JP4280171B2 - Copper and copper alloy surface roughening solution - Google Patents
Copper and copper alloy surface roughening solution Download PDFInfo
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- JP4280171B2 JP4280171B2 JP2004017768A JP2004017768A JP4280171B2 JP 4280171 B2 JP4280171 B2 JP 4280171B2 JP 2004017768 A JP2004017768 A JP 2004017768A JP 2004017768 A JP2004017768 A JP 2004017768A JP 4280171 B2 JP4280171 B2 JP 4280171B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 36
- 239000010949 copper Substances 0.000 title claims description 33
- 238000007788 roughening Methods 0.000 title claims description 27
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 17
- 150000001565 benzotriazoles Chemical class 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 23
- 238000000635 electron micrograph Methods 0.000 description 15
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 11
- 239000012964 benzotriazole Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- -1 sulfuric acid) Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 description 1
- MXJIHEXYGRXHGP-UHFFFAOYSA-N benzotriazol-1-ylmethanol Chemical compound C1=CC=C2N(CO)N=NC2=C1 MXJIHEXYGRXHGP-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- ing And Chemical Polishing (AREA)
Description
本発明は、プリント配線板、特に多層プリント配線板の製造の際に用いる、銅及び銅合金の表面粗化処理液に関する。更に詳細には、銅表面とプリプレグ等の高分子材料の接着性を強固にするための銅及び銅合金の表面粗化処理液に関する。 The present invention relates to a surface roughening solution for copper and copper alloy used in the production of printed wiring boards, particularly multilayer printed wiring boards. More specifically, the present invention relates to a surface roughening solution for copper and copper alloy for strengthening the adhesion between the copper surface and a polymer material such as a prepreg.
多層プリント配線板は、回路形成を行なった内装材に、外装材、プリプレグ等を積層、加熱加圧して一体化したものにスルーホールを形成し、メッキ、外装回路形成を行なって製造される。この工程で、各層の接着性を高めるために内装銅箔表面を粗化することが行われる。 A multilayer printed wiring board is manufactured by laminating an exterior material, a prepreg, and the like on an interior material subjected to circuit formation, forming a through hole in the integrated body by heating and pressurizing, and performing plating and exterior circuit formation. In this step, the surface of the interior copper foil is roughened in order to improve the adhesion of each layer.
粗化方法としては、亜塩素酸ナトリウム等を用いて酸化処理する方法が一般的であり、この方法は銅箔表面に黒色の酸化銅の層を形成する方法であり、通常、黒化処理と呼ばれている。しかし、黒化処理には、スルーホール形成後のメッキ工程で、メッキ液がしみこみ酸化銅がとけるという現象（ピンクリング）が発生し易いという欠点がある。また、作業性が悪く、時間がかかるという問題もある。そのため、工程数が少なく、生産性に優れ、しかもピンクリングが発生しない内装銅箔の処理方法として、過酸化水素及び硫酸を主剤として用いる粗化方法が検討されている。 As a roughening method, a method of oxidizing using sodium chlorite or the like is generally used, and this method is a method of forming a black copper oxide layer on the surface of the copper foil. being called. However, the blackening treatment has a drawback that a phenomenon (pink ring) in which the plating solution penetrates and the copper oxide is dissolved easily occurs in the plating step after the formation of the through hole. There is also a problem that workability is poor and time is required. Therefore, a roughening method using hydrogen peroxide and sulfuric acid as a main agent has been studied as a method for treating an internal copper foil with a small number of steps, excellent productivity, and no pink ring.
例えば、特許文献1には、過酸化水素、無機酸（特に、硫酸）、トリアゾールなどの腐食防止剤及び第4級アンモニウム界面活性剤を含む接着促進組成物に金属表面を接触させ、微細粗面化された変換被覆した表面を形成する方法が、特許文献2には、過酸化水素と、無機酸と、第一級アミン、第二級アミン、第三級アミン、第４級アンモニウム化合物からなり、（該アミンが界面活性を含まない）さらに腐食防止剤（ベンゾトリアゾール）を含有する組成物を金属表面に接触させてミクロに粗面化された変換コーティング層表面を形成させてなる金属表面処理方法が述べられている。特許文献3には、オキソ酸（特に、硫酸）、過酸化物（特に、過酸化水素）、アゾール（特に、ベンゾトリアゾール）及びハロゲン化物を含むエッチング液で銅表面を針状にエッチングする方法が、特許文献4には、酸化剤（特に過酸化水素）、酸（特に硫酸）、腐食防止剤（トリアゾール、ベンゾトリアゾールなど）、ハライドイオン源（特にクロライドイオン）及び任意に水溶性ポリマーからなる接着促進組成物を金属表面と接触させて、金属表面上に微少な粗さをもつ変換被覆表面を生成させ、その後に、高分子材料を該金属と結合させることが述べられている。 For example, Patent Document 1 discloses that a metal surface is brought into contact with an adhesion promoting composition containing a corrosion inhibitor such as hydrogen peroxide, an inorganic acid (particularly sulfuric acid), triazole, and a quaternary ammonium surfactant. Patent Document 2 discloses a method for forming a converted conversion coated surface comprising hydrogen peroxide, an inorganic acid, a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium compound. Metal surface treatment obtained by bringing a composition containing a corrosion inhibitor (benzotriazole) (in which the amine does not contain surface activity) into contact with the metal surface to form a micro-roughened conversion coating layer surface A method is described. Patent Document 3 discloses a method of etching a copper surface in an acicular shape with an etching solution containing oxo acid (particularly sulfuric acid), peroxide (particularly hydrogen peroxide), azole (particularly benzotriazole) and halide. Patent Document 4 describes an adhesive comprising an oxidizing agent (particularly hydrogen peroxide), an acid (particularly sulfuric acid), a corrosion inhibitor (triazole, benzotriazole, etc.), a halide ion source (particularly chloride ion), and optionally a water-soluble polymer. It is stated that the accelerating composition is brought into contact with the metal surface to produce a conversion coated surface with a slight roughness on the metal surface, after which the polymeric material is bonded to the metal.
しかしながら、これらの方法では、粗化が不十分であったり、粗化表面の色調にムラが生じる欠点がある。また粗化表面の色調が従来の黒化処理と比べて異なることから、従来の黒化処理品に近い色調の粗化表面が得られる粗化処理液の開発がユーザー側から望まれている。
本発明者等は、前記欠点のない粗面化処理液、即ち、十分に、かつ均一に粗化され、また従来の黒化処理品に近い暗い色調が得られる、銅及び銅合金の表面粗化処理液を提供することを目的に、鋭意、検討した結果、過酸化水素、硫酸、ベンゾトリアゾール類、及び塩化物イオンからなる特定組成の処理液で処理すると、所望の粗化面が得られることを見出し、本発明を完成した。 The present inventors have made a roughening treatment solution free of the above-mentioned defects, that is, a surface roughness of copper and copper alloy that is sufficiently and uniformly roughened and obtains a dark color tone close to that of a conventional blackened product. As a result of earnest and examination for the purpose of providing a chemical treatment liquid, a desired roughened surface can be obtained by treatment with a treatment liquid having a specific composition comprising hydrogen peroxide, sulfuric acid, benzotriazoles, and chloride ions. As a result, the present invention has been completed.
即ち、本発明は、過酸化水素1.0〜2.5重量％、硫酸2.0〜20重量％、ベンゾトリアゾール類0.2〜0.8重量％、塩化物イオン0.0003〜0.0015重量％を含有する水溶液からなり、ベンゾトリアゾール類濃度に対する塩化物イオン濃度の比が0.001〜0.003である銅及び銅合金の表面粗化処理液に関する。 That is, the present invention comprises an aqueous solution containing hydrogen peroxide 1.0 to 2.5% by weight, sulfuric acid 2.0 to 20% by weight, benzotriazoles 0.2 to 0.8% by weight, chloride ions 0.0003 to 0.0015% by weight, and the concentration of benzotriazoles The present invention relates to a surface roughening treatment liquid for copper and copper alloys having a chloride ion concentration ratio of 0.001 to 0.003.
本発明の表面粗化処理液によって、銅及び銅合金の表面を処理すれば、銅表面に微小で均一な粗さの、従来の黒化処理品に近い、暗い茶褐色の被膜を形成することができるために、外観上も従来の黒化処理品と差異がなく、かつ銅表面とプリプレグ等の高分子材料の接着性を強固にすることができる。
本発明の表面粗化処理液は、黒化処理の代替として用いることができるだけでなく、ドライフィルムレジスト、ソルダーレジスト等との密着性を改善するためにも使用できる。
By treating the surface of copper and copper alloy with the surface roughening treatment liquid of the present invention, it is possible to form a dark brown film with a fine and uniform roughness on the copper surface, which is close to a conventional blackened product. Therefore, there is no difference in appearance from the conventional blackened product, and the adhesion between the copper surface and a polymer material such as a prepreg can be strengthened.
The surface roughening treatment liquid of the present invention can be used not only as an alternative to the blackening treatment, but also for improving the adhesion with a dry film resist, a solder resist or the like.
本発明の表面粗化処理液は、過酸化水素、硫酸、ベンゾトリアゾール類、及び塩化物イオンを、それぞれ特定の濃度範囲で含有し、かつベンゾトリアゾール類濃度に対する塩化物イオン濃度が一定の比率に維持されなければならない。
本発明における過酸化水素濃度は、1.0〜2.5重量％であり、好ましくは、1.2〜2.0重量％である。過酸化水素濃度が1.0重量％未満であると銅の溶解量が少なく十分な粗化ができない。2.5重量％を越えると濃度の増加に伴う効果が得られないばかりか、逆に十分な粗化ができなくなる。
本発明における硫酸濃度は、2〜20重量％であり、好ましくは、3〜10重量％である。
The surface roughening treatment liquid of the present invention contains hydrogen peroxide, sulfuric acid, benzotriazoles, and chloride ions in specific concentration ranges, respectively, and the chloride ion concentration with respect to the benzotriazole concentration is a constant ratio. Must be maintained.
The hydrogen peroxide concentration in the present invention is 1.0 to 2.5% by weight, and preferably 1.2 to 2.0% by weight. When the hydrogen peroxide concentration is less than 1.0% by weight, the amount of copper dissolved is small and sufficient roughening cannot be performed. If it exceeds 2.5% by weight, not only the effect associated with the increase in concentration cannot be obtained, but also roughening cannot be achieved.
The sulfuric acid concentration in the present invention is 2 to 20% by weight, preferably 3 to 10% by weight.
本発明におけるベンゾトリアゾール類は、ベンゾトリアゾール、1-ヒドロキシベンゾトリアゾール、1-アミノベンゾトリアゾール、1-（ヒドロキシメチル）ベンゾトリアゾール、及びカルボキシベンゾトリアゾール等であり、ベンゾトリアゾール類の濃度は、0.2〜0.8重量％である。
本発明における塩化物イオン源は、塩化ナトリウム、塩化カリウム、塩酸、塩化アンモニウム、塩化マグネシウム、及び塩化カルシウム等であり、塩化物イオンの濃度は0.0003〜0.0015重量％である。
The benzotriazoles in the present invention are benzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 1- (hydroxymethyl) benzotriazole, carboxybenzotriazole, and the like. The concentration of benzotriazoles is 0.2 to 0.8. % By weight.
The chloride ion source in the present invention is sodium chloride, potassium chloride, hydrochloric acid, ammonium chloride, magnesium chloride, calcium chloride and the like, and the concentration of chloride ions is 0.0003 to 0.0015% by weight.
本発明において、ベンゾトリアゾール類濃度に対する塩化物イオン濃度を一定の比率に調整することが極めて重要であり、その比率は、0.001〜0.003である。
ベンゾトリアゾール類濃度に対する、塩化物イオンの濃度の比が、0.001より小さいときは、溶解速度が速く、溶解量に相当する深い凸凹な粗面が得られず、かつ処理表面の色調にムラ（まばら模様）が生じる。
ベンゾトリアゾール類濃度に対する、塩化物イオンの濃度の比が、0.003より大きいときは、溶解速度が遅く、十分粗化されず、また処理表面の色調が、従来の黒化処理品に比べて色調が明るい。
過酸化水素等の必須成分が前記濃度に調整され、ベンゾトリアゾール類濃度に対する、塩化物イオンの濃度の比が、0.001〜0.003に調整された場合は、前記組成液の溶解速度は１分当たり1〜2.5μｍであり、微小で均一な粗さに銅表面を粗化でき、かつその色調は、従来の黒化処理品に近い、暗い茶褐色である。
In the present invention, it is extremely important to adjust the chloride ion concentration to the benzotriazole concentration to a certain ratio, and the ratio is 0.001 to 0.003.
When the ratio of the chloride ion concentration to the benzotriazole concentration is less than 0.001, the dissolution rate is high, a deep uneven rough surface corresponding to the amount of dissolution cannot be obtained, and the color of the treated surface is uneven (sparse). Pattern).
When the ratio of the chloride ion concentration to the benzotriazole concentration is greater than 0.003, the dissolution rate is slow, the surface is not sufficiently roughened, and the color tone of the treated surface is inferior to that of the conventional blackened product. bright.
When an essential component such as hydrogen peroxide is adjusted to the above concentration and the ratio of the chloride ion concentration to the benzotriazole concentration is adjusted to 0.001 to 0.003, the dissolution rate of the composition solution is 1 per minute. The copper surface can be roughened to a fine and uniform roughness, and the color tone is dark brown, which is close to a conventional blackened product.
色調（明暗の度合い）は色差計を用いて測定することができ、その測定値（Ｌ値）で数値化できる。本発明の表面粗化処理液によれば、Ｌ値が35以下の、従来の黒化処理品の色調に近い、暗い茶褐色の粗化面が得られる。 The color tone (degree of light and darkness) can be measured using a color difference meter, and can be quantified by the measured value (L value). According to the surface roughening treatment liquid of the present invention, a dark brown rough surface having an L value of 35 or less and close to the color tone of a conventional blackened product can be obtained.
本発明おいて、銅及び銅合金表面の処理方法は、フラッドと呼ばれる浸漬法又は噴霧法などで行うことができる。処理温度は10〜60℃の範囲が好ましく、20〜40℃がより好ましい。処理時間は処理温度や処理方法により変わるが、10秒〜10分の範囲が好ましく、30秒〜2分がより好ましい。 In the present invention, the copper and copper alloy surface can be treated by a dipping method called a flood or a spraying method. The treatment temperature is preferably in the range of 10 to 60 ° C, more preferably 20 to 40 ° C. The treatment time varies depending on the treatment temperature and treatment method, but is preferably in the range of 10 seconds to 10 minutes, more preferably 30 seconds to 2 minutes.
本発明の表面粗化処理液には、必要に応じてたとえばアルコール類、アミン類、スルホン酸類などの過酸化水素の安定剤、その他添加剤を添加しても良い。
The surface roughening treatment liquid of the present invention may contain a hydrogen peroxide stabilizer such as alcohols, amines and sulfonic acids, and other additives as necessary.
以下に、実施例をもって本発明を説明する。
実施例１〜5及び比較例１〜７
表１及び表２に示す組成の表面粗化処理液に30℃で1分間、プリント配線板用銅張積層板をロッキング遥動しながら漬浸し、銅張積層板の銅表面をエッチングして粗化した。表中、添加剤の比率は、ベンゾトリアゾール濃度に対する塩化物イオン濃度の比率を示し（塩化物イオンは塩化ナトリウムを用いた。）、溶解厚さは、銅の表面積及び比重と溶解した銅の重量から計算した平均の厚さを示す。
Ｌ値は、処理表面の色の暗さを日本電色工業（株）製、色差計ＳＺ−シグマ80で測定した値（Ｌ値は数字が小さいほど暗い。）であり、外観（目視）は色調のムラの有無を示した。
実施例及び比較例で処理して得られた表面を30°の角度で撮影した電子顕微鏡写真を図２〜１３に示す。また、粗面化処理前の銅表面の電子顕微鏡写真を図１に示す。
比較例から、ベンゾトリアゾール濃度と塩化物イオン濃度の比によって、均一な暗い色の表面が得られないこと、及び十分な粗化面が得られないことが分かる。また、過酸化水素の濃度によっては、良好な粗化がなされないことが分かる。
Hereinafter, the present invention will be described with reference to examples.
Examples 1-5 and Comparative Examples 1-7
A copper-clad laminate for printed wiring boards is immersed in a surface-roughening treatment solution having the composition shown in Tables 1 and 2 at 30 ° C for 1 minute while rocking, and the copper surface of the copper-clad laminate is etched and roughened. Turned into. In the table, the ratio of the additive indicates the ratio of the chloride ion concentration to the benzotriazole concentration (sodium chloride was used as the chloride ion), and the dissolved thickness indicates the copper surface area and specific gravity and the weight of the dissolved copper. The average thickness calculated from
The L value is a value obtained by measuring the color darkness of the treated surface with a color difference meter SZ-Sigma 80 manufactured by Nippon Denshoku Industries Co., Ltd. (L value is darker as the number is smaller), and the appearance (visually) is The presence or absence of uneven color tone was indicated.
The electron micrograph which image | photographed the surface obtained by processing in an Example and a comparative example at an angle of 30 degrees is shown in FIGS. Moreover, the electron micrograph of the copper surface before a roughening process is shown in FIG.
From the comparative example, it can be seen that a uniform dark surface cannot be obtained and a sufficient roughened surface cannot be obtained depending on the ratio between the benzotriazole concentration and the chloride ion concentration. Moreover, it turns out that favorable roughening is not made | formed depending on the density | concentration of hydrogen peroxide.
Claims (2)
2. The surface roughening solution according to claim 1, wherein when the surfaces of copper and copper alloy are roughened, the L value of the surface to be treated of the copper and copper alloy is 35 or less.
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| JP5273710B2 (en) * | 2007-11-27 | 2013-08-28 | メック株式会社 | Etching agent |
| WO2009078466A1 (en) * | 2007-12-18 | 2009-06-25 | Taisei Plas Co., Ltd. | Composites of metal with resin and processes for producing the same |
| JP6464578B2 (en) | 2013-08-01 | 2019-02-06 | 三菱瓦斯化学株式会社 | Method for manufacturing printed wiring board |
| JP6424559B2 (en) | 2013-11-22 | 2018-11-21 | 三菱瓦斯化学株式会社 | Composition for etching and method of manufacturing printed wiring board using the same |
| CN111349937B (en) * | 2020-03-20 | 2022-03-22 | 盐城维信电子有限公司 | Micro-etching solution for copper or copper alloy surface and treatment method thereof |
| CA3110357A1 (en) * | 2021-02-25 | 2022-08-25 | Sixring Inc. | Modified sulfuric acid and uses thereof |
| CN114686885B (en) * | 2022-06-02 | 2022-08-19 | 深圳市板明科技股份有限公司 | Copper surface super-roughening solution for circuit board, preparation method and application thereof |
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