HK1194111B

HK1194111B - Copper foil excellent in adhesion with resin, method for manufacturing same, and printed wiring board or battery negative electrode material using electrolytic copper foil

Info

Publication number: HK1194111B
Application number: HK14107439.8A
Authority: HK
Inventors: 伦也古曳; 晃正森山
Original assignee: Jx日矿日石金属株式会社
Priority date: 2011-09-30
Filing date: 2012-09-18
Publication date: 2019-10-18

Description

Copper foil with excellent resin adhesion, method for producing the same, and printed wiring board or battery negative electrode material using the same

技术领域Technical Field

本发明涉及与树脂粘接性优良的铜箔、其制造方法以及使用所述电解铜箔的印刷布线板或电池用负极材料，特别地，本发明提供与通用的环氧树脂类基材(FR-4等)相比，将通常与铜箔粘着力低的半导体封装用基材或液晶聚合物基材和电解铜箔组合使用时，可得到剥离强度更高的电解铜箔、所述电解铜箔的制造方法以及使用所述电解铜箔的印刷布线板或电池用负极材料。所述电解铜箔作为印刷布线板或电池(LiB等)用负极材料使用的电解铜箔是有用的。The present invention relates to a copper foil having excellent resin adhesion, a method for producing the same, and a printed wiring board or battery negative electrode material using the same. In particular, the present invention provides an electrolytic copper foil that, when used in combination with a semiconductor package substrate or a liquid crystal polymer substrate, which generally has low adhesion to copper foil, and an electrolytic copper foil, can provide a higher peel strength than that of a general-purpose epoxy resin substrate (FR-4, etc.), a method for producing the electrolytic copper foil, and a printed wiring board or battery negative electrode material using the same. The electrolytic copper foil is useful as an electrolytic copper foil for use in printed wiring boards or batteries (such as LiBs).

背景技术Background Art

对作为现有技术的印刷布线板进行说明，所述印刷布线板通常按照下述工序制作：首先，在高温高压下，将铜箔层叠粘接到合成树脂等基材上；接着，为在基板上形成目标导电性电路，用耐蚀刻性树脂等材料在铜箔上印刷与所述电路等同的电路。A printed wiring board (PCB) as a conventional technology is described. The PCB is generally manufactured according to the following process: first, copper foil is laminated and bonded to a substrate such as a synthetic resin under high temperature and high pressure; then, in order to form a target conductive circuit on the substrate, a circuit equivalent to the circuit is printed on the copper foil using a material such as an etching-resistant resin.

接下来，通过蚀刻处理除去暴露的铜箔中的不需要部分。蚀刻后，除去残存的铜(电路部分)上由树脂(耐蚀刻树脂)等材料构成的印刷部分，在基板上形成导电性电路。在形成的导电性电路中，最终对特定的元件进行焊接，形成电子器件用的各种印刷电路板。最后，与抗蚀剂或叠增(ビルドアップ)树脂基板接合。Next, the exposed copper foil is etched to remove unnecessary portions. After etching, the printed portion, made of a material such as resin (etch-resistant resin), on the remaining copper (circuit area) is removed, forming a conductive circuit on the substrate. Specific components are ultimately soldered to this formed conductive circuit, creating various printed circuit boards for electronic devices. Finally, the printed circuit is bonded to a resist or laminated resin substrate.

对于与树脂的粘接面邻接的铜箔的粗化面，主要的是，要求与树脂基材具有充分的剥离强度，并且所述剥离强度在经过高温加热、湿法处理、焊接、化学品处理等之后仍能得以充分保持。The roughened surface of the copper foil adjacent to the resin bonding surface is primarily required to have sufficient peel strength with the resin substrate, and the peel strength must be sufficiently maintained even after high-temperature heating, wet processing, soldering, chemical treatment, and the like.

作为提高电解铜箔和树脂基材之间的剥离强度的方法，一般地，以在增大了表面轮廓(凸凹、粗度)的未加工的铜箔上附着大量粗化粒子的方法为代表。然而，在印刷布线板中有必要形成特别微细电路图案的半导体封装基板上，使用这种增大了轮廓(凸凹、粗度)的铜箔时，会在电路蚀刻时残留不需要的铜粒子，产生电路图案间的绝缘不良等问题。A common method for improving the peel strength between electrolytic copper foil and a resin substrate is to attach a large amount of roughening particles to an unprocessed copper foil with an increased surface profile (convexoconcavity, roughness). However, when using this type of copper foil with an increased surface profile (convexoconcavity, roughness) on semiconductor package substrates, where extremely fine circuit patterns must be formed in printed wiring boards, unwanted copper particles can remain during circuit etching, leading to problems such as poor insulation between circuit patterns.

因此，作为以半导体封装基板作为初始的微细电路用铜箔，使用低轮廓铜箔，所谓低轮廓铜箔是在确保与基材粘着性的基础上，在降低了轮廓的未加工的铜箔上实施最低限度的粗化处理的铜箔。这种低轮廓铜箔与树脂的粘着性(剥离强度)受其低轮廓(凹凸、粗糙度、粗度)的影响，与一般的印刷布线板用铜箔相比，所述粘着性有降低的倾向。Therefore, low-profile copper foil is used as the primary copper foil for fine circuits, primarily for semiconductor package substrates. Low-profile copper foil is a copper foil that has been subjected to minimal roughening treatment on an unprocessed copper foil with a reduced profile, while ensuring adhesion to the substrate. The adhesion (peel strength) of this low-profile copper foil to resin is affected by its low profile (concavity, roughness, and coarseness), and this adhesion tends to be lower than that of copper foil for general printed wiring boards.

此外，与FR-4等通用的环氧树脂类基材相比，通常半导体封装基板用树脂基材或液晶聚合物基材与铜箔的粘着性较低，与前述铜箔的低轮廓化相结合，铜箔与树脂基材之间的剥离强度有进一步降低的倾向。In addition, compared with general-purpose epoxy resin substrates such as FR-4, resin substrates or liquid crystal polymer substrates used for semiconductor packaging substrates generally have lower adhesion to copper foil. Combined with the low profile of the copper foil mentioned above, the peel strength between the copper foil and the resin substrate tends to be further reduced.

从而，作为这种细微布线用的铜箔，要求兼具与树脂基材粘接面的低轮廓化以及与树脂基材的高粘着性(剥离强度)。Therefore, copper foil for such fine wiring is required to have both a low profile of the bonding surface with the resin substrate and high adhesion (peel strength) with the resin substrate.

进一步地，伴随着通信的高速化、大容量化，电子信号的高频化的不断发展，个人计算机和移动通信设备等电子仪器要求能适应上述发展的印刷布线板和铜箔。当电子信号的频率达到1GHz以上时，电流仅在导体表面流过的趋肤效应的影响变得显著，因表面的凹凸使得电流传送的路径发生变化，无法忽视阻抗增大的影响。从这个观点出发，也希望铜箔的表面粗糙度小。由于高频电子信号具有传输损耗少的优点，在近年来使用持续扩大的液晶聚合物基材中，特别是由于与铜箔的粘着性变低，兼具铜箔的低轮廓化和粘着性(剥离强度)同样重要。Furthermore, with the continuous development of high-speed and large-capacity communications and high-frequency electronic signals, electronic devices such as personal computers and mobile communication devices require printed wiring boards and copper foils that can adapt to the above developments. When the frequency of the electronic signal reaches 1GHz or above, the influence of the skin effect, in which the current flows only on the surface of the conductor, becomes significant. The path of current transmission changes due to the unevenness of the surface, and the influence of increased impedance cannot be ignored. From this point of view, it is also hoped that the surface roughness of the copper foil is small. Since high-frequency electronic signals have the advantage of low transmission loss, in the liquid crystal polymer substrates that have been continuously used in recent years, especially since the adhesion to the copper foil has decreased, it is equally important to have both low profile and adhesion (peel strength) of the copper foil.

一般地，印刷布线板用铜箔的表面处理方法如下进行：在未加工的压延铜箔或电解铜箔上，首先，为提高铜箔与树脂的粘接力(剥离强度)，一般在铜箔表面进行表面粗化处理，所述表面粗化处理是在铜箔表面提供由铜和氧化铜构成的微粒。接着，为防止粗化处理粒子脱落、提高其粘着性，用硫酸铜镀浴进行覆镀(かぶせメッキ)。Generally, the surface treatment method for copper foil used in printed wiring boards is as follows: Unprocessed rolled copper foil or electrolytic copper foil is first subjected to a surface roughening treatment to improve the adhesion (peel strength) between the copper foil and the resin. This surface roughening treatment involves adding microparticles composed of copper and copper oxide to the surface of the copper foil. Next, to prevent the roughening particles from falling off and improve adhesion, a copper sulfate plating bath is used for overcoating.

进一步地，为使所述铜箔具有耐热性/耐候性，在进行过上述覆镀的铜箔上，形成黄铜或锌等的耐热处理层(阻挡层)。Furthermore, in order to impart heat resistance and weather resistance to the copper foil, a heat-resistant treated layer (barrier layer) of brass, zinc, or the like is formed on the copper foil subjected to the above-mentioned plating.

然后，为防止在搬运或保管中的表面氧化等，在形成耐热处理层的铜箔上，实施浸渍或电解铬酸盐处理或者电解铬/锌处理等的防锈处理，得到制品。Then, in order to prevent surface oxidation during transportation or storage, the copper foil having the heat-resistant treatment layer formed thereon is subjected to rust-proofing treatment such as immersion, electrolytic chromate treatment, or electrolytic chromium/zinc treatment to obtain a product.

其中，特别是在提供铜箔(电解)与树脂基材的粘接力(剥离强度)方面，粗化粒子层发挥着最重要的作用。在印刷布线板用铜箔与树脂的粘接面上，一般形成耐热/防锈处理层。作为形成耐热处理层的金属或合金的实例，形成有Zn、Cu-Ni、Cu-Co和Cu-Zn等的覆盖层的多种铜箔正得以实用化(例如，参照专利文献3)。Among them, the roughened particle layer plays a particularly important role in providing adhesion (peel strength) between the copper foil (electrolytic) and the resin substrate. A heat-resistant/rust-proof treatment layer is generally formed on the bonding surface of the copper foil for printed wiring boards and the resin. As examples of metals or alloys forming the heat-resistant treatment layer, various copper foils with covering layers such as Zn, Cu-Ni, Cu-Co, and Cu-Zn are being put into practical use (for example, see Patent Document 3).

其中，形成由Cu-Zn(黄铜)构成的耐热处理层后的铜箔具有如下优异特性：与环氧树脂等构成的印刷电路板层叠时，没有树脂层的污渍且高温加热后剥离强度的劣化小等，因而在工业上得到广泛使用。Among them, copper foil formed with a heat-resistant layer composed of Cu-Zn (brass) has the following excellent properties: when laminated with a printed wiring board composed of epoxy resin, there is no contamination from the resin layer and the deterioration of peel strength after high-temperature heating is minimal. Therefore, it is widely used in industry.

对于形成这种由黄铜构成的耐热处理层的方法，在专利文献4和专利文献5中有详细描述。The method of forming such a heat-resistant treatment layer made of brass is described in detail in Patent Documents 4 and 5.

进而，在上述耐热处理层上进行铬酸盐处理后，在铬酸盐处理后的表面上吸附有硅烷偶联剂以提高与树脂基材的粘着性的方法也在工业上得到广泛使用。作为上述粗化处理的方法，可列举几种公知技术。例如，专利文献8中公开了一种印刷电路用铜箔，所述印刷电路用铜箔在铜箔的被粘接面上具有粗化处理层，所述粗化处理层由多个突起状电沉积物构成，所述突起状电沉积物含有铬或钨中的一种或两种。所述粗化处理层以提高粘接强度和耐热性、抑制落粉为目的。Furthermore, a method in which a silane coupling agent is adsorbed onto the heat-resistant treated layer after chromating to improve adhesion to a resin substrate is also widely used in industry. Several known techniques are available for roughening the layer. For example, Patent Document 8 discloses a copper foil for printed circuits having a roughening layer on the bonded surface of the foil. The roughening layer comprises a plurality of protruding electrodeposits containing one or both of chromium and tungsten. The roughening layer is intended to improve bonding strength and heat resistance and to suppress powder shedding.

进而，在专利文献9中公开了一种印刷电路用铜箔，所述印刷电路用铜箔在铜箔的被粘接面上具有粗化处理层，所述粗化处理层由金属的多个突起状电沉积物构成，所述金属是从含有铬或钨中的一种或两种的第一组金属和由镍、铁、钴、锌构成的第二组金属选择的金属。所述粗化处理层以提高粘接强度和耐热性、抑制落粉为目的，是作为上述专利文献8的改良技术提出来的。Furthermore, Patent Document 9 discloses a copper foil for printed circuits having a roughened layer on the bonded surface of the copper foil. The roughened layer is composed of a plurality of protruding electrodeposits of a metal selected from a first group of metals containing one or both of chromium and tungsten and a second group of metals consisting of nickel, iron, cobalt, and zinc. This roughened layer is proposed as an improvement to Patent Document 8, aiming to enhance bonding strength and heat resistance while suppressing powder fall.

此外，在专利文献10中，提出了一种粗化处理铜箔，所述粗化处理铜箔在铜箔的被粘接面上设有复合金属层，进而在复合金属层上设有粗化处理层，所述复合金属层是由铜、钨、钼中的1种以上的金属和选自镍、钴、铁、锌的1种以上的金属构成的。In addition, in patent document 10, a roughened copper foil is proposed, wherein the roughened copper foil is provided with a composite metal layer on the bonded surface of the copper foil, and a roughening layer is further provided on the composite metal layer, and the composite metal layer is composed of one or more metals selected from copper, tungsten, and molybdenum and one or more metals selected from nickel, cobalt, iron, and zinc.

另一方面，在专利文献11中，提出了一种形成粗化处理的技术，所述技术是：在铜箔表面上形成粗化处理时，即使使用在铜箔表面具有凹凸的铜箔，铜粒子也未集中在凸的部分，在凹的部分也有附着，均一地形成结节状的铜粒子，提高粘接强度，蚀刻时难以产生残铜现象，蚀刻性变好，在以硫酸铜和硫酸为主要成分的酸性铜电镀浴中，使用添加了选自铁、镍、钴、钼、钨、钛、铝的金属和聚乙二醇的电镀浴，形成所述粗化处理。On the other hand, Patent Document 11 proposes a technology for forming a roughening treatment. The technology is as follows: when forming a roughening treatment on the surface of a copper foil, even if a copper foil with uneven surfaces is used, copper particles are not concentrated in the convex parts, but are also attached to the concave parts, and nodular copper particles are uniformly formed, thereby improving the bonding strength, making it difficult to produce residual copper during etching, and improving the etching property. The roughening treatment is formed by using an electroplating bath to which a metal selected from iron, nickel, cobalt, molybdenum, tungsten, titanium, and aluminum and polyethylene glycol are added to an acidic copper electroplating bath composed mainly of copper sulfate and sulfuric acid.

此外，在专利文献12中，提出了一种形成粗化处理的技术，所述技术替换了上述聚乙二醇，使用添加有明胶的电镀浴，形成所述粗化处理。由此，即便是向以硫酸铜和硫酸为主要成分的酸性铜电镀浴中添加添加剂的想法，其效果仍有限，希望得到进一步的改善。Furthermore, Patent Document 12 proposes a technique for forming a roughening treatment using a plating bath containing gelatin, instead of the polyethylene glycol. Therefore, even the idea of adding additives to an acidic copper plating bath primarily composed of copper sulfate and sulfuric acid has limited effectiveness, and further improvements are desired.

现有技术文献Prior art literature

专利文献1：特开平8-236930号公报Patent Document 1: Japanese Patent Application Laid-Open No. 8-236930

专利文献2：特许第3459964号公报Patent Document 2: Japanese Patent No. 3459964

专利文献3：特公昭51-35711号公报Patent Document 3: Japanese Patent Publication No. 51-35711

专利文献4：特公昭54-6701号公报Patent Document 4: Japanese Patent Publication No. 54-6701

专利文献5：特许第3306404号公报Patent Document 5: Japanese Patent No. 3306404

专利文献6：特愿2002-170827号公报Patent Document 6: Japanese Patent Application No. 2002-170827

专利文献7：特开平3-122298号公报Patent Document 7: Japanese Patent Application Laid-Open No. 3-122298

专利文献8：特许第2717911号公报Patent Document 8: Japanese Patent No. 2717911

专利文献9：特许第2920083号公报Patent Document 9: Japanese Patent No. 2920083

专利文献10：特开2001-226795号公报Patent Document 10: Japanese Patent Application Laid-Open No. 2001-226795

专利文献11：特开2005-353919号公报Patent Document 11: Japanese Patent Application Laid-Open No. 2005-353919

专利文献12：特开2005-353920号公报Patent Document 12: Japanese Patent Application Laid-Open No. 2005-353920

发明内容Summary of the Invention

本发明的课题在于提供可提高电解铜箔与树脂基材的粘接强度、增大剥离强度的电解铜箔、它的制造方法以及使用所述电解铜箔的印刷布线板或电池用负极材料。即，本发明以如下内容作为课题：通过在电解铜箔的粗面(M面)上形成本发明的粗化粒子，大幅提高铜箔自身与树脂基材的粘接强度，电解铜箔的各项特性没有劣化，改善铜箔上的粗化处理层，提高铜箔与树脂基材的粘接强度。特别地，本发明以提供如下电解铜箔和它的制造方法作为课题：与通用的环氧树脂类基材(FR-4等)相比，将通常与铜箔粘着性低的半导体封装用基材或液晶聚合物基材和电解铜箔组合使用时，可得到剥离强度更高的电解铜箔。特别地，本发明以提供如下电解铜箔作为课题：作为适应电路细微化和高频化发展的半导体封装基板用铜箔或液晶聚合物基板用铜箔或电池(LiB等)用负极材料中使用的电解铜箔是有用的。The present invention aims to provide an electrolytic copper foil that can improve the bonding strength and peel strength between the electrolytic copper foil and a resin substrate, a method for producing the same, and a printed wiring board or battery negative electrode material using the electrolytic copper foil. Specifically, the present invention aims to significantly improve the bonding strength between the copper foil itself and the resin substrate by forming the roughened particles of the present invention on the rough surface (M surface) of the electrolytic copper foil, without degrading the various properties of the electrolytic copper foil, thereby improving the roughened layer on the copper foil and improving the bonding strength between the copper foil and the resin substrate. In particular, the present invention aims to provide an electrolytic copper foil and a method for producing the same that, when used in combination with a semiconductor package substrate or a liquid crystal polymer substrate, which typically has low adhesion to copper foil, compared to a general-purpose epoxy resin substrate (FR-4, etc.), can produce an electrolytic copper foil with higher peel strength. In particular, the present invention aims to provide an electrolytic copper foil useful as a copper foil for semiconductor package substrates, a copper foil for liquid crystal polymer substrates, or a negative electrode material for batteries (such as LiB) in response to the advancement of miniaturization and high frequency of circuits.

为解决所述课题，本发明人反复进行了深入研究，结果，提出了以下1)～12)的电解铜箔、它的制造方法、使用所述电解铜箔的印刷布线板或电池用负极材料。To solve the above problems, the present inventors have conducted intensive studies and, as a result, have proposed the following electrolytic copper foils 1) to 12), methods for producing the same, and printed wiring boards or battery negative electrode materials using the same.

1)一种电解铜箔，所述电解铜箔是在电解铜箔的粗化面(M面)上形成粗化粒子的电解铜箔，其特征在于，所述粗化粒子的平均大小为0.1～1.0μm。1) An electrolytic copper foil having roughened particles formed on a roughened surface (M surface) of the electrolytic copper foil, wherein the average size of the roughened particles is 0.1 to 1.0 μm.

2)根据1)所述的电解铜箔，其特征在于，粗化粒子数平均为1～2个/μm²。2) The electrolytic copper foil according to 1), wherein the number of roughened particles is 1 to 2 particles/μm ² on average.

3)根据1)～2)中任一项所述的电解铜箔，其特征在于，所述电解铜箔的粗化面(M面)的表面粗糙度Rz为3.0μm以下，Ra低于0.6μm，Rt低于4.0μm。3) The electrolytic copper foil according to any one of 1) to 2), wherein the roughened surface (M surface) of the electrolytic copper foil has a surface roughness Rz of 3.0 μm or less, Ra of less than 0.6 μm, and Rt of less than 4.0 μm.

4)根据1)～3)中任一项所述的电解铜箔，其特征在于，所述电解铜箔与BT基材的常态剥离强度为1.0kN/m以上。此外，BT基材为双马来酰亚胺三嗪树脂，是代表性的半导体封装基板用基材。以下，BT基材表示相同的意义。4) The electrolytic copper foil according to any one of 1) to 3), characterized in that the normal peel strength between the electrolytic copper foil and the BT substrate is 1.0 kN/m or greater. Furthermore, the BT substrate is a bismaleimide triazine resin, a typical substrate for semiconductor package substrates. Hereinafter, the term "BT substrate" has the same meaning.

5)根据1)～4)中任一项所述的电解铜箔，其特征在于，所述电解铜箔与BT基材的焊接后的剥离强度为0.98kN/m以上。5) The electrolytic copper foil according to any one of 1) to 4), wherein the peel strength after welding between the electrolytic copper foil and the BT substrate is 0.98 kN/m or more.

6)根据1)～5)中任一项所述的电解铜箔，其特征在于，在所述粗化粒子层上，具有覆铜镀层。6) The electrolytic copper foil according to any one of 1) to 5), further comprising a copper plating layer on the roughened particle layer.

7)根据1)～6)中任一项所述的电解铜箔，其特征在于，在所述粗化粒子层或所述覆镀处理层上，设有耐热/防锈层，所述耐热/防锈层含有选自锌、镍、铜、磷的至少一种元素。7) The electrolytic copper foil according to any one of 1) to 6), wherein a heat-resistant/rust-proof layer is provided on the roughened particle layer or the plating treatment layer, wherein the heat-resistant/rust-proof layer contains at least one element selected from zinc, nickel, copper, and phosphorus.

8)根据7)中所述的电解铜箔，其特征在于，在所述耐热/防锈层上，具有铬酸盐覆膜层。8) The electrolytic copper foil according to 7), characterized in that a chromate coating layer is provided on the heat-resistant/rust-proof layer.

9)根据8)中所述的电解铜箔，其特征在于，在所述铬酸盐覆膜层上，具有硅烷偶联剂层。9) The electrolytic copper foil according to 8), further comprising a silane coupling agent layer on the chromate coating layer.

10)一种使用了1)～9)中任一项所述的电解铜箔的印刷布线板或电池用负极材料。10) A printed wiring board or a negative electrode material for a battery using the electrolytic copper foil according to any one of 1) to 9).

11)一种电解铜箔的制造方法，所述电解铜箔的制造方法是在电解铜箔的粗化面(M面)上，使用含有硫酸/硫酸铜的电解浴形成粗化粒子的电解铜箔的制造方法，其特征在于，使电解浴中的铜浓度为10～20g/L进行电解，制造1)～9)中所述的电解铜箔。11) A method for producing an electrolytic copper foil, wherein roughened particles are formed on the roughened surface (M surface) of the electrolytic copper foil using an electrolytic bath containing sulfuric acid/copper sulfate, wherein electrolysis is performed at a copper concentration in the electrolytic bath of 10 to 20 g/L to produce the electrolytic copper foil described in 1) to 9).

12)根据11)所述的电解铜箔的制造方法，其特征在于，使用含钨离子的含有硫酸/硫酸铜的电解浴形成铜的粗化粒子。12) The method for producing an electrolytic copper foil according to 11), wherein the roughened copper particles are formed using an electrolytic bath containing sulfuric acid/copper sulfate and containing tungsten ions.

所述含有硫酸/硫酸铜的电解浴中，不含砷离子。The electrolytic bath containing sulfuric acid/copper sulfate does not contain arsenic ions.

如上所示，本发明的电解铜箔具有如下显著效果：可提高铜箔表面粗糙度不高的铜箔与树脂基材的粘接强度、增大剥离强度，可提供铜箔和它的制造方法。即，通过在电解铜箔的粗面(M面)上形成本发明的粗化粒子，大幅提高铜箔自身与树脂基材的粘接强度，电解铜箔的各项特性没有劣化，改善铜箔上的粗化处理层，提高铜箔与树脂基材的粘接强度。特别地，提供如下电解铜箔和它的制造方法：与通用的环氧树脂类基材(FR-4等)相比，将通常与铜箔粘着性低的半导体封装用基材或液晶聚合物基材和电解铜箔组合使用时，可得到剥离强度更高的电解铜箔。所述电解铜箔作为适应电路细微化和高频化发展的半导体封装基板用铜箔或液晶聚合物基板用铜箔或电池(LiB等)用负极材料中使用的电解铜箔是有效的。As described above, the electrolytic copper foil of the present invention has the following significant effects: it can improve the bonding strength and peel strength of copper foil with low surface roughness and resin substrates, and can provide copper foil and its production method. Specifically, by forming the roughened particles of the present invention on the rough surface (M surface) of the electrolytic copper foil, the bonding strength between the copper foil itself and the resin substrate is greatly improved without degrading the various properties of the electrolytic copper foil. The roughened layer on the copper foil is improved, and the bonding strength between the copper foil and the resin substrate is improved. In particular, the following electrolytic copper foil and its production method are provided: when the electrolytic copper foil is used in combination with semiconductor packaging substrates or liquid crystal polymer substrates, which generally have low adhesion to copper foil, compared to general epoxy resin substrates (FR-4, etc.), an electrolytic copper foil with higher peel strength can be obtained. The electrolytic copper foil is effective as a copper foil for semiconductor packaging substrates or liquid crystal polymer substrates, or as an electrolytic copper foil for negative electrode materials for batteries (such as LiB), which adapt to the development of miniaturized circuits and higher frequencies.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1是在实施例1的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。FIG. 1 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of a 12 μm-thick electrolytic copper foil in Example 1. FIG.

图2是在实施例2的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。FIG. 2 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 2. FIG.

图3是在实施例3的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。3 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 3. FIG.

图4是在实施例4的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。FIG. 4 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 4. FIG.

图5是在实施例5的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。FIG. 5 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 5. FIG.

图6是在比较例1的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。FIG6 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Comparative Example 1. FIG.

图7是在比较例2的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。7 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of a 12 μm-thick electrolytic copper foil in Comparative Example 2. FIG.

图8是在比较例3的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。8 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of a 12 μm-thick electrolytic copper foil in Comparative Example 3. FIG.

图9是在比较例4的12μm厚的电解铜箔的M面上形成粗化粒子的表面SEM观察照片(10000倍)。9 is a surface SEM observation photograph (10,000 times) of roughened particles formed on the M surface of a 12 μm-thick electrolytic copper foil in Comparative Example 4. FIG.

具体实施方式DETAILED DESCRIPTION

下面，为使本发明容易理解，对本发明进行具体且详细地说明。本发明中使用的铜箔为电解铜箔。伴随着半导体电路的高集成化，印刷电路布线板等中也要求微细电路，为提高铜箔与树脂层的粘着力(剥离强度)，形成粗化处理层。To facilitate understanding, the present invention will be described in detail below. The copper foil used in the present invention is electrolytic copper foil. With the increasing integration of semiconductor circuits, finer circuits are also required in printed wiring boards, etc. Therefore, a roughening layer is formed to improve the adhesion (peel strength) between the copper foil and the resin layer.

在微细电路形成中，粗化处理层的粗度很重要，期待表现出低粗糙度且高剥离强度的铜箔。在通过锚定效应达到提高剥离强度目的的粗化处理层上，形成粗化粒子层。本发明通过将粒子大小缩小至以往的约1/4以下、粒子数增大至以往的约5～20倍，提供一种表现出低粗糙度且高强度的电解铜箔。The roughness of the roughened layer is crucial for forming fine circuits, and copper foil exhibiting low roughness and high peel strength is desired. A roughened particle layer is formed on the roughened layer, which improves peel strength through the anchoring effect. This invention provides an electrolytic copper foil exhibiting low roughness and high strength by reducing particle size to approximately one-quarter of conventional values and increasing the number of particles by approximately 5 to 20 times.

在电解铜箔的制造工序中，将与鼓表面(ドラム面)接触的面作为光泽面(S面)，其相对侧的面，作为粗化面(M面)。本发明是在电解铜箔的粗化面(M面)上形成粗化粒子的电解铜箔，所述粗化粒子的平均大小为0.1～1.0μm。In the manufacturing process of electrolytic copper foil, the surface in contact with the drum surface (dragon surface) is designated as the shiny surface (S surface), and the surface opposite it is designated as the roughened surface (M surface). The present invention provides an electrolytic copper foil having roughened particles formed on the roughened surface (M surface), wherein the average size of the roughened particles is 0.1 to 1.0 μm.

本申请发明的显著特征在于所述粗化粒子的平均大小为以往粗化粒子大小的约1/4以下。如果粗化粒子的平均大小在0.1～1.0μm的范围内，可以有效提高剥离强度。此外，此时形成的粗化粒子数平均为1～2个/μm²，细微的粒子保持密集的形态。结果，通过锚定效应可能使剥离强度提高。A significant feature of the present invention is that the average size of the roughened particles is approximately one-quarter or less of the size of conventional roughened particles. When the average size of the roughened particles is within the range of 0.1 to 1.0 μm, peel strength can be effectively improved. Furthermore, the average number of roughened particles formed is 1 to 2 per ^μm² , maintaining a densely packed structure. As a result, the anchoring effect can potentially enhance peel strength.

另一方面，上述电解铜箔的粗化面(M面)的表面粗糙度也很重要，在本申请发明中，可以控制Rz为3.0μm以下，Ra低于0.6μm，Rt低于4.0μm。从现有技术的角度来看，这些值小。即，在现有技术中，粗化面(M面)的表面粗糙度越粗，可使剥离强度更高。但是，本申请发明的电解铜箔的粗化面(M面)自身为低粗糙度，且如上所述，以细微粒子密集的形态为特征，由此提高剥离强度。On the other hand, the surface roughness of the roughened surface (M surface) of the electrolytic copper foil is also important. In the present invention, Rz can be controlled to be less than 3.0 μm, Ra less than 0.6 μm, and Rt less than 4.0 μm. From the perspective of the prior art, these values are small. That is, in the prior art, the greater the surface roughness of the roughened surface (M surface), the higher the peel strength. However, the roughened surface (M surface) of the electrolytic copper foil of the present invention itself has a low roughness and, as mentioned above, is characterized by a dense morphology of fine particles, thereby improving the peel strength.

由此，本申请发明的电解铜箔与BT基材的常态剥离强度可达到1.0kN/m以上，与BT基材的焊接后的剥离强度可达到0.98kN/m以上。Therefore, the normal peel strength between the electrolytic copper foil and the BT substrate can reach 1.0 kN/m or more, and the peel strength after welding with the BT substrate can reach 0.98 kN/m or more.

此外，上述粗化粒子的大小和个数是指：在由铜和氧化铜构成的微粒上进一步形成覆铜镀层，进而形成耐热/防锈层(所述耐热/防锈层含有选自锌、镍、铜、磷的至少一种元素)，并且在所述耐热/防锈层上形成铬酸盐覆膜层以及在所述铬酸盐覆膜层上形成硅烷偶联剂层之后的大小和个数。本发明可以制造使用具有上述特征的电解铜箔提高了铜箔与树脂粘着性(剥离强度)的印刷布线板或电池用负极材料。The size and number of roughened particles described above refer to the size and number after forming a copper plating layer on fine particles composed of copper and copper oxide, further forming a heat-resistant/rust-proof layer (the heat-resistant/rust-proof layer containing at least one element selected from zinc, nickel, copper, and phosphorus), forming a chromate coating layer on the heat-resistant/rust-proof layer, and forming a silane coupling agent layer on the chromate coating layer. The present invention enables the production of printed wiring boards or battery negative electrode materials having improved adhesion (peel strength) between the copper foil and resin using the electrolytic copper foil having the above-mentioned characteristics.

本申请发明的特征在于使用含有硫酸/硫酸铜的电解浴，所述电解浴中的铜浓度为10～20g/L，在上述电解铜箔的粗化面(M面)上形成由细微且多个粒子构成的粗化粒子层。以往的粗化粒子形成中，以20～40g/L的铜浓度进行处理，因此，粗化粒子形成时的极限电流密度值较高。但与此相对，通过将上述电解浴中的铜浓度降低至10～20g/L，降低极限电流密度且保持低值，这样在同一电流密度下，使粗化粒子形成效率提高，结果使每个粒子的大小变得细微，可能制造出使位铜面积以及多粒子形成数增加的电解铜箔。The present invention is characterized by using an electrolytic bath containing sulfuric acid/copper sulfate, wherein the copper concentration in the electrolytic bath is 10 to 20 g/L, to form a roughened particle layer composed of fine, numerous particles on the roughened surface (M-side) of the electrolytic copper foil. Conventional roughened particle formation is performed at a copper concentration of 20 to 40 g/L, resulting in a high limiting current density for roughened particle formation. However, by reducing the copper concentration in the electrolytic bath to 10 to 20 g/L, the limiting current density is lowered and maintained at a low value. This improves the efficiency of roughened particle formation at the same current density, resulting in a finer individual particle size and the ability to produce an electrolytic copper foil with an increased copper area and a greater number of formed particles.

若电解浴中的铜浓度不足10g/L，则粒子生长速度变缓，生产速度降低，故不优选。此外，若电解浴中的铜浓度超过20g/L，则与以往相同，生成的粒子过大，无法达成本发明申请的目的，故优选上述铜浓度。If the copper concentration in the electrolytic bath is less than 10 g/L, the particle growth rate slows down and the production rate decreases, which is not preferred. In addition, if the copper concentration in the electrolytic bath exceeds 20 g/L, the particles generated are too large as in the past, and the purpose of the present invention cannot be achieved. Therefore, the above copper concentration is preferred.

由此，通过缩小每个粒子的大小并且可能形成多个粒子，则无论是否是低粗糙度，均可增加与树脂层结合的粗化粒子表面积，可获得高剥离强度。Thus, by reducing the size of each particle and possibly forming a plurality of particles, the surface area of the roughened particles that can be bonded to the resin layer can be increased regardless of whether the roughness is low, and high peel strength can be obtained.

此外，在本申请说明书中说明的粗化粒子数，是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算。此外，对于粒子大小，是对以SEM 1万倍图像观察到的粒子进行线性分析法后计量。对于剥离强度，使用三菱ガス化制造的基材GHPL-830，参照JIS-C-6481规定的方法测定。使用触针式、参照JIS-B-0601规定的方法测定表面粗糙度。The number of roughened particles described in this specification is calculated based on the number of particles observed in a 10,000x SEM image and converted to the number of particles from the image area. Furthermore, particle size is measured using linear analysis of particles observed in a 10,000x SEM image. Peel strength was measured using Mitsubishi Gas Chemical's GHPL-830 substrate according to JIS-C-6481. Surface roughness was measured using a stylus method according to JIS-B-0601.

在形成上述铜的粗化粒子的电解浴中，可以使用含钨离子的含有硫酸/硫酸铜的电解浴来形成铜的粗化粒子。此外，所述含有硫酸/硫酸铜的电解浴中，希望不含有砷离子。The electrolytic bath for forming the roughened copper particles may be an electrolytic bath containing sulfuric acid/copper sulfate and tungsten ions. The electrolytic bath containing sulfuric acid/copper sulfate desirably does not contain arsenic ions.

形成本发明的典型性的粗化粒子的处理条件，如下所示：Typical processing conditions for forming the roughened particles of the present invention are as follows:

(电解液组成)(Electrolyte composition)

Cu：10～20g/LCu: 10-20 g/L

H₂SO₄：10～200g/LH ₂ SO ₄ ：10～200g/L

十二烷基硫酸钠：0.1～100mg/LSodium lauryl sulfate: 0.1～100mg/L

(电镀条件)(Electroplating conditions)

温度：25～60℃Temperature: 25-60°C

(电流条件)(Current conditions)

电流密度：25～54A/dm²(在电镀浴的极限电流密度以上)Current density: 25 to 54 A/dm ² (above the limiting current density of the plating bath)

在上述电镀液组成1中添加以下成分。此外，不添加砷(As)。The following components were added to the above-mentioned electroplating solution composition 1. In addition, arsenic (As) was not added.

(选择的电解液组成2)(Selected electrolyte composition 2)

W(以钨酸盐的形式添加)：0.1～100mg/LW (added in the form of tungstate): 0.1～100 mg/L

进而，在上述粗化处理层上，可以用含有硫酸/硫酸铜的电解浴进行覆镀。进而，可以形成含有选自锌、镍、钴、铜、磷的至少一种元素的耐热/防锈层，在该耐热/防锈层上形成铬酸盐覆膜层，在该铬酸盐覆膜层上形成硅烷偶联剂层。Furthermore, the roughened layer may be plated using an electrolytic bath containing sulfuric acid/copper sulfate. Furthermore, a heat-resistant/rust-proof layer containing at least one element selected from zinc, nickel, cobalt, copper, and phosphorus may be formed, a chromate coating layer may be formed on the heat-resistant/rust-proof layer, and a silane coupling agent layer may be formed on the chromate coating layer.

作为与本发明组合使用的覆镀处理、耐热/防锈处理、铬酸盐处理、硅烷偶联剂，可以使用以往的耐热/防锈层。As the plating treatment, heat-resistant/rust-proof treatment, chromate treatment, and silane coupling agent used in combination with the present invention, conventional heat-resistant/rust-proof layers can be used.

作为覆镀处理，无特别限定，可以使用公知的处理。具体实例如下所示。The plating treatment is not particularly limited, and a known treatment can be used. Specific examples are shown below.

(电解液组成)(Electrolyte composition)

Cu：20～100g/LCu: 20～100g/L

H₂SO₄：50～150g/LH ₂ SO ₄ ：50～150g/L

(电解液的温度)(Electrolyte temperature)

25～60℃25～60℃

(电流条件)(Current conditions)

电流密度：1～50A/dm²(在电镀浴的极限电流密度以下)Current density: 1 to 50 A/dm ² (below the limiting current density of the plating bath)

电镀时间：1～20秒Plating time: 1 to 20 seconds

作为耐热/防锈层，无特别限定，可以使用公知的处理。例如，对于印刷布线板用铜箔，可以使用以往使用的黄铜覆层。The heat-resistant/rust-proof layer is not particularly limited, and a known treatment can be used. For example, a brass coating conventionally used can be used for copper foil for printed wiring boards.

下面示出具体例：A specific example is shown below:

(电解液组成)(Electrolyte composition)

NaOH：40～200g/LNaOH: 40～200g/L

NaCN：70～250g/LNaCN: 70～250g/L

CuCN：50～200g/LCuCN: 50～200g/L

Zn(CN)₂：2～100g/LZn(CN) ₂ ：2～100g/L

As₂O₃：0.01～1g/LAs ₂ O ₃ ：0.01～1g/L

(电解液的温度)(Electrolyte temperature)

40～90℃40～90℃

(电流条件)(Current conditions)

电流密度：1～50A/dm² Current density: 1～50A/ ^dm2

电镀时间：1～20秒Plating time: 1 to 20 seconds

对于上述铬酸盐覆膜层，可使用电解铬酸盐覆膜层或浸渍铬酸盐覆膜层。所述铬酸盐覆膜层中，希望Cr含量为25～150μg/dm²。当Cr含量不足25μg/dm²时，无防锈效果。此外，当Cr含量超过150μg/dm²时，效果饱和，造成浪费。因此，Cr含量为25～150μg/dm²为好。The chromate coating can be an electrolytic chromate coating or an immersion chromate coating. The chromate coating preferably has a Cr content of 25 to 150 μg/ ^dm² . A Cr content of less than 25 μg/ ^dm² will not provide any rust-preventive effect. Furthermore, a Cr content exceeding 150 μg/ ^dm² will saturate the effect, resulting in waste. Therefore, a Cr content of 25 to 150 μg/dm² ^is preferred.

下面记载为形成上述铬酸盐覆膜层的条件的实例。但是，如上所述，不必限定于该条件，可以使用任一公知的铬酸盐处理。所述防锈处理是影响耐酸性的因素之一，通过铬酸盐处理，提高耐酸性。The following describes an example of conditions for forming the chromate coating layer. However, as mentioned above, these conditions are not necessarily limiting, and any known chromate treatment can be used. The aforementioned rust-proofing treatment is one factor that affects acid resistance, and chromate treatment improves acid resistance.

(a)浸渍铬酸盐处理(a) Immersion chromate treatment

K₂Cr₂O₇：1～5g/L；pH：2.5～5.5；温度：25～60℃；时间：0.5～8秒K ₂ Cr ₂ O ₇ : 1-5 g/L; pH: 2.5-5.5; Temperature: 25-60°C; Time: 0.5-8 seconds

(c)电解铬锌处理(c) Electrolytic chromium zinc treatment

K₂Cr₂O₇(Na₂Cr₂O₇或CrO₃)：2～10g/L；ZnOH或ZnSO₄·7H₂O：0.05～10g/L；pH：2.5～5.5；浴温：20～80℃；电流密度：0.05～5A/dm²；时间：0.1～10秒 _K2Cr2O7 ₍ _Na2Cr2O7 or _CrO3 ) _: 2-10 g/L; ZnOH or _ZnSO4·7H2O _: 0.05-10 g/L _; pH: 2.5-5.5; Bath temperature: 20-80°C; Current density: 0.05-5 _A / ^dm2 ; Time: 0.1-10 seconds

作为本发明的印刷布线板用铜箔使用的硅烷偶联剂，可以使用普通铜箔使用的任意硅烷偶联剂，无特别限定。作为硅烷偶联剂处理的具体实例，条件如下所示。As the silane coupling agent used in the copper foil for printed wiring boards of the present invention, any silane coupling agent used for general copper foils can be used without particular limitation. Specific examples of the silane coupling agent treatment conditions are as follows.

向铜箔粗化面喷0.2％的环氧硅烷水溶液后，干燥。A 0.2% epoxy silane aqueous solution was sprayed onto the roughened surface of the copper foil and then dried.

虽然硅烷偶联剂的选择是任意的，但可以说希望在考虑了铜箔与层叠树脂基材的亲和性后进行选择。Although the selection of the silane coupling agent is arbitrary, it is desirable to select it after considering the affinity between the copper foil and the laminated resin substrate.

实施例Example

下面，对实施例和比较例进行说明。此外，本实施例表示适宜的例子，因而本发明不受这些实施例的限制。因此，含有本发明技术思想的变形、其他实施例和实施方式均属于本发明。为与本发明对比，记载了比较例。The following describes embodiments and comparative examples. Furthermore, these embodiments represent suitable examples, and the present invention is not limited to these embodiments. Therefore, variations, other embodiments, and implementations that incorporate the technical concept of the present invention all fall within the scope of the present invention. Comparative examples are provided for comparison with the present invention.

(实施例1)(Example 1)

使用厚度为12μm的IPC 3级电解铜箔，在所述铜箔的粗面上，进行形成粗化粒子的处理。An IPC 3-grade electrolytic copper foil having a thickness of 12 μm was used, and a treatment for forming roughened particles was performed on the rough surface of the copper foil.

形成粗化粒子的处理(电镀)电解液的镀浴组成和电解处理条件如下所示。The plating bath composition of the treatment (electroplating) electrolyte solution for forming roughened particles and the electrolytic treatment conditions are as follows.

(电解液组成)(Electrolyte composition)

Cu：15g/LCu: 15g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

W添加量：3mg/L(以钨酸钠二水合物的形式添加，下同)W addition amount: 3 mg/L (added in the form of sodium tungstate dihydrate, the same below)

十二烷基硫酸钠添加量：4mg/LDosage of sodium lauryl sulfate: 4 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：54A/dm² Current density: 54A/ ^dm2

下面，在上述粗化处理面上，为防止粗化粒子的脱落并提高剥离强度，用含有硫酸/硫酸铜的电解浴进行覆镀。覆镀的处理条件如下所示。Next, the roughened surface was plated using an electrolytic bath containing sulfuric acid/copper sulfate to prevent the roughened particles from falling off and to improve the peel strength. The plating conditions are as follows.

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

电流密度：29A/dm²(未达到电解浴的极限电流密度)Current density: 29A/ ^dm2 (does not reach the limiting current density of the electrolytic bath)

进而，在上述覆镀处理之上，形成耐热/防锈层，在所述耐热/防锈层之上，进行电解铬酸盐处理，在所述铬酸盐覆膜层之上，(通过涂布)实施硅烷处理。Furthermore, a heat-resistant/rust-proof layer is formed on the above-mentioned plating treatment, an electrolytic chromate treatment is performed on the above-mentioned heat-resistant/rust-proof layer, and a silane treatment is performed (by coating) on the above-mentioned chromate coating layer.

在上述条件下进行形成粗化粒子处理的结果是，粗化粒子数为1.38个/μm²，粒子大小平均为0.53μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The result of the roughening treatment under the above conditions was a roughening particle count of 1.38 particles/ ^μm² , with an average particle size of 0.53 μm. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The roughening particle count was calculated by counting particles observed in a 10,000x SEM image and converting the number of particles from the image area.

此外，粒子大小是以SEM 1万倍图像观察到的粒子进行线性分析法后计量的结果。此外，所述粒子大小是从粗化面的任意2点观察到的垂直剖面上的粒子大小和任意2点观察到的水平面上的粒子大小的平均值。The particle size is measured by linear analysis of particles observed at 10,000 magnification using a SEM image. The particle size is the average of the particle size observed at two arbitrary points on a vertical cross section of the roughened surface and the particle size observed at two arbitrary points on a horizontal surface.

在实施例1的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(左起1000倍、3000倍、6000倍、10000倍)如图1所示。如图1所示，可知每个粒子大小变得细微，单位铜面积的粒子形成数增加。Figure 1 shows SEM photographs (magnifications from left: 1000x, 3000x, 6000x, and 10000x) of the surface of the 12 μm-thick electrolytic copper foil of Example 1, where roughened particles are formed. As shown in Figure 1, the size of each particle has become finer, and the number of particles formed per unit copper area has increased.

对于如此制作而成的铜箔，对以下项目进行测定。对于剥离强度的测定，使用BT基材(双马来酰亚胺三嗪树脂，三菱ガス化学株式会社制造的GHPL-830MBT)层叠粘接。BT基材是代表性的半导体封装基板用基材。The copper foil thus prepared was measured for the following parameters: Peel strength was measured by laminating and bonding using a BT substrate (bismaleimide triazine resin, GHPL-830MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.). BT substrate is a typical substrate for semiconductor package substrates.

若与BT基材层叠时铜箔的剥离强度在0.98kN/m以上，可以说作为半导体封装基板用途的铜箔，具有足够的粘接强度。If the peel strength of the copper foil when laminated with the BT substrate is 0.98 kN/m or more, it can be said that the copper foil has sufficient adhesive strength for use as a semiconductor package substrate.

(剥离强度测定)(Peel strength measurement)

将铜箔与上述两种基材在规定条件下进行热压得到覆铜叠层板，利用湿法蚀刻制作宽度为10mm的电路后，剥离铜箔，测定90度剥离强度。The copper foil and the two substrates were hot pressed under specified conditions to obtain a copper-clad laminate. A circuit with a width of 10 mm was produced by wet etching. The copper foil was then peeled off and the 90-degree peel strength was measured.

如上所述，剥离强度是使用三菱ガス化制造的GHPL-830、参照JIS-C-6481规定的方法测定的结果。As described above, the peel strength is the result of measurement using GHPL-830 manufactured by Mitsubishi Gas Chemical Co., Ltd. in accordance with the method specified in JIS-C-6481.

其结果是，剥离强度大幅提高，BT树脂层叠时的剥离强度为1.12kN/m、焊接后的剥离强度达到1.12kN/m。此外，表面粗糙度变为Ra：0.57μm、Rt：3.70μm、Rz：3.00μm。As a result, the peel strength was significantly improved, reaching 1.12 kN/m when laminating with BT resin and 1.12 kN/m after welding. Furthermore, the surface roughness was Ra: 0.57 μm, Rt: 3.70 μm, and Rz: 3.00 μm.

实施例1中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)如表1所示。Table 1 shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Example 1.

表1Table 1

(实施例2)(Example 2)

形成粗化粒子处理(电镀)时的电解液的镀浴组成和电解处理条件如下所示。The plating bath composition of the electrolyte solution and the electrolytic treatment conditions in the roughened particle formation treatment (electroplating) are as follows.

(电解液组成)(Electrolyte composition)

Cu：15g/LCu: 15g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

十二烷基硫酸钠添加量：4mg/LDosage of sodium lauryl sulfate: 4 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：54A/dm² Current density: 54A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

电流密度：31A/dm²(未达到电解浴的极限电流密度)Current density: 31A/ ^dm2 (does not reach the limiting current density of the electrolytic bath)

在上述条件下进行形成粗化粒子处理的结果是，粗化粒子数为1.29个/μm²，粒子大小平均为0.56μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The result of the roughening treatment under the above conditions was a roughening particle count of 1.29 particles/ ^μm² , with an average particle size of 0.56 μm. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The roughening particle count was calculated by counting particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在实施例2的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(10000倍)如图2所示。如图2所示，可知每个粒子大小变得细微，单位铜面积的粒子形成数增加。Figure 2 shows a SEM photograph (10,000x magnification) of the surface with roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 2. As shown in Figure 2 , it can be seen that the size of each particle is finer, and the number of particles formed per copper area is increased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅提高，BT树脂层叠时的剥离强度为1.01kN/m、焊接后的剥离强度达到0.98kN/m，结果优良。此外，表面粗糙度变为Ra：0.43μm、Rt：2.97μm、Rz：2.60μm。As a result, peel strength was significantly improved, reaching 1.01 kN/m when laminating with BT resin and 0.98 kN/m after welding, both excellent results. Furthermore, the surface roughness was Ra: 0.43 μm, Rt: 2.97 μm, and Rz: 2.60 μm.

实施例2中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Example 2.

(实施例3)(Example 3)

使用厚度为12μm的IPC 3级电解铜箔，在所述铜箔的粗面上，进行形成粗化粒子的处理。An IPC 3 grade electrolytic copper foil having a thickness of 12 μm was used, and a treatment for forming roughened particles was performed on the rough surface of the copper foil.

(电解液组成)(Electrolyte composition)

Cu：20g/LCu: 20g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

十二烷基硫酸钠添加量：4mg/LDosage of sodium lauryl sulfate: 4 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：54A/dm² Current density: 54A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

电流密度：33A/dm²(未达到电解浴的极限电流密度)Current density: 33A/ ^dm2 (does not reach the limiting current density of the electrolytic bath)

在上述条件下进行形成粗化粒子处理的结果是，粗化粒子数为1.47个/μm²，粒子大小平均为0.67μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The result of the roughening treatment under the above conditions was a roughening particle count of 1.47 particles/ ^μm² , with an average particle size of 0.67 μm. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The roughening particle count was calculated by counting the number of particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在实施例3的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(10000倍)如图3所示。如图3所示，可知每个粒子大小变得细微，单位铜面积的粒子形成数增加。Figure 3 shows a SEM photograph (10,000x magnification) of the surface with roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 3. As shown in Figure 3 , it can be seen that the size of each particle is finer, and the number of particles formed per copper area is increased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅提高，BT树脂层叠时的剥离强度为1.24kN/m、焊接后的剥离强度达到1.21kN/m，结果优良。此外，表面粗糙度变为Ra：0.43μm、Rt：3.13μm、Rz：2.70μm。As a result, peel strength was significantly improved, reaching 1.24 kN/m when laminating with BT resin and 1.21 kN/m after welding, both excellent results. Furthermore, the surface roughness was Ra: 0.43 μm, Rt: 3.13 μm, and Rz: 2.70 μm.

实施例3中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Example 3.

(实施例4)(Example 4)

(电解液组成)(Electrolyte composition)

Cu：10g/LCu: 10g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

十二烷基硫酸钠添加量：4mg/LDosage of sodium lauryl sulfate: 4 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：48A/dm² Current density: 48A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

在上述条件下进行形成粗化粒子处理的结果是，粗化粒子数为1.54个/μm²，粒子大小平均为0.49μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The result of the roughening treatment under the above conditions was a roughening particle count of 1.54 particles/ ^μm² , with an average particle size of 0.49 μm. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The roughening particle count was calculated by counting particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在实施例4的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(10000倍)如图4所示。如图4所示，可知每个粒子大小变得细微，单位铜面积的粒子形成数增加。Figure 4 shows a SEM photograph (10,000x magnification) of the surface with roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 4. As shown in Figure 4 , it can be seen that the size of each particle is finer, and the number of particles formed per copper area is increased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅提高，BT树脂层叠时的剥离强度1.04kN/m、焊接后的剥离强度达到1.03kN/m，结果优良。此外，表面粗糙度变为Ra：0.43μm、Rt：3.13μm、Rz：2.57μm。As a result, peel strength was significantly improved, reaching 1.04 kN/m when laminating with BT resin and 1.03 kN/m after welding, both excellent results. Furthermore, the surface roughness was Ra: 0.43 μm, Rt: 3.13 μm, and Rz: 2.57 μm.

实施例4中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Example 4.

(实施例5)(Example 5)

(电解液组成)(Electrolyte composition)

Cu：15g/LCu: 15g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

十二烷基硫酸钠添加量：4mg/LDosage of sodium lauryl sulfate: 4 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：45A/dm² Current density: 45A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：100g/LH ₂ SO ₄ ：100g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

电流密度：21A/dm²(未达到电解浴的极限电流密度)Current density: 21A/ ^dm2 (does not reach the limiting current density of the electrolytic bath)

在上述条件下进行形成粗化粒子处理的结果是，粗化粒子数为1.40个/μm²，粒子大小平均为0.61μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The result of the roughening treatment under the above conditions was a roughening particle count of 1.40 particles/ ^μm² , with an average particle size of 0.61μm. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The roughening particle count was calculated by counting the number of particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在实施例5的厚度为12μm的电解铜箔的M面上，形成粗化粒子的表面的SEM观察照片(10000倍)如图5所示。如图5所示，可知每个粒子大小变得细微，单位铜面积的粒子形成数增加。Figure 5 shows a SEM photograph (10,000x magnification) of the surface of roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Example 5. As shown in Figure 5 , it can be seen that the size of each particle is finer, and the number of particles formed per copper area is increased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅提高，BT树脂层叠时的剥离强度为1.10kN/m、焊接后的剥离强度达到1.10kN/m，结果优良。此外，表面粗糙度变为Ra：0.50μm、Rt：3.20μm、Rz：2.67μm。As a result, peel strength was significantly improved, reaching 1.10 kN/m when laminating with BT resin and 1.10 kN/m after welding, both excellent results. Furthermore, the surface roughness was Ra: 0.50 μm, Rt: 3.20 μm, and Rz: 2.67 μm.

实施例5中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Example 5.

(比较例1)(Comparative Example 1)

(电解液组成)(Electrolyte composition)

Cu：35g/LCu: 35g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

As添加量：1.6mg/LAs addition amount: 1.6 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：70A/dm² Current density: 70A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

电流密度：41A/dm²(未达到电解浴的极限电流密度)Current density: 41A/ ^dm2 (does not reach the limiting current density of the electrolytic bath)

在上述条件下进行形成粗化粒子处理的结果，与实施例相比，粗化粒子数减少为0.30个/μm²，粒子大小平均增大到2.55μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The results of the roughening treatment under the above conditions showed that the number of roughened particles was reduced to 0.30 particles/ ^μm² , and the average particle size was increased to 2.55μm, compared to the example. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The number of roughened particles was calculated by counting the number of particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在比较例1的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(10000倍)如图6所示。如图6所示，可知每个粒子大小变得粗大，单位铜面积的粒子形成数减少。Figure 6 shows a SEM photograph (10,000x magnification) of the surface with roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Comparative Example 1. As shown in Figure 6 , it can be seen that the size of each particle has increased, and the number of particles formed per copper area has decreased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅降低，BT树脂层叠时的剥离强度为0.80kN/m、焊接后的剥离强度为0.80kN/m，与实施例相比，效果不佳。此外，表面粗糙度变为Ra：0.67μm、Rt：4.60μm、Rz：4.07μm，任一值均增大。As a result, the peel strength was significantly reduced, reaching 0.80 kN/m when laminating with BT resin and 0.80 kN/m after welding, which was inferior to the results of the examples. Furthermore, the surface roughness increased to Ra: 0.67 μm, Rt: 4.60 μm, and Rz: 4.07 μm.

比较例1中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Comparative Example 1.

(比较例2)(Comparative Example 2)

(电解液组成)(Electrolyte composition)

Cu：25g/LCu: 25g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

As添加量：1.6mg/LAs addition amount: 1.6 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：70A/dm² Current density: 70A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

在上述条件下进行形成粗化粒子处理的结果，与实施例相比，粗化粒子数减少为0.63个/μm²，粒子大小平均增大到1.16μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The results of the roughening treatment under the above conditions showed that the number of roughened particles was reduced to 0.63 particles/ ^μm² , and the average particle size was increased to 1.16μm, compared to the example. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The number of roughened particles was calculated by counting the number of particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在比较例2的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(10000倍)如图7所示。如图7所示，可知每个粒子大小变得粗大，单位铜面积的粒子形成数减少。Figure 7 shows a SEM photograph (10,000x magnification) of the surface with roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Comparative Example 2. As shown in Figure 7 , it can be seen that the size of each particle has increased, and the number of particles formed per copper area has decreased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅降低，BT树脂层叠时的剥离强度为0.85kN/m、焊接后的剥离强度为0.85kN/m，与实施例相比，效果不佳。此外，表面粗糙度变为Ra：0.73μm、Rt：4.73μm、Rz：4.40μm，任一值均增大。As a result, the peel strength was significantly reduced, reaching 0.85 kN/m when laminating with BT resin and 0.85 kN/m after welding, which was inferior to the Example. Furthermore, the surface roughness increased to Ra: 0.73 μm, Rt: 4.73 μm, and Rz: 4.40 μm.

比较例2中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Comparative Example 2.

(比较例3)(Comparative Example 3)

(电解液组成)(Electrolyte composition)

Cu：25g/LCu: 25g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

As添加量：1.6mg/LAs addition amount: 1.6 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：44A/dm² Current density: 44A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

电流密度：36A/dm²(未达到电解浴的极限电流密度)Current density: 36A/ ^dm2 (does not reach the limiting current density of the electrolytic bath)

在上述条件下进行形成粗化粒子处理的结果，与实施例相比，粗化粒子数减少为0.12个/μm²，粒子大小平均增大到1.99μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The results of the roughening treatment under the above conditions showed that the number of roughened particles was reduced to 0.12 particles/ ^μm² , and the average particle size was increased to 1.99μm, compared to the example. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The number of roughened particles was calculated by counting the number of particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在比较例3的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(10000倍)如图8所示。如图8所示，可知每个粒子大小变得粗大，单位铜面积的粒子形成数减少。Figure 8 shows a SEM photograph (10,000x magnification) of the surface with roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Comparative Example 3. As shown in Figure 8 , it can be seen that the size of each particle has increased, and the number of particles formed per copper area has decreased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅降低，BT树脂层叠时的剥离强度为0.82kN/m、焊接后的剥离强度达到0.79kN/m，与实施例相比，效果不佳。此外，表面粗糙度变为Ra：0.60μm、Rt：4.17μm、Rz：3.70μm，任一值均增大。As a result, the peel strength was significantly reduced, reaching 0.82 kN/m when laminating with BT resin and 0.79 kN/m after welding, which were inferior to the examples. Furthermore, the surface roughness increased to Ra: 0.60 μm, Rt: 4.17 μm, and Rz: 3.70 μm.

比较例3中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Comparative Example 3.

(比较例4)(Comparative Example 4)

(电解液组成)(Electrolyte composition)

Cu：25g/LCu: 25g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

As添加量：1.6mg/LAs addition amount: 1.6 mg/L

(电解液温度)38℃(Electrolyte temperature) 38℃

(电流条件)(Current conditions)

电流密度：52A/dm² Current density: 52A/ ^dm2

(覆镀液组成)(Composition of plating solution)

Cu：45g/LCu: 45g/L

H₂SO₄：97.5g/LH ₂ SO ₄ ：97.5g/L

(电解液温度)45℃(Electrolyte temperature) 45℃

(电流条件)(Current conditions)

在上述条件下进行形成粗化粒子处理的结果，与实施例相比，粗化粒子数减少为0.18个/μm²，粒子大小平均增大到1.46μm。此外，如上所述，表面粗糙度是使用触针式、参照JIS-B-0601规定的方法测定，粗化粒子数是对以SEM 1万倍图像观察到的粒子数进行计量，对来自图像区域的个数进行换算的结果。The results of the roughening treatment under the above conditions showed that the number of roughened particles was reduced to 0.18 particles/ ^μm² , and the average particle size was increased to 1.46μm, compared to the example. As mentioned above, surface roughness was measured using a stylus method in accordance with JIS-B-0601. The number of roughened particles was calculated by counting the number of particles observed in a 10,000x SEM image and converting the number of particles from the image area.

在比较例4的厚度为12μm的电解铜箔的M面上，形成有粗化粒子的表面的SEM观察照片(10000倍)如图9所示。如图9所示，可知每个粒子大小变得粗大，单位铜面积的粒子形成数减少。Figure 9 shows a SEM photograph (10,000x magnification) of the surface with roughened particles formed on the M surface of the 12 μm-thick electrolytic copper foil of Comparative Example 4. As shown in Figure 9 , it can be seen that the size of each particle has increased, and the number of particles formed per copper area has decreased.

(剥离强度测定)(Peel strength measurement)

其结果是，剥离强度大幅降低，BT树脂层叠时的剥离强度为0.99kN/m、焊接后的剥离强度达到0.94kN/m，与实施例相比，效果不佳。此外，表面粗糙度变为Ra：0.63μm、Rt：4.83μm、Rz：4.13μm，任一值均增大。As a result, the peel strength was significantly reduced, reaching 0.99 kN/m when laminating with BT resin and 0.94 kN/m after welding, which were inferior to the examples. Furthermore, the surface roughness increased to Ra: 0.63 μm, Rt: 4.83 μm, and Rz: 4.13 μm.

比较例4中测定的粗化粒子数(个/μm²)、粒子大小(平均μm)、表面粗糙度(Ra、Rt、Rz)和剥离强度(BT基材剥离强度(kN/m)：常态和焊接后的剥离强度)，同样如表1所示。Table 1 also shows the number of roughened particles (particles/μm ² ), particle size (average μm), surface roughness (Ra, Rt, Rz), and peel strength (BT substrate peel strength (kN/m): normal state and peel strength after welding) measured in Comparative Example 4.

工业实用性Industrial Applicability

通过在电解铜箔的粗面(M面)上形成本发明的粗化粒子，具有大幅提高铜箔自身与树脂基材的粘接强度的显著效果。即，电解铜箔的各项特性没有劣化，可以改善铜箔上的粗化处理层，提高铜箔与树脂基材的粘接强度，特别地，提供一种电解铜箔和它的制造方法，与通用的环氧树脂类基材(FR-4等)相比，将通常与铜箔粘着性低的半导体封装用基材或液晶聚合物基材和电解铜箔组合使用时，可得到剥离强度更高的电解铜箔。所述电解铜箔作为适应电路细微化和高频化发展的半导体封装基板用铜箔或液晶聚合物基板用铜箔或电池(LiB等)用负极材料中使用的电解铜箔是有用的。By forming the roughened particles of the present invention on the rough surface (M surface) of the electrolytic copper foil, the bonding strength between the copper foil itself and the resin substrate is significantly improved. That is, the various properties of the electrolytic copper foil are not degraded, the roughened layer on the copper foil can be improved, and the bonding strength between the copper foil and the resin substrate can be increased. In particular, an electrolytic copper foil and a method for manufacturing the same are provided. Compared to general epoxy resin substrates (FR-4, etc.), when the electrolytic copper foil is used in combination with a semiconductor packaging substrate or a liquid crystal polymer substrate, which generally has low adhesion to copper foil, an electrolytic copper foil with higher peel strength can be obtained. The electrolytic copper foil is useful as a copper foil for semiconductor packaging substrates or liquid crystal polymer substrates, which adapt to the development of miniaturized circuits and high frequencies, or as an electrolytic copper foil for use in negative electrode materials for batteries (such as LiB).

Claims

1. An electrolytic copper foil, wherein the electrolytic copper foil is an electrolytic copper foil in which coarsened particles are formed on a roughened surface (M surface) of the electrolytic copper foil, characterized in that the average size of the coarsened particles is 0.1 to 1.0 μm, the average number of coarsened particles is 1 to 2 particles/ ^μm² , the surface roughness Rz of the roughened surface (M surface) of the electrolytic copper foil is less than 3.0 μm, and the average size is the average of the particle size on a vertical cross-section observed from any two points on the roughened surface and the particle size on a horizontal plane observed from any two points, wherein the particle size is the result of linear analysis of the coarsened particles observed in a 10,000x SEM image.

2. The electrolytic copper foil according to claim 1, characterized in that the surface roughness Ra of the roughened surface (M surface) of the electrolytic copper foil is less than 0.6 μm and Rt is less than 4.0 μm.

3. The electrolytic copper foil according to claim 1, wherein the normal peel strength between the electrolytic copper foil and the BT substrate is above 1.0 kN/m.

4. The electrolytic copper foil according to claim 2, wherein the normal peel strength between the electrolytic copper foil and the BT substrate is above 1.0 kN/m.

5. The electrolytic copper foil according to claim 1, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

6. The electrolytic copper foil according to claim 2, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

7. The electrolytic copper foil according to claim 3, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

8. The electrolytic copper foil according to claim 4, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

9. The electrolytic copper foil according to any one of claims 1 to 8, characterized in that a copper plating layer is formed on the roughened particle layer.

10. The electrolytic copper foil according to any one of claims 1 to 8, characterized in that a heat-resistant/rust-proof layer is provided on the roughened particle layer or the plating treatment layer, the heat-resistant/rust-proof layer containing at least one element selected from zinc, nickel, copper, and phosphorus.

11. The electrolytic copper foil according to claim 9, characterized in that a heat-resistant/rust-proof layer is provided on the roughened particle layer or the plating treatment layer, the heat-resistant/rust-proof layer containing at least one element selected from zinc, nickel, copper, and phosphorus.

12. The electrolytic copper foil according to claim 10, characterized in that a chromate coating layer is provided on the heat-resistant/rust-proof layer.

13. The electrolytic copper foil according to claim 11, characterized in that a chromate coating layer is provided on the heat-resistant/rust-proof layer.

14. The electrolytic copper foil according to claim 12, characterized in that a silane coupling agent layer is present on the chromate coating layer.

15. The electrolytic copper foil according to claim 13, characterized in that a silane coupling agent layer is present on the chromate coating layer.

16. An electrolytic copper foil, wherein the electrolytic copper foil is an electrolytic copper foil in which coarsened particles are formed on the roughened surface (M surface) of the electrolytic copper foil, characterized in that the average size of the coarsened particles is 0.1 to 1.0 μm, the average number of coarsened particles is 1 to 2 particles/ ^μm² , the average size is the average of the particle size on a vertical cross-section observed from any two points on the roughened surface of the coarsened particle and the particle size on a horizontal plane observed from any two points, and the particle size is the result of linear analysis of the coarsened particles observed in a 10,000x SEM image.

17. The electrolytic copper foil according to claim 16, characterized in that the surface roughness Rz of the roughened surface (M surface) of the electrolytic copper foil is less than 3.0 μm, Ra is less than 0.6 μm, and Rt is less than 4.0 μm.

18. The electrolytic copper foil according to claim 16, wherein the normal peel strength between the electrolytic copper foil and the BT substrate is above 1.0 kN/m.

19. The electrolytic copper foil according to claim 17, wherein the normal peel strength between the electrolytic copper foil and the BT substrate is above 1.0 kN/m.

20. The electrolytic copper foil according to claim 16, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

21. The electrolytic copper foil according to claim 17, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

22. The electrolytic copper foil according to claim 18, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

23. The electrolytic copper foil according to claim 19, wherein the peel strength of the electrolytic copper foil after welding with the BT substrate is above 0.98 kN/m.

24. The electrolytic copper foil according to any one of claims 16 to 23, characterized in that a copper plating layer is formed on the coarsened particle layer.

25. The electrolytic copper foil according to any one of claims 16 to 23, characterized in that a heat-resistant/rust-proof layer is provided on the roughened particle layer or the plating treatment layer, the heat-resistant/rust-proof layer containing at least one element selected from zinc, nickel, copper, and phosphorus.

26. The electrolytic copper foil according to claim 24, characterized in that a heat-resistant/rust-proof layer is provided on the roughened particle layer or the plating treatment layer, the heat-resistant/rust-proof layer containing at least one element selected from zinc, nickel, copper, and phosphorus.

27. The electrolytic copper foil according to claim 25, characterized in that a chromate coating layer is provided on the heat-resistant/rust-proof layer.

28. The electrolytic copper foil according to claim 26, characterized in that a chromate coating layer is provided on the heat-resistant/rust-proof layer.

29. The electrolytic copper foil according to claim 27, characterized in that a silane coupling agent layer is present on the chromate coating layer.

30. The electrolytic copper foil according to claim 28, characterized in that a silane coupling agent layer is present on the chromate coating layer.

31. A printed wiring board or a negative electrode material for a battery that uses the electrolytic copper foil according to any one of claims 1 to 30.

32. A method for manufacturing electrolytic copper foil, wherein the method involves forming coarse particles on the roughened surface (M surface) of the electrolytic copper foil using an electrolytic bath containing sulfuric acid/copper sulfate, characterized in that the copper concentration in the electrolytic bath is 10-20 g/L during electrolysis to manufacture the electrolytic copper foil according to any one of claims 1-30.

33. The method for manufacturing electrolytic copper foil according to claim 32, characterized in that a copper coarsening particle is formed using an electrolytic bath containing tungsten ions and sulfuric acid/copper sulfate.