TW200528585A

TW200528585A - Copper electrolysis solution for production of electrolytic copper foil and process for producing electrolytic copper foil

Info

Publication number: TW200528585A
Application number: TW093134090A
Authority: TW
Inventors: Akiko Sugimoto
Original assignee: Mitsui Mining & Smelting Co
Priority date: 2003-11-21
Filing date: 2004-11-09
Publication date: 2005-09-01
Also published as: CN1748048A; JP2005154815A; KR20060037433A; WO2005049895A1; TWI267566B; US20070017816A1

Abstract

This invention is to provide a copper electrolysis solution for production of electrolytic copper foil, with which a foil of low roughness, in which the configuration and size of heaps of rough surface of deposited foil are uniformalized can be obtained while substantially inhibiting any occurrence of yielding of deposited foil attributed to control of the molecular weight and concentration of protein, etc.; and a process for producing an electrolytic copper foil with the use of the copper electrolysis solution. There is provided a copper electrolysis solution for production of electrolytic copper foil, in which a protein of 1000 to 2300 number average molecular weight Mn is contained in a concentration of 2 to 4.5 ppm. The Cu<SP>2+</SP> concentration of the electrolysis solution is preferably in the range of 60 to 100 g/l. Further, the free SO4<SP>2-</SP> concentration of the electrolysis solution is preferably in the range of 60 to 250 g/l. Still further, the Cl<SP>-</SP> concentration of the electrolysis solution is preferably in the range of 0.5 to 2.0 ppm. Moreover, there is provided a process for producing an electrolytic copper foil, in which use is made of the above copper electrolysis solution for production of electrolytic copper foil.

Description

200528585 九、發明說明【發明所屬之技術領域】本發明係有關於_ 解電解㈣㈣電解液以及電粗楚面之ίΓ 細說明之，係錢於-種適於製造 '、一致、低粗糙度的電解銅箔之製 =電解mi用銅電解液以及電解㈣之製造方法。【先前技術】電解銅箱係由含有銅離子的銅電解液在由鈦等所形成的陰^上使銅電析出來而得到的箱（析出箱）、或者在 :析出泊的表面形成瘤狀物等同時設置金屬層或有機成 :之名（表面處理泊）’而被廣泛用來作為印刷電路板的製作材料等。再者，#出㈣、由於在如上述的陰極上電析出來而得到纟’一般而言，陰極側的面（光澤面、有光睪勺面或S面）以及光澤面的相反面（粗糖面、無光粗链勺面或Μ面）兩者表面的形狀或粗糙度不同。亦即，一般而言，析出箔的光澤面大致被複製成陰極表面的形狀而呈現平滑狀，另一方面，粗糙面係在電析時於成長的銅的表面呈現很多咼低差（粗糙度）為數μπι左右的山形突起者。而表面處理猪通常並未對析出荡的粗糙面之山形突起特別加以研磨等，大致在照原來的狀態下進一步實施形成瘤狀物等的表面處理，故其粗糙面的表面形狀深受析出箔的粗糙面之表面形狀的影響。亦即，對於電解鋼箔，控制析出落的粗糙面之山形突起（以下亦僅稱為「山」）的形狀及大小是相當重要的。 2213-6640-pp 5 200528585 然而’電解銅箔用作印刷電路板的製作材料時，由於銅》I與聚酯膠片等別種材料之間的黏合性等要求較高，故主要使用藉由表面形狀的控制等而改善黏合強度等的表面處理箔。然而，表面處理箔如上述，其表面形狀由於深受成為基底的析出箔之表面形狀的影響，故對於或是作成使黏σ強度等的物性穩定者、或是在進行積層時確保絕緣性，期望析出箔的粗糙面之山的形狀及其大小能一致。另一方面，由於近年來與其對於印刷電路板的薄型化之要求丄不如要求銅笛本身的薄型化，故表面處理箱、進而析出箱的粗鞭面之山的粗趟度亦期望能較小些。作為析出羯的粗糙面之山的粗糙唐 f A # J丁k度具體而S，期望析出箔的厚度為 35μιη、Rz 為 4·2μιη 以下。對於析出荡的粗糖面，作為使山的形狀-致且降低粗糙度的技術係，以往銅電解液中 J合禋離子的濃度之控制等各種技術被揭露出來。苴中 ⑬出來#中將蛋白質或動物質的朦（以下亦％為「蛋白質等）下亦#支「疋合解於銅電解液之水溶液（以下亦％為蛋白質等水溶液」。），一邊# _ 此猶光、、六、、右遺持績添加既定量的心'，一邊進行電解來製造析出箔，此A 糙度箔之製造作A π 此為對於低粗衣k作為重要的原因而為習知者。亦即，一般認為在銅電解液中的蛋白子量會影響到、寻的/辰度或分听出V白的粗链面之山的他的物性，因此 >丨6 ^ 的形狀或粗糙度等其 U此測疋在銅電解液中的蛋子量之方法係習4 、等的/辰度及分友你I知者（特開2001 — 3 蛋白質等僅靜署報）。並且，静置於銅電解液中即會 s刀解而使分子量變200528585 IX. Description of the invention [Technical field to which the invention belongs] The present invention is a detailed explanation of _ electrolytic solution and electrolytic rough surface, which is a kind of suitable for manufacturing, consistent, low roughness Production of electrolytic copper foil = copper electrolytic solution for electrolytic mi and manufacturing method of electrolytic tincture. [Prior art] The electrolytic copper box is a box (precipitation box) obtained by electrolytically depositing copper on a cathode formed of titanium or the like using a copper electrolyte containing copper ions, or a nodular surface is formed on the surface of the precipitation poise It is also widely used as a material for the production of printed circuit boards. In addition, # 出㈣ is obtained by electrolysis on the cathode as described above. In general, the cathode-side surface (glossy surface, shiny spoon surface, or S-surface) and the opposite surface of the glossy surface (crude sugar) Surface, matte rough chain spoon surface, or M surface) The shapes or roughness of the two surfaces are different. That is, generally speaking, the glossy surface of the precipitation foil is roughly copied to the shape of the cathode surface and appears smooth. On the other hand, the rough surface shows a large difference in roughness (roughness) on the surface of the copper grown during electrolysis. ) Are mountain-shaped protrusions of several μm. The surface-treated pigs usually do not specifically grind the mountain-shaped protrusions of the rough surface that precipitates, and roughly perform the surface treatment such as forming nodules in the original state. Therefore, the surface shape of the rough surface is deeply affected by the precipitation foil. Influence of the surface shape of the rough surface. That is, for electrolytic steel foil, it is important to control the shape and size of the mountain-shaped protrusions (hereinafter also simply referred to as "mountains") of the rough surface that has fallen out. 2213-6640-pp 5 200528585 However, when the electrolytic copper foil is used as a material for the production of printed circuit boards, the surface shape is mainly used because of the high adhesion between copper and other materials such as polyester film. It is a surface-treated foil for improving the adhesive strength and the like. However, as described above, the surface shape of the surface-treated foil is greatly affected by the surface shape of the precipitation foil that becomes the base. Therefore, it is necessary to make a stable physical property such as viscosity σ strength, or to ensure insulation during lamination. It is desirable that the shape and size of the rough surface mountains of the deposited foil be consistent. On the other hand, in recent years, rather than reducing the thickness of printed circuit boards, the thickness of the copper flute itself is not as good. Therefore, the roughness of the rough surface of the surface processing box and the precipitation box is also expected to be smaller. some. The rough surface f A # J, which is the mountain of the rough surface where precipitates are deposited, is specifically S, and it is desirable that the thickness of the deposited foil is 35 μm and Rz is 4 · 2 μm or less. Various techniques such as controlling the concentration of J complex ions in copper electrolytes have been exposed as a technique for uniformly precipitating the rough sugar surface of the mountain and reducing the roughness.苴中 ⑬ 出 ## in the protein or animal matter (hereinafter also referred to as "proteins"), also under the "branch solution in copper electrolyte solution (hereinafter also referred to as protein and other aqueous solutions.)", One side # _ Adding a given amount of heart to this light, six, and right legacy, while conducting electrolysis to produce a precipitation foil, this A roughness foil is manufactured as A π. This is an important reason for low coarse k For learners. That is, it is generally believed that the amount of protons in the copper electrolyte will affect the physical properties of the white chains of the thick chain surface of V, or the degree of appearance, and therefore the shape or roughness of> 6 ^ The method of measuring the amount of eggs in the copper electrolyte is Xi 4, etc. / Chen Du and friends who know you (Japanese Patent Application No. 2001-3 only static report). In addition, when left in the copper electrolytic solution, it will break down and change the molecular weight.

2213-6640-PF 6 2005285852213-6640-PF 6 200528585

/JV ㈣破消耗掉導致在銅電解係習知者。〜/辰度减低然而，在現場的操作方面，作為控及分子量的方法係，藉由胜A 貝寺的/辰度控制蛋白質等水溶液在製、寻的口口牌來續添加既定量的該蛋白五稭由持度控制於一定量，、/水洛液而將銅電解液中的濃不過疋依經驗上來實施為其實情。亦即，在現場的操作方面 ^ ,^ ^ ^ 寺、，冰加既定量的使用既定品牌的蛋白貝專之蛋白質裳ρ 貝寺水洛液，若不施行此種屬的方式，則難以製得叙中屬吊狀想低粗糙度的析出箱。 1八例如’在電解時弄 ,^ ± 、’曰蛋白貝荨水溶液的添加時間戋承加Ϊ的情形、哎新制 A _ 作銅電解液的情形，對於前者的情形，雖追加蛋白暂 1月曰、、、不足分量，如此即使添加不足分篁’所得到的析出箔的相疋刀之山的形狀或粗糙度也難以 σ復丨正㊉狀態的良好壯能 . 低的狀態，而有此η 1心即山的形狀整齊且粗糖度 —人析出泊的產率顯著降低的問題。而對於俊者的情形，/士丄，吏在作業正常狀態的條件下添加蛋白質的=命次，也難以得到粗糙面之山的形狀整齊且粗糙度低 1 有在作業開始初期的析出落的產率顯著降低的問 ^ 吏使用同一品牌的蛋白質，僅電解製造的生屋綠不同，；§Ρ Α女也有所侍到的箱的Μ面之山的形狀等發生變 1匕的問7^。因，JL· I月的目的在於提供一種製造電解銅箔用銅 2213 -6640 ~pp 200528585 電解液以及使用此銅電解液的電解銅箱之使起因於蛋白質等的分子量及濃度的管理:::二其中率問題實際上並不致發生，而能夠得到析：的產山的形狀及大小一致且具低粗糙度的箔。、迎輪面之【發明内容】對於上述實情’經本發明者專心致志研究的壯現’在製造電解銅ϋ用的銅電解液中所包含的蛋數均分子量幻農度各別在既定範圍内的銅電解液使種銅電解液，則_的粗糙面之山的形狀及大小一致且具低粗糙度，以至完成本發明。亦即’本發明提供一種萝斤表乂電解銅、治用銅電解液，係製造電解銅箔用的銅電解 ” 所包含的蛋白質係數均分j电解及中 J刀子里為1000〜2300、且濃度為 2ppm〜4_5ppm。另於本發明中，箭 „ n 1A 則述銅電解液係Cix2 +濃度為 60g/l〜l〇〇g/l 較佳。又於本發明中，俞、+、 71 月j34鋼電解液係游離S042-濃度為60g/l 〜250g/l較佳。 6 並且於本發明φ α Γ τ ’刚述銅電解液係 cr濃度為 0.5ppm〜2.0ppm 較佳。而且於本發明中，/ JV Depleted consumption leads to knowledge in copper electrolysis. ~ / Chen degree reduction However, in terms of on-site operation, as a method of controlling molecular weight, a solution of Katsu Abeji's / Chen degree control protein and other aqueous solutions are manufactured and searched to continue to add a predetermined amount of the The protein five straw is controlled by a certain amount, and the concentration in the copper electrolyte is not based on experience. That is, in the field operation ^, ^ ^ ^, ice, the use of a predetermined amount of protein of the established brand of protein shellfish, pei temple water liquid, if you do not implement this method, it is difficult to make In the description, it is a precipitation box with a low roughness and a hanging shape. 18 For example, 'During the electrolysis, ^ ±,' said the time when the protein shellfish aqueous solution was added, and the new system A _ was used as the copper electrolyte. For the former case, although the protein was temporarily added for 1 month, Said, ,, insufficient, so that even if the amount of precipitated foil obtained by adding insufficient tillering's shape, the shape or roughness of the ridges of the swords are difficult to sigma 丨 the good state of the normal state. Low state, but this The shape of the η 1 heart, that is, the mountain is neat and the degree of coarse sugar is a problem that the yield of human precipitation is significantly reduced. However, in the case of a handsome person, it is difficult to get the shape of the rough surface mountain and the roughness to be low when the protein is added under the condition of normal operation. 1 There are precipitations at the beginning of the operation. Questions about significantly reduced yield ^ The official uses the same brand of protein, but only the green house made by electrolysis is different; §Ρ Α is also changed in the shape of the M-faced mountain of the box 7 ^ . Therefore, the purpose of JL · I month is to provide a 2222 -6640 ~ pp 200528585 electrolytic copper foil for electrolytic copper foil and the electrolytic copper box using the copper electrolytic solution to manage the molecular weight and concentration due to proteins and the like ::: The second rate problem does not actually occur, but it is possible to obtain a foil with a uniform shape and size and a low roughness. [Content of the invention] For the above-mentioned facts "Emerging from the intensive research of the present inventors", the number-average molecular weight of the eggs contained in the copper electrolyte used in the production of electrolytic copper tins, and the phantom degrees within the predetermined range, respectively. The copper electrolyte is a copper electrolyte, and the shape and size of the rough surface mountains are consistent and have low roughness, so that the present invention is completed. In other words, the present invention provides a “roofing table” electrolytic copper and copper electrolytic solution, which are used in the manufacture of electrolytic copper foil. ”The protein coefficients are divided into j electrolysis and middle j knives from 1,000 to 2300, and The concentration is 2 ppm to 4-5 ppm. In the present invention, the arrow “n 1A” indicates that the concentration of the copper electrolyte Cix2 + is 60 g / l to 100 g / l. In the present invention, it is preferable that the concentration of free S042- of the electrolyte solution of Yu, +, and 71 month j34 steel is 60 g / l to 250 g / l. 6 In the present invention, φ α Γ τ ′ The copper electrolyte-based cr concentration described above is preferably 0.5 ppm to 2.0 ppm. And in the present invention,

月y述銅電解液係溫度為40°C〜60°C 較佳。於：更且本發明提供一種使用前述製造電解鋼電解銅箔之製造方法，其特徵在箔用銅電解液。The copper electrolyte system temperature is preferably 40 ° C ~ 60 ° C. In addition, the present invention also provides a method for manufacturing electrolytic copper foil using the foregoing method, which is characterized by a copper electrolyte for foil.

2213-6640-PF 8 200528585 毛月提4共種電解鋼箱之製造方法，其特徵在於.則述電解電流密度為30A/cm2〜則⑽、發明效果：將雷紘t ;有關本發明的製造電解銅笛用銅電解液，由於 =:的銅電解液中所包含的蛋白質之數均分子量Mn t 於既定範圍内，故能夠得到析㈣的粗糖面之 :=且：低粗輪度的箔。並且，由於蛋白質通常丨(很谷易被分解，因此即使是數均分子量Μη L定範圍以上的蛋白質’因能夠使用此種蛋白質作為原料，故可使用的蛋白質的選擇範圍相當廣。更且，由的粗糖面之山的形狀整齊且具低粗糖度古 ' 貝的分子量及濃度的管理範圍明確，以往，一面對蛋白質的使用品牌予以特定來實際管 ::之數均分子量Μη，一方面添加既定量的該蛋白質的驟，而能夠在短二：:=驗上的作業標準步可製得i…，銅電解液，此銅電解液 t * 的粗糙面之山的形狀整齊且具低粗糙度的釣朽ΐ且，由於如此能夠在短時間内調製銅電解液，故能 =題咸少：因於銅電解液中的蛋白質的管理之析屋旱問述。甚且，由於你φ # 於使電解液中的蛋白質之目桿分早旦 2度儘量配合既定的管理值而解決蛋白質的管里 =容易：進行每條生產線的電解液之調製，而能夠快 .—線。又右利用有關本發明的電解銅箔之製造 …則藉由使用上述銅電解液，而能夠得到析出箱的粗糙2213-6640-PF 8 200528585 Maoyueti 4 manufacturing method of electrolytic steel box, which is characterized in that the electrolytic current density is 30A / cm2 ~ then, the effect of the invention: the thunder will be t; related to the manufacture of the present invention As the copper electrolyte for electrolytic copper flute, the number average molecular weight Mn t of the protein contained in the copper electrolyte of =: is within a predetermined range. Therefore, it is possible to obtain the analysis of the coarse sugar surface: = and: a foil with a low degree of roundness . In addition, since proteins are usually easily decomposed, even proteins having a number-average molecular weight Mη L or more within a certain range can be used as raw materials, so the selection of proteins that can be used is quite wide. Moreover, From the shape of the mountain of coarse sugar noodles, the management range of the molecular weight and concentration of the ancient shellfish with a low coarse sugar content is clear. In the past, the brand of protein was used to specify the actual number of molecular weights: Adding a given amount of the protein, and in a short 2 :: = test, you can prepare i ..., a copper electrolyte, and the shape of the rough surface mountain of this copper electrolyte t * is neat and low. Roughness of fishing and the copper electrolyte can be adjusted in a short time, so it can = less salty: due to the analysis of the management of the protein in the copper electrolyte, and even because of your φ # In order to make the protein of the electrolyte in the electrolyte 2 degrees earlier, try to match the predetermined management value to solve the protein in the tube = easy: the electrolyte of each production line is adjusted, and it can be fast. —Line For a right turn by the production of electrodeposited copper foil according to the present invention by using the above-described copper ... electrolyte solution, it is possible to obtain a rough precipitation tank

2213-6640-PF 200528585 面之山的形狀整齊且具低粗糙度的箔。【實施方式】 (有關本發明的製造電解銅箔用銅電解液）2213-6640-PF 200528585 The face of the mountain is neatly shaped and has a low roughness foil. [Embodiment] (Copper electrolyte for producing electrolytic copper foil of the present invention)

斤有關本發明的製造電解用銅電解液係^電解銅洛用的銅電解液。作為該銅電解液可為包含钢離子（Cy + )之可電解溶液，例如可使用酸性^，作為酸性浴，例如可使用硫酸浴等。硫酸浴係，由於所得到的析出荡的物J 良好、廢水處理容易’又能夠很容易地溶解係銅電解液的原料之銅線等，故較佳。、上述銅電解液係Cu2+濃度通常為6〇g/i〜i〇〇g/i、而 7〇g/卜90g"較佳。Cu2+濃度若小於6〇g/i，則由於溶液電阻較高’故不佳；又若超㉟1〇〇g/卜則由於容易析出硫酸銅的結晶，故不佳。上述銅電解液若為硫酸浴的情形，則游離s〇严濃度通常為2 SOg/MOgm 100g/1〜200g/1較佳。此處所‘離 SO’濃度係表示，將銅電解液中的Cu2+濃度換算為如山而得到S〇4 /辰度，並將此so/-濃度由在銅電解液中所包含的總SO,濃度減去後的乘m漢度。游離s〇42_漢度若小於60g/l，則由於溶液電阻較高，故不佳；又若超過 25 0g/l，則由於析出箔容易發生析出異常的情形，故不佳。本么月中所明析出磘係意指由包含銅離子的銅電解液中在由鈦等所形成的陰極上電析出銅所得到的銅绪，而未進行瘤狀物處理等的表面處理之銅箔，亦即未作表面處理銅箔。上述銅電解液係C1·濃度通常為〇 5ppm〜2 〇ppm、而 2213-6640-PF 10 200528585 up㈣七啊心。再者，以示mg/l。Cr濃度若小於 θ中所明ppm係表中由於山的形狀不良不’則於本發明的蛋白質濃度析出以產幻以孔，/又若料2.G州，則由於濃度及分子量譲之山的形狀等：;=範圍内的情形’由於 W 好有關析出箱之山的形狀之扯制，推測在蛋白質的濃戶 Β 二The present invention relates to a copper electrolytic solution for manufacturing electrolytic copper, which is a copper electrolytic solution for electrolytic copper. The copper electrolyte may be an electrolytic solution containing steel ions (Cy +). For example, an acid bath may be used, and as an acid bath, for example, a sulfuric acid bath may be used. The sulfuric acid bath system is preferable because the obtained precipitated substance J is good, wastewater treatment is easy, and the copper wire of the copper electrolyte raw material can be easily dissolved. The concentration of the above-mentioned copper electrolyte system Cu2 + is usually 60 g / i to 100 g / i, and 70 g / 90 g is preferred. If the Cu2 + concentration is less than 60 g / i, it is not good because the solution resistance is high; and when it is more than 100 g / b, it is not good because the crystals of copper sulfate are easily precipitated. When the copper electrolytic solution is a sulfuric acid bath, the free so concentration is usually 2 SOg / MOgm 100g / 1 to 200g / 1. Here, the "off SO" concentration means that the Cu2 + concentration in the copper electrolyte is converted into Rushan to obtain S04 / Chen, and the so / -concentration is the total SO, concentration contained in the copper electrolyte. Multiply the m-degrees after subtraction. Free 〇〇42_ Han degree If it is less than 60g / l, the solution resistance is high, so it is not good; if it is more than 250g / l, it is not good because the precipitation foil is prone to abnormal precipitation. The term "precipitated" as described in this month means the copper thread obtained by the electrolytic precipitation of copper on a cathode formed of titanium or the like in a copper electrolyte containing copper ions without surface treatment such as a nodule treatment. Copper foil, that is, copper foil without surface treatment. The concentration of the above-mentioned copper electrolyte system C1 · is usually from 5 ppm to 2 ppm, and 2213-6640-PF 10 200528585 up. Furthermore, is shown as mg / l. If the Cr concentration is less than the ppm shown in θ, it is because of the bad shape of the mountain in the table, the protein concentration of the present invention is precipitated to produce pores, and if the state is 2.G, the concentration and molecular weight of the mountain The shape, etc.:; = The range of the situation 'due to the good shape of the mountain of precipitation box, it is speculated that the protein is concentrated

/辰度及刀子$、與C 著某些相關關係。夂 < 間應存在上述銅電解液含有蛋白質。明膠、骨膠等。並且，為了；：二蛋白質，可舉出例如：為了使銅電解液含有蛋白質，通當將蛋白質溶解於水之後，、天 ^ 、傻/4、加该蛋白質水溶液於銅電解液所…、而作為氣作δ亥蛋白質水溶液時所使用的原料之蛋白質’係使用數均分子量Μη為⑽以上者。此理由係，蛋白質基於在銅電解液中或水溶液中會被分解等，由於數均分子量Μη降低，而將銅電解液中的數均分子量Μη作成後述的1000〜23 00，此#者八初你亏慮到分解，故比該下限值稍高些較佳。作為原料的蛋白質，例如，由於若能將銅電解液中的數均分子量Μη作成該範圍内者為佳，故未特別加以限定，但可使用例如：旭陽化學工業股份公司製DVM8〇、新田 GELATIN股份公司製UDB、新田GELATm股份公司製 SCP5000、新田GELATIN股份公司製7〇〇F等。上述銅電解液中所包含的蛋白質係數均分子量通常為1000〜2300、而1200〜2100較佳；且濃度通常為 2213-6640-PF 11 200528585 2ppm〜4.5Ppm、2.0ppm〜3 6ppm 較佳 3·6ΡΡχη以下更佳。銅電解液中的蛋^。過_2.5_並在及濃度若在上述範圍内，則由於可貝之數均分子量Μη 山的形狀及大小一致且呈低粗 ,斤出珀的粗糙面之於本發明中，所d度的箱，故較佳。再者，又θ γ所明蛋白質之數均分子旦均分子量Μη4 790以上的蛋白心：η及濃度意指數度。、數均为子量Μη及濃此處，將上述銅電解液中所量Μη及濃度、盥折〜龙白貝之數均分子示於第19圖，·將lit 之抗拉強度之間的關係顯 ^將上述銅電解液中所包含的蛋白里η及浪度、與析出箔的粗糙的刀係顯示於第20圖。於第19圖_ 度^之間的關包含的蛋白質之數均分子量表示銅電解液中所抗拉強度。並且，於第 4析出泊的常態之含的蛋白質之數均乂子^圖中’横轴表示鋼電解液中所包粗糙度Rze 'w，縱轴表示析出箱的粗越面之並且於第19圖及第2〇圖中濃度係將小於〗s 解液中的蛋白質的 Λ 收 PPm的試樣以正方形圖（以下箍灸「 A」，將形成圖A的群稱為、A群（Yf為「圖 1· 一.5Ppm的試樣以三角稱為)「表示；將形成圖B的群稱為冉為® B」，將試樣以縱菱形圖（以…)表示；將超過“Ppm的「圖C群」。）表示。」將形成圖C的群稱為由第19圖及第20圖，若比較孕乂圖Α群、圖Β群以及圖/ 辰度 and knife $, have some correlation with C.夂 < between the above copper electrolyte contains protein. Gelatin, bone glue, etc. In addition, for: two proteins, for example: In order to make the copper electrolyte contain protein, after dissolving the protein in water, add the aqueous solution of the protein to the copper electrolyte ... As the protein used as a raw material for the δ-hein protein aqueous solution, a protein having a number average molecular weight Mη of ⑽ or more is used. The reason is that the protein is decomposed in a copper electrolytic solution or an aqueous solution, and the number average molecular weight η decreases in the copper electrolyte, and the number average molecular weight η in the copper electrolytic solution is set to 1000 to 23 00, which will be described later. This # 者八初You are worried about decomposition, so it's better to be slightly higher than the lower limit. As a raw material, for example, the number-average molecular weight Mn in the copper electrolyte is preferably in this range, so it is not particularly limited. For example, DVM80 manufactured by Asahi Chemical Industry Co., Ltd. UDB made by Tian GELATIN Co., Ltd., SCP5000 made by Xintian Gelatm Co., Ltd., 700F made by Nitta GELATIN, and so on. The protein coefficient average molecular weight contained in the above copper electrolyte is usually 1000 ~ 2300, and preferably 1200 ~ 2100; and the concentration is usually 2213-6640-PF 11 200528585 2ppm ~ 4.5Ppm, 2.0ppm ~ 3 6ppm, preferably 3 · It is more preferable to be less than 6PPxη. Eggs in copper electrolyte ^. If the concentration and concentration are within the above range, the shape and size of the number-average molecular weight Mη of the scallop are the same and the thickness is low. Box, so it's better. In addition, protein cores having a number-average molecular weight and an average molecular weight Mη4 of 790 or more as indicated by θ γ: η and concentration index. The numbers are all the sub-quantity Mn and the concentration. Here, the number-average molecular Mn and concentration measured in the copper electrolyte described above are shown in Fig. 19. · The tensile strength between lit and The relationship is shown in FIG. 20 with the η and the wave length of the protein contained in the copper electrolyte and the rough blade system of the precipitation foil. The number average molecular weight of the protein included in Fig. 19 represents the tensile strength in the copper electrolyte. In addition, the number of proteins contained in the 4th normal state of precipitation is equal to ^. The 'horizontal axis' in the figure represents the roughness Rze' w contained in the steel electrolyte, and the vertical axis represents the rough surface of the precipitation box. The concentration in Figure 19 and Figure 20 is a square plot of the samples with PPm less than Λ of the protein in the solution (the following hoop moxibustion "A", the group forming Figure A is referred to as the A group (Yf Samples that are "Figure 1.1.5Ppm are represented by triangles" "; the group forming Figure B is called Ran Wei ® B", and the samples are represented by rhomboid diagrams (by ...); exceeding "Ppm "Picture C group." The groups that form graph C are called from graphs 19 and 20. If you compare the pregnancy graph A group, graph B group, and graph

2213-664 0-PF 12 200528585 μ ^則可判定銅電解液中所包含的蛋白質的濃度若為同等程度’則銅電解液中所包含的蛋白質之數均分子量Μη 越小、，析出箱的常態之抗拉強度有昇高的趨勢、且粗糙度、,Ζ有減1的趨勢。而且，若比較圖Α群、目β群以及圖C ^則可鋼電解液中所包含的蛋白質之數均分子量Μη 古二5等私度’則鋼電解液中所包含的蛋白質的濃度越、斤出省的#恶之抗拉強度有昇高的趨勢、且粗糙度Rz 有減小的趨勢。因而，可判定蛋白質之數均分子量論越 t且蛋白質的濃度越高，則析出荡的常態之抗拉強度有昇冋的趨勢、且粗糙度RZ有減小的趨勢。，如j述由於蛋白質之數均分子量Mn越小且蛋白質的 /辰度越阿’則析出箔的常態之抗拉強度越高、且粗糙度Rz 二j、故奴佳。然而，另-方面，蛋白質的濃度若太高，2213-664 0-PF 12 200528585 μ ^, it can be judged that if the concentration of the protein contained in the copper electrolyte is the same level, the smaller the number average molecular weight Mη of the protein contained in the copper electrolyte, the normal state of the precipitation box The tensile strength tends to increase, and the roughness and Z tend to decrease by 1. Furthermore, if the group A, the group β, and the figure C ^ are compared, the number average molecular weight of the proteins contained in the steel electrolyte may be equal to the degree of privacy. The tensile strength of #evil in the province has a tendency to increase, and the roughness Rz has a tendency to decrease. Therefore, it can be determined that as the number-average molecular weight of a protein increases and the concentration of the protein increases, the tensile strength of the precipitated normal state tends to increase and the roughness RZ tends to decrease. As described in j, since the smaller the number average molecular weight Mn of the protein and the greater the protein's / ° C, the higher the normal tensile strength of the precipitated foil, and the higher the roughness Rz, the better. However, on the other hand, if the protein concentration is too high,

則銅電解液的斑g A 黏度過局而有易起泡不甚理想的問題；並且’蛋白質之备始八 e 数句刀子$ Μη若太小，則由於在銅電解中所需的蛋白皙沾、曲Λ Α 电肝從、勺/辰度較高，如上述銅電解液的黏度過高而有易起泡不甚理想的問題’故本發明對於如上述蛋白質之數均分+吾Λ/Γ 艾㈡貝 Μη設置下限值以及對於蛋白質的濃度設置上限值。更且相對於鋼電解液中所包含的蛋白質之數均量Μη減小，則士戶丁則析出、冶的常態之抗拉強度昇高的情形，即對於第19圖 ^亦 ^軸（蛋白質之數均分子量Μη)之圖Α 群、圖Β群以；5 R ρThe copper electrolyte's spot g A viscosity is too high and there is a problem that it is not easy to blister; and 'If the protein is prepared, the number of knifes $ Μη is too small, because of the protein required in copper electrolysis. Zhan, Qu Λ Α electric liver, spoon / Chen degree is high, such as the above-mentioned copper electrolyte viscosity is too high and there is a problem of easy foaming is not ideal 'so the present invention is equal to the above number of proteins + Wu Λ / Γ Set the lower limit value and the upper limit value for the protein concentration. Moreover, compared with the decrease in the number average protein Mη of the protein contained in the steel electrolyte, the normal tensile strength of Shi Ruding precipitation and smelting will increase, that is, for the 19th figure ^ also ^ axis (protein Figure A group and Figure B group of the number average molecular weight Mη); 5 R ρ

、及圖C群各別形成的趨勢，可判定圖A 成的趨勢、圖只避 ^ B群形成的趨勢以及圖C群形成的趨勢之順, And the trend of the formation of graph C group, you can determine the trend of the formation of graph A, the trend that the graph only avoids ^ formation of group B, and the trend of the trend of formation of graph C group

2213-6640-PF 13 200528585 序越疋别者趨勢向右下 ^ ^ ΓΙ拿的私度越大，而越是後者趨勢向右下降的程度越小，趨勢接近水平。因此，銅電解液中的蛋白質的濃度越高’則相對於蛋白質之數均分子量Μη 的變化之析出箱的常態之抗拉強度的變化越遲純，可知受到銅電解液中的蛋白質的濃度之變化的影響以致析出“ 吊悲之抗拉強度較不容易零散分佈。另一方面，銅電解液中的蛋白質的濃度越低’則相對於蛋白質之數均分子量Μη 的變化之析出羯的常態之抗拉強度的變化越敏銳，可知受 =電解液中的蛋白質的漠度之變化的影響以致析出箱的常悲之抗拉強度較容易零散分佈。 —並且，相對於銅電解液中所包含的蛋白質之數均分子罝_減小，則粗趟度Rz減小的情形，亦即對於第2〇圖的檢軸（蛋白質之數灼分；数均刀子里Mn)之圖A群、圖b群以及圖C群各別形成的趨勢’可判定圖A群形成的趨勢、圖 B群形成的趨勢以及圖c群形成的趨勢之順 :勢向右上昇的程度越大，而越是後者趨勢向右上昇的； :越小’趨勢接近水平。因此’銅電解液中的蛋白質的濃度越面，則相對於蛋白質之數均分子4 Mn的變化之析出羯的粗糙度RZ的變化越遲鈍，可知受到銅電解液中的蛋白質的漠度之變化的影響以致析出落的粗糙度&較不容易零散分佈。另-方面，銅電解液中的蛋白質的濃度越低，： Γ於蛋白質之數均分子量胞的變化之析出箱的粗趟度 I的變化越敏銳，可知受到銅電解液中的蛋白質的濃声之變化的影響以致析出箱的粗糙度^較容易零散分佈艰又之 2213-6640-PF 14 200528585 此處’相電解液中所包含的蛋白f之數均分子量及f度的測定方法加以說明。該測定方法可使用特開扇一 337081號公報所揭露的方法，具體而言’可使用二用管柱並聯法的高i乘^ a』 Η更用基於併所測定的蛋白質之濃声月八工曰ν 士这層析法辰度及刀子直分布的測定方法等。該測 / 為移動相係使用乙膳3容量％以上“農別處理官柱❸真充劑係使用排除極限分子量為⑽以下 =尺寸排除模式的填充劑；而作為分離管柱的填充劑係使用排除極限分子量為彳nn 000以上的尺寸排除模式的填充劑 =用上離管柱係以2隻以上串聯接續者較佳。 : 的測疋方法來測定銅電解液中所包含的蛋白 ::分子量分布及濃度，從該分子量分布以算2213-6640-PF 13 200528585 The more the others tend to move to the lower right ^ ^ Γ Γ the greater the degree of privacy, and the more the latter tends to decrease to the right, the smaller the trend, the trend approaches the level. Therefore, the higher the concentration of the protein in the copper electrolyte, the later the purity of the precipitation box changes with respect to the change in the number average molecular weight Mη of the protein. The effect of the change results in the precipitation of "the tensile strength of the sorrow is less easily scattered. On the other hand, the lower the concentration of the protein in the copper electrolyte ', the lower the normal state of the precipitation relative to the change in the number average molecular weight Mη of the protein. The sharper the change in tensile strength, it can be seen that the tensile strength of the precipitation box is more likely to be scattered due to the influence of the change in the inertia of the protein in the electrolyte. And, compared with the copper electrolyte, When the number-average molecular 罝 _ of a protein decreases, the coarse degree Rz decreases, that is, the graph A group and graph b of the parity axis of Fig. 20 (number of protein burning points; number-averaging knife Mn). The trend of the formation of the group and the group C of the graph 'can determine the trend of the group A of the graph A, the group B of the graph, and the trend of the group c of graphs: the more the trend goes to the right, the more the latter trend to Ascending; "smaller" tends to approach the level. Therefore, the more concentrated the concentration of protein in the copper electrolyte, the slower the change in the roughness RZ of the precipitated radon relative to the change in the number-average molecular number 4 Mn of the protein. The influence of the change in protein in the copper electrolyte makes the roughness & of the precipitation less likely to be scattered. On the other hand, the lower the concentration of the protein in the copper electrolyte, the higher the number average molecular weight of the protein The change in the thickness of the precipitation box is more acute as the cell changes. It can be seen that the roughness of the precipitation box is affected by the change of the thick sound of the protein in the copper electrolyte. The roughness of the precipitation box is more easily scattered and difficult. 2213-6640-PF 14 200528585 Here, the method of measuring the number-average molecular weight of protein f and the degree of f contained in the phase electrolyte is described. The measurement method can be the method disclosed in Japanese Patent Application No. 337081, and specifically, it can be used. The high i multiplying ^ a ′ using the two-column parallel method is also based on the method of measuring the degree of protein concentration and the measurement of the straight distribution of the knife. The mobile phase uses more than 3% by volume of ethyl acetate. "Agricultural processing official column ❸ true charge system uses fillers with the exclusion limit molecular weight of ⑽ or less = size exclusion mode; and as the fillers of the separation column column uses the exclusion limit molecular weight is彳 nn 000 or more filler in size exclusion mode = It is better to use two or more serial connections in series from the upper column. : Method for measuring radon in copper electrolytes :: molecular weight distribution and concentration, calculated from the molecular weight distribution

I Μη。 J 刀 J 進7對蛋白f之數均分子量Μη及度的測定方法 4圖面加以詳細說明。第21圖係表示於本發明的蛋白質之數均分子量Μη及漠度之測定方法所使用的裝置之一實例的概略說明圖。第2】圖辦主- 、 W # 21圖所“的測定裝置具有··輸送泵、六通轉換間3、連接配置於輸送泵丨與六通轉換闊3的弟1連接口 4之間的注射哭？、由& 〇 ] 7耵σσ 2、連接配置於轉換閥的第2 接口 5之前處理管柱10、連接配置於前處理管柱10與，換閥的第5連接口 8之間的第j檢測器i2隻串聯地連接配置於轉換閥的第6連接口 9之分離管柱Μ. η、連接配置於分離管柱12與轉換間的第3連接口 6之間的第2 2213-6640 -PF 15 200528585 檢測器1 3、依擄在第2檢、、則„。白質的濃度及分子量分布之數棱卢的檢測數據用以求得蛋連接配置於轉換闕的第:連之=理裝置(未加以圖示)、對前處理管柱及該分離管^ 以及用以管最好使用p舰製或TE=7溫度的恒溫槽…配你^ , ⑽（註冊商標）製的管線。I Mη. J Knife J In 7 The method for measuring the number average molecular weight Mn and degree of protein f is described in detail on the drawing. Fig. 21 is a schematic explanatory diagram showing an example of an apparatus used in the method for measuring the number average molecular weight Mη and the degree of indifference of the protein of the present invention. No. 2] Master of measurement, W # 21 The measuring device "as shown in the figure has a transfer pump, a six-way conversion room 3, and is connected between the transfer pump and the brother 1 connection port 4 of the six-way conversion space 3. Injection cry ?, by & 〇] 7 耵 σσ 2. Connect the pre-treatment tubing string 10 arranged at the second interface 5 of the switching valve, and connect the pre-treatment tubing string 10 and the fifth connection port 8 of the valve changer. The j-th detector i2 is connected in series only to the separation column M. arranged at the sixth connection port 9 of the switching valve, and the second 2213 connected between the separation pipe string 12 and the third connection port 6 between the transitions. -6640 -PF 15 200528585 Detector 1 3, Depend on the 2nd inspection, then ... The detection data of the concentration and molecular weight distribution of white matter are used to obtain the number of eggs connected to the conversion tube: Lianzhi = Physical device (not shown), the pretreatment column and the separation tube ^, and For the pipe, it is best to use a thermostatic bath of p-ship system or TE = 7 temperature ... with your ^, ⑽ (registered trademark) pipeline.

作為檢測器11及13，处私认t R 此夠祆出mg/I級的蛋白質，使用-般：於高速液相層析法之檢測器，例如可使用光度檢測态。並且，於本於明中’基於以檢測器Η及13 欢的數據用以求得蛋白質的濃度及分子量分布，可使用具備此種演算功能的任何數據處理裝置。 ” 使用如上述的測定裝置加以測定時，首換閥3使第丨連接口 4與轉 …第6連接”連通=、:通、使第5連接連通並使弟3連接口 6與第4連接 :7連通。在這種狀態下，例如由〇〇〇5μ硫酸與置：亡、:5J 5的混合溶液所形成的移動相，藉由輸送泵^ 以-定流量使此移動相依以下順序來流動：移動相容哭 Μ輸送泵i注射器2六通轉換閥3前處理管柱1〇°° 第1檢測器11六通轉換閥3分離管柱12、12第2檢測器13六通轉換閥3廢液泵14。在這種狀態下，將= f蛋白質的電解液2004直接地或以純水稀釋的試樣200μ1 ’射。。中。電解液流入了填充著排除極限分子量為以下的水系之尺寸排除模式填充劑之前處理管柱 1〇例如收納著 Amersham Pharmacia Biotech Co· Ltd 制、As the detectors 11 and 13, t R is sufficient to detect the mg / I class protein, and is generally used as a detector in high-speed liquid chromatography, for example, a photometric detection state can be used. In addition, in the present invention, the concentration and molecular weight distribution of the protein are determined based on the data of the detector Η and 欢, and any data processing device having such a calculation function can be used. ”When the measurement is performed using the measurement device as described above, the first valve 3 is connected to connect the fourth connection port 4 to the sixth connection”. : 7 connected. In this state, for example, a mobile phase formed by a mixed solution of 005 μ sulfuric acid and acetic acid: 5J 5 is transported by a pump ^ at a fixed flow rate in the following order: mobile phase Rongmei M Delivery pump i Syringe 2 Six-way switching valve 3 Pre-treatment column 10 ° First detector 11 Six-way switching valve 3 Separation pipe string 12, 12 Second detector 13 Six-way switching valve 3 Waste liquid pump 14. In this state, an electrolyte solution 2004 of f protein was shot directly or a sample 200 µ1 'diluted with pure water was shot. . in. The electrolyte solution flows into the pre-treatment column 10 filled with a water-based size exclusion mode filler with an exclusion limit molecular weight of 10 or less. For example, Amersham Pharmacia Biotech Co. Ltd.

Sephadex G — 15(排除極限分子量為1500 )的内徑7 5mm、 2213-6640 -PF 16 200528585 長度25〇細^ ?咖製管柱中。流入前處理管柱ι〇之電解液係猎由尺寸排除層析法的分離原理加以分離，分子量 =大：蛋白質先溶出’其後係低分子量物質的電分再溶出。 :由前處理管柱10所溶出的蛋白質及電解質成分於 -心11、例如吸收光度檢測器以測定波I 21〇麵來 ^:蛋白料人分離管柱12、12之後而在大量的電解貝成刀導入分離管故彳9 1 9十上· &往12 12之剛，切換六通轉換閥使第1 連接口4與第6連接口9連通，使第3連接口6與第2連接口5連通，並使第5連接口8與第4連接口7連通。在此狀恶下，移動相依以下順序來流動：移動相容器Μ輸达泵1注射器2六通轉換閥3分離管柱12、12第2 =測器13 $通轉換閥3冑處理管柱H)帛1檢測器六通轉換閥3舰泵14，將電解質成分經由廢液栗 I:排出系統外。再者，若採用上述蛋白質的濃度及分子量分:之測定方法，則由於可測定一般分子量79〇以上的蛋白質’故當六通轉換閥切換時’需注意勿使分子量79〇以上的蛋白質排出系統外。旦導入分離管柱12的蛋白質係依其分子量的大小、分子里分布來加以分離並溶出。所溶出的蛋白質於第2檢測器、例如吸收光度檢測器以測定波長2i〇nm來檢測，基於該檢測數據以數據處理裝置來求得蛋白質的濃度及分布。於上述測疋方法中，藉由在分離管柱之前連接前處王」 22l3~664〇-pp 17 200528585 官柱，因能夠在移動相的流動中自動地分離蛋白質與電解 I成分，故不需要在注入注射器之前施行預處理，因此可在測定中儘量抑制蛋白質的分解。並且，因大量共存的電解質成分可藉由切換六通轉換閥而排出系統外，故亦少受到共存物質的影響。更且，因能夠測定分離管柱中的蛋白質之分子量分布，故亦可得到分子量的資訊，而能測定蛋白質的隨時間變化之分解情形。。上述銅電解液通常將銅電解時的溫度設為4〇t〜6〇 C 5 5 c車乂佳。溫度若在該範圍内，則所得到析出箔，由於粗糙面之山你 ^ 的形狀及大小一致且易具低粗糙度’故較佳。再者，、、W疮4 , 概度右小於40 c，則由於粗糙面之山的形狀易顯粗裂，故$社. 总… m ’又若超過贼，則由於氯乙烯官線等的設備容易加速老化、劣化，故不佳。 ^ 上述銅電解液能夠藉由 :曲危-Γ立丨m 〜表/ίΓ木裝造。例如，銅展度可利用既有的銅電解液以趄古.V9 岭蜱釗m屑4的銅原料而予以&同，游離so?-濃度或而+ _古^ θ 飞U/辰度可猎由添加硫酸或鹽酸而予以“。並且’銅電解液中的及濃度，可藉由在利用上述、之數均刀子里· 需要量的經調整至所需的數二方:：以測定之後，添加來加以調整。里Μη之蛋白質水溶液 (有闕本發明的電解銅箔之製造方去） =就有關本發明的電解… 明。该方法係使用上述製造電解鋼落用銅^方法加兒出箔者，作為製造析出羯的方、1解液來製造析〆σ使用習知的方法。作為 2213-6640-ρρ 18 200528585 習知的析出落之製造方法，可舉出例如：在旋轉極的曲面狀陰極表面與陽極之間供給銅電解液，進;; :’在陰極表面析編笛，並對此㈣連續捲:: 本發明所使用的銅電解液在電解時的溫度通常設為4〇 C、而45°C〜55t較佳。溫度若在該範圍内，則所得到的析嶋粗糙面之山的形狀及大小一：：度，故較佳。再者，溫度若 'v j於40 c，則由於粗糙面之山的形狀易顯粗裂，故不佳· 山管線等的設備容“速:化度通=:電::在電解時的電解電流密而 40A/cm2〜60A/cm2 較佳。電解電流密度若在該範圍 y 則所得到的析出箔係粗糙面之山的形狀及大小一致且異 ^ 且易具低粗糙度，故較佳。並且，陰極表面作適當的研磨較較佳。 W思Μ土’例如’將K作成1.2陣〜1.5pm 銅電解液可用作製造粗糙面之山的形狀及大小一且具低粗糙度的析出箔之原枓。該低粗糙度的析出箔係泊与為35μιη的析出箔，斗粗&面的粗糙度Rz通常為4·2μπι 45 0k f/而〜3.2_車交佳，且常態的抗拉強度通常為 45.0kgf/mm以上。此處，所-^〜立北各所明I意指十點平均粗糙度；斤口月吊悲思才曰在常溫的測定之製有關本發明的電解銅羯便用於上述析出荡之製造。以下雖係顯示實施例，然本發明並不限於這些實施例Sephadex G-15 (excludes the limiting molecular weight of 1500) in an inner diameter of 7 5mm, 2213-6640-PF 16 200528585 length of 250 mm thin? The electrolytic solution flowing into the pre-treatment column ι〇 is separated by the principle of size exclusion chromatography. Molecular weight = large: protein is dissolved first ', and then the low-molecular-weight substances are dissolved again. : Protein and electrolyte components eluted from the pre-treatment column 10 in the core 11 such as the absorption photometric detector to measure the wave I 21 ° surface ^: Protein material is separated from the column 12 and 12 in a large amount of electrolytic shell Introduce the separation tube into the knife, so 9 1 9 is up. &Amp; To 12 12, just switch the six-way switching valve to connect the first connection port 4 and the sixth connection port 9 and connect the third connection port 6 to the second connection port. The interface 5 is in communication, and the fifth connection port 8 and the fourth connection port 7 are in communication. In this situation, the mobile phase flows in the following order: mobile phase container M delivery pump 1 syringe 2 six-way switching valve 3 separation pipe string 12, 12th = tester 13 $ pass switching valve 3 胄 processing pipe string H ) 帛 1 detector six-way switching valve 3 pump 14 to discharge the electrolyte components through the waste liquid pump I: outside the system. In addition, if the above method for measuring the concentration and molecular weight of a protein is used, it is possible to measure proteins with a general molecular weight of 79 or more 'so when the six-way switching valve is switched', be careful not to let proteins with a molecular weight of 79 or more out of the system outer. Once introduced into the separation column 12, the protein is separated and eluted according to its molecular weight and molecular distribution. The eluted protein is detected by a second detector, such as an absorption photometric detector, at a measurement wavelength of 2 nm, and the concentration and distribution of the protein are determined by a data processing device based on the detection data. In the above radon measurement method, by connecting the former king before separating the column "22l3 ~ 664〇-pp 17 200528585 official column, because the protein and electrolytic I components can be automatically separated in the mobile phase flow, so no need Pretreatment is performed before injection into the syringe, so protein degradation can be suppressed as much as possible during the measurement. In addition, since a large amount of coexisting electrolytic components can be discharged out of the system by switching the six-way switching valve, it is also less affected by coexisting substances. Furthermore, since the molecular weight distribution of the protein in the separation column can be measured, the molecular weight information can also be obtained, and the degradation of the protein over time can be measured. . In the above-mentioned copper electrolytic solution, the temperature during copper electrolysis is usually set to 40 to 60 C 5 5 c. If the temperature is within this range, the precipitated foil obtained is preferable because the shape and size of the rough surface mountain are consistent and easy to have low roughness'. Moreover, W and W ulcer 4, the probability is less than 40 c, because the shape of the rough surface mountain is easy to be cracked, so the total agency. M ... If it exceeds the thief, because of the official vinyl chloride line, etc. Equipment is not easy to accelerate aging and deterioration. ^ The above copper electrolyte can be made of: Qu Wei-Γ 立丨 m ~ 表 / ίΓ wood. For example, the copper spread can be obtained from the copper raw material of the ancient Cu. V9 Lingzhao m chip 4 using the existing copper electrolyte. The same, free so? -Concentration or + _ ancient ^ θ Fei U / Chen degree It can be added by adding sulfuric acid or hydrochloric acid. And the concentration and concentration of the copper electrolyte can be adjusted by using the above and the number of the knife. The required amount can be adjusted to the required number of two :: to determine After that, it is added for adjustment. The protein solution of Mη (the manufacturing method of the electrolytic copper foil of the present invention) = for the electrolysis of the present invention ... This method uses the above-mentioned method of manufacturing copper for electrolytic steel. For those who produce foil, a conventional method is used as a method for producing precipitated tritium, and a solution is used to produce precipitated sigma. As a conventional method for manufacturing precipitated drop 2213-6640-ρρ 18 200528585, for example, rotating A copper electrolyte is supplied between the curved surface of the cathode and the anode;; ': The flute is analyzed on the surface of the cathode, and the coil is continuously rolled :: The temperature of the copper electrolyte used in the present invention during electrolysis is usually set It is preferably 40 ° C and 45 ° C ~ 55t. If the temperature is within this range, The shape and size of the obtained mountain of rough surface analysis is 1: degree, so it is better. Moreover, if the temperature is' vj at 40 c, the shape of the mountain of rough surface is easy to crack, so it is not good. The capacity of equipment such as mountain pipelines is: speed: chemical degree =: electricity :: The electrolytic current during electrolysis is dense and 40A / cm2 ~ 60A / cm2 is preferred. If the electrolytic current density is in the range y, the shape and size of the mountains of the precipitated foil-based rough surface obtained are consistent and different, and it is easy to have low roughness, so it is preferable. In addition, it is better to properly polish the cathode surface. For example, W can be used to make K from 1.2 arrays to 1.5 pm. The copper electrolyte can be used as the source of the precipitated foil having a shape and size of a mountain with a rough surface and low roughness. The low-roughness precipitation foil is moored with a precipitation foil of 35 μm. The roughness Rz of the rough & surface is usually 4 · 2 μm 45 0k f /, and ~ 3.2_ the car is good, and the normal tensile strength is usually 45.0kgf / mm or more. Here, each of the north and south states I means ten-point average roughness; Jinkouyue sorrowful thought that the electrolytic copper tincture of the present invention, which is measured at room temperature, is used for the above-mentioned precipitation. Although the examples are shown below, the present invention is not limited to these examples.

2213-6640-PF 19 200528585 所解釋者。〔比較例1〕作為製作析出箔之電解裝係截面長方形，且一方面使用續供給電解液，一方面使用可數0 •槽内液量 •陽極面與陰極面之大小 •陽極的材質 •陰極的材質 •陽極一陰極之間的距離作為銅電解液係添加硫酸於.、、屯水中並加以溶解以調製一 A ) 〇置’陽極一陰極之間的流路循環系在陽極一陰極之間連電解的下述規範之材質與參 ·· 4.5公升 ·· 6cmx 11 cm ·· DSE :鈦板 :5mm 硫酸銅5水合物、及鹽酸述組成的溶液（基本溶液2213-6640-PF 19 200528585 Explained. [Comparative Example 1] As an electrolytic device for producing a precipitation foil, the cross section is rectangular, and on the one hand, it is used to continuously supply the electrolyte, on the other hand, it can be counted as 0. • The amount of liquid in the tank • The size of the anode and cathode surfaces • The material of the anode • the cathode Material • The distance between the anode and the cathode is added as sulfuric acid to the copper electrolyte system, and dissolved in water to prepare an A). The circulation path between the anode and the cathode is between the anode and the cathode. Materials and parameters of the following specifications with electrolysis: 4.5 liters. 6cmx 11 cm. DSE: Titanium plate: 5mm copper sulfate pentahydrate and a solution (basic solution)

• Cu2+濃度 :82.5g/l :150g/l •游離S〇42_濃度• Cu2 + concentration: 82.5g / l: 150g / l • Free S〇42_ concentration

• cr濃度 ^ ' i.7ppm UDR — 作為明膠係使用新田gelatin股份公 DB，將此UDB溶解^^ p 膠水溶液A)。解於純水中調製¥的明膠水溶液由A'、 ^力S膠水溶液A於基本溶液A中至明膠成為1 ·8ρριη為止，奋八的明㈣刀授拌’調製電解液Α。電解液之數均刀子ϊ Μη及濃度如第】表所示。再者，明膠之數蛉八7 Θ 句刀子$ Μη及濃度係使用第21 2213一6640-pp 20 200528585 示的裝置，以下述測定條件所求得者。 (測定條件） •前處理管柱：收納Amersham Pharmacia• cr concentration ^ 'i.7ppm UDR — As a gelatin system, Nitta Gelatin Co., Ltd. DB was used, and this UDB was dissolved ^^ p Aqueous Solution A). A solution of gelatin solution prepared in pure water was prepared from A 'and A solution of gelatin A in the basic solution A until gelatin became 1.8 ρριη. The number and the concentration of electrolytes are shown in the table below. In addition, the number of gelatin 蛉 87 7 Θ sentence $ Μη and concentration were obtained using the apparatus shown in 21 2213-6640-pp 20 200528585 under the following measurement conditions. (Measurement conditions) • Pre-treatment column: Amersham Pharmacia

Biotech Co·，Ltd·製、Sephadex G — 15 的粒徑 66μιη 以下的填充劑（排除極限分子量1500 )之内徑7.5mm、長度250mm 的PEEK製管柱。 •分離管柱 ··昭和電工（股份）公司製、A PEEK column made of Biotech Co., Ltd., Sephadex G-15, a filler with a particle size of 66 μm or less (excluding the limiting molecular weight of 1500), with an inner diameter of 7.5 mm and a length of 250 mm. • Separation column • Showa Denko Corporation

Asahipak GS — 320HQ (排除極限分子量 40000、内徑 7.6mm、長度 300mm)Asahipak GS — 320HQ (Excluding limiting molecular weight 40,000, inner diameter 7.6mm, length 300mm)

•溫度：25°C •移動相的種類與流量：乙腈20容量％與稀硫酸 (0.005 Μ ) 80容量％的混合溶液0.6ml/分鐘 •注入量 ·· 200μ1 •檢測法：210nm的UV吸收再者，對於明膠的數均分子量Μη之測定係，使用於校正曲線之製作的試藥如下所示。而明膠的濃度係藉由使用同種的明膠的已知濃度之水溶液來製作校正曲線加以測定。 (試藥） • ALBUMIN.BOVINE SERUM ( Sigma-Aldrich Japan 股份公司製、分子量66000 ) • CYTOCHROME C( Sigma-Aldrich Japan 股份公司製、分子量12400 ) • APROTININ ( Sigma-Aldrich Japan 股份公司製、分 2213-6640-PF 21 200528585 子量6500 ) • INSULIN ( Sigma-Aldrich Japan 股份公司製、分子量 5734 ) • INSULIN CHAIN B?OXIDIZED ( Sigma-Aldrich Japan 股份公司製、分子量3496 ) • NEUROTENSIN ( Sigma-Aldrich Japan 股份公司製、分子量1673 ) • ANGIOTENSIN II ( Sigma-Aldrich Japan 股份公司製、分子量1046 ) • VAL-GLU-GLU-ALA-GLU ( Sigma-Aldrich Japan 股份公司製、分子量576 ) 於調製電解液A之後，立即以下述條件施行電解來製作析出箔。• Temperature: 25 ° C • Type and flow rate of mobile phase: Mixed solution of 20% by volume of acetonitrile and 80% by volume of dilute sulfuric acid (0.005 Μ) 0.6ml / min • Injection volume: 200μ1 • Detection method: UV absorption at 210nm The measurement system for the number-average molecular weight Mη of gelatin is as follows. The concentration of gelatin is determined by using a calibration curve of an aqueous solution of a known concentration of the same kind of gelatin. (Test drug) • ALBUMIN.BOVINE SERUM (manufactured by Sigma-Aldrich Japan Co., Ltd., molecular weight 66000) • CYTOCHROME C (manufactured by Sigma-Aldrich Japan Co., Ltd., molecular weight 12400) • APROTININ (manufactured by Sigma-Aldrich Japan Co., Ltd., sub 2221- 6640-PF 21 200528585 Sub-weight 6500) • INSULIN (Sigma-Aldrich Japan Co., Ltd., molecular weight 5734) • INSULIN CHAIN B? OXIDIZED (Sigma-Aldrich Japan Co., Ltd., molecular weight 3496) • NEUROTENSIN (Sigma-Aldrich Japan Co., Ltd. (Molecular weight, 1673) • ANGIOTENSIN II (manufactured by Sigma-Aldrich Japan Co., Ltd., molecular weight 1046) • VAL-GLU-GLU-ALA-GLU (manufactured by Sigma-Aldrich Japan Co., Ltd., molecular weight 576) Immediately after preparing electrolyte A, Electrolysis was performed under the following conditions to produce a deposited foil.

•銅電解液的溫度 ·· 52°C •電解電流密度：50A/cm2 •析出猪的厚度：3 5 μ m 對於所得到的析出箔，測定粗糙面的粗糙度Ra、Rmax 及Rz、常態的抗拉強度、以及常態的拉伸。測定方法係如下所述。測定結果如第2表及第3表所示。並且，拍攝所得到的析出箔之粗糙面的表面之掃描型電子顯微鏡（SEM ) 照片。其結果如第1圖所示。 •粗糙度Ra、Rmax及Rz :使用尖端係Φ2μπι的鑽石球之接觸式的表面粗糙度計（小坂股份公司製、商品名稱： SEF — 3 0D )，測定所得到的析出箔的粗韆面之表面粗糙 2213-6640-PF 22 200528585 度。測定長度設為0.8mm。Ra、u &係依據mB〇6〇i 來加以測定，具體而言’ 1表示中心線平均粗糙度，· U 表示最大粗糙度；Rz表示十點平均值粗糙度。 •常溫抗拉強度：裁剪所得到的析出領以製作寬度 1⑽X長度10cm的測定試樣，將該試樣的長邊方向的兩ς 利用各別設置於裝置的上下方向的2處之類似老虎甜的央頭予以夾緊，設置妥使試樣的長邊方向成為上下方向，在常溫下將下方的夹頭仍然夹緊試樣並以速度5〇mm/min向 ^伸’而將所敎的抗拉強度之最大負荷當作常溫抗拉 :常溫拉伸··在測定常溫抗拉強度時，將所測定的拉伸之琅大值當作常溫拉伸。〔比較例2〕• Temperature of copper electrolyte: 52 ° C • Electrolytic current density: 50A / cm2 • Thickness of precipitated pigs: 3 5 μm For the obtained precipitated foils, the roughness Ra, Rmax, and Rz of the rough surface were measured. Tensile strength and normal tensile. The measurement method is described below. The measurement results are shown in Tables 2 and 3. Then, a scanning electron microscope (SEM) photograph of the surface of the rough surface of the deposited foil obtained was taken. The results are shown in Figure 1. Roughness Ra, Rmax, and Rz: The surface roughness meter (produced by Kosaka Co., Ltd., product name: SEF — 3 0D) of a contact-type surface roughness meter with a diamond ball of Φ 2 μm was used to measure the thickness of the rough surface of the deposited foil. Rough surface 2213-6640-PF 22 200528585 degrees. The measurement length was set to 0.8 mm. Ra, u & are measured in accordance with mB〇60i. Specifically, '1 represents the centerline average roughness, · U represents the maximum roughness, and Rz represents the ten-point average roughness. • Tensile strength at room temperature: The obtained precipitation collar was cut to make a measurement sample with a width of 1⑽X and a length of 10 cm. Two samples in the longitudinal direction of the sample were made using two tiger-like sweets which were respectively arranged at two places in the vertical direction of the device. The central head of the specimen is clamped, and the longitudinal direction of the sample is set up and down. At normal temperature, the lower clamp is still clamping the specimen and stretched at a speed of 50 mm / min. The maximum load of the tensile strength is regarded as the normal temperature tensile: normal temperature tensile ... When measuring the normal temperature tensile strength, the measured maximum value of tensile is regarded as the normal temperature tensile. [Comparative Example 2]

Up二7 =溶液”直到明_成為時，調製電解液B。電解：^乂:溶液δ" 及濃度如第1表所示。、月膠之數均分子量Μη 與比件由添加明膠水溶液Α 8°小時後，利用二？樣條件施行電解來製作析出落。態的拉伸。測定，士盅MX及I、常態的抗拉強度、以及常所得到的析出第3表所示。並且，拍攝 2圖所示。 "面的表面之SEM照片。其結果如第 2213-6640-ρρ 23 200528585 〔比較例3〕 ~酸鋼5水合物、及鹽酸述組成的溶液（基本溶液作為銅電解液係添加硫酸、於純水中並加以溶解以調製下 B ) 〇 • Cu2+濃度 :84.0g/l 150g/l •游離SO,濃度 • cr濃度 i A · 1.7ppmUp 2 7 = solution "until Ming_ becomes, prepare electrolyte B. Electrolysis: ^ 乂: solution δ " and the concentration are shown in Table 1. The number average molecular weight Mη of meniscus and the ratio by adding gelatin aqueous solution A After 8 ° hours, electrolysis was performed under two conditions to produce precipitates. Tensile strength was measured. The results are shown in Table 3 of the cup MX and I, the tensile strength in the normal state, and the precipitation that is usually obtained. Take the SEM picture of the surface shown in Figure 2. The results are shown in 2213-6640-ρρ 23 200528585 [Comparative Example 3] A solution of acid steel 5 hydrate and hydrochloric acid (the basic solution is used as copper electrolysis) Sulfuric acid was added to the liquid system, dissolved in pure water to prepare B) 〇 • Cu2 + concentration: 84.0g / l 150g / l • Free SO, concentration • cr concentration i A · 1.7ppm

二’添加日特水料a於基本成為2.7Ppm為止，充錢拌月“2 ’Add the Japanese special water material a until it basically reaches 2.7Ppm.

的明膠之數均分早、心電解液C。電解液C 數均刀子里Μη及濃度如第.^所示。於調製電解液C之德，办p 作析出箔。卩以下述條件施行電解來The number of gelatin is evenly divided, and the electrolyte C is early. The number of electrolytes and the concentration of Mη in the knife are shown in section ^. For preparing electrolyte C, do p as precipitation foil.电解 Electrolysis is performed under the following conditions

•銅電解液的溫度 •電解電流密度 •析出箔的厚度對於所得到的析出箔，粗糙面的粗糙度R、 a ^max 態的拉伸。測定結果如第2 所得到的析出箔之粗糙面的 3圖所示。：52〇C ·· 50A/cm2 :3 5 μηι 比較例1同樣地實施，測定 RZ、常態的抗拉強度、以及常表及第3表所示。並且，拍攝表面之SEM照片。其結果如第 L貫施例1〕對於電解液C，在1天巾添加明料溶液A共6 —PPm ( 口 δ十3PPm )，此係換算為電解液中的濃肩仃充分的攪拌，對於電解液〇在最初添加明膠水溶液• Temperature of copper electrolyte • Electrolytic current density • Thickness of precipitated foil About the obtained precipitated foil, the roughness R and a ^ max of the rough surface were stretched. The measurement results are shown in Fig. 3 of the rough surface of the deposited foil obtained in the second. : 52 ° C · 50 A / cm2: 3 5 µm Comparative Example 1 was carried out in the same manner, and RZ, the tensile strength in the normal state, and the normal and third tables are measured. Also, take a SEM picture of the surface. The results are the same as those in the first embodiment.] For electrolytic solution C, a total of 6-PPm (mouth δ ten 3PPm) of Ming material solution A was added to the towel for one day. For electrolytes, initially add an aqueous gelatin solution

2213 -6640-PF 24 200528585 後，§周製經過1 i M f 八^3 天的電解液D。電解液D中的明膠之數分子量Μη及濃度如第丨表所示。數均 ^用f解液D，㈣與比較们㈣條件製作析出箔。」电鮮木對於所付到的析出$，與比較例^㈣地實施粗键面的組糸ik ；§： "Ρ ΤΊ 、疋 . 。又3及RZ、常態的抗拉強度、以及常悲的拉伸。測定纟士果疋、、、口果如弟2表及第3表所示。所得到的析出箔之舨枓；拍攝 +檢面的表面之SEM照片。其社果士筮 4圖所示。乃，、、、口果如弟〔實施例2〕 ▲對於電解液D，在1天中添加明膠水溶液Α共6次每 Κ〇·5ρρηι (人斗 q 、母 PPm )，此係換算為電解液中的濃度，再 Μ的中重複進仃充分的攪拌，對於電解液C在最初添加明膠水溶液Α夕炫 #取仍从、加吏，調製經過6天的電解液Ε。電解液Ρ 中的明膠之數均分子量―濃度如D表所示Ε 製解液Ε’利用與比較例3同樣條件施行電解來奸得㈣析料㈣1同㈣實施，測定粗縫面的粗輪庶R 心此k a、R㈣及Rz、常態的抗拉強度、以及當悲的拉伸。測定結果如 >e ,,, 苐2表及弟3表所不。並且，拍攝所仔到的析出箱之斗之粗钛面的表面之SEM照片。其結果如M 5圖所示。 ^ 〔實施例3〕對於電解液E，— 在1天中添加明膠水溶液A共6次每2213 -6640-PF 24 200528585, § weekly produced electrolyte D after 1 i M f 8 ^ 3 days. The number of gelatin in the electrolytic solution D, the molecular weight Mn and the concentration are shown in Table 丨. Number average ^ Precipitation foil was prepared using f solution D, ㈣ and comparison conditions. "Electrical fresh wood For the precipitation $ paid, the rough bond surface group 糸 ik was implemented in accordance with the comparative example; §: " Ρ ΤΊ, 疋. 3 and RZ, normal tensile strength, and often sad stretch. Measurement of Shishiguo 疋 ,, and mouth fruits are shown in Table 2 and Table 3.舨枓 of the obtained precipitated foil; SEM photograph of the surface of the + inspection surface. Its social fruit is shown in Figure 4. ，，，果果如弟 [Example 2] ▲ For electrolyte D, gelatin aqueous solution A was added 6 times per day per KO · 5ρρηι (human bucket q, female PPm), which is converted into electrolysis The concentration in the liquid was repeatedly stirred in the medium, and the electrolyte C was initially added with a gelatin aqueous solution A 夕炫 #, and the electrolyte E was prepared after 6 days. Number average molecular weight of gelatin in electrolytic solution P-Concentration is as shown in Table D. Solution E is prepared under the same conditions as Comparative Example 3. Electrolysis is performed to obtain the precipitate, which is carried out in the same way. The rough wheel of the rough surface is measured.庶 R is the ka, R㈣, and Rz, the normal tensile strength, and the sad stretch. The measurement results are as shown by > e ,,, 表 2 and 3. Then, an SEM photograph of the surface of the rough titanium surface of the bucket of the precipitation box was taken. The results are shown in the M 5 diagram. ^ [Example 3] For electrolytic solution E,-gelatin aqueous solution A was added a total of 6 times per day

2213-6640-PF 25 200528585 次〇.5ppm (合計3ppm )，此位始μ 於7*由舌此係換鼻為電解液中的濃度，再於7天中重複進行充分的攪拌，對於電解液再明膠水溶液Α之後，調製經取初添加 13天的電解液F。雷赵2213-6640-PF 25 200528585 times 0.5ppm (total 3ppm), this position starts from 7 * Change the nose to the concentration in the electrolyte from the tongue, and then repeat sufficient stirring in 7 days. For the electrolyte After re-gelatin aqueous solution A, electrolytic solution F was prepared for 13 days. Lei Zhao

中的明膠之數均分子量M 電解液F u及/辰度如第1表所示。使用電解液F，利用φ h 製作析出箱。比“"同樣條件施行電解來奸=Γ寻到的析出辖，與比較例1同樣地實施，測定能❹伸 Ra、Rmax及Rz、常態的抗拉強度、以及常 I、的拉伸。測定結果如帛餅4曰釗衣及弟3表所不。並且，拍攝于、斤出箔之粗糙面的表面之議 6圖所示。、A ，、、、、口果如第〔比較例4〕作為明膠係你用身 , 斫田GELATIN股份公司製SCP5000，將此SCP5000溶解於紐^丄水溶液B ) 、、’、屯水中調製1 g/i的明膠水溶液（明膠 .% \ 』加月膠水溶液B於基本溶液B中至明膠濃度风馬4·5ρριγ|為止右的明膠之數均，、、八工一攪拌，調製電解液G，電解液G中刀子置Μη及濃度如第1表所示。调製電解液G之尨 ^ ^ ^ <傻，立即利用與比較例3同樣條件施订電解來製作析出箱。對於所得到的4 相权二、祈出箔，與比較例1同樣地實施，測定粗趟面的粗糙度 ^ ^ 能沾3 max及Rz、常態的抗拉強度、以及常所俨u A 疋W果如第2表及第3表所示。並|，拍攝所侍到的析出箔之如之粗^面的表面之SEM照片。其、结果如第The number-average molecular weight M of the gelatin in the electrolytic solution Fu and / ° C are shown in Table 1. Using electrolytic solution F, a precipitation box was produced using φ h. Precipitation was found under the same conditions as "" under the same conditions as in electrolytic electrolysis = Γ, and it was implemented in the same manner as in Comparative Example 1. The Ra, Rmax, and Rz, normal tensile strength, and normal tensile strength were measured. The measurement results are shown in Figure 4 and Figure 3, as shown in Figure 6. Figures taken on the surface of the rough surface of the foil are shown in Figure 6. Figure A, Comparative Example 4] As a gelatin system, use your own body, SCP5000 manufactured by Putian GELATIN Co., Ltd., and dissolve this SCP5000 in the aqueous solution of 纽丄丄 Aqueous solution B), 、, and tun water to prepare a 1 g / i gelatin aqueous solution (gelatin.% \ ” The aqueous gelatin solution B is in the basic solution B until the gelatin concentration is equal to the number of gelatins up to 4 · 5ρριγ |. As shown in the figure below: 傻 ^^^ for preparing electrolyte G, and immediately used the same conditions as in Comparative Example 3 to make a precipitation box. For the obtained 4-phase weight II, praying foil, and Comparative Example 1 The same is carried out to measure the roughness of the rough surface ^ ^ can be 3 max and Rz, normal tensile strength, And the usual results are shown in Tables 2 and 3. And |, the SEM photographs of the surface of the rough surface of the precipitated foil that were served were taken.

)~PF 2213-( 200528585) ~ PF 2213- (200528585

7圖所示D 〔實施例4〕、對於電解液G，在1天中添加明勝水溶液B共6次每 = 〇.5PPm (合計3ppm)，此係換算為電解液中的濃度，進 :充=掉’對於電解液G在最初添加明膠水溶… 调衣經過i天的電解液Η。電解液H中的明膠之刀子量Mn及濃度如第1表所示。 _ H’利用與比較例3同樣條D shown in Figure 7 [Example 4] For electrolyte G, Mingsheng aqueous solution B was added 6 times a day each = 0.5 PPm (total 3 ppm), which is converted into the concentration in the electrolyte. Charge = drop 'For electrolyte G, add gelatin and water-soluble at the beginning ... Adjust the electrolyte solution after i days. The knife amount Mn and concentration of the gelatin in the electrolytic solution H are shown in Table 1. _ H ’use the same as in Comparative Example 3

製作析出箔。 ^丁电鮮木二對於所得到的析出箱，與比較例1同樣地實施’測定粗韃面的粗键户R、R ，、A precipitation foil was produced. ^ 丁电鲜木 Second, the obtained precipitation box was carried out in the same manner as in Comparative Example 1, and the measurement was performed on the rough bond R, R,,

At 又a max及Rz、常態的抗拉強度、以及當恶的拉伸。測定么士果士楚 J疋、、、口果如弟2表及第3表所示。並且，拍s 所得到的析出箱之粗糙 8圖所示。的表面之SEM知、片。其結果如第〔實施例5〕 ▲對於電解液D，在1天中添加明膠水溶液B共6次每At and a max and Rz, the normal tensile strength, and the tensile strength. Determination of Mo Shi Guo Shi Chu J 疋 ,,, mouth fruit as shown in Table 2 and Table 3. In addition, the roughness of the precipitation box obtained by taking s is shown in FIG. 8. SEM image of the surface. The results are shown in [Example 5] ▲ For electrolyte D, gelatin aqueous solution B was added 6 times per day

、PPln ( D汁3ppm)，此係換算為電解液中的濃度，再重複進行充分的㈣，對於電解液g在最初添加月膠水 >谷液B之德，便调製經過6天的電解液I。雷解液τ 中的明膠之數均分子旦μ 刀子里Μη及濃度如第1表所示。使用電解液I，女丨田 J用與比較例3同樣條件施行電解來製作析出箔。對於所得到的松ψ # 出治，與比較例1同樣地實施，測定粗糙面的粗糙度rd a 及Rz、常態的抗拉強度、以及常, PPln (3ppm of D juice), which is converted to the concentration in the electrolyte, and then repeat the full ㈣, for the electrolyte g in the initial addition of moon glue > Valley liquid B virtue, it is prepared after 6 days of electrolysis液 I。 Liquid I. The number-average molecular weight of the gelatin in the thunder solution τ is shown in Table 1 and the concentration of Mn in the knife. Using electrolytic solution I, female and female J were subjected to electrolysis under the same conditions as in Comparative Example 3 to prepare a deposited foil. The obtained loose ψ # treatment was performed in the same manner as in Comparative Example 1, and the roughness rd a and Rz of the rough surface, the normal tensile strength, and the normal

2213-6640-PF 27 200528585 戶j拉伸。測定結果如第2表及第3表所示。並且，拍攝斤知到的析出箔之粗糙面的表面之SE昭 9圖所示。 …、月/…Q果如第〔實施例6〕次對於電解液E ’在1天中添加明膠水溶液B共6次每 :;.5Ppm (合計3ppm)，此係換算為電解液中的濃度，再明m重複進行充分的㈣，對於電解液g在最初添加中的:月：液B之後，調製經過13天的電解液J。電解液J 、，之數均分子量Mn及濃度如第丨表所示。作析出1電解液J，利用與比較例3同樣條件施行電解來製粗楚的析心1 ’與比較例1同樣地實施，測定祖才把面的粗糙产 ^ 能又a max及RZ、常態的抗拉強度、以及常心的拉伸。測定結果如第所得到的析出节…表及弟3表所不。並且’拍攝 1〇圖所*。，面的表面之SEM照片。其結果如第〔比較例5〕作為明膠伟# 此7〇〇F溶解於, GELATIN股份公司製7〇〇F，將液c)。； ”、屯水中調製1 g/i的明膠水溶液（明膠水溶2213-6640-PF 27 200528585 Household j stretch. The measurement results are shown in Tables 2 and 3. In addition, the SE image of the surface of the rough surface on which the foil was deposited was taken. …, Month /… Q as in the [Example 6] times For electrolyte E ', gelatin aqueous solution B was added 6 times a day each: .. 5Ppm (total 3ppm), which is converted into the concentration in the electrolyte Then, repeat the full repetition with m, and prepare electrolyte solution J after 13 days for electrolyte: g after the initial addition: month: solution B. The number average molecular weight Mn and the concentration of the electrolytic solution J are shown in Table 丨. Electrolyte J was used as precipitation 1 and rough centrifugation 1 'was carried out under the same conditions as in Comparative Example 3. Electrolysis was performed in the same manner as in Comparative Example 1. The roughness of the surface was measured by zucai. Tensile strength, and normal stretching. The measurement results are the same as in the precipitation section obtained in Table ... and Table 3. And ‘shoot the 10 map place’. SEM photo of surface. The results are shown in [Comparative Example 5] as gelatin. This 700F was dissolved in 700F manufactured by GELATIN Co., Ltd., and liquid c). ; ", 1 g / i gelatin aqueous solution prepared in water (gelatin water soluble

其次’添加明膦P W 成為I6ppm為止，谷液C於基本溶液B中至明膠濃度的明膠之數均八止，曰充分攪拌，調製電解液K。電解液K中士劊：刀子里Μη及濃度如第1表所示。凋製電解液Κ之播 η 设’立即利用與比較例3同樣條件施 2213-6640-pp 28 200528585 行電解來製作析出箱。對於所得到的析出箱，粗糙面的粗糙度R、 X 同樣地貫施，測定又〜、Rmax及Rz、當能从> ^ ^ 態的拉伸。測定結果如第2表及第^、几拉強度、以及常所得到的析以之粗糙面的表面之S腕:。，拍攝 11圖所示。、、〃、結果如第〔比較例6〕添加明膠水溶液c Ί ^ 於基本溶液Β中至明髁：曲命1 1.6ppm為止，且德月爆^辰度成為便不添加明膠而在時，調製電解液L。電解 ”…谷液0.5小及濃度如第！表所示 ^的明膠之數均分子量他使用電解液L’利用與_ 製作析出箔。银惊仵轭仃電解來奸IT:到的析出箱，與比較例1同樣地實施，測定租k面的粗糙唐β ^ ^ Λ匕u a、Rmax及Rz、常態的抗拉強度、以；5登態的拉伸。測定結果如第…帛…一所得到的析出％ #2表及弟3表所不。並且，拍攝冶之粗糙面的表面之SEM照片。 12圖所示。 /、、、、ϋ果如弟〔實施例7〕 —,、電解液Κ ’在7小時中添加明膠水溶液c共5，每次〇.5ppm(人斗人、— σ叶2.5PPm)，此係換算為電解液中的濃产，進行充分的谱j：坐 .t 夂Next, the number of gelatins in the valley solution C to the gelatin concentration in the base solution B is eight until the addition of the phosphine P W to 16 ppm, and the electrolyte K is prepared by sufficiently stirring. Electrolyte K 刽: The η and concentration in the knife are shown in Table 1. The seed bath of the withered electrolyte K was set to immediately use 2213-6640-pp 28 200528585 under the same conditions as in Comparative Example 3 to produce a precipitation box. About the obtained precipitation box, the roughness R and X of the rough surface were applied in the same manner, and Rmax, Rmax, and Rz were measured, and the stretching from the > ^^ state was measured. The measurement results are shown in Table 2 and Table ^, Chiral tensile strength, and S-wrist surface of the rough surface that is often obtained. , Shooting 11 shown in the picture. The results are as in [Comparative Example 6] Add the gelatin aqueous solution c Ί ^ to the basic solution B until the gelatin: Qu Ming 1 1.6ppm, and when the German moon bursts, it will be added without gelatin. The electrolytic solution L was prepared. "Electrolysis" ... Valley liquid 0.5 is small and the concentration is as shown in the table! The number average molecular weight of gelatin shown in the table ^ He uses the electrolyte L 'to make a precipitation foil. The measurement was carried out in the same manner as in Comparative Example 1. Rough surface β ^ ^ ^ ^ ua, Rmax, and Rz of the k-plane were measured, and the normal tensile strength and tensile strength were measured. The obtained precipitation% # 2 and 3 are not. Also, the SEM photograph of the surface of the rough surface was taken. It is shown in Fig. 12. / ,,,, ϋ 果如弟 [Example 7]-,, Electrolysis Liquid K 'added a total of 5 gelatin aqueous solution c in 7 hours, each time 0.5ppm (human fighting person,-σ leaf 2.5PPm), this system is converted to the concentrated production in the electrolyte, for a full spectrum j: sit. t 夂

半’對於電解液K在最初添加明膠水溶液之後，調製诚讲7 C 曰、，，二過7小％的電解液L。電解液L中的明膠之二刀子里Μη及濃度如第1表所示。 2213-6640 ~pp 29 200528585 利用與比較例使用電解液L，製作析出绪。同樣條件施行電解來比較例1同樣地實施，測定 z、常態的抗拉強度、以及常及第3表所示。並且，拍攝面之SEM照片。其結果如第After the electrolyte solution K was first added with an aqueous gelatin solution, the electrolyte solution L was prepared by 7C, and 2% by less than 7%. The η and the concentration of the gelatin in the electrolytic solution L are shown in Table 1. 2213-6640 ~ pp 29 200528585 Use and Comparative Example The electrolytic solution L was used to produce a precipitation thread. Electrolysis was performed under the same conditions, and Comparative Example 1 was performed in the same manner, and z, normal tensile strength, and normal and Table 3 were measured. Also, take a SEM picture of the surface. The result is as

對於所得到的析出箔，與粗糙面的粗糙度RRoughness R of the obtained deposited foil

a ^max 及 R 態的拉伸。測定結果如第2表所得到的析出箔之粗糙面的表 1 3圖所示。 L貫施例a ^ max and R state stretching. The measurement results are shown in Table 1 and Table 3 of the rough surface of the deposited foil obtained in Table 2. L

柞I二加月膠水洛液A於基本溶液B中，施行2天的添作業母天1〇次每攻Λ ^ u，5PPm合計i〇ppm，此係換算為電的/辰度’進行充分的授拌，調製電解液0。電解液中的明膠之數均公；曰歎^刀子$ Μη及濃度如第1表所示。用電解液〇，利用與比較例3同樣條件施行電解製作析出箱。對於所侍到的析出箔，與比較例1同樣地實施，測粗糙面的粗糙产R^ 負匕又a、Rmax及Rz、常態的抗拉強度、以及柞 I Erjiaojiao glue solution A in the basic solution B, performing 2 days of adding operation 10 times per day ^ ^ u, 5PPm total i0ppm per attack, this is converted to electrical / Chen degrees' to fully Of mixing, to prepare the electrolyte 0. The number of gelatins in the electrolyte are all common; the value of the knife and the concentration are shown in Table 1. An electrolytic solution was used and electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a precipitation box. The precipitated foil that was served was carried out in the same manner as in Comparative Example 1, and the roughness R ^ of the rough surface was measured. A, Rmax, and Rz, normal tensile strength, and

拉伸。測定結果如帛2表及第3表所示。並且，拍: 斤侍到的析出箔之粗糙面的表面之SEM照片。其結果如 14圖所示。〔比較例7〕冰加明膠水溶液B於基本溶液B中，施行2天的添作業每天1〇今夂Α Λ 、 _人母认〇.5ppm合計lOppm，此係換算為電液中的丨農$ 、又’添加後靜置3天，調製電解液P。電解液中的明腰夕缸α、 ’ 數均为子量Μη及濃度如第1表所示。 ΡΡ 2213-6640 - 30 200528585 同樣條件施行電解來使用電解液P’利用與比較例製作析出箔。對於所得到的析出箔粗糖面的粗糙度R、R a Rma: 表所示。，與比較例1同樣地實施，測定及。測定結果如第2表及第3 L貫施例9〕添加明膠水溶液B於基本作業每天!。次每-欠。5d ί 中’施行2天的添加液中n m °计1Gppm，此係換算為電解Stretch. The measurement results are shown in Table 2 and Table 3. In addition, a SEM photograph of the surface of the rough surface on which the foil was deposited was taken. The results are shown in Figure 14. [Comparative Example 7] A gelatin aqueous solution B was added to the basic solution B in ice, and the addition operation was performed for 10 days every day. 10 Λ Λ, _ mother's recognition 0.5 ppm, a total of 10 ppm, which is converted into the electro-hydraulic solution. $ 、 '' After adding for 3 days, the electrolyte P was prepared. The numbers α and ′ of the bright waist cylinder in the electrolytic solution are both the sub-quantity Mη and the concentrations are shown in Table 1. PP 2213-6640-30 200528585 Electrolysis was performed under the same conditions, and electrolytic solution P 'was used and a comparative example was used to produce a precipitation foil. The roughness R, R a Rma of the coarse sugar surface of the obtained precipitated foil is shown in the table. The measurement was performed in the same manner as in Comparative Example 1. The measurement results are shown in Table 2 and Example 3] Example 9] Gelatin aqueous solution B was added to the basic operation every day !. Times per-owed. 5d ί Medium ’added for 2 days 1 gppm in n m ° in the liquid, which is converted into electrolysis

Φ ^ , 視仵凋製電解液Q。電解液Q 夕之數均分子量Mn及濃度如第1表所示。用電解液Q ,利用與比較例3同樣條製作析出箔。 U电解木粗糙=所的析出帛’與比較例1同樣地實施，測定能二拉伸粗糙度Ra、u Rz、常態的抗拉強度、以及常心的拉伸。測定結果如帛2表及第3表所Φ ^, withered electrolyte Q. The number average molecular weight Mn and the concentration of the electrolytic solution Q are shown in Table 1. Using electrolytic solution Q, a precipitation foil was produced in the same manner as in Comparative Example 3. U electrolytic wood Roughness = Precipitated 帛 'was carried out in the same manner as in Comparative Example 1, and the tensile strengths Ra, u Rz, normal tensile strength, and normal tensile strength were measured. The measurement results are shown in Table 帛 2 and Table 3.

所得到的析出笔> # ^ 3 W /白之粗板面的表面之SEM照片。其結果如第 1 5圖所示。〔比較例8〕作為明膠係使用旭陽化學股份公司製Λ1576，將此 c)岭解於純水中調製1以1的明膠水溶液（明膠水溶液 :曲/、、、外加明膠水溶液C於基本溶液B中使溶液中的展度成為5Ppm，充分攪拌後，靜置5小時，調製電解液厌。電解液R中的明膠之數均分子量Μη及濃度如帛1表所示。SEM photograph of the obtained precipitation pen ># ^ 3 W / white rough surface. The results are shown in Figure 15. [Comparative Example 8] As a gelatin system, Λ1576 manufactured by Asahi Chemical Co., Ltd. was used. This c) was hydrolyzed in pure water to prepare a 1 to 1 gelatin aqueous solution (aqueous gelatin solution: koji / ,,, and gelatin aqueous solution C in a basic solution). In B, the spread in the solution was adjusted to 5 Ppm, and after sufficiently stirring, the solution was allowed to stand for 5 hours to prepare an electrolyte solution. The number average molecular weight Mη and the concentration of the gelatin in the electrolyte solution R are shown in Table 帛 1.

PF 2213-6640- 31 200528585 使用電解液R，利用與比較例製作析出箔、、’、；所传到的析出箔，與比較例1同樣地實施，測定 ::糙面的粗糙度Ra、Rmad Rz、常態的抗拉強度1及常〜：拉伸。測定結果如帛2表及第3表所示。並且，拍攝斤伃到的析出箔之粗糙面的表面之SEM照片。其結果如第 16圖所示。〔實施例1 〇〕PF 2213-6640- 31 200528585 Using electrolytic solution R, a precipitation foil was prepared using the same method as in Comparative Example. The transferred precipitation foil was carried out in the same manner as in Comparative Example 1. Measurement: Roughness Ra, Rmad of the rough surface Rz, normal tensile strength 1 and normal ~: tensile. The measurement results are shown in Table 2 and Table 3. Then, an SEM photograph of the surface of the rough surface of the deposited foil was taken. The results are shown in Figure 16. [Example 1 〇]

添加明膠水溶液A於基本溶液B中，施行2天、”母天15 — 人母次〇 5ppm合計i5ppm，此係換算為電解液中的/辰度，調製電解液s。電解液s中的明膠之數均分子量Mn及濃度如第！表所示。使用電解液S ’利用與比較例3同樣條件施行製作析出落。解；Add the gelatin aqueous solution A to the basic solution B, and execute it for 2 days, "mother day 15-mother and mother 0,5ppm total i5ppm, which is converted into / Chen in the electrolyte, to prepare the electrolyte s. Gelatin in the electrolyte s The number-average molecular weight Mn and the concentration are shown in Table 1. The electrolytic solution S ′ was used to produce precipitates under the same conditions as in Comparative Example 3. Solution;

、，對於所得到的析出箱，與比較例1同樣地實施，測定 :糙面的粗糙度Ra、Rmj I、常態的抗拉強度、以及常〜的拉伸。測定結果如帛2表及第3表所示。並且，拍攝所侍到的析出箔之粗糙面的表面之SEM照片。其結果如第〔比較例9〕加明膠水溶液A於基本溶液B中，施行2天的添加、業每天15 —人每次〇.5PPm合計15ppm，此係換算為電解液中的，辰度，其後使此溶液靜置80小時，調製電解液τ。電解液Τ中的明膠之數均分子量及濃度如帛工表所示。The obtained precipitation box was carried out in the same manner as in Comparative Example 1. The roughness Ra, Rmj I of the rough surface, the normal tensile strength, and the normal tensile strength were measured. The measurement results are shown in Table 2 and Table 3. Then, an SEM photograph of the surface of the rough surface of the deposited foil was taken. The result is as in [Comparative Example 9] Adding gelatin aqueous solution A to basic solution B, and adding it for 2 days, 15 per person per day, 0.5 PPm total 15 ppm, which is converted into the electrolytic solution. Thereafter, this solution was allowed to stand for 80 hours to prepare an electrolytic solution τ. The number average molecular weight and concentration of the gelatin in the electrolytic solution T are shown in the worksheet.

2213-6640-PF 32 200528585 使用電解液Τ，利用與比較例3同樣條件施行電解來製作析出箔。對於所得到的析出箔，與比較例1同樣地實施，測定粗糙面的粗糙度Ra、Rmax及Rz、常態的抗拉強度、以及常態的拉伸。測定結果如第2表及第3表所示。並且，拍攝所得到的析出箔之粗糙面的表面之SEM照片。其結果如第 1 8圖所示。〔第1表〕基本溶液的種類明膠水溶液的種類電解液的種類電解液中的明膠之Μη 電解液中的明膠之濃度（ppm) 比較例1 A A A 3400 1.8 比較例2 A A B 1400 0.6 比較例3 B A C 3100 2.7 實施例1 B A D 2000 3.0 實施例2 B A E 1600 2.4 實施例3 B A F 1300 2.2 比較例4 B B G 3200 4.5 實施例4 B B H 2000 3.0 實施例5 B B I 1700 2.6 實施例6 B B J 1400 2.4 比較例5 B C K 2500 1.6 比較例6 B C L 1700 0.8 實施例7 B C M 1700 2.2 實施例8 B A 0 1300 3.0 比較例7 B B P 1000 0.8 實施例9 B B Q 1300 2.6 比較例8 B C R 1500 1.4 實施例10 B A S 1500 3.2 比較例9 B A T 1300 0.8 〔第2表〕粗糙:面的粗糙度Ra (μηι) 粗才造面的粗糙度 (μηι) 粗糙:面的粗糙度Rz (μιη) 粗才造面之山的形狀之評估η 有關於粗糙面之山的備考圖比較例1 0.80 5.2 4.7 △ 山大而形狀不一致第1圖比較例2 1.36 9.0 7.2 Δ 山大而形狀不一致第2圖 2213-6640-PF 33 200528585 比較例3 0.77 5.8 4.8 △ 山大而形狀不一致第3圖實施例1 0.54 3.7 3.4 〇第4圖實施例2 0.66 4.2 4.0 〇第5圖實施例3 0.55 3.9 3.6 〇第6圖比較例4 0.61 4.4 4.0 〇第7圖實施例4 0.54 5.0 3.6 〇第8圖實施例5 0.58 3.9 3.6 〇第9圖實施例6 0.56 4.0 3.4 〇第10圖比較例5 0.85 5.9 5.1 X 山的大小零亂第11圖比較例6 1.04 7.3 6.3 X 山的大小零亂第12圖實施例7 0.47 3.5 3.0 〇第13圖實施例8 0.35 2.7 2.4 〇第14圖比較例7 0.52 3.7 3.3 — 無實施例9 0.40 3.0 2.8 〇第15圖比較例8 0.67 4.9 4.3 X 山的大小零亂第16圖實施例10 0.43 2.7 2.6 〇第17圖比較例9 1.0 6.9 5.4 X 山的大小零亂第18圖氺1〇·· 良好、△ 1 肖差、X :不良〔第3表〕常態抗拉強度 (kgf/mm2) 常態拉伸 (%) 比較例1 48.6 15.9 比較例2 45.5 11.7 比較例3 49.0 18.0 實施例1 51.1 8.3 實施例2 48.4 16.0 實施例3 51.2 16.4 比較例4 49.5 15.9 實施例4 51.7 15.3 實施例5 52.8 13.4 實施例6 51.7 16.4 比較例5 48.2 13.9 比較例6 46.0 15.5 實施例7 49.5 17.2 實施例8 58.1 11.2 比較例7 _ *1 __*1 實施例9 58.3 9.3 比較例8 44.7 16.6 實施例10 58.6 10.3 比較例9 55.8 9.1 *1 無數4 濛 2213-6640-PF 34 200528585 由弟1表〜第3表可判定，子量Μη及濃度在既定範圍内的粗糙面之山的形狀及大小一產業上可利用性：銅電解液中的明膠之數均分的電解液，所得到的析出箔致且具低粗糙度。 • 有關本發明的製造電解鋼箔用铜雷絲、产^ ^ ^ 9用硐電解液以及電解鋼每之製造方法能夠使用於電解鋼箔 / r 、 j /白之中的析出箔之製造。【圖式簡單說明】第1圖係於比較例1所得到的％ — i , ]的泊之粗糙面的SEM (掃拖式電子顯微鏡）照片。 v 第2圖係於比較例2所得到的％的v白之粗糙面的SEM照片。弟3圖係於比較例3所得刹沾# ^ 、冶之粗輪面的SEM照片。弟4圖係於實施例丨所得〃、v白之粗糙面的SEM照片。弟5圖係於實施例2所得的自之粗糙面的SEM照片。弟6圖係於實施例3所得 ^ Ί m r 的v白之粗糙面的SEM照片。弟7圖係於比較例4所得到的# ^ 8 FI ^ ^白之粗糙面的SEM照片。弟8圖係於貫施合"所得之筮Q同说狄—^丨，白之粗梭面的SEM照片。弟9圖係於貫施例5所得茧1 η同a μ — & , /白之粗糙面的SEM照片。弟1〇圖係於貫施例6所得至丨丨沾μ 片。的治之粗糙面的SEM照片 11圖係於比較例所得到的箱之粗糙面的 SEM照第12圖係於比較例6所得到的荡之粗輪面的靡照2213-6640-PF 32 200528585 An electrolytic solution T was used and electrolysis was performed under the same conditions as in Comparative Example 3 to produce a precipitation foil. About the obtained precipitation foil, it carried out similarly to the comparative example 1, and measured the roughness Ra, Rmax, and Rz of a rough surface, the normal tensile strength, and the normal tensile. The measurement results are shown in Tables 2 and 3. Then, an SEM photograph of the surface of the rough surface of the deposited foil was obtained. The results are shown in Figure 18. [Table 1] Kind of basic solution Kind of gelatin aqueous solution Kind of electrolytic solution Kind of gelatin in electrolytic solution Gelatin concentration (ppm) in electrolytic solution Comparative Example 1 AAA 3400 1.8 Comparative Example 2 AAB 1400 0.6 Comparative Example 3 BAC 3100 2.7 Example 1 BAD 2000 3.0 Example 2 BAE 1600 2.4 Example 3 BAF 1300 2.2 Comparative Example 4 BBG 3200 4.5 Example 4 BBH 2000 3.0 Example 5 BBI 1700 2.6 Example 6 BBJ 1400 2.4 Comparative Example 5 BCK 2500 1.6 Comparative Example 6 BCL 1700 0.8 Example 7 BCM 1700 2.2 Example 8 BA 0 1300 3.0 Comparative Example 7 BBP 1000 0.8 Example 9 BBQ 1300 2.6 Comparative Example 8 BCR 1500 1.4 Example 10 BAS 1500 3.2 Comparative Example 9 BAT 1300 0.8 [ Table 2] Roughness: Roughness of surface Ra (μηι) Roughness of rough surface (μηι) Roughness: Roughness of surface Rz (μιη) Evaluation of the shape of the rough surfaced mountain Comparative example 1 of mountain preparation chart 0.80 5.2 4.7 △ Mountain is large but shape is inconsistent Figure 1 Comparative example 2 1.36 9.0 7.2 Δ Mountain is large and shape is not consistent 2 Figure 2213-6640-PF 33 200528585 Comparative example 3 0.77 5.8 4.8 △ Large and inconsistent shape Figure 3 Example 1 0.54 3.7 3.4 〇 Figure 4 Example 2 0.66 4.2 4.0 〇 Figure 5 Example 3 0.55 3.9 3.6 〇 Figure 6 Comparative Example 4 0.61 4.4 4.0 〇 Figure 7 Example 4 0.54 5.0 3.6 〇 Figure 8 Example 5 0.58 3.9 3.6 〇 Figure 9 Example 6 0.56 4.0 3.4 〇 Figure 10 Comparative Example 5 0.85 5.9 5.1 X Mountain size disorder Comparative Example 6 1.04 7.3 6.3 The size of the X mountain is disordered Figure 12 Example 7 0.47 3.5 3.0 〇 Figure 13 Example 8 0.35 2.7 2.4 〇 Figure 14 Comparative Example 7 0.52 3.7 3.3 — No Example 9 0.40 3.0 2.8 〇 Figure 15 Comparative Example 8 0.67 4.9 4.3 Size of the X mountain is disordered Figure 16 Example 10 0.43 2.7 2.6 〇 Figure 17 Comparative Example 9 1.0 6.9 5.4 Size of the X mountain is disordered Figure 18 氺 1 ·· Good, △ 1 Shaw Poor, X: Bad [Table 3] Normal tensile strength (kgf / mm2) Normal tensile (%) Comparative Example 1 48.6 15.9 Comparative Example 2 45.5 11.7 Comparative Example 3 49.0 18.0 Example 1 51.1 8.3 Example 2 48.4 16.0 Example 3 51.2 16.4 Comparative Examples 4 49.5 15.9 Example 4 51.7 15.3 Example 5 52.8 13.4 Example 6 51.7 16.4 Comparative Example 5 48.2 13.9 Comparative Example 6 46.0 15.5 Example 7 49.5 17.2 Example 8 58.1 11.2 Comparative Example 7 _ * 1 __ * 1 Example 9 58.3 9.3 Comparative Example 8 44.7 16.6 Example 10 58.6 10.3 Comparative Example 9 55.8 9.1 * 1 Countless 4 Mongolia 2213-6640-PF 34 200528585 It can be determined from Table 1 to Table 3 that the sub-quantity Mn and concentration are within a predetermined range. The shape and size of the mountain with a rough surface-Industrial applicability: The electrolytic solution of the gelatin in the copper electrolyte is evenly divided, and the resulting precipitated foil has low roughness. • The manufacturing method of the copper wire for electrolytic steel foil, the electrolytic solution for producing ^ ^ ^ 9 and electrolytic steel pertaining to the present invention can be used for the production of precipitation foils among electrolytic steel foils / r and j / white. [Brief Description of the Drawings] Figure 1 is a SEM (scanning electron microscope) photograph of the rough surface of% -i,] obtained in Comparative Example 1. v Figure 2 is a SEM photograph of the rough surface of v white obtained in Comparative Example 2. Figure 3 is an SEM photograph of the chakra # ^ and Yezhi's rough wheel surface obtained in Comparative Example 3. Figure 4 is an SEM photograph of the rough surface of 〃 and v white obtained in Example 丨. Figure 5 is a SEM photograph of the rough surface of Zi obtained in Example 2. Figure 6 is an SEM photograph of the rough surface of v white obtained in Example 3. Figure 7 is a SEM photograph of # ^ 8 FI ^^^ white rough surface obtained in Comparative Example 4. Figure 8 is a SEM picture of the 梭 Q and Talking Di- ^ 丨 by Bai Shihe. Figure 9 is a SEM photograph of the rough surface of cocoon 1 η and a μ — / white obtained in Example 5. The picture of Brother 10 is obtained from Example 6 to μ μ. The SEM photograph of the rough surface of the surface of FIG. 11 is a SEM image of the rough surface of the box obtained in the comparative example. The 12th image is a photograph of the rough surface of the rough surface obtained in the comparative example 6.

2213-6640-PF 35 200528585 第1 3圖係於實施例7所得丨片片片片片片、卞則的箔之粗糙面的SEM照第14圖係於實施例8所得刭从# 、則的洎之粗糙面的SEM照第1 5圖係於實施例9所得丁 j的泊之粗糙面的SEM照第1 6圖係於比較例第17圖係於實施例第1 8圖係於比較例 8所传到的箔之粗糙面的SEM照 1 〇所侍到的箔之粗糙面的SEM照 9所得到的箔之粗糙面的SEM照所包含的蛋白質之數均態之抗拉強度之間的關第19圖係表示於銅電解液中分子量Μη及濃度、與析出箔的常係之曲線圖。第20圖係表示於銅電解液中所包含的蛋分子量-及濃度、與析出箱的粗糖面之粗键均關係之曲線圖。 & Ζ之間的第21圖係表示於本發明中的蛋白質之數均旦及濃度之測定方法所使用的裝置之一實例刀：Μη 【主要元件符號說明】 ”兄明圖。 1 一輸送泵、 2 —注射器、 3 —六通轉換閥、 2213-6640-PF 36 200528585 4 一第1連接口、 5 —第2連接口、 6 —第3連接口、 7—第4連接口、 8 —第5連接口、 9 —第6連接口、 I 0 —前處理管柱、 II —第1檢測益、 12—分離管柱（2隻串聯）、 1 3 —第2檢測器、 1 4 —廢液系、 1 5 —恒溫槽、 16 —移動相容裔。2213-6640-PF 35 200528585 Figure 1 3 is a SEM image of the rough surface of the foil obtained in Example 7 from piece 7 and piece 14 is a sample of the rough surface of the foil obtained in Example 8. Figure 15 of the SEM image of the rough surface of 洎 is a SEM picture of the rough surface of Ding Po's obtained in Example 9 Figure 16 is a comparative example Figure 17 is a comparative example Example 18 is a comparative example 8 SEM photograph of the rough surface of the foil transmitted 1 SEM photograph of the rough surface of the foil transmitted 10 SEM photograph of the rough surface of the foil obtained 9 Between the number-average tensile strength of the protein included Fig. 19 is a graph showing the molecular weight Mn and the concentration in a copper electrolytic solution and the conventional system of the precipitation foil. Fig. 20 is a graph showing the relationship between the molecular weight and concentration of eggs contained in the copper electrolyte and the coarse bonds of the crude sugar surface of the precipitation box. & Figure 21 between Z is an example of a device used in the method for measuring the number average density and concentration of a protein in the present invention. Knife: Μη [Description of Symbols of Main Components] Pump, 2-syringe, 3-six-way switching valve, 2213-6640-PF 36 200528585 4-1st connection port, 5-2nd connection port, 6-3rd connection port, 7-4th connection port, 8- 5th connection port, 9 — 6th connection port, I 0 — pretreatment tubing string, II — 1st test benefit, 12 — separation tube string (2 in series), 1 3 — 2nd detector, 1 4 — waste Liquid system, 1 5 — constant temperature bath, 16 — mobile compatible.

2213-6640-PF 372213-6640-PF 37

Claims

200528585 十、申請專利範園·· l種襄造電解銅荡用銅電解液，係製造電解銅的銅電解液，其牿M _ 係數均分子量⑽為H ^所一㈣白f 主、、〜2300、且濃度係2ppm〜4.5ppm 〇月專利範圍第1項所述的製造電解銅箔用銅電解液，其中f述鋼電解液係CU、度為6Gg/1〜10_。申1專利範圍第1項所述的製造電解銅箔用銅電解液’其中前述銅電解液係游離SCV-漠度為6〇g/1〜250g/1。申明專利範圍第1項所述的製造電解銅箔用銅電解液’其中前述銅電解㈣cr濃度為G.5ppm〜2.0ppm。、5.如申請專利範圍第W所述的製造電解銅箱用銅電解液，其中前述銅電解液係溫度為40亡〜60。。。咬直6.-種電解銅〉自之製造方法，其特徵在於：使用如申相專利範Μ 1項所述的製造電解㈣用銅電解液。種電解銅治之製造方法’其特徵在於：使用如申請專利範圍第2項所述的製造電解㈣用銅電解液。 ^種電解mi之製造方法’其特徵在於：使用如申 s月專利範圍第3項所述的製造電解mi用銅電解液。 9-種電解銅箱之製造方法，其特徵在於：使用如申言月專利範㈣4項所述的製造電解㈣用銅電解液。 10.-種電解銅箔之製造方法，其特徵在於：使用如申 Μ專利範圍第5項所述的製造電解㈣用銅電解液。、η·如中請專利範圍第6項所述的電解銅箱之製造方法，其中電解電流密度係3〇A/cm2〜7〇A/em2。 ~β64〇~ρρ 38 200528585 1 2.如申請專利範圍第7項所述的電解銅 '名之製造方法，其中電解電流密度係30A/cm2〜70A/cm ° 1 3 ·如申請專利範圍第8項所述的電解銅箔之製造方法，其中電解電流密度係30A/cm2〜7〇A/cm2。 14·如申請專利範圍第9項所述的電解銅箔之製造方法，其中電解電流密度係30A/cm2〜70A/cm2。 15.如申請專利範圍第10項所述的電解銅箔之製造方法’其中電解電流密度係30A/cm2〜7〇A/cm2。200528585 X. Apply for a patent Fan Yuan ·· A copper electrolyte for electrolytic copper smelting, which is a copper electrolytic solution for manufacturing electrolytic copper. Its 牿 M _ coefficient average molecular weight ⑽ is H ^ ㈣ white f main,, ~ 2300, and the concentration is 2ppm ~ 4.5ppm. The copper electrolyte for manufacturing electrolytic copper foil described in the first item of the patent scope in January, wherein the steel electrolyte is CU with a degree of 6Gg / 1 ~ 10 ~. The copper electrolytic solution for producing electrolytic copper foil according to item 1 of the scope of the application of claim 1, wherein the aforementioned copper electrolytic system has a free SCV-freeness of 60 g / 1 to 250 g / 1. The copper electrolytic solution for producing electrolytic copper foil according to item 1 of the stated patent scope, wherein the aforementioned copper electrolytic ㈣cr concentration is G.5 ppm to 2.0 ppm. 5. The copper electrolytic solution for manufacturing an electrolytic copper box as described in the scope of the patent application No. W, wherein the temperature of the aforementioned copper electrolytic solution is 40 to 60 ° C. . . Straight 6. A kind of electrolytic copper> The manufacturing method is characterized by using a copper electrolytic solution for manufacturing electrolytic tincture as described in item M1 of the patent application. A manufacturing method of electrolytic copper treatment is characterized by using a copper electrolytic solution for manufacturing electrolytic tincture as described in item 2 of the patent application scope. ^ A kind of manufacturing method of electrolytic mi 'is characterized by using a copper electrolytic solution for manufacturing electrolytic mi as described in item 3 of the patent application. 9- A method for manufacturing an electrolytic copper box, characterized in that a copper electrolytic solution for manufacturing electrolytic tincture is used as described in item 4 of the patent application. 10. A method for manufacturing an electrolytic copper foil, characterized by using a copper electrolytic solution for manufacturing electrolytic tincture as described in item 5 of the patent application. Η · The method for manufacturing an electrolytic copper box as described in item 6 of the Chinese Patent Application, wherein the electrolytic current density is 30A / cm2 to 70A / em2. ~ β64〇 ~ ρρ 38 200528585 1 2. The manufacturing method of the electrolytic copper name as described in item 7 of the scope of patent application, wherein the electrolytic current density is 30A / cm2 ~ 70A / cm ° 1 3 The method for manufacturing an electrolytic copper foil according to the item, wherein the electrolytic current density is 30 A / cm2 to 70 A / cm2. 14. The method for manufacturing an electrolytic copper foil according to item 9 of the scope of the patent application, wherein the electrolytic current density is 30 A / cm2 to 70 A / cm2. 15. The method for manufacturing an electrolytic copper foil according to item 10 of the scope of the patent application, wherein the electrolytic current density is 30 A / cm2 to 70 A / cm2.

2213-6640-PF 392213-6640-PF 39