N) until Y=maximum in the measurement range. The regions (1) to (N) determined here are voids. Alternatively, the void can also be determined by the cross-sectional SEM image of the composite copper member after laminating the resin substrate in the same step. Binarization is to process the image by dividing the intensity of the image by a predetermined threshold, and the value above the threshold is 1, and the value below the threshold is 0. The binarization system can be binarized by the OTSU method (discriminatory analysis method), Sauvola method, Goto method, etc.

空隙的最大水平弦長較佳為將倍率30000倍、解析度1024×768像素之SEM截面影像二值化時可偵測到的大小。較佳為邊長500nm以下、邊長400nm以下、邊長300nm以下、邊長200nm以下、邊長100nm以下、或邊長50nm以下，且邊長4nm以上、邊長5nm以上、邊長10nm以上、邊長15nm以上、邊長20nm以上、邊長25nm以上、邊長50nm以上、邊長100nm以上或邊長200nm以上，但不特別限定。經二值化之SEM截面影像中，在與形成有包含銅氧化物之層的面平行的方向測量時，任意每3.8μm中空隙的數量較佳為25個以上、30個以上、40個以上或50個以上，且500個以下、400個以下、300個以下、200個以下、100個以下、90個以下、80個以下、70個以下或60個以下。此外，亦可在影像上算出空隙間的距離，以算出空隙間的距離。空隙間的平均距離較佳為200nm以下、150nm以下、100nm以下、90nm以下、80nm以下、70nm以下、60nm以下或50nm以下，且40nm以上、30nm以上、20nm以上或10nm以上。又，空隙間的距離分布較佳係50nm以下的比例占空隙間整體的35%、40%、45%或50%以上。The maximum horizontal chord length of the gap is preferably a size that can be detected when a SEM cross-sectional image with a magnification of 30,000 times and a resolution of 1024×768 pixels is binarized. Preferably, the side length is 500 nm or less, the side length is 400 nm or less, the side length is 300 nm or less, the side length is 200 nm or less, the side length is 100 nm or less, or the side length is 50 nm or less, and the side length is 4 nm or more, the side length is 5 nm or more, and the side length is 10 nm or more. The side length is 15 nm or more, the side length is 20 nm or more, the side length is 25 nm or more, the side length is 50 nm or more, the side length is 100 nm or more, or the side length is 200 nm or more, but it is not particularly limited. In the binarized SEM cross-sectional image, when measured in a direction parallel to the surface on which the copper oxide-containing layer is formed, the number of voids per 3.8 μm is preferably 25 or more, 30 or more, or 40 or more Or 50 or more, and 500 or less, 400 or less, 300 or less, 200 or less, 100 or less, 90 or less, 80 or less, 70 or less or 60 or less. In addition, the distance between the gaps can also be calculated on the image to calculate the distance between the gaps. The average distance between the voids is preferably 200 nm or less, 150 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less or 50 nm or less, and 40 nm or more, 30 nm or more, 20 nm or more or 10 nm or more. In addition, the distance distribution between the gaps is preferably 50 nm or less, which accounts for 35%, 40%, 45%, or 50% or more of the entire gap.

藉由此空隙之存在，包含銅氧化物之層變得容易由銅構件分離。包含銅氧化物之層與該銅構件的表面之間的剝離強度較佳為0.30kgf/cm以下、0.20kgf/cm以下、0.15kgf/cm以下或0.15kgf/cm以下，且0.001kgf/cm以上、0.002kgf/cm以上、0.003kgf/cm以上或0.004kgf/cm以上，但不特別限定。剝離強度可在包含銅氧化物之層上熱壓接樹脂基材後，基於90度剝離試驗（日本工業規格（JIS）C5016「可撓性印刷佈線板試驗方法」；對應之國際規格IEC249-1:1982、IEC326-2:1990），測量剝離時的剝離強度。With the existence of this void, the layer containing the copper oxide becomes easily separated from the copper member. The peel strength between the copper oxide-containing layer and the surface of the copper member is preferably 0.30kgf/cm or less, 0.20kgf/cm or less, 0.15kgf/cm or less, or 0.15kgf/cm or less, and 0.001kgf/cm or more , 0.002kgf/cm or more, 0.003kgf/cm or more, or 0.004kgf/cm or more, but not particularly limited. The peel strength can be based on a 90-degree peel test (Japanese Industrial Standards (JIS) C5016 "Test Method for Flexible Printed Wiring Boards"" after thermocompression bonding of the resin substrate on the layer containing copper oxide; the corresponding international standard IEC249-1 :1982, IEC326-2:1990), to measure the peel strength during peeling.

包含銅氧化物之層可包含銅以外之金屬。所包含的金屬不特別限定，可包含選自由錫、銀、鋅、鋁、鈦、鉍、鉻、鐵、鈷、鎳、鈀、金及鉑組成之群組中至少一種之金屬。特別是為了使其具有耐酸性及耐熱性，較佳包含耐酸性及耐熱性比銅高之金屬，例如鎳、鈀、金及鉑。銅以外之金屬可藉由鍍敷形成於銅構件的表面。鍍敷的方法不特別限定，可舉例如電鍍、無電解鍍、真空蒸鍍、化成處理等，較佳為形成均一的薄鍍敷層，故以電鍍為佳。對氧化處理後之銅箔表面施加電鍍的情況下，首先表面的氧化銅被還原，形成氧化亞銅或純銅時使用電荷，因此，至形成鍍敷為止會產生時間的延遲，之後形成金屬層之金屬開始析出。其電荷量係因鍍敷液種類或銅氧化物量而不同，例如對銅構件施加鎳鍍的情況下，為了使其厚度形成於較佳範圍，較佳係給予所電鍍處理之銅構件的每dm2 面積15C以上且75C以下之電荷，更佳係給予25C以上且65C以下之電荷。藉由鍍敷形成於銅構件的最外表面的銅以外之金屬於垂直方向的平均厚度不特別限定，較佳為6nm以上，更佳為10nm以上、14nm以上、18nm以上或20nm以上。惟，較佳為80nm以下，更佳為70nm以下或60nm以下。又，包含銅氧化物之層所包含的銅以外之金屬於垂直方向的平均厚度係可以將包含銅氧化物之層以酸性溶液溶解，藉由ICP分析測定金屬量，將其測定量除以複合銅構件的面積來算出。或者，亦可藉由將複合銅構件本身溶解，僅測定包含銅氧化物之層所包含的金屬的量來算出。The layer containing copper oxide may contain metals other than copper. The included metal is not particularly limited, and may include at least one metal selected from the group consisting of tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold, and platinum. In particular, in order to have acid resistance and heat resistance, it is preferable to include metals with higher acid resistance and heat resistance than copper, such as nickel, palladium, gold, and platinum. Metals other than copper can be formed on the surface of the copper member by plating. The method of plating is not particularly limited, and examples include electroplating, electroless plating, vacuum evaporation, chemical conversion treatment, and the like. It is preferable to form a uniform thin plating layer, so electroplating is preferred. When electroplating is applied to the surface of the copper foil after oxidation treatment, the copper oxide on the surface is first reduced to form cuprous oxide or pure copper. Therefore, there will be a time delay until the plating is formed, and then the metal layer is formed. Metal began to precipitate. The amount of charge varies depending on the type of plating solution or the amount of copper oxide. For example, when nickel plating is applied to a copper member, in order to make the thickness within a preferable range, it is better to give every dm of the copper member to be electroplated 2 Charges with an area of 15C or more and 75C or less are more preferably given with a charge of 25C or more and 65C or less. The average thickness in the vertical direction of metals other than copper formed on the outermost surface of the copper member by plating is not particularly limited, but is preferably 6 nm or more, more preferably 10 nm or more, 14 nm or more, 18 nm or more, or 20 nm or more. However, it is preferably 80 nm or less, more preferably 70 nm or less or 60 nm or less. In addition, the average thickness in the vertical direction of the metal other than copper contained in the copper oxide-containing layer can be obtained by dissolving the copper oxide-containing layer in an acid solution, and measuring the amount of metal by ICP analysis, and dividing the measured amount by the composite Calculate the area of the copper member. Alternatively, it can also be calculated by dissolving the composite copper member itself and measuring only the amount of metal contained in the layer containing copper oxide.

將形成有包含銅氧化物之層的複合銅構件的表面熱壓接（thermal press fitting）於樹脂基材時，複合銅構件的表面輪廓被轉印至樹脂基材。並且，由熱壓接後之樹脂基材剝離複合銅構件時，包含銅氧化物之層所包含的金屬由複合銅構件轉移至樹脂基材。複合銅構件之一實施態樣係例示於第1圖。When the surface of the composite copper member formed with the layer containing copper oxide is thermally press-fitted to the resin base material, the surface profile of the composite copper member is transferred to the resin base material. In addition, when the composite copper member is peeled from the resin substrate after thermocompression bonding, the metal contained in the copper oxide-containing layer is transferred from the composite copper member to the resin substrate. An example of an embodiment of the composite copper member is shown in Fig. 1.

樹脂基材係含有樹脂作為主成分之材料，可用於形成印刷佈線板及半導體封裝基板等的電路。樹脂不特別限定，可為熱塑性樹脂或熱固性樹脂，較佳為聚苯醚（PPE）、環氧樹脂、聚氧二甲苯（PPO）、聚苯噁唑（PBO）、聚四氟乙烯（PTFE）、液晶聚合物（LCP）、亞磷酸三苯酯（TPPI）、氟樹脂、聚醚醯亞胺、聚醚醚酮、聚環烯烴、雙馬來醯亞胺樹脂、低電容率聚醯亞胺、氰酸樹脂或該等之混合樹脂。樹脂基材可另包含無機填充物或玻璃纖維。The resin base material contains resin as a main component, and can be used to form circuits such as printed wiring boards and semiconductor package substrates. The resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin, preferably polyphenylene ether (PPE), epoxy resin, polyoxyxylene (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE) , Liquid crystal polymer (LCP), triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide , Cyanate resin or mixed resins of these. The resin substrate may additionally contain inorganic fillers or glass fibers.

為了將樹脂基材熱壓接於複合銅構件的表面，例如使樹脂基材與複合銅構件密著而積層後，以規定條件處理，藉此使樹脂基材與複合銅構件黏著即可。規定條件（如溫度、壓力、時間）係可使用各基材製造商推薦的條件。規定條件例如可考量以下條件。In order to thermocompression-bond the resin substrate to the surface of the composite copper member, for example, the resin substrate and the composite copper member are laminated in close contact with each other, and then processed under predetermined conditions to adhere the resin substrate and the composite copper member. The specified conditions (such as temperature, pressure, time) can be the conditions recommended by each substrate manufacturer. The prescribed conditions may consider the following conditions, for example.

1）樹脂基材包含環氧樹脂，或由環氧樹脂形成的情況下，較佳係在50℃～300℃之溫度施加0～20MPa之壓力1分鐘～5小時，藉此將複合銅構件熱壓接於樹脂基材。例如， 1-1）樹脂基材為R-1551（Panasonic製）的情況下，於1MPa之壓力下加熱，到達100℃後於該溫度維持5～10分鐘，之後於3.3MPa之壓力下進一步加熱，到達170～180℃後於該溫度維持50分鐘，以進行熱壓接。 1-2）樹脂基材為R-1410A（Panasonic製）的情況下，於1MPa之壓力下加熱，到達130℃後於該溫度維持10分鐘，之後於2.9MPa之壓力下進一步加熱，到達200℃後於該溫度維持70分鐘，以進行熱壓接。 1-3）樹脂基材為EM-285（EMC製）的情況下，於0.4MPa之壓力下加熱，到達100℃後，提升壓力至2.4～2.9MPa再進一步加熱，到達195℃後於該溫度維持50分鐘，以進行熱壓接。 1-4）樹脂基材為GX13（味之素製）的情況下，一邊以1.0MPa加壓一邊加熱，於180℃維持60分鐘以進行熱壓接。1) In the case where the resin substrate contains epoxy resin or is formed of epoxy resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 300°C for 1 minute to 5 hours to heat the composite copper component. Crimped to the resin substrate. E.g, 1-1) When the resin substrate is R-1551 (manufactured by Panasonic), it is heated at a pressure of 1 MPa, and after reaching 100°C, the temperature is maintained at that temperature for 5 to 10 minutes, and then further heated at a pressure of 3.3 MPa to reach After 170-180°C, maintain the temperature for 50 minutes to perform thermocompression bonding. 1-2) When the resin substrate is R-1410A (manufactured by Panasonic), heat it at a pressure of 1 MPa. After reaching 130°C, maintain the temperature for 10 minutes, and then further heat it at a pressure of 2.9 MPa to reach 200°C. After that, the temperature was maintained for 70 minutes to perform thermocompression bonding. 1-3) When the resin base material is EM-285 (manufactured by EMC), heat it at a pressure of 0.4 MPa. After reaching 100°C, increase the pressure to 2.4 to 2.9 MPa and then further heat it. After reaching 195°C, it will be heated at this temperature. Maintain for 50 minutes for thermocompression bonding. 1-4) When the resin substrate is GX13 (manufactured by Ajinomoto), heat it while applying pressure at 1.0 MPa, and maintain it at 180°C for 60 minutes to perform thermocompression bonding.

2）樹脂基材包含PPE樹脂，或由PPE樹脂形成的情況下，較佳係在50℃～350℃之溫度施加0～20MPa之壓力1分鐘～5小時，藉此將複合銅構件熱壓接於樹脂基材。例如， 2-1）樹脂基材為R5620（Panasonic製）的情況下，一邊於0.5MPa之壓力下加熱至100℃一邊熱壓接後，提升溫度及壓力，於2.0～3.0MPa、200～210℃維持120分鐘以進一步熱壓接。 2-2）樹脂基材為R5670（Panasonic製）的情況下，一邊於0.49MPa之壓力下加熱至110℃一邊熱壓接後，提升溫度及壓力，於2.94MPa、210℃維持120分鐘以進行熱壓接。 2-3）樹脂基材為R5680（Panasonic製）的情況下，一邊於0.5MPa之壓力下加熱至110℃一邊熱壓接後，提升溫度及壓力，於3.0～4.0MPa、195℃維持75分鐘以進行熱壓接。 2-4）樹脂基材為N-22（Nelco製）的情況下，一邊以1.6～2.3MPa加壓一邊加熱，於177℃維持30分鐘後，進一步加熱，於216℃維持60分鐘以進行熱壓接。2) When the resin base material contains PPE resin or is formed of PPE resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 350°C for 1 minute to 5 hours, thereby thermocompression bonding of the composite copper member For resin substrate. E.g, 2-1) When the resin substrate is R5620 (manufactured by Panasonic), after heating to 100°C under a pressure of 0.5 MPa, after thermo-compression bonding, raise the temperature and pressure to maintain at 2.0 to 3.0 MPa and 200 to 210°C 120 minutes for further thermal compression bonding. 2-2) When the resin substrate is R5670 (manufactured by Panasonic), after heating to 110°C under a pressure of 0.49 MPa, after thermo-compression bonding, raise the temperature and pressure and maintain at 2.94 MPa and 210°C for 120 minutes. Hot crimping. 2-3) When the resin base material is R5680 (manufactured by Panasonic), after heating to 110°C under a pressure of 0.5 MPa, after thermo-compression bonding, raise the temperature and pressure and maintain at 3.0 to 4.0 MPa at 195°C for 75 minutes For thermal compression. 2-4) When the resin base material is N-22 (manufactured by Nelco), heat it while applying pressure at 1.6 to 2.3 MPa. After maintaining it at 177°C for 30 minutes, it is further heated and heated at 216°C for 60 minutes. Crimping.

3）樹脂基材包含PTFE樹脂，或由PTFE樹脂形成的情況下，較佳係在50℃～400℃之溫度施加0～20MPa之壓力1分鐘～5小時，藉此將複合銅構件熱壓接於樹脂基材。例如， 3-1）樹脂基材為NX9255（Park Electrochemical製）的情況下，一邊以0.69MPa加壓一邊加熱至260℃，提升壓力至1.03～1.72MPa並加熱至385℃，於385℃維持10分鐘以進行熱壓接。 3-2）樹脂基材為RO3003（Rogers製）的情況下，壓製開始50分鐘（約220℃）以後，加壓至2.4MPa，於371℃維持30～60分鐘以進行熱壓接。3) When the resin base material contains PTFE resin or is formed of PTFE resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 400°C for 1 minute to 5 hours, thereby thermocompression bonding of the composite copper member For resin substrate. E.g, 3-1) When the resin substrate is NX9255 (manufactured by Park Electrochemical), heat to 260°C while applying pressure at 0.69 MPa, increase the pressure to 1.03 to 1.72 MPa and heat to 385°C, and maintain at 385°C for 10 minutes Perform thermo-compression bonding. 3-2) When the resin substrate is RO3003 (manufactured by Rogers), 50 minutes (approximately 220°C) after the start of pressing, pressurize to 2.4 MPa and maintain at 371°C for 30 to 60 minutes to perform thermocompression bonding.

由樹脂基材剝離銅構件的條件不特別限定，可基於90°剝離測試（日本工業規格（JIS）C5016「可撓性印刷佈線板試驗方法」；對應國際規格IEC249-1:1982、IEC326-2:1990）來進行。The conditions for peeling the copper member from the resin base material are not particularly limited, and it can be based on a 90° peel test (Japanese Industrial Standards (JIS) C5016 "Test Method for Flexible Printed Wiring Boards"; International Standards IEC249-1:1982, IEC326-2) :1990) to proceed.

包含銅氧化物之層所包含的金屬轉移至剝離銅構件後之樹脂基材。轉移至剝離銅構件後之樹脂基材表面的金屬可使用各種方法（例如X射線光電子能譜法（XPS）、能量散射X射線能譜法（EDS）、ICP發射光譜法（感應耦合電漿發射光譜法，ICP-OES/ICP-AES））偵測出。XPS係將X射線照射於物體，將伴隨物體之離子化而放出的光電子e-捕捉來進行能量分析的手法。藉由XPS可探查試料表面或由表面至規定深度為止（例如至深度6nm為止）所存在的元素種類、存在量、化學鍵結狀態等。分析點口徑（亦即將可分析之圓柱形部分切割以使截面形成圓形時的截面直徑）適合1μm以上～1mm以下。The metal contained in the copper oxide-containing layer is transferred to the resin substrate after peeling off the copper member. Various methods (such as X-ray photoelectron spectroscopy (XPS), energy scattering X-ray spectroscopy (EDS), ICP emission spectroscopy (inductively coupled plasma emission) Spectroscopy, ICP-OES/ICP-AES)). XPS is a technique in which X-rays are irradiated to an object, and the photoelectrons emitted by the ionization of the object are e-captured for energy analysis. With XPS, it is possible to detect the type, amount, chemical bonding state, etc. of the elements present on the surface of the sample or from the surface to a predetermined depth (for example, to a depth of 6nm). The analysis point diameter (that is, the cross-sectional diameter when the cylindrical part that can be analyzed is cut to make the cross-section circular) is suitable for 1μm or more to 1mm or less.

形成有包含銅氧化物之層的複合銅構件之表面的算數平均粗度（Ra）較佳為0.04μm以上，更佳為0.1μm以上，又，較佳為0.3μm以下，更佳為0.2μm以下。形成有包含銅氧化物之層的複合銅構件之表面的最大高度粗度（Rz）較佳為0.2μm以上，更佳為1.0μm以上，又，較佳為2.0μm以下，更佳為1.7μm以下。若Ra、Rz太小則與樹脂基材的密著性不足，若太大則微細佈線形成性或高頻特性差。在此，算數平均粗度（Ra）係表示基準長度l中，以下式表示之輪廓曲線（y=Z(x)）中Z(x)（即峰高及谷深）之絕對值的平均值。 數式1：

Figure 02_image001
最大高度粗度（Rz）係表示基準長度l中，輪廓曲線（y=Z(x)）的峰高Zp之最大值與谷深Zv之最大值的和。Ra、Rz係根據JIS B 0601:2001（基於國際標準ISO4287-1997）規定之方法算出。形成有包含銅氧化物之層的複合銅構件之表面，其剝離後之Ra相對於熱壓接前之Ra的比例，較佳為未滿100%、未滿96%、未滿95%、未滿94%、未滿93%、未滿92%、未滿91%、未滿90%、未滿80%、未滿70%、未滿65%或未滿60%。此比例越小，則越表示形成包含銅氧化物之層的金屬已轉移至樹脂基材。The arithmetic average roughness (Ra) of the surface of the composite copper member on which the layer containing copper oxide is formed is preferably 0.04 μm or more, more preferably 0.1 μm or more, more preferably 0.3 μm or less, more preferably 0.2 μm the following. The maximum height roughness (Rz) of the surface of the composite copper member on which the layer containing copper oxide is formed is preferably 0.2 μm or more, more preferably 1.0 μm or more, more preferably 2.0 μm or less, more preferably 1.7 μm the following. If Ra and Rz are too small, the adhesion to the resin substrate will be insufficient, and if they are too large, the fine wiring formation and high-frequency characteristics will be poor. Here, the arithmetic average roughness (Ra) represents the average value of the absolute value of Z(x) (ie peak height and valley depth) in the profile curve (y=Z(x)) expressed by the following formula in the reference length l . Mathematical formula 1:
Figure 02_image001
The maximum height roughness (Rz) is the sum of the maximum value of the peak height Zp and the maximum value of the valley depth Zv of the profile curve (y=Z(x)) in the reference length l. Ra and Rz are calculated according to the method stipulated in JIS B 0601:2001 (based on the international standard ISO4287-1997). On the surface of the composite copper member on which the layer containing copper oxide is formed, the ratio of the Ra after peeling to the Ra before the thermocompression bonding is preferably less than 100%, less than 96%, less than 95%, and less than 100%. Full 94%, less than 93%, less than 92%, less than 91%, less than 90%, less than 80%, less than 70%, less than 65%, or less than 60%. The smaller this ratio is, the more it means that the metal forming the layer containing copper oxide has been transferred to the resin substrate.

形成有包含銅氧化物之層的複合銅構件，其剝離後之表面積相對於熱壓接前之表面積的比例，較佳為未滿100%、未滿98%、未滿97%、未滿96%、未滿95%、未滿94%、未滿93%、未滿92%、未滿91%、未滿90%、未滿80%或未滿75%。此比例越小，則越表示形成包含銅氧化物之層的金屬已轉移至樹脂基材。表面積係可用共軛焦顯微鏡或原子力顯微鏡來測定。The ratio of the surface area after peeling to the surface area before thermocompression bonding of the composite copper member formed with a layer containing copper oxide is preferably less than 100%, less than 98%, less than 97%, less than 96 %, less than 95%, less than 94%, less than 93%, less than 92%, less than 91%, less than 90%, less than 80%, or less than 75%. The smaller this ratio is, the more it means that the metal forming the layer containing copper oxide has been transferred to the resin substrate. The surface area can be measured with a conjugate focus microscope or an atomic force microscope.

本發明之一實施態樣的複合銅構件中，形成有包含銅氧化物之層的複合銅構件之表面的粗度曲線參數的平均長度（RSm）不特別限定，較佳為1500nm以下、1400nm以下、1300nm以下、1200nm以下、1100nm以下、1000nm以下、900nm以下、800nm以下、750nm以下、700nm以下、650nm以下、600nm以下、550nm以下、450nm以下或350nm以下，且較佳為100nm以上、200nm以上或300nm以上。在此，RSm表示一個基準長度（lr）之粗度曲線所包含的一個週期量的凹凸產生的長度（即輪廓曲線參數的長度：Xs1～Xsm）之平均，用下述式子算出。 數式2：

Figure 02_image003
在此，算數平均粗度（Ra）的10%作為凹凸的最小高度，基準長度（lr）的1%作為最小長度以定義一個週期量的凹凸。舉例如，Rsm可根據「利用原子力顯微鏡之精密陶瓷薄膜的表面粗度測定方法（JIS R 1683:2007）」來測定並算出。In the composite copper member of one embodiment of the present invention, the average length (RSm) of the roughness curve parameter of the surface of the composite copper member on which the layer containing copper oxide is formed is not particularly limited, and is preferably 1500 nm or less and 1400 nm or less , 1300nm or less, 1200nm or less, 1100nm or less, 1000nm or less, 900nm or less, 800nm or less, 750nm or less, 700nm or less, 650nm or less, 600nm or less, 550nm or less, 450nm or less, or 350nm or less, and preferably 100nm or more, 200nm or more 300nm or more. Here, RSm represents the average length (that is, the length of the profile curve parameter: Xs1 to Xsm) of the unevenness of one period included in the roughness curve of one reference length (lr), and is calculated by the following formula. Mathematical formula 2:
Figure 02_image003
Here, 10% of the arithmetic average roughness (Ra) is taken as the minimum height of the concavity and convexity, and 1% of the reference length (lr) is taken as the minimum length to define one period of concavity and convexity. For example, Rsm can be measured and calculated according to "Method for Measuring Surface Roughness of Precision Ceramic Thin Films Using Atomic Force Microscope (JIS R 1683:2007)".

熱壓接前之複合銅構件的表面及被剝離後之銅構件的表面的ΔE*ab較佳為13以上、15以上、20以上、25以上、30以上或35以上。此差越大則越表示形成包含銅氧化物之層的金屬（即形成凹凸之金屬）已轉移至樹脂基材。The ΔE*ab of the surface of the composite copper member before thermocompression bonding and the surface of the copper member after peeling is preferably 13 or more, 15 or more, 20 or more, 25 or more, 30 or more or 35 or more. The larger the difference, the more it means that the metal forming the layer containing copper oxide (that is, the metal forming the unevenness) has been transferred to the resin substrate.

複合銅構件的製造方法：本發明之一實施態樣係複合銅構件的製造方法，包含：在包含銅氧化物之層設置空隙，使包含銅氧化物之層容易從銅構件斷裂的步驟。Method for manufacturing a composite copper component: One embodiment of the present invention is a method for manufacturing a composite copper component, including the step of providing a gap in the layer containing copper oxide so that the layer containing copper oxide is easily broken from the copper component.

此步驟中，在包含銅氧化物之層設置空隙，使包含銅氧化物之層容易從銅構件斷裂的方法不特別限定，有1）氧化處理前以矽烷耦合劑等塗覆劑將銅構件表面作部分塗覆、2）氧化處理後以氯化鎳等修飾劑處理包含銅氧化物之層，或上述方法之組合等。In this step, the method of providing voids in the copper oxide-containing layer so that the copper oxide-containing layer can be easily broken from the copper member is not particularly limited. There are 1) The surface of the copper member is coated with a coating agent such as a silane coupling agent before the oxidation treatment. For partial coating, 2) After oxidation treatment, treat the layer containing copper oxide with a modifier such as nickel chloride, or a combination of the above methods.

包含銅氧化物之層較佳係藉由使用氧化劑處理銅構件表面來形成。氧化劑不特別限定，例如可使用亞氯酸鈉、次氯酸鈉、氯酸鉀、過氯酸鉀、過硫酸鉀等水溶液。氧化劑中可添加各種添加劑（例如磷酸三鈉十二水合物這樣的磷酸鹽）。The layer containing copper oxide is preferably formed by treating the surface of the copper member with an oxidizing agent. The oxidizing agent is not particularly limited. For example, aqueous solutions such as sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, and potassium persulfate can be used. Various additives (such as phosphate such as trisodium phosphate dodecahydrate) can be added to the oxidizing agent.

氧化反應條件不特別限定，反應溫度較佳為40～95℃，更佳為45～80℃。反應時間較佳為0.5～30分，更佳為1～10分。The oxidation reaction conditions are not particularly limited, and the reaction temperature is preferably 40 to 95°C, more preferably 45 to 80°C. The reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.

氧化處理前可進行脫脂處理、去除自然氧化膜以進行均一化處理之酸洗、或在酸洗後進行鹼處理以防止酸被帶入氧化步驟。酸洗可例如將銅表面浸漬於液溫20～50℃且5～20重量%之硫酸中1～5分鐘後水洗來進行。酸處理後，為了減少處理不均，且防止清洗處理所使用之酸混入氧化劑，可進一步進行鹼處理。鹼處理的方法不特別限定，較佳可用0.1～10g/L之鹼性水溶液，更佳可用1～2g/L之鹼性水溶液，鹼性水溶液例如氫氧化鈉水溶液，於30～50℃處理0.5～2分鐘程度即可。又，可將包含銅氧化物之層用包含溶解劑之溶解用藥液溶解，以調整銅構件表面的凸部，亦可用包含還原劑之還原用藥液將包含銅氧化物之層的氧化銅還原。Before oxidation treatment, degreasing treatment, removal of natural oxide film for acid cleaning for homogenization treatment, or alkali treatment after acid cleaning can be carried out to prevent acid from being carried into the oxidation step. The pickling can be performed by immersing the copper surface in sulfuric acid at a liquid temperature of 20 to 50°C and 5 to 20% by weight for 1 to 5 minutes, and then washing with water. After the acid treatment, in order to reduce the unevenness of the treatment and prevent the acid used in the cleaning treatment from being mixed with the oxidant, further alkali treatment can be carried out. The method of alkali treatment is not particularly limited, preferably 0.1-10g/L alkaline aqueous solution, more preferably 1-2g/L alkaline aqueous solution, alkaline aqueous solution such as sodium hydroxide aqueous solution, treated at 30-50°C for 0.5 ~2 minutes is enough. In addition, the copper oxide-containing layer can be dissolved with a dissolving chemical solution containing a dissolving agent to adjust the protrusions on the surface of the copper member, and the reducing chemical solution containing a reducing agent can also be used to reduce the copper oxide of the copper oxide-containing layer.

溶解劑不特別限定，較佳為螯合劑，特別是生物分解性螯合劑，可舉例如L-麩胺酸二乙酸四鈉（CMG-40）、乙二胺四乙酸（鈉鹽）、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉、葡萄糖酸鈉等。The dissolving agent is not particularly limited. It is preferably a chelating agent, particularly a biodegradable chelating agent, such as L-glutamic acid tetrasodium diacetate (CMG-40), ethylenediaminetetraacetic acid (sodium salt), dihydroxy Ethylglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-imino sodium disuccinate, methylglycamine Trisodium diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl) iminodiacetate, sodium gluconate, etc.

還原劑可使用DMAB（二甲基胺硼烷）、乙硼烷、硼氫化鈉、聯氨等。又，還原用藥液為包含還原劑、鹼性化合物（例如氫氧化鈉、氫氧化鉀等）及溶劑（例如純水等）之液體。The reducing agent can be DMAB (dimethylamine borane), diborane, sodium borohydride, hydrazine, etc. In addition, the chemical solution for reduction is a liquid containing a reducing agent, an alkaline compound (for example, sodium hydroxide, potassium hydroxide, etc.), and a solvent (for example, pure water, etc.).

包含銅氧化物之層可包含銅以外之金屬。銅以外之金屬例如可藉由以銅以外之金屬將包含銅氧化物之層作鍍敷處理來包含。鍍敷處理方法可使用習知技術，銅以外之金屬可使用例如錫、銀、鋅、鋁、鈦、鉍、鉻、鐵、鈷、鎳、鈀、金、鉑或各種合金。鍍敷步驟亦不特別限定，可藉由電鍍、無電解鍍、真空蒸鍍、化成處理等鍍敷，較佳為形成均一的薄鍍敷層，故以電鍍為佳。The layer containing copper oxide may contain metals other than copper. Metals other than copper can be included, for example, by plating a layer containing copper oxide with a metal other than copper. The plating treatment method can use the conventional technology, and the metal other than copper can be tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold, platinum or various alloys. The plating step is also not particularly limited, and plating, electroless plating, vacuum evaporation, chemical conversion treatment, etc. can be used, and it is preferable to form a uniform thin plating layer, so electroplating is preferred.

電鍍的情況下，較佳為鎳鍍及鎳合金鍍。以鎳鍍及鎳合金鍍形成之金屬可舉例如純鎳、鎳銅合金、鎳鉻合金、鎳鈷合金、鎳鋅合金、鎳錳合金、鎳鉛合金、鎳磷合金等。用於鍍敷之金屬鹽可舉例如硫酸鎳、氨基磺酸鎳、氯化鎳、溴化鎳、氧化鋅、氯化鋅、二胺二氯鈀、硫酸鐵、氯化鐵、無水鉻酸、氯化鉻、硫酸鉻鈉、硫酸銅、焦磷酸銅、硫酸鈷、硫酸錳等。鎳鍍中，其建浴組成較佳包含例如硫酸鎳（100g/L以上且350g/L以下）、氨基磺酸鎳（100g/L以上且600g/L以下）、氯化鎳（0g/L以上且300g/L以下）及該等之混合物，亦可包含檸檬酸鈉（0g/L以上且100g/L以下）或硼酸（0g/L以上且60g/L以下）作為添加劑。In the case of electroplating, nickel plating and nickel alloy plating are preferable. Metals formed by nickel plating and nickel alloy plating include, for example, pure nickel, nickel-copper alloys, nickel-chromium alloys, nickel-cobalt alloys, nickel-zinc alloys, nickel-manganese alloys, nickel-lead alloys, and nickel-phosphorus alloys. Metal salts used for plating include, for example, nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, zinc oxide, zinc chloride, diamine dichloropalladium, iron sulfate, iron chloride, anhydrous chromic acid, Chromium chloride, sodium chromium sulfate, copper sulfate, copper pyrophosphate, cobalt sulfate, manganese sulfate, etc. In nickel plating, the bath composition preferably contains, for example, nickel sulfate (100g/L or more and 350g/L or less), nickel sulfamate (100g/L or more and 600g/L or less), nickel chloride (0g/L or more) And 300g/L or less) and these mixtures may also contain sodium citrate (0 g/L or more and 100 g/L or less) or boric acid (0 g/L or more and 60 g/L or less) as additives.

無電解鍍鎳的情況下，較佳係使用觸媒之無電解鍍。觸媒可使用鐵、鈷、鎳、釕、銠、鈀、鋨、銥或該等之鹽。藉由進行使用觸媒之無電解鍍，可提升複合銅箔的耐熱性。In the case of electroless nickel plating, electroless plating using a catalyst is preferred. The catalyst can use iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or their salts. By performing electroless plating using a catalyst, the heat resistance of the composite copper foil can be improved.

本發明之複合銅構件的製造方法的一實施態樣係包含1）以矽烷耦合劑將銅構件表面作部分塗覆的步驟；及2）將被部分塗覆之銅構件表面氧化處理的步驟；或者，包含1）以矽烷耦合劑將銅構件表面作部分塗覆的步驟；2）將被部分塗覆之銅構件表面氧化處理的步驟；及3）在經氧化處理之銅構件表面形成包含銅以外之金屬的層的步驟。藉由以矽烷耦合劑等塗覆劑將銅構件表面作部分塗覆，則該部分免於受到氧化處理，包含銅氧化物之層中特別是與銅構件之界面附近產生空隙，包含銅氧化物之層變得容易從銅構件斷裂。因此，矽烷耦合劑之處理較佳係將銅構件表面的部分（例如1%、5%、10%、20%、30%、40%、50%、60%、70%、80%或90%以上且未滿100%）塗覆，為此，較佳係使矽烷耦合劑以0.1%、0.5%、1%或2%以上之濃度，於室溫進行反應30秒、1分鐘或2分鐘以上。An embodiment of the method for manufacturing a composite copper component of the present invention includes 1) the step of partially coating the surface of the copper component with a silane coupling agent; and 2) the step of oxidizing the surface of the partially coated copper component; Or, it includes 1) the step of partially coating the surface of the copper component with a silane coupling agent; 2) the step of oxidizing the surface of the partially coated copper component; and 3) forming a copper component on the surface of the oxidized copper component. Steps other than the metal layer. By partially coating the surface of the copper component with a coating agent such as silane coupling agent, the part is protected from oxidation treatment, and voids are generated in the layer containing copper oxide, especially near the interface with the copper component, including copper oxide The layer becomes easy to break from the copper component. Therefore, the treatment of the silane coupling agent is better to remove the part of the surface of the copper component (such as 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%). Above and less than 100%) coating. For this, it is better to make the silane coupling agent at a concentration of 0.1%, 0.5%, 1% or 2% at room temperature to react for 30 seconds, 1 minute or 2 minutes or more .

矽烷耦合劑不特別限定，可選自矽烷、四有機基-矽烷、胺基乙基-胺基丙基-三甲氧基矽烷、(3-胺基丙基)三甲氧基矽烷、(1-[3-(三甲氧基矽基)丙基]尿素)（l-[3-(Trimethoxysilyl)propyl]urea）、(3-胺基丙基)三乙氧基矽烷、(3-環氧丙基氧丙基)三甲氧基矽烷、(3-氯丙基)三甲氧基矽烷、(3-環氧丙基氧丙基)三甲氧基矽烷、二甲基二氯矽烷、3-(三甲氧基矽基)丙基甲基丙烯酸酯、乙基三乙醯氧基矽烷、三乙氧基(異丁基)矽烷、三乙氧基(辛基)矽烷、參(2-甲氧基乙氧基)(乙烯基)矽烷、氯三甲基矽烷、甲基三氯矽烷、四氯化矽、四乙氧基矽烷、苯基三甲氧基矽烷、氯三乙氧基矽烷、乙烯基-三甲氧基矽烷等。矽烷耦合劑之處理只要是在氧化處理前進行則何時進行均可，可與脫脂處理、藉由去除自然氧化膜以進行均一化處理之酸洗、或在酸洗後進行以防止酸被帶入氧化步驟的鹼處理一併進行。The silane coupling agent is not particularly limited, and can be selected from silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[ 3-(Trimethoxysilyl)propyl]urea) (l-[3-(Trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilane, (3-epoxypropyl oxygen Propyl)trimethoxysilane, (3-chloropropyl)trimethoxysilane, (3-epoxypropyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilane) Yl) propyl methacrylate, ethyl triacetoxysilane, triethoxy (isobutyl) silane, triethoxy (octyl) silane, ginseng (2-methoxyethoxy) (Vinyl) Silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, vinyl-trimethoxysilane Wait. The treatment of the silane coupling agent can be carried out at any time as long as it is carried out before the oxidation treatment. It can be combined with degreasing treatment, acid washing by removing natural oxide film for homogenization treatment, or after acid washing to prevent acid from being carried in The alkali treatment in the oxidation step is carried out at the same time.

本發明之複合銅構件的製造方法的一實施態樣係包含1）將銅構件表面氧化處理的步驟；及2）將經氧化處理之銅構件表面以修飾劑處理的步驟，或者，包含1）將銅構件表面氧化處理的步驟；2）將經氧化處理之銅構件表面以修飾劑處理的步驟；及3）在經修飾劑處理之複合銅構件表面，形成包含銅以外之金屬的層的步驟。推測係藉由以修飾劑處理，在銅構件與包含銅氧化物之層的界面附近的銅氧化物係一部分被溶解，產生空隙，包含銅氧化物之層變得容易從銅構件斷裂。用以使包含銅氧化物之層變得容易從銅構件斷裂的修飾劑，不限定於氯化鎳，亦可為氯化物（氯化鋅、氯化鐵、氯化鉻等）、銨鹽（檸檬酸銨、氯化銨、硫酸銨、硫酸鎳銨等）、螯合劑（乙二胺四乙酸、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉、葡萄糖酸鈉）等。以氯化鎳處理的情況下係不特別限定，較佳將形成有包含銅氧化物之層的銅構件，在室溫或比室溫高之溫度浸漬於氯化鎳溶液（濃度45g/L以上）5秒以上。又，不僅是單獨以氯化鎳處理，亦可與氧化處理同時進行，亦可在氧化處理後與鍍敷處理同時進行。例如，可以使鍍敷液中含有氯化鎳，在鍍敷前將形成有包含銅氧化物之層的銅構件浸漬於鍍敷液中5秒、10秒、15秒、20秒、30秒、1分鐘或2分鐘。浸漬時間可根據氧化膜厚度適當地變更。An embodiment of the method for manufacturing a composite copper member of the present invention includes 1) the step of oxidizing the surface of the copper member; and 2) the step of treating the surface of the oxidized copper member with a modifier, or, including 1) The step of oxidizing the surface of the copper component; 2) the step of treating the surface of the oxidized copper component with a modifier; and 3) the step of forming a layer containing a metal other than copper on the surface of the composite copper component treated with the modifier . It is presumed that part of the copper oxide system near the interface between the copper member and the copper oxide-containing layer is dissolved by the treatment with the modifier, resulting in voids, and the copper oxide-containing layer becomes easy to break from the copper member. The modifier used to make the layer containing copper oxide easy to break from the copper member is not limited to nickel chloride, but may also be chloride (zinc chloride, iron chloride, chromium chloride, etc.), ammonium salt ( Ammonium citrate, ammonium chloride, ammonium sulfate, nickel ammonium sulfate, etc.), chelating agents (ethylenediaminetetraacetic acid, dihydroxyethylglycine, tetrasodium L-glutamic acid diacetate, ethylenediamine-N, N'-disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl Group) disodium iminodiacetate, sodium gluconate) and so on. It is not particularly limited when treated with nickel chloride. It is preferable to immerse the copper member on which the layer containing copper oxide is formed in a nickel chloride solution (concentration of 45g/L or more) at room temperature or a temperature higher than room temperature. ) More than 5 seconds. Moreover, not only the nickel chloride treatment alone, but also the oxidation treatment may be performed simultaneously, or the plating treatment may be performed simultaneously after the oxidation treatment. For example, nickel chloride can be contained in the plating solution, and the copper member on which the layer containing copper oxide is formed is immersed in the plating solution for 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 1 minute or 2 minutes. The immersion time can be appropriately changed according to the thickness of the oxide film.

本發明之複合銅構件的製造方法的一實施態樣係包含1）以矽烷耦合劑將銅構件表面作部分塗覆的步驟；2）將被部分塗覆之銅構件表面氧化處理的步驟；及3）將經氧化處理之銅構件表面以修飾劑處理的步驟，或者，包含1）以矽烷耦合劑將銅構件表面作部分塗覆的步驟；2）將被部分塗覆之銅構件表面氧化處理的步驟；3）將經氧化處理之銅構件表面以修飾劑處理的步驟；及4）在經修飾劑處理之銅構件表面形成包含銅以外之金屬的層的步驟。An embodiment of the method for manufacturing a composite copper component of the present invention includes 1) the step of partially coating the surface of the copper component with a silane coupling agent; 2) the step of oxidizing the surface of the partially coated copper component; and 3) The step of treating the surface of the oxidized copper component with a modifier, or including 1) the step of partially coating the surface of the copper component with a silane coupling agent; 2) oxidizing the surface of the partially coated copper component 3) the step of treating the surface of the oxidized copper member with a modifier; and 4) the step of forming a layer containing a metal other than copper on the surface of the copper member treated with the modifier.

複合銅構件的使用方法：本發明之複合銅構件可用於 （1）壓接於樹脂基材以製造積層體； （2）壓接於樹脂基材並剝離，得到樹脂基材係具有形成包含銅氧化物之層的金屬之一部分或全部； （3）於SAP法或MSAP法中，壓接於樹脂基材並剝離，得到樹脂基材係具有形成包含銅氧化物之層的金屬之一部分或全部，對剝離之樹脂基材的面進行銅鍍處理，藉此製造印刷佈線板； （4）在包含銅氧化物之層上，施加銅或銅以外之金屬的鍍敷以形成金屬箔，將銅構件作為載體，包含銅氧化物之層及銅或銅以外之金屬的鍍敷作為金屬箔來使用，以製造附載體金屬箔等。 （1）～（3）中，樹脂基材及熱壓接於樹脂基材的條件可與取得SEM截面影像時的條件相同或不同。（2）～（3）中，剝離的條件可與取得SEM截面影像時的條件相同或不同。（3）中，銅鍍方法可為電鍍或無電解鍍。（4）中，對包含銅氧化物之層的最外表面施加鍍敷的方法，可為電鍍或無電解鍍，金屬可為合金。Use method of composite copper component: The composite copper component of the present invention can be used for (1) Crimping on the resin base material to manufacture a laminate; (2) It is crimped on the resin substrate and peeled off to obtain a part or all of the metal that forms the layer containing copper oxide on the resin substrate; (3) In the SAP method or the MSAP method, the resin substrate is crimped and peeled to obtain a resin substrate with a part or all of the metal forming the layer containing copper oxide. Copper is applied to the surface of the peeled resin substrate. Plating treatment to manufacture printed wiring boards; (4) On the layer containing copper oxide, plating of copper or a metal other than copper is applied to form a metal foil, the copper member is used as a carrier, and the layer containing copper oxide and the plating of copper or a metal other than copper are used as Metal foil is used to manufacture metal foil with a carrier, etc. In (1) to (3), the resin base material and the conditions for thermocompression bonding to the resin base material may be the same as or different from the conditions when the SEM cross-sectional image is obtained. In (2) to (3), the peeling conditions may be the same as or different from the conditions when the SEM cross-sectional image is obtained. In (3), the copper plating method can be electroplating or electroless plating. In (4), the method of applying plating to the outermost surface of the layer containing copper oxide may be electroplating or electroless plating, and the metal may be an alloy.

＜1.複合銅箔之製造＞：在實施例1～3、比較例2、3使用古河電工股份有限公司製之銅箔（DR-WS，厚度：18μm）的亮面（光澤面，與相反面比較時為平坦之面）。在比較例1使用古河電工股份有限公司製之銅箔（FV-WS，厚度：18μm）的褪光面，以未處理之狀態作為測試片。<1. Manufacturing of composite copper foil>: In Examples 1 to 3, Comparative Examples 2 and 3, the bright surface (glossy surface) of the copper foil (DR-WS, thickness: 18μm) manufactured by Furukawa Electric Co., Ltd. was used. When comparing the surface, it is a flat surface). In Comparative Example 1, the matte surface of copper foil (FV-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. was used, and the untreated state was used as a test piece.

（1）前處理：實施例1、2係在碳酸鉀5g/L；KBE-903（3-胺基丙基三乙氧基矽烷；信越Silicone公司製）1vol%之溶液，於25℃浸漬1分鐘。比較例2、3及實施例3係在碳酸鉀5g/L之溶液，於25℃浸漬1分鐘。(1) Pretreatment: Examples 1 and 2 are made in potassium carbonate 5g/L; KBE-903 (3-aminopropyl triethoxysilane; manufactured by Shin-Etsu Silicone) 1 vol% solution, immersed at 25°C minute. Comparative Examples 2, 3, and Example 3 were immersed in a solution of 5 g/L of potassium carbonate at 25°C for 1 minute.

（2）氧化處理：將經前處理之銅箔浸漬於氧化劑來進行氧化處理。實施例1、2係使用亞氯酸鈉52.5g/L；氫氧化鉀18g/L；碳酸鉀35g/L之溶液作為氧化劑。實施例3係使用亞氯酸鈉37.5g/L；氫氧化鉀10g/L；KBM-403（3-環氧丙基氧丙基三甲氧基矽烷；信越Silicone公司製）1.5g/L之溶液作為氧化劑。比較例2係使用亞氯酸鈉53.5g/L；氫氧化鉀8g/L；碳酸鉀2g/L；KBM-403（3-環氧丙基氧丙基三甲氧基矽烷；信越Silicone公司製）1.5g/L之溶液作為氧化劑。比較例3係使用亞氯酸鈉195g/L；氫氧化鉀18g/L；KBM-403（3-環氧丙基氧丙基三甲氧基矽烷；信越Silicone公司製）0.5g/L之溶液作為氧化劑。實施例1及2係於73℃浸漬於氧化劑6分鐘，實施例3及比較例2係於73℃浸漬於氧化劑2分鐘。比較例3係於50℃浸漬於氧化劑1分鐘。 （3）電鍍處理：氧化處理後，實施例2、3及比較例2係使用鎳電鍍液（硫酸鎳250g/L；氯化鎳50g/L；檸檬酸鈉25g/L）進行電鍍。比較例3係使用鎳電鍍液（硫酸鎳250g/L；硼酸35g/L）進行電鍍。實施例3係在電鍍前浸漬於鎳電鍍液1分鐘。比較例2、3及實施例2、3係於50℃、電流密度0.5A/dm2 ×45秒（=22.5C/dm2 銅箔面積）進行電鍍。(2) Oxidation treatment: the pre-treated copper foil is immersed in an oxidant for oxidation treatment. Examples 1 and 2 used sodium chlorite 52.5g/L; potassium hydroxide 18g/L; potassium carbonate 35g/L solution as the oxidant. Example 3 uses 37.5g/L sodium chlorite; 10g/L potassium hydroxide; KBM-403 (3-epoxypropyloxypropyltrimethoxysilane; manufactured by Shin-Etsu Silicone) 1.5g/L solution As an oxidant. Comparative Example 2 uses 53.5g/L of sodium chlorite; 8g/L of potassium hydroxide; 2g/L of potassium carbonate; KBM-403 (3-epoxypropyloxypropyltrimethoxysilane; manufactured by Shin-Etsu Silicone) 1.5g/L solution is used as oxidant. Comparative example 3 uses sodium chlorite 195g/L; potassium hydroxide 18g/L; KBM-403 (3-epoxypropyloxypropyltrimethoxysilane; Shin-Etsu Silicone) 0.5g/L solution as Oxidant. Examples 1 and 2 were immersed in the oxidizing agent at 73°C for 6 minutes, and Example 3 and Comparative Example 2 were immersed in the oxidizing agent at 73°C for 2 minutes. Comparative Example 3 was immersed in the oxidizing agent at 50°C for 1 minute. (3) Electroplating treatment: After oxidation treatment, Examples 2, 3 and Comparative Example 2 used nickel electroplating solution (nickel sulfate 250g/L; nickel chloride 50g/L; sodium citrate 25g/L) for electroplating. Comparative Example 3 uses nickel electroplating solution (nickel sulfate 250g/L; boric acid 35g/L) for electroplating. In Example 3, immersion in a nickel electroplating solution for 1 minute before electroplating. Comparative Examples 2 and 3 and Examples 2 and 3 were electroplated at 50° C. and a current density of 0.5 A/dm 2 ×45 seconds (=22.5 C/dm 2 copper foil area).

關於實施例及比較例，分別以相同條件製作數個測試片（第1表）。 第1表   實施例 比較例 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 前處理 調配 碳酸鉀 g/L 5 5 5 － 5 5 KBE-903 vol% 1 1 0 － 0 0 處理 溫度 ℃ 25 25 25 － 25 25 時間 分鐘 1 1 1 － 1 1 氧化處理 調配 亞氯酸鈉 g/L 52.5 52.5 37.5 － 53.5 195 氫氧化鉀 g/L 18 18 10 － 8 18 碳酸鉀 g/L 35 35 0 － 2 0 KBM-403 g/L 0 0 1.5 － 1.5 0.5 處理 溫度 ℃ 73 73 73 － 73 50 時間 分鐘 6 6 2 － 2 1 鍍敷處理 調配 硫酸鎳 g/L － 250 250 － 250 250 氯化鎳 g/L － 50 50 － 50 0 檸檬酸鈉 g/L － 25 25 － 25 0 硼酸 g/L － 0 0 － 0 35 通電前浸泡時間 － 分鐘 － 0 1 － 0 0 Regarding the Examples and Comparative Examples, several test pieces were produced under the same conditions (Table 1). Table 1 Example Comparative example Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Pretreatment Deployment Potassium Carbonate g/L 5 5 5 - 5 5 KBE-903 vol% 1 1 0 - 0 0 deal with temperature °C 25 25 25 - 25 25 time minute 1 1 1 - 1 1 Oxidation treatment Deployment Sodium chlorite g/L 52.5 52.5 37.5 - 53.5 195 Potassium hydroxide g/L 18 18 10 - 8 18 Potassium Carbonate g/L 35 35 0 - 2 0 KBM-403 g/L 0 0 1.5 - 1.5 0.5 deal with temperature °C 73 73 73 - 73 50 time minute 6 6 2 - 2 1 Plating treatment Deployment Nickel Sulfate g/L - 250 250 - 250 250 Nickel chloride g/L - 50 50 - 50 0 Sodium citrate g/L - 25 25 - 25 0 Boric acid g/L - 0 0 - 0 35 Soaking time before power on - minute - 0 1 - 0 0

＜2.樹脂基材之壓接及剝離＞：實施例1～3及比較例1～3之測試片係去除在積層預浸體前之處理所使用的溶液，並充分地乾燥。對該等測試片積層預浸體（R5670KJ，Panasonic製），用真空高壓壓製機於真空中以壓力2.9MPa、溫度210℃、加壓時間120分鐘之條件熱壓接，藉此得到積層體試料。所得到之積層體試料的截面係藉由加速電壓30kV、探針電流4nA之條件進行FIB（聚焦離子束）加工來得到。使用聚焦離子束掃描式電子顯微鏡（Auriga，Carl Zeiss公司製）以倍率30000倍、解析度1024×768之條件觀察所得到的截面，得到SEM截面影像（第3圖）。對於該等積層體試料，基於90度剝離試驗（日本工業規格（JIS）C5016）將銅構件由樹脂基材剝離。剝離後之測試片的影像及剝離強度（kgf/cm）顯示於第2圖，剝離前後之積層體試料的SEM截面影像顯示於第6圖。第6圖中，關於比較例3，將用以保護加工面的Pt沉積層積層於樹脂基材側後，取得影像。如第2圖及第6圖所示，僅有實施例中，針狀結晶銅氧化物或來自針狀結晶銅氧化物的粗細幾乎相同且施有鎳鍍之針狀凸部，係幾乎由銅箔分離，轉移至樹脂基材側。又，實施例與比較例相比，剝離強度亦非常小。<2. Crimping and peeling of resin base material>: The test pieces of Examples 1 to 3 and Comparative Examples 1 to 3 removed the solution used in the treatment before the build-up prepreg and dried it sufficiently. The laminated prepregs (R5670KJ, manufactured by Panasonic) of these test pieces were thermocompression bonded in a vacuum with a vacuum high-pressure press under the conditions of a pressure of 2.9 MPa, a temperature of 210°C, and a pressing time of 120 minutes to obtain a sample of the laminated body. . The cross section of the obtained laminate sample was obtained by FIB (focused ion beam) processing under the conditions of an acceleration voltage of 30 kV and a probe current of 4 nA. A focused ion beam scanning electron microscope (Auriga, manufactured by Carl Zeiss) was used to observe the obtained cross section at a magnification of 30,000 times and a resolution of 1024×768 to obtain an SEM cross-sectional image (Figure 3). With respect to these laminate samples, the copper member was peeled from the resin base material based on a 90-degree peel test (Japanese Industrial Standards (JIS) C5016). The image and peel strength (kgf/cm) of the test piece after peeling are shown in Figure 2, and the SEM cross-sectional image of the laminate sample before and after peeling is shown in Figure 6. In Fig. 6, with regard to Comparative Example 3, Pt deposits for protecting the processed surface were layered on the resin substrate side, and then an image was taken. As shown in Figures 2 and 6, in only the embodiment, the needle-shaped crystalline copper oxide or the needle-shaped crystalline copper oxide derived from the needle-shaped crystalline copper oxide has almost the same thickness and the needle-shaped protrusions coated with nickel are almost made of copper The foil is separated and transferred to the resin substrate side. In addition, the peel strength of the examples is also very small compared with the comparative examples.

＜3.熱壓接後的SEM截面影像之二值化＞：將所得到之積層體試料的SEM截面影像（配置使針狀凸部朝向影像上方；影像大小=3.78μm×2.61μm；解析度1024×768）用影像解析軟體WinROOF2018（三谷商事股份有限公司，ver4.5.5）經過以下步驟進行二值化。 ＜操作＞ 1）選擇範圍（長方形ROI）：與通過存在於最靠近銅側之空隙頂點之被積層面平行的直線、及與通過形成於銅表面之最高凸部的頂點之被積層面平行的直線所包圍的區域作為測量範圍。 2）影像處理→強調（明度±0、對比+20）：為了容易進行影像處理，進行對比之調整。 3）影像處理→強調→反相：為了在二值化處理選擇空隙，進行反相處理，使影像的明亮部分及暗部分互換。 4）自動二值化（判別分析法）：進行自動二值化，選擇銅及銅氧化物所包圍的區域及銅氧化物所包圍的區域。閾值之決定係以判別分析法進行。 5）去除雜訊：將邊長1像素者視為雜訊，刪除面積為15nm2 以下者。 6）算出空隙間距離：配置影像使凸部的方向朝向影像上方時，將影像的左上方作為原點，影像中往下之方向作為X軸，往右之方向作為Y軸。以自動二值化選擇的存在於X=最大、Y=最小之區域作為起點，其與在Y軸方向位於最近距離之區域的距離作為兩點間距離來求出。求出兩點間距離時將所選擇之各領域定義為空隙。 7）空隙尺寸測定：求出空隙的最大水平弦長，將此作為各空隙的尺寸。反相二值化後之各積層體試料的SEM截面影像顯示於第4圖。又，算出空隙及空隙間的平均距離之結果顯示於第5圖。<3. Binarization of the SEM cross-sectional image after thermocompression bonding>: The SEM cross-sectional image of the obtained laminate sample (arranged so that the needle-shaped convex part faces upwards of the image; image size=3.78μm×2.61μm; resolution 1024×768) Use the image analysis software WinROOF2018 (Mitsukoshi Corporation, ver4.5.5) to perform binarization through the following steps. <Operation> 1) Selection range (rectangular ROI): a straight line parallel to the lapped plane passing through the apex of the void closest to the copper side, and a line parallel to the lapped plane passing through the apex of the highest protrusion formed on the copper surface The area enclosed by the straight line serves as the measurement range. 2) Image processing → Emphasis (lightness ±0, contrast +20): In order to facilitate image processing, adjust the contrast. 3) Image processing → Emphasis → Inversion: In order to select the gap in the binarization process, perform inversion processing so that the bright part and the dark part of the image are interchanged. 4) Automatic binarization (discrimination analysis method): Perform automatic binarization, select the area surrounded by copper and copper oxide and the area surrounded by copper oxide. The decision of the threshold is carried out by discriminant analysis. 5) Removal of noise: treat those with a side length of 1 pixel as noise, and delete those with an area of 15nm 2 or less. 6) Calculate the distance between the gaps: When arranging the image so that the direction of the convex part is toward the top of the image, use the upper left of the image as the origin, the downward direction in the image as the X axis, and the right direction as the Y axis. The area where X=maximum and Y=minimum selected by automatic binarization is taken as the starting point, and the distance between the area and the area at the closest distance in the Y-axis direction is calculated as the distance between two points. When calculating the distance between two points, the selected areas are defined as gaps. 7) Measurement of gap size: Find the maximum horizontal chord length of the gap and use this as the size of each gap. The SEM cross-sectional image of each laminate sample after inversion binarization is shown in Fig. 4. In addition, the result of calculating the gap and the average distance between the gaps is shown in Fig. 5.

比較例2、3僅計算銅氧化物所包圍的區域（即銅氧化物層之凹凸的縫隙）作為空隙，相較於此，實施例中係計算銅氧化物所包圍的區域與銅及銅氧化物所包圍的區域（即存在於包含銅氧化物之層與銅箔的界面之區域）作為空隙，故實施例所計算的空隙數量較多，其空隙間的距離亦短。又，實施例中，空隙間的距離在50nm以下的比例占整體的40%以上。In Comparative Examples 2 and 3, only the area surrounded by copper oxide (that is, the gap between the unevenness of the copper oxide layer) is calculated as the void. In contrast, in the embodiment, the area surrounded by the copper oxide and the copper and copper oxidation are calculated. The area surrounded by the object (that is, the area existing at the interface between the copper oxide-containing layer and the copper foil) serves as a void. Therefore, the number of voids calculated in the embodiment is larger, and the distance between the voids is also short. In addition, in the examples, the proportion of the distance between the gaps of 50 nm or less accounted for 40% or more of the whole.

＜4.熱壓接前及剝離後之複合銅箔的Ra及表面積測定＞ （1）方法 對實施例1～3及比較例1、2之複合銅箔測試片，使用共軛焦掃描式電子顯微鏡OPTELICS H1200（Lasertec股份有限公司製）算出熱壓接前及剝離後的表面積。測定條件：模式為共軛焦模式、掃描面積為100μm×100μm、光源為藍光、Cut-off值為1/5。接物鏡x100、目鏡x14、數位變焦x1、Z間距設為10nm，取得3個位置之資料，表面積為3個位置之平均值。 （2）結果 如第2表之記載，於熱壓接前及剝離後，實施例中Ra及表面積減少，相對於此，比較例反而增加。此係表示實施例中複合銅構件的全部或一部分凸部轉移至樹脂側，相對於此，比較例中反而是樹脂的一部分轉移至複合銅構件。 第2表   實施例1 實施例2 實施例3 比較例1 比較例2 熱壓接前 粗度 Ra μm 0.18 0.21 0.04 0.18 0.04 剝離後 粗度 Ra μm 0.12 0.12 0.03 0.21 0.05 變化率 剝離後/熱壓接前 % 64.48 59.42 94.29 117.71 130.56 熱壓接前 表面積 μm2 21453 21578 10897 19033 10915 剝離後 表面積 μm2 15573 16157 10642 21839 11599 變化率 剝離後/熱壓接前 % 72.59 74.88 97.66 114.74 106.27 <4. Measurement of Ra and surface area of composite copper foil before thermocompression bonding and after peeling> (1) Method For the composite copper foil test pieces of Examples 1 to 3 and Comparative Examples 1 and 2, conjugate focus scanning electrons were used Microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.) calculates the surface area before and after thermal compression bonding. Measurement conditions: The mode is conjugate focus mode, the scanning area is 100μm×100μm, the light source is blue light, and the Cut-off value is 1/5. Attach objective lens x100, eyepiece x14, digital zoom x1, and set Z pitch to 10nm. Obtain data from 3 positions, and the surface area is the average of 3 positions. (2) Results As described in Table 2, before and after the thermocompression bonding, the Ra and the surface area decreased in the examples, while the comparative examples increased instead. This indicates that all or part of the convex portions of the composite copper member in the examples are transferred to the resin side, while in the comparative example, instead, part of the resin is transferred to the composite copper member. Table 2 Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Before thermal crimping roughness Ra μm 0.18 0.21 0.04 0.18 0.04 After peeling roughness Ra μm 0.12 0.12 0.03 0.21 0.05 Rate of change After peeling/before thermocompression % 64.48 59.42 94.29 117.71 130.56 Before thermal crimping Surface area μm 2 21453 21578 10897 19033 10915 After peeling Surface area μm 2 15573 16,157 10642 21839 11599 Rate of change After peeling/before thermocompression % 72.59 74.88 97.66 114.74 106.27

根據本發明，可提供新穎的複合銅構件。該複合銅構件適合用於SAP法或MSAP法（第7圖）。為了使鍍敷液浸入凹部的最底部，凹部的形狀需要大到一定程度，不適合形成微細佈線（日本特開2017-034216號公報）。然而，使用本發明之複合銅箔的情況下，形成凹凸之包含銅氧化物之層本身會轉移，故不需要使鍍敷液浸入凹部的最底部，在包含經轉移之銅氧化物且無凹凸的層上進行（圖案）銅鍍即可，即使原本的複合銅構件表面具有的凹部形狀細長，樹脂基材與（圖案）銅鍍層之間產生空隙的可能性低，適合形成微細佈線。此外，由於在包含銅氧化物之層上進行銅鍍，故銅鍍對於包含氧化銅之層的結合親和性高，樹脂基材與（圖案）銅鍍層之間的剝離強度係藉由與銅鍍層結合的包含銅氧化物之層的結合來確保。已知將被氧化之金屬作為剝離層來製作載體箔亦無法使剝離強度穩定（國際公開第2010/027052號公報）。然而，藉由在包含銅氧化物之層形成空隙，本發明之複合銅構件可以直接作為附載體金屬箔而作用之銅構件，或用於製造該銅構件。即使是附載體箔，亦因其過薄的金屬箔，由強度的觀點而言無法承受對樹脂基材之熱壓接步驟。例如實施例2或3的複合銅箔，顯示銅箔部分作為載體來作用，可使包含銅氧化物之層及鎳鍍層轉移，故可將僅有數十nm厚之導電性鎳熱壓接於樹脂基材。包含銅氧化物之層亦被一併轉移，故鎳層的物理性強度藉由一併轉移的包含銅氧化物之層的存在而補強，另一方面，包含銅氧化物之層的導電率極低，故不導電，幾乎不會產生包含銅氧化物之層的存在導致的傳輸損失。According to the present invention, a novel composite copper member can be provided. This composite copper member is suitable for SAP method or MSAP method (Figure 7). In order for the plating solution to infiltrate the bottommost part of the recess, the shape of the recess needs to be large to a certain extent, which is not suitable for forming fine wiring (Japanese Patent Application Laid-Open No. 2017-034216). However, in the case of using the composite copper foil of the present invention, the copper oxide-containing layer that forms the unevenness will transfer itself, so there is no need to dip the plating solution into the bottom of the recessed portion, and it contains the transferred copper oxide without unevenness. (Pattern) copper plating is sufficient on the layer of, even if the concave shape on the surface of the original composite copper member is elongated, the possibility of voids between the resin substrate and the (pattern) copper plating layer is low, and it is suitable for the formation of fine wiring. In addition, since copper plating is performed on the layer containing copper oxide, the bonding affinity of copper plating to the layer containing copper oxide is high, and the peel strength between the resin substrate and the (pattern) copper plating layer The bonding of the bonded copper oxide-containing layer is ensured. It is known that using an oxidized metal as a peeling layer to make a carrier foil cannot stabilize the peel strength (International Publication No. 2010/027052). However, by forming voids in the layer containing copper oxide, the composite copper component of the present invention can be used directly as a copper component with a metal foil with a carrier, or used to manufacture the copper component. Even with carrier foil, because of its too thin metal foil, it cannot withstand the thermal compression bonding step to the resin substrate from the standpoint of strength. For example, the composite copper foil of Example 2 or 3 shows that the part of the copper foil acts as a carrier and can transfer the layer containing copper oxide and the nickel plating layer, so that conductive nickel with a thickness of only tens of nm can be thermally compressed on Resin substrate. The copper oxide-containing layer is also transferred together, so the physical strength of the nickel layer is reinforced by the presence of the copper oxide-containing layer transferred together. On the other hand, the conductivity of the copper oxide-containing layer is extremely high. Low, so non-conductive, almost no transmission loss caused by the presence of copper oxide-containing layers.

無without

［第1圖］  熱壓接前與剝離後的本發明之複合銅構件的截面之一例的概略圖。 ［第2圖］  將實施例及比較例之複合銅箔壓接於樹脂基材且剝離後的剝離面之影像。數值表示剝離時的剝離強度。 ［第3圖］  將實施例1～3及比較例2、3之複合銅箔熱壓接於樹脂基材後以掃描式電子顯微鏡（SEM）觀察的截面影像（倍率30000倍）。以虛線表示包含銅氧化物之層與銅構件之界面。 ［第4圖］  將第3圖的截面影像反相並二值化之圖。反白部分為空隙。僅在實施例1之影像加上顯示空隙間的距離之直線。 ［第5圖］  將第4圖作影像解析所得到的空隙的數量與大小（A）、空隙間的平均距離（B）及空隙間距離之分布（C）的圖表。 ［第6圖］  將實施例3及比較例3之複合銅箔熱壓接於樹脂基材並剝離後的複合銅箔的截面以SEM觀察之影像。 ［第7圖］  本發明之一實施態樣的複合銅箔（「轉印＋轉移」）與習知轉印用銅箔（僅「轉印」）用於SAP法之情況下，各處理步驟中截面的概略圖。[Figure 1] A schematic view of an example of the cross section of the composite copper member of the present invention before and after thermal compression bonding. [Figure 2] The image of the peeled surface after the composite copper foil of the example and the comparative example is crimped on the resin substrate and peeled off. The numerical value indicates the peel strength during peeling. [Figure 3] The cross-sectional image of the composite copper foils of Examples 1 to 3 and Comparative Examples 2 and 3 that were thermally bonded to a resin substrate and observed with a scanning electron microscope (SEM) (30000 times magnification). The dashed line indicates the interface between the copper oxide-containing layer and the copper member. [Picture 4] The cross-sectional image of Fig. 3 is inverted and binarized. The inverted part is a gap. Only a straight line showing the distance between the gaps is added to the image of Example 1. [Picture 5] The number and size of gaps (A), the average distance between gaps (B), and the distribution of gap distances (C) obtained by image analysis in Fig. 4. [Figure 6] The cross-sections of the composite copper foils of Example 3 and Comparative Example 3 after thermal compression bonding to the resin substrate and peeling off were observed with SEM. [Figure 7] When the composite copper foil ("transfer + transfer") of one embodiment of the present invention and the conventional copper foil for transfer (only "transfer") are used in the SAP method, each processing step Schematic drawing of the middle section.

Claims (26)

一種複合銅構件，係於銅構件的表面的至少一部分形成有包含銅氧化物之層，該包含銅氧化物之層具有數個空隙。A composite copper component has a layer containing copper oxide formed on at least a part of the surface of the copper component, and the layer containing copper oxide has several voids. 如請求項1之複合銅構件，其中，該數個空隙中，至少一部分的空隙存在於該包含銅氧化物之層與該銅構件的表面之界面。The composite copper component of claim 1, wherein, among the plurality of voids, at least a part of the voids exists at the interface between the copper oxide-containing layer and the surface of the copper component. 如請求項1或2之複合銅構件，其中，該包含銅氧化物之層與該銅構件的表面之間的剝離強度為0.001kgf/cm以上且0.30kgf/cm以下。The composite copper member of claim 1 or 2, wherein the peel strength between the copper oxide-containing layer and the surface of the copper member is 0.001 kgf/cm or more and 0.30 kgf/cm or less. 如請求項1至3中任一項之複合銅構件，其中，取得掃描式電子顯微鏡之截面的拍攝影像，將該拍攝影像二值化，在與該包含銅氧化物之層平行的方向測量時，任意每3.8μm中偵測到之該空隙的數量為30個以上。The composite copper component of any one of claims 1 to 3, wherein a photographed image of a cross-section of a scanning electron microscope is obtained, the photographed image is binarized, and the measurement is performed in a direction parallel to the copper oxide-containing layer , The number of the gaps detected in any 3.8μm is more than 30. 如請求項1至4中任一項之複合銅構件，其中，將該複合銅構件的該包含銅氧化物之層的表面以規定條件熱壓接於樹脂基材，形成積層體，取得該積層體的掃描式電子顯微鏡之截面的拍攝影像，將該拍攝影像二值化時，在與被積層之面平行的方向測量時，任意每3.8μm中偵測到之該空隙的數量為30個以上。The composite copper component according to any one of claims 1 to 4, wherein the surface of the copper oxide-containing layer of the composite copper component is thermocompression-bonded to a resin substrate under prescribed conditions to form a laminate, and the laminate is obtained A cross-sectional image taken by a scanning electron microscope of a body. When the taken image is binarized, when measured in a direction parallel to the layered surface, the number of gaps detected in any 3.8μm is more than 30 . 如請求項4或5之複合銅構件，其中，該二值化之截面的拍攝影像中，該空隙間的平均距離為100nm以下。The composite copper member of claim 4 or 5, wherein in the captured image of the binarized cross-section, the average distance between the voids is 100 nm or less. 如請求項4或5之複合銅構件，其中，該二值化之截面的拍攝影像中，該空隙間的距離為50nm以下的比例占空隙間整體的40%以上。The composite copper member of claim 4 or 5, wherein, in the captured image of the binarized cross-section, the ratio of the distance between the voids of 50 nm or less accounts for more than 40% of the entire void. 如請求項5至7中任一項之複合銅構件，其中，該樹脂基材含有選自由聚苯醚、環氧樹脂、聚氧二甲苯、聚苯噁唑、聚四氟乙烯、液晶聚合物、亞磷酸三苯酯、氟樹脂、聚醚醯亞胺、聚醚醚酮、聚環烯烴、雙馬來醯亞胺樹脂、低電容率聚醯亞胺及氰酸樹脂所組成之群組中的至少一種絕緣性樹脂。The composite copper component according to any one of claims 5 to 7, wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, and liquid crystal polymer , Triphenyl phosphite, fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin At least one insulating resin. 如請求項5至8中任一項之複合銅構件，其中，該熱壓接的規定條件係於50℃～400℃之溫度、0～20MPa之壓力及1分鐘～5小時之時間的範圍內。The composite copper component of any one of claims 5 to 8, wherein the prescribed conditions of the thermal compression bonding are within the range of a temperature of 50°C to 400°C, a pressure of 0 to 20 MPa, and a time of 1 minute to 5 hours . 如請求項5至9中任一項之複合銅構件，其中，形成有該包含銅氧化物之層的表面的Ra為0.03μm以上，相對於該Ra，由該樹脂基材剝離之該銅構件的表面的Ra之比例為未滿100%。The composite copper member according to any one of claims 5 to 9, wherein Ra of the surface on which the copper oxide-containing layer is formed is 0.03 μm or more, and the copper member peeled from the resin substrate with respect to the Ra The ratio of Ra on the surface is less than 100%. 如請求項5至10中任一項之複合銅構件，其中，熱壓接後由該樹脂基材剝離之該銅構件的表面積相對於形成有該包含銅氧化物之層的表面之表面積的比例為未滿100%。The composite copper component according to any one of claims 5 to 10, wherein the ratio of the surface area of the copper component peeled from the resin substrate after thermocompression bonding to the surface area of the surface on which the copper oxide-containing layer is formed Is less than 100%. 如請求項1至11中任一項之複合銅構件，其中，該包含銅氧化物之層包含銅以外之金屬。The composite copper component according to any one of claims 1 to 11, wherein the layer containing copper oxide contains a metal other than copper. 如請求項12之複合銅構件，其中，該銅以外之金屬為鎳。Such as the composite copper component of claim 12, wherein the metal other than copper is nickel. 如請求項1至11中任一項之複合銅構件，其中，該包含銅氧化物之層包含銅鍍層。The composite copper component according to any one of claims 1 to 11, wherein the layer containing copper oxide includes a copper plating layer. 一種附載體金屬箔，包含如請求項12至14中任一項之複合銅構件，該包含銅氧化物之層作為金屬箔使用，該銅構件作為相對於該金屬箔之載體使用。A metal foil with a carrier, comprising the composite copper member according to any one of claims 12 to 14, the layer containing copper oxide is used as a metal foil, and the copper member is used as a carrier with respect to the metal foil. 一種積層體，係於如請求項1至14中任一項之複合銅構件的該包含銅氧化物之層的至少一部分表面積層有樹脂基材。A laminate in which at least a part of the surface area of the copper oxide-containing layer of the composite copper member according to any one of claims 1 to 14 is layered with a resin substrate. 如請求項16之積層體，其中，該樹脂基材含有選自由聚苯醚、環氧樹脂、聚氧二甲苯、聚苯噁唑、聚四氟乙烯、液晶聚合物、亞磷酸三苯酯、氟樹脂、聚醚醯亞胺、聚醚醚酮、聚環烯烴、雙馬來醯亞胺樹脂、低電容率聚醯亞胺及氰酸樹脂所組成之群組中的至少一種絕緣性樹脂。The laminate of claim 16, wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer, triphenyl phosphite, At least one insulating resin selected from the group consisting of fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide, and cyanate resin. 如請求項1至14中任一項之複合銅構件，係用於製作印刷佈線板。The composite copper component of any one of claims 1 to 14 is used to make printed wiring boards. 如請求項18之複合銅構件，係用於以半加成法或M-SAP法製作印刷佈線板。For example, the composite copper component of claim 18 is used to make printed wiring boards by the semi-additive method or the M-SAP method. 一種印刷佈線板的製造方法，係使用如請求項1至14中任一項之複合銅構件的印刷佈線板的製造方法，包含： 1）在該複合銅構件的該包含銅氧化物之層上將樹脂基材以規定條件熱壓接的步驟； 2）由該樹脂基材以規定條件將該銅構件剝離，得到具有形成該包含銅氧化物之層的金屬之一部分或全部之樹脂基材的步驟；及 3）在具有形成該包含銅氧化物之層的金屬之一部分或全部之樹脂基材的表面進行銅鍍處理的步驟。A method for manufacturing a printed wiring board is a method for manufacturing a printed wiring board using a composite copper member as claimed in any one of claims 1 to 14, comprising: 1) A step of thermocompression bonding a resin substrate under specified conditions on the copper oxide-containing layer of the composite copper component; 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having part or all of the metal forming the copper oxide-containing layer; and 3) A step of performing copper plating treatment on the surface of a resin substrate having part or all of the metal forming the copper oxide-containing layer. 一種具有金屬之樹脂基材的製造方法，包含： 1）在如請求項1至14中任一項之複合銅構件的該包含銅氧化物之層上將樹脂基材以規定條件熱壓接的步驟；及 2）由該樹脂基材以規定條件將該銅構件剝離，得到具有形成該包含銅氧化物之層的金屬之一部分或全部之樹脂基材的步驟。A method for manufacturing a resin substrate with metal, including: 1) A step of thermocompression bonding a resin base material under prescribed conditions on the copper oxide-containing layer of the composite copper component according to any one of claims 1 to 14; and 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having a part or all of the metal forming the copper oxide-containing layer. 一種複合銅構件的製造方法，係如請求項1～11中任一項之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之表面作部分塗覆的步驟；及 2）藉由將該被部分塗覆之該表面氧化處理，形成該包含銅氧化物之層的步驟。A method for manufacturing a composite copper component is the method for manufacturing a composite copper component according to any one of claims 1 to 11, comprising: 1) The step of partially coating the surface of the copper component with silane coupling agent; and 2) The step of forming the layer containing copper oxide by oxidizing the partially coated surface. 一種複合銅構件的製造方法，係如請求項1～11中任一項之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之表面作部分塗覆的步驟； 2）將該被部分塗覆之該表面氧化處理的步驟；及 3）將所形成之包含銅氧化物之層的表面以修飾劑處理的步驟，在此，該修飾劑包含選自由氯化鎳、氯化鋅、氯化鐵、氯化鉻、檸檬酸銨、氯化銨、氯化鉀、硫酸銨、硫酸鎳銨、乙二胺四乙酸、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉及葡萄糖酸鈉所組成之群組的化合物。A method for manufacturing a composite copper component is the method for manufacturing a composite copper component according to any one of claims 1 to 11, comprising: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) The step of treating the surface of the formed copper oxide-containing layer with a modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, Ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinate Acid, 3-hydroxy-2,2'-imino sodium disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl)imino A compound of the group consisting of disodium diacetate and sodium gluconate. 一種複合銅構件的製造方法，係如請求項12之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之表面作部分塗覆的步驟； 2）將該被部分塗覆之該表面氧化處理的步驟；及 3）在經氧化處理之該表面形成包含銅以外之金屬的層的步驟。A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in claim 12, including: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) A step of forming a layer containing a metal other than copper on the surface that has been oxidized. 一種複合銅構件的製造方法，係如請求項12之複合銅構件的製造方法，包含： 1）將該銅構件之該表面氧化處理的步驟； 2）將經該氧化處理之該表面以修飾劑處理的步驟；及 3）在經該修飾劑處理之該表面，形成包含銅以外之金屬的層的步驟，在此，該修飾劑包含選自由氯化鎳、氯化鋅、氯化鐵、氯化鉻、檸檬酸銨、氯化銨、氯化鉀、硫酸銨、硫酸鎳銨、乙二胺四乙酸、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉及葡萄糖酸鈉所組成之群組的化合物。A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in claim 12, including: 1) The step of oxidizing the surface of the copper component; 2) The step of treating the surface after the oxidation treatment with a modifier; and 3) A step of forming a layer containing metals other than copper on the surface treated with the modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate. 一種複合銅構件的製造方法，係如請求項12之複合銅構件的製造方法，包含： 1）以矽烷耦合劑將該銅構件之該表面作部分塗覆的步驟； 2）將該被部分塗覆之該表面氧化處理的步驟； 3）將經該氧化處理之該表面以修飾劑處理的步驟，及 4）在經該修飾劑處理之該表面，形成包含銅以外之金屬的層的步驟，在此，該修飾劑包含選自由氯化鎳、氯化鋅、氯化鐵、氯化鉻、檸檬酸銨、氯化銨、氯化鉀、硫酸銨、硫酸鎳銨、乙二胺四乙酸、二羥乙基甘胺酸、L-麩胺酸二乙酸四鈉、乙二胺-N,N’-二琥珀酸、3-羥基-2,2’-亞胺基二琥珀酸鈉、甲基甘胺酸二乙酸三鈉、天門冬胺酸二乙酸四鈉、N-(2-羥基乙基)亞胺基二乙酸二鈉及葡萄糖酸鈉所組成之群組的化合物。A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in claim 12, including: 1) The step of partially coating the surface of the copper component with a silane coupling agent; 2) The step of oxidizing the partially coated surface; 3) The step of treating the surface after the oxidation treatment with a modifier, and 4) A step of forming a layer containing metals other than copper on the surface treated with the modifier. Here, the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate.
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