TWI402009B - Surface treatment of copper foil and circuit substrate - Google Patents
Surface treatment of copper foil and circuit substrate Download PDFInfo
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- TWI402009B TWI402009B TW097147376A TW97147376A TWI402009B TW I402009 B TWI402009 B TW I402009B TW 097147376 A TW097147376 A TW 097147376A TW 97147376 A TW97147376 A TW 97147376A TW I402009 B TWI402009 B TW I402009B
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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
- B32B15/02—Layer formed of wires, e.g. mesh
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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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- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
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- Parts Printed On Printed Circuit Boards (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
Description
本發明係有關於表面處理銅箔,特別是關於適用於以導電性組成物(導電糊(paste))導通設置於正、背面的電路(線路)的層積電路基板(多層印刷電路板)。The present invention relates to a surface-treated copper foil, and more particularly to a laminated circuit board (multilayer printed wiring board) which is suitable for conducting a circuit (line) provided on a front side and a back side with a conductive composition (conductive paste).
另外,本發明是有關於使用上述表面處理銅箔形成電路的電路基板。Further, the present invention relates to a circuit board in which a circuit is formed using the above surface-treated copper foil.
習知的層積電路基板的製造方法,具有貫穿孔鍍膜法,其在多層電路基板用基材多層層積之後,在絕緣層形成導通孔,而藉由在上述導通孔的內周面進行鍍膜處理而成的鍍層,來作層間導通。而藉由上述貫穿孔鍍膜法所形成的層積電路基板的優點是可以以低且穩定的接觸電阻來連接各層電路,但是製程複雜、步驟多、成本高則是層積電路基板的用途受限的重要因素。A method of manufacturing a conventional laminated circuit board includes a through-hole plating method in which a via hole is formed in an insulating layer after laminating a plurality of substrates for a multilayer circuit substrate, and coating is performed on an inner peripheral surface of the via hole. The treated coating is used to conduct interlayer conduction. The laminated circuit substrate formed by the through-hole plating method has the advantage that the layers can be connected with a low and stable contact resistance, but the process is complicated, the steps are large, and the cost is high, and the use of the laminated circuit substrate is limited. An important factor.
另外,藉由貫穿孔鍍膜法所形成的層積電路基板中,亦具有貫穿孔的正上方無法組裝零件而使線路佈局的自由度較低的缺點。Further, in the laminated circuit board formed by the through hole plating method, there is a disadvantage that the components cannot be assembled directly above the through hole, and the degree of freedom in line layout is low.
為了解決上述缺點,在藉由貫穿孔鍍膜法所形成的層積電路基板中,甚至採用使貫穿孔相對於基板表面傾斜而形成的手法,以避開組裝零件的配置位置。In order to solve the above disadvantages, in the laminated circuit board formed by the through hole plating method, even a method of forming the through hole with respect to the substrate surface is used to avoid the arrangement position of the assembled component.
另外,近年來取代貫穿孔鍍膜法的層間連接法中,是藉由在貫穿孔充填導電糊的間隙導孔技術(interstitial via hole;IVH)所形成的層積電路基板基板已達實用化的狀態。此一使用導電糊的層積電路基板與藉由貫穿孔鍍膜法所形成的層積電路基板相比,可達成製造步驟的簡潔化、低成本化。Further, in recent years, in the interlayer connection method which replaces the through-hole plating method, the laminated circuit substrate formed by the interstitial via hole (IVH) in which the conductive paste is filled in the through-hole has been put into practical use. . The laminated circuit board using the conductive paste can achieve a simplification and cost reduction of the manufacturing steps as compared with the laminated circuit board formed by the through hole plating method.
使用IVH法來製造層積電路的代表性的方法,是為ALIVH(請參考非專利文獻1)。A representative method for manufacturing a laminated circuit using the IVH method is ALIVH (please refer to Non-Patent Document 1).
在ALIVH中,是使用醯胺環氧樹脂預浸布(aramid epoxy prepreg)來作為絕緣基板,而以雷射明孔加工來形成貫穿孔。接下來在已以導電糊充填貫穿孔的絕緣基板的雙面層積銅箔,再以熱壓法黏著銅箔與絕緣基板。之後,圖形化(蝕刻)銅箔而形成既定的電路。重複上述步驟而形成層積電路基板。In the ALIVH, an aramid epoxy prepreg is used as an insulating substrate, and a through hole is formed by laser drilling. Next, a copper foil is laminated on both sides of the insulating substrate on which the through holes are filled with a conductive paste, and the copper foil and the insulating substrate are adhered by hot pressing. Thereafter, the copper foil is patterned (etched) to form a predetermined circuit. The above steps are repeated to form a laminated circuit substrate.
用於ALIVH等的IVH法的銅箔,為了與醯胺環氧樹脂預浸布的黏著性及與導電糊的連接性,進展為使用表面粗糙度為4μm(含)以上的雙面粗化處理銅箔或單面粗化處理銅箔。然而近年來更進一步發展的家電製品‧可攜式電子機器等持續進行著薄型化‧小型化,而有微細圖形化的需求,但是目前使用的表面處理銅箔並無法滿足此一需求。The copper foil used for the IVH method such as ALIVH has been developed to have a double-sided roughening treatment using a surface roughness of 4 μm or more in order to adhere to the adhesion of the guanamine epoxy resin prepreg and the connection with the conductive paste. Copper foil or single-sided roughening of copper foil. However, in recent years, home electric appliances and portable electronic devices that have been further developed have been continuously thinned and miniaturized, and there is a demand for fine patterning, but the surface-treated copper foil currently used cannot satisfy this demand.
【非專利文獻1】請參考CMC出版股份有限公司(CMC Publishing Co.,Ltd.)於2005年1月31日發行的「電子組裝用高機能性基板材料(High Performance Materials for Electronics Package Substrate)」第18頁[Non-Patent Document 1] Please refer to "High Performance Materials for Electronics Package Substrate" issued by CMC Publishing Co., Ltd. on January 31, 2005. Page 18
本發明是提供在家電製品‧可攜式電子機器等的薄型化‧小型化的進行中,可滿足微細圖形化需求的表面處理銅箔;特別是提供適用於IVH法的電路結構的低表面粗糙度、且與絕緣基板的黏著性良好、與導電糊金屬粒子的接觸電阻低的表面處理銅箔。The present invention provides a surface-treated copper foil which can meet the requirements for fine patterning in the progress of miniaturization and miniaturization of household electrical appliances, portable electronic equipment, etc.; in particular, low surface roughness of a circuit structure suitable for the IVH method is provided. A surface-treated copper foil having a good adhesion to an insulating substrate and a low contact resistance with conductive paste metal particles.
另外,本發明是提供以上述表面處理銅箔形成電路、藉此可構成微細圖形的電路的電路基板。Moreover, the present invention provides a circuit board in which a circuit is formed by the above-described surface-treated copper foil, whereby a circuit capable of forming a fine pattern is provided.
本發明之表面處理銅箔,是在一層積基板構成銅箔線路的表面處理銅箔,其中在上述層積基板中,是在一絕緣基板的正面與背面設置有上述銅箔線路,而藉由設置於上述絕緣基板的導通孔中充填的金屬粒子連接上述銅箔線路,而上述表面處理銅箔的特徵在於包含:設置於一銅箔基箔的至少一表面的一表面處理層,而使上述銅箔基箔的表面中與上述金屬粒子接合的接合部之與上述金屬粒子的接合面的面積,為上述銅箔基箔的表面積的30%以上。The surface-treated copper foil of the present invention is a surface-treated copper foil in which a copper foil line is formed on a laminated substrate, wherein the laminated substrate is provided with the copper foil line on the front and back surfaces of an insulating substrate. The metal particles filled in the via holes of the insulating substrate are connected to the copper foil line, and the surface treated copper foil is characterized by comprising: a surface treatment layer disposed on at least one surface of a copper foil base foil, The area of the joint surface of the joint portion of the copper foil-based foil bonded to the metal particles and the metal particles is 30% or more of the surface area of the copper foil-based foil.
較好為上述表面處理層是在上述銅箔基箔的表面附著粗化粒子的層,上述表面處理層的表面的Rz為1.0~3.0μm、明度(brightness)值為25(含)以下。Preferably, the surface treatment layer is a layer in which roughened particles are adhered to the surface of the copper foil-based foil, and the surface of the surface treatment layer has an Rz of 1.0 to 3.0 μm and a brightness value of 25 or less.
在此處,Rz是定義於JIS B 0601-1194「表面粗糙度的定義與表示」中,其為「十點平均粗糙度」。Here, Rz is defined in "Definition and Expression of Surface Roughness" in JIS B 0601-1194, which is "ten-point average roughness".
另外,根據JIS Z 8105(1982),在同一條件下照明的白色面為基準之物體表面的相對性的明暗相關顏色的屬性,明度值就是將此一相對性的明暗相關顏色的屬性尺度化的值。In addition, according to JIS Z 8105 (1982), the white surface illuminated by the same condition is the property of the relative brightness-related color of the surface of the reference object, and the brightness value is the scale of the property of the relative brightness-related color. value.
較好為上述表面處理層係在該表面處理層的100μm×100μm的面積中,分佈有200~25000個高度為1~5μm之由上述粗化粒子所構成的突起物。It is preferable that the surface treatment layer has 200 to 25,000 protrusions composed of the roughened particles having a height of 1 to 5 μm distributed in an area of 100 μm × 100 μm of the surface treatment layer.
較好為上述表面處理層係在上述表面處理層的觀察截面25μm的範圍中,大致平均分佈有6~35個高度為1~5μm之由上述粗化粒子所構成的突起物。In the range of 25 μm in the observation cross section of the surface treatment layer, the surface treatment layer preferably has 6 to 35 protrusions composed of the roughened particles having a height of 1 to 5 μm.
較好為在上述表面處理層中的上述突起物之間的最大寬度為0.01μm以上、25μm除以存在於觀察截面25μm的範圍內的上述突起物的個數所得長度的2倍以下。It is preferable that the maximum width between the protrusions in the surface treatment layer is 0.01 μm or more and 25 μm divided by twice or less the length of the number of the protrusions present in the range of 25 μm in the observation cross section.
本發明的電路基板的特徵在於係使用表面處理銅箔所製成。The circuit substrate of the present invention is characterized in that it is made of a surface-treated copper foil.
本發明可提供可因應家電製品‧可攜式電子機器等的薄型化‧小型化、滿足微細圖形化的需求的表面處理銅箔,特別適用於IVH法的電路結構的低表面粗糙度、且與絕緣基板的黏著性良好、與導電糊金屬粒子的接觸電阻低的表面處理銅箔。The present invention can provide a surface-treated copper foil that can be thinned, sized, and miniaturized in order to meet the requirements of fine patterning, and is particularly suitable for the low surface roughness of the circuit structure of the IVH method, and A surface-treated copper foil having good adhesion to an insulating substrate and low contact resistance with conductive paste metal particles.
另外,本發明可提供以上述表面處理銅箔形成電路、藉此可構成微細圖形的電路的電路基板。Further, the present invention can provide a circuit board in which a circuit is formed by the surface-treated copper foil described above, whereby a circuit capable of forming a fine pattern can be provided.
本實施例之銅箔為表面處理銅箔,特別是適用於以IVH法構成電路的表面處理銅箔。The copper foil of this embodiment is a surface-treated copper foil, and is particularly suitable for a surface-treated copper foil which is formed by an IVH method.
關於使用IVH法來製成層積電路的代表性的方法,是以ALIVH來進行說明。第1(a)~1(i)圖為顯示以ALIVH來製造層積電路基板的方法的步驟的剖面圖。A representative method for forming a laminated circuit using the IVH method will be described with ALIVH. 1(a) to 1(i) are cross-sectional views showing the steps of a method of manufacturing a laminated circuit substrate by ALIVH.
首先,如第1(a)圖所示,使用醯胺環氧樹脂預浸布作為絕緣基板1;再如第1(b)圖所示,以雷射明孔加工形成貫穿孔2。First, as shown in Fig. 1(a), a ruthenium epoxy resin prepreg is used as the insulating substrate 1; as shown in Fig. 1(b), the through hole 2 is formed by laser drilling.
接下來如第1(c)圖所示,在貫穿孔2充填導電糊3。Next, as shown in FIG. 1(c), the conductive paste 3 is filled in the through hole 2.
接下來如第1(c)圖所示,在已於貫穿孔2充填導電糊3的絕緣基板1的雙面層積銅箔4、5;再如第1(d)圖所示,以熱壓法黏著銅箔4與絕緣基板1。藉由此熱壓步驟的熱將導電糊3熔化而經由貫穿孔2連接雙面的銅箔4、5而成為導通狀態。Next, as shown in FIG. 1(c), the copper foils 4 and 5 are laminated on both sides of the insulating substrate 1 in which the conductive paste 3 is filled in the through holes 2; and as shown in the first (d), heat is applied. The copper foil 4 and the insulating substrate 1 are adhered by pressure. The conductive paste 3 is melted by the heat of the hot pressing step, and the copper foils 4 and 5 on both sides are connected via the through holes 2 to be in an on state.
接下來如第1(e)圖所示,圖形化(蝕刻)銅箔而形成既定的電路。如上所述而形成單層的基板10。Next, as shown in Fig. 1(e), the copper foil is patterned (etched) to form a predetermined circuit. The single layer substrate 10 is formed as described above.
為了使層積基板多層化而重複進行上述步驟。例如如第1(f)圖所示,形成與第1(a)~1(c)圖所示步驟同樣的基板11、12,而將其分別層積於基板10的上表面與下表面,並在此層積體的雙面層積銅箔13、14,接著如第1(g)圖所示,以熱壓法黏著基板10、11、12及銅箔13、14。藉由此熱壓步驟的熱將導電糊熔化而經由貫穿孔使雙面的銅箔4、5連接成為導通狀態。之後,如第1(h)圖所示,圖形化(蝕刻)銅箔而形成既定的電路。如上所述而形成三層層積的層積電路基板。The above steps are repeated in order to multilayer the laminated substrate. For example, as shown in FIG. 1(f), the substrates 11 and 12 which are the same as the steps shown in the first (a) to (c) are formed, and are laminated on the upper surface and the lower surface of the substrate 10, respectively. Further, the copper foils 13, 14 are laminated on both sides of the laminate, and then the substrates 10, 11, 12 and the copper foils 13, 14 are adhered by hot pressing as shown in Fig. 1(g). The conductive paste is melted by the heat of the hot pressing step, and the double-sided copper foils 4 and 5 are connected to each other via the through holes. Thereafter, as shown in Fig. 1(h), the copper foil is patterned (etched) to form a predetermined circuit. As described above, a three-layer laminated laminated circuit substrate is formed.
另外,視需求重複上述的製程。也就是在上述層積電路基板的上表面與下表面分別沈積上述基板15、16,並在此層積體的雙面層積銅箔17、18,再以熱壓法黏著各基板與銅箔,並圖形化(蝕刻)銅箔17、18而形成既定的電路。藉此如第1(i)圖所示,而形成五層層積的層積電路基板。In addition, the above process is repeated as needed. That is, the substrates 15 and 16 are respectively deposited on the upper surface and the lower surface of the laminated circuit substrate, and the copper foils 17 and 18 are laminated on both sides of the laminate, and the substrates and the copper foil are adhered by hot pressing. And the copper foils 17, 18 are patterned (etched) to form a predetermined circuit. Thereby, as shown in Fig. 1(i), a five-layer laminated circuit board is formed.
在本實施例中,表面處理前的銅箔(後文稱為「銅箔基箔」),是以電解或軋延所製造的銅箔或銅合金箔(在不需區別二者的情況則通稱為銅箔)。銅箔的厚度較好為1μm~200μm。關於銅箔的厚度,厚度在1μm以下則非常難以在銅箔的表面上進行粗化處理,故1μm以下的厚度不佳。所使用的銅箔的厚度可依據其用途作適當的選擇。In the present embodiment, the copper foil before the surface treatment (hereinafter referred to as "copper foil base foil") is a copper foil or a copper alloy foil produced by electrolysis or rolling (if there is no need to distinguish between the two) Known as copper foil). The thickness of the copper foil is preferably from 1 μm to 200 μm. When the thickness of the copper foil is 1 μm or less, it is very difficult to carry out the roughening treatment on the surface of the copper foil, so the thickness of 1 μm or less is not preferable. The thickness of the copper foil used can be appropriately selected depending on the use thereof.
銅箔(銅箔基箔)的表面粗糙度較好為Rz 0.01μm~2μm。關於銅箔基箔的表面粗糙度,Rz 0.01μm以下的銅箔基箔在現實上是難以製造出來,即使能夠製造出來,所耗費的製造成本也不符合現實的要求;另外雖然仍可以使用Rz 2.0μm以上的銅箔基箔,但是一旦考慮到高頻特性及微細圖形化,則銅箔基箔的表面粗糙度Rz較好為2μm(含)以下。The surface roughness of the copper foil (copper foil base foil) is preferably from Rz 0.01 μm to 2 μm. Regarding the surface roughness of the copper foil-based foil, a copper foil-based foil having a Rz of 0.01 μm or less is practically difficult to manufacture, and even if it can be manufactured, the manufacturing cost is not in accordance with actual requirements; in addition, Rz can still be used. The copper foil-based foil of 2.0 μm or more is preferably 2 μm or less in consideration of high-frequency characteristics and fine patterning of the copper foil-based foil.
在此處,所謂的表面粗糙度Rz是規定於JIS B 0601-1994「表面粗糙度的定義與表示」,為十點平均粗糙度。Here, the surface roughness Rz is defined as "Definition and Expression of Surface Roughness" in JIS B 0601-1994, and is a ten-point average roughness.
在本實施例中,對上述銅箔基箔的至少單面施以表面處理。In the present embodiment, at least one side of the above-mentioned copper foil-based foil is subjected to a surface treatment.
銅箔基箔的表面粗化處理,是使粗化粒子附著於銅箔基箔的表面而成為粗化面。粗化面的表面粗糙度Rz較好為1.0~3.0μm。Rz不滿1.0μm的情況,由於剝離強度低而無法滿足以達成提升剝離強度為目的的表面處理銅箔;另外若Rz大於3.0μm,則其高頻特性不佳而無法達成微細圖形化。The surface roughening treatment of the copper foil-based foil is such that the roughened particles adhere to the surface of the copper foil-based foil to form a roughened surface. The surface roughness Rz of the roughened surface is preferably from 1.0 to 3.0 μm. When Rz is less than 1.0 μm, the surface-treated copper foil for the purpose of achieving improved peeling strength cannot be satisfied because the peel strength is low. Further, when Rz is more than 3.0 μm, the high-frequency characteristics are not good and fine patterning cannot be achieved.
在本實施例中,關於銅箔基箔的表面處理方法,較好為使銅箔基箔或銅合金附著於銅箔基箔的表面上,銅或銅合金的附著量較好為2mg/dm2 ~400mg/dm2 。附著量不滿2mg/dm2 的情況,由於剝離強度低而無法滿足以達成提升剝離強度為目的的表面處理銅箔。In the present embodiment, as for the surface treatment method of the copper foil-based foil, it is preferred that the copper foil-based foil or the copper alloy is adhered to the surface of the copper foil-based foil, and the adhesion amount of the copper or copper alloy is preferably 2 mg/dm. 2 ~ 400mg / dm 2 . When the adhesion amount is less than 2 mg/dm 2 , the surface-treated copper foil for the purpose of achieving the improved peel strength cannot be satisfied because the peel strength is low.
若附著量大於400mg/dm2 ,則其高頻特性下降而使資訊傳達量下降,其原因在於若是銅或銅合金的附著量多,則粗化粒子就較大,而使表面粗糙度變大。在高頻下電流在導體流動時,頻率愈高則電流會趨向於在表面部分流動(集膚效應)。因此若導體表面的粗糙度增加,則電流流動的表面的長度變長而增加電阻,因而電流的損失增加而使資訊傳達量不足。因此,銅或銅合金的附著量較好為400mg/dm2 (含)以下,但是用途可忽略高頻特性的情況則亦可忽略附著量的上限。When the adhesion amount is more than 400 mg/dm 2 , the high-frequency characteristics are lowered and the amount of information transmission is lowered. The reason is that if the amount of adhesion of copper or copper alloy is large, the roughened particles are large, and the surface roughness is increased. . When a current flows through a conductor at a high frequency, the higher the frequency, the more the current tends to flow on the surface portion (skin effect). Therefore, if the roughness of the surface of the conductor increases, the length of the surface on which the current flows becomes longer and the resistance is increased, so that the loss of current increases and the amount of information transmission is insufficient. Therefore, the adhesion amount of copper or a copper alloy is preferably 400 mg/dm 2 or less, but the upper limit of the adhesion amount may be ignored in the case where the use of the high-frequency characteristics is negligible.
在本實施例中,銅箔基箔的表面處理,是使此表面與一導電糊接合,並使此表面中與包含於上述導電糊的金屬粒子接合的接合部之與上述金屬粒子的接合面的面積,為銅箔的表面積的30%以上。In the present embodiment, the surface treatment of the copper foil-based foil is such that the surface is bonded to a conductive paste, and the joint portion of the surface with the metal particles contained in the conductive paste is bonded to the metal particles. The area is 30% or more of the surface area of the copper foil.
金屬粒子與銅箔表面的接觸面積,為以下所示所測定的面積。The contact area between the metal particles and the surface of the copper foil is the area measured as shown below.
首先,測定銅箔的表面積。也就是進行銅箔的寬度方向及長度方向的截面測定。若以測定銅箔表面的截面部而得的寬度方向的長度為L、以相同方法測定的長度方向的長度為L’,將L與L’相乘的結果為銅箔表面面積。截面部的長度測定,是使用影像解析軟體(BioArts股份有限公司(BioArts,Co.,Ltd.)的影像解析軟體ImageJ 2006),沿著粗化粒子的外圍測定銅箔表面的長度。First, the surface area of the copper foil was measured. That is, the cross section of the copper foil in the width direction and the longitudinal direction was measured. The length in the width direction obtained by measuring the cross-sectional portion of the surface of the copper foil was L, and the length in the longitudinal direction measured by the same method was L', and the result of multiplying L and L' was the surface area of the copper foil. The length of the cross-sectional portion was measured by using an image analysis software (Image Analysis Software ImageJ 2006 of BioArts Co., Ltd.), and the length of the surface of the copper foil was measured along the periphery of the roughened particles.
銅箔表面的寬度L內的與導電糊的金屬粒子接合的部分的長度全部相加的值為S、銅箔表面的長度L’內的與導電糊的金屬粒子接合的部分的長度全部相加的值為S’,以S與S’相乘的值為接合面積。The total value of the length of the portion of the width L of the surface of the copper foil bonded to the metal particles of the conductive paste is S, and the length of the portion of the length L' of the surface of the copper foil bonded to the metal particles of the conductive paste is added. The value of S is the sum of the values of S and S'.
此時的接合面積較好為銅箔表面面積的30%(含)以上。接合面積若為銅箔表面面積的30%(含)以上,則可滿足黏著力並降低銅箔(配線電路)與金屬粒子的接觸電阻,而可以在兩者之間得到滿足的連接部。而接觸面積在30%以下的情況則黏著力會不足,而會有發生接觸電阻增加而發熱等的問題之虞,故不佳。The joint area at this time is preferably 30% or more of the surface area of the copper foil. When the bonding area is 30% or more of the surface area of the copper foil, the adhesion can be satisfied, and the contact resistance between the copper foil (wiring circuit) and the metal particles can be lowered, and the connection portion can be satisfied between the two. When the contact area is 30% or less, the adhesion is insufficient, and there is a problem that the contact resistance increases and the heat is generated, which is not preferable.
關於混入導電糊的金屬粒子,可在鋁、鎢、鉛、鋅、金、銀、銅、鎳、鈷等選用適合者。The metal particles mixed in the conductive paste may be selected from aluminum, tungsten, lead, zinc, gold, silver, copper, nickel, cobalt, and the like.
另外,在本實施例中進行表面粗化處理的粗化處理銅箔,其明度值為30以下、較好為25以下。本實施例中的明度值通常是用於觀測表面粗糙度的指標,其測定方法是將光照射在測定樣品表面而測定光的反射量而表為明度值的方法。在此處,根據JIS Z 8105(1982),明度值是將物體的相對性明暗的相關顏色的屬性尺度化的值,其是以同一條件下照明的白色面為基準。若是藉由此方法測定表面處理銅箔的處理面的明度,表面粗糙度Rz較大或是粗化粒子間的溝槽深度較深時,由於光的反射量少而使明度值有偏低的傾向,而若表面平滑則光的反射量大而使明度有偏高的傾向。為了使表面處理銅箔與絕緣基板的剝離強度提升,使表面處理銅箔的明度值為30以下、較好為25以下。另外,若明度超過30,即使粗化面的Rz值大,但是由於其凹凸為和緩的凹凸,而使表面處理銅箔與絕緣基板的咬合不佳,而無法提升剝離強度。Further, in the present embodiment, the roughened copper foil subjected to the surface roughening treatment has a lightness value of 30 or less, preferably 25 or less. The brightness value in the present embodiment is generally an index for observing the surface roughness, and the measurement method is a method in which light is irradiated on the surface of the measurement sample to measure the amount of reflection of light and is expressed as a brightness value. Here, according to JIS Z 8105 (1982), the brightness value is a value that scales the attribute of the related color of the relative brightness of the object, and is based on the white surface illuminated under the same condition. If the brightness of the treated surface of the surface-treated copper foil is measured by this method, the surface roughness Rz is large or the groove depth between the roughened particles is deep, and the lightness is low due to the small amount of light reflection. There is a tendency, and if the surface is smooth, the amount of reflection of light is large and the brightness tends to be high. In order to improve the peeling strength of the surface-treated copper foil and the insulating substrate, the surface-treated copper foil has a lightness value of 30 or less, preferably 25 or less. In addition, when the brightness exceeds 30, even if the Rz value of the roughened surface is large, the unevenness is a gentle unevenness, and the surface-treated copper foil and the insulating substrate are not well bonded, and the peel strength cannot be improved.
而明度的測定是在對被測定銅箔施以The brightness is measured by applying the copper foil to be tested.
Ni:0.01~0.5mg/dm2 Ni: 0.01~0.5mg/dm 2
Zn:0.01~0.5mg/dm2 Zn: 0.01~0.5mg/dm 2
Cr:0.01~0.3mg/dm2 Cr: 0.01~0.3mg/dm 2
的範圍內的防鏽處理之後,使用明度計(SUGA試驗機股份有限公司(SUGA TEST INSTRUMENTS CO.,LTD)的機種名:S&M Colour Computer型號SM-4)進行測定。After the rust-preventing treatment in the range, the measurement was carried out using a light meter (model name of SUGA TEST INSTRUMENTS CO., LTD: S&M Colour Computer model SM-4).
兼具上述之表面粗糙度(Rz)及明度值的本實施例之表面處理銅箔在層積.複合化之後,是具有優異的剝離強度及微細圖形化特性,藉由此一表面處理銅箔的使用,可製造優異的電路基板。The surface treated copper foil of the present embodiment having the above surface roughness (Rz) and brightness value is laminated. After the compounding, it has excellent peel strength and fine patterning characteristics, and an excellent circuit substrate can be manufactured by using the surface-treated copper foil.
在本實施例中,如上所述是進行銅箔基箔表面的粗化處理,而由為了在表面內達成平均的剝離強度的粗化粒子所形成的突起物,較好為在100μm×100μm的面積中,具有200~25000個突起物。突起物的個數若少於200個,則突起物間的間隙較寬而無法切割出微細圖形;突起物若達25000個以上,則突起物過窄而無法提供足夠的剝離強度,故不佳。In the present embodiment, as described above, the roughening treatment is performed on the surface of the copper foil-based foil, and the projections formed by the roughened particles for achieving the average peel strength in the surface are preferably 100 μm × 100 μm. In the area, there are 200~25,000 protrusions. If the number of the protrusions is less than 200, the gap between the protrusions is wide and the fine pattern cannot be cut; if the number of protrusions is 25,000 or more, the protrusion is too narrow to provide sufficient peel strength, which is not preferable. .
還有為了得到在表面內具有不具變異之優異剝離強度及微細圖形特性,較好為以後文所述的粗化粒子所形成的突起物是大致均勻地存在(分佈)。也就是突起物的高度較好為1.0μm~5.0μm。形成於銅箔基箔表面的突起物的高度在1.0μm以下的情況,則因為高度低則無法得到提升剝離強度的效果;突起物的高度在5.0μm的情況,則突起物無法分佈均勻,表面處理銅箔的表面粗糙度Rz在每個範圍的變異會變大,而無法保持具有穩定性的剝離強度,且其高頻特性不佳而無法達成微細圖形化。而此處所稱高度,為銅箔基箔表面與突起物的頂點的距離。Further, in order to obtain excellent peel strength and fine pattern characteristics without variation in the surface, it is preferred that the projections formed by the roughened particles described later are substantially uniformly distributed (distributed). That is, the height of the protrusions is preferably from 1.0 μm to 5.0 μm. When the height of the protrusion formed on the surface of the copper foil-based foil is 1.0 μm or less, the effect of improving the peel strength cannot be obtained because the height is low; when the height of the protrusion is 5.0 μm, the protrusion cannot be uniformly distributed, and the surface is not uniform. The surface roughness Rz of the treated copper foil becomes large in variation in each range, and the peel strength with stability cannot be maintained, and the high frequency characteristics are not good, and fine patterning cannot be achieved. The height referred to herein is the distance between the surface of the copper foil base foil and the apex of the protrusion.
另外,突起物的個數若少,則無法達成剝離強度;又若個數多,則銅箔表面與突起物的黏著性低的數量亦多,則其效果反而降低,因此觀察截面的25μm內較好為具有6個~35個的突起物、特別是最好為10個~20個突起物。Further, if the number of the projections is small, the peel strength cannot be achieved. If the number of the projections is large, the adhesion between the surface of the copper foil and the projections is small, and the effect is rather lowered. Therefore, the cross section is observed within 25 μm. It is preferred to have 6 to 35 protrusions, particularly preferably 10 to 20 protrusions.
在此處,針對本實施例所稱突起物的概念進行說明。形成於鄰接的突起物之間的溝槽部的底部與突起物的頂點的距離(以下稱為溝槽深度)為不滿0.3μm的情況,是將這樣的鄰接突起物視為一個突起物;另外,突起物的深度為0.3μm以上的情況,則將這樣的鄰接突起物視為二個突起物。相對於上述突起物的高度為銅箔基箔的表面與突起物的頂點的距離,此一溝槽深度與其不同之點在於其是進行表面處理之後的溝槽部的底部與突起物的頂點的距離。Here, the concept of the protrusion referred to in the present embodiment will be described. The distance between the bottom of the groove portion formed between the adjacent protrusions and the apex of the protrusion (hereinafter referred to as the groove depth) is less than 0.3 μm, and such adjacent protrusion is regarded as one protrusion; When the depth of the projections is 0.3 μm or more, such adjacent projections are regarded as two projections. The height of the protrusion relative to the protrusion is the distance between the surface of the copper foil-based foil and the apex of the protrusion, and the depth of the groove is different from that of the bottom of the groove portion and the apex of the protrusion after the surface treatment. distance.
突起物的數量的計數方法,是將表面處理銅箔鑲埋在樹脂中,對於以掃瞄式電子顯微鏡(SEM)觀察進行研磨後的截面所得的觀察照片中,以計數在25μm的長度範圍內的上述定義的突起物的個數為何的方法來進行測定。The method of counting the number of the protrusions is to embed the surface-treated copper foil in the resin, and to observe the cross section obtained by scanning with a scanning electron microscope (SEM), the count is in the range of 25 μm. The method of determining the number of the protrusions defined above is carried out.
還有高度為1.0μm~5.0μm的突起物的個數,在25μm的範圍內存在6個~35個、且在上述突起物間存在深度0.3μm以上的溝槽並使其大致均勻分佈,則可以避免突起物集中於25μm以內的局部,而達成銅箔的寬度方向‧長度方向的剝離強度的穩定化。Further, the number of protrusions having a height of 1.0 μm to 5.0 μm is 6 to 35 in the range of 25 μm, and a groove having a depth of 0.3 μm or more exists between the protrusions and is substantially uniformly distributed. It is possible to prevent the projections from being concentrated on a portion within 25 μm, and to stabilize the peel strength in the longitudinal direction of the copper foil in the longitudinal direction.
在本實施例中的「大致均勻分佈」,是指以突起物的頂點與銅箔表面之間的高度為1.0μm~5.0μm的突起物的個數為n(個),而在截面觀察突起物時的觀察寬度為25(μm)時,在(25/n)(μm)的寬度的區域中,至少有上述突起物之一的一部分存在於此一區域中。The term "substantially uniform distribution" in the present embodiment means that the number of protrusions having a height between 1.0 pm and 5.0 μm between the apex of the protrusion and the surface of the copper foil is n (pieces), and the protrusion is observed in section. When the observation width at the time of the object is 25 (μm), at least a part of one of the above-mentioned protrusions exists in the region of the width of (25/n) (μm).
另外,為了謀求剝離強度的穩定化,所形成的突起物的寬度較好為具有均一性,各突起物的最大寬度較好為0.01μm(含)以上、25μm除以存在於25μm的範圍內的突起物的個數所得長度的2倍(含)以下。而此處所稱最大寬度是指上述截面的SEM觀察中,與突起物的高度方向垂直的方向的距離的最大值。Further, in order to stabilize the peel strength, the width of the formed protrusions is preferably uniform, and the maximum width of each of the protrusions is preferably 0.01 μm or more and 25 μm divided by 25 μm. The number of the projections is twice or less the length of the obtained length. The maximum width referred to herein means the maximum value of the distance in the direction perpendicular to the height direction of the projections in the SEM observation of the cross section.
另外,突起物間的溝槽深度中,突起物間的平均溝槽深度更好為0.5μm(含)以上。突起物間的平均溝槽深度是對於溝槽深度在0.3μm(含)以上的突起物n個中,測定各突起物的二側的溝槽深度,以此時的值為A1(μm)B1(μm)……An(μm)Bn(μm)時,以下式求得的值即為突起物間的平均溝槽深度。Further, in the groove depth between the protrusions, the average groove depth between the protrusions is more preferably 0.5 μm or more. The average groove depth between the protrusions is the number of the protrusions on the two sides of the protrusions in the n-th projection having a groove depth of 0.3 μm or more, and the value at this time is A1 (μm) B1. (μm) ... An (μm) Bn (μm), the value obtained by the following formula is the average groove depth between the protrusions.
以{[(A1+B1)+……+(An+Bn)]/2/n}來求得。It is obtained by {[(A1+B1)+...+(An+Bn)]/2/n}.
第2圖為本發明實施例中測定表面處理銅箔的觀察截面的圖。Fig. 2 is a view showing the observation cross section of the surface-treated copper foil in the embodiment of the present invention.
在未處理銅箔表面SU形成有突起物P。突起物P的數量n在25μm以內為6個(含)以上,例如為存在有6~35個,其高度是在1~5μm的範圍內。以a所示的溝槽深度不滿0.3μm的情況並未計入突起物,而是計入以b所示溝槽深度在0.3μm(含)以上的突起物。突起物P的最大寬度W為0.01μm(含)以上、25μm除以存在於25μm的範圍內的突起物P的個數所得長度的2倍(含)以下。A protrusion P is formed on the surface of the untreated copper foil SU. The number n of the projections P is 6 or more within 25 μm, for example, 6 to 35 are present, and the height thereof is in the range of 1 to 5 μm. When the groove depth indicated by a is less than 0.3 μm, the projections are not counted, but the projections having a groove depth of 0.3 μm or more as indicated by b are included. The maximum width W of the projections P is 0.01 μm or more, and 25 μm is divided by two times or less the length of the number of the projections P existing in the range of 25 μm.
第3圖為不佳的表面處理銅箔的觀察截面的圖。Fig. 3 is a view showing an observation cross section of a poor surface-treated copper foil.
在未處理銅箔表面SU形成有突起物P。突起物P的最大寬度W為0.01μm(含)以上、且存在有寬度為大於25μm除以存在於25μm的範圍內的突起物P的個數所得長度的2倍之異常寬度的突起物P。A protrusion P is formed on the surface of the untreated copper foil SU. The maximum width W of the projections P is 0.01 μm or more, and there is a projection P having an abnormal width which is greater than 25 μm in width and divided by the number of projections P present in the range of 25 μm.
第4圖為不佳的表面處理銅箔的觀察截面的圖。Fig. 4 is a view showing an observation cross section of a poor surface-treated copper foil.
在未處理銅箔表面SU形成有突起物P,其顯示出突起物P未均勻分佈的截面。在第4圖中,具有以c所示的並未存在突起物P任一部分的區域,此一情況無法視為大致均勻分佈。On the untreated copper foil surface SU, a protrusion P is formed which shows a cross section in which the protrusion P is not uniformly distributed. In Fig. 4, there is a region where there is no portion of the protrusion P as indicated by c, and this case cannot be regarded as a substantially uniform distribution.
在上述構成的粗化處理面的銅箔上,形成鉻及/或鉻酸鹽(chromate)被覆膜而進行防鏽處理,或是視需求進行矽烷(silane)偶合劑(coupling agent)處理或防鏽處理加上矽烷偶合劑處理。A chromium and/or chromate coating film is formed on the copper foil of the roughened surface having the above-described configuration to perform rust prevention treatment, or a silane coupling agent treatment may be performed as needed or Anti-rust treatment plus decane coupling agent treatment.
以下根據實施例對本發明進行更詳細地說明,但本發明並不受限於以下的說明中。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the following description.
準備以下的銅箔基箔一至四。Prepare the following copper foil base foils one to four.
厚度:12μm;暗面粗糙度:Rz=1.26μm;光澤面粗糙度:Rz=1.82μm的電解銅箔。Thickness: 12 μm; dark surface roughness: Rz = 1.26 μm; glossy surface roughness: Rz = 1.82 μm.
厚度:12μm;暗面粗糙度:Rz=1.52μm;光澤面粗糙度:Rz=1.46μm的電解銅箔。Thickness: 12 μm; dark surface roughness: Rz = 1.52 μm; gloss surface roughness: Rz = 1.46 μm.
厚度:12μm;暗面粗糙度:Rz=1.86μm;光澤面粗糙度:Rz=1.20μm的電解銅箔。Thickness: 12 μm; dark surface roughness: Rz = 1.86 μm; glossy surface roughness: Rz = 1.20 μm.
厚度:12μm;雙面的粗糙度:Rz=1.20μm的軋延銅箔。Thickness: 12 μm; roughness of both sides: rolled copper foil of Rz=1.20 μm.
將準備的銅箔基箔一至四以下列的電鍍條件A、B、或C施以表面處理。在表1顯示銅箔基箔的種類與電鍍條件的組合。而各實施例是將銅箔基箔一至四以電鍍條件A、B、或C的鍍浴1至鍍浴2的順序進行至少一次的鍍膜所得的表面處理銅箔。The prepared copper foil-based foils were subjected to surface treatment with the following plating conditions A, B, or C from one to four. Table 1 shows the combination of the type of the copper foil-based foil and the plating conditions. Each of the examples is a surface-treated copper foil obtained by subjecting the copper foil-based foils to at least one plating in the order of plating bath 1 to plating bath 2 of plating conditions A, B, or C.
以完成製作的表面處理銅箔的表面形狀為實施例1~8示於表1中。The surface shapes of the finished surface-treated copper foil were shown in Table 1 as Examples 1 to 8.
還有,在有些實施例的粗化處理面施以鍍鎳(0.3mg/dm2 )、鍍鋅(0.1mg/dm2 ),而在其上施以鉻酸鹽處理。Further, in the roughened surface of some of the examples, nickel plating (0.3 mg/dm 2 ), galvanization (0.1 mg/dm 2 ) was applied, and chromate treatment was applied thereto.
硫酸銅(銅金屬來源) 5~10g/dm3 Copper sulfate (source of copper metal) 5~10g/dm 3
硫酸 30~120g/dm3 Sulfuric acid 30~120g/dm 3
鉬酸銨(鉬金屬來源) 0.1~5.0g/dm3 Ammonium molybdate (source of molybdenum metal) 0.1~5.0g/dm 3
電流密度 10~60A/dm2 Current density 10~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~60℃Bath temperature 20~60°C
硫酸銅(銅金屬來源) 20~70g/dm3 Copper sulfate (source of copper metal) 20~70g/dm 3
硫酸 30~120g/dm3 Sulfuric acid 30~120g/dm 3
電流密度 5~60A/dm2 Current density 5~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~65℃Bath temperature 20~65°C
硫酸銅(銅金屬來源) 1~50g/dm2 Copper sulfate (source of copper metal) 1~50g/dm 2
硫酸鎳(鎳金屬來源) 2~25g/dm3 Nickel sulfate (source of nickel metal) 2~25g/dm 3
偏釩酸銨(ammonium metavanadate;釩金屬來源) 0.1~15g/dm3 Ammonium metavanadate (source of vanadium metal) 0.1~15g/dm 3
pH值 1.0~4.5pH 1.0~4.5
電流密度 1~60A/dm2 Current density 1~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~60℃Bath temperature 20~60°C
硫酸銅(銅金屬來源) 10~70g/dm2 Copper sulfate (source of copper metal) 10~70g/dm 2
硫酸 30~120g/dm2 Sulfuric acid 30~120g/dm 2
電流密度 5~60A/dm2 Current density 5~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~65℃Bath temperature 20~65°C
硫酸銅(銅金屬來源) 1~50g/dm2 Copper sulfate (source of copper metal) 1~50g/dm 2
硫酸鈷(鈷金屬來源) 1~50g/dm3 Cobalt sulfate (cobalt metal source) 1~50g/dm 3
鉬酸銨(鉬金屬來源) 0.1~10g/dm3 Ammonium molybdate (source of molybdenum metal) 0.1~10g/dm 3
pH值 0.5~4.0pH 0.5~4.0
電流密度 1~60A/dm2 Current density 1~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~60℃Bath temperature 20~60°C
硫酸銅(銅金屬來源) 10~70g/dm2 Copper sulfate (source of copper metal) 10~70g/dm 2
硫酸 30~120g/dm2 Sulfuric acid 30~120g/dm 2
電流密度 5~60A/dm2 Current density 5~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~65℃Bath temperature 20~65°C
將準備的銅箔基箔一、三、四以下列的電鍍條件A’或B’施以表面處理。在表1一併記錄銅箔基箔的種類與電鍍條件的組合。而各比較例是將銅箔基箔一或三以上述電鍍條件A’或B’的鍍浴1至鍍浴2的順序進行至少一次的鍍膜所得的表面處理銅箔。而在比較例製成的表面處理銅箔之與絕緣基板的接合面(粗化處理面)那一側的表面,施以鍍鎳(0.3mg/dm2 )、鍍鋅(0.1mg/dm2 ),再於其上進行鉻酸鹽處理,而成為比較例的試片。The prepared copper foil base foils one, three, and four were subjected to surface treatment with the following plating conditions A' or B'. The combination of the type of the copper foil-based foil and the plating conditions was recorded in Table 1. Each of the comparative examples is a surface-treated copper foil obtained by subjecting the copper foil-based foil to one or three plating baths 1 to B in the order of plating conditions A' or B'. In Comparative Example prepared surface-treated surface side of the engagement surface (roughened surface) of the copper foil and the insulating substrate, subjected to nickel plating (0.3mg / dm 2), zinc (0.1mg / dm 2 Then, chromate treatment was carried out thereon, and it became a test piece of a comparative example.
以完成製作的表面處理銅箔的表面形狀為比較例1~6一併記錄於表1中。The surface shapes of the surface-treated copper foil which were produced were the same as Comparative Examples 1 to 6, and are shown in Table 1.
硫酸銅(銅金屬來源) 5~10g/dm3 Copper sulfate (source of copper metal) 5~10g/dm 3
硫酸 30~120g/dm3 Sulfuric acid 30~120g/dm 3
鉬酸銨(鉬金屬來源) 0.1~5.0g/dm3 Ammonium molybdate (source of molybdenum metal) 0.1~5.0g/dm 3
電流密度 10~60A/dm2 Current density 10~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~60℃Bath temperature 20~60°C
硫酸銅(銅金屬來源) 20~70g/dm3 Copper sulfate (source of copper metal) 20~70g/dm 3
硫酸 30~120g/dm3 Sulfuric acid 30~120g/dm 3
電流密度 3A/dm2 Current density 3A/dm 2
通電時間 2分鐘以上(依照表面粗糙度變更時間)Power-on time 2 minutes or more (change time according to surface roughness)
鍍浴溫度 15℃Bath temperature 15 °C
硫酸銅(銅金屬來源) 1~50g/dm2 Copper sulfate (source of copper metal) 1~50g/dm 2
硫酸鎳(鎳金屬來源) 2~25g/dm3 Nickel sulfate (source of nickel metal) 2~25g/dm 3
偏釩酸銨(釩金屬來源) 0.1~15g/dm3 Ammonium metavanadate (source of vanadium metal) 0.1~15g/dm 3
pH值 1.0~4.5pH 1.0~4.5
電流密度 1~60A/dm2 Current density 1~60A/dm 2
通電時間 1秒~2分鐘Power-on time 1 second ~ 2 minutes
鍍浴溫度 20~60℃Bath temperature 20~60°C
硫酸銅(銅金屬來源) 20~70g/dm2 Copper sulfate (source of copper metal) 20~70g/dm 2
硫酸 30~120g/dm2 Sulfuric acid 30~120g/dm 2
電流密度 3A/dm2 Current density 3A/dm 2
通電時間 2分鐘以上(依照表面粗糙度變更時間)Power-on time 2 minutes or more (change time according to surface roughness)
鍍浴溫度 15℃Bath temperature 15 °C
將實施例及比較例製成的表面處理銅箔裁切為長250mm、寬250mm之後,將其已施以粗化處理的面置於熱壓合後會成為1mm厚度的張數的BT樹脂(三菱瓦斯化學股份有限公司的商標,是由雙馬來亞醯胺-三氮雜苯(bismaleimide triazine)樹脂所構成的熱硬化樹脂)之上,將全體夾置於二片平滑的不銹鋼板之間,進行溫度190℃、壓力50kg/cm2 之下90分鐘的熱壓合,而測定貼附的剝離強度。After the surface-treated copper foil prepared in the examples and the comparative examples was cut into a length of 250 mm and a width of 250 mm, the surface subjected to the roughening treatment was placed in a BT resin having a thickness of 1 mm after thermocompression bonding ( The trademark of Mitsubishi Gas Chemical Co., Ltd. is a thermosetting resin composed of bismaleimide triazine resin, which is sandwiched between two smooth stainless steel plates. The peeling strength of the attached was measured by thermocompression bonding at a temperature of 190 ° C and a pressure of 50 kg/cm 2 for 90 minutes.
剝離強度的測定,是根據JIS C6471,以180度方向拉出、剝離。The peel strength was measured and peeled off in a 180 degree direction in accordance with JIS C6471.
從表1明確顯示,各實施例均滿足0.9KN/m以上的剝離強度,但是比較例1~6中的剝離強度為0.8KN/m,而未滿足剝離強度的要求。As is clear from Table 1, each of the examples satisfies the peel strength of 0.9 KN/m or more, but the peel strength in Comparative Examples 1 to 6 is 0.8 KN/m, and the peel strength is not satisfied.
第5圖為將上述製成的表面處理銅箔F貼附於BT樹脂等的基板SB,再如下文所述進行加工時的截面概略圖。Fig. 5 is a schematic cross-sectional view showing the surface-treated copper foil F produced as described above attached to a substrate SB of a BT resin or the like, and processed as described below.
如第5圖所示,將已形成決定線寬:L、間隔寬:S的阻劑R的銅箔F以氯化鐵浴進行蝕刻。以線寬的頂部寬度與阻劑寬度相同為準則決定蝕刻時間,以各n=10的條件製成已形成決定各線寬及各間隔寬(在一片基板形成10條線)的阻劑R的基板,在氯化鐵浴中以上述決定的時間進行蝕刻。在各基板中,觀察導線間無發生橋接、無殘留根部、及導線的頂部寬度與阻劑相同的情況。以n=10的條件製成的各基板中未觀察到橋接及殘留根部情況中最小的L‧S的值示於表1。As shown in Fig. 5, the copper foil F on which the resist R having the line width: L and the width: S is formed is etched with a ferric chloride bath. The etching time is determined by the same width of the top of the line width and the width of the resist. The substrate having the resist R which determines the width of each line and the width of each interval (forming 10 lines on one substrate) is formed under the condition of n=10. Etching was performed in the ferric chloride bath at the time determined above. In each of the substrates, it was observed that no bridging occurred between the wires, no residual root portion, and the top width of the wires was the same as that of the resist. The values of the smallest L‧S in the case where no bridge and residual root were observed in each of the substrates prepared under the condition of n = 10 are shown in Table 1.
從表1明確顯示,在各實施例中,可以製成L/S=30/30(含)以下的微細圖形。比較例6以外的各比較例雖可勉強製成30/30的圖形,但已不可能再縮小。另外,比較例6由於表面處理粗糙度小,而適用於製成微細圖形。As is clear from Table 1, in each of the examples, a fine pattern of L/S = 30/30 or less can be produced. Although each of the comparative examples other than Comparative Example 6 can be made into a 30/30 pattern, it is impossible to reduce it. Further, Comparative Example 6 was suitable for forming a fine pattern because the surface treatment roughness was small.
在BT樹脂開出核心孔並充填導電糊後進行壓合,使銅粒子與銅箔接合而測定其電阻值。將此測定結果作為因上述壓合而加熱後的電阻值增加率顯示於表1。After the core hole was opened from the BT resin and the conductive paste was filled, press-bonding was performed to bond the copper particles to the copper foil, and the resistance value was measured. The measurement results are shown in Table 1 as the increase rate of the resistance value after heating by the above-described press-fitting.
從表1明確顯示,在各實施例的熱處理後的電阻值的增加率均在60%以下,相對於此,比較例1~6的熱處理後的電阻值的增加率均超過140%。As is clear from Table 1, the increase rate of the electric resistance value after the heat treatment of each of the examples was 60% or less. On the other hand, the increase rates of the electric resistance values after the heat treatment of Comparative Examples 1 to 6 exceeded 140%.
另外,進行耐溼試驗後測定同樣地方的電阻值而計算在耐溼試驗前後的電阻值的增加率,並確認其優劣。Further, after the moisture resistance test, the resistance value in the same place was measured, and the increase rate of the resistance value before and after the moisture resistance test was calculated, and the advantages and disadvantages thereof were confirmed.
從表1明確顯示,在各實施例的耐溼試驗後的電阻值的增加率均在100%以下,相對於此,比較例1~6的耐溼試驗後的電阻值的增加率均超過140%。As is clear from Table 1, the increase rate of the electric resistance value after the moisture resistance test of each of the examples was 100% or less. On the other hand, the increase rates of the electric resistance values after the moisture resistance test of Comparative Examples 1 to 6 exceeded 140. %.
關於明度的測定方法與前文所述相同。在個實施例中的明度為25(含)以下,而比較例1~6則為30以上。The method of measuring the brightness is the same as described above. In one embodiment, the lightness is 25 or less, and in Comparative Examples 1 to 6, it is 30 or more.
如上所述,在各實施例中,金屬粒子與銅箔的接合面積為30%(含)以上,而可製成滿足剝離強度、明度、電阻值、加熱試驗及耐溼試驗後的電阻值增加的比例、微細圖形的製成的條件的銅箔。相對於此,比較例1~6的金屬粒子與銅箔的接合面積為30%以下,並無法得到滿足明度、電阻值、加熱試驗及耐溼試驗後的電阻值增加的比例的結果,另外亦不能滿足剝離強度、微細圖形的製成的條件,而未得到滿足全部條件的銅箔。As described above, in each of the examples, the bonding area of the metal particles and the copper foil is 30% or more, and the resistance value after the peeling strength, the brightness, the electric resistance value, the heating test, and the moisture resistance test can be made. The ratio of the micro-patterns to the conditions of the copper foil. On the other hand, the joint area of the metal particles of Comparative Examples 1 to 6 and the copper foil was 30% or less, and the results of satisfying the increase in the resistance value after the heat resistance test and the moisture resistance test were not obtained. The conditions for the peel strength and the formation of the fine pattern could not be satisfied, and the copper foil satisfying all the conditions was not obtained.
本發明是完成使突起物形成於銅箔表面的表面處理銅箔,而上述突起物顯示出由粗化粒子所形成的特定的形狀與分佈,藉此即使粗糙度小,亦確保強力的黏著性及與導電糊的金屬粒子的接合面積,而可以提供保有穩定的電傳導性的表面處理銅箔。The present invention is to complete a surface-treated copper foil in which protrusions are formed on the surface of a copper foil, and the protrusions exhibit a specific shape and distribution formed by roughened particles, thereby ensuring strong adhesion even if the roughness is small. And a bonding area with the metal particles of the conductive paste, and a surface-treated copper foil which maintains stable electrical conductivity can be provided.
1...絕緣基板1. . . Insulating substrate
2...貫穿孔2. . . Through hole
3...導電糊3. . . Conductive paste
4...銅箔4. . . Copper foil
5...銅箔5. . . Copper foil
10...基板10. . . Substrate
11...基板11. . . Substrate
12...基板12. . . Substrate
13...銅箔13. . . Copper foil
14...銅箔14. . . Copper foil
15...基板15. . . Substrate
16...基板16. . . Substrate
17...銅箔17. . . Copper foil
18...銅箔18. . . Copper foil
a...溝槽深度不滿0.3μm的情況a. . . When the groove depth is less than 0.3μm
b...溝槽深度在0.3μm(含)以上的情況b. . . When the groove depth is 0.3 μm or more
c...未存在突起物P任一部分的區域c. . . Area where no part of the protrusion P exists
P...突起物P. . . Protrusion
R...阻劑R. . . Resistor
SB...基板SB. . . Substrate
SU...未處理銅箔表面SU. . . Untreated copper foil surface
W...最大寬度W. . . Maximum width
第1(a)~1(i)圖是說明IVH法的步驟的步驟圖。The first (a) to (i)th drawings are step diagrams illustrating the steps of the IVH method.
第2圖是本發明的一實施例的截面概略圖。Fig. 2 is a schematic cross-sectional view showing an embodiment of the present invention.
第3圖是顯示表面處理銅箔中具有不佳的截面形狀的表面處理銅箔的截面的概略截面圖。Fig. 3 is a schematic cross-sectional view showing a cross section of a surface-treated copper foil having a poor cross-sectional shape in a surface-treated copper foil.
第4圖是顯示表面處理銅箔中具有不佳的截面形狀的表面處理銅箔的截面的概略截面圖。Fig. 4 is a schematic cross-sectional view showing a cross section of a surface-treated copper foil having a poor cross-sectional shape in a surface-treated copper foil.
第5圖是說明微細圖形形成中的蝕刻寬度的截面說明圖。Fig. 5 is a cross-sectional explanatory view for explaining an etching width in formation of a fine pattern.
1...絕緣基板1. . . Insulating substrate
2...貫穿孔2. . . Through hole
3...導電糊3. . . Conductive paste
4...銅箔4. . . Copper foil
5...銅箔5. . . Copper foil
10...基板10. . . Substrate
11...基板11. . . Substrate
12...基板12. . . Substrate
13...銅箔13. . . Copper foil
14...銅箔14. . . Copper foil
15...基板15. . . Substrate
16...基板16. . . Substrate
17...銅箔17. . . Copper foil
18...銅箔18. . . Copper foil
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JP5676401B2 (en) * | 2011-09-21 | 2015-02-25 | Jx日鉱日石金属株式会社 | Copper foil for flexible printed wiring boards |
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CN104735929B (en) * | 2013-12-24 | 2017-12-29 | 深南电路有限公司 | Circuit board processing method and equipment |
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US10051746B2 (en) * | 2014-12-16 | 2018-08-14 | Amphenol Corporation | High-speed interconnects for printed circuit boards |
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JP4974186B2 (en) | 2012-07-11 |
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TW200936003A (en) | 2009-08-16 |
CN101541142A (en) | 2009-09-23 |
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