TW499508B - Roughening treated copper foil and producing method therefor - Google Patents

Abstract

A roughening treated copper foil comprises a composite metal formed of (I) Cu, (II) more than one metal selected from W and Mo, and (III) at least one metal selected from Ni, Co, Fe and Zn, on the adhesion face of the copper foil; and a roughened layer formed of Cu on this layer.

Description

499508 A7 B7 Revised (corrected) Corrected replacement page Printed by the Ministry of Economic Affairs, Intellectual Property Office, Bureau of Labor and Economics Cooperatives 5. The description of the invention (5) can also be double-sided. On the adhered surface of this copper foil, (I) copper is preferably attached in an amount of 5,000 to 10,000 / zg / dm2, and (II) more than one metal is selected by tungsten and I. 10 ~ 1,000 jug / dm2, more preferably 100 ~ 1,000 ren g / dm2, (III) The adhesion amount of at least one metal selected from nickel, iron, cobalt and zinc should be 10 ~ 1, 〇〇〇Ag / dm2, more preferably 10 ~ 300 yg / dm2 composite metal layer. When the adhesion amount of at least one metal selected from nickel, iron, cobalt, and zinc is less than 10 V g / dm2, nodular copper is not formed on the copper foil even if nodular copper is formed by electroplating. Concavity and tend to be concentrated and formed. When it exceeds 1,000 # g / dni2, copper and circuit are formed, and the etching time of the plating layer is significantly changed when copper is removed by etching. Slow tendency. The adhesion amount of at least one metal selected from nickel, cobalt, iron, and zinc is related to the composition of the plating bath or the setting of the processing conditions, and can be appropriately selected from the bath composition and electrolytic conditions described below. In addition, if the copper adhesion amount of the composite metal layer is less than 5,000 μ g / dm2, there is a tendency that nodular copper is not formed in the entire recess, and if it exceeds 10,000eg / dm2 • in the entire recess. The effect of forming nodular copper on the surface is small, and it tends to increase the manufacturing cost. If the adhesion amount of at least one metal selected from tungsten and molybdenum of the composite metal layer is less than 10 # g / dm2, there is a tendency that nodular copper is not formed in the entire concave portion * and if it exceeds 1, 〇〇〇 / ig / dm2, then I nnn will be approved. III i 11 Order I n! LI Township (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 Mm) -8- 499508

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) The nodular copper tends not to become larger. The thickness of the composite metal layer should be 0. 05 ~ 0 · 15 # m. More preferably, it is 0.07 to 0_12 βm. In the formation of the composite metal layer of the present invention, a metal ion containing one or more metals selected from the group consisting of (i) copper ions and (ii) tungsten and molybdenum is used on the adhered surface of the copper foil used as a cathode and (Iii) a plating bath of metal ions of at least one metal selected from nickel, cobalt, iron, and zinc and (S. 1 ii) metal ions of one or more metals selected from nickel, cobalt, iron, and zinc; The current density of the bath below the limit current density is subjected to electrolytic treatment. The surface of the copper foil to be adhered is preferably acid-washed and degreased in advance. The source of each metal ion in this plating bath is selected from water-soluble metal salts and used. A more suitable bath composition is preferably selected from the following ranges, but it is not particularly limited. Copper ion source—copper sulfate pentahydrate: 10 ~ 100 g / L Tungsten ion source monosodium tungstate dihydrate: 0.011 ~ 20g / L Molybdenum ion source monosodium molybdate dihydrate: 0. 5 ~ 20g / L Nickel ion source-Nickel sulfate hexahydrate Ming ion source-Cobalt sulfate heptahydrate iron ion source-Ferrous sulfate heptahydrate ion source-Sulfate sulfate heptahydrate • Nickel sulfate hexahydrate, sulfuric acid The total of cobalt heptahydrate, ferrous sulfate heptahydrate, and zinc sulfate heptahydrate: 10 ～ 100g / L More suitable electrolysis conditions if the limit current density of the electroplating bath is less than the limit ----- ： ----- 粜-(Please read the precautions on the reverse side before filling out this page) The paper size is applicable to the Chinese National Standard (CNS) / U specifications (2 丨 0X297 mm) -9- 499508 P 1. 13 A7 B7 Revised (revised) the replacement page of the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs to print V. Description of Invention (7), it is generally appropriate to choose from the following range. Current density: 1 ~ IOA / dm2, electrolytic treatment time: 1 ~ 30 seconds, bath temperature is 10 ~ 60 ° C. The pH of the plating bath is preferably selected from a range of 1.5 to 5.0. When the pH is lower than 1.5, the appropriate range of the adhesion amount of one or more metals selected from tungsten and molybdenum in the composite metal layer and the adhesion amount of at least one metal selected from nickel, cobalt, iron, and zinc becomes It is narrow. Even if nodular copper is formed by the plating method, nodular copper is not formed in the concave portion of the copper foil, and tends to concentrate on the convex portion and form it. In the case where the pH is higher than 5.0, the dissolution time of the metal ions of one or more metals selected from tungsten and molybdenum becomes significantly delayed, and the productivity tends to deteriorate. The preferable p Η is in the range of 2.0 to 4.0. Using the formation of a composite metal layer, fine grains occur on the copper foil protrusions, but this state is maintained or only coated with copper by baking or coating plating. On this layer, sufficient adhesion strength was not obtained. Therefore, a combination of baking plating and coating plating on this layer is used to precipitate nodular copper from the copper-coarse roughened layer to the recessed portion of the copper foil, and the strength is improved. That is, the copper foil obtained under the above conditions is washed with water, and on the obtained composite metal layer, a plating bath having copper ions is used, and a current density above the limit current density of the bath is used to form a branch by electrolytic plating. Copper-like copper electrode layer • A nodular copper is formed by electrolytic plating with a current density that is less than the limit current density of the full bath, and a roughened layer made of copper is provided. The copper adhesion amount of the roughened layer made of copper should preferably be 30,000 ~ 3 0,000gg / dm2. If it is less than 30, 0 0 0 I ^ 1 Pack — I order the I n line (please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 〇 > < 297 mm) -10- 499508

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (9) Hereinafter, the present invention will be described more specifically using examples and comparative examples, but the present invention is not limited by these examples. Example 1-8 and Comparative Example 1-8 Example 1 (1) A 10% sulfuric acid solution was used for an electrolytic copper foil with a thickness of 3 5 (roughness side surface roughness RaO. 9 # m, JISB 0 6 0 1 It is subject to measurement) Pickling treatment for 20 seconds. (2) The copper foil was washed with water, and an electroplating bath made of 50 g / L of copper sulfate pentahydrate, 2 g / L of sodium molybdate dihydrate, and 50 g / L of sulfate hexahydrate was used. An electroplating bath with a pH of 3 · 0 and a bath temperature of 30 ° C is electrolytically treated at a current density of 6 A / dm2 to the rough surface side (adhered surface) of the copper foil for 4 seconds, and copper-containing, Composite metal layer of molybdenum and nickel. When the ICP (inductively coupled plasma luminescence) analysis device was used to quantify the amount of each metal in the composite metal layer, the copper adhesion amount was 7, 900 // g / dm2, the molybdenum adhesion amount was 178 yg / dm2, and the nickel adhesion amount was 1 45gg / dm2, the surface roughness of the treated surface after the treatment is R a 0.9 vm. (3) Secondly, wash the copper foil with water, and use an electroplating bath adjusted to copper sulfate pentahydrate 130 g / L · sulfuric acid 100 g / L and bath temperature 30 ° C on the composite metal layer. , Electrolytic treatment at ① current density 30 A / dm2 for 3 seconds (above the limit current density), ② electrolytic treatment at current density 5 A / dm 2 for 80 seconds (below the limit current density), forming copper and Into a roughened layer. Attachment of the roughened layer made of copper ϋ J mount II order I line (please read the precautions on the back before filling this page) This paper applies the Chinese National Standard (CNS) Α4 pit (2 丨 0X297 mm) -12- 499508 A7 B7 isrrrrz-1 Revised (revised) Correction page Printed by the Consumers ’Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs 5. Description of the invention (10) The quantity is 150, 000 # g / dm2, the surface is rough The obtained pretreated electrolytic copper foil having a degree of Ra 1.4 .4 m was observed to form nodular copper on the entire unevenness of the copper foil. Scanning electron microscope photography of the roughened surface (magnification: 2000 times) (Photographing angle 45 °) is shown in Figure 1. (4) Secondly wash this copper. Fan and immerse it in sodium dichromate dihydrate adjusted to 3.5g / L * pH 4.2, bath temperature 28 ° C An anti-rust treatment layer was formed in the aqueous solution for 10 seconds. (5) Furthermore, the copper foil was washed with water and immersed in a 3-glycidoxypropyltrimethoxysilane 0.1% by weight aqueous solution after 10 seconds. , Immediately dried at 80 ° C to form a silane coupling agent treatment layer. (6) Next, in order to measure the bonding strength, an epoxy resin impregnated group of glass equivalent to FR-5 was used. The laminated surface of the copper foil and the aforementioned copper foil was laminated to form a laminated sheet of copper foil to produce a test piece. Based on JIS C6481, the adhesion strength between the copper foil and the resin substrate of this test piece was measured at room temperature. (The width of the copper foil is 1mm). After the copper foil is etched and removed with a copper chloride aqueous solution, the scale amplifier (magnification: 60 times • field of view: 2mm 0) is applied to any ten of the substrate surface. The position was observed on the resin substrate for the presence of nodular copper residues. Furthermore, a commercially available adhesive tape roll (manufactured by Lintech, CR roll) was rolled over the entire surface of the roughened surface of the copper foil. Make the sticky tape on the surface of the roll (width 80mm X length 200mm) adhere to the white paper surface face down, and use a scale magnifier (magnification: 60 times, field of view = 10 times) at any ten positions on the surface of the tape. 2 mm #) Observe the nodular copper for shedding (powder). Will be measured and observed ----: ----- ^ ------ 1T ------ ^. (Please read first Note on the back, please fill out this page again) This paper size applies to Chinese National Standard (CNS) A4 (210X297mm) -13- 499508

Employees' Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs, Consumer Cooperatives 5. Inventive Notes (u) The results are all summarized in Table 1. Example 2 The same electrolytic copper foil was used as in Example 1. The same pickling was performed as in Example 1. After the same pickling and water washing, 50 g / L of copper sulfate pentahydrate and 2 g of sodium molybdate dihydrate were used. / L, electroplating bath made of cobalt sulfate heptahydrate 30 g / L and ferrous sulfate heptahydrate 30 g / L is adjusted to pH 2 · 〇, bath temperature 30 ° C plating bath, current density 6 A / dm2 Electrolytically treats the rough surface side (adhered surface) of the aforementioned copper foil for 4 seconds and forms a composite metal layer containing molybdenum, copper, cobalt, and iron on the adhered surface side of the copper foil. When using an ICP (inductively coupled plasma luminescence) analysis device to quantify the amount of each metal in the composite metal layer, the adhesion amount of copper is 7,900 Z / g / dm2, the adhesion amount of molybdenum is 1 80 # g / dm2, and the adhesion of cobalt The amount is 1 2 # g / dm2, and the iron adhesion amount is 5 Oe.g / dm2. The surface roughness of the treated surface after the treatment was Ra 0.9 // m. Next, as in Example 1, a roughened layer made of copper was formed. The copper adhesion amount of this roughened layer was 15 000 // g / dm2, and the surface roughness was Ra1.5 # m. The obtained roughened electrolytic copper foil was observed to form nodular copper on the entire unevenness of the copper foil. Furthermore, after the treatments (4) and (5) of Example 1 were performed, the adhesion strength measurement and residual copper were performed in the same manner as in (6) of Example 1 and the results of the powder dropping test are shown in Table 1. Example 3 This standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Packing ------ order ------ line (please read the note $ on the back before filling in this萸) -14- 499508 A7 B7 ΤΤχΓΓ ~ ——---- Replacement (revised) is printed on the page of the year, month, day, day, day, month, day, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, month, week, month, month, week, month, week, month and month at a time (replaced) The amount is 7,900eg / dm2, the adhesion amount of tungsten is 200yg / dm2, the adhesion amount of cobalt is 1 2 # g / dm2, and the adhesion amount of iron is 50 / zg / dm2. The surface roughness of the treated surface after the treatment was Ra 0.9 // m. Next, a roughened layer made of copper was formed in the same manner as in Example 1. The surface roughness was Ra 1 .5 # m »The obtained roughened electrolytic copper foil was observed to form nodular copper on the entire unevenness of the copper foil. Furthermore, after the treatments (4) and (5) of Example 1 were performed, the adhesion strength measurement and residual copper were performed in the same manner as in (6) of Example 1 and the results of the powder dropping test are shown in Table 1. Example 6 The same electrolytic copper foil as in Example 1 was used, and acid pickling was performed in the same manner as in Example 1. After washing with water, copper sulfate pentahydrate 50 g / L and sodium tungstate dihydrate lg / L were used. Electroplating bath made of sodium molybdate dihydrate 2 g / L and zinc sulfate heptahydrate 50 g / L adjusted to pH 2.5, bath temperature 30 ° C, and current density 7 A / dm2 The rough surface side (bonded surface) of the aforementioned copper foil was electrolytically treated for 4 seconds and a composite metal layer containing copper, tungsten, molybdenum, and zinc was formed on the bonded surface side of the copper foil. When the amount of each metal in the composite metal layer was quantified by an ICP (inductively coupled plasma luminescence) analysis device, the adhesion amount of copper was 9, 200 / zg / dm2 'the adhesion amount of tungsten was 50 # g / dm2, and the adhesion amount of molybdenum was 180 # g / dm2, the amount of zinc attached is 160 gg / dm2 »The surface roughness of the treated surface is Ra.9 II ΙΊ n III Packing — IIII order III line (please read the note on the back first) (Fill in this page again) The paper size is applicable to China National Standard (CNS) A4 (2 丨 OX297 mm) -17-

499508 V. Description of the invention (17) Comparative example 3 The copper foil same as that in Example 1 was used for the treatment of (1) and (2) in Example 4, and the copper foil was washed with water, and 130 g of copper sulfate pentahydrate was used. / L 'Electroplating bath adjusted to a bath temperature of 3 Ot made from 100 g / L of sulfuric acid' is electrolytically treated at a current density of 3 ΑΑ / dm2 (above the limit current density) for 3 seconds to form a dendritic copper layer (roast plating ). The copper adhesion amount of the dendritic copper layer was 3 0, 0 0 0 # g / dm2, and the coarseness of the surface was Ra 1. Furthermore, after the treatments of (4) and (5) of Example 1 were performed, and the examples were 1 (6) The measurement of the bonding strength and the residual copper in the same method, and the results of the powder dropping test are shown in Table 1. Comparative Example 4 After the treatments of (1) and (2) of Example 4 were performed using the same copper foil as in Example 1, the copper foil was washed with water, and copper sulfate pentahydrate 130 g / L and sulfuric acid 1 were used. 〇g / L electroplating bath adjusted to a bath temperature of 30 ° C, electrolytic treatment at a current density of 5A / dm2 (under the limit current density) for 80 seconds, and a smooth copper layer (coated plating) is formed. The copper adhesion of the smooth copper layer was 132, OOOyg / dm2, and the surface roughness was Ral.1 in m. Furthermore, after the treatments (4) and (5) of Example 1 were performed, the adhesion strength measurement and residual copper were performed in the same manner as in (6) of Example 1 and the results of the powder dropping test are shown in Table 1. This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) [I " " «II 1 Binding III line (please read the precautions on the back before filling out this page) Ministry of Economic Affairs Intellectual Property Employee Consumption Cooperation Wang Yinting -20- 499508 A7 B7 ^ I. Corrected (revised) 13/13 Replacement Page V. Invention Description (2 (J) Pentahydrate 1 100g / L, sulfuric acid 1 20g / L, sodium tungstate An electroplating bath adjusted to a bath temperature of 35 ° C with 0.6 g / L of dihydrate and I5 g / L of ferrous sulfate heptahydrate, and an electric current is applied to the rough surface side (the surface to be bonded) of the aforementioned copper foil. Density 4 〇Α / dm2 electrolytic treatment (above the limit current density) 3.5 seconds, followed by ② using a plating bath made of copper sulfate pentahydrate 250g / L and sulfuric acid 100g / L, adjusted to a bath temperature of 50 ° C, Electrolytic treatment at a current density of 5A / dm2 (less than the limit current density) for 80 seconds. • A copper roughened layer containing tungsten and iron was formed with a surface roughness of Ra1.7ym. Furthermore, (4) and (1) 5) After the treatment, the same method as in Example 1 (6) was used to measure the adhesion strength and copper residue, and the results of the powder drop test are shown in Table 1. I ^ 装Ordering (please read the precautions on the back before filling this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies Chinese national standards (CMS > A4 (210 X297 mm) -23 -499508

V. Description of the invention (21 Table 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, followed by the intensity-unit: kN / m, and then the strength of the residual copper drops off powder Example 1 2.0 Button M Example 2 1.9 Μ j \ w -frrr. Till Φ * \\ Example 3 1.9 Group M / »Example 4 Group 2.0, \ 4τττ. TCTT! / · ,, Example 5 2.1 Μ /» χ > Μ j \ w Example 6 1.9 Bottleless V t ,, Example 7 1.0 Μ / i \\ Μ J \ w Example 8 0.9 Μ > ι, ν J 1 Comparative Example 1 0.9 Μ diameter 0.1 #m order countless comparative example 2 0.9 κ diameter 0.1 β m order countless comparative example 3 1.0 ίκ / ΟΝ diameter 1 " m-class countless comparative examples 4 1.3 dirty / ον «Μ ,, comparative example 5 1.6 diameter 1 0 // m or less 1 5 diameters 2 to 10 μm 23 comparative examples 6 0.5 diameter 1 8 diameters below 0 m 2 ~ 1 0 mm 15 comparative examples 7 0.5 diameter 1 0 // m below 7 diameters 2 to 1 0 // m 18 comparative examples 8 1.7 diameter 10 μm 2 diameters 2-10 / Z m 3 (please read the notes on the back before filling this page)-$ This paper size is applicable to Chinese National Standard (CNS) A4 (210 × 297 mm) -2 4- 499508 No. 090 1 095 8 0 Patent application text Scope of the original patent application Kunming ?! Republic of China 丨 丨 on the 13th of November Amendment D8 VI. Patent application scope 1 · A roughened copper foil, which It is characterized in that copper foil is provided with (I) copper, (II) one or more metals selected from tungsten and molybdenum, and (III) at least one metal selected from nickel, cobalt, iron, and zinc. Into a composite metal layer, and the copper adhesion amount is .5, 000 ~ 10, 〇OO / zg / dm2, and the adhesion amount of more than one metal selected from tungsten and molybdenum is 10 ~ 1, 〇〇〇 # g / dm2, a composite metal layer with an adhesion amount of at least one metal selected from nickel, cobalt, iron, and zinc of 10 to 1, 00 / zg / dm2, and then disposed on this layer on a dendritic copper electrode layer Formed by a nodular copper made of a roughened layer made of copper. 2. For example, the roughened copper foil of item 1 of the patent application scope, wherein the roughened layer made of copper is made of copper. The adhesion amount is 30,000 ~ 300,000 / ^ g / dm2 " 3. A method for manufacturing a roughened copper foil, which is characterized in that the copper foil is used as a cathode, Containing (i) a copper ion, (i i) a metal ion selected from tungsten and molybdenum metal and one or more of (i i i) a nickel, read back of the note

I t Gutter line Electrolyzed on the electroplating on the printing and plating office of the Consumer Cooperative Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs I kind of electricity I limit € less bounded, to the bath of copper > full I choose not {zinc reason and by iron borrowed 1 > cobalt bath reason ο kind ο I ο less-to 5 ½. In order to measure the amount of iron, copper, zinc, and cobalt that are attached to zinc, and the layer of nickel is composed of a compound I and I, I and C, and the metal is above the gold g ο less y 1 to ο ο Selected, attached zinc ο 1 is iron ~ gold, the amount d. is / attached to g of y. is ο gold, ο 2 ο above m, with d 1 species of cobalt, with nickel species Choose from 1 »2 out of m and select d. Molybdenum / This paper size applies to China National Standards (CNS) A4 (210X297 mm) _1 · 499508

6. The scope of patent application is 1, 0 0 0 // g / dm2 composite metal layer, and then on this composite metal layer, an electroplating bath containing copper ions is used, and electrolytic treatment is performed at a current density above the limit current density of the bath and A dendritic copper electrode layer is formed, and then electrolytic treatment is performed at a current density that is less than the limit current density of the full bath to form nodular copper, and a roughened layer made of copper is provided. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) • v * ··

This paper size applies to China National Standard (CNS) A4 (210X297 mm)-2-