WO2018180988A1 - Surface treatment fluid and surface treatment method for rolled copper foil, and method for manufacturing rolled copper foil - Google Patents
Surface treatment fluid and surface treatment method for rolled copper foil, and method for manufacturing rolled copper foil Download PDFInfo
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- WO2018180988A1 WO2018180988A1 PCT/JP2018/011707 JP2018011707W WO2018180988A1 WO 2018180988 A1 WO2018180988 A1 WO 2018180988A1 JP 2018011707 W JP2018011707 W JP 2018011707W WO 2018180988 A1 WO2018180988 A1 WO 2018180988A1
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- hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a surface treatment solution for rolled copper foil, a surface treatment method for rolled copper foil using the same, and a method for producing rolled copper foil.
- Rolled copper foil is used for flexible printed circuit boards (FPC), and has recently been rolled to reduce transmission loss in the high-frequency region, as well as to achieve higher density, thinner thickness, and finer / fine pitch. It is desired to treat copper foil smoothly.
- FPC flexible printed circuit boards
- Patent Document 1 a method using azoles, halogen ions and silver ions is known (Patent Document 1).
- Patent Document 1 a method using azoles, halogen ions and silver ions.
- etching progresses along the crystal grain boundary, and crater-like etching and pits occur, making it difficult to smooth the surface.
- the rolled copper foil is known to have excellent flexibility, and the crystal orientation is controlled so that a cubic texture after recrystallization annealing develops in order to improve the flexibility.
- crystal grains having locally different crystal grain orientations exist in the uniform crystal structure, and the etching rate of the part is different from the surrounding etching rate. It is considered that crater-like etching and pits are formed on the surface (for example, see Patent Documents 2 and 3).
- Non-Patent Document 1 Non-Patent Document 1
- the present invention relates to a surface treatment solution and a surface treatment method suitable for surface treatment of a rolled copper foil, and a method for producing the rolled copper foil.
- the present inventors have found that the above problems can be solved by a surface treatment liquid having a specific composition in which hydrogen peroxide and sulfuric acid are mixed in a specific molar ratio and an alcohol-based additive is added. That is, the present invention is as follows.
- Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3.
- this invention is as follows.
- Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3.
- the manufacturing method of rolled copper foil including processing a rolled copper foil surface by making a process liquid contact the rolled copper foil surface and dissolving the rolled copper foil surface.
- [5a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively: Hydrogen peroxide (A): 0.5-3.0% by mass Phenylurea (D): 0.005 to 0.3% by mass
- Phenylurea (D): 0.005 to 0.3% by mass The method for producing a rolled copper foil according to any one of [1a] to [4a].
- [7a] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3.
- Rolling in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0% by mass and the content of alcohol (C) is in the range of 0.1 to 5.0% by mass A surface treatment method for a rolled copper foil, comprising dissolving the surface of the rolled copper foil using a surface treatment solution for copper foil.
- [11a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively: Hydrogen peroxide (A): 0.5-3.0% by mass Phenylurea (D): 0.005 to 0.3% by mass
- Phenylurea (D): 0.005 to 0.3% by mass The surface treatment method for rolled copper foil according to any one of [7a] to [10a].
- [14a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively: Hydrogen peroxide (A): 0.5-3.0% by mass Phenylurea (D): 0.005 to 0.3% by mass
- a rolled copper foil having excellent smoothness can be obtained by using the processing solution for rolled copper foil of the present invention.
- a flexible printed circuit film capable of reducing transmission loss in a high frequency region, increasing the density, reducing the thickness, and further reducing the size and fine pitch is manufactured. be able to.
- FIG. 10 is a surface observation image by SEM (magnification 1000 times) of Examples 10 to 14.
- FIG. 6 is a surface observation image by SEM (magnification 1000 times) of Comparative Examples 1 to 6.
- the method for producing a rolled copper foil of the present invention comprises hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D), and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B).
- the ratio is in the range of 0.3 to 3.0
- the sulfuric acid (B) is in the range of 0.5 to 15.0% by mass
- the alcohol (C) is in the range of 0.1 to 5.0% by mass.
- a surface treatment liquid is brought into contact with the rolled copper foil surface to dissolve the rolled copper foil surface, thereby treating the rolled copper foil surface.
- the surface treatment liquid having the above composition is brought into contact with the surface of the rolled copper foil to dissolve the surface of the rolled copper foil.
- a rolled copper foil having excellent properties can be obtained.
- the surface treatment solution for rolled copper foil used in the present invention contains hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D). These will be described in detail below.
- Hydrogen peroxide (A) in the present invention is a component that functions as an oxidizing agent for copper.
- the hydrogen peroxide (A) used in the present invention is not limited, and a commercially available aqueous hydrogen peroxide solution can be used.
- a 60% industrial / electronic industry grade product manufactured by Mitsubishi Gas Chemical Co., Ltd. is preferably used. can do.
- the concentration of hydrogen peroxide (A) in the surface treatment liquid is preferably 0.5 to 3.0% by mass, more preferably 0.6 to 2.5% by mass, and particularly preferably 0.8. It is -2.0 mass%. When the concentration of hydrogen peroxide is in the above range, a good copper surface state and a suitable copper dissolution rate can be obtained.
- the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3 to 3.0, preferably 0.4 to 3.0, and more preferably 0.5 to 3. 0.
- the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is particularly preferably 0.5 to 0.9.
- the sulfuric acid (B) in the present invention is a component that functions as an etching agent for copper oxidized by hydrogen peroxide.
- the sulfuric acid (B) used by this invention For example, 95% special grade reagent made from Wako Pure Chemical Industries Ltd. can be used conveniently.
- the concentration of sulfuric acid (B) in the surface treatment liquid is 0.5 to 15.0 mass%, preferably 0.6 to 15.0 mass%, and more preferably 1.0 to 5.0 mass%. %. By being in this range, a good copper surface state and a suitable copper dissolution rate can be obtained.
- the alcohol (C) in the present invention includes all common alcohols, and is a component that improves the smoothness of the rolled copper foil surface.
- Specific examples of the alcohol (C) include monohydric alcohols such as methanol, ethanol and propanol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols and glycol ethers such as polyethylene glycol. Two or more of these can be used in combination.
- the concentration of the alcohol (C) in the surface treatment liquid is 0.1 to 5.0% by mass, preferably 0.5 to 5.0% by mass. By being in this range, a smooth surface state of the rolled copper foil can be obtained.
- Phenylurea (D) in the present invention is a component that improves the stability of hydrogen peroxide.
- limiting in the phenylurea (D) used by this invention For example, Wako Pure Chemical Industries Ltd. phenylurea can be used conveniently.
- the concentration of phenylurea (D) in the surface treatment liquid is preferably 0.005 to 0.3% by mass, more preferably 0.005 to 0.15% by mass, and still more preferably 0.005 to 0.3% by mass. 0.1% by mass. By being in this range, decomposition of hydrogen peroxide can be suppressed.
- the smoothness of the surface of rolled copper foil can be made more excellent by adjusting the amount ratio of phenylurea (D) as appropriate.
- the surface treatment liquid of the present invention can further contain water and other commonly used additives as long as the effects of the present invention are not impaired.
- a known etching rate adjusting agent such as an alkali, organic carboxylic acid, organic amine compound, or a copper ion supply source may be added as necessary to stabilize the etching rate.
- the water is preferably one from which metal ions, organic impurities, particle particles, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., more preferably pure water, and particularly preferably ultrapure water. .
- the surface treatment solution for rolled copper foil is prepared by uniformly stirring hydrogen peroxide (A), sulfuric acid (B), alcohol (C), phenylurea (D) and other components as required.
- the surface of the rolled copper foil is treated by bringing the surface treatment liquid into contact with the surface of the rolled copper foil to dissolve the surface of the rolled copper foil.
- the smoothness of the rolled copper foil surface can be made excellent by processing the rolled copper foil surface using the said surface treatment liquid.
- the method for bringing the surface treatment liquid into contact with the surface of the rolled copper foil is not particularly limited, and a known method such as dipping or spraying can be employed.
- the surface treatment liquid for rolled copper foil of this invention can be used for the surface treatment method of the well-known rolled copper foil by immersion, spraying, etc.
- the rolled copper foil used in the present invention is a generally known rolled copper foil, which is produced by repeating plastic processing and heat treatment of a copper or copper alloy ingot with a rolling roll, and has high flexibility and high crystal orientation. It is a copper foil having properties.
- the use temperature of the surface treatment liquid is not limited, but is usually 20 to 50 ° C., preferably 25 to 40 ° C., more preferably 25 to 35 ° C.
- the higher the use temperature of the surface treatment solution the faster the dissolution rate of copper.
- the temperature exceeds 50 ° C. the decomposition of hydrogen peroxide becomes undesirably severe.
- the treatment time of the surface of the rolled copper foil with the surface treatment liquid is not limited, but is usually 1 to 600 seconds, preferably 5 to 300 seconds, more preferably 10 to 180 seconds, and particularly preferably 15 to 120 seconds.
- the dissolution rate of the rolled copper foil by the surface treatment liquid is not limited, but the etching rate (E / R) is usually 0.4 to 4.0 ⁇ m / min, for example, under the treatment condition of 35 ° C., preferably 1 0.0 to 3.5 ⁇ m / min, and 1.5 to 3.0 ⁇ m / min is particularly preferable because the etching time can be shortened.
- the rolled copper foil of the present invention surface-treated with the surface treatment liquid is excellent in surface smoothness, and therefore can be suitably used for flexible printed wiring boards and the like.
- SEM scanning electron microscope
- the brightness of the rolled copper foil before and after the surface treatment was determined using the standard deviation by setting the single-threshold value of the contrast of the concave and convex portions on the surface of the copper foil to 47, using the histogram as the series, and using the standard deviation.
- the relationship is satisfied, and the smoothness is excellent.
- the numerical value (%) represented by the above formula is more preferably ⁇ 5% or less, and further preferably ⁇ 10% or less.
- ⁇ (Luminance of copper foil after treatment) ⁇ (luminance of untreated copper foil) ⁇ / (luminance of untreated copper foil) ⁇ 100% ⁇ (Brightness of copper foil after treatment) ⁇ 28.4 ⁇ /28.4 ⁇ 100% -10% or less: “Excellent” Less than -10% to -5% or less: “Good” -Less than -5% to less than 0% 0% or more: “Not possible”.
- Etching rate [ ⁇ m / min] (mass before treatment [g] ⁇ 1 mass after treatment [g]) / (treatment area [m 2 ] ⁇ ⁇ specific gravity of copper> 8.92 [g / cm 3 ] )
- Example 1 Hydrogen peroxide (A) 2.00 g (Mitsubishi Gas Chemical Co., Ltd. 60% hydrogen peroxide), sulfuric acid (B) 8.42 g (Wako Pure Chemical Industries, Ltd. 95% special grade reagent), alcohol (C) 1.00 g (polyethylene glycol 600 (PEG 600) (Wako first grade) manufactured by Wako Pure Chemical Industries, Ltd.), 0.06 g of phenylurea (D) (produced by Wako Pure Chemical Industries, Ltd.), and copper sulfate pentahydrate 23 .60 g (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed, and ultrapure water was added so that the total mass became 200 g, followed by stirring until uniform to prepare a surface treatment solution for rolled copper foil.
- PEG 600 polyethylene glycol 600
- D phenylurea
- D copper sulfate pentahydrate 23 .60 g
- the rolled copper foil HA-V2 foil cut into a 30 mm square was etched using a surface treatment solution at a stirring speed of 200 rpm and a liquid temperature of 30 ° C., and subjected to a 3 ⁇ m etching process by immersion stirring.
- the results are shown in Table 1 and FIG.
- the luminance measurement result is smaller than 28.4 of the untreated substrate, and FIG. 2 shows that the surface is not etched into a crater shape, so that the smoothness is good.
- Examples 2 to 9 The operation was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and FIG. 2 shows that the surface is not etched into a crater shape, so that the smoothness is good.
- Example 10 to 14 The operation was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and it can be seen from FIG. 3 that the surface is not etched into a crater shape, so that the smoothness is good.
- Example 6 An experiment was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3 (Example of Patent Document 1). The results are shown in Table 3 and FIG. Although the surface is not etched into a crater shape from FIG. 4, it can be seen that good smoothness cannot be obtained because the luminance measurement result is larger than 28.4 of the untreated substrate.
- the rolled copper foil obtained by the production method of the present invention is excellent in surface smoothness, it can be suitably used for a flexible printed wiring board (FPC) or the like.
Abstract
The present invention relates to a method for manufacturing rolled copper foil, a method for surface treating rolled copper foil, and a surface treatment fluid for rolled copper foil. In the present invention, the surface of the rolled copper foil is treated by dissolution of the rolled copper foil surface by contact of the surface treatment fluid that includes hydrogen peroxide (A), sulfuric acid (B), alcohol (C), and phenylurea (D), in a range of a mole ratio of 0.3 – 3.0 for the hydrogen peroxide (A)/sulfuric acid (B), a range of 0.5 – 15.0% by mass for the sulfuric acid (B), and a range of 0.1 – 5.0% by mass for the alcohol (C), with the rolled copper foil surface. According to a preferable embodiment of the present invention, smoothing of the rolled copper foil surface is possible without giving rise to crater-like etching and pitting.
Description
本発明は、圧延銅箔の表面処理液及びこれを用いた圧延銅箔の表面処理方法、さらには圧延銅箔の製造方法に関する。
The present invention relates to a surface treatment solution for rolled copper foil, a surface treatment method for rolled copper foil using the same, and a method for producing rolled copper foil.
圧延銅箔は、フレキシブルプリント配線板（ＦＰＣ）向けに使用され、近年、高周波領域での伝送ロスの低減や、高密度化、薄型化、さらには微細化・ファインピッチ化に対応するため、圧延銅箔を平滑に処理することが望まれている。
銅板や銅箔の表面の平滑化処理を行うためには、アゾール類、ハロゲンイオン及び銀イオンを用いる方法が知られている（特許文献１）。しかしながら、この方法を圧延銅箔に使用すると、結晶粒界に沿ってエッチングが進行してしまい、クレーター状のエッチングやピットの発生などが起こり、平滑化することは困難であった。
圧延銅箔は、屈曲性が優れていることが知られており、屈曲性を向上させるために、再結晶焼鈍後の立方体集合組織が発達するように結晶方位が制御されている。しかし、その均一な結晶組織の中に、局部的に異なる結晶粒方位をもつ結晶粒子が存在しており、その部分のエッチング速度が周囲のエッチング速度と異なることで、エッチング後に、圧延銅箔の表面にクレーター状のエッチングやピットが形成されると考えられている（例えば、特許文献２、３参照）。 Rolled copper foil is used for flexible printed circuit boards (FPC), and has recently been rolled to reduce transmission loss in the high-frequency region, as well as to achieve higher density, thinner thickness, and finer / fine pitch. It is desired to treat copper foil smoothly.
In order to perform the smoothing process of the surface of a copper plate or copper foil, a method using azoles, halogen ions and silver ions is known (Patent Document 1). However, when this method is used for a rolled copper foil, etching progresses along the crystal grain boundary, and crater-like etching and pits occur, making it difficult to smooth the surface.
The rolled copper foil is known to have excellent flexibility, and the crystal orientation is controlled so that a cubic texture after recrystallization annealing develops in order to improve the flexibility. However, crystal grains having locally different crystal grain orientations exist in the uniform crystal structure, and the etching rate of the part is different from the surrounding etching rate. It is considered that crater-like etching and pits are formed on the surface (for example, see Patent Documents 2 and 3).
銅板や銅箔の表面の平滑化処理を行うためには、アゾール類、ハロゲンイオン及び銀イオンを用いる方法が知られている（特許文献１）。しかしながら、この方法を圧延銅箔に使用すると、結晶粒界に沿ってエッチングが進行してしまい、クレーター状のエッチングやピットの発生などが起こり、平滑化することは困難であった。
圧延銅箔は、屈曲性が優れていることが知られており、屈曲性を向上させるために、再結晶焼鈍後の立方体集合組織が発達するように結晶方位が制御されている。しかし、その均一な結晶組織の中に、局部的に異なる結晶粒方位をもつ結晶粒子が存在しており、その部分のエッチング速度が周囲のエッチング速度と異なることで、エッチング後に、圧延銅箔の表面にクレーター状のエッチングやピットが形成されると考えられている（例えば、特許文献２、３参照）。 Rolled copper foil is used for flexible printed circuit boards (FPC), and has recently been rolled to reduce transmission loss in the high-frequency region, as well as to achieve higher density, thinner thickness, and finer / fine pitch. It is desired to treat copper foil smoothly.
In order to perform the smoothing process of the surface of a copper plate or copper foil, a method using azoles, halogen ions and silver ions is known (Patent Document 1). However, when this method is used for a rolled copper foil, etching progresses along the crystal grain boundary, and crater-like etching and pits occur, making it difficult to smooth the surface.
The rolled copper foil is known to have excellent flexibility, and the crystal orientation is controlled so that a cubic texture after recrystallization annealing develops in order to improve the flexibility. However, crystal grains having locally different crystal grain orientations exist in the uniform crystal structure, and the etching rate of the part is different from the surrounding etching rate. It is considered that crater-like etching and pits are formed on the surface (for example, see Patent Documents 2 and 3).
このような状況の下、圧延銅箔を、クレーター状のエッチングやピットの発生なく平滑化できる表面処理液及び表面処理方法、さらには平滑性に優れた圧延銅箔の製造方法の提供が求められている。
ところで、銅箔には圧延銅箔と電解銅箔があるが、電解銅箔は、結晶粒子の大きさを小さくし、ほぼ均一に揃えてランダム配向させることにより、エッチングのばらつきを抑えられることが知られている（非特許文献１）。このように、圧延銅箔と電解銅箔とでは銅の結晶組織が異なり、それ故、エッチング特性も異なることが知られている。本発明は、これらの銅箔のうち、圧延銅箔の表面処理に適した表面処理液及び表面処理方法、さらには圧延銅箔の製造方法に関する。 Under such circumstances, it is required to provide a surface treatment solution and a surface treatment method that can smooth the rolled copper foil without the occurrence of crater-like etching or pits, and a method for producing a rolled copper foil that is excellent in smoothness. ing.
By the way, there are rolled copper foil and electrolytic copper foil in copper foil, but electrolytic copper foil can suppress variation in etching by reducing the size of crystal particles and aligning them almost uniformly and randomly. It is known (Non-Patent Document 1). Thus, it is known that the copper crystal structure is different between the rolled copper foil and the electrolytic copper foil, and therefore the etching characteristics are also different. The present invention relates to a surface treatment solution and a surface treatment method suitable for surface treatment of a rolled copper foil, and a method for producing the rolled copper foil.
ところで、銅箔には圧延銅箔と電解銅箔があるが、電解銅箔は、結晶粒子の大きさを小さくし、ほぼ均一に揃えてランダム配向させることにより、エッチングのばらつきを抑えられることが知られている（非特許文献１）。このように、圧延銅箔と電解銅箔とでは銅の結晶組織が異なり、それ故、エッチング特性も異なることが知られている。本発明は、これらの銅箔のうち、圧延銅箔の表面処理に適した表面処理液及び表面処理方法、さらには圧延銅箔の製造方法に関する。 Under such circumstances, it is required to provide a surface treatment solution and a surface treatment method that can smooth the rolled copper foil without the occurrence of crater-like etching or pits, and a method for producing a rolled copper foil that is excellent in smoothness. ing.
By the way, there are rolled copper foil and electrolytic copper foil in copper foil, but electrolytic copper foil can suppress variation in etching by reducing the size of crystal particles and aligning them almost uniformly and randomly. It is known (Non-Patent Document 1). Thus, it is known that the copper crystal structure is different between the rolled copper foil and the electrolytic copper foil, and therefore the etching characteristics are also different. The present invention relates to a surface treatment solution and a surface treatment method suitable for surface treatment of a rolled copper foil, and a method for producing the rolled copper foil.
本発明者等は鋭意検討した結果、過酸化水素及び硫酸を特定のモル比に配合し、アルコール系添加剤を加えた特定組成の表面処理液により上記課題を解決できることを見出した。即ち本発明は以下のとおりである。
As a result of intensive studies, the present inventors have found that the above problems can be solved by a surface treatment liquid having a specific composition in which hydrogen peroxide and sulfuric acid are mixed in a specific molar ratio and an alcohol-based additive is added. That is, the present invention is as follows.
［１］ 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲、硫酸（Ｂ）が０．５～１５．０質量％の範囲、及びアルコール（Ｃ）が０．１～５．０質量％の範囲にある圧延銅箔用表面処理液。
[1] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3. A surface treatment solution for rolled copper foil in which the range is 0, the sulfuric acid (B) is in the range of 0.5 to 15.0% by mass, and the alcohol (C) is in the range of 0.1 to 5.0% by mass.
［２］ 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲にある［１］に記載の圧延銅箔用表面処理液。
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％ [2] The surface treatment liquid for rolled copper foil according to [1], wherein contents of the hydrogen peroxide (A) and phenylurea (D) are in the following ranges, respectively.
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％ [2] The surface treatment liquid for rolled copper foil according to [1], wherein contents of the hydrogen peroxide (A) and phenylurea (D) are in the following ranges, respectively.
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
［３］ ［１］又は［２］に記載の圧延銅箔用表面処理液を用いて、エッチングレート０．４～４．０μｍ／ｍｉｎの速度で圧延銅箔表面を溶解させる圧延銅箔の表面処理方法。
[3] The surface of the rolled copper foil that dissolves the surface of the rolled copper foil at a rate of 0.4 to 4.0 μm / min using the surface treatment liquid for rolled copper foil according to [1] or [2]. Processing method.
また、本発明は、以下のとおりである。
［１ａ］ 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある表面処理液を、圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより、圧延銅箔表面を処理することを含む、圧延銅箔の製造方法。
［２ａ］ ３５℃の処理条件下で測定される次式：
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］）
で示される圧延銅箔のエッチングレート（Ｅ／Ｒ）が、０．４～４．０μｍ／分の範囲にある、［１ａ］に記載の圧延銅箔の製造方法。
［３ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たす、［１ａ］又は［２ａ］に記載の圧延銅箔の製造方法。
［４ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％≦－５％
の関係を満たす、［１ａ］又は［２ａ］に記載の圧延銅箔の製造方法。
［５ａ］ 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、［１ａ］から［４ａ］のいずれか一項に記載の圧延銅箔の製造方法。
［６ａ］ 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、［１ａ］から［５ａ］のいずれか一項に記載の圧延銅箔の製造方法。
［７ａ］ 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある圧延銅箔用表面処理液を用いて、圧延銅箔表面を溶解させることを含む、圧延銅箔の表面処理方法。
［８ａ］ ３５℃の処理条件下で測定される次式：
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］）
で示される圧延銅箔のエッチングレート０．４～４．０μｍ／ｍｉｎの速度で圧延銅箔表面を溶解させることを含む、［７ａ］に記載の圧延銅箔の表面処理方法。
［９ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たす、［７ａ］又は［８ａ］に記載の圧延銅箔の表面処理方法。
［１０ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％≦－５％
の関係を満たす、［７ａ］又は［８ａ］に記載の圧延銅箔の表面処理方法。
［１１ａ］ 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、［７ａ］から［１０ａ］のいずれか一項に記載の圧延銅箔の表面処理方法。
［１２ａ］ 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、［７ａ］から［１１ａ］のいずれか一項に記載の圧延銅箔の表面処理方法。
［１３ａ］ 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある圧延銅箔用表面処理液。
［１４ａ］ 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、［１３ａ］に記載の圧延銅箔用表面処理液。
［１５ａ］ 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、［１３ａ］又は［１４ａ］に記載の圧延銅箔用表面処理液。 Moreover, this invention is as follows.
[1a] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3. Surface having a range of 0, a content of sulfuric acid (B) in the range of 0.5 to 15.0% by mass, and a content of alcohol (C) in the range of 0.1 to 5.0% by mass The manufacturing method of rolled copper foil including processing a rolled copper foil surface by making a process liquid contact the rolled copper foil surface and dissolving the rolled copper foil surface.
[2a] The following equation measured under the treatment condition of 35 ° C .:
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
The method for producing a rolled copper foil according to [1a], wherein the etching rate (E / R) of the rolled copper foil represented by the formula is in the range of 0.4 to 4.0 μm / min.
[3a] Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The manufacturing method of the rolled copper foil as described in [1a] or [2a] which satisfy | fills the relationship of these.
[4a] Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% ≦ −5%
The manufacturing method of the rolled copper foil as described in [1a] or [2a] which satisfy | fills the relationship of these.
[5a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The method for producing a rolled copper foil according to any one of [1a] to [4a].
[6a] Production of rolled copper foil according to any one of [1a] to [5a], wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9. Method.
[7a] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3. Rolling in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0% by mass and the content of alcohol (C) is in the range of 0.1 to 5.0% by mass A surface treatment method for a rolled copper foil, comprising dissolving the surface of the rolled copper foil using a surface treatment solution for copper foil.
[8a] The following formula measured under the treatment condition of 35 ° C .:
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
The surface treatment method for a rolled copper foil according to [7a], comprising dissolving the rolled copper foil surface at a rate of 0.4 to 4.0 μm / min.
[9a] Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The surface treatment method of the rolled copper foil according to [7a] or [8a], which satisfies the above relationship.
[10a] Using a scanning electron microscope (SEM), an SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% ≦ −5%
The surface treatment method of the rolled copper foil according to [7a] or [8a], which satisfies the above relationship.
[11a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The surface treatment method for rolled copper foil according to any one of [7a] to [10a].
[12a] The surface of the rolled copper foil according to any one of [7a] to [11a], wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9. Processing method.
[13a] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3. Rolling in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0% by mass and the content of alcohol (C) is in the range of 0.1 to 5.0% by mass Surface treatment solution for copper foil.
[14a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The surface treatment liquid for rolled copper foil according to [13a].
[15a] The surface treatment liquid for rolled copper foil according to [13a] or [14a], wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9.
［１ａ］ 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある表面処理液を、圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより、圧延銅箔表面を処理することを含む、圧延銅箔の製造方法。
［２ａ］ ３５℃の処理条件下で測定される次式：
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］）
で示される圧延銅箔のエッチングレート（Ｅ／Ｒ）が、０．４～４．０μｍ／分の範囲にある、［１ａ］に記載の圧延銅箔の製造方法。
［３ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たす、［１ａ］又は［２ａ］に記載の圧延銅箔の製造方法。
［４ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％≦－５％
の関係を満たす、［１ａ］又は［２ａ］に記載の圧延銅箔の製造方法。
［５ａ］ 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、［１ａ］から［４ａ］のいずれか一項に記載の圧延銅箔の製造方法。
［６ａ］ 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、［１ａ］から［５ａ］のいずれか一項に記載の圧延銅箔の製造方法。
［７ａ］ 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある圧延銅箔用表面処理液を用いて、圧延銅箔表面を溶解させることを含む、圧延銅箔の表面処理方法。
［８ａ］ ３５℃の処理条件下で測定される次式：
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］）
で示される圧延銅箔のエッチングレート０．４～４．０μｍ／ｍｉｎの速度で圧延銅箔表面を溶解させることを含む、［７ａ］に記載の圧延銅箔の表面処理方法。
［９ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たす、［７ａ］又は［８ａ］に記載の圧延銅箔の表面処理方法。
［１０ａ］ 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％≦－５％
の関係を満たす、［７ａ］又は［８ａ］に記載の圧延銅箔の表面処理方法。
［１１ａ］ 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、［７ａ］から［１０ａ］のいずれか一項に記載の圧延銅箔の表面処理方法。
［１２ａ］ 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、［７ａ］から［１１ａ］のいずれか一項に記載の圧延銅箔の表面処理方法。
［１３ａ］ 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある圧延銅箔用表面処理液。
［１４ａ］ 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、［１３ａ］に記載の圧延銅箔用表面処理液。
［１５ａ］ 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、［１３ａ］又は［１４ａ］に記載の圧延銅箔用表面処理液。 Moreover, this invention is as follows.
[1a] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3. Surface having a range of 0, a content of sulfuric acid (B) in the range of 0.5 to 15.0% by mass, and a content of alcohol (C) in the range of 0.1 to 5.0% by mass The manufacturing method of rolled copper foil including processing a rolled copper foil surface by making a process liquid contact the rolled copper foil surface and dissolving the rolled copper foil surface.
[2a] The following equation measured under the treatment condition of 35 ° C .:
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
The method for producing a rolled copper foil according to [1a], wherein the etching rate (E / R) of the rolled copper foil represented by the formula is in the range of 0.4 to 4.0 μm / min.
[3a] Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The manufacturing method of the rolled copper foil as described in [1a] or [2a] which satisfy | fills the relationship of these.
[4a] Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% ≦ −5%
The manufacturing method of the rolled copper foil as described in [1a] or [2a] which satisfy | fills the relationship of these.
[5a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The method for producing a rolled copper foil according to any one of [1a] to [4a].
[6a] Production of rolled copper foil according to any one of [1a] to [5a], wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9. Method.
[7a] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3. Rolling in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0% by mass and the content of alcohol (C) is in the range of 0.1 to 5.0% by mass A surface treatment method for a rolled copper foil, comprising dissolving the surface of the rolled copper foil using a surface treatment solution for copper foil.
[8a] The following formula measured under the treatment condition of 35 ° C .:
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
The surface treatment method for a rolled copper foil according to [7a], comprising dissolving the rolled copper foil surface at a rate of 0.4 to 4.0 μm / min.
[9a] Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The surface treatment method of the rolled copper foil according to [7a] or [8a], which satisfies the above relationship.
[10a] Using a scanning electron microscope (SEM), an SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the concavo-convex portion on the surface of the rolled copper foil is set to a single threshold value. Is set to 47, the series is set to 20 using a histogram, and the brightness of the rolled copper foil before and after the surface treatment obtained using the standard deviation is expressed by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% ≦ −5%
The surface treatment method of the rolled copper foil according to [7a] or [8a], which satisfies the above relationship.
[11a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The surface treatment method for rolled copper foil according to any one of [7a] to [10a].
[12a] The surface of the rolled copper foil according to any one of [7a] to [11a], wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9. Processing method.
[13a] Hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D) are contained, and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3-3. Rolling in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0% by mass and the content of alcohol (C) is in the range of 0.1 to 5.0% by mass Surface treatment solution for copper foil.
[14a] Content of the hydrogen peroxide (A) and phenylurea (D) is within the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The surface treatment liquid for rolled copper foil according to [13a].
[15a] The surface treatment liquid for rolled copper foil according to [13a] or [14a], wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9.
本発明の好ましい態様によれば、本発明の圧延銅箔用処理液を用いることで優れた平滑性を有する圧延銅箔を得ることができる。本発明で得られた圧延銅箔を用いることにより高周波領域での伝送ロスの低減や、高密度化、薄型化、さらには微細化・ファインピッチ化にも対応しうるフレキシブルプリント回路フィルムを製造することができる。
According to a preferred embodiment of the present invention, a rolled copper foil having excellent smoothness can be obtained by using the processing solution for rolled copper foil of the present invention. By using the rolled copper foil obtained in the present invention, a flexible printed circuit film capable of reducing transmission loss in a high frequency region, increasing the density, reducing the thickness, and further reducing the size and fine pitch is manufactured. be able to.
［圧延銅箔の製造方法］
本発明の圧延銅箔の製造方法は、過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）が０．１～５．０質量％の範囲にある表面処理液を、圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより、圧延銅箔表面を処理することを特徴としている。
本発明の好ましい態様によれば、上記の組成を有する表面処理液を圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより、結晶粒界に沿ったエッチングが起こり難く、表面の平滑性に優れた圧延銅箔を得ることができる。 [Method for producing rolled copper foil]
The method for producing a rolled copper foil of the present invention comprises hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D), and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B). The ratio is in the range of 0.3 to 3.0, the sulfuric acid (B) is in the range of 0.5 to 15.0% by mass, and the alcohol (C) is in the range of 0.1 to 5.0% by mass. A surface treatment liquid is brought into contact with the rolled copper foil surface to dissolve the rolled copper foil surface, thereby treating the rolled copper foil surface.
According to a preferred embodiment of the present invention, the surface treatment liquid having the above composition is brought into contact with the surface of the rolled copper foil to dissolve the surface of the rolled copper foil. A rolled copper foil having excellent properties can be obtained.
本発明の圧延銅箔の製造方法は、過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）が０．１～５．０質量％の範囲にある表面処理液を、圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより、圧延銅箔表面を処理することを特徴としている。
本発明の好ましい態様によれば、上記の組成を有する表面処理液を圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより、結晶粒界に沿ったエッチングが起こり難く、表面の平滑性に優れた圧延銅箔を得ることができる。 [Method for producing rolled copper foil]
The method for producing a rolled copper foil of the present invention comprises hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D), and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B). The ratio is in the range of 0.3 to 3.0, the sulfuric acid (B) is in the range of 0.5 to 15.0% by mass, and the alcohol (C) is in the range of 0.1 to 5.0% by mass. A surface treatment liquid is brought into contact with the rolled copper foil surface to dissolve the rolled copper foil surface, thereby treating the rolled copper foil surface.
According to a preferred embodiment of the present invention, the surface treatment liquid having the above composition is brought into contact with the surface of the rolled copper foil to dissolve the surface of the rolled copper foil. A rolled copper foil having excellent properties can be obtained.
［圧延銅箔用表面処理液］
本発明に用いる圧延銅箔用表面処理液は過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有する。以下これらについて詳細に説明する。 [Surface treatment solution for rolled copper foil]
The surface treatment solution for rolled copper foil used in the present invention contains hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D). These will be described in detail below.
本発明に用いる圧延銅箔用表面処理液は過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有する。以下これらについて詳細に説明する。 [Surface treatment solution for rolled copper foil]
The surface treatment solution for rolled copper foil used in the present invention contains hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D). These will be described in detail below.
［過酸化水素（Ａ）］
本発明における過酸化水素（Ａ）は銅の酸化剤として機能する成分である。
本発明で用いられる過酸化水素（Ａ）に制限はなく、市販の過酸化水素水溶液を用いることができ、例えば三菱ガス化学株式会社製の６０％工業用・電子工業用グレード品を好適に使用することができる。
表面処理液中の過酸化水素（Ａ）の濃度は、好ましくは０．５～３．０質量％であり、更に好ましくは０．６～２．５質量％であり、特に好ましくは０．８～２．０質量％である。上記範囲に過酸化水素の濃度があるとき、良好な銅の表面状態と好適な銅の溶解速度が得られる。
また、過酸化水素（Ａ）／硫酸（Ｂ）のモル比は、０．３～３．０であり、好ましくは、０．４～３．０であり、更に好ましくは０．５～３．０である。過酸化水素（Ａ）／硫酸（Ｂ）のモル比は、特に好ましくは０．５～０．９である。この範囲にモル比をコントロールすることによって良好な銅の表面状態と好適な銅の溶解速度が得られる。また、圧延銅箔表面の平滑性をより優れたものとすることが出来る。 [Hydrogen peroxide (A)]
Hydrogen peroxide (A) in the present invention is a component that functions as an oxidizing agent for copper.
The hydrogen peroxide (A) used in the present invention is not limited, and a commercially available aqueous hydrogen peroxide solution can be used. For example, a 60% industrial / electronic industry grade product manufactured by Mitsubishi Gas Chemical Co., Ltd. is preferably used. can do.
The concentration of hydrogen peroxide (A) in the surface treatment liquid is preferably 0.5 to 3.0% by mass, more preferably 0.6 to 2.5% by mass, and particularly preferably 0.8. It is -2.0 mass%. When the concentration of hydrogen peroxide is in the above range, a good copper surface state and a suitable copper dissolution rate can be obtained.
The molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3 to 3.0, preferably 0.4 to 3.0, and more preferably 0.5 to 3. 0. The molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is particularly preferably 0.5 to 0.9. By controlling the molar ratio within this range, a good copper surface state and a suitable copper dissolution rate can be obtained. Moreover, the smoothness of the rolled copper foil surface can be made more excellent.
本発明における過酸化水素（Ａ）は銅の酸化剤として機能する成分である。
本発明で用いられる過酸化水素（Ａ）に制限はなく、市販の過酸化水素水溶液を用いることができ、例えば三菱ガス化学株式会社製の６０％工業用・電子工業用グレード品を好適に使用することができる。
表面処理液中の過酸化水素（Ａ）の濃度は、好ましくは０．５～３．０質量％であり、更に好ましくは０．６～２．５質量％であり、特に好ましくは０．８～２．０質量％である。上記範囲に過酸化水素の濃度があるとき、良好な銅の表面状態と好適な銅の溶解速度が得られる。
また、過酸化水素（Ａ）／硫酸（Ｂ）のモル比は、０．３～３．０であり、好ましくは、０．４～３．０であり、更に好ましくは０．５～３．０である。過酸化水素（Ａ）／硫酸（Ｂ）のモル比は、特に好ましくは０．５～０．９である。この範囲にモル比をコントロールすることによって良好な銅の表面状態と好適な銅の溶解速度が得られる。また、圧延銅箔表面の平滑性をより優れたものとすることが出来る。 [Hydrogen peroxide (A)]
Hydrogen peroxide (A) in the present invention is a component that functions as an oxidizing agent for copper.
The hydrogen peroxide (A) used in the present invention is not limited, and a commercially available aqueous hydrogen peroxide solution can be used. For example, a 60% industrial / electronic industry grade product manufactured by Mitsubishi Gas Chemical Co., Ltd. is preferably used. can do.
The concentration of hydrogen peroxide (A) in the surface treatment liquid is preferably 0.5 to 3.0% by mass, more preferably 0.6 to 2.5% by mass, and particularly preferably 0.8. It is -2.0 mass%. When the concentration of hydrogen peroxide is in the above range, a good copper surface state and a suitable copper dissolution rate can be obtained.
The molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is 0.3 to 3.0, preferably 0.4 to 3.0, and more preferably 0.5 to 3. 0. The molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is particularly preferably 0.5 to 0.9. By controlling the molar ratio within this range, a good copper surface state and a suitable copper dissolution rate can be obtained. Moreover, the smoothness of the rolled copper foil surface can be made more excellent.
［硫酸（Ｂ）］
本発明における硫酸（Ｂ）は過酸化水素によって酸化された銅のエッチング剤として機能する成分である。
本発明で用いられる硫酸（Ｂ）に制限はなく、例えば和光純薬工業株式会社製の９５％の特級試薬を好適に使用することができる。
表面処理液中の硫酸（Ｂ）の濃度は、０．５～１５．０質量％であり、好ましくは０．６～１５．０質量％であり、更に好ましくは１．０～５．０質量％である。この範囲にあることで、良好な銅の表面状態と好適な銅の溶解速度が得られる。 [Sulfuric acid (B)]
The sulfuric acid (B) in the present invention is a component that functions as an etching agent for copper oxidized by hydrogen peroxide.
There is no restriction | limiting in the sulfuric acid (B) used by this invention, For example, 95% special grade reagent made from Wako Pure Chemical Industries Ltd. can be used conveniently.
The concentration of sulfuric acid (B) in the surface treatment liquid is 0.5 to 15.0 mass%, preferably 0.6 to 15.0 mass%, and more preferably 1.0 to 5.0 mass%. %. By being in this range, a good copper surface state and a suitable copper dissolution rate can be obtained.
本発明における硫酸（Ｂ）は過酸化水素によって酸化された銅のエッチング剤として機能する成分である。
本発明で用いられる硫酸（Ｂ）に制限はなく、例えば和光純薬工業株式会社製の９５％の特級試薬を好適に使用することができる。
表面処理液中の硫酸（Ｂ）の濃度は、０．５～１５．０質量％であり、好ましくは０．６～１５．０質量％であり、更に好ましくは１．０～５．０質量％である。この範囲にあることで、良好な銅の表面状態と好適な銅の溶解速度が得られる。 [Sulfuric acid (B)]
The sulfuric acid (B) in the present invention is a component that functions as an etching agent for copper oxidized by hydrogen peroxide.
There is no restriction | limiting in the sulfuric acid (B) used by this invention, For example, 95% special grade reagent made from Wako Pure Chemical Industries Ltd. can be used conveniently.
The concentration of sulfuric acid (B) in the surface treatment liquid is 0.5 to 15.0 mass%, preferably 0.6 to 15.0 mass%, and more preferably 1.0 to 5.0 mass%. %. By being in this range, a good copper surface state and a suitable copper dissolution rate can be obtained.
［アルコール（Ｃ）］
本発明におけるアルコール（Ｃ）は一般的なアルコールを全て包含するものであり、圧延銅箔表面の平滑性を向上させる成分である。
アルコール（Ｃ）の具体例としては、メタノール、エタノール、プロパノール等の１価アルコール、エチレングリコール、プロピレングリコール等の２価のアルコール、３価以上のアルコール、及びポリエチレングリコールなどのグリコールエーテルが挙げられる。これらの２種以上を併用することもできる。
表面処理液中のアルコール（Ｃ）の濃度は、０．１～５．０質量％であり、好ましくは０．５～５．０質量％である。この範囲にあることで圧延銅箔の平滑な表面状態を得ることが出来る。 [Alcohol (C)]
The alcohol (C) in the present invention includes all common alcohols, and is a component that improves the smoothness of the rolled copper foil surface.
Specific examples of the alcohol (C) include monohydric alcohols such as methanol, ethanol and propanol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols and glycol ethers such as polyethylene glycol. Two or more of these can be used in combination.
The concentration of the alcohol (C) in the surface treatment liquid is 0.1 to 5.0% by mass, preferably 0.5 to 5.0% by mass. By being in this range, a smooth surface state of the rolled copper foil can be obtained.
本発明におけるアルコール（Ｃ）は一般的なアルコールを全て包含するものであり、圧延銅箔表面の平滑性を向上させる成分である。
アルコール（Ｃ）の具体例としては、メタノール、エタノール、プロパノール等の１価アルコール、エチレングリコール、プロピレングリコール等の２価のアルコール、３価以上のアルコール、及びポリエチレングリコールなどのグリコールエーテルが挙げられる。これらの２種以上を併用することもできる。
表面処理液中のアルコール（Ｃ）の濃度は、０．１～５．０質量％であり、好ましくは０．５～５．０質量％である。この範囲にあることで圧延銅箔の平滑な表面状態を得ることが出来る。 [Alcohol (C)]
The alcohol (C) in the present invention includes all common alcohols, and is a component that improves the smoothness of the rolled copper foil surface.
Specific examples of the alcohol (C) include monohydric alcohols such as methanol, ethanol and propanol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols and glycol ethers such as polyethylene glycol. Two or more of these can be used in combination.
The concentration of the alcohol (C) in the surface treatment liquid is 0.1 to 5.0% by mass, preferably 0.5 to 5.0% by mass. By being in this range, a smooth surface state of the rolled copper foil can be obtained.
［フェニル尿素（Ｄ）］
本発明におけるフェニル尿素（Ｄ）は過酸化水素の安定性を向上させる成分である。
本発明で用いられるフェニル尿素（Ｄ）に制限は無く、例えば和光純薬工業株式会社製のフェニル尿素を好適に使用することが出来る。
表面処理液中のフェニル尿素（Ｄ）の濃度は、好ましくは、０．００５～０．３質量％であり、より好ましくは、０．００５～０．１５質量％、更に好ましくは０．００５～０．１質量％である。この範囲にあることで過酸化水素の分解を抑えることが出来る。また、フェニル尿素（Ｄ）の量比を適宜調整することで、圧延銅箔表面の平滑性をより優れたものとすることが出来る。 [Phenylurea (D)]
Phenylurea (D) in the present invention is a component that improves the stability of hydrogen peroxide.
There is no restriction | limiting in the phenylurea (D) used by this invention, For example, Wako Pure Chemical Industries Ltd. phenylurea can be used conveniently.
The concentration of phenylurea (D) in the surface treatment liquid is preferably 0.005 to 0.3% by mass, more preferably 0.005 to 0.15% by mass, and still more preferably 0.005 to 0.3% by mass. 0.1% by mass. By being in this range, decomposition of hydrogen peroxide can be suppressed. Moreover, the smoothness of the surface of rolled copper foil can be made more excellent by adjusting the amount ratio of phenylurea (D) as appropriate.
本発明におけるフェニル尿素（Ｄ）は過酸化水素の安定性を向上させる成分である。
本発明で用いられるフェニル尿素（Ｄ）に制限は無く、例えば和光純薬工業株式会社製のフェニル尿素を好適に使用することが出来る。
表面処理液中のフェニル尿素（Ｄ）の濃度は、好ましくは、０．００５～０．３質量％であり、より好ましくは、０．００５～０．１５質量％、更に好ましくは０．００５～０．１質量％である。この範囲にあることで過酸化水素の分解を抑えることが出来る。また、フェニル尿素（Ｄ）の量比を適宜調整することで、圧延銅箔表面の平滑性をより優れたものとすることが出来る。 [Phenylurea (D)]
Phenylurea (D) in the present invention is a component that improves the stability of hydrogen peroxide.
There is no restriction | limiting in the phenylurea (D) used by this invention, For example, Wako Pure Chemical Industries Ltd. phenylurea can be used conveniently.
The concentration of phenylurea (D) in the surface treatment liquid is preferably 0.005 to 0.3% by mass, more preferably 0.005 to 0.15% by mass, and still more preferably 0.005 to 0.3% by mass. 0.1% by mass. By being in this range, decomposition of hydrogen peroxide can be suppressed. Moreover, the smoothness of the surface of rolled copper foil can be made more excellent by adjusting the amount ratio of phenylurea (D) as appropriate.
［その他の成分］
本発明の表面処理液は、さらに水、その他、通常用いられる各種添加剤を、本発明の効果を害しない範囲で含むことができる。
例えば、アルカリ、有機カルボン酸類、有機アミン化合物類等の公知のエッチング速度調製剤やエッチングレートを安定化するために銅イオン供給源を必要に応じ添加しても良い。
また、水としては、蒸留、イオン交換処理、フイルター処理、各種吸着処理などによって、金属イオンや有機不純物、パーテイクル粒子などが除去されたものが好ましく、純水がより好ましく、特に超純水が好ましい。 [Other ingredients]
The surface treatment liquid of the present invention can further contain water and other commonly used additives as long as the effects of the present invention are not impaired.
For example, a known etching rate adjusting agent such as an alkali, organic carboxylic acid, organic amine compound, or a copper ion supply source may be added as necessary to stabilize the etching rate.
The water is preferably one from which metal ions, organic impurities, particle particles, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., more preferably pure water, and particularly preferably ultrapure water. .
本発明の表面処理液は、さらに水、その他、通常用いられる各種添加剤を、本発明の効果を害しない範囲で含むことができる。
例えば、アルカリ、有機カルボン酸類、有機アミン化合物類等の公知のエッチング速度調製剤やエッチングレートを安定化するために銅イオン供給源を必要に応じ添加しても良い。
また、水としては、蒸留、イオン交換処理、フイルター処理、各種吸着処理などによって、金属イオンや有機不純物、パーテイクル粒子などが除去されたものが好ましく、純水がより好ましく、特に超純水が好ましい。 [Other ingredients]
The surface treatment liquid of the present invention can further contain water and other commonly used additives as long as the effects of the present invention are not impaired.
For example, a known etching rate adjusting agent such as an alkali, organic carboxylic acid, organic amine compound, or a copper ion supply source may be added as necessary to stabilize the etching rate.
The water is preferably one from which metal ions, organic impurities, particle particles, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., more preferably pure water, and particularly preferably ultrapure water. .
［圧延銅箔用表面処理液の調製］
圧延銅箔用表面処理液は過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）、フェニル尿素（Ｄ）及び必要に応じてその他の成分を均一に攪拌することにより調製される。 [Preparation of surface treatment solution for rolled copper foil]
The surface treatment solution for rolled copper foil is prepared by uniformly stirring hydrogen peroxide (A), sulfuric acid (B), alcohol (C), phenylurea (D) and other components as required.
圧延銅箔用表面処理液は過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）、フェニル尿素（Ｄ）及び必要に応じてその他の成分を均一に攪拌することにより調製される。 [Preparation of surface treatment solution for rolled copper foil]
The surface treatment solution for rolled copper foil is prepared by uniformly stirring hydrogen peroxide (A), sulfuric acid (B), alcohol (C), phenylurea (D) and other components as required.
［圧延銅箔の表面処理方法］
本発明においては、前記表面処理液を圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより圧延銅箔表面を処理する。本発明の好ましい態様によれば、前記表面処理液を用いて圧延銅箔表面を処理することにより、圧延銅箔表面の平滑性を優れたものとすることが出来る。表面処理液を圧延銅箔表面と接触させる方法は特に制限されなく、浸漬、噴霧等の公知の方法を採用することができる。
上記のとおり、本発明の圧延銅箔用表面処理液は、浸漬、噴霧等による公知の圧延銅箔の表面処理方法に用いることができる。本発明に用いられる圧延銅箔は、一般的に知られている圧延銅箔であり、銅または銅合金のインゴットを圧延ロールによって塑性加工と熱処理を繰り返して製造された、屈曲性や高い結晶配向性を有する銅箔である。 [Surface treatment method for rolled copper foil]
In the present invention, the surface of the rolled copper foil is treated by bringing the surface treatment liquid into contact with the surface of the rolled copper foil to dissolve the surface of the rolled copper foil. According to the preferable aspect of this invention, the smoothness of the rolled copper foil surface can be made excellent by processing the rolled copper foil surface using the said surface treatment liquid. The method for bringing the surface treatment liquid into contact with the surface of the rolled copper foil is not particularly limited, and a known method such as dipping or spraying can be employed.
As above-mentioned, the surface treatment liquid for rolled copper foil of this invention can be used for the surface treatment method of the well-known rolled copper foil by immersion, spraying, etc. The rolled copper foil used in the present invention is a generally known rolled copper foil, which is produced by repeating plastic processing and heat treatment of a copper or copper alloy ingot with a rolling roll, and has high flexibility and high crystal orientation. It is a copper foil having properties.
本発明においては、前記表面処理液を圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより圧延銅箔表面を処理する。本発明の好ましい態様によれば、前記表面処理液を用いて圧延銅箔表面を処理することにより、圧延銅箔表面の平滑性を優れたものとすることが出来る。表面処理液を圧延銅箔表面と接触させる方法は特に制限されなく、浸漬、噴霧等の公知の方法を採用することができる。
上記のとおり、本発明の圧延銅箔用表面処理液は、浸漬、噴霧等による公知の圧延銅箔の表面処理方法に用いることができる。本発明に用いられる圧延銅箔は、一般的に知られている圧延銅箔であり、銅または銅合金のインゴットを圧延ロールによって塑性加工と熱処理を繰り返して製造された、屈曲性や高い結晶配向性を有する銅箔である。 [Surface treatment method for rolled copper foil]
In the present invention, the surface of the rolled copper foil is treated by bringing the surface treatment liquid into contact with the surface of the rolled copper foil to dissolve the surface of the rolled copper foil. According to the preferable aspect of this invention, the smoothness of the rolled copper foil surface can be made excellent by processing the rolled copper foil surface using the said surface treatment liquid. The method for bringing the surface treatment liquid into contact with the surface of the rolled copper foil is not particularly limited, and a known method such as dipping or spraying can be employed.
As above-mentioned, the surface treatment liquid for rolled copper foil of this invention can be used for the surface treatment method of the well-known rolled copper foil by immersion, spraying, etc. The rolled copper foil used in the present invention is a generally known rolled copper foil, which is produced by repeating plastic processing and heat treatment of a copper or copper alloy ingot with a rolling roll, and has high flexibility and high crystal orientation. It is a copper foil having properties.
前記表面処理液の使用温度に制限はないが、通常２０～５０℃であり、好ましくは２５～４０℃で、更に好ましくは２５～３５℃である。前記表面処理液の使用温度が高いほど銅の溶解速度は早くなるが、５０℃を越えると過酸化水素の分解が激しくなり好ましくない。
The use temperature of the surface treatment liquid is not limited, but is usually 20 to 50 ° C., preferably 25 to 40 ° C., more preferably 25 to 35 ° C. The higher the use temperature of the surface treatment solution, the faster the dissolution rate of copper. However, when the temperature exceeds 50 ° C., the decomposition of hydrogen peroxide becomes undesirably severe.
前記表面処理液による圧延銅箔表面の処理時間も制限はないが、通常１～６００秒であり、５～３００秒が好ましく、１０～１８０秒が更に好ましく、１５～１２０秒が特に好ましい。
The treatment time of the surface of the rolled copper foil with the surface treatment liquid is not limited, but is usually 1 to 600 seconds, preferably 5 to 300 seconds, more preferably 10 to 180 seconds, and particularly preferably 15 to 120 seconds.
前記表面処理液による圧延銅箔の溶解速度も制限はないが、エッチングレート（Ｅ／Ｒ）は例えば３５℃の処理条件下で、通常０．４～４．０μｍ／分であり、好ましくは１．０～３．５μｍ／分であり、１．５～３．０μｍ／分であるとエッチング時間を短縮することが出来るため特に好ましい。
The dissolution rate of the rolled copper foil by the surface treatment liquid is not limited, but the etching rate (E / R) is usually 0.4 to 4.0 μm / min, for example, under the treatment condition of 35 ° C., preferably 1 0.0 to 3.5 μm / min, and 1.5 to 3.0 μm / min is particularly preferable because the etching time can be shortened.
本発明の好ましい態様によれば、前記表面処理液を用いて表面処理された本発明の圧延銅箔は、表面の平滑性に優れているため、フレキシブルプリント配線板等に好適に用いることができる。
本発明の好ましい態様によれば、得られた圧延銅箔は、走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たすことができ、平滑性に優れている。上記式で示される数値（％）は、より好ましくは－５％以下であり、さらに好ましくは－１０％以下である。 According to a preferred aspect of the present invention, the rolled copper foil of the present invention surface-treated with the surface treatment liquid is excellent in surface smoothness, and therefore can be suitably used for flexible printed wiring boards and the like. .
According to the preferable aspect of this invention, the obtained rolled copper foil image-processed the SEM image obtained on condition of acceleration voltage 5kV and 1000 times of magnification using a scanning electron microscope (SEM), and rolled. The brightness of the rolled copper foil before and after the surface treatment was determined using the standard deviation by setting the single-threshold value of the contrast of the concave and convex portions on the surface of the copper foil to 47, using the histogram as the series, and using the standard deviation. :
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The relationship is satisfied, and the smoothness is excellent. The numerical value (%) represented by the above formula is more preferably −5% or less, and further preferably −10% or less.
本発明の好ましい態様によれば、得られた圧延銅箔は、走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たすことができ、平滑性に優れている。上記式で示される数値（％）は、より好ましくは－５％以下であり、さらに好ましくは－１０％以下である。 According to a preferred aspect of the present invention, the rolled copper foil of the present invention surface-treated with the surface treatment liquid is excellent in surface smoothness, and therefore can be suitably used for flexible printed wiring boards and the like. .
According to the preferable aspect of this invention, the obtained rolled copper foil image-processed the SEM image obtained on condition of acceleration voltage 5kV and 1000 times of magnification using a scanning electron microscope (SEM), and rolled. The brightness of the rolled copper foil before and after the surface treatment was determined using the standard deviation by setting the single-threshold value of the contrast of the concave and convex portions on the surface of the copper foil to 47, using the histogram as the series, and using the standard deviation. :
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The relationship is satisfied, and the smoothness is excellent. The numerical value (%) represented by the above formula is more preferably −5% or less, and further preferably −10% or less.
以下、実施例により本発明を具体的に説明するが、本発明の効果を奏する限りにおいて適宜実施形態を変更することが出来る。
Hereinafter, the present invention will be specifically described by way of examples. However, as long as the effects of the present invention are exhibited, the embodiments can be appropriately changed.
［評価方法］
＜ＳＥＭ観察＞
走査型電子顕微鏡（ＳＥＭ：株式会社日立ハイテクノロジーズ製 Ｓ－３４００Ｎ）を用いて、加速電圧５ｋＶ、倍率１０００倍の条件で圧延銅箔の表面状態を測定した。
ＳＥＭ画像より、粒界エッチングされていないものを平滑化されているとした。
表面状態の評価は次のように行った。
粒界エッチングが起こっていないもの：「優」
粒界エッチングが起こっているもの ：「不可」 [Evaluation methods]
<SEM observation>
Using a scanning electron microscope (SEM: Hitachi High-Technologies Corporation S-3400N), the surface state of the rolled copper foil was measured under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times.
From the SEM image, it was assumed that the material that had not been subjected to the grain boundary etching was smoothed.
The surface condition was evaluated as follows.
No grain boundary etching has occurred: “Excellent”
Intergranular etching occurs: "No"
＜ＳＥＭ観察＞
走査型電子顕微鏡（ＳＥＭ：株式会社日立ハイテクノロジーズ製 Ｓ－３４００Ｎ）を用いて、加速電圧５ｋＶ、倍率１０００倍の条件で圧延銅箔の表面状態を測定した。
ＳＥＭ画像より、粒界エッチングされていないものを平滑化されているとした。
表面状態の評価は次のように行った。
粒界エッチングが起こっていないもの：「優」
粒界エッチングが起こっているもの ：「不可」 [Evaluation methods]
<SEM observation>
Using a scanning electron microscope (SEM: Hitachi High-Technologies Corporation S-3400N), the surface state of the rolled copper foil was measured under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times.
From the SEM image, it was assumed that the material that had not been subjected to the grain boundary etching was smoothed.
The surface condition was evaluated as follows.
No grain boundary etching has occurred: “Excellent”
Intergranular etching occurs: "No"
＜銅表面の輝度測定＞
ＳＥＭ画像を解析ソフトＷｉｎＲＯＯＦ２０１３（三谷商事株式会社製）を用いて解析した。圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差により輝度を求めた。
輝度が低いほど平滑性が高く、輝度が高いほど平滑性が低い。未処理銅箔の輝度２８．４を基準として、処理後の銅箔の平滑性を下記式に基づいて判断した。
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％
＝｛（処理後の銅箔の輝度）－２８．４｝／２８．４×１００％
－１０％以下 ：「優」
－１０％未満～－５％以下：「良」
－５％未満～０％未満 ：「可」
０％以上 ：「不可」とした。 <Measurement of brightness on copper surface>
The SEM image was analyzed using analysis software WinROOF2013 (manufactured by Mitani Corporation). The contrast of the uneven portion on the surface of the rolled copper foil was set to a single threshold value of 47, the series was set to 20 using a histogram, and the luminance was obtained from the standard deviation.
The lower the luminance, the higher the smoothness, and the higher the luminance, the lower the smoothness. Based on the brightness of 28.4 of the untreated copper foil, the smoothness of the treated copper foil was judged based on the following formula.
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100%
= {(Brightness of copper foil after treatment) −28.4} /28.4×100%
-10% or less: “Excellent”
Less than -10% to -5% or less: “Good”
-Less than -5% to less than 0%
0% or more: “Not possible”.
ＳＥＭ画像を解析ソフトＷｉｎＲＯＯＦ２０１３（三谷商事株式会社製）を用いて解析した。圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差により輝度を求めた。
輝度が低いほど平滑性が高く、輝度が高いほど平滑性が低い。未処理銅箔の輝度２８．４を基準として、処理後の銅箔の平滑性を下記式に基づいて判断した。
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％
＝｛（処理後の銅箔の輝度）－２８．４｝／２８．４×１００％
－１０％以下 ：「優」
－１０％未満～－５％以下：「良」
－５％未満～０％未満 ：「可」
０％以上 ：「不可」とした。 <Measurement of brightness on copper surface>
The SEM image was analyzed using analysis software WinROOF2013 (manufactured by Mitani Corporation). The contrast of the uneven portion on the surface of the rolled copper foil was set to a single threshold value of 47, the series was set to 20 using a histogram, and the luminance was obtained from the standard deviation.
The lower the luminance, the higher the smoothness, and the higher the luminance, the lower the smoothness. Based on the brightness of 28.4 of the untreated copper foil, the smoothness of the treated copper foil was judged based on the following formula.
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100%
= {(Brightness of copper foil after treatment) −28.4} /28.4×100%
-10% or less: “Excellent”
Less than -10% to -5% or less: “Good”
-Less than -5% to less than 0%
0% or more: “Not possible”.
＜エッチングレート（Ｅ／Ｒ）測定方法＞
１分間浸漬攪拌処理を行い、以下の式に基づいて質量法にて算出した。
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］） <Etching rate (E / R) measurement method>
The immersion stirring process was performed for 1 minute, and it computed with the mass method based on the following formula | equation.
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
１分間浸漬攪拌処理を行い、以下の式に基づいて質量法にて算出した。
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］） <Etching rate (E / R) measurement method>
The immersion stirring process was performed for 1 minute, and it computed with the mass method based on the following formula | equation.
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
［実施例１］
過酸化水素（Ａ）２．００ｇ（三菱ガス化学株式会社製６０％過酸化水素）、硫酸（Ｂ）８．４２ｇ（和光純薬工業株式会社製の９５％の特級試薬）、アルコール（Ｃ）１．００ｇ（和光純薬工業株式会社製ポリエチレングリコール６００（ＰＥＧ６００）（和光一級））、フェニル尿素（Ｄ）０．０６ｇ（和光純薬工業株式会社製）、及び硫酸銅五水和物を２３．６０ｇ（和光純薬工業株式会社製）を計りとり、更に総質量が２００ｇになるように超純水を加えて、均一になるまで攪拌して圧延銅箔用表面処理液を調製した。
３０ｍｍ四方に裁断した圧延銅箔ＨＡ－Ｖ２箔を、上記表面処理液を用いて攪拌速度を２００ｒｐｍ、液温を３０度に設定し、浸漬攪拌処理にて３μｍエッチング処理した。
結果を表１及び図２に示した。輝度の測定結果が未処理基板の２８．４より小さく、また図２より表面がクレーター状にエッチングされていないことから良好な平滑性であることが分かる。 [Example 1]
Hydrogen peroxide (A) 2.00 g (Mitsubishi Gas Chemical Co., Ltd. 60% hydrogen peroxide), sulfuric acid (B) 8.42 g (Wako Pure Chemical Industries, Ltd. 95% special grade reagent), alcohol (C) 1.00 g (polyethylene glycol 600 (PEG 600) (Wako first grade) manufactured by Wako Pure Chemical Industries, Ltd.), 0.06 g of phenylurea (D) (produced by Wako Pure Chemical Industries, Ltd.), and copper sulfate pentahydrate 23 .60 g (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed, and ultrapure water was added so that the total mass became 200 g, followed by stirring until uniform to prepare a surface treatment solution for rolled copper foil.
The rolled copper foil HA-V2 foil cut into a 30 mm square was etched using a surface treatment solution at a stirring speed of 200 rpm and a liquid temperature of 30 ° C., and subjected to a 3 μm etching process by immersion stirring.
The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and FIG. 2 shows that the surface is not etched into a crater shape, so that the smoothness is good.
過酸化水素（Ａ）２．００ｇ（三菱ガス化学株式会社製６０％過酸化水素）、硫酸（Ｂ）８．４２ｇ（和光純薬工業株式会社製の９５％の特級試薬）、アルコール（Ｃ）１．００ｇ（和光純薬工業株式会社製ポリエチレングリコール６００（ＰＥＧ６００）（和光一級））、フェニル尿素（Ｄ）０．０６ｇ（和光純薬工業株式会社製）、及び硫酸銅五水和物を２３．６０ｇ（和光純薬工業株式会社製）を計りとり、更に総質量が２００ｇになるように超純水を加えて、均一になるまで攪拌して圧延銅箔用表面処理液を調製した。
３０ｍｍ四方に裁断した圧延銅箔ＨＡ－Ｖ２箔を、上記表面処理液を用いて攪拌速度を２００ｒｐｍ、液温を３０度に設定し、浸漬攪拌処理にて３μｍエッチング処理した。
結果を表１及び図２に示した。輝度の測定結果が未処理基板の２８．４より小さく、また図２より表面がクレーター状にエッチングされていないことから良好な平滑性であることが分かる。 [Example 1]
Hydrogen peroxide (A) 2.00 g (Mitsubishi Gas Chemical Co., Ltd. 60% hydrogen peroxide), sulfuric acid (B) 8.42 g (Wako Pure Chemical Industries, Ltd. 95% special grade reagent), alcohol (C) 1.00 g (polyethylene glycol 600 (PEG 600) (Wako first grade) manufactured by Wako Pure Chemical Industries, Ltd.), 0.06 g of phenylurea (D) (produced by Wako Pure Chemical Industries, Ltd.), and copper sulfate pentahydrate 23 .60 g (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed, and ultrapure water was added so that the total mass became 200 g, followed by stirring until uniform to prepare a surface treatment solution for rolled copper foil.
The rolled copper foil HA-V2 foil cut into a 30 mm square was etched using a surface treatment solution at a stirring speed of 200 rpm and a liquid temperature of 30 ° C., and subjected to a 3 μm etching process by immersion stirring.
The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and FIG. 2 shows that the surface is not etched into a crater shape, so that the smoothness is good.
［実施例２～９］
表１に示した組成に変更した以外は、実施例１と同様に操作を行った。結果を表１及び図２に示した。輝度の測定結果が未処理基板の２８．４より小さく、また図２より表面がクレーター状にエッチングされていないことから良好な平滑性であることが分かる。 [Examples 2 to 9]
The operation was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and FIG. 2 shows that the surface is not etched into a crater shape, so that the smoothness is good.
表１に示した組成に変更した以外は、実施例１と同様に操作を行った。結果を表１及び図２に示した。輝度の測定結果が未処理基板の２８．４より小さく、また図２より表面がクレーター状にエッチングされていないことから良好な平滑性であることが分かる。 [Examples 2 to 9]
The operation was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and FIG. 2 shows that the surface is not etched into a crater shape, so that the smoothness is good.
［実施例１０～１４］
表１に示した組成に変更した以外は、実施例１と同様に操作を行った。結果を表１及び図３に示した。輝度の測定結果が未処理基板の２８．４より小さく、また図３より表面がクレーター状にエッチングされていないことから良好な平滑性であることが分かる。 [Examples 10 to 14]
The operation was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and it can be seen from FIG. 3 that the surface is not etched into a crater shape, so that the smoothness is good.
表１に示した組成に変更した以外は、実施例１と同様に操作を行った。結果を表１及び図３に示した。輝度の測定結果が未処理基板の２８．４より小さく、また図３より表面がクレーター状にエッチングされていないことから良好な平滑性であることが分かる。 [Examples 10 to 14]
The operation was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The results are shown in Table 1 and FIG. The luminance measurement result is smaller than 28.4 of the untreated substrate, and it can be seen from FIG. 3 that the surface is not etched into a crater shape, so that the smoothness is good.
［比較例１～５］
表２に示した組成に変更した以外は、実施例１と同様に実験を行った。結果を表２及び図４に示した。輝度の測定結果が未処理基板の２８．４より大きいものや、また図４より表面がクレーター状にエッチングされているものがあることから良好な平滑性を得ることは出来ないことがわかる。 [Comparative Examples 1 to 5]
The experiment was performed in the same manner as in Example 1 except that the composition shown in Table 2 was changed. The results are shown in Table 2 and FIG. It can be seen that good smoothness cannot be obtained because the measurement result of the luminance is larger than 28.4 of the untreated substrate and the surface is etched in a crater shape from FIG.
表２に示した組成に変更した以外は、実施例１と同様に実験を行った。結果を表２及び図４に示した。輝度の測定結果が未処理基板の２８．４より大きいものや、また図４より表面がクレーター状にエッチングされているものがあることから良好な平滑性を得ることは出来ないことがわかる。 [Comparative Examples 1 to 5]
The experiment was performed in the same manner as in Example 1 except that the composition shown in Table 2 was changed. The results are shown in Table 2 and FIG. It can be seen that good smoothness cannot be obtained because the measurement result of the luminance is larger than 28.4 of the untreated substrate and the surface is etched in a crater shape from FIG.
［比較例６］
表３に示した組成（特許文献１の実施例）に変更した以外は、実施例１と同様に実験を行った。結果を表３及び図４に示した。図４より表面がクレーター状にエッチングされていないが、輝度の測定結果が未処理基板の２８．４より大きいことから良好な平滑性を得ることは出来ないことがわかる。 [Comparative Example 6]
An experiment was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3 (Example of Patent Document 1). The results are shown in Table 3 and FIG. Although the surface is not etched into a crater shape from FIG. 4, it can be seen that good smoothness cannot be obtained because the luminance measurement result is larger than 28.4 of the untreated substrate.
表３に示した組成（特許文献１の実施例）に変更した以外は、実施例１と同様に実験を行った。結果を表３及び図４に示した。図４より表面がクレーター状にエッチングされていないが、輝度の測定結果が未処理基板の２８．４より大きいことから良好な平滑性を得ることは出来ないことがわかる。 [Comparative Example 6]
An experiment was performed in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3 (Example of Patent Document 1). The results are shown in Table 3 and FIG. Although the surface is not etched into a crater shape from FIG. 4, it can be seen that good smoothness cannot be obtained because the luminance measurement result is larger than 28.4 of the untreated substrate.
本発明の製造方法により得られた圧延銅箔は、表面の平滑性に優れているため、フレキシブルプリント配線板（ＦＰＣ）等に好適に用いることができる。
Since the rolled copper foil obtained by the production method of the present invention is excellent in surface smoothness, it can be suitably used for a flexible printed wiring board (FPC) or the like.
Since the rolled copper foil obtained by the production method of the present invention is excellent in surface smoothness, it can be suitably used for a flexible printed wiring board (FPC) or the like.
Claims (15)
- 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある表面処理液を、圧延銅箔表面と接触させて圧延銅箔表面を溶解させることにより、圧延銅箔表面を処理することを含む、圧延銅箔の製造方法。 Contains hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D), and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.3 to 3.0 A surface treatment liquid in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0 mass% and the content of alcohol (C) is in the range of 0.1 to 5.0 mass%. The manufacturing method of the rolled copper foil including processing a rolled copper foil surface by making it contact with a rolled copper foil surface and dissolving the rolled copper foil surface.
- ３５℃の処理条件下で測定される次式：
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］）
で示される圧延銅箔のエッチングレート（Ｅ／Ｒ）が、０．４～４．０μｍ／分の範囲にある、請求項１に記載の圧延銅箔の製造方法。 The following equation, measured under 35 ° C processing conditions:
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
The method for producing a rolled copper foil according to claim 1, wherein an etching rate (E / R) of the rolled copper foil represented by the formula is in the range of 0.4 to 4.0 µm / min. - 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たす、請求項１又は２に記載の圧延銅箔の製造方法。 Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the irregularities on the surface of the rolled copper foil is set to a single threshold value of 47. The brightness of the rolled copper foil before and after the surface treatment, which was set and set to a series of 20 using a histogram and obtained using a standard deviation, is given by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The manufacturing method of the rolled copper foil of Claim 1 or 2 which satisfy | fills the relationship of these. - 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％≦－５％
の関係を満たす、請求項１又は２に記載の圧延銅箔の製造方法。 Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the irregularities on the surface of the rolled copper foil is set to a single threshold value of 47. The brightness of the rolled copper foil before and after the surface treatment, which was set and set to a series of 20 using a histogram and obtained using a standard deviation, is given by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% ≦ −5%
The manufacturing method of the rolled copper foil of Claim 1 or 2 which satisfy | fills the relationship of these. - 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、請求項１から４のいずれか一項に記載の圧延銅箔の製造方法。 The contents of the hydrogen peroxide (A) and phenylurea (D) are in the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The manufacturing method of the rolled copper foil as described in any one of Claim 1 to 4 which exists in. - 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、請求項１から５のいずれか一項に記載の圧延銅箔の製造方法。 The method for producing a rolled copper foil according to any one of claims 1 to 5, wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9.
- 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある圧延銅箔用表面処理液を用いて、圧延銅箔表面を溶解させることを含む、圧延銅箔の表面処理方法。 Contains hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D), and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.3 to 3.0 For rolled copper foil in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0 mass% and the content of alcohol (C) is in the range of 0.1 to 5.0 mass% A surface treatment method for a rolled copper foil, comprising dissolving the surface of the rolled copper foil using a surface treatment liquid.
- ３５℃の処理条件下で測定される次式：
エッチングレート［μｍ／ｍｉｎ］＝（処理前の質量［ｇ］－１分間処理後の質量［ｇ］）／（処理面積［ｍ２］×＜銅の比重＞８．９２［ｇ／ｃｍ３］）
で示される圧延銅箔のエッチングレート０．４～４．０μｍ／ｍｉｎの速度で圧延銅箔表面を溶解させることを含む、請求項７に記載の圧延銅箔の表面処理方法。 The following equation, measured under 35 ° C processing conditions:
Etching rate [μm / min] = (mass before treatment [g] −1 mass after treatment [g]) / (treatment area [m 2 ] × <specific gravity of copper> 8.92 [g / cm 3 ] )
The rolled copper foil surface treatment method according to claim 7, comprising dissolving the rolled copper foil surface at a rate of 0.4 to 4.0 μm / min. - 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％＜０％
の関係を満たす、請求項７又は８に記載の圧延銅箔の表面処理方法。 Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the irregularities on the surface of the rolled copper foil is set to a single threshold value of 47. The brightness of the rolled copper foil before and after the surface treatment, which was set and set to a series of 20 using a histogram and obtained using a standard deviation, is given by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% <0%
The surface treatment method of the rolled copper foil of Claim 7 or 8 satisfy | filling the relationship of these. - 走査型電子顕微鏡（ＳＥＭ）を用いて、加速電圧５ｋＶ及び倍率１０００倍の条件下で得られたＳＥＭ画像を画像処理し、圧延銅箔表面の凹凸部のコントラストを単一しきい値を４７に設定し、ヒストグラムを用いて級数を２０とし、標準偏差を用いて求めた前記表面処理前後の圧延銅箔の輝度が、次式：
｛（処理後の銅箔の輝度）－（未処理銅箔の輝度）｝／（未処理銅箔の輝度）×１００％≦－５％
の関係を満たす、請求項７又は８に記載の圧延銅箔の表面処理方法。 Using a scanning electron microscope (SEM), the SEM image obtained under the conditions of an acceleration voltage of 5 kV and a magnification of 1000 times is subjected to image processing, and the contrast of the irregularities on the surface of the rolled copper foil is set to a single threshold value of 47. The brightness of the rolled copper foil before and after the surface treatment, which was set and set to a series of 20 using a histogram and obtained using a standard deviation, is given by the following formula:
{(Luminance of copper foil after treatment) − (luminance of untreated copper foil)} / (luminance of untreated copper foil) × 100% ≦ −5%
The surface treatment method of the rolled copper foil of Claim 7 or 8 satisfy | filling the relationship of these. - 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、請求項７から１０のいずれか一項に記載の圧延銅箔の表面処理方法。 The contents of the hydrogen peroxide (A) and phenylurea (D) are in the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The surface treatment method of the rolled copper foil according to any one of claims 7 to 10, - 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、請求項７から１１のいずれか一項に記載の圧延銅箔の表面処理方法。 The surface treatment method for a rolled copper foil according to any one of claims 7 to 11, wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9.
- 過酸化水素（Ａ）、硫酸（Ｂ）、アルコール（Ｃ）及びフェニル尿素（Ｄ）を含有し、過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．３～３．０の範囲にあり、硫酸（Ｂ）の含有量が０．５～１５．０質量％の範囲にあり、アルコール（Ｃ）の含有量が０．１～５．０質量％の範囲にある、圧延銅箔用表面処理液。 Contains hydrogen peroxide (A), sulfuric acid (B), alcohol (C) and phenylurea (D), and the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.3 to 3.0 A rolled copper foil in which the content of sulfuric acid (B) is in the range of 0.5 to 15.0 mass% and the content of alcohol (C) is in the range of 0.1 to 5.0 mass% Surface treatment liquid.
- 前記過酸化水素（Ａ）、及びフェニル尿素（Ｄ）の含有量がそれぞれ下記の範囲：
過酸化水素（Ａ）：０．５～３．０質量％
フェニル尿素（Ｄ）：０．００５～０．３質量％
にある、請求項１３に記載の圧延銅箔用表面処理液。 The contents of the hydrogen peroxide (A) and phenylurea (D) are in the following ranges, respectively:
Hydrogen peroxide (A): 0.5-3.0% by mass
Phenylurea (D): 0.005 to 0.3% by mass
The surface treatment liquid for rolled copper foil according to claim 13. - 過酸化水素（Ａ）／硫酸（Ｂ）のモル比が０．５～０．９の範囲にある、請求項１３又は１４に記載の圧延銅箔用表面処理液。
The surface treatment liquid for rolled copper foil according to claim 13 or 14, wherein the molar ratio of hydrogen peroxide (A) / sulfuric acid (B) is in the range of 0.5 to 0.9.
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| CN201880021257.1A CN110462103A (en) | 2017-03-31 | 2018-03-23 | The surface treatment liquid and surface treatment method of rolled copper foil and the manufacturing method of rolled copper foil |
| KR1020197027199A KR102568740B1 (en) | 2017-03-31 | 2018-03-23 | Surface treatment liquid and surface treatment method of rolled copper foil and manufacturing method of rolled copper foil |
| JP2019509711A JP7074127B2 (en) | 2017-03-31 | 2018-03-23 | Surface treatment liquid and surface treatment method for rolled copper foil and manufacturing method for rolled copper foil |
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| KR (1) | KR102568740B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981447A (en) * | 2021-11-10 | 2022-01-28 | 纳然电子技术(苏州)有限公司 | Etching solution |
| CN115928071A (en) * | 2022-12-02 | 2023-04-07 | 江西荣晖电子有限公司 | Pretreatment method of copper foil for PCB |
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- 2018-03-23 JP JP2019509711A patent/JP7074127B2/en active Active
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| JPH0260189A (en) * | 1988-08-26 | 1990-02-28 | Mitsubishi Gas Chem Co Inc | Manufacture of thin copper foil plated circuit board |
| JP2012229460A (en) * | 2011-04-25 | 2012-11-22 | Mitsubishi Gas Chemical Co Inc | Treatment agent for copper or copper alloy surface |
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| CN115928071A (en) * | 2022-12-02 | 2023-04-07 | 江西荣晖电子有限公司 | Pretreatment method of copper foil for PCB |
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| KR102568740B1 (en) | 2023-08-21 |
| JP7074127B2 (en) | 2022-05-24 |
| JPWO2018180988A1 (en) | 2020-02-06 |
| TW201843349A (en) | 2018-12-16 |
| TWI808075B (en) | 2023-07-11 |
| KR20190133164A (en) | 2019-12-02 |
| CN110462103A (en) | 2019-11-15 |
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