JP2012112009A - Copper foil, and method for producing copper foil - Google Patents
Copper foil, and method for producing copper foil Download PDFInfo
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- JP2012112009A JP2012112009A JP2010263195A JP2010263195A JP2012112009A JP 2012112009 A JP2012112009 A JP 2012112009A JP 2010263195 A JP2010263195 A JP 2010263195A JP 2010263195 A JP2010263195 A JP 2010263195A JP 2012112009 A JP2012112009 A JP 2012112009A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000011889 copper foil Substances 0.000 title claims abstract description 139
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 91
- 238000005498 polishing Methods 0.000 claims abstract description 56
- 238000007747 plating Methods 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 47
- 238000007788 roughening Methods 0.000 claims abstract description 36
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000002265 prevention Effects 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 description 32
- 239000010949 copper Substances 0.000 description 32
- 239000011888 foil Substances 0.000 description 17
- 239000010408 film Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Electroplating Methods And Accessories (AREA)
- ing And Chemical Polishing (AREA)
Abstract
【課題】屈曲性及び密着性を向上させることを可能とした銅箔、及び銅箔の製造方法を提供する。
【解決手段】銅箔１は、銅箔材１０の少なくとも一方の表面上に形成された粗化処理層２０と、粗化処理層２０上に形成された１層以上の防錆処理層３０とを有している。粗化処理層２０は、下地めっき層を施さずに化学研磨した後の銅箔材１０の表面上に形成されている。化学研磨した後の銅箔材１０の表面に形成された凹部１１の深さの平均値は、０．０５μｍ以上０．３μｍ以下である。
【選択図】図１The present invention provides a copper foil and a method for producing the copper foil capable of improving flexibility and adhesion.
A copper foil 1 includes a roughening treatment layer 20 formed on at least one surface of a copper foil material 10, and one or more rust prevention treatment layers 30 formed on the roughening treatment layer 20. have. The roughening treatment layer 20 is formed on the surface of the copper foil material 10 after chemical polishing without applying a base plating layer. The average value of the depth of the recess 11 formed on the surface of the copper foil material 10 after chemical polishing is 0.05 μm or more and 0.3 μm or less.
[Selection] Figure 1
Description
本発明は、銅箔、及び銅箔の製造方法に係わり、特に、プリント配線基板等に好適に用いられる銅箔、及び銅箔の製造方法に関するものである。 The present invention relates to a copper foil and a copper foil manufacturing method, and particularly to a copper foil suitably used for a printed wiring board and the like, and a copper foil manufacturing method.
ノート型パーソナルコンピュータや携帯電話機などの折り畳み可能な電気・電子機器に使用されるフレキシブルプリント配線基板（以下、「ＦＰＣ」という。）は、相手方の樹脂基材に銅箔を貼り合わせ、フォトリソグラフィー法を用いて銅箔をエッチングすることで回路パターンを形成している。このＦＰＣとしての重要な性能の一つは、屈曲性を有することであり、もう一つの重要な性能としては、銅箔及び樹脂基材との間に強固な密着強度を有することである。 A flexible printed circuit board (hereinafter referred to as “FPC”) used in foldable electrical and electronic equipment such as notebook personal computers and mobile phones is a photolithography method in which a copper foil is bonded to a resin substrate of the other party. The circuit pattern is formed by etching the copper foil using One important performance as this FPC is that it has flexibility, and another important performance is that it has a strong adhesion strength between the copper foil and the resin substrate.
銅箔の屈曲性としては、電解銅箔に比較して圧延銅箔の方が高いのが一般的である。一方、銅箔及び樹脂基材に高い密着強度を得るのには、粗化粒子が銅箔表面に均一に析出していることである。この銅箔の表面には、粗化処理による凹凸を形成する表面処理を施すことが一般に行われているが、この銅箔表面の凹部のエッジ部には電流が集中し、粗化粒子が成長しやすく、その凹部の底部には粗化粒子が成長しにくい。このため、粗化粒子のバラツキが発生してしまい、このバラツキがピール強度の低下、及び面内均一性の低下を引き起こす要因となってしまう。これを防止することを目的として、粗化処理を施す前に、銅箔表面に下地銅めっきを施すことで、銅箔表面の凹部を埋める方法がある（例えば、特許文献１参照）。 As for the flexibility of the copper foil, the rolled copper foil is generally higher than the electrolytic copper foil. On the other hand, in order to obtain high adhesion strength to the copper foil and the resin base material, the roughened particles are uniformly deposited on the copper foil surface. The surface of this copper foil is generally subjected to a surface treatment that forms irregularities by roughening treatment, but current concentrates on the edge of the concave portion of this copper foil surface, and roughened particles grow. It is easy to roughen, and it is difficult for the coarse particles to grow at the bottom of the recess. For this reason, variation of roughened particles occurs, and this variation causes a decrease in peel strength and a decrease in in-plane uniformity. In order to prevent this, there is a method of filling a concave portion on the surface of the copper foil by performing base copper plating on the surface of the copper foil before the roughening treatment (see, for example, Patent Document 1).
ところで、電気・電子機器の更なる小型化・薄型化が進むのに伴い、ＦＰＣには高い屈曲性が求められている。このＦＰＣ用の銅箔の屈曲性を向上させるためには、銅箔自体の改善、もしくはめっきの薄肉化が考えられる。このめっきの薄肉化については、銅箔上に順番に施す下地銅めっきと粗化銅めっきの薄肉化が考えられる。しかしながら、下地銅めっきを薄くすると、銅箔表面の凹部が埋められず、不均一な粗化粒子が形成されてしまい、その下地銅めっき上に粗化銅めっきを形成しても、不均一な粗化粒子が形成されてしまう。 Incidentally, as electric and electronic devices are further reduced in size and thickness, FPCs are required to have high flexibility. In order to improve the flexibility of the FPC copper foil, it is conceivable to improve the copper foil itself or to reduce the thickness of the plating. As for the thinning of the plating, it is conceivable to reduce the thickness of the base copper plating and the roughened copper plating which are sequentially applied on the copper foil. However, when the base copper plating is thinned, the concave portions on the surface of the copper foil are not filled, and uneven rough particles are formed. Even if the rough copper plating is formed on the base copper plating, the uneven copper plating is not uniform. Roughened particles are formed.
本発明の目的は、屈曲性及び密着性を向上させることを可能とした銅箔、及び銅箔の製造方法を提供することにある。 An object of the present invention is to provide a copper foil and a copper foil manufacturing method capable of improving flexibility and adhesion.
［１］本発明は、銅箔材と、前記銅箔材の少なくとも一方の表面上に形成された粗化処理層と、前記粗化処理層上に形成された１層以上の防錆処理層とを有し、前記粗化処理層は、下地めっき層を施さずに化学研磨した後の前記銅箔材の表面上に形成されたものであり、前記化学研磨した後の前記銅箔材の表面に形成された凹部の深さの平均値が、０．０５μｍ以上０．３μｍ以下であることを特徴とする銅箔が提供される。 [1] The present invention provides a copper foil material, a roughening treatment layer formed on at least one surface of the copper foil material, and one or more rust prevention treatment layers formed on the roughening treatment layer. And the roughening treatment layer is formed on the surface of the copper foil material after chemical polishing without applying a base plating layer, and the copper foil material after chemical polishing An average value of the depths of the recesses formed on the surface is 0.05 μm or more and 0.3 μm or less.
［２］上記［１］記載の発明にあって、前記銅箔材の前記粗化処理層とは反対側の他方の表面における下地めっき層を施さずに化学研磨した後に形成された凹部の深さの平均値が、０．０５μｍ以上０．３μｍ以下であることを特徴とする。 [2] In the invention described in [1] above, the depth of the recess formed after chemical polishing without applying a base plating layer on the other surface of the copper foil material opposite to the roughening treatment layer. The average value is 0.05 μm or more and 0.3 μm or less.
［３］本発明は更に、銅箔材の少なくとも一方の表面に粗化処理層を形成する工程と、前記粗化処理層上に１層以上の防錆処理層を形成する工程とを有し、前記粗化処理層を形成する工程前に、前記銅箔材の表面に、下地めっき層を施さずに化学研磨処理を行う化学研磨工程を含み、前記化学研磨工程は、過酸化水素と硫酸を主成分とする研磨液を用い、前記研磨液の温度を３０℃以上６０℃以下に設定し、かつ、スプレー法、又は浸漬法により１０秒以上６０秒以下の処理時間で行うことを特徴とする銅箔の製造方法が提供される。 [3] The present invention further includes a step of forming a roughening treatment layer on at least one surface of the copper foil material, and a step of forming one or more rust prevention treatment layers on the roughening treatment layer. Before the step of forming the roughening layer, a chemical polishing step is performed in which the surface of the copper foil material is subjected to a chemical polishing treatment without applying a base plating layer, and the chemical polishing step includes hydrogen peroxide and sulfuric acid. Characterized in that the temperature of the polishing liquid is set to 30 ° C. or higher and 60 ° C. or lower and the processing time is 10 seconds or longer and 60 seconds or shorter by a spray method or an immersion method. A method for producing a copper foil is provided.
［４］上記［３］記載の発明にあって、前記化学研磨工程後の前記銅箔材の厚みの減少が、片面あたり０．３μｍ以上１．２μｍ以下であることを特徴とする。 [4] In the invention described in [3] above, the reduction in thickness of the copper foil material after the chemical polishing step is 0.3 μm or more and 1.2 μm or less per side.
［５］上記［３］記載の発明にあって、前記研磨液は、前記過酸化水素を１０％以上２５％以下、前記硫酸を１％以上５％以下、メタノールを０．５％以上５％以下の濃度でそれぞれ含有させ、水で２倍以上５倍以下に希釈して使用することを特徴とする。 [5] In the invention according to the above [3], the polishing liquid is 10% to 25% of the hydrogen peroxide, 1% to 5% of the sulfuric acid, and 0.5% to 5% of methanol. Each of them is contained at the following concentrations, and is diluted to 2 to 5 times with water and used.
［６］上記［３］記載の発明にあって、前記化学研磨工程後に、濃度１０％以上３０％以下の希硫酸水溶液を用い、浸漬時間を５秒以上３０秒以下、液温を２０℃以上３５℃以下の条件で、前記銅箔材の表面に形成された酸化膜を除去する工程を含むことを特徴とする。 [6] In the invention described in [3] above, after the chemical polishing step, a dilute sulfuric acid aqueous solution having a concentration of 10% to 30% is used, the immersion time is 5 seconds to 30 seconds, and the liquid temperature is 20 ° C. or higher. It includes a step of removing an oxide film formed on the surface of the copper foil material under a condition of 35 ° C. or lower.
本発明によると、薄い平坦性、優れた屈曲性を有し、均一で安定した銅箔が得られるとともに、ピール強度を高めることができる。 According to the present invention, it is possible to obtain a uniform and stable copper foil having thin flatness and excellent flexibility, and to increase the peel strength.
以下、本発明の好適な実施の形態を添付図面に基づいて具体的に説明する。 Preferred embodiments of the present invention will be specifically described below with reference to the accompanying drawings.
（銅箔の構成）
図１において、全体を示す符号１は、銅箔を模式的に示している。この銅箔１は、少なくとも一方の表面に凹部１１を有する銅箔材１０と、その銅箔材１０の基材接合面側に粗化処理層２０、及び防錆処理層３０を順次積層形成した薄膜積層構造からなり、フレキシブルプリント配線板（ＦＰＣ）などの配線基材の導電体として好適に用いられる。
(Composition of copper foil)
In FIG. 1, the code | symbol 1 which shows the whole has shown the copper foil typically. This copper foil 1 was formed by sequentially laminating a copper foil material 10 having a recess 11 on at least one surface, and a roughening treatment layer 20 and a rust prevention treatment layer 30 on the base material bonding surface side of the copper foil material 10. It has a thin film laminated structure and is suitably used as a conductor of a wiring substrate such as a flexible printed wiring board (FPC).
一方、銅箔１と貼り合わせて用いる基材としては、例えばポリイミド樹脂材料やガラスエポキシ樹脂材料等からなるシート状又はフィルム状をなす絶縁性の基材が用いられる。この基材の表面に銅箔１を貼り合わせることで、ＣＣＬ（copper clad laminate）である銅張積層板が得られる。エッチングにより銅張積層板の銅箔面に配線パターンを形成することでフレキシブルプリント配線板が製造される。 On the other hand, as the base material used by being bonded to the copper foil 1, for example, an insulating base material in the form of a sheet or film made of a polyimide resin material, a glass epoxy resin material, or the like is used. A copper clad laminate which is a CCL (copper clad laminate) is obtained by bonding the copper foil 1 to the surface of this base material. A flexible printed wiring board is manufactured by forming a wiring pattern on the copper foil surface of the copper-clad laminate by etching.
（銅箔材の構成）
この銅箔材１０は、所定の厚さを有するとともに、定法に従い電解銅箔又は圧延銅箔から形成される。この実施の形態にあっては、銅箔材１０を圧延銅箔の形態で用いることで、銅箔材１０の表面の平坦性を確保するとともに、銅箔１に優れた折り曲げ性（屈曲性）を付与している。この銅箔材１０の材料としては、例えばタフピッチ銅（ＴＰＣ）又は無酸素銅（ＯＦＣ）からなる高純度の銅、又は各種の銅合金材を用いることができる。
(Composition of copper foil material)
The copper foil material 10 has a predetermined thickness and is formed from an electrolytic copper foil or a rolled copper foil according to a conventional method. In this embodiment, by using the copper foil material 10 in the form of a rolled copper foil, the flatness of the surface of the copper foil material 10 is ensured and the bendability (flexibility) excellent in the copper foil 1 is ensured. Is granted. As the material of the copper foil material 10, for example, high-purity copper made of tough pitch copper (TPC) or oxygen-free copper (OFC), or various copper alloy materials can be used.
この実施の形態の構成は、銅箔材１０の薄い平坦性を確保するとともに、銅箔１に優れた折り曲げ性、及びピール強度を付与することを目的として、銅箔材１０の表面に下地めっきを施していない。即ち、この実施の形態の主要な基本の構成は、下地めっきを施さずに銅箔材１０の表面を化学研磨することにあり、化学研磨した後の銅箔材１０の少なくとも基材接合面側に粗化処理層２０、及び防錆処理層３０を順次積層形成している。化学研磨した後の銅箔材１０の基材接合面側の表面に形成された凹部１１、及び銅箔材１０の基材接合面側とは反対側の表面に形成された凹部１１の深さの平均値は、０．０５μｍ以上０．３μｍ以下となることが肝要である。 The configuration of this embodiment is to undercoat the surface of the copper foil material 10 for the purpose of ensuring the thin flatness of the copper foil material 10 and providing the copper foil 1 with excellent bendability and peel strength. Is not given. That is, the main basic configuration of this embodiment is to chemically polish the surface of the copper foil material 10 without performing base plating, and at least the base material bonding surface side of the copper foil material 10 after chemical polishing. The roughening treatment layer 20 and the rust prevention treatment layer 30 are sequentially laminated. Depth 11 formed on the surface of the copper foil material 10 on the base material bonding surface side after the chemical polishing, and depth of the concave portion 11 formed on the surface opposite to the base material bonding surface side of the copper foil material 10 It is important that the average value of is 0.05 μm or more and 0.3 μm or less.
ところで、この化学研磨処理では、研磨液に銅箔材１０を浸漬させると、以下の反応が起こる。
Ｈ２Ｏ２→Ｈ２Ｏ＋Ｏ
Ｃｕ＋Ｏ→ＣｕＯ
By the way, in this chemical polishing treatment, when the copper foil material 10 is immersed in the polishing liquid, the following reaction occurs.
H 2 O 2 → H 2 O + O
Cu + O → CuO
このように銅箔表面に酸化膜が形成される。その後、希硫酸水溶液に浸漬させることで以下の反応が起こり、銅が溶解する。
ＣｕＯ＋Ｈ２ＳＯ４→ＣｕＳＯ４＋Ｈ２Ｏ
Thus, an oxide film is formed on the copper foil surface. Then, the following reaction occurs by being immersed in dilute sulfuric acid aqueous solution, and copper dissolves.
CuO + H 2 SO 4 → CuSO 4 + H 2 O
このような金属の溶解による表面の平滑化の原理は、拡散速度の調整から説明される。即ち、凹凸のある金属表面を浴に浸すと、研磨液との界面に溶解反応で生じた金属酸化物の拡散層が形成される。この拡散層を通して、金属は浴中に塩として溶解するが、この段階での拡散速度の差で平滑化する拡散速度Ｖは、次式で示される。
Ｖ＝Ｄ（Ｃｏ−Ｃｅ）／σ
ここで、Ｄ：拡散定数、Ｃｏ：浴中の金属イオン濃度、Ｃｅ：金属表面上の金属イオン濃度、σ：拡散層の厚さ
The principle of smoothing the surface by melting the metal is explained by adjusting the diffusion rate. That is, when an uneven metal surface is immersed in a bath, a diffusion layer of a metal oxide generated by a dissolution reaction is formed at the interface with the polishing liquid. Through this diffusion layer, the metal dissolves as a salt in the bath, and the diffusion rate V smoothed by the difference in diffusion rate at this stage is expressed by the following equation.
V = D (Co-Ce) / σ
Where D: diffusion constant, Co: metal ion concentration in the bath, Ce: metal ion concentration on the metal surface, σ: thickness of the diffusion layer
上記式の拡散層の厚さσが見かけの金属表面に対して一様であるとすれば、凸部では薄く、凹部では厚くなり、逆に、拡散速度Ｖは凸部で早くなり、凹部では遅くなるため、金属表面の平滑化が行われる。 If the thickness σ of the diffusion layer in the above equation is uniform with respect to the apparent metal surface, the convex portion is thin, the concave portion is thick, and conversely, the diffusion rate V is high at the convex portion, and the concave portion is Since it becomes slow, the metal surface is smoothed.
（粗化銅めっき層の構成）
この粗化銅めっき層２０は、図１に示すように、化学研磨した後の銅箔材１０の表面に粗化銅めっきを行うことで樹枝状に形成される。粗化銅めっき層２０は、定法に従い、所定の表面粗さ、及び所定の膜厚をもって粗化処理を施されており、表面全域にわたって均一な粗面化形状を有している。粗化銅めっき層２０の表面粗度を上げることで、防錆処理層３０に対するアンカー効果が得られる。
(Configuration of roughened copper plating layer)
As shown in FIG. 1, the roughened copper plating layer 20 is formed in a dendritic shape by performing roughening copper plating on the surface of the copper foil material 10 after chemical polishing. The roughened copper plating layer 20 is subjected to a roughening process with a predetermined surface roughness and a predetermined film thickness according to a conventional method, and has a uniform roughened shape over the entire surface. By increasing the surface roughness of the roughened copper plating layer 20, an anchor effect for the antirust treatment layer 30 is obtained.
（防錆処理層の構成）
この防錆処理層３０は、定法に従い、所定の処理条件、及び所定の膜厚をもって、例えばニッケル−コバルト合金めっき層、亜鉛めっき層、クロメート処理層、及びシランカップリング層からなる多層のめっき層により構成される。この防錆処理層３０は、相手方の樹脂基材とのピール強度低下を抑制するとともに、ＣＣＬに回路配線を形成するときのエッチング性の低下を抑制する。
(Configuration of rust prevention layer)
This rust prevention treatment layer 30 is a multilayer plating layer comprising, for example, a nickel-cobalt alloy plating layer, a zinc plating layer, a chromate treatment layer, and a silane coupling layer according to a conventional method, with a prescribed treatment condition and a prescribed film thickness. Consists of. The rust prevention treatment layer 30 suppresses a decrease in peel strength with the counterpart resin base material and suppresses a decrease in etching property when forming circuit wiring on the CCL.
以上のように構成された実施の形態に係る銅箔１によれば、銅箔材１０の表面に下地めっきを施さずに化学研磨を施し、化学研磨した後の銅箔材１０の少なくとも基材接合面側に粗化処理層２０、及び防錆処理層３０を順次積層形成する。これにより、銅箔材１０の表面の平坦性を確保するとともに、銅箔１に優れた折り曲げ性、及び相手方の樹脂基材とのピール強度を高め、均一で安定した銅箔１が得られる。 According to the copper foil 1 according to the embodiment configured as described above, the surface of the copper foil material 10 is subjected to chemical polishing without applying base plating, and at least the base material of the copper foil material 10 after chemical polishing. A roughening treatment layer 20 and a rust prevention treatment layer 30 are sequentially laminated on the joint surface side. Thereby, while ensuring the flatness of the surface of the copper foil material 10, the bendability excellent in the copper foil 1 and the peel strength with the counterpart resin base material are increased, and the uniform and stable copper foil 1 is obtained.
（銅箔の製造方法）
図２を参照すると、図２には、この実施の形態に係る銅箔を製造するための典型的な製造工程が示されている。この銅箔１を製造する工程は、銅箔準備工程（図２（ａ））、前処理工程、化学研磨工程（図２（ｂ））、酸化膜除去工程、粗化処理工程、防錆処理工程を有する一連の工程からなる。これらの工程のうち、少なくとも銅箔準備、化学研磨、粗化処理、及び防錆処理を順番に行うことで初期の目的とする銅箔（図２（ｃ））が効果的に得られる。
(Manufacturing method of copper foil)
Referring to FIG. 2, FIG. 2 shows a typical manufacturing process for manufacturing a copper foil according to this embodiment. The steps for producing the copper foil 1 are: a copper foil preparation step (FIG. 2A), a pretreatment step, a chemical polishing step (FIG. 2B), an oxide film removal step, a roughening treatment step, and a rust prevention treatment. It consists of a series of steps having steps. Among these steps, at least the copper foil preparation, chemical polishing, roughening treatment, and rust prevention treatment are sequentially performed to effectively obtain the initial intended copper foil (FIG. 2C).
（銅箔準備工程）
先ず、所定の形状、所定の箔厚、及び所定の表面粗さを有する圧延銅箔からなる銅箔材１０を準備する。
(Copper foil preparation process)
First, a copper foil material 10 made of a rolled copper foil having a predetermined shape, a predetermined foil thickness, and a predetermined surface roughness is prepared.
（前処理工程）
この前処理工程は、次工程の化学研磨工程前に銅箔材１０の表面を洗浄する工程であり、銅箔材１０の表面に付着した付着物や油性の汚れなどを除去する。前処理工程では、めっき処理やエッチング処理などの表面処理を行う際に通常行われる洗浄処理を用いることができる。この洗浄処理としては、例えば電解脱脂、酸洗浄などを挙げることができる。
(Pretreatment process)
This pretreatment step is a step of cleaning the surface of the copper foil material 10 before the next chemical polishing step, and removes deposits, oily dirt, and the like attached to the surface of the copper foil material 10. In the pretreatment process, it is possible to use a cleaning process that is normally performed when performing a surface treatment such as plating or etching. Examples of the cleaning treatment include electrolytic degreasing and acid cleaning.
（化学研磨工程）
この化学研磨処理は、前処理工程後であって粗化処理工程の前に行い、前処理工程後の銅箔材１０の表面に下地めっきを施さない。この化学研磨工程では、過酸化水素と硫酸を主成分とする研磨液を用いることができる。この研磨液としては、過酸化水素を１０％以上２５％以下、硫酸を１％以上５％以下、メタノールを０．５％以上５％以下の濃度でそれぞれ含有させ、水で２倍以上５倍以下に希釈して使用することができる。
(Chemical polishing process)
This chemical polishing treatment is performed after the pretreatment step and before the roughening treatment step, and the surface of the copper foil material 10 after the pretreatment step is not subjected to base plating. In this chemical polishing step, a polishing liquid mainly containing hydrogen peroxide and sulfuric acid can be used. As this polishing liquid, hydrogen peroxide is contained in a concentration of 10% to 25%, sulfuric acid is contained in a concentration of 1% to 5%, and methanol is contained in a concentration of 0.5% to 5%. It can be used after diluted as follows.
化学研磨方法としては、スプレー法、又は浸漬法等を挙げることができる。処理時間としては、１０秒以上６０秒以下、好ましくは１５秒以上４０秒以下で行うことが望ましい。研磨液の温度としては、３０℃以上６０℃以下、好ましくは４５秒以上５５秒以下に設定することが望ましい。この液温が高いほど、銅箔材１０の研磨速度（溶解速度）が速くなり、短時間で処理が可能であるが、液温が６０℃を超えると、研磨液が沸騰してしまうので実用的には好ましくない。 Examples of the chemical polishing method include a spray method and an immersion method. The treatment time is 10 seconds to 60 seconds, preferably 15 seconds to 40 seconds. The temperature of the polishing liquid is preferably set to 30 ° C. or more and 60 ° C. or less, preferably 45 seconds or more and 55 seconds or less. The higher the liquid temperature, the higher the polishing rate (dissolution rate) of the copper foil material 10 and the shorter the processing time is possible. However, when the liquid temperature exceeds 60 ° C., the polishing liquid will boil, so it is practical. It is not preferable.
以上の条件により銅箔材１０の表面に化学研磨を行うことで、化学研磨後の銅箔材１０の厚みの減少は、片面あたり０．３μｍ以上１．２μｍ以下となる。好ましくは、０．５以上１．０μｍ以下であることが好適である。なお、研磨液には、過酸化水素、硫酸、メタノール以外にも光沢剤を含む場合もある。 By performing chemical polishing on the surface of the copper foil material 10 under the above conditions, the thickness reduction of the copper foil material 10 after chemical polishing is 0.3 μm or more and 1.2 μm or less per side. Preferably, it is 0.5 or more and 1.0 μm or less. Note that the polishing liquid may contain a brightener in addition to hydrogen peroxide, sulfuric acid, and methanol.
（酸化膜除去工程）
化学研磨工程の直後に、銅箔材１０の表面に形成された酸化膜を除去する。この酸化膜除去工程では、濃度１０％以上３０％以下の希硫酸水溶液を用い、浸漬時間を５秒以上３０秒以下、液温を２０℃以上３５℃以下の条件で行うことができる。
(Oxide film removal process)
Immediately after the chemical polishing step, the oxide film formed on the surface of the copper foil material 10 is removed. In this oxide film removing step, a dilute sulfuric acid aqueous solution having a concentration of 10% or more and 30% or less can be used under the conditions of an immersion time of 5 seconds or more and 30 seconds or less and a liquid temperature of 20 ° C. or more and 35 ° C. or less.
（粗化処理工程）
酸化膜除去工程後の銅箔材１０の少なくとも一方の表面に粗化銅めっき層２０を定法に従い形成することができる。この粗化銅めっき層２０は、化学研磨した後の銅箔材１０の表面に粗化銅めっきを施すことで樹枝状に形成される。
(Roughening process)
The roughened copper plating layer 20 can be formed on at least one surface of the copper foil material 10 after the oxide film removing step according to a conventional method. The roughened copper plating layer 20 is formed in a dendritic shape by performing roughening copper plating on the surface of the copper foil material 10 after chemical polishing.
（防錆処理工程）
所定の樹脂基材に対する銅箔１の密着性を更に向上させることを目的として、粗化処理層上に１層以上の防錆処理層を形成する。定法に従い、粗化処理層上にニッケル−コバルト合金めっき層を、ニッケル−コバルト合金めっき層上に亜鉛めっき層を、亜鉛めっき層上にクロメート処理層を、クロメート処理層上にシランカップリング処理層を順次形成することができる。
(Rust prevention process)
For the purpose of further improving the adhesion of the copper foil 1 to a predetermined resin substrate, one or more rust prevention treatment layers are formed on the roughening treatment layer. According to an ordinary method, a nickel-cobalt alloy plating layer is formed on the roughening treatment layer, a zinc plating layer is formed on the nickel-cobalt alloy plating layer, a chromate treatment layer is formed on the zinc plating layer, and a silane coupling treatment layer is formed on the chromate treatment layer. Can be formed sequentially.
（実施の形態の効果）
従来の銅箔の製造においては、粗化処理前の銅箔材の表面形状を平坦化させるために下地銅めっきを施していた。この下地銅めっきにより、銅箔材の粗化粒子の均一性を向上させ、それに伴いピール強度を改善していた。しかしながら、めっき膜厚を厚くすることは屈曲性の低下に繋がるという問題があった。そこで、この実施の形態では、銅箔材の表面に下地銅めっきを施さないで、銅箔材の表面に化学研磨処理を行うことで平坦化させたので、次の効果が得られる。
（１）粗化粒子の均一性によるピール強度を維持することができるようになり、銅箔材の屈曲性を向上させることができる。
（２）化学研磨処理を施して、例えば従来と同じ厚みを有する銅箔材を製造すると、素材である原箔の厚みは、従来よりも厚い材料が必要になる。このため、材料を製作する際の圧延パス数が減り、材料の製造コストダウンが期待できる。その一例としては、例えば１２μｍ厚の銅箔材を製造する場合は、従来では１０．５μｍ厚の材料が必要であった。これに対し、銅箔材の表面に下地銅めっきを施すことなく、銅箔材の表面に化学研磨処理を行う場合には１２μｍ厚の材料で済むので、化学研磨処理後のめっき膜厚を薄くすることができるようになる。
（３）以上より、粗化粒子の均一性を保つとともに、めっき膜厚を薄くすることができるようになり、銅箔材の屈曲性、銅箔及び樹脂基材の間の密着性をも向上させることができる。
(Effect of embodiment)
In the manufacture of conventional copper foil, base copper plating has been applied to flatten the surface shape of the copper foil material before the roughening treatment. By this base copper plating, the uniformity of the roughened particles of the copper foil material was improved, and the peel strength was improved accordingly. However, there is a problem that increasing the plating film thickness leads to a decrease in flexibility. Therefore, in this embodiment, since the surface of the copper foil material is flattened by performing chemical polishing treatment on the surface of the copper foil material without performing base copper plating, the following effects are obtained.
(1) The peel strength due to the uniformity of the roughened particles can be maintained, and the flexibility of the copper foil material can be improved.
(2) When a chemical polishing treatment is performed to produce, for example, a copper foil material having the same thickness as the conventional one, a material that is thicker than the conventional one is required for the thickness of the raw foil that is a raw material. For this reason, the number of rolling passes when producing the material is reduced, and the production cost of the material can be expected to be reduced. As an example, in the case of producing a copper foil material having a thickness of 12 μm, for example, a material having a thickness of 10.5 μm has been conventionally required. On the other hand, if the surface of the copper foil material is subjected to a chemical polishing process without applying a base copper plating to the surface of the copper foil material, a material having a thickness of 12 μm is sufficient. Will be able to.
(3) From the above, while maintaining the uniformity of the roughened particles, the plating film thickness can be reduced, and the flexibility of the copper foil material and the adhesion between the copper foil and the resin base material are also improved. Can be made.
以下に、図３及び図４を参照しながら、本発明の更に具体的な実施の形態として、実施例を挙げて詳細に説明する。なお、この実施例では、上記実施の形態である銅箔の典型的な一例を挙げており、本発明は、この実施例に限定されるものではないことは勿論である。 Hereinafter, examples will be described in detail as specific embodiments of the present invention with reference to FIGS. 3 and 4. In this example, a typical example of the copper foil according to the above embodiment is given, and the present invention is of course not limited to this example.
１２μｍ厚の銅箔材を材料として準備した。始めに、脱脂、酸洗の前処理を行う。その後、化学研磨処理として、菱江化学株式会社製ＣＰＢ−１０（過酸化水素２１％、硫酸５％以下、メタノール５％以下）を水で３倍に希釈し、液温５５℃の条件で、銅箔材を２０秒間浸漬させた。銅箔材の厚みの減少が、片面あたり０．７μｍの値となった。その後、５％の希硫酸水溶液に銅箔材を２０秒間浸漬させた。その後更に、定法に従い、粗化処理と防錆処理とを施して銅箔（粗化箔）を作製した。 A 12 μm thick copper foil material was prepared as a material. First, pretreatment of degreasing and pickling is performed. Thereafter, CPB-10 (Hydrogen 21%, sulfuric acid 5% or less, methanol 5% or less) 3 times diluted with water as a chemical polishing treatment with copper at a liquid temperature of 55 ° C. The foil material was immersed for 20 seconds. The decrease in the thickness of the copper foil material was 0.7 μm per side. Thereafter, the copper foil material was immersed in a 5% dilute sulfuric acid aqueous solution for 20 seconds. Thereafter, according to a conventional method, a roughening treatment and an antirust treatment were performed to produce a copper foil (roughened foil).
図３にキーエンス社製のレーザー顕微鏡ＶＫ−８７００により観察した銅箔材の表面外観を示す。図３（ａ）は原箔の表面外観であり、図３（ｂ）は化学研磨処理後の表面外観である。化学研磨処理後の表面は、原箔の表面よりも、表面全域にわたって粗化粒子が銅箔表面に均一に析出していることが分かる。 FIG. 3 shows the surface appearance of the copper foil material observed with a laser microscope VK-8700 manufactured by Keyence Corporation. 3A shows the surface appearance of the raw foil, and FIG. 3B shows the surface appearance after the chemical polishing treatment. It can be seen that the roughened particles are uniformly deposited on the surface of the copper foil over the entire surface of the surface after the chemical polishing treatment, rather than the surface of the original foil.
この粗化箔の製作にあたり、表面に下地銅めっきを施した銅箔材と、下地銅めっきを施さないで、表面に化学研磨処理を行った銅箔材とにおける屈曲性とピール強度とを評価した。このときの銅箔材の厚みと表面粗さは、ほぼ同等のレベルであった。 In producing this roughened foil, the flexibility and peel strength of the copper foil material with the base copper plating on the surface and the copper foil material with the surface subjected to chemical polishing treatment without the base copper plating were evaluated. did. At this time, the thickness and surface roughness of the copper foil material were substantially equal.
屈曲試験は、粗化箔を熱処理した後に行った。ここで、ピール強度は、ポリイミドワニスをキャスト方式で粗化箔と貼り合わせ速度５０ｍｍ／ｍｉｎ、９０°に引き剥がした強度をいう。これらの結果を、図４にまとめて示す。 The bending test was performed after heat-treating the roughened foil. Here, the peel strength refers to the strength at which the polyimide varnish is peeled off at 90 ° at a bonding speed of 50 mm / min and the roughened foil by a casting method. These results are summarized in FIG.
図４に示す原箔の屈曲を１とすると、下地銅めっきを施さずに、表面に化学研磨処理により素材を平坦化させると、総めっき膜厚が薄くなり、下地銅めっきを施した粗化箔よりも屈曲の低下が抑えられた。 If the bending of the raw foil shown in FIG. 4 is 1, if the surface is flattened by chemical polishing on the surface without applying base copper plating, the total plating film thickness becomes thin, and roughening with base copper plating The decrease in bending was suppressed as compared with the foil.
下地銅めっきを施した粗化箔と、下地銅めっきを施さないで、化学研磨処理を行った粗化箔とは、粗化粒子の均一性がほぼ同等であるため、ピール強度は変わらなかった。図４から明らかなように、表面に化学研磨処理を施した粗化箔は、ピール強度を維持したままで屈曲性を上げることができた。 The peel strength did not change because the roughened foil with the base copper plating and the roughened foil with the chemical polishing treatment without the base copper plating had almost the same uniformity of the roughened particles. . As is apparent from FIG. 4, the roughened foil having the surface subjected to the chemical polishing treatment was able to increase the flexibility while maintaining the peel strength.
以上の説明からも明らかなように、本発明の銅箔、及び銅箔の製造方法の代表的な構成例を上記実施の形態、実施例、及び図示例を挙げて説明したが、上記実施の形態、実施例、及び図示例は特許請求の範囲に係る発明を限定するものではない。上記実施の形態、実施例、及び図示例の中で説明した特徴の組合せの全てが本発明の課題を解決するための手段に必須であるとは限らない点に留意すべきであり、本発明の技術思想の範囲内において種々の構成が可能であることは勿論である。 As is clear from the above description, a typical configuration example of the copper foil of the present invention and a method for producing the copper foil has been described with reference to the above embodiment, examples, and illustrated examples. The forms, the examples, and the illustrated examples do not limit the invention according to the claims. It should be noted that not all the combinations of features described in the above embodiments, examples, and illustrated examples are essential to the means for solving the problems of the present invention. Of course, various configurations are possible within the scope of this technical idea.
１ 銅箔
１０ 銅箔材
１１ 凹部
２０ 粗化処理層
３０ 防錆処理層
1 Copper foil 10 Copper foil material 11 Recess 20 Roughening treatment layer 30 Rust prevention treatment layer
Claims (6)
前記銅箔材の少なくとも一方の表面上に形成された粗化処理層と、
前記粗化処理層上に形成された１層以上の防錆処理層とを有し、
前記粗化処理層は、下地めっき層を施さずに化学研磨した後の前記銅箔材の表面上に形成されたものであり、
前記化学研磨した後の前記銅箔材の表面に形成された凹部の深さの平均値が、０．０５μｍ以上０．３μｍ以下であることを特徴とする銅箔。 Copper foil material,
A roughening treatment layer formed on at least one surface of the copper foil material;
Having one or more antirust treatment layers formed on the roughening treatment layer,
The roughening treatment layer is formed on the surface of the copper foil material after chemical polishing without applying a base plating layer,
The copper foil, wherein an average value of the depths of the recesses formed on the surface of the copper foil material after the chemical polishing is 0.05 μm or more and 0.3 μm or less.
前記粗化処理層を形成する工程前に、前記銅箔材の表面に、下地めっき層を施さずに化学研磨処理を行う化学研磨工程を含み、
前記化学研磨工程は、過酸化水素と硫酸を主成分とする研磨液を用い、前記研磨液の温度を３０℃以上６０℃以下に設定し、かつ、スプレー法、又は浸漬法により１０秒以上６０秒以下の処理時間で行うことを特徴とする銅箔の製造方法。 A step of forming a roughening treatment layer on at least one surface of the copper foil material, and a step of forming one or more rust prevention treatment layers on the roughening treatment layer,
Before the step of forming the roughening treatment layer, the surface of the copper foil material includes a chemical polishing step of performing a chemical polishing treatment without applying a base plating layer,
In the chemical polishing step, a polishing liquid mainly composed of hydrogen peroxide and sulfuric acid is used, the temperature of the polishing liquid is set to 30 ° C. or more and 60 ° C. or less, and 60 seconds or more by a spray method or an immersion method. The manufacturing method of the copper foil characterized by performing with the processing time of a second or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010263195A JP2012112009A (en) | 2010-11-26 | 2010-11-26 | Copper foil, and method for producing copper foil |
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| JP2010263195A JP2012112009A (en) | 2010-11-26 | 2010-11-26 | Copper foil, and method for producing copper foil |
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| JP2012112009A true JP2012112009A (en) | 2012-06-14 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018225409A1 (en) * | 2017-06-09 | 2018-12-13 | Ｊｘ金属株式会社 | Surface-treated copper foil, method for producing same, and copper-clad laminate |
| KR20200100138A (en) | 2018-03-29 | 2020-08-25 | 제이엑스금속주식회사 | Surface-treated copper foil and copper clad laminate |
| KR20220087525A (en) | 2019-12-13 | 2022-06-24 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230104700A (en) | 2021-01-15 | 2023-07-10 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230110591A (en) | 2021-07-09 | 2023-07-24 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230113357A (en) | 2021-07-09 | 2023-07-28 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230121117A (en) | 2021-07-09 | 2023-08-17 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230154812A (en) | 2021-07-09 | 2023-11-09 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230154808A (en) | 2021-07-09 | 2023-11-09 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| JP2024547091A (en) * | 2021-12-22 | 2024-12-26 | ロッテエナジーマテリアルズ株式会社 | Heat-resistant surface-treated copper foil, copper foil laminate and printed wiring board containing the same |
| KR20250011680A (en) | 2022-09-28 | 2025-01-21 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250012123A (en) | 2022-11-29 | 2025-01-23 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250016231A (en) | 2022-09-28 | 2025-02-03 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250018535A (en) | 2022-09-28 | 2025-02-06 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250018551A (en) | 2022-09-28 | 2025-02-06 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250023530A (en) | 2022-11-29 | 2025-02-18 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250036885A (en) | 2022-11-29 | 2025-03-14 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
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| JP2001073171A (en) * | 1999-09-06 | 2001-03-21 | Mitsui Mining & Smelting Co Ltd | Surface-regulated electrolytic copper foil, its production method and its use |
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| JP2004238647A (en) * | 2003-02-04 | 2004-08-26 | Furukawa Techno Research Kk | Smoothed copper foil and method for producing the same |
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| JP2001073171A (en) * | 1999-09-06 | 2001-03-21 | Mitsui Mining & Smelting Co Ltd | Surface-regulated electrolytic copper foil, its production method and its use |
| JP2002134858A (en) * | 2000-10-25 | 2002-05-10 | Hitachi Cable Ltd | Copper foil for printed circuit boards |
| JP2004238647A (en) * | 2003-02-04 | 2004-08-26 | Furukawa Techno Research Kk | Smoothed copper foil and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018225409A1 (en) * | 2017-06-09 | 2018-12-13 | Ｊｘ金属株式会社 | Surface-treated copper foil, method for producing same, and copper-clad laminate |
| KR20200100138A (en) | 2018-03-29 | 2020-08-25 | 제이엑스금속주식회사 | Surface-treated copper foil and copper clad laminate |
| KR20220087525A (en) | 2019-12-13 | 2022-06-24 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230104700A (en) | 2021-01-15 | 2023-07-10 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230154808A (en) | 2021-07-09 | 2023-11-09 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230113357A (en) | 2021-07-09 | 2023-07-28 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230121117A (en) | 2021-07-09 | 2023-08-17 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230154812A (en) | 2021-07-09 | 2023-11-09 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| KR20230110591A (en) | 2021-07-09 | 2023-07-24 | 제이엑스금속주식회사 | Surface treatment copper foil, copper clad laminate and printed wiring board |
| JP2024547091A (en) * | 2021-12-22 | 2024-12-26 | ロッテエナジーマテリアルズ株式会社 | Heat-resistant surface-treated copper foil, copper foil laminate and printed wiring board containing the same |
| KR20250011680A (en) | 2022-09-28 | 2025-01-21 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250016231A (en) | 2022-09-28 | 2025-02-03 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250018535A (en) | 2022-09-28 | 2025-02-06 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250018551A (en) | 2022-09-28 | 2025-02-06 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250012123A (en) | 2022-11-29 | 2025-01-23 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250023530A (en) | 2022-11-29 | 2025-02-18 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
| KR20250036885A (en) | 2022-11-29 | 2025-03-14 | 제이엑스금속주식회사 | Surface treated copper foil, copper laminate and printed wiring board |
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