TWI745668B - Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board - Google Patents
Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board Download PDFInfo
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- TWI745668B TWI745668B TW108110462A TW108110462A TWI745668B TW I745668 B TWI745668 B TW I745668B TW 108110462 A TW108110462 A TW 108110462A TW 108110462 A TW108110462 A TW 108110462A TW I745668 B TWI745668 B TW I745668B
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
本發明提供粗化處理銅箔,其係適於細線電路形成之低粗度的粗化處理銅箔,同時使用於SAP法時,不僅可對積層體賦予對於無電解銅鍍敷之蝕刻性及乾膜解像性,且基於剪切強度之觀點的電路密著性亦優異之表面輪廓。該粗化處理銅箔係於至少一側具有粗化處理面之粗化處理銅箔,粗化處理面具備複數粗化粒子,粗化處理銅箔之長度10μm之剖面中粗化粒子的周圍長L(μm)之平方相對於粗化粒子的面積S(μm2 )之比L2 /S的平均值為16以上30以下,且粗化處理面之十點平均粗糙度Rz為0.7μm以上1.7μm以下。The present invention provides a roughened copper foil, which is a low-thickness roughened copper foil suitable for the formation of thin-line circuits. When used in the SAP method, it can not only impart etching properties for electroless copper plating to a laminate and Dry film resolution and circuit adhesion based on shear strength are also excellent in surface profile. The roughened copper foil is a roughened copper foil with a roughened surface on at least one side. The roughened surface is provided with a plurality of roughened particles. The roughened copper foil has a length of 10μm in the cross section of the roughened particles. The ratio of the square of L (μm) to the area S (μm 2 ) of the roughened particles. The average value of L 2 /S is 16 or more and 30 or less, and the ten-point average roughness Rz of the roughened surface is 0.7 μm or more and 1.7 Below μm.
Description
本發明有關粗化處理銅箔、附載體銅箔、覆銅積層板及印刷配線板。The present invention relates to a roughened copper foil, a copper foil with a carrier, a copper clad laminate, and a printed wiring board.
近幾年來,最為適於電路之微細化之印刷配線板的製造方法,已廣泛採用SAP(Semiadditive process:半加成製程)法。SAP法係適於形成極微細電路之方法,作為其一例係使用附載體之粗化處理銅箔而進行。例如,如圖1及2所示,使用預浸片112與底塗層113將粗化處理銅箔110壓接密著於在基底基材111a上具備下層電路111b之絕緣樹脂基板111上(步驟(a)),自粗化處理銅箔110剝離載體(未圖示)後,根據需要藉由雷射穿孔形成通孔(114)(步驟(b))。其次,藉由蝕刻去除粗化處理銅箔110,使經賦予粗化表面輪廓之底塗層113露出(步驟(c))。於該粗化表面實施無電解銅鍍敷115(步驟(d))後,藉由使用乾膜116之曝光及顯像以特定圖型遮蔽(步驟(e)),實施電鍍銅117(步驟(f))。去除乾膜116,形成配線部分117a(步驟(g))後,藉由蝕刻去除相鄰配線部分117a、117a間之不要的無電解銅鍍敷115(步驟(h)),獲得以特定圖型形成之配線118。In recent years, the most suitable method of manufacturing printed wiring boards for the miniaturization of circuits has been widely adopted by the SAP (Semiadditive process: semi-additive process) method. The SAP method is a method suitable for forming extremely fine circuits. As an example, it is performed using a copper foil with a carrier for roughening treatment. For example, as shown in Figures 1 and 2, the roughened
如此使用粗化處理銅箔之SAP法,粗化處理銅箔本身於雷射穿孔後藉由蝕刻去除(步驟(c))。而且,由於於粗化處理銅箔經去除之積層體表面轉印粗化處理銅箔之粗化處理面之凹凸形狀,故於隨後步驟中可確保絕緣層(例如底塗層113或無底塗層113時為預浸片112)與鍍敷電路(例如配線118)之密著性。然而,適於提高與鍍敷電路之密著性之表面輪廓由於有成為大略粗糙的凹凸之傾向,故於步驟(h)中,對於無電解銅鍍敷之蝕刻性容易降低。亦即於無電解銅鍍敷咬入粗糙凹凸之部分,為了使銅不殘留而需要更多之蝕刻。In this way, the SAP method of roughening copper foil is used, and the roughening copper foil itself is removed by etching after laser perforation (step (c)). Moreover, since the roughened copper foil has been removed from the laminate surface, the roughened copper foil has a roughened surface of the roughened surface. The roughened surface of the roughened copper foil can ensure an insulating layer (such as
因此,提案有藉由減小粗化粒子且具有縮頸形狀,而使用於SAP法時,可邊確保必要之鍍敷電路密著性邊實現良好蝕刻性之方法。例如專利文獻1(國際公開第2016/158775號)中,揭示於至少一側具有粗化處理面之粗化處理銅箔,粗化處理面具備由銅粒子所成之複數略球狀突起,略球狀突起之平均高度為2.60μm以下。 [先前技術文獻] [專利文獻]Therefore, it is proposed to reduce the roughened particles and have a necked shape. When used in the SAP method, it is possible to achieve good etching properties while ensuring the necessary adhesion of the plating circuit. For example, Patent Document 1 (International Publication No. 2016/158775) discloses a roughened copper foil having a roughened surface on at least one side. The roughened surface is provided with a plurality of spherical protrusions made of copper particles. The average height of the spherical protrusions is 2.60 μm or less. [Prior Technical Literature] [Patent Literature]
[專利文獻1] 國際公開第2016/158775號[Patent Document 1] International Publication No. 2016/158775
近幾年來,伴隨SAP所要求之電路之進一步微細化,而使電路與基板之密著強度(絕對值)降低。不過,如圖3A及圖3B所示,形成於基板112上之電路124有於其長邊方向之側面由阻焊劑126覆蓋之情況(圖3A)及未覆蓋之情況(圖3B)。電路124以阻焊劑126覆蓋之情況,由於電路124以阻焊劑126保護,故作業步驟中電路124自基板122剝落之風險較小,亦即損及電路124與基板122之密著性之風險較小。另一方面,電路124未以阻焊劑126覆蓋之情況,由於電路124未被阻焊劑126保護,故因電路124之微細化而與基板122之密著強度降低時,作業步驟中電路124剝落之風險變大。就此而言,電路與基板之物理密著指標之一為剪切強度(shear strength),為了避免作業步驟中電路剝落,目前現狀為電路之微細化僅能進行至可確保一定以上剪切強度之線寬。因此,為使未經阻焊劑126覆蓋之電路124微細化,除了蝕刻性及乾膜解像性以外,亦期望即使為細的線寬仍可確保充分之剪切強度。然而,即使以專利文獻1中揭示之方法可確保良好之剝離強度(peel strength),亦難以確保可對應於細線化之充分剪切強度。In recent years, with the further miniaturization of circuits required by SAP, the adhesion strength (absolute value) between the circuit and the substrate has decreased. However, as shown in FIGS. 3A and 3B, the
本發明人等如今得到之見解為藉由控制粗化粒子之形狀,而可為適於十點平均粗糙度Rz 1.7μm以下之細線電路形成的等級之低粗度的粗化處理銅箔,且可實現基於剪切強度之觀點之優異電路密著性。亦即,得到之見解為適於細線電路形成之低粗度的粗化處理銅箔,且使用於SAP法時,不僅可對積層體賦予對於無電解銅鍍敷之蝕刻性,且基於剪切強度之觀點的電路密著性亦優異之表面輪廓。且亦得到之見解為藉由使用上述粗化處理銅箔,於SAP法中乾膜顯像步驟中,可實現極微細之乾膜解像性。The findings obtained by the present inventors today are that by controlling the shape of the roughened particles, it can be a low-thickness roughening copper foil suitable for the formation of fine-line circuits with a ten-point average roughness Rz of 1.7 μm or less, and It can achieve excellent circuit adhesion based on the viewpoint of shear strength. That is, the knowledge obtained is that a low-thickness roughening copper foil suitable for the formation of thin-line circuits, and when used in the SAP method, not only can provide the layered body with etching properties for electroless copper plating, but also based on shearing. The surface profile of the circuit adhesion is also excellent from the viewpoint of strength. The knowledge also obtained is that by using the above-mentioned roughening treatment copper foil, in the dry film development step of the SAP method, extremely fine dry film resolution can be achieved.
因此,本發明之目的在於提供粗化處理銅箔,其係適於細線電路形成之低粗度的粗化處理銅箔,同時使用於SAP法時,不僅可對積層體賦予對於無電解銅鍍敷之蝕刻性及乾膜解像性,且基於剪切強度之觀點的電路密著性亦優異之表面輪廓。且本發明之其他目的在於提供具備此等粗化處理銅箔之附載體銅箔。Therefore, the object of the present invention is to provide a roughened copper foil, which is a low-thickness roughened copper foil suitable for the formation of thin-line circuits, and when used in the SAP method, it can not only impart an electroless copper plating to the laminate The etching performance and dry film resolution of the coating, and the surface profile of the circuit adhesion based on the viewpoint of the shear strength are also excellent. And another object of this invention is to provide the copper foil with a carrier provided with such a roughening process copper foil.
依據本發明之一態樣,提供一種粗化處理銅箔,其係於至少一側具有粗化處理面之粗化處理銅箔,前述粗化處理面具備複數粗化粒子, 前述粗化處理銅箔之長度10μm之剖面中前述粗化粒子的周圍長L(μm)之平方相對於前述粗化粒子的面積S(μm2 )之比L2 /S的平均值為16以上30以下,且前述粗化處理面之十點平均粗糙度Rz為0.7μm以上1.7μm以下。According to one aspect of the present invention, there is provided a roughened copper foil, which is a roughened copper foil having a roughened surface on at least one side, the roughened surface is provided with a plurality of roughened particles, and the roughened copper The average value of the ratio L 2 /S of the square of the peripheral length L (μm) of the roughened particles to the area S (μm 2 ) of the roughened particles in the cross section of the foil with a length of 10 μm is 16 or more and 30 or less, and The ten-point average roughness Rz of the roughened surface is 0.7 μm or more and 1.7 μm or less.
依據本發明之另一態樣,提供一種附載體銅箔,其具備載體、設於該載體上之剝離層、及於該剝離層上以前述粗化處理面作為外側而設置之前述粗化處理銅箔。According to another aspect of the present invention, there is provided a copper foil with a carrier, which includes a carrier, a peeling layer provided on the carrier, and the roughening treatment provided on the peeling layer with the roughening treatment surface as the outer side Copper foil.
依據本發明之另一態樣,提供一種覆銅積層板,其具備前述粗化處理銅箔或前述附載體銅箔。According to another aspect of the present invention, there is provided a copper-clad laminate including the aforementioned roughened copper foil or the aforementioned copper foil with a carrier.
依據本發明之另一態樣,提供一種印刷配線板,其係使用前述粗化處理銅箔或前述附載體銅箔而得。或者,依據本發明之另一態樣,提供一種印刷配線板之製造方法,其特徵係使用前述粗化處理銅箔或前述附載體銅箔製造印刷配線板。According to another aspect of the present invention, a printed wiring board is provided, which is obtained by using the aforementioned roughened copper foil or the aforementioned copper foil with a carrier. Or, according to another aspect of the present invention, there is provided a method of manufacturing a printed wiring board, which is characterized by using the aforementioned roughened copper foil or the aforementioned copper foil with a carrier to manufacture a printed wiring board.
定義 用以特定本發明所用之用語及參數之定義示於以下。definition The definitions of terms and parameters used to specify the present invention are shown below.
本說明書中,所謂「粗化粒子」係如圖4示意性所示,於粗化處理銅箔10之基底面10a表面直接形成之高度超過150nm之尺寸的粒子12,包含略球狀、針狀、柱狀、細長形狀等之所有形狀,但較好為具有「略球狀突起」之形態。本說明書中,所謂「略球狀突起」係具有略球狀之帶圓之概略形狀的突起,且可與針狀、柱狀、細長形狀等之不規則形狀之突起或粒子有所區別者。如圖4中作為粗化粒子12所示,略球狀突起由於於與銅箔基底面10a連結之縮頸根基部分與銅箔之基底面10a連結,故無法成為完全球體,但只要根基部分以外之部分為大致球狀即可。因此,略球狀突起只要能保持略球狀之帶圓之概略形狀,則亦容許存在微細凹凸或變形等。又,上述突起有時亦簡稱為球狀突起,由於如上述無法成為完全球體,故應可理解為意指上述略球狀突起。又,未直接形成於粗化處理銅箔10之基底面10a,而形成於粗化粒子12表面之突起12a亦可構成粗化粒子12之一部分。In this specification, the so-called "roughened particles" are as shown schematically in FIG. 4. The
本說明書中所謂「粗化粒子周圍長L」,如圖5示意性所示,係粗化粒子12之剖面輪廓線12p(圖5之實線部分)的長Lp
與將輪廓線12p與粗化處理銅箔10之基底面10a之接點c1
及c2
間連結之線段12s(圖5之點線部分)之長Ls
之合計長(Lp
+Ls
)。又,所謂「粗化粒子之面積S」,如圖5示意性所示,係粗化粒子12之剖面中,輪廓線12p及線段12s所包圍之圖形面積(剖面積)。粗化粒子12之周圍長L及面積S,可藉由SEM觀察取得之粗化處理銅箔10之剖面圖像使用市售軟體進行解析而特定出。例如,可使用圖像解析軟體Image-Pro Plus 5.1J (Media Cybernetics, Inc.製),針對圖像解析依據本說明書之實施例所記載之諸條件進行。The present specification, the term "coarse particles around the length L", as shown schematically in FIG. 5, based
本說明書中,所謂載體之「電極面」係指載體製作時與陰極接觸之側的面。In this specification, the "electrode surface" of the carrier refers to the surface on the side in contact with the cathode when the carrier is manufactured.
本說明書中,所謂載體之「析出面」係指載體製作時金屬電解析出之側的面,亦即未與陰極接觸之側的面。In this specification, the "precipitation surface" of the carrier refers to the surface on the side where the metal is electrolytically resolved during the production of the carrier, that is, the surface on the side that is not in contact with the cathode.
粗化處理銅箔
本發明之銅箔係粗化處理銅箔。該粗化處理銅箔於至少一側具有粗化處理面。粗化處理面如圖4示意性所示,具備複數粗化粒子12。粗化處理銅箔10之長10μm之剖面中粗化粒子12的周圍長L(μm)之平方相對於粗化粒子12的面積S(μm2
)之比L2
/S的平均值為16以上30以下。且粗化處理面之十點平均粗糙度Rz為0.7μm以上1.7μm以下。藉由如此控制粗化粒子之形狀,可為適於十點平均粗糙度Rz為1.7μm以下之細線電路形成之等級之低粗度的粗化處理銅箔,且可實現基於剪切強度之觀點優異之電路密著性。亦即,可為適於細線電路形成之低粗度的粗化處理銅箔,同時使用於SAP法時,不僅可對積層體賦予對於無電解銅鍍敷之蝕刻性,且基於剪切強度之觀點的電路密著性亦優異之表面輪廓。又,藉由使用上述粗化處理銅箔,於SAP法中之乾膜顯像步驟中,可實現極微細之乾膜解像性。Roughened Copper Foil The copper foil of the present invention is a roughened copper foil. The roughened copper foil has a roughened surface on at least one side. The roughening treatment surface is schematically shown in FIG. 4, and includes a plurality of
鍍敷電路密著性與對於無電解銅鍍敷之蝕刻性本來即難以兼具。亦即,如前述,適於提高與鍍敷電路之密著性之表面輪廓由於有成為概略較粗凹凸之傾向,故圖2之步驟(h)中,無電解銅鍍敷之蝕刻性容易降低。亦即,於無電解銅鍍敷咬入粗糙凹凸之部分,為了使銅不殘留而需要更多之蝕刻。就此點而言,依據專利文獻1之粗化處理銅箔,可實現蝕刻量之減低,並且可確保優異之鍍敷電路密著性。然而,近幾年來,伴隨SAP法所要求之電路進一步微細化,電路與基板之密著強度(絕對值)降低,結果以專利文獻1中揭示之方法即可使確保良好剝離強度,但亦難以確保可對應於細線化之充分剪切強度。因此,於電路未以阻焊劑覆蓋之情況,作業步驟中產生電路剝落之風險增大。相對於此,本發明中,藉由控制粗化粒子12之形狀,可實現粗化粒子之大幅小徑化至適於十點平均粗糙度Rz為1.7μm以下之細線電路形成之等級,且可大幅改善基於剪切強度之觀點的電路密著性。亦即,藉由以上述範圍內之Rz表示之粗化粒子12之小徑化,若是本來會使電路密著性降低,但本發明中藉由將表示粗化粒子12之剖面形狀之參數的比L2
/S的平均值設為16以上30以下,則可實現基於剪切強度之觀點的優異電路密著性。而且,由於可兼具此等優異密著性及對於無電解銅鍍敷之優異蝕刻性,故認為於SAP法之乾膜顯像步驟中,可實現極微細之乾膜解像性。因此,本發明之粗化處理銅箔10可較好地使用於利用半加成法(SAP)之印刷配線板之製作。若為其他表現,則亦可說本發明之粗化處理銅箔10較好使用於用以對印刷配線板用之絕緣樹脂層轉印凹凸形狀者。It is inherently difficult to have both the adhesion of the plated circuit and the etching properties for electroless copper plating. That is, as mentioned above, the surface profile suitable for improving the adhesion to the plated circuit tends to become rougher roughness. Therefore, in the step (h) of FIG. 2, the etching property of electroless copper plating tends to decrease. . That is, in the part where the roughness is bitten in the electroless copper plating, more etching is required in order to prevent the copper from remaining. In this regard, according to the roughening treatment copper foil of Patent Document 1, the amount of etching can be reduced, and excellent plating circuit adhesion can be ensured. However, in recent years, with the further miniaturization of circuits required by the SAP method, the adhesion strength (absolute value) between the circuit and the substrate has decreased. As a result, the method disclosed in Patent Document 1 can ensure good peel strength, but it is also difficult. Ensure sufficient shear strength corresponding to thinning. Therefore, when the circuit is not covered with solder resist, the risk of circuit peeling during the operation steps increases. In contrast, in the present invention, by controlling the shape of the roughened
本發明之粗化處理銅箔10於至少一側具有粗化處理面。亦即粗化處理銅箔可為於兩側具有粗化處理面者,亦可為僅於一側具有粗化處理面者。於兩側具有粗化處理面時,使用於SAP法之情況下,由於雷射照射側之面(自密著於絕緣樹脂面遠離之側的面)亦成為粗化,故雷射吸收性提高的結果,雷射穿孔性亦可提高。The roughened
粗化處理面具備複數粗化粒子12,該等複數粗化粒子12較好各由銅粒子所成。銅粒子可為由金屬銅所成者,亦可為由銅合金所成者。然而,銅粒子為銅合金時,由於有對於銅蝕刻液之溶解性降低,或因合金成分混入銅蝕刻液中而使蝕刻液壽命降低之情況,故銅粒子較好由金屬銅所成。The roughening treatment surface is provided with a plurality of
粗化處理銅箔10之長度10μm之剖面中粗化粒子12的周圍長L(μm)之平方相對於粗化粒子12的面積S(μm2
)之比L2
/S的平均值為16以上30以下,較好為19以上27以下,更好為19以上26以下,又更好為19以上25以下,特佳為20以上24以下。若為該等範圍內,可有效防止粗化粒子12之脫落,並且可更提高剪切強度。
粗化處理面之十點平均粗糙度Rz為0.7μm以上1.7μm以下,較好為0.7μm以上1.6μm以下,更好為0.8μm以上1.5μm以下。若為該等範圍內,可確保期望之剪切強度,並且可更提高細線形成性。Rz係依據JIS B 0601-1994而決定。The ten-point average roughness Rz of the roughened surface is 0.7 μm or more and 1.7 μm or less, preferably 0.7 μm or more and 1.6 μm or less, more preferably 0.8 μm or more and 1.5 μm or less. If it is within these ranges, the desired shear strength can be ensured, and the fine line forming properties can be further improved. Rz is determined in accordance with JIS B 0601-1994.
粗化處理銅箔10之長度10μm之剖面中粗化粒子12之個數較好為20個以上70個以下,更好為20個以上60個以下,又更好為20個以上40個以下。若為該等範圍內,可有效防止粗化粒子12之脫落,可更提高剪切強度。The number of roughened
本發明之粗化處理銅箔10的厚度並未特別限定,較好為0.1μm以上18μm以下,更好為0.5μm以上7μm以下,又更好為0.5μm以上5μm以下,特佳為0.5μm以上3μm以下。該厚度係包含粗化粒子12之厚度。又,本發明之粗化處理銅箔10不限於對通常之銅箔表面進行粗化處理者,亦可為對附載體銅箔之銅箔表面進行粗化處理者。The thickness of the roughened
粗化處理銅箔之製造方法 雖說明本發明之粗化處理銅箔之較佳製造方法之一例,但本發明之粗化處理銅箔不限於以下說明之方法,只要能實現本發明之粗化處理銅箔之表面輪廓,則可為藉由所有方法製造者。Manufacturing method of roughened copper foil Although an example of a preferable manufacturing method of the roughened copper foil of the present invention is described, the roughened copper foil of the present invention is not limited to the method described below, as long as the surface profile of the roughened copper foil of the present invention can be realized. Can be made by all methods.
(1)銅箔之準備 作為粗化處理銅箔之製造所使用之銅箔,可使用電解銅箔及壓延銅箔之兩者。銅箔厚度並未特別限制,但較好為0.1μm以上18μm以下,更好為0.5μm以上7μm以下,又更好為0.5μm以上5μm以下,特佳為0.5μm以上3μm以下。銅箔以附載體銅箔之形態準備時,銅箔可為藉由無電解銅鍍敷法及電解銅鍍敷法等之濕式成膜法、濺鍍及化學蒸鍍等之乾式成膜法或該等之組合而形成者。(1) Preparation of copper foil As the copper foil used in the manufacture of the roughened copper foil, both electrolytic copper foil and rolled copper foil can be used. The thickness of the copper foil is not particularly limited, but is preferably 0.1 μm or more and 18 μm or less, more preferably 0.5 μm or more and 7 μm or less, still more preferably 0.5 μm or more and 5 μm or less, particularly preferably 0.5 μm or more and 3 μm or less. When the copper foil is prepared in the form of a copper foil with a carrier, the copper foil can be a wet film forming method such as electroless copper plating and electrolytic copper plating, and a dry film forming method such as sputtering and chemical vapor deposition. Or a combination of these.
(2)粗化處理 使用銅粒子將銅箔至少一表面粗化。該粗化係藉由使用粗化處理用銅電解溶液之電解進行。該電解較好為經過3階段鍍敷步驟而進行。第1階段之鍍敷步驟中,較好使用包含銅濃度5g/L以上20g/L以下、硫酸濃度30g/L以上200g/L以下、氯濃度20ppm以上100ppm以下、及9-苯基吖啶(9PA)濃度20ppm以上100ppm以下之硫酸銅溶液,於液溫20℃以上40℃以下、電流密度5A/dm2 以上25A/dm2 以下、時間2秒以上10秒以下之鍍敷條件進行電鍍。第2階段之鍍敷步驟中,較好使用包含銅濃度65g/L以上80g/L以下及硫酸濃度200g/L以上280g/L以下之硫酸銅溶液,於液溫45℃以上55℃以下及電流密度1A/dm2 以上10A/dm2 以下、時間2秒以上25秒以下之鍍敷條件進行電鍍。第3階段之鍍敷步驟中,較好使用包含銅濃度10g/L以上20g/L以下、硫酸濃度30g/L以上130g/L以下、氯濃度20ppm以上100ppm以下、及9PA濃度100ppm以上200ppm以下之硫酸銅溶液,於液溫20℃以上40℃以下、電流密度10A/dm2 以上40A/dm2 以下、時間0.3秒以上1.0秒以下之鍍敷條件進行電鍍。藉由進行使用9PA等之添加劑之第3階段之鍍敷步驟,於第1階段及第2階段之鍍敷步驟中形成之粗化粒子表面形成微小突起,可增大比L2 /S。尤其較好第1階段之鍍敷步驟使用9PA等之添加劑等進行,第1階段之鍍敷步驟中之電量Q1 與第2階段之鍍敷步驟之電量Q2 之合計電量(Q1 +Q2 )較好設定為100C/dm2 以下。又,第1~3階段之鍍敷步驟中鍍敷液對於銅箔之線流速均較好為0.10m/s以上0.50m/s以下,更好為0.15m/s以上0.45m/s以下。如此,可形成滿足十點平均粗糙度Rz≦1.7μm之比較低粗度之表面輪廓,並且第3階段之鍍敷可遍及粗化粒子表面全體,形成比L2 /S較大之粗化粒子。(2) The roughening treatment uses copper particles to roughen at least one surface of the copper foil. The roughening is performed by electrolysis using a copper electrolytic solution for roughening treatment. This electrolysis is preferably carried out through a three-stage plating step. In the plating step of the first stage, it is preferable to use a copper concentration of 5 g/L or more and 20 g/L or less, a sulfuric acid concentration of 30 g/L or more and 200 g/L or less, a chlorine concentration of 20 ppm or more and 100 ppm or less, and 9-phenyl acridine ( 9PA) A copper sulfate solution with a concentration of 20 ppm or more and 100 ppm or less is electroplated under the plating conditions of a liquid temperature of 20°C or more and 40°C, a current density of 5 A/dm 2 or more and 25 A/dm 2 or less, and a time of 2 seconds or more and 10 seconds or less. In the second plating step, it is better to use a copper sulfate solution containing a copper concentration of 65g/L or more and 80g/L or less and a sulfuric acid concentration of 200g/L or more and 280g/L or less, at a liquid temperature of 45℃ or more and 55℃ or less and current Electroplating is performed on plating conditions with a density of 1 A/dm 2 or more and 10 A/dm 2 or less, and a time of 2 seconds or more and 25 seconds or less. In the plating step of the third stage, it is preferable to use a copper concentration of 10 g/L or more and 20 g/L or less, a sulfuric acid concentration of 30 g/L or more and 130 g/L or less, a chlorine concentration of 20 ppm or more and 100 ppm or less, and a 9PA concentration of 100 ppm or more and 200 ppm or less. The copper sulfate solution is electroplated under the plating conditions of a liquid temperature of 20°C or more and 40°C or less, a current density of 10 A/dm 2 or more and 40 A/dm 2 or less, and a time of 0.3 seconds or more and 1.0 seconds or less. By performing the third-stage plating process using additives such as 9PA, the surface of the roughened particles formed in the first-stage and second-stage plating processes forms minute protrusions, and the ratio L 2 /S can be increased. It is particularly preferable to use additives such as 9PA in the first stage of the plating step. The total amount of electricity Q 1 in the first stage of plating step and the amount of electricity Q 2 in the second stage of plating step (Q 1 + Q 2 ) It is preferably set to 100 C/dm 2 or less. In addition, the linear flow velocity of the plating solution to the copper foil in the plating steps of the first to third stages is preferably 0.10 m/s or more and 0.50 m/s or less, more preferably 0.15 m/s or more and 0.45 m/s or less. In this way, a relatively low roughness surface profile that satisfies the ten-point average roughness Rz≦1.7μm can be formed, and the third-stage plating can cover the entire surface of the roughened particles to form roughened particles larger than L 2 /S .
(3)防鏽處理 防鏽處理由於對於粗化粒子之形狀、周圍長及面積、以及粗化處裡面之十點平均粗糙度Rz不會造成影響,故可依據期望對粗化處理後之銅箔實施防鏽處理。防鏽處理較好包含使用鋅之鍍敷處理。使用鋅之鍍敷處理可為鋅鍍敷處理及鋅合金鍍敷處理之任一者,鋅合金鍍敷處理特佳為鋅-鎳合金處理。鋅-鎳合金處理若為至少包含Ni及Zn之鍍敷處理即可,亦可進而包含Sn、Cr、Co等之其他元素。鋅-鎳合金鍍敷中Ni/Zn附著比例,以質量比計,較好為1.2以上10以下,更好為2以上7以下,又更好為2.7以上4以下。又,防鏽處理較好進而包含鉻酸鹽處理。此鉻酸鹽處理更好係於使用鋅之鍍敷處理後,對包含鋅之鍍敷表面進行。若如此則可進而提高防鏽性。特佳之防鏽處理係鋅-鎳合金鍍敷處理與其後之鉻酸鹽處理之組合。(3) Anti-rust treatment Anti-rust treatment has no effect on the shape, surrounding length and area of the roughened particles, and the ten-point average roughness Rz inside the roughened part. Therefore, the roughened copper foil can be subjected to anti-rust treatment according to expectations. The anti-rust treatment preferably includes a plating treatment using zinc. The plating treatment using zinc may be either zinc plating treatment or zinc alloy plating treatment, and zinc alloy plating treatment is particularly preferably zinc-nickel alloy treatment. The zinc-nickel alloy treatment may be a plating treatment including at least Ni and Zn, and may further include other elements such as Sn, Cr, and Co. The Ni/Zn adhesion ratio in zinc-nickel alloy plating is preferably 1.2 or more and 10 or less in mass ratio, more preferably 2 or more and 7 or less, and still more preferably 2.7 or more and 4 or less. In addition, the rust prevention treatment preferably further includes chromate treatment. This chromate treatment is preferably performed on the plating surface containing zinc after the plating treatment using zinc. If so, the rust resistance can be further improved. The best anti-rust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.
(4)矽烷偶合劑處理 依據期望,亦可於銅箔實施矽烷偶合劑處理,形成矽烷偶合劑層。藉此可提高耐濕性、耐藥品性及與接著劑等之密著性。矽烷偶合劑層可藉由適當稀釋矽烷偶合劑並塗佈、乾燥而形成。作為矽烷偶合劑之例舉例為4-縮水甘油基丁基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷等之環氧官能性矽烷偶合劑,或3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷等之胺基官能性矽烷偶合劑,或3-巰基丙基三甲氧基矽烷等之巰基官能性矽烷偶合劑,或乙烯基三甲氧基矽烷、乙烯基苯基三甲氧基矽烷等之烯烴官能性矽烷偶合劑,或3-甲基丙烯醯氧基丙基三甲氧基矽烷等之丙烯酸官能性矽烷偶合劑,或咪唑矽烷等之咪唑官能性矽烷偶合劑,或三嗪矽烷等之三嗪官能性矽烷偶合劑等。(4) Silane coupling agent treatment According to expectations, the copper foil can also be treated with a silane coupling agent to form a silane coupling agent layer. This can improve moisture resistance, chemical resistance, and adhesion to adhesives. The silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, coating, and drying. Examples of silane coupling agents include epoxy functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane. Ethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3- Amino-functional silane coupling agent such as aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, or mercapto-functional silane such as 3-mercaptopropyltrimethoxysilane Coupling agent, or olefin functional silane coupling agent such as vinyl trimethoxy silane, vinyl phenyl trimethoxy silane, or acrylic functional silane coupling agent such as 3-methacryloxypropyl trimethoxy silane Mixture, or imidazole functional silane coupling agent such as imidazole silane, or triazine functional silane coupling agent such as triazine silane, etc.
附載體銅箔 本發明之粗化處理銅箔可以附載體之銅箔形態提供。該情況下,附載體銅箔具備載體、設於該載體上之剝離層及於該剝離層上以使粗化處理面為外側而設置之本發明之粗化處理銅箔。不過,附載體銅箔除使用本發明之粗化處理銅箔以外,可採用習知層構成。Copper foil with carrier The roughened copper foil of the present invention can be provided in the form of a copper foil with a carrier. In this case, the copper foil with a carrier is equipped with the carrier, the peeling layer provided on this carrier, and the roughening process copper foil of this invention provided on this peeling layer so that a roughening process surface may be an outer side. However, the copper foil with a carrier can adopt a conventional layer structure other than the roughening process copper foil of this invention.
載體係支持粗化處理銅箔且用以提高其處理性之層(典型上為箔)。作為載體之例舉例為鋁箔、銅箔、表面以銅等金屬塗佈之樹脂膜或玻璃板等,較好為銅箔。銅箔可為壓延銅箔及電解銅箔之任一者。載體厚度典型上為200μm以下,較好為12μm以上35μm以下。The carrier system supports the roughening process of the copper foil and is used to improve its handleability (typically a foil). Examples of the carrier include aluminum foil, copper foil, a resin film coated with a metal such as copper or a glass plate on the surface, and copper foil is preferred. The copper foil may be any of rolled copper foil and electrolytic copper foil. The thickness of the carrier is typically 200 μm or less, preferably 12 μm or more and 35 μm or less.
附載體之剝離層側之面較好具有0.5μm以上1.5μm以下,更好為0.6μm以上1.0μm以下之十點平均粗糙度Rz。Rz可依據JIS B 0601-1994決定。藉由於載體之剝離層側之面賦予如此十點表面粗糙度Rz,容易對於其上經由剝離層而製作之本發明之粗化處理銅箔賦予期望之表面輪廓。The surface on the side of the release layer with the carrier preferably has a ten-point average roughness Rz of 0.5 μm or more and 1.5 μm or less, more preferably 0.6 μm or more and 1.0 μm or less. Rz can be determined in accordance with JIS B 0601-1994. By imparting such a ten-point surface roughness Rz to the surface on the release layer side of the carrier, it is easy to impart a desired surface profile to the roughening treatment copper foil of the present invention produced through the release layer thereon.
剝離層係具有使載體之剝離強度較弱,擔保該強度安定性,進而抑制於高溫之加壓成形時於載體與銅箔間引起之相互擴散的功能之層。剝離層一般係形成於載體之一面,但亦可形成於兩面。剝離層可為有機剝離層及無機剝離層之任一者。作為有機剝離層所用之有機成分之例舉例為含氮有機化合物、含硫有機化合物、羧酸等。作為含氮有機化合物之例舉例為三唑化合物、咪唑化合物等,其中三唑化合物就剝離性易安定之方面係較佳。作為三唑化合物之例舉例為1,2,3-苯并三唑、羧基苯并三唑、N’,N’-雙(苯并三唑基甲基)脲、1H-1,2,4-三唑及3-胺基-1H-1,2,4-三唑等。作為含硫有機化合物之例,舉例為巰基苯并噻唑、硫氰脲酸、2-苯并咪唑硫醇等。作為羧酸之例舉例為單羧酸、二羧酸等。另一方面,作為無機剝離層所用之無機成分之例舉例為Ni、Mo、Co、Cr、Fe、Ti、W、P、Zn、鉻酸鹽處理膜等。又,剝離層之形成藉由將載體之至少一表面與含剝離層成分之溶液接觸,將剝離層成分固定於載體表面而進行即可。載體與含剝離層成分之溶液的接觸,藉由朝含剝離層成分之溶液之浸漬、含剝離層成分之溶液之噴霧、含剝離層成分之溶液之流下等而進行即可。又,剝離層成分於載體表面之固定藉由含剝離層成分之溶液之吸附或乾燥、含剝離層成分之溶液中之剝離層成分之電鍍等而進行即可。剝離層厚度典型上為1nm以上1μm以下,較好為5nm以上500nm以下。The peeling layer has the function of weakening the peeling strength of the carrier, ensuring the strength stability, and inhibiting the mutual diffusion between the carrier and the copper foil during high-temperature press molding. The release layer is generally formed on one side of the carrier, but can also be formed on both sides. The peeling layer may be any one of an organic peeling layer and an inorganic peeling layer. Examples of organic components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids, and the like. As examples of nitrogen-containing organic compounds, triazole compounds, imidazole compounds, etc. are exemplified. Among them, triazole compounds are preferred in terms of easy and stable releasability. Examples of triazole compounds are 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4 -Triazole and 3-amino-1H-1,2,4-triazole, etc. Examples of sulfur-containing organic compounds include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazole thiol, and the like. As an example of a carboxylic acid, monocarboxylic acid, dicarboxylic acid, etc. are mentioned. On the other hand, as examples of the inorganic components used in the inorganic release layer, Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate treatment films, and the like are exemplified. In addition, the formation of the release layer may be performed by contacting at least one surface of the carrier with a solution containing the release layer component to fix the release layer component on the surface of the carrier. The contact between the carrier and the solution containing the peeling layer component may be performed by immersing the solution containing the peeling layer component, spraying the solution containing the peeling layer component, or flowing down the solution containing the peeling layer component. In addition, the fixing of the release layer component on the surface of the carrier may be performed by adsorption or drying of the solution containing the release layer component, electroplating of the release layer component in the solution containing the release layer component, or the like. The thickness of the peeling layer is typically 1 nm or more and 1 μm or less, preferably 5 nm or more and 500 nm or less.
作為粗化處理銅箔係使用上述本發明之粗化處理銅箔。本發明之粗化處理係實施使用銅粒子而粗化者,但作為其順序,首先於剝離層表面形成銅層作為銅箔,隨後至少進行粗化即可。關於粗化細節如前述。又,銅箔較好活用作為附載體銅箔之優點而以極薄銅箔之形態構成。作為極薄銅箔之較佳厚度為0.1μm以上7μm以下,較好為0.5μm以上5μm以下,又更好為0.5μm以上3μm以下。As the roughened copper foil, the roughened copper foil of the present invention described above is used. The roughening treatment of the present invention implements roughening using copper particles, but as the procedure, first, a copper layer is formed on the surface of the peeling layer as a copper foil, and then at least the roughening is performed. The details of the roughening are as described above. In addition, copper foil is preferably constructed in the form of ultra-thin copper foil by utilizing the advantages of copper foil with a carrier. The preferable thickness of the ultra-thin copper foil is 0.1 μm or more and 7 μm or less, preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less.
於剝離層與載體及/或銅箔之間亦可設置其他功能層。作為此等其他功能層之例舉例為輔助金屬層。輔助金屬層較好由鎳及/或鈷所成。藉由於載體之剝離層側及/或粗化處理銅箔之剝離層側形成此輔助金屬層,可進一步抑制高溫或長時間熱加壓成形時於載體及粗化處理銅箔之間引起之相互擴散,可擔保載體之剝離強度之安定性。輔助金屬層厚度較好為0.001μm以上3μm以下。Other functional layers can also be arranged between the peeling layer and the carrier and/or the copper foil. An example of these other functional layers is an auxiliary metal layer. The auxiliary metal layer is preferably made of nickel and/or cobalt. By forming this auxiliary metal layer due to the peeling layer side of the carrier and/or the peeling layer side of the roughened copper foil, it is possible to further suppress the interaction between the carrier and the roughened copper foil during high temperature or long-term hot press molding. Diffusion can guarantee the stability of the peel strength of the carrier. The thickness of the auxiliary metal layer is preferably from 0.001 μm to 3 μm.
覆銅積層板 本發明之粗化處理銅箔或附載體銅箔較好使用於印刷配線板用覆銅積層板之製作。亦即,依據本發明之較佳態樣,提供具備上述粗化處理銅箔或上述附載體銅箔之覆銅積層板。藉由使用本發明之粗化處理銅箔或附載體銅箔,可提供特別適於SAP法之覆銅積層板。該覆銅積層板具備本發明之粗化處理銅箔與密著於該粗化處理銅箔之粗化處理面而設置之樹脂層而成,或者具備本發明之附載體銅箔與密著於該附載體銅箔之粗化處理銅箔之粗化處理面而設置之樹脂層而成。粗化處理銅箔或附載體銅箔可設於樹脂層之單面,亦可設於兩面。樹脂層包含樹脂,較好包含絕緣性樹脂。樹脂層較好為預浸片及/或樹脂薄片。所謂預浸片係於合成樹脂板、玻璃板、玻璃織布、玻璃不織布、紙等之基材中含浸合成樹脂之複合材料的總稱。作為絕緣性樹脂之較佳例舉例為環氧樹脂、氰酸酯樹脂、雙馬來醯亞胺三嗪樹脂(BT樹脂)、聚苯醚樹脂、酚樹脂等。且,作為構成樹脂薄片之絕緣性樹脂舉例為環氧樹脂、聚醯亞胺樹脂、聚酯樹脂等之絕緣性樹脂。又,基於對樹脂層提高絕緣性等之觀點,亦可含有由氧化矽、氧化鋁等之各種無機粒子而成之填料粒子等。樹脂層的厚度並未特別限定,但較好為1μm以上1000μm以下,更好為2μm以上400μm以下,再更好為3μm以上200μm以下。樹脂層亦可以複數層構成。預浸片及/或樹脂薄片等之樹脂層亦可經由預先塗佈於粗化處理銅箔之粗化處理表面之底塗樹脂層而設於粗化處理銅箔或附載體銅箔上。Copper Clad Laminate The roughened copper foil or copper foil with a carrier of the present invention is preferably used in the production of copper-clad laminates for printed wiring boards. That is, according to a preferable aspect of the present invention, a copper-clad laminated board provided with the above-mentioned roughened copper foil or the above-mentioned copper foil with a carrier is provided. By using the roughened copper foil or copper foil with a carrier of the present invention, it is possible to provide a copper-clad laminate that is particularly suitable for the SAP method. The copper-clad laminated board is made up of the roughened copper foil of the present invention and a resin layer that is provided in close contact with the roughened surface of the roughened copper foil, or it has the copper foil with a carrier of the present invention and adhered to The roughening treatment of the copper foil with a carrier is formed by a resin layer provided on the roughening treatment surface of the copper foil. The roughened copper foil or copper foil with a carrier can be provided on one side of the resin layer or on both sides. The resin layer contains resin, and preferably contains insulating resin. The resin layer is preferably a prepreg sheet and/or a resin sheet. The so-called prepreg is a general term for composite materials in which synthetic resin plates, glass plates, glass woven fabrics, glass non-woven fabrics, paper, etc. are impregnated with synthetic resins. Examples of preferred insulating resins include epoxy resins, cyanate ester resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, phenol resins, and the like. In addition, examples of the insulating resin constituting the resin sheet include insulating resins such as epoxy resin, polyimide resin, and polyester resin. In addition, based on the viewpoint of improving the insulation of the resin layer, etc., filler particles made of various inorganic particles such as silica and alumina may also be contained. The thickness of the resin layer is not particularly limited, but is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 400 μm or less, and still more preferably 3 μm or more and 200 μm or less. The resin layer may be composed of multiple layers. A resin layer such as a prepreg sheet and/or a resin sheet can also be provided on a roughened copper foil or a copper foil with a carrier through an undercoating resin layer pre-coated on the roughened surface of the roughened copper foil.
印刷配線板 本發明之粗化處理銅箔或附載體銅箔較好使用於製作印刷配線板,特佳係用於利用半加成法(SAP)之印刷配線板之製作。亦即依據本發明之較佳態樣,提供具備上述粗化處理銅箔或上述附載體銅箔所得之印刷配線板。藉由使用本發明之粗化處理銅箔或附載體銅箔,於印刷配線板之製造中,可對積層體賦予確保充分之剪切強度且有效防止作業步驟中之電路剝落,並且賦予對無電解銅鍍敷之蝕刻性亦優異之表面輪廓。又,藉由使用上述粗化處理銅箔,於SAP法之乾膜顯像步驟中,可實現極微細乾膜解像性。因此,可提供經實施極微細電路形成之印刷配線板。本態樣之印刷配線板包含樹脂層與銅層積層而成之層構成。於SAP法之情況下,本發明之粗化處理銅箔由於在圖1之步驟(c)中已去除,故藉由SAP法製作之印刷配線板已不包含本發明之粗化處理銅箔,僅為殘存自粗化處理銅箔之粗化處理面轉印之表面輪廓。又,針對樹脂層關於覆銅積層板係如上述。總之,印刷配線板可採用習知之層構成。關於印刷配線板之具體例,舉例為於預浸片之單面或雙面接著本發明之粗化處理銅箔並硬化作成積層體之後,形成電路之單面或雙面印刷配線板或使該等多層化之多層印刷配線板等。又,作為其他具體例亦舉例有於樹脂膜上形成本發明之粗化處理銅箔或附載體銅箔並形成電路之可撓性印刷配線板、COF、TAB帶等。作為進而其他具體例舉例為形成於本發明之粗化處理銅箔或附載體銅箔上塗佈上述樹脂層後之附樹脂銅箔(RCC),將該樹脂層作為絕緣接著材層積層於上述印刷基板後,將粗化處理銅箔作為配線層之全部或一部分而藉改良・半加成(MSAP)法、減去法等之方法形成電路之增層配線板、或去除粗化處理銅箔並藉半加成法(SAP)形成電路之增層配線板、重複交替對半導體積體電路上積層附樹脂銅箔與電路形成之晶圓上直接增層(Direct Buildup On Wafer)等。作為更發展之具體例,亦舉例為將上述附樹脂銅箔積層於基材上形成電路之天線元件、經由接著劑層積層於玻璃或樹脂膜並形成圖型之面板・顯示器用電子材料或窗玻璃用電子材料、於本發明之粗化處理銅箔上塗佈導電性接著劑之電磁波遮蔽膜等。尤其,本發明之粗化處理銅箔或附載體銅箔適於SAP法。例如藉由SAP法形成電路時,可採用如圖1及2所示之構成。 [實施例]Printed wiring board The roughened copper foil or copper foil with a carrier of the present invention is preferably used in the production of printed wiring boards, and is particularly preferably used in the production of printed wiring boards using the semi-additive method (SAP). That is, according to a preferred aspect of the present invention, a printed wiring board provided with the above-mentioned roughened copper foil or the above-mentioned copper foil with a carrier is provided. By using the roughened copper foil or copper foil with a carrier of the present invention, in the manufacture of printed wiring boards, it is possible to impart sufficient shear strength to the laminate and effectively prevent the circuit from peeling off in the working steps, and to provide protection against The surface profile of electrolytic copper plating is also excellent in etching properties. In addition, by using the above-mentioned roughening treatment copper foil, in the dry film development step of the SAP method, extremely fine dry film resolution can be achieved. Therefore, it is possible to provide a printed wiring board formed by implementing extremely fine circuits. The printed wiring board of this aspect includes a layered structure in which a resin layer and a copper layer are laminated. In the case of the SAP method, the roughened copper foil of the present invention has been removed in step (c) of FIG. 1, so the printed wiring board produced by the SAP method does not include the roughened copper foil of the present invention. It is only the surface contour transferred from the roughened surface of the roughened copper foil. In addition, the resin layer is as described above for the copper-clad laminate system. In short, the printed wiring board can be constructed with conventional layers. For specific examples of printed wiring boards, for example, the roughened copper foil of the present invention is adhered to one or both sides of a prepreg and hardened to form a laminate, and then a single-sided or double-sided printed wiring board of a circuit is formed or the Multi-layered printed wiring boards, etc. In addition, as other specific examples, there are flexible printed wiring boards, COF, TAB tapes, etc. in which the roughened copper foil or copper foil with a carrier of the present invention is formed on a resin film and a circuit is formed. As yet another specific example, a copper foil with resin formed on the roughened copper foil of the present invention or copper foil with a carrier coated with the above resin layer (RCC), and the resin layer is laminated as an insulating adhesive material on the above After the substrate is printed, the roughened copper foil is used as all or a part of the wiring layer to form a build-up wiring board for the circuit by a method such as the improved semi-additive (MSAP) method, subtractive method, etc., or the roughened copper foil is removed The build-up wiring board of the circuit is formed by the semi-additive method (SAP), and the direct buildup on wafer (Direct Buildup On Wafer) of the semiconductor integrated circuit is repeatedly and alternately laminated with resin copper foil and the circuit formed. As a more developed specific example, there are also examples of the antenna element in which the resin-attached copper foil is laminated on the substrate to form a circuit, and the patterned panel/display electronic material or window is laminated on a glass or resin film via an adhesive. Electronic material for glass, electromagnetic wave shielding film coated with conductive adhesive on the roughened copper foil of the present invention, etc. In particular, the roughened copper foil or copper foil with a carrier of the present invention is suitable for the SAP method. For example, when the circuit is formed by the SAP method, the configuration shown in Figures 1 and 2 can be used. [Example]
本發明藉由以下之例進一步具體說明。The present invention is further specifically illustrated by the following examples.
例1~3 附載體銅箔之製作及評價如以下。Examples 1~3 The production and evaluation of copper foil with carrier are as follows.
(1)載體之製作 準備表面以#2000之研磨布研磨之鈦製電極作為陰極。又準備DSA(尺寸安定性陽極)作為陽極。使用該等電極,浸漬於銅濃度80g/L、硫酸濃度260g/L之硫酸銅溶液中,於溶液溫度45℃、電流密度55A/dm2 電解,獲得厚18μm之電解銅箔作為載體。(1) Preparation of the carrier. The surface is prepared with a titanium electrode polished with #2000 abrasive cloth as the cathode. Also prepare DSA (Dimensional Stability Anode) as the anode. Using these electrodes, they were immersed in a copper sulfate solution with a copper concentration of 80 g/L and a sulfuric acid concentration of 260 g/L, and electrolyzed at a solution temperature of 45° C. and a current density of 55 A/dm 2 to obtain an electrolytic copper foil with a thickness of 18 μm as a carrier.
(2)剝離層之形成 經酸洗處理之載體的電極面側於CBTA(羧基苯并三唑)濃度1g/L、硫酸濃度150g/L及銅濃度10g/L之CBTA水溶液中於液溫30℃浸漬30秒,將CBTA成分吸附於載體之電極面。如此,於載體之電極面表面形成CBTA層作為有機剝離層。(2) Formation of peeling layer The electrode surface side of the acid-washed carrier is immersed in a CBTA aqueous solution with a CBTA (carboxybenzotriazole) concentration of 1g/L, a sulfuric acid concentration of 150g/L, and a copper concentration of 10g/L for 30 seconds at a liquid temperature of 30°C, and the CBTA The components are adsorbed on the electrode surface of the carrier. In this way, a CBTA layer is formed on the surface of the electrode surface of the carrier as an organic release layer.
(3)輔助金屬層之形成 形成有機剝離層之載體浸漬於使用硫酸鎳製作之鎳濃度20g/L之溶液中,於液溫45℃、pH3、電流密度5A/dm2 之條件,於有機剝離層上附著相當於厚度0.001μm之附著量的鎳。如此,於有機剝離層上形成鎳層作為輔助金屬層。Carrier organic release layers (3) forming an auxiliary metal layer is formed is immersed in a nickel concentration of nickel produced sulphate 20g / L of solution at a liquid temperature of 45 ℃, pH3, a current density of 5A / dm condition 2, the organic release The layer is deposited with an amount of nickel equivalent to a thickness of 0.001 μm. In this way, a nickel layer is formed as an auxiliary metal layer on the organic peeling layer.
(4)極薄銅箔之形成 將形成輔助金屬層之載體浸漬於銅濃度60g/L及硫酸濃度200g/L的硫酸銅溶液中,以溶液溫度50℃、電流密度5A/dm2 以上30A/dm2 以下電解,於輔助金屬層上形成厚度1.2μm之極薄銅箔。(4) forming the ultra-thin copper foil forming the auxiliary support impregnated metal layer 60g / L and the copper concentration in the sulfuric acid concentration of 200g / L of copper sulfate solution, a solution temperature of 50 ℃, a current density of 5A / dm 2 or more 30A / Electrolysis below dm 2 to form an ultra-thin copper foil with a thickness of 1.2 μm on the auxiliary metal layer.
(5)粗化處理 對上述極薄銅箔之析出面進行粗化處理。該粗化處理藉由以下3階段鍍敷進行。各階段之鍍敷步驟係使用具有表1所示之銅濃度、硫酸濃度、氯濃度及9-苯基吖啶(9PA)濃度之硫酸銅溶液,於表1所示之液溫,以表2所示之電流密度進行電鍍。第1階段及第2階段之鍍敷中之通電時間設為每次4.4秒,第3階段之鍍敷中之通電時間設為0.6秒。又,對於極薄銅箔之鍍敷液之線流速均為0.25m/s以上0.35m/s以下。如此製作例1~3之3種粗化處理銅箔。(5) Coarse treatment The precipitation surface of the above-mentioned ultra-thin copper foil is roughened. This roughening treatment is performed by the following three-stage plating. The plating steps of each stage use copper sulfate solution with copper concentration, sulfuric acid concentration, chlorine concentration and 9-phenyl acridine (9PA) concentration shown in Table 1. The liquid temperature shown in Table 1 is shown in Table 2. Electroplating is performed at the current density shown. The energizing time in the first and second stages of plating is set to 4.4 seconds each time, and the energizing time in the third stage of plating is set to 0.6 seconds. In addition, the linear flow velocity of the plating solution for ultra-thin copper foil is 0.25 m/s or more and 0.35 m/s or less. In this way, three types of roughened copper foils of Examples 1 to 3 were produced.
(6)防鏽處理 對所得附載體銅箔之粗化處理層之表面進行由鋅-鎳合金鍍敷處理及鉻酸鹽處理而成之防鏽處理。首先使用鋅濃度0.2g/L、鎳濃度2g/L及焦磷酸鉀濃度300g/L之電解液,於液溫40℃、電流密度0.5A/dm2 之條件,於粗化處理層及載體表面進行鋅-鎳合金鍍敷處理。其次,使用鉻酸1g/L水溶液,於pH11、液溫25℃、電流密度1A/dm2 之條件於經鋅-鎳合金鍍敷處理之表面進行鉻酸鹽處理。(6) Anti-rust treatment The surface of the roughened layer of the obtained copper foil with a carrier is subjected to anti-rust treatment by zinc-nickel alloy plating treatment and chromate treatment. First use an electrolyte with a zinc concentration of 0.2g/L, a nickel concentration of 2g/L, and a potassium pyrophosphate concentration of 300g/L at a temperature of 40°C and a current density of 0.5A/dm 2 on the roughened layer and the surface of the carrier Perform zinc-nickel alloy plating treatment. Next, use a 1g/L aqueous solution of chromic acid to perform chromate treatment on the surface treated with zinc-nickel alloy plating under the conditions of pH 11, liquid temperature 25°C, and current density 1A/dm 2.
(7)矽烷偶合劑處理 藉由於附載體銅箔之銅箔側表面吸附含3-胺基丙基三甲氧基矽烷3g/L之水溶液,藉由電熱器使水分蒸散,進行矽烷偶合劑處理。此時,於載體側不進行矽烷偶合劑處理。(7) Silane coupling agent treatment The copper foil side surface of the copper foil with a carrier absorbs an aqueous solution containing 3 g/L of 3-aminopropyltrimethoxysilane, and the water is evaporated by an electric heater to perform silane coupling agent treatment. At this time, no silane coupling agent treatment was performed on the carrier side.
(8)粗化處理銅箔表面之評價 針對所得粗化處理銅箔,如以下評價表面輪廓之諸特性。(8) Evaluation of the surface of roughened copper foil With respect to the obtained roughened copper foil, various characteristics of the surface profile were evaluated as follows.
(8-1)粗化粒子之觀察 取得所得粗化處理銅箔之剖面圖像,如以下求出比L2 /S之平均值及粗化處理銅箔每10μm之粗化粒子個數。(8-1) Observation of roughened particles Obtain the cross-sectional image of the roughened copper foil obtained, and calculate the average value of the ratio L 2 /S and the number of roughened particles per 10 μm of the roughened copper foil as follows.
(8-1-1)剖面圖像之取得 使用FIB-SEM裝置(SII技術股份有限公司製,SMI3200SE),自粗化處理銅箔表面進行FIB(聚焦離子束)加工,製作與銅箔厚度方向平行之剖面,以對於粗化處理面為60°之方向對該剖面進行SEM觀察(倍率:36000倍),而取得剖面圖像。(8-1-1) Obtaining cross-sectional images Using FIB-SEM equipment (manufactured by SII Technology Co., Ltd., SMI3200SE), FIB (focused ion beam) processing is performed from the surface of the roughened copper foil, and a cross section parallel to the thickness of the copper foil is made, so that the roughened surface is 60 The cross-section is observed by SEM in the direction of ° (magnification: 36000 times), and a cross-sectional image is obtained.
(8-1-2) 比L2 /S之計算 將粗化處理銅箔之長10μm量之剖面圖像取入圖像解析軟體Image-Pro Plus 5.1J (Media Cybernetics, Inc.製),藉由該解析軟體之功能「自由曲線AO」逐一擷取剖面中之粗化粒子。擷取出剖面圖像中所含之所有粗化粒子後,以粗化粒子之內側成為白色之方式調整對比度。其次,使用解析軟體之功能「計數/尺寸」,自動辨識變成明亮色之粗化粒子後,藉由測定功能測定各個粗化粒子之周圍長L及面積S,算出比L2 /S。針對各例於不同3個視野進行以上操作,採用所觀察到之全部粗化粒子中比L2 /S之平均值作為該樣品的比L2 /S之平均值。(8-1-2) Calculate the ratio of L 2 /S to take the cross-sectional image of the roughened copper foil 10μm in length into the image analysis software Image-Pro Plus 5.1J (manufactured by Media Cybernetics, Inc.), borrow The function "free curve AO" of the analysis software captures the coarsened particles in the section one by one. After extracting all the roughened particles contained in the cross-sectional image, adjust the contrast so that the inside of the roughened particles becomes white. Next, use the analysis software's function "count/size" to automatically identify the roughened particles that have become bright colors, and use the measurement function to measure the surrounding length L and area S of each roughened particle to calculate the ratio L 2 /S. Roughening particles for all embodiments of each of the above operations at different three fields of view, using the ratio of observed / mean S L 2 as an average of the sample than L 2 / S ratio.
(8-1-3)粗化粒子之個數 測定剖面圖像中視野中之粗化粒子個數與視野之橫寬,換算為每長10μm之個數。針對各例於不同3個視野進行測定,採用該平均值作為該樣品之每長10μm之粗化粒子個數。(8-1-3) Number of coarsening particles Measure the number of roughened particles in the field of view in the cross-sectional image and the horizontal width of the field of view, and convert them to the number per length of 10μm. For each case, the measurement was performed in three different fields of view, and the average value was used as the number of coarsened particles per 10 μm in length of the sample.
(8-2)十點平均粗糙度Rz之測定 使用具備150倍物鏡之雷射顯微鏡(KYENCE股份有限公司製,VK-9510)觀察粗化處理面,取得6550.11μm2 之視野圖像。自所得視野圖像以互不重複之範圍任意選取10處10μm×10μm之區域,依據JIS B 0601-1994分別測定十點平均值Rz。採用10處之Rz平均值作為該樣品之Rz。(8-2) Measurement of ten-point average roughness Rz A laser microscope (manufactured by KYENCE Co., Ltd., VK-9510) equipped with a 150-fold objective lens was used to observe the roughened surface to obtain a field of view image of 6550.11 μm 2. From the obtained visual field image, 10 areas of 10 μm×10 μm are randomly selected in a range that does not overlap each other, and the ten-point average value Rz is measured in accordance with JIS B 0601-1994. The average value of Rz at 10 locations is used as the Rz of the sample.
(9)覆銅積層板之製作 使用附載體銅箔製作覆銅積層板。首先,於內層基板表面經由預浸片(三菱瓦斯化學股份有限公司製,GHPL-830NSF,厚0.1mm)積層附載體銅箔之粗化處理銅箔,以壓力4.0MPa、溫度220℃熱壓著90分鐘後,剝離載體,製作覆銅積層板。(9) Production of copper clad laminate Use copper foil with carrier to make copper clad laminate. First, a prepreg (GHPL-830NSF made by Mitsubishi Gas Chemical Co., Ltd., GHPL-830NSF, thickness 0.1mm) is laminated on the surface of the inner substrate to roughen the copper foil with a carrier, and it is hot pressed at a pressure of 4.0 MPa and a temperature of 220°C. After 90 minutes, the carrier was peeled off to produce a copper-clad laminate.
(10) SAP評價用積層體之製作 其次,以硫酸-過氧化氫系蝕刻液去除表面所有銅箔後,進行脫脂、Pd系觸媒賦予及活性化處理。如此於經活性化表面進行無電解銅鍍敷(厚:1μm),於SAP法中獲得欲貼合乾膜之前之積層體(以下稱為SAP評價用積層體)。該等步驟係依據SAP法之習知條件進行。(10) Production of laminates for SAP evaluation Next, after removing all the copper foil on the surface with a sulfuric acid-hydrogen peroxide-based etching solution, degreasing, Pd-based catalyst application, and activation treatment are performed. In this way, electroless copper plating (thickness: 1 μm) was performed on the activated surface to obtain a laminate (hereinafter referred to as a laminate for SAP evaluation) before the dry film was to be bonded by the SAP method. These steps are carried out in accordance with the known conditions of the SAP law.
(11) SAP評價用積層體之評價 針對上述所得之SAP評價用積層體,如以下進行各種特性之評價。(11) Evaluation of laminates for SAP evaluation With respect to the above-obtained SAP evaluation laminate, various characteristics were evaluated as follows.
<鍍敷電路密著性(剪切強度)>
對SAP評價用積層體貼合乾膜,進行曝光及顯像。於以經顯像之乾膜遮蔽之積層體以圖型鍍敷析出14μm之銅層後,剝離乾膜。以硫酸-過氧化氫系蝕刻液去除露出之無電解銅鍍敷,製作高15μm、寬10μm、長150μm之剪切強度測定用電路樣品。使用接合強度試驗機(Nordson DAGE公司製,4000Plus黏合測定機),測定自橫向將剪切強度測定用電路樣品壓倒時之剪切強度。亦即,如圖6所示,將形成電路136之積層體134載置於可動台132上,連同可動台132於圖中箭頭方向移動,將電路136碰觸於預先固定之檢測器138上,而對電路136之側面賦予橫方向之力而壓倒,以檢測器138測定此時之力(gf),並採取作為剪切強度。此時,測試種類係設為破壞試驗,以測試高度10μm、降下速度0.050mm/s、測試速度100.0μm/s、工具移動量0.05mm、破壞認識點10%之條件進行測定。<Plating circuit adhesion (shear strength)>
A dry film was attached to the SAP evaluation laminate, and exposed and developed. After the laminate body masked by the developed dry film is pattern-plated to deposit a 14μm copper layer, the dry film is peeled off. The exposed electroless copper plating was removed with a sulfuric acid-hydrogen peroxide-based etching solution to prepare a circuit sample for measuring shear strength with a height of 15 μm, a width of 10 μm, and a length of 150 μm. Using a bonding strength tester (manufactured by Nordson DAGE, 4000Plus Adhesion Tester), the shear strength when the circuit sample for shear strength measurement was overwhelmed from the lateral direction was measured. That is, as shown in FIG. 6, the
<蝕刻性> 對於SAP評價用基板,以硫酸-過氧化氫系蝕刻液,進行0.2μm逐次蝕刻,測量直至表面銅完全消失之量(深度)。該計測係藉由以光學顯微鏡(500倍)確認而進行。更詳言之,重複每0.2μm蝕刻以光學顯微鏡確認銅的有無之作業,使用藉由將(蝕刻次數)×0.2μm所得之值(μm)作為蝕刻性之指標。例如蝕刻性為1.2μm,意指藉由進行6次0.2μm之蝕刻,成為以光學顯微鏡未檢測出殘存銅(亦即0.2μm×6次=1.2μm)。亦即,該值越小意指以越少次數之蝕刻即可去除表面的銅。換言之,該值越小意指蝕刻性越良好。<etchability> The substrate for SAP evaluation was etched step by step with a sulfuric acid-hydrogen peroxide-based etching solution at 0.2 μm, and the amount (depth) until the copper on the surface was completely disappeared was measured. This measurement was performed by confirming with an optical microscope (500 times). More specifically, the operation of confirming the presence or absence of copper with an optical microscope every 0.2 μm etching is repeated, and the value (μm) obtained by (the number of times of etching)×0.2 μm is used as an index of the etching property. For example, the etching property of 1.2 μm means that by performing etching of 0.2 μm six times, the remaining copper is not detected by an optical microscope (that is, 0.2 μm×6 times=1.2 μm). That is, the smaller the value means that the copper on the surface can be removed with fewer etchings. In other words, the smaller the value, the better the etching properties.
<乾膜解像性(最小L/S)> 於SAP評價用積層體之表面貼合厚25μm之乾膜,使用形成有線/間隔(L/S)自2μm/2μm至15μm/15μm之圖型之遮罩,進行曝光及顯像。此時之曝光量設為125mJ。顯像後之樣品表面以光學顯微鏡(倍率:500倍)觀察,採用可毫無問題地進行顯像之L/S中之最小(亦即最微細)L/S作為乾膜解像性之指標。例如乾膜解像性評價之指標的最小L/S=10μm/10μm意指L/S自15μm/15μm至10μm/10μm可無問題地解像。例如可無問題地解像時,乾膜圖型間觀察到鮮明對比度,相對地,於無法良好進行解像時,於乾膜圖型間觀察到變黑部分,無法觀察到鮮明對比度。<Dry film resolution (minimum L/S)> Laminate a 25μm thick dry film on the surface of the SAP evaluation laminate, and use a mask that forms a line/space (L/S) pattern from 2μm/2μm to 15μm/15μm for exposure and development. The exposure at this time is set to 125mJ. The surface of the sample after imaging is observed with an optical microscope (magnification: 500 times), and the smallest (that is, the smallest) L/S of the L/S that can be developed without any problem is used as the index of dry film resolution . For example, the minimum L/S=10μm/10μm of the index of dry film resolution evaluation means that L/S from 15μm/15μm to 10μm/10μm can be resolved without problems. For example, when the image can be resolved without problems, a sharp contrast is observed between the dry film patterns. On the other hand, when the resolution cannot be performed well, a darkened portion is observed between the dry film patterns, and the sharp contrast cannot be observed.
結果 例1~3所得之評價結果彙總示於表3。result The evaluation results obtained in Examples 1 to 3 are summarized in Table 3.
10‧‧‧粗化處理銅箔
10a‧‧‧基底面
12‧‧‧粗化粒子
12a‧‧‧突起
12p‧‧‧輪廓線
12s‧‧‧線段
110‧‧‧粗化處理銅箔
111‧‧‧絕緣樹脂基板
111a‧‧‧基底基材
111b‧‧‧下層電路
112‧‧‧預浸片
113‧‧‧底塗層
114‧‧‧通孔
115‧‧‧無電解銅鍍敷
116‧‧‧乾膜
117‧‧‧電鍍銅
117a‧‧‧配線部分
118‧‧‧配線
122‧‧‧基板
124‧‧‧電路
126‧‧‧阻焊劑
132‧‧‧可動台
134‧‧‧積層體
136‧‧‧電路
138‧‧‧檢測器
c1‧‧‧接點
c2‧‧‧接點10‧‧‧
圖1係用以說明SAP法之步驟流程之圖,顯示前半步驟(步驟(a)~ (d))之圖。 圖2係用以說明SAP法之步驟流程之圖,顯示後半步驟(步驟(e)~ (h))之圖。 圖3A係顯示電路之長邊方向的側面經阻焊劑覆蓋時之示意剖面圖。 圖3B係顯示電路未經阻焊劑覆蓋時之示意剖面圖。 圖4係顯示本發明之粗化處理銅箔之粗化處理面之示意剖面圖。 圖5係用以說明圖4之粗化處理銅箔之粗化粒子周圍長L及面積S之示意剖面圖。 圖6係用以說明剪切強度之測定方法之示意圖。Figure 1 is a diagram used to illustrate the step flow of the SAP method, showing the first half of the steps (steps (a) ~ (d)). Figure 2 is a diagram used to illustrate the step flow of the SAP method, showing the second half of the steps (steps (e) ~ (h)). FIG. 3A is a schematic cross-sectional view showing the side surface of the circuit in the longitudinal direction when covered with solder resist. Figure 3B shows a schematic cross-sectional view of the circuit without being covered with solder resist. 4 is a schematic cross-sectional view showing the roughened surface of the roughened copper foil of the present invention. 5 is a schematic cross-sectional view for explaining the length L and the area S around the roughened particles of the roughened copper foil of FIG. 4. Fig. 6 is a schematic diagram for explaining the method of measuring the shear strength.
10‧‧‧粗化處理銅箔 10‧‧‧Roughened copper foil
10a‧‧‧基底面 10a‧‧‧Base surface
12‧‧‧粗化粒子 12‧‧‧Coarse particles
12a‧‧‧突起 12a‧‧‧Protrusion
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JP6591893B2 (en) | 2013-06-04 | 2019-10-16 | Jx金属株式会社 | Copper foil with carrier, copper clad laminate, printed wiring board, electronic device, resin layer, method for producing copper foil with carrier, and method for producing printed wiring board |
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KR102230999B1 (en) | 2016-02-10 | 2021-03-22 | 후루카와 덴키 고교 가부시키가이샤 | Surface-treated copper foil and copper clad laminate manufactured using the same |
JP2017193778A (en) * | 2016-04-15 | 2017-10-26 | Jx金属株式会社 | Copper foil, copper foil for high frequency circuit, copper foil with carrier, copper foil with carrier for high frequency circuit, laminate, method for manufacturing printed wiring board and method for producing electronic apparatus |
JP6430092B1 (en) * | 2017-05-19 | 2018-11-28 | 三井金属鉱業株式会社 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
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2019
- 2019-03-20 WO PCT/JP2019/011864 patent/WO2019188712A1/en active Application Filing
- 2019-03-20 JP JP2020510808A patent/JP7166335B2/en active Active
- 2019-03-20 CN CN201980020819.5A patent/CN111886367B/en active Active
- 2019-03-20 KR KR1020207023015A patent/KR102647658B1/en active IP Right Grant
- 2019-03-26 TW TW108110462A patent/TWI745668B/en active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201706457A (en) * | 2015-04-28 | 2017-02-16 | Mitsui Mining & Smelting Co | Roughened copper foil and printed wiring board |
Also Published As
Publication number | Publication date |
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KR102647658B1 (en) | 2024-03-15 |
TW201942370A (en) | 2019-11-01 |
JPWO2019188712A1 (en) | 2021-04-22 |
CN111886367A (en) | 2020-11-03 |
JP7166335B2 (en) | 2022-11-07 |
CN111886367B (en) | 2023-05-16 |
WO2019188712A1 (en) | 2019-10-03 |
KR20200135303A (en) | 2020-12-02 |
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