JPWO2020171051A1 - Etching solution for silver and manufacturing method of printed wiring board using it - Google Patents
Etching solution for silver and manufacturing method of printed wiring board using it Download PDFInfo
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- JPWO2020171051A1 JPWO2020171051A1 JP2020543124A JP2020543124A JPWO2020171051A1 JP WO2020171051 A1 JPWO2020171051 A1 JP WO2020171051A1 JP 2020543124 A JP2020543124 A JP 2020543124A JP 2020543124 A JP2020543124 A JP 2020543124A JP WO2020171051 A1 JPWO2020171051 A1 JP WO2020171051A1
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- Prior art keywords
- silver
- mass
- layer
- etching solution
- acid
- Prior art date
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- Granted
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 218
- 239000004332 silver Substances 0.000 title claims abstract description 218
- 238000005530 etching Methods 0.000 title claims abstract description 124
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 222
- 239000000243 solution Substances 0.000 claims abstract description 138
- 238000000034 method Methods 0.000 claims abstract description 92
- 238000007747 plating Methods 0.000 claims abstract description 66
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
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- 230000008569 process Effects 0.000 claims description 14
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 179
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 60
- 239000002585 base Substances 0.000 description 59
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- YGNGABUJMXJPIJ-UHFFFAOYSA-N thiatriazole Chemical compound C1=NN=NS1 YGNGABUJMXJPIJ-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
Abstract
本発明は、カルボン酸、過酸化水素及びアルコールを含有する水溶液である銀用エッチング液を提供する。また、絶縁性基材（Ａ）上に、めっき下地層として銀層（Ｍ１）を形成した後、不要となった前記銀層（Ｍ１）を上記の銀用エッチング液で除去する工程を有するプリント配線板の製造方法を提供する。当該銀用エッチング液を用いることで、銀をめっき下地層に用いるプリント配線板の製造において、不要なめっき下地層を効率よく除去することができ、プリント配線板の配線部にサイドエッチやアンダーカットの少ないプリント配線板が得られる。 The present invention provides an etching solution for silver which is an aqueous solution containing carboxylic acid, hydrogen peroxide and alcohol. Further, a print having a step of forming a silver layer (M1) as a plating base layer on the insulating base material (A) and then removing the unnecessary silver layer (M1) with the above-mentioned etching solution for silver. A method for manufacturing a wiring board is provided. By using the etching solution for silver, it is possible to efficiently remove an unnecessary plating base layer in the production of a printed wiring board using silver as a plating base layer, and side etch or undercut on the wiring part of the printed wiring board. A printed wiring board with less is obtained.
Description
本発明は、銀用エッチング液、及びそれを用いたプリント配線板の製造方法に関する。 The present invention relates to an etching solution for silver and a method for manufacturing a printed wiring board using the etching solution.
プリント配線板の配線形成方法としてサブトラクティブ法、セミアディティブ法（ＳＡＰ）及びモディファイドＳＡＰ（ＭＳＡＰ）があり、このうち微細配線形成にはＳＡＰ、ＭＳＡＰが適している。ＳＡＰ、ＭＳＡＰの配線形成方法は共通しており、めっき下地層（薄い導電層又はめっき触媒層）上の回路パターンの非配線部にレジストを形成し、レジストを形成していない配線部にめっきで厚付けした後にレジストを剥離し、不要となった非配線部のめっき下地層をエッチングにより除去する方法である。 There are a subtractive method, a semi-additive method (SAP) and a modified SAP (MSAP) as a wiring forming method of a printed wiring board, and among them, SAP and MSAP are suitable for forming fine wiring. The wiring formation method for SAP and MSAP is common. A resist is formed on the non-wiring part of the circuit pattern on the plating base layer (thin conductive layer or plating catalyst layer), and the wiring part where the resist is not formed is plated. This is a method in which the resist is peeled off after thickening, and the plating base layer of the non-wiring portion that is no longer needed is removed by etching.
めっき下地層のエッチング工程に起因するプリント配線板の問題として、エッチング残渣による回路絶縁信頼性の低下、過度なエッチングによる配線幅の減少（サイドエッチ）による回路の電気抵抗増大、配線部のめっき下地層のエッチング過剰進行（アンダーカット）による配線／基材間の接着強度低下等が知られている。このため、めっき下地層のエッチング工程においては、めっき下地層の残渣が無いこと、サイドエッチが小さいこと、めっき下地層のアンダーカットが無いことが要求される。 Problems with the printed wiring board caused by the etching process of the plating base layer include a decrease in circuit insulation reliability due to etching residue, an increase in circuit electrical resistance due to a decrease in wiring width (side etching) due to excessive etching, and under-plating of the wiring part. It is known that the adhesion strength between wiring / substrate is reduced due to excessive etching of the formation (undercut). Therefore, in the etching process of the plating base layer, it is required that there is no residue of the plating base layer, the side etch is small, and there is no undercut of the plating base layer.
ＳＡＰ、ＭＳＡＰのめっき下地層として用いられる金属は、種々のものが知られているが、めっき金属とめっき下地層の金属種が同じ場合と、異なる場合の２つに分類できる。めっき金属とめっき下地層の金属種が同じ場合、配線部のサイドエッチを低減しつつ、めっき下地層をエッチングする工夫がなされているが、配線の狭ピッチ化要求に伴い困難になっている。一方、めっき金属とめっき下地層の金属種が異なる場合、各金属種に対する除去性が大幅に異なるエッチング液を適切に選択すれば、狭ピッチであっても配線金属をほとんどエッチングすることなく、めっき下地層の金属のみをエッチングすることが可能である。めっき金属とめっき下地層に異なる金属種を用いたＭＳＡＰとして、銀をめっき下地層とする銅配線形成プロセスが報告されている（例えば、非特許文献１を参照。）。 Various metals are known as the metal used as the plating base layer of SAP and MSAP, and they can be classified into two cases, one is the same type of metal and the other is different from the metal type of the plating metal and the plating base layer. When the metal type of the plating metal and the metal type of the plating base layer are the same, some measures have been taken to etch the plating base layer while reducing the side etching of the wiring portion, but this has become difficult due to the demand for narrowing the pitch of the wiring. On the other hand, when the metal type of the plating metal and the metal type of the plating base layer are different, if an etching solution having significantly different removability for each metal type is appropriately selected, plating is performed with almost no etching of the wiring metal even at a narrow pitch. It is possible to etch only the metal of the base layer. As an MSAP using different metal types for the plating metal and the plating base layer, a copper wiring formation process using silver as the plating base layer has been reported (see, for example, Non-Patent Document 1).
上記の、銀をめっき下地層として銅配線を形成するＭＳＡＰでは、銀めっき下地層をエッチングにより除去する必要がある。この工程で用いられるエッチング液としては、銀は溶解するが銅は溶解しないという反応性が要求される。この要求を満たし、かつ、環境負荷の小さい非シアン系の銀のエッチング方法としては、モノクロル酢酸、酢酸及び過酸化水素の混合物を用いた銀めっき層の有害金属分析方法が知られている（例えば、特許文献１を参照。）。また、酢酸と過酸化水素の混合物を含有することを特徴とする銀めっき層溶解液及び銀めっき層溶解方法が報告されている（例えば、特許文献２を参照。）。 In the above-mentioned MSAP in which the copper wiring is formed by using silver as the plating base layer, it is necessary to remove the silver plating base layer by etching. The etching solution used in this step is required to have reactivity that silver dissolves but copper does not dissolve. As a method for etching non-cyan silver that satisfies this requirement and has a small environmental load, a method for analyzing harmful metals in a silver-plated layer using a mixture of monochloroacetic acid, acetic acid and hydrogen peroxide is known (for example). , Patent Document 1). Further, a silver plating layer dissolution liquid and a silver plating layer dissolution method characterized by containing a mixture of acetic acid and hydrogen peroxide have been reported (see, for example, Patent Document 2).
しかしながら、上記の特許文献１及び２に開示されている銀用エッチング液を回路形成に使用した場合、銀が残渣として残り、回路製造の歩留まりの低下、回路の絶縁信頼性の低下、等が起こることが問題であった。 However, when the etching solution for silver disclosed in Patent Documents 1 and 2 is used for circuit formation, silver remains as a residue, resulting in a decrease in circuit manufacturing yield, a decrease in circuit insulation reliability, and the like. Was the problem.
本発明が解決しようとする課題は、銀をめっき下地層に用いるプリント配線板の製造において、不要なめっき下地層を効率よくエッチングすることができ、得られるプリント配線板の配線部にサイドエッチやアンダーカットが少ない銀用エッチング液を提供することである。また、前記銀用エッチング液を用いたプリント配線板の製造方法を提供することである。 The problem to be solved by the present invention is that in the production of a printed wiring board using silver as a plating base layer, an unnecessary plating base layer can be efficiently etched, and side etching or side etching is performed on the wiring portion of the obtained printed wiring board. The purpose of the present invention is to provide an etching solution for silver with less undercut. Another object of the present invention is to provide a method for manufacturing a printed wiring board using the etching solution for silver.
本発明者らは、上記の課題を解決すべく鋭意研究した結果、銀用エッチング液にアルコールを添加したものを用いることで、銀をめっき下地層に用いるプリント配線板の製造において、不要なめっき下地層を効率よく除去することができ、得られるプリント配線板の配線部にサイドエッチやアンダーカットが少ないことを見出し、本発明を完成した。 As a result of diligent research to solve the above problems, the present inventors have made unnecessary plating in the production of a printed wiring board using silver as a plating base layer by using an etching solution for silver to which alcohol is added. The present invention has been completed by finding that the underlying layer can be efficiently removed and that the resulting printed wiring board has less side etching and undercut.
すなわち、本発明は、カルボン酸、過酸化水素及びアルコールを含有する水溶液であることを特徴とする銀用エッチング液を提供するものである。 That is, the present invention provides an etching solution for silver, which is an aqueous solution containing a carboxylic acid, hydrogen peroxide and alcohol.
また、本発明は、絶縁性基材（Ａ）上に、めっき下地層として銀層（Ｍ１）を形成した後、不要となった前記銀層（Ｍ１）を前記の銀用エッチング液で除去する工程を有することを特徴とするプリント配線板の製造方法を提供するものである。 Further, in the present invention, after forming a silver layer (M1) as a plating base layer on the insulating base material (A), the unnecessary silver layer (M1) is removed by the silver etching solution. It provides a method of manufacturing a printed wiring board characterized by having a process.
本発明の銀用エッチング液は、配線部をほとんど溶解することなく、銀からなるめっき下地層のみを選択的に除去できる。また、本発明の銀用エッチング液は、狭ピッチの微細配線、狭隘なトレンチ部の底にあるめっき下地層であっても効率よく、残渣を残すことなく除去することができる。 The etching solution for silver of the present invention can selectively remove only the plating base layer made of silver with almost no dissolution of the wiring portion. Further, the etching solution for silver of the present invention can efficiently remove even a narrow pitch fine wiring and a plating base layer at the bottom of a narrow trench portion without leaving a residue.
したがって、本発明の銀用エッチング液を用いることで、レジストパターンからの寸法変化がほとんど無く、狭ピッチの微細配線であっても、配線パターン形成が可能となる。例えば、銀からなるめっき下地層上に電解銅めっきにより銅配線を形成した場合、本発明の銀用エッチング液は、銅を溶解しにくいため、形成された銅配線の表面を溶解しないことから、銅配線の表面粗度が極めて低く、高性能のプリント配線板を、低コストかつ高い歩留まりで提供することができる。また、本発明のプリント配線板の製造方法により製造されたプリント配線板は、通常のプリント配線板のみならず、基材表面にパターン化された金属層を有する種々の電子部材に用いることができ、例えば、コネクター、電磁波シールド、ＲＦＩＤ等のアンテナ、フィルムコンデンサーなどにも応用できる。さらに、本発明のプリント配線板の製造方法は、種々の形状、サイズの基材上にパターン化された金属層を有する装飾めっき用途で用いることもできる。 Therefore, by using the etching solution for silver of the present invention, there is almost no dimensional change from the resist pattern, and it is possible to form a wiring pattern even with fine wiring having a narrow pitch. For example, when copper wiring is formed by electrolytic copper plating on a plating base layer made of silver, the etching solution for silver of the present invention does not dissolve copper, and therefore does not dissolve the surface of the formed copper wiring. It is possible to provide a high-performance printed wiring board having extremely low surface roughness of copper wiring at low cost and high yield. Further, the printed wiring board manufactured by the method for manufacturing a printed wiring board of the present invention can be used not only for a normal printed wiring board but also for various electronic members having a patterned metal layer on the surface of a base material. For example, it can be applied to a connector, an electromagnetic wave shield, an antenna such as RFID, a film capacitor, and the like. Further, the method for manufacturing a printed wiring board of the present invention can also be used for decorative plating applications having a metal layer patterned on a substrate of various shapes and sizes.
本発明の銀用エッチング液は、カルボン酸、過酸化水素及びアルコールを含有する水溶液である。 The etching solution for silver of the present invention is an aqueous solution containing carboxylic acid, hydrogen peroxide and alcohol.
前記カルボン酸としては、例えば、酢酸、蟻酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、マルガリン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸、エイコサペンタエン酸、ドコサヘキサエン酸、シュウ酸、マロン酸、コハク酸、安息香酸、サリチル酸、フタル酸、イソフタル酸、テレフタル酸、没食子酸、メリト酸、ケイ皮酸、ピルビン酸、乳酸、リンゴ酸、クエン酸、フマル酸、マレイン酸、アコニット酸、グルタル酸、アジピン酸、アミノ酸等が挙げられる。これらのカルボン酸は、１種で用いることも２種以上併用することもできる。 Examples of the carboxylic acid include acetic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid and stearic acid. Oleic acid, linoleic acid, linolenic acid, arachidonic acid, eikosapentaenoic acid, docosahexaenoic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, gallic acid, melitonic acid, coconut husk Examples thereof include acids, pyruvate, lactic acid, malic acid, citric acid, fumaric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, amino acids and the like. These carboxylic acids can be used alone or in combination of two or more.
また、前記カルボン酸の中でも、水中でのｐＫａが２．５〜５．１の範囲のものが好ましい。ｐＫａがこの範囲のカルボン酸としては、例えば、酢酸（ｐＫａ＝４．７６）、モノクロロ酢酸（ｐＫａ＝２．８１）、ギ酸（ｐＫａ＝３．７７）、１−プロピオン酸（ｐＫａ＝４．８８）等が挙げられる。さらに、これらのカルボン酸の中でも、取り扱いが容易であることから、酢酸、及びモノクロロ酢酸が特に好ましい。 Further, among the carboxylic acids, those having a pKa in water in the range of 2.5 to 5.1 are preferable. Examples of carboxylic acids having pKa in this range include acetic acid (pKa = 4.76), monochloroacetic acid (pKa = 2.81), formic acid (pKa = 3.77), and 1-propionic acid (pKa = 4.88). ) Etc. can be mentioned. Further, among these carboxylic acids, acetic acid and monochloroacetic acid are particularly preferable because they are easy to handle.
前記カルボン酸と過酸化水素の含有率としては、後述する導体回路層（Ｍ２）を構成する金属の溶解を抑制できることから、本発明の銀用エッチング液中のカルボン酸の含有率は、１〜１５質量％の範囲が好ましく、２〜１０質量％の範囲がより好ましい。また、本発明の銀用エッチング液中の過酸化水素の含有率は１〜２５質量％の範囲が好ましく、２〜２０質量％の範囲がより好ましい。 As the content of the carboxylic acid and hydrogen peroxide, the dissolution of the metal constituting the conductor circuit layer (M2) described later can be suppressed. Therefore, the content of the carboxylic acid in the etching solution for silver of the present invention is 1 to 1. The range of 15% by mass is preferable, and the range of 2 to 10% by mass is more preferable. The content of hydrogen peroxide in the etching solution for silver of the present invention is preferably in the range of 1 to 25% by mass, more preferably in the range of 2 to 20% by mass.
前記アルコールとしては、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール（ＩＰＡ）、１−ブタノール、２−ブタノール、２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、２−（２−ブトキシエトキシ）エタノール、エチレングリコール、プロピレングリコール、１，２―ブタンジオール、１，３−ブタンジオール、グリセリン等が挙げられる。これらのアルコールは、１種で用いることも２種以上併用することもできる。また、これらのアルコールの中でも、後述する銀層（Ｍ１）の除去性に優れることから、メタノール、エタノール、１−プロパノール、２−プロパノール（ＩＰＡ）、１−ブタノール、２−ブタノール、２−ブトキシエタノールが好ましく、特に２−ブトキシエタノールが好ましい。 Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol (IPA), 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2- (2- (2-). Butoxyethoxy) ethanol, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, glycerin and the like can be mentioned. These alcohols can be used alone or in combination of two or more. Among these alcohols, methanol, ethanol, 1-propanol, 2-propanol (IPA), 1-butanol, 2-butanol, 2-butoxyethanol are excellent in removing the silver layer (M1) described later. Is preferable, and 2-butoxyethanol is particularly preferable.
本発明の銀用エッチング液中の前記アルコールの含有率は、銀を効率よく除去できることから、２５質量％以下が好ましく、１０質量％以下がより好ましい。また、本発明の銀用エッチング液中の前記アルコールの含有率は、１質量％以上が好ましく、５質量％以上がより好ましい。 The content of the alcohol in the etching solution for silver of the present invention is preferably 25% by mass or less, more preferably 10% by mass or less, because silver can be efficiently removed. Further, the content of the alcohol in the etching solution for silver of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more.
本発明の銀用エッチング液は、前記のカルボン酸、過酸化水素及びアルコールを、水で希釈することで調製できる。 The etching solution for silver of the present invention can be prepared by diluting the above-mentioned carboxylic acid, hydrogen peroxide and alcohol with water.
本発明の銀用エッチング液には、後述する導体回路層（Ｍ２）の溶解を抑制するための保護剤をさらに添加してもよい。例えば、前記導体回路層（Ｍ２）が銅めっき層の場合、保護剤として、アゾール化合物を用いることが好ましい。 A protective agent for suppressing the dissolution of the conductor circuit layer (M2), which will be described later, may be further added to the etching solution for silver of the present invention. For example, when the conductor circuit layer (M2) is a copper-plated layer, it is preferable to use an azole compound as a protective agent.
前記アゾール化合物としては、例えば、イミダゾール、ピラゾール、トリアゾール、テトラゾール、オキソゾール、チアゾール、セレナゾール、オキサジアゾール、チアジアゾール、オキサトリアゾール、チアトリアゾール等が挙げられる。 Examples of the azole compound include imidazole, pyrazole, triazole, tetrazole, oxozole, thiazole, selenazole, oxadiazole, thiadiazole, oxatriazole, and thiatriazole.
前記アゾール化合物の具体例としては、例えば、２−メチルベンゾイミダゾール、アミノトリアゾール、１，２，３−ベンゾトリアゾール、４−アミノベンゾトリアゾール、１−ビスアミノメチルベンゾトリアゾール、アミノテトラゾール、フェニルテトラゾール、２−フェニルチアゾール、ベンゾチアゾール等が挙げられる。これらのアゾール化合物は、１種で用いることも２種以上併用することもできる。 Specific examples of the azole compound include 2-methylbenzimidazole, aminotriazole, 1,2,3-benzotriazole, 4-aminobenzotriazole, 1-bisaminomethylbenzotriazole, aminotetrazole, phenyltetrazole, 2 -Phenylthiazole, benzotriazole and the like can be mentioned. These azole compounds can be used alone or in combination of two or more.
本発明の銀用エッチング液に前記アゾール化合物を用いる場合、銀用エッチング液中の含有率は、０．００１〜２質量％の範囲が好ましく、０．０１〜０．２質量％の範囲がより好ましい。 When the azole compound is used in the etching solution for silver of the present invention, the content in the etching solution for silver is preferably in the range of 0.001 to 2% by mass, more preferably in the range of 0.01 to 0.2% by mass. preferable.
また、前記エッチング液には、前記導体回路層（Ｍ２）が銅めっき層の場合、銅めっき層の溶解を抑制できることから、保護剤として、ポリアルキレングリコールを添加することが好ましい。 Further, when the conductor circuit layer (M2) is a copper-plated layer, the etching solution can suppress the dissolution of the copper-plated layer. Therefore, it is preferable to add polyalkylene glycol as a protective agent.
前記ポリアルキレングリコールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレンポリオキシプロピレンブロックコポリマー等の水溶性のポリアルキレングリコールが挙げられる。これらの中でも、ポリエチレングリコールが好ましい。また、ポリアルキレングリコールの数平均分子量としては、２００〜２０，０００の範囲が好ましい。 Examples of the polyalkylene glycol include water-soluble polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene block copolymer. Among these, polyethylene glycol is preferable. The number average molecular weight of the polyalkylene glycol is preferably in the range of 200 to 20,000.
本発明の銀用エッチング液に前記ポリアルキレングリコールを用いる場合、銀用エッチング液中の含有率は、０．００１〜２質量％の範囲が好ましく、０．０１〜１質量％の範囲がより好ましい。 When the polyalkylene glycol is used in the etching solution for silver of the present invention, the content in the etching solution for silver is preferably in the range of 0.001 to 2% by mass, more preferably in the range of 0.01 to 1% by mass. ..
また、本発明の銀用エッチング液には、ｐＨの変動を抑制するため、有機酸のナトリウム塩、カリウム塩、アンモニウム塩等の添加剤を必要に応じて配合してもよい。 Further, in the etching solution for silver of the present invention, additives such as sodium salt, potassium salt and ammonium salt of organic acids may be added as necessary in order to suppress fluctuations in pH.
本発明の銀用エッチング液には、さらに必要に応じて、界面活性剤、消泡剤、防腐剤、キレート剤などの有機化合物等を配合してもよい。 If necessary, the etching solution for silver of the present invention may further contain an organic compound such as a surfactant, an antifoaming agent, a preservative, or a chelating agent.
前記界面活性剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビトールテトラオレエート、ポリオキシエチレン・ポリオキシプロピレン共重合体等のノニオン系界面活性剤；オレイン酸ナトリウム等の脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、ナフタレンスルホン酸塩、ポリオキシエチレンアルキル硫酸塩、アルカンスルホネートナトリウム塩、アルキルジフェニルエーテルスルホン酸ナトリウム塩等のアニオン系界面活性剤；アルキルアミン塩、アルキルトリメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩等のカチオン系界面活性剤などが挙げられる。 Examples of the surfactant include nonions such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Surfactants; fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyldiphenyl ether sulfonates Anionic surfactants such as salts; cationic surfactants such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts can be mentioned.
前記消泡剤としては、一般的な消泡剤を使用することができ、例えば、シリコーン系消泡剤、ノニオン系界面活性剤、ポリエーテル，高級アルコール、ポリマー系界面活性剤等が挙げられる。 As the defoaming agent, a general defoaming agent can be used, and examples thereof include silicone-based defoaming agents, nonionic-based surfactants, polyethers, higher alcohols, and polymer-based surfactants.
前記防腐剤としては、一般的な防腐剤を使用することができ、例えば、イソチアゾリン系防腐剤、トリアジン系防腐剤、イミダゾール系防腐剤、ピリジン系防腐剤、アゾール系防腐剤、ピリチオン系防腐剤等が挙げられる。 As the preservative, general preservatives can be used, for example, isothiazoline preservatives, triazine preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, pyrithion preservatives and the like. Can be mentioned.
本発明のプリント配線板の製造方法は、絶縁性基材（Ａ）上に、めっき下地層として銀層（Ｍ１）を形成した後、不要となった前記銀層（Ｍ１）を本発明の銀用エッチング液で除去する工程を有するものである。 In the method for producing a printed wiring board of the present invention, a silver layer (M1) is formed as a plating base layer on an insulating base material (A), and then the silver layer (M1) that is no longer needed is made of silver of the present invention. It has a step of removing with an etching solution for use.
前記銀層（Ｍ１）を本発明の銀用エッチング液で除去する方法としては、前記銀層（Ｍ１）を形成した基材を前記銀用エッチング液に浸漬するか、前記基材上に前記銀用エッチング液をスプレー等で噴霧する方法が挙げられる。 As a method of removing the silver layer (M1) with the etching solution for silver of the present invention, the base material on which the silver layer (M1) is formed is immersed in the etching solution for silver, or the silver is placed on the base material. Examples thereof include a method of spraying the etching solution for use with a spray or the like.
エッチング装置を用いて、銀層（Ｍ１）を除去する場合には、例えば、前記銀用エッチング液の全成分を所定の組成になるように調製した後、エッチング装置に供給してもよく、前記銀用エッチング液の各成分を個別にエッチング装置に供給し、装置内で、前記各成分を混合して、所定の組成になるように調製してもよい。 When the silver layer (M1) is removed by using an etching apparatus, for example, all the components of the etching solution for silver may be prepared to have a predetermined composition and then supplied to the etching apparatus. Each component of the etching solution for silver may be individually supplied to an etching apparatus, and the respective components may be mixed in the apparatus to prepare a predetermined composition.
前記銀用エッチング液は、１０〜３５℃の温度範囲で用いることが好ましく、過酸化水素の分解を抑制できることから、３０℃以下の温度範囲で用いることが好ましい。 The etching solution for silver is preferably used in a temperature range of 10 to 35 ° C., and is preferably used in a temperature range of 30 ° C. or lower because decomposition of hydrogen peroxide can be suppressed.
本発明のプリント配線板の製造方法の、より具体的な方法としては、例えば、絶縁性基材（Ａ）上に、銀層（Ｍ１）を形成する工程１、前記銀層（Ｍ１）上にレジストを形成した後、配線部のレジストを除去してパターンレジストを形成する工程２、めっき処理により導体回路層（Ｍ２）を形成する工程３、パターンレジストを剥離し、非配線部の銀層（Ｍ１）を、前記銀用エッチング液により除去する工程４を有するプリント配線板の製造方法が挙げられる。 As a more specific method of manufacturing the printed wiring board of the present invention, for example, a step 1 of forming a silver layer (M1) on an insulating base material (A), on the silver layer (M1). After forming the resist, the step 2 of removing the resist in the wiring part to form the pattern resist, the step 3 of forming the conductor circuit layer (M2) by the plating process, and the step 3 of peeling off the pattern resist to form the silver layer in the non-wiring part ( Examples thereof include a method for manufacturing a printed wiring board having the step 4 of removing M1) with the silver etching solution.
また、本発明のプリント配線板の製造方法の、より具体的な別の方法としては、例えば、絶縁性基材（Ａ）上に、プライマー層（Ｂ）を形成した後、プライマー層（Ｂ）上に、銀層（Ｍ１）を形成する工程１’、前記銀層（Ｍ１）上にレジストを形成した後、配線部のレジストを除去してパターンレジストを形成する工程２、めっき処理により導体回路層（Ｍ２）を形成する工程３、パターンレジストを剥離し、非配線部の銀層（Ｍ１）を前記銀用エッチング液により除去する工程４を有するプリント配線板の製造方法も挙げられる。 Further, as another more specific method of manufacturing the printed wiring board of the present invention, for example, after forming the primer layer (B) on the insulating base material (A), the primer layer (B) Step 1'for forming a silver layer (M1) on the top, step 2 for forming a resist on the silver layer (M1) and then removing the resist in the wiring portion to form a pattern resist, a conductor circuit by plating. There is also a method of manufacturing a printed wiring board having a step 3 of forming the layer (M2) and a step 4 of peeling off the pattern resist and removing the silver layer (M1) of the non-wiring portion with the etching solution for silver.
前記の工程１又は工程１’で用いる前記絶縁性基材（Ａ）の材料としては、例えば、ポリイミド樹脂、ポリアミドイミド樹脂、ポリアミド樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリカーボネート樹脂、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂、ポリアリレート樹脂、ポリアセタール樹脂、ポリ（メタ）アクリル酸メチル等のアクリル樹脂、ポリフッ化ビニリデン樹脂、ポリテトラフルオロエチレン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、アクリル樹脂をグラフト共重合化した塩化ビニル樹脂、ポリビニルアルコール樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ウレタン樹脂、シクロオレフィン樹脂、ポリスチレン、液晶ポリマー（ＬＣＰ）、ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂、ポリフェニレンスルフィド（ＰＰＳ）、ポリフェニレンスルホン（ＰＰＳＵ）、セルロースナノファイバー、シリコン、シリコンカーバイド、窒化ガリウム、サファイア、セラミックス、ガラス、ダイヤモンドライクカーボン（ＤＬＣ）、アルミナ等が挙げられる。 Examples of the material of the insulating base material (A) used in the step 1 or the step 1'include a polyimide resin, a polyamideimide resin, a polyamide resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyethylene naphthalate resin, and a polycarbonate. Resin, acrylonitrile-butadiene-styrene (ABS) resin, polyallylate resin, polyacetal resin, acrylic resin such as poly (meth) methyl acrylate, polyvinylidene fluoride resin, polytetrafluoroethylene resin, polyvinyl chloride resin, vinylidene chloride Vinyl chloride resin graft-copolymerized with resin and acrylic resin, polyvinyl alcohol resin, polyethylene resin, polypropylene resin, urethane resin, cycloolefin resin, polystyrene, liquid crystal polymer (LCP), polyether ether ketone (PEEK) resin, polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), cellulose nanofibers, silicon, silicon carbide, gallium nitride, sapphire, ceramics, glass, diamond-like carbon (DLC), alumina and the like.
また、前記絶縁性基材（Ａ）として、熱硬化性樹脂及び無機充填材を含有する樹脂基材を好適に用いることもできる。前記熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、不飽和イミド樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂、メラミン樹脂等が挙げられる。一方、前記無機充填材としては、例えば、シリカ、アルミナ、タルク、マイカ、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、ホウ酸アルミニウム、ホウ珪酸ガラス等が挙げられる。これらの熱硬化性樹脂と無機充填剤は、それぞれ１種で用いることも２種以上併用することもできる。 Further, as the insulating base material (A), a resin base material containing a thermosetting resin and an inorganic filler can also be preferably used. Examples of the thermosetting resin include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, and dicyclopentadiene resin. Examples thereof include silicone resin, triazine resin, and melamine resin. On the other hand, examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. These thermosetting resins and inorganic fillers can be used alone or in combination of two or more.
前記絶縁性基材（Ａ）の形態としては、フレキシブル材、リジッド材、リジッドフレキシブル材のいずれのものも用いることができる。より具体的には、前記絶縁性基材（Ａ）にフィルム、シート、板状に成形された市販材料を用いてもよいし、上記した樹脂の溶液、溶融液、分散液から、任意の形状に成形した材料を用いてもよい。また、前記絶縁性基材（Ａ）は、金属等の導電性材料の上に、上記した樹脂の材料を形成した基材であってもよい。 As the form of the insulating base material (A), any of a flexible material, a rigid material, and a rigid flexible material can be used. More specifically, a film, a sheet, or a commercially available material formed into a plate may be used for the insulating base material (A), or any shape may be used from the above-mentioned resin solution, melt, and dispersion. You may use the material formed in. Further, the insulating base material (A) may be a base material obtained by forming the above-mentioned resin material on a conductive material such as metal.
また、前記絶縁性基材（Ａ）の形態としては、フィルム、シート、板等、平面状基材の両面を貫通する貫通孔を有してもよく、基材が積層体であって、外層が貫通孔を有しており、積層体全体としては非貫通孔を有し、内層部に達する孔を持つ構造を有してもよい。 Further, the form of the insulating base material (A) may have through holes penetrating both sides of a flat base material such as a film, a sheet, a plate, etc., and the base material is a laminated body and is an outer layer. Has a through hole, the laminated body as a whole may have a non-through hole, and may have a structure having a hole reaching the inner layer portion.
さらに、前記絶縁性基材（Ａ）は、後述する工程３で形成する導体回路層（Ｍ２）の基材への密着性を向上させる目的で、銀層（Ｍ１）を形成する前に、表面処理を行ってもよい。このような表面処理方法としては、例えば、ＵＶ処理、気相オゾン処理、液層オゾン処理、コロナ処理、プラズマ処理等が挙げられる。これらの表面処理方法は、１種の方法で行うことも２種以上の方法を併用することもできる。 Further, the insulating base material (A) has a surface before forming the silver layer (M1) for the purpose of improving the adhesion of the conductor circuit layer (M2) formed in the step 3 described later to the base material. Processing may be performed. Examples of such a surface treatment method include UV treatment, vapor phase ozone treatment, liquid layer ozone treatment, corona treatment, plasma treatment and the like. These surface treatment methods may be carried out by one kind of method or a combination of two or more kinds of methods.
前記の工程１は、前記絶縁性基材（Ａ）上に、銀層（Ｍ１）を形成する工程である。この銀層（Ｍ１）は、後述する工程３において、めっき処理により導体回路層（Ｍ２）を形成する際のめっき下地層となる。 The step 1 is a step of forming a silver layer (M1) on the insulating base material (A). This silver layer (M1) serves as a plating base layer when the conductor circuit layer (M2) is formed by the plating process in step 3 described later.
前記銀層（Ｍ１）に銀以外の金属が含有される場合、銀以外の金属の割合は、後述する工程４におけるエッチング除去性をより向上できることから、銀１００質量部に対して５質量部以下が好ましく、２質量部以下がより好ましい。 When the silver layer (M1) contains a metal other than silver, the proportion of the metal other than silver is 5 parts by mass or less with respect to 100 parts by mass of silver because the etching removability in step 4 described later can be further improved. Is preferable, and 2 parts by mass or less is more preferable.
前記銀層（Ｍ１）を形成する方法は特に限定されるものではなく、例えば、スパッタ法、蒸着法での形成方法；銀粒子分散液を基材に塗工、印刷する方法；基材を銀粒子分散液へ浸漬する方法；銀箔を基材に接着する方法等の公知の方法を用いることができる。 The method for forming the silver layer (M1) is not particularly limited, and for example, a method for forming the silver layer (M1) by a sputtering method or a vapor deposition method; a method of coating and printing a silver particle dispersion on a base material; A known method such as a method of immersing in a particle dispersion liquid; a method of adhering a silver foil to a base material can be used.
前記の工程２においては、前記銀層（Ｍ１）上に配線部のレジストが除去されたパターンレジストを形成する。パターンレジストの形成方法としては、特に制限はなく、公知の方法で行うことができ、前記銀層（Ｍ１）上に液体の感光性レジストを塗工、乾燥するか、感光性ドライフィルムレジストを、ラミネーターを用いて、前記銀層（Ｍ１）が形成された基材に加熱圧着することによって、レジスト層を形成する。前記銀層（Ｍ１）の表面は、レジスト形成前に、レジスト層との密着性向上を目的として、酸性又はアルカリ性の洗浄液による洗浄処理、コロナ処理、プラズマ処理、ＵＶ処理、気相オゾン処理、液相オゾン処理、表面処理剤による処理等の表面処理を行ってもよい。これらの表面処理は、１種の方法で行うことも２種以上の方法を併用することもできる。 In the step 2, a pattern resist from which the resist of the wiring portion is removed is formed on the silver layer (M1). The method for forming the pattern resist is not particularly limited and can be carried out by a known method. A liquid photosensitive resist is applied and dried on the silver layer (M1), or a photosensitive dry film resist is applied. A resist layer is formed by heat-pressing the base material on which the silver layer (M1) is formed using a laminator. Before forming the resist, the surface of the silver layer (M1) is cleaned with an acidic or alkaline cleaning solution, corona treatment, plasma treatment, UV treatment, vapor phase ozone treatment, liquid for the purpose of improving adhesion with the resist layer. Surface treatment such as phase ozone treatment and treatment with a surface treatment agent may be performed. These surface treatments can be performed by one method or a combination of two or more methods.
前記の表面処理剤による処理としては、例えば、特開平７−２５８８７０号公報に記載されている、トリアゾール系化合物、シランカップリング剤および有機酸からなる防錆剤を用いて処理する方法、特開２０００−２８６５４６号公報に記載されている、有機酸、ベンゾトリアゾール系防錆剤およびシランカップリング剤を用いて処理する方法、特開２００２−３６３１８９号公報に記載されている、トリアゾールやチアジアゾール等の含窒素複素環と、トリメトキシシリル基やトリエトキシシリル基等のシリル基が、チオエーテル（スルフィド）結合等を有する有機基を介して結合された構造の物質を用いて処理する方法、ＷＯ２０１３／１８６９４１号公報に記載されている、トリアジン環とアミノ基を有するシラン化合物を用いて処理する方法、特開２０１５−２１４７４３号公報に記載されている、ホルミルイミダゾール化合物と、アミノプロピルシラン化合物とを反応させて得られるイミダゾールシラン化合物を用いて処理する方法、特開２０１６−１３４４５４号公報に記載されているアゾールシラン化合物を用いて処理する方法、特開２０１７−２０３０７３号公報に記載されている、一分子中にアミノ基および芳香環を有する芳香族化合物と２以上のカルボキシル基を有する多塩基酸、ならびにハロゲン化物イオンを含む溶液で処理する方法、特開２０１８−１６８６５号公報に記載されているトリアゾールシラン化合物を含有する表面処理剤で処理する方法、などを用いることができる。 Examples of the treatment with the surface treatment agent include a method described in JP-A-7-258870, which comprises a method of treating with a rust preventive agent composed of a triazole compound, a silane coupling agent and an organic acid. A method for treating with an organic acid, a benzotriazole-based rust preventive agent and a silane coupling agent described in Japanese Patent Application Laid-Open No. 2000-286546, and the methods of triazole, thiazizol and the like described in JP-A-2002-363189. A method for treating a nitrogen-containing heterocycle with a substance having a structure in which a silyl group such as a trimethoxysilyl group or a triethoxysilyl group is bonded via an organic group having a thioether (sulfide) bond or the like, WO2013 / 186941. A method for treating with a silane compound having a triazole ring and an amino group described in Japanese Patent Application Laid-Open No. 2015, a formylimidazole compound described in JP-A-2015-214743 is reacted with an aminopropylsilane compound. The method for treating with the imidazole silane compound obtained in the above, the method for treating with the azolesilane compound described in JP-A-2016-134454, the single molecule described in JP-A-2017-203073. A method for treating with a solution containing an aromatic compound having an amino group and an aromatic ring, a polybasic acid having two or more carboxyl groups, and a halide ion, triazolesilane described in JP-A-2018-16865. A method of treating with a surface treatment agent containing a compound, or the like can be used.
次に、前記銀層（Ｍ１）上に形成されたレジスト層にフォトマスクを通すか、ダイレクト露光機を用いて、活性光で回路パターンを露光する。露光量は、必要に応じて適宜設定すればよい。露光によりレジスト層に形成された潜像を、現像液を用いて除去することによって、パターンレジストを形成する。 Next, a photomask is passed through the resist layer formed on the silver layer (M1), or a direct exposure machine is used to expose the circuit pattern with active light. The exposure amount may be appropriately set as needed. A pattern resist is formed by removing the latent image formed on the resist layer by exposure with a developing solution.
前記現像液としては、炭酸ナトリウム、炭酸カリウム等の水溶液が挙げられる。また、上記で露光した基材を、現像液に浸漬するか、現像液をスプレー等でレジスト上に噴霧することにより現像を行ない、この現像によって、配線部が除去されたパターンレジストを形成できる。 Examples of the developing solution include aqueous solutions of sodium carbonate, potassium carbonate and the like. Further, the substrate exposed above can be developed by immersing it in a developing solution or spraying the developing solution onto a resist with a spray or the like, and this development can form a pattern resist from which the wiring portion has been removed.
パターンレジストを形成する際には、さらに、プラズマによるデスカム処理や、市販のレジスト残渣除去剤を用いて、硬化レジストと基板との境界部分に生じた裾引き部分や基板表面に残存したレジスト付着物などのレジスト残渣を除去してもよい。 When forming the pattern resist, further, using plasma descum treatment or a commercially available resist residue remover, a resist deposit remaining on the hemming portion formed at the boundary portion between the cured resist and the substrate and the surface of the substrate. The resist residue such as may be removed.
本発明でパターンレジストを形成するために用いるレジストとしては、市販の種々のレジスト材料を用いることができ、目的とするパターンの解像度、使用する露光機の種類等によって適宜選択すればよいが、後工程で電解銅めっきを行うことから、セミアディティブ工法用のドライフィルムを特に好適に用いることができる。市販のドライフィルムとしては、例えば、ニッコーマテリアルズ株式会社製の「ＡＬＦＯ ＬＤＦ５００」、「ＮＩＴ２７００」、旭化成株式会社製の「サンフォート ＵＦＧ―２５８」、日立化成株式会社製の「ＲＤシリーズ（ＲＤ−２０１５、１２２５）」、「ＲＹシリーズ（ＲＹ−５３１９、５３２５）」、デュポン社製の「ＰｌａｔｅＭａｓｔｅｒシリーズ（ＰＭ２００、３００）」等を用いることができる。 As the resist used for forming the pattern resist in the present invention, various commercially available resist materials can be used, and may be appropriately selected depending on the resolution of the target pattern, the type of the exposure machine to be used, and the like. Since electrolytic copper plating is performed in the process, a dry film for the semi-additive method can be particularly preferably used. Examples of commercially available dry films include "ALFO LDF500" and "NIT2700" manufactured by Nikko Materials Co., Ltd., "Sunfort UFG-258" manufactured by Asahi Kasei Corporation, and "RD series (RD-)" manufactured by Hitachi Kasei Co., Ltd. 2015, 1225) ”,“ RY series (RY-5319, 5325) ”,“ PlateMaster series (PM200, 300) ”manufactured by DuPont, etc. can be used.
前記の工程３においては、上記のようにして、現像により露出した銀層（Ｍ１）の上に、めっき処理を行うことにより、導体回路層（Ｍ２）を形成する。 In the above step 3, the conductor circuit layer (M2) is formed by performing a plating treatment on the silver layer (M1) exposed by development as described above.
工程３で形成する導体回路層（Ｍ２）を形成するために行うめっき処理は、無電解めっき法、電解めっき法、又はそれらの組み合わせのいずれでもよい。 The plating process performed to form the conductor circuit layer (M2) formed in step 3 may be an electroless plating method, an electrolytic plating method, or a combination thereof.
工程３で形成する導体回路層（Ｍ２）を電解めっき法で形成する場合、前記銀層（Ｍ１）の厚さは、電気抵抗値を低くできることから、３０〜５００ｎｍの範囲が好ましい。さらに、工程４の除去工程における除去性をより向上できることから、４０〜２００ｎｍの範囲がより好ましい。 When the conductor circuit layer (M2) formed in the step 3 is formed by the electrolytic plating method, the thickness of the silver layer (M1) is preferably in the range of 30 to 500 nm because the electric resistance value can be lowered. Further, the range of 40 to 200 nm is more preferable because the removability in the removal step of the step 4 can be further improved.
前記銀層（Ｍ１）の厚さは、公知慣用の種々の方法によって見積もることができ、例えば、電子顕微鏡を用いた断面観察法や、蛍光Ｘ線による方法を用いることができるが、蛍光Ｘ線法を用いることが、簡便で好ましい。 The thickness of the silver layer (M1) can be estimated by various known and commonly used methods. For example, a cross-section observation method using an electron microscope or a method using fluorescent X-rays can be used, but fluorescent X-rays can be used. It is convenient and preferable to use the method.
また、前記銀層（Ｍ１）の導電性としては、工程３において、電解めっき法を行う場合、導電性が高い、すなわち電気抵抗値が低いほどよいが、電解めっきが実施できる導電性があればよく、本発明によって作製しようとするプリント配線板のサイズ、使用する電源装置、電極、めっき薬液に応じて適宜、選択すればよい。 Further, as the conductivity of the silver layer (M1), when the electrolytic plating method is performed in step 3, the higher the conductivity, that is, the lower the electric resistance value is, the better, but if there is conductivity that allows electrolytic plating to be performed. It may be appropriately selected according to the size of the printed wiring board to be produced according to the present invention, the power supply device to be used, the electrodes, and the plating solution.
前記銀層（Ｍ１）を銀粒子から構成される層として形成する場合、工程３において電解めっきを容易に実施できることから、前記銀層（Ｍ１）を構成する銀粒子同士が密着、接合しており導電性が高いものが好ましい。また、配線部の銀層（Ｍ１）は、銀粒子間の空隙が、導体回路層（Ｍ２）を構成するめっき金属によって充填されているものであってもよい。銀粒子間の空隙がめっき金属によって充填されると、めっき金属の存在によって、後述する工程４の、非配線部の銀層（Ｍ１）を前記銀用エッチング液により除去する工程において、導体回路層（Ｍ２）下の銀層（Ｍ１）のエッチングが抑制され、配線部のアンダーカットが起こりにくくなるので好ましい。 When the silver layer (M1) is formed as a layer composed of silver particles, electrolytic plating can be easily performed in step 3, so that the silver particles constituting the silver layer (M1) are in close contact with each other and bonded to each other. Those with high conductivity are preferable. Further, the silver layer (M1) of the wiring portion may be one in which the voids between the silver particles are filled with the plating metal constituting the conductor circuit layer (M2). When the voids between the silver particles are filled with the plating metal, the conductor circuit layer is used in the step of removing the silver layer (M1) of the non-wiring portion with the silver etching solution in the step 4 described later due to the presence of the plating metal. It is preferable because the etching of the silver layer (M1) under (M2) is suppressed and the undercut of the wiring portion is less likely to occur.
工程３で形成する導体回路層（Ｍ２）を無電解めっき法で形成する場合、前記銀層（Ｍ１）は、銀粒子から構成される層として形成することが好ましい。この場合の基材上の銀粒子の担持量は、０．０１〜０．５ｇ／ｍ２の範囲が好ましい。When the conductor circuit layer (M2) formed in step 3 is formed by an electroless plating method, the silver layer (M1) is preferably formed as a layer composed of silver particles. In this case, the amount of silver particles supported on the substrate is preferably in the range of 0.01 to 0.5 g / m 2.
工程３において形成する導体回路層（Ｍ２）を構成する金属は、導電性が高い金属が好ましく、例えば、銅、金、ニッケル、スズ、鉛、チタン、パラジウム、白金、アルミニウム、亜鉛、タングステン、モリブデン等が挙げられる。これらの金属の中でも、比較的安価で導電性が高く、加工が容易であり、機械的性質及び耐食性が高いことから、銅が好ましい。 The metal forming the conductor circuit layer (M2) formed in step 3 is preferably a metal having high conductivity, for example, copper, gold, nickel, tin, lead, titanium, palladium, platinum, aluminum, zinc, tungsten, molybdenum. And so on. Among these metals, copper is preferable because it is relatively inexpensive, has high conductivity, is easy to process, and has high mechanical properties and corrosion resistance.
また前記導体回路層（Ｍ２）は、１種の金属からなるものであってもよく、２種以上の金属からなるものであってもよい。また、前記導体回路層（Ｍ２）は、樹脂やシリカ微粒子等の非金属物質を金属めっき皮膜中に取り込んだ複合めっき物であってもよい。 Further, the conductor circuit layer (M2) may be made of one kind of metal or may be made of two or more kinds of metals. Further, the conductor circuit layer (M2) may be a composite plated product in which a non-metal substance such as a resin or silica fine particles is incorporated into a metal plating film.
前記の工程１’において、プライマー層（Ｂ）を形成する樹脂としては、例えば、ウレタン樹脂、アクリル樹脂、ウレタン樹脂をシェルとしアクリル樹脂をコアとするコア・シェル型複合樹脂、エポキシ樹脂、イミド樹脂、アミド樹脂、メラミン樹脂、フェノール樹脂、尿素ホルムアルデヒド樹脂、ポリイソシアネートにフェノール等のブロック化剤を反応させて得られたブロックイソシアネートポリビニルアルコール、ポリビニルピロリドン等が挙げられる。なお、ウレタン樹脂をシェルとしアクリル樹脂をコアとするコア・シェル型複合樹脂は、例えば、ウレタン樹脂存在下でアクリル単量体を重合することにより得られる。また、これらの樹脂は、１種で用いることも２種以上併用することもできる。 In the above step 1', examples of the resin forming the primer layer (B) include a urethane resin, an acrylic resin, a core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core, an epoxy resin, and an imide resin. , Amido resin, melamine resin, phenol resin, urea formaldehyde resin, blocked isocyanate polyvinyl alcohol obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinylpyrrolidone and the like. A core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core can be obtained, for example, by polymerizing an acrylic monomer in the presence of a urethane resin. Further, these resins can be used alone or in combination of two or more.
前記プライマー層（Ｂ）は、上記の樹脂を溶媒に溶解又は分散させた液を前記絶縁性基材（Ａ）上に、塗工し乾燥することで形成できる。前記溶媒としては、各種有機溶剤、水性媒体が挙げられる。前記有機溶剤としては、例えば、トルエン、酢酸エチル、メチルエチルケトン、シクロヘキサノン等が挙げられ、前記水性媒体としては、水、水と混和する有機溶剤、及び、これらの混合物が挙げられる。 The primer layer (B) can be formed by applying a liquid in which the above resin is dissolved or dispersed in a solvent onto the insulating base material (A) and drying it. Examples of the solvent include various organic solvents and aqueous media. Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, cyclohexanone and the like, and examples of the aqueous medium include water, an organic solvent miscible with water, and a mixture thereof.
前記の工程４においては、パターンレジストを剥離し、非配線部の銀層（Ｍ１）を前記銀用エッチング液により除去する。パターンレジストの剥離は、使用するレジストのカタログ、仕様書等に記載されている推奨条件で行えばよい。また、パターンレジストの剥離の際に用いるレジスト剥離液としては、市販のレジスト剥離液や、４５〜６０℃に設定した水酸化ナトリウムもしくは水酸化カリウムの１．５〜３質量％水溶液を用いることができる。レジストの剥離は、前記導体回路層（Ｍ２）を形成した基材を、剥離液に浸漬するか、剥離液をスプレー等で噴霧することによって行うことができる。 In the step 4, the pattern resist is peeled off, and the silver layer (M1) in the non-wiring portion is removed by the silver etching solution. The pattern resist may be peeled off under the recommended conditions described in the catalog, specifications, etc. of the resist to be used. As the resist stripping solution used for stripping the pattern resist, a commercially available resist stripping solution or a 1.5 to 3% by mass aqueous solution of sodium hydroxide or potassium hydroxide set at 45 to 60 ° C. may be used. it can. The resist can be peeled off by immersing the base material on which the conductor circuit layer (M2) is formed in a stripping solution or by spraying the stripping solution with a spray or the like.
また、工程４における非配線部の銀層（Ｍ１）の前記銀用エッチング液での除去は、前記導体回路層（Ｍ２）を形成した後、パターンレジストを剥離した基材を前記銀用エッチング液に浸漬するか、前記基材上に銀用エッチング液をスプレー等で噴霧することによって行うことができる。 Further, in the removal of the silver layer (M1) of the non-wiring portion in the step 4 with the silver etching solution, the base material from which the pattern resist has been peeled off after forming the conductor circuit layer (M2) is removed with the silver etching solution. It can be carried out by immersing in the substrate or by spraying an etching solution for silver on the substrate with a spray or the like.
エッチング装置を用いて、非配線部の銀層（Ｍ１）を除去する場合には、例えば、前記銀用エッチング液の全成分を所定の組成になるように調製した後、エッチング装置に供給してもよく、前記銀用エッチング液の各成分を個別にエッチング装置に供給し、装置内で、前記各成分を混合して、所定の組成になるように調製してもよい。 When the silver layer (M1) of the non-wiring portion is removed by using an etching apparatus, for example, all the components of the silver etching solution are prepared so as to have a predetermined composition, and then supplied to the etching apparatus. Alternatively, each component of the silver etching solution may be individually supplied to an etching apparatus, and the respective components may be mixed in the apparatus to prepare a predetermined composition.
前記銀用エッチング液は、１０〜３５℃の温度範囲で用いることが好ましく、過酸化水素の分解を抑制できることから、３０℃以下の温度範囲で用いることが好ましい。 The etching solution for silver is preferably used in a temperature range of 10 to 35 ° C., and is preferably used in a temperature range of 30 ° C. or lower because decomposition of hydrogen peroxide can be suppressed.
なお、前記銀用エッチング液の作用としては、前記銀用エッチング液に含まれるカルボン酸と過酸化水素とが反応することによって、過カルボン酸（ぺルオキシカルボン酸）が生成し、生成した過カルボン酸は、導体回路層（Ｍ２）を構成する金属の溶解を抑制しながら、めっき下地層である銀層（Ｍ１）を構成する銀を優先的に溶解するものと推測される。 As for the action of the etching solution for silver, a percarboxylic acid (peroxycarboxylic acid) is generated by the reaction of the carboxylic acid contained in the etching solution for silver with hydrogen peroxide. It is presumed that the carboxylic acid preferentially dissolves the silver constituting the silver layer (M1) which is the plating base layer while suppressing the dissolution of the metal constituting the conductor circuit layer (M2).
また、前記工程４において、非配線部の銀層（Ｍ１）を前記銀用エッチング液により除去する前に、必要に応じて銀層（Ｍ１）を公知の方法で表面処理してもよい。この表面処理とは、例えば、酸性洗浄液、アルカリ性洗浄液、界面活性剤の水溶液、又は水溶性有機溶剤の水溶液を用いた洗浄処理、超音波処理、コロナ処理、プラズマ処理、ＵＶ処理、気相オゾン処理、液相オゾン処理、表面処理剤による処理等が挙げられる。これらの表面処理は、１種の方法で行うことも２種以上の方法を併用することもできる。 Further, in the step 4, the silver layer (M1) may be surface-treated by a known method, if necessary, before the silver layer (M1) of the non-wiring portion is removed by the silver etching solution. The surface treatment includes, for example, a cleaning treatment using an acidic cleaning liquid, an alkaline cleaning liquid, an aqueous solution of a surfactant, or an aqueous solution of a water-soluble organic solvent, an ultrasonic treatment, a corona treatment, a plasma treatment, a UV treatment, and a vapor phase ozone treatment. , Liquid phase ozone treatment, treatment with a surface treatment agent, etc. These surface treatments can be performed by one method or a combination of two or more methods.
上記の表面処理の中でも、酸性洗浄液、アルカリ性洗浄液、水溶性有機溶剤の水溶液を用いた洗浄処理が好ましい。前記酸性洗浄液は、前記非配線部の銀層（Ｍ１）表面の硫化銀による変色被膜を除去するのに用いることができ、前記非配線部の銀層（Ｍ１）のエッチングのばらつきを抑制できるため好ましい。例えば、非特許文献（Ｊｏｕｒｎａｌ ｏｆ Ｃｕｌｔｕｒａｌ Ｈｅｒｉｔａｇｅ（２０１６）１７，Ｐ．２０−２６）には、チオ尿素をキレート剤として含む酸性洗浄液により、硫化銀被膜が溶解、除去されることが記載されている。また、前記アルカリ性洗浄液は、前記非配線部の銀層（Ｍ１）の金属表面の油脂汚れを除去することができ、前記非配線部の銀層（Ｍ１）のエッチングのばらつきを抑制できるため好ましい。さらに、前記水溶性有機溶剤の水溶液は、次工程のエッチング液の配線間への濡れ性を向上することができ、配線間の前記非配線部の銀層（Ｍ１）のエッチングのばらつきを抑制できるため好ましい。特に、前記銀用エッチング液に含まれるカルボン酸と水溶性有機溶剤と界面活性剤の混合水溶液を用いると、前記非配線部の銀層（Ｍ１）のエッチングのばらつきを抑制でき、かつ銀エッチング液槽内へ異種の洗浄液混入による銀エッチング性の経時変化が抑制できるため、より好ましい。 Among the above surface treatments, a cleaning treatment using an acidic cleaning solution, an alkaline cleaning solution, or an aqueous solution of a water-soluble organic solvent is preferable. The acidic cleaning liquid can be used to remove the discolored film due to silver sulfide on the surface of the silver layer (M1) of the non-wiring portion, and can suppress variations in etching of the silver layer (M1) of the non-wiring portion. preferable. For example, a non-patent document (Journal of Cultural Heritage (2016) 17, P.20-26) describes that the silver sulfide film is dissolved and removed by an acidic cleaning solution containing thiourea as a chelating agent. .. Further, the alkaline cleaning liquid is preferable because it can remove oil and fat stains on the metal surface of the silver layer (M1) of the non-wiring portion and can suppress variations in etching of the silver layer (M1) of the non-wiring portion. Further, the aqueous solution of the water-soluble organic solvent can improve the wettability of the etching solution in the next step between the wirings, and can suppress the variation in etching of the silver layer (M1) of the non-wiring portion between the wirings. Therefore, it is preferable. In particular, when a mixed aqueous solution of a carboxylic acid, a water-soluble organic solvent and a surfactant contained in the silver etching solution is used, variation in etching of the silver layer (M1) of the non-wiring portion can be suppressed and the silver etching solution can be used. It is more preferable because the change in silver etching property with time due to the mixing of different kinds of cleaning liquids in the tank can be suppressed.
また、前記工程４において、非配線部の銀層（Ｍ１）を前記銀用エッチング液により除去した後、エッチング液中に溶解した銀成分がプリント配線板上に付着、残留するのを防ぐ目的で、水洗以外に、さらに洗浄操作を行ってもよい。このとき、洗浄液としては酸化銀、塩化銀、硫化銀を溶解するが、銀をほとんど溶解しないものがが好ましい。具体的には過酸化水素水、又は、チオ硫酸塩もしくはトリス（３−ヒドロキシアルキル）ホスフィン、又は、メルカプトカルボン酸もしくはその塩、又は、チオ尿素を含有する水溶液を洗浄液として用いることが好ましい。これらの中でも過酸化水素水は強い酸化力を有するため、洗浄液中に溶解した銀イオンが還元されて基材や銅配線上に析出することなく洗浄することができるため、より好ましい。 Further, in the step 4, after removing the silver layer (M1) of the non-wiring portion with the etching solution for silver, the purpose is to prevent the silver component dissolved in the etching solution from adhering to and remaining on the printed wiring board. , In addition to washing with water, a further washing operation may be performed. At this time, as the cleaning liquid, silver oxide, silver chloride, and silver sulfide are dissolved, but those that hardly dissolve silver are preferable. Specifically, it is preferable to use a hydrogen peroxide solution, a thiosulfate or tris (3-hydroxyalkyl) phosphine, a mercaptocarboxylic acid or a salt thereof, or an aqueous solution containing thiourea as a cleaning solution. Among these, hydrogen peroxide solution is more preferable because it has a strong oxidizing power and can be washed without reducing silver ions dissolved in the cleaning liquid and precipitating on the base material or copper wiring.
前記洗浄液として、過酸化水素水を用いる場合の濃度としては０．１〜１０質量％の範囲が好ましく、連続使用時の薬液の安定性の観点から０．１〜２質量％の範囲がより好ましい。 When a hydrogen peroxide solution is used as the cleaning solution, the concentration is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.1 to 2% by mass from the viewpoint of the stability of the chemical solution during continuous use. ..
前記チオ硫酸塩としては、例えば、チオ硫酸アンモニウム、チオ硫酸ナトリウム、チオ硫酸カリウム等が挙げられる。 Examples of the thiosulfate include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate and the like.
チオ硫酸塩を含有する水溶液を用いる場合の濃度としては、工程時間、用いる洗浄装置の特性等によって適宜設定すればよいが、０．１〜４０質量％の範囲が好ましく、洗浄効率や連続使用時の薬液の安定性の観点から、１〜３０質量％の範囲がより好ましい。 The concentration when using an aqueous solution containing a thiosulfate may be appropriately set depending on the process time, the characteristics of the cleaning device used, etc., but is preferably in the range of 0.1 to 40% by mass, and during continuous use and cleaning efficiency. From the viewpoint of the stability of the chemical solution, the range of 1 to 30% by mass is more preferable.
また、前記トリス（３−ヒドロキシアルキル）ホスフィンとしては、例えば、トリス（３−ヒドロキシメチル）ホスフィン、トリス（３−ヒドロキシエチル）ホスフィン、トリス（３−ヒドロキシプロピル）ホスフィン等が挙げられる。これらのチオ硫酸塩又はトリス（３−ヒドロキシアルキル）ホスフィンは、それぞれ１種で用いることも２種以上併用することもできる。 Examples of the tris (3-hydroxyalkyl) phosphine include tris (3-hydroxymethyl) phosphine, tris (3-hydroxyethyl) phosphine, and tris (3-hydroxypropyl) phosphine. These thiosulfates or tris (3-hydroxyalkyl) phosphines can be used alone or in combination of two or more.
前記トリス（３−ヒドロキシアルキル）ホスフィンを含有する水溶液を用いる場合の濃度としては、工程時間、用いる洗浄装置の特性等によって適宜設定すればよいが、０．１〜５０質量％の範囲が好ましく、洗浄効率や連続使用時の薬液の安定性の観点から、１〜４０質量％の範囲がより好ましい。 When the aqueous solution containing tris (3-hydroxyalkyl) phosphine is used, the concentration may be appropriately set depending on the process time, the characteristics of the cleaning device used, and the like, but is preferably in the range of 0.1 to 50% by mass. From the viewpoint of cleaning efficiency and stability of the chemical solution during continuous use, the range of 1 to 40% by mass is more preferable.
前記メルカプトカルボン酸としては、例えば、チオグリコール酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオリンゴ酸、システイン、Ｎ―アセチルシステイン等が挙げられる。また、前記メルカプトカルボン酸の塩としては、例えば、アルカリ金属塩、アンモニウム塩、アミン塩等が挙げられる。 Examples of the mercaptocarboxylic acid include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioapple acid, cysteine, N-acetylcysteine and the like. Examples of the salt of the mercaptocarboxylic acid include alkali metal salts, ammonium salts, amine salts and the like.
メルカプトカルボン酸又はその塩の水溶液を用いる場合の濃度としては、０．１〜２０質量％の範囲が好ましく、洗浄効率や大量に処理する場合のプロセスコストの観点から、０．５〜１５質量％の範囲がより好ましい。 When an aqueous solution of mercaptocarboxylic acid or a salt thereof is used, the concentration is preferably in the range of 0.1 to 20% by mass, and from the viewpoint of cleaning efficiency and process cost when processing a large amount, 0.5 to 15% by mass. The range of is more preferable.
銀が硫化銀として残留している場合、例えば、特許文献（特開２００５−１８７８５２号公報）に記載のように、アルミニウム存在下に、アルカリ金属炭酸塩を含有した洗浄液を使用して除去することができる。また、市販の液体タイプのシルバークリーナーを使用して除去することができる。 When silver remains as silver sulfide, for example, as described in Patent Document (Japanese Unexamined Patent Publication No. 2005-187852), it should be removed by using a cleaning solution containing an alkali metal carbonate in the presence of aluminum. Can be done. It can also be removed using a commercially available liquid type silver cleaner.
上記の洗浄操作を行う方法としては、例えば、前記工程４で得られたプリント配線板を前記洗浄溶液に浸漬する方法、前記プリント配線板にスプレー等で洗浄溶液を噴霧する方法等が挙げられる。洗浄溶液の温度は、室温（２５℃）で用いることができるが、外気温に影響を受けずに安定的に洗浄処理を行えることから、例えば、３０℃に温度設定して用いてもよい。 Examples of the method of performing the above-mentioned cleaning operation include a method of immersing the printed wiring board obtained in the step 4 in the cleaning solution, a method of spraying the cleaning solution on the printed wiring board by a spray or the like, and the like. The temperature of the cleaning solution can be used at room temperature (25 ° C.), but since the cleaning process can be performed stably without being affected by the outside air temperature, the temperature may be set to 30 ° C. for use.
また、前記工程４の非配線部の銀層（Ｍ１）をエッチング液により除去する工程と洗浄操作は、必要に応じて繰り返して行うことができる。特に、配線間隔が２０μｍより狭い場合は、過酸化水素水による洗浄後にチオ硫酸塩、トリス（３−ヒドロキシアルキル）ホスフィン、チオ尿素、メルカプトカルボン酸又はその塩による洗浄操作を行うことにより絶縁信頼性が向上するため好ましい。 Further, the step of removing the silver layer (M1) of the non-wiring portion in the step 4 with an etching solution and the cleaning operation can be repeated as necessary. In particular, when the wiring interval is narrower than 20 μm, insulation reliability is achieved by performing a cleaning operation with thiosulfate, tris (3-hydroxyalkyl) phosphine, thiourea, mercaptocarboxylic acid or a salt thereof after cleaning with hydrogen peroxide solution. Is preferable because it improves.
洗浄後は公知公用の方法で乾燥することができる。具体的には空気又は窒素のブローにより配線、及び、配線間に付着した洗浄液を除去した後、熱風乾燥機やホットプレートを用いて乾燥することが好ましい。乾燥は５０〜１２０℃の温度範囲が好ましく、水が揮発しやすく銅配線の酸化を抑制するため、６０〜１００℃の温度範囲がより好ましい。 After washing, it can be dried by a known public method. Specifically, it is preferable to remove the wiring and the cleaning liquid adhering between the wiring by blowing air or nitrogen, and then dry using a hot air dryer or a hot plate. Drying is preferably in a temperature range of 50 to 120 ° C., and more preferably in a temperature range of 60 to 100 ° C. because water easily volatilizes and suppresses oxidation of copper wiring.
本発明の工程４においては、前記エッチング液で非配線部の銀層（Ｍ１）を除去処理した後、非配線部の絶縁性を、さらに向上させる目的で、必要に応じて、さらに絶縁層の最表層の有機物を酸化分解させて除去する洗浄操作を行ってもよい。この洗浄操作には、例えば、水酸化カリウム又は水酸化ナトリウムの水溶液に、過マンガン酸カリウム又は過マンガン酸ナトリウムを溶解したアルカリ性過マンガン酸溶液を用いることができる。 In step 4 of the present invention, after the silver layer (M1) of the non-wiring portion is removed with the etching solution, the insulating layer of the non-wiring portion is further improved as necessary for the purpose of further improving the insulating property of the non-wiring portion. A cleaning operation may be performed to remove the organic matter on the outermost layer by oxidative decomposition. For this cleaning operation, for example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of potassium hydroxide or sodium hydroxide can be used.
前記アルカリ性過マンガン酸溶液を用いた洗浄は、２０〜８０℃に設定したアルカリ性過マンガン酸溶液に、前記工程４で得られたプリント配線板を浸漬する方法、前記プリント配線板にスプレー等でアルカリ性過マンガン酸溶液を噴霧する方法等が挙げられる。前記プリント配線板は、アルカリ性過マンガン酸溶液の基材表面への濡れ性及び洗浄効率を向上させる目的で、洗浄前に、アルコール性水酸基を有する水溶性の有機溶媒に接触させる処理を行ってもよい。前記有機溶媒としては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール等が挙げられる。これらの有機溶媒は、１種で用いることも２種以上併用することもできる。 Cleaning using the alkaline permanganate solution is a method of immersing the printed wiring board obtained in the step 4 in the alkaline permanganate solution set at 20 to 80 ° C., or the printed wiring board is alkaline by spraying or the like. Examples thereof include a method of spraying a permanganate solution. The printed wiring board may be subjected to a treatment of contacting the printed wiring board with a water-soluble organic solvent having an alcoholic hydroxyl group before cleaning for the purpose of improving the wettability of the alkaline permanganate solution to the surface of the substrate and the cleaning efficiency. Good. Examples of the organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and the like. These organic solvents can be used alone or in combination of two or more.
前記アルカリ性過マンガン酸溶液の濃度は、必要に応じて適宜選択すればよいが、０．１〜１０質量％の水酸化カリウム又は水酸化ナトリウム水溶液１００質量部に、過マンガン酸カリウム又は過マンガン酸ナトリウムを０．１〜１０質量部溶解させたものが好ましく、洗浄効率の観点から、１〜６質量％の水酸化カリウム又は水酸化ナトリウム水溶液１００質量部に、過マンガン酸カリウム又は過マンガン酸ナトリウムを１〜６質量部溶解させたものがより好ましい。 The concentration of the alkaline permanganate solution may be appropriately selected as needed, but potassium permanganate or permanganate is added to 100 parts by mass of 0.1 to 10% by mass of potassium hydroxide or sodium hydroxide aqueous solution. It is preferable that 0.1 to 10 parts by mass of sodium is dissolved, and from the viewpoint of cleaning efficiency, potassium permanganate or sodium permanganate is added to 100 parts by mass of 1 to 6% by mass of potassium hydroxide or sodium hydroxide aqueous solution. Is more preferably dissolved in 1 to 6 parts by mass.
上記のアルカリ性過マンガン酸塩溶液を用いた洗浄を行う場合には、アルカリ性過マンガン酸塩溶液の洗浄後に、洗浄した前記プリント配線板を、中和作用のある液を用いて洗浄することが好ましい。前記中和作用のある液としては、例えば、０．５〜１５質量％の硫酸、又は有機酸を含有する水溶液が挙げられる。また、前記有機酸としては、例えば、ギ酸、酢酸、シュウ酸、クエン酸、アスコルビン酸、メチオニン等が挙げられる。さらに、０．１〜５質量％の過酸化水素水を併用しても構わない。これら洗浄液は１種で用いることも２種以上をそれぞれ単独で併用する、又は２種以上を混合して用いても構わない。また繰り返し洗浄を行っても構わない。また、過マンガン酸塩が基材に残留するのを防ぐために、０．５〜５質量％の硫酸又は酢酸の水溶液で処理することがより好ましく、０．５〜５質量％のアスコルビン酸水溶液で処理するとアルカリ性の中和と過マンガン酸塩の還元を同時に行えるため（過マンガン酸塩の還元を行えると、除去できる。）、さらに好ましい。 When cleaning with the above alkaline permanganate solution, it is preferable to wash the washed printed wiring board with a neutralizing solution after cleaning the alkaline permanganate solution. .. Examples of the liquid having a neutralizing action include an aqueous solution containing 0.5 to 15% by mass of sulfuric acid or an organic acid. Examples of the organic acid include formic acid, acetic acid, oxalic acid, citric acid, ascorbic acid, methionine and the like. Further, 0.1 to 5% by mass of hydrogen peroxide solution may be used in combination. These cleaning solutions may be used alone, in combination of two or more, or in combination of two or more. Further, repeated washing may be performed. Further, in order to prevent the permanganate from remaining on the substrate, it is more preferable to treat with an aqueous solution of 0.5 to 5% by mass of sulfuric acid or acetic acid, and a 0.5 to 5% by mass of an aqueous solution of ascorbic acid. The treatment is more preferable because it can neutralize the alkalinity and reduce the permanganate at the same time (it can be removed if the permanganate can be reduced).
過マンガン酸塩溶液の洗浄後に中和処理した後は、イオン交換水、アルコール性水酸基を有する水溶性の有機溶媒で洗浄処理を行ってもよい。前記有機溶媒としては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール等が挙げられる。これらの有機溶媒は、１種で用いることも２種以上併用することもできる。 After the permanganate solution has been washed and then neutralized, the washing may be carried out with ion-exchanged water or a water-soluble organic solvent having an alcoholic hydroxyl group. Examples of the organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and the like. These organic solvents can be used alone or in combination of two or more.
洗浄後は公知公用の方法で乾燥することができる。具体的には空気または窒素のブローにより配線、及び、配線間に付着した洗浄液を除去した後、熱風乾燥機やホットプレートを用いて乾燥することが好ましい。乾燥温度は５０〜１２０℃の温度範囲が好ましく、水が揮発しやすく銅配線の酸化を抑制するために６０〜１００℃の温度範囲がより好ましい。 After washing, it can be dried by a known public method. Specifically, it is preferable to remove the wiring and the cleaning liquid adhering between the wiring by blowing air or nitrogen, and then dry using a hot air dryer or a hot plate. The drying temperature is preferably in the temperature range of 50 to 120 ° C., and more preferably in the temperature range of 60 to 100 ° C. in order to easily volatilize water and suppress oxidation of copper wiring.
上記のアルカリ性過マンガン酸溶液による洗浄は、前記エッチング液中に溶解した銀成分がプリント配線板上に付着、残留するのを防ぐ目的で行う洗浄の後に行ってもよいし、前記エッチング液中に溶解した銀成分がプリント配線板上に付着、残留するのを防ぐ目的で、洗浄を行う代わりに、アルカリ性過マンガン酸溶液による洗浄のみを行ってもよい。 The cleaning with the alkaline permanganate solution may be performed after the cleaning for the purpose of preventing the silver component dissolved in the etching solution from adhering to and remaining on the printed wiring board, or may be performed in the etching solution. For the purpose of preventing the dissolved silver component from adhering to and remaining on the printed wiring board, instead of cleaning, only cleaning with an alkaline permanganate solution may be performed.
また、本発明のプリント配線板の製造方法においては、めっき膜の応力緩和や密着力向上を目的として、工程３のめっき処理後にアニーリングを行ってもよい。アニーリングは、工程４の非配線部の銀層（Ｍ１）を除去する前に行ってもよいし、除去した後に行ってもよく、除去前後の両方で行ってもよい。 Further, in the method for manufacturing a printed wiring board of the present invention, annealing may be performed after the plating treatment in step 3 for the purpose of stress relaxation and improvement of adhesion of the plating film. Annealing may be performed before removing the silver layer (M1) of the non-wiring portion in step 4, may be performed after removing the silver layer (M1), or may be performed both before and after removal.
アニーリングの温度は、用いる基材の耐熱性や使用目的によって４０〜３００℃の温度範囲で適宜選択すればよいが、４０〜２５０℃の範囲が好ましく、めっき膜の酸化劣化を抑制する目的から、４０〜２００℃の範囲がより好ましい。また、アニーリングの時間は、４０〜２００℃の温度範囲の場合には、１０分〜１０日間、２００℃を超える温度でのアニーリングは、５分〜１０時間程度がよい。また、めっき膜をアニーリングする際には、適宜、めっき膜表面に防錆剤を付与してもよい。 The annealing temperature may be appropriately selected in the temperature range of 40 to 300 ° C. depending on the heat resistance of the substrate to be used and the purpose of use, but is preferably in the range of 40 to 250 ° C. for the purpose of suppressing oxidative deterioration of the plating film. The range of 40 to 200 ° C. is more preferable. The annealing time is preferably 10 minutes to 10 days in the temperature range of 40 to 200 ° C., and about 5 minutes to 10 hours for the annealing at a temperature exceeding 200 ° C. Further, when annealing the plating film, a rust preventive may be appropriately applied to the surface of the plating film.
本発明の製造方法で得られたプリント配線板は、適宜、必要に応じて、回路パターン上へのソルダーレジスト層の形成、及び、導体回路層（Ｍ２）の最終表面処理として、スズめっき、ニッケル／金めっき、ニッケル／パラジウム／金めっき、パラジウム／金めっきを施してもよい。 The printed wiring board obtained by the manufacturing method of the present invention is appropriately tin-plated or nickel-plated as necessary for forming a solder resist layer on a circuit pattern and as a final surface treatment for the conductor circuit layer (M2). / Gold plating, nickel / palladium / gold plating, palladium / gold plating may be applied.
以上に述べた本発明の銀用エッチング液、及びそれを用いたプリント配線板の製造方法により、狭隘部の銀層（Ｍ１）であっても選択的に溶解し除去できる。したがって、本発明の技術を用いることで、レジストパターンからの寸法変化がほとんど無く、めっき処理により形成された導体回路層（Ｍ２）の表面粗度がめっき下地層の除去によってほとんど増大せず、良好な矩形断面形状の回路配線を有する高性能のプリント配線板を、低コストかつ高い歩留まりで提供することができる。また、本発明のプリント配線板の製造方法により製造されたプリント配線板は、通常のプリント配線板のみならず、基材表面にパターン化された金属層を有する種々の電子部材に用いることができ、例えば、コネクター、電磁波シールド、ＲＦＩＤ等のアンテナ、フィルムコンデンサーなどにも応用できる。さらに、本発明のプリント配線板の製造方法は、種々の形状、サイズの基材上にパターン化された金属層を有する装飾めっき用途で用いることもできる。 By the above-described silver etching solution of the present invention and the method for producing a printed wiring board using the same, even a narrow silver layer (M1) can be selectively dissolved and removed. Therefore, by using the technique of the present invention, there is almost no dimensional change from the resist pattern, and the surface roughness of the conductor circuit layer (M2) formed by the plating treatment is hardly increased by the removal of the plating base layer, which is good. It is possible to provide a high-performance printed wiring board having a circuit wiring having a rectangular cross-sectional shape at a low cost and a high yield. Further, the printed wiring board manufactured by the method for manufacturing a printed wiring board of the present invention can be used not only for a normal printed wiring board but also for various electronic members having a patterned metal layer on the surface of a base material. For example, it can be applied to a connector, an electromagnetic wave shield, an antenna such as RFID, a film capacitor, and the like. Further, the method for manufacturing a printed wiring board of the present invention can also be used for decorative plating applications having a metal layer patterned on a substrate of various shapes and sizes.
以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to Examples.
［製造例１：プライマー（Ｂ−１）の製造］
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール（１，４−シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール）１００質量部、２，２―ジメチロールプロピオン酸１７．６質量部、１，４−シクロヘキサンジメタノール２１．７質量部及びジシクロヘキシルメタン−４，４’−ジイソシアネート１０６．２質量部を、メチルエチルケトン１７８質量部の混合溶剤中で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマー溶液を得た。[Production Example 1: Production of Primer (B-1)]
Polyester polyol (polyester polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol, and adipic acid) 100 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. Parts by mass, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, 178 parts by mass of methylethylketone A urethane prepolymer solution having an isocyanate group at the terminal was obtained by reacting in the mixed solvent of.
次いで、前記ウレタンプレポリマー溶液にトリエチルアミン１３．３質量部を加えて、前記ウレタンプレポリマーが有するカルボキシル基を中和し、さらに水３８０質量部を加えて十分に攪拌することにより、ウレタンプレポリマーの水性分散液を得た。 Next, 13.3 parts by mass of triethylamine was added to the urethane prepolymer solution to neutralize the carboxyl group of the urethane prepolymer, and 380 parts by mass of water was further added and sufficiently stirred to obtain the urethane prepolymer. An aqueous dispersion was obtained.
上記で得られたウレタンプレポリマーの水性分散液に、２５質量％エチレンジアミン水溶液８．８質量部を加え、攪拌することによって、ウレタンプレポリマーを鎖伸長した。次いでエージング・脱溶剤することによって、ウレタン樹脂の水性分散液（不揮発分３０質量％）を得た。前記ウレタン樹脂の重量平均分子量は５３，０００であった。 The urethane prepolymer was chain-extended by adding 8.8 parts by mass of a 25% by mass aqueous ethylenediamine solution to the aqueous dispersion of the urethane prepolymer obtained above and stirring the mixture. Then, by aging and removing the solvent, an aqueous dispersion of urethane resin (nonvolatile content: 30% by mass) was obtained. The weight average molecular weight of the urethane resin was 53,000.
次に、攪拌機、還流冷却管、窒素導入管、温度計、単量体混合物滴下用滴下漏斗、重合触媒滴下用滴下漏斗を備えた反応容器に脱イオン水１４０質量部、上記で得られたウレタン樹脂の水分散液１００質量部を入れ、窒素を吹き込みながら８０℃まで昇温した。その後、攪拌しながら、メタクリル酸メチル６０質量部、アクリル酸ｎ−ブチル３０質量部及びＮ−ｎ−ブトキシメチルアクリルアミド１０質量部からなる単量体混合物と、０．５質量％過硫酸アンモニウム水溶液２０質量部とを別々の滴下漏斗から、反応容器内温度を８０℃に保ちながら１２０分間かけて滴下した。 Next, 140 parts by mass of deionized water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. 100 parts by mass of the aqueous dispersion of the resin was added, and the temperature was raised to 80 ° C. while blowing nitrogen. Then, with stirring, a monomer mixture consisting of 60 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl acrylate and 10 parts by mass of Nn-butoxymethylacrylamide, and 20 parts by mass of a 0.5% by mass ammonium persulfate aqueous solution were added. The parts were added dropwise from a separate dropping funnel over 120 minutes while maintaining the temperature inside the reaction vessel at 80 ° C.
滴下終了後、さらに同温度にて６０分間攪拌した後、反応容器内の温度を４０℃に冷却して、不揮発分が２０質量％になるように脱イオン水で希釈した後、２００メッシュ濾布で濾過することによって、前記ウレタン樹脂をシェル層とし、メタクリル酸メチル等を原料とするアクリル樹脂をコア層とするコア・シェル型複合樹脂であるプライマー層用樹脂組成物の水分散液を得た。次に、イソプロパノールと水の質量割合が７／３となり、不揮発分が２質量％となるように、この水分散液にイソプピルアルコールと脱イオン水を加えて混合し、プライマー（Ｂ−１）を得た。 After completion of the dropping, the mixture was further stirred at the same temperature for 60 minutes, cooled to 40 ° C., diluted with deionized water so that the non-volatile content was 20% by mass, and then 200 mesh filter cloth was used. By filtering with, an aqueous dispersion of a resin composition for a primer layer, which is a core-shell type composite resin having the urethane resin as a shell layer and an acrylic resin made of methyl methacrylate or the like as a core layer, was obtained. .. Next, isopropanol alcohol and deionized water were added to this aqueous dispersion and mixed so that the mass ratio of isopropanol and water was 7/3 and the non-volatile content was 2% by mass, and the primer (B-1) was added. Got
［調製例１：銀粒子分散液の調製］
エチレングリコール４５質量部及びイオン交換水５５質量部の混合溶媒に、分散剤としてポリエチレンイミンにポリオキシエチレンが付加した化合物を用いて平均粒径３０ｎｍの銀粒子を分散させることによって、銀粒子及び分散剤を含有する分散体を調製した。次いで、得られた分散体に、イオン交換水、エタノール及び界面活性剤を添加して、５質量％の銀粒子分散液を調製した。[Preparation Example 1: Preparation of silver particle dispersion]
Silver particles and dispersion by dispersing silver particles with an average particle size of 30 nm in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water using a compound in which polyoxyethylene is added to polyethyleneimine as a dispersant. A dispersion containing the agent was prepared. Next, ion-exchanged water, ethanol and a surfactant were added to the obtained dispersion to prepare a 5% by mass silver particle dispersion.
［作製例１：ポリフェニレンスルフィド（ＰＰＳ）基材の作製］
リニア型ポリフェニレンスルフィド（ＡＳＴＭ Ｄ１２３８−８６によるＭＦＲ：６００ｇ／１０分）１００質量部、チョップドガラス繊維（旭ファイバーグラス株式会社製「ＦＴ５６２」、繊維状無機充填剤）５８．８質量部、エチレン−メタクリル酸共重合体亜鉛イオンタイプ（三井デュポンケミカル株式会社製「ハイミラン１８５５」）、８．４質量部及びモンタン酸複合エステルワックス（クラリアントジャパン株式会社製「リコルブＷＥ４０」）０．８質量部を均一に混合した後、３５ｍｍφの２軸押出機を用いて２９０〜３３０℃で溶融混錬し、ポリフェニレンスルフィド樹脂組成物を得た。得られたポリフェニレンスルフィド樹脂組成物を射出成形機で成形することにより、５０ｍｍ×１０５ｍｍ×２ｍｍのサイズのＰＰＳ基材を作製した。[Production Example 1: Preparation of polyphenylene sulfide (PPS) base material]
100 parts by mass of linear polyphenylene sulfide (MFR by ASTM D1238-86: 600 g / 10 minutes), 58.8 parts by mass of chopped glass fiber (“FT562” manufactured by Asahi Fiberglass Co., Ltd., fibrous inorganic filler), ethylene-methacryl Acid copolymer zinc ion type (“Himilan 1855” manufactured by Mitsui DuPont Chemical Co., Ltd.), 8.4 parts by mass and 0.8 parts by mass of montanic acid composite ester wax (“Recolve WE40” manufactured by Clariant Japan Co., Ltd.) uniformly After mixing, the mixture was melt-kneaded at 290 to 330 ° C. using a 35 mmφ twin-screw extruder to obtain a polyphenylene sulfide resin composition. The obtained polyphenylene sulfide resin composition was molded by an injection molding machine to prepare a PPS substrate having a size of 50 mm × 105 mm × 2 mm.
［作製例２：ポリイミドフィルム上の櫛歯電極（線間隔２０μｍ）の作製］
ポリイミドフィルム（東レ・デュポン株式会社製「カプトン １５０ＥＮ−Ｃ」；厚さ３８μｍ）の表面に、製造例１で得られたプライマー（Ｂ−１）を、卓上型小型コーター（ＲＫプリントコートインストルメント社製「Ｋプリンティングプローファー」）を用いて、乾燥後の平均厚さが２００ｎｍとなるように塗工した。次いで、１２０℃で５分間乾燥することによって、ポリイミドフィルムの表面にプライマー層を形成した。
調製例１で得られた銀粒子分散液を、卓上型小型コーター（ＲＫプリントコートインストルメント社製「Ｋプリンティングプローファー」）を用いて、乾燥後の平均厚さが１００ｎｍとなるように塗工した。次いで、熱風乾燥機を用いて２００℃で３０分間乾燥することによって、プライマー層の上に銀粒子を含有する銀層を形成した。[Production Example 2: Fabrication of comb tooth electrode (line spacing 20 μm) on polyimide film]
On the surface of a polyimide film (“Kapton 150EN-C” manufactured by Toray DuPont Co., Ltd .; thickness 38 μm), the primer (B-1) obtained in Production Example 1 was applied to a desktop compact coater (RK Print Coat Instrument Co., Ltd.). The coating was performed so that the average thickness after drying was 200 nm using a “K printing loafer” manufactured by K. Co., Ltd.). Then, a primer layer was formed on the surface of the polyimide film by drying at 120 ° C. for 5 minutes.
The silver particle dispersion obtained in Preparation Example 1 is coated with a small desktop coater (“K printing loafers” manufactured by RK Print Coat Instrument Co., Ltd.) so that the average thickness after drying is 100 nm. did. Then, a silver layer containing silver particles was formed on the primer layer by drying at 200 ° C. for 30 minutes using a hot air dryer.
銀層の上に、ドライフィルムレジスト（日立化成株式会社製「フォテックＲＤ−１２２５」；レジスト膜厚２５μｍ）を、ロールラミネーターを用いて１００℃で圧着することで、ポリイミド基材上に、銀粒子を含有する銀層、感光性樹脂層が積層された積層体を作製した。 A dry film resist (“Fortec RD-1225” manufactured by Hitachi Kasei Co., Ltd .; resist film thickness 25 μm) is pressure-bonded onto the silver layer at 100 ° C. using a roll laminator to form silver particles on the polyimide substrate. A laminated body in which a silver layer and a photosensitive resin layer containing the above were laminated was prepared.
上記で得られた積層体を用い、ダイレクト露光デジタルイメージング装置（オルボテック社製「Ｎｕｖｏｇｏ１０００Ｒ」）を用いて、レジスト上にＬ／Ｓ＝２０／２０μｍの櫛歯パターンを露光した。次いで、１質量％炭酸ナトリウム水溶液を用いて現像を行うことによって、銀層上に櫛歯電極パターン部が除去されたパターンレジストを形成した。 Using the laminate obtained above, a comb tooth pattern of L / S = 20/20 μm was exposed on the resist using a direct exposure digital imaging device (“Nuvogo1000R” manufactured by Orbotech). Then, by developing with a 1 mass% sodium carbonate aqueous solution, a pattern resist from which the comb tooth electrode pattern portion was removed was formed on the silver layer.
次いで、銀層をカソードに設定し、含リン銅をアノードとして、硫酸銅を含有する電解めっき液（硫酸銅７０ｇ／Ｌ、硫酸２００ｇ／Ｌ、塩素イオン５０ｍｇ／Ｌ、添加剤（奥野製薬工業株式会社製「トップルチナＳＦ−Ｍ」）を用いて電流密度２．５Ａ／ｄｍ２で２０分間電解めっきを行うことによって、レジストの除去されたパターン部に電解銅めっきによる導体回路層（膜厚１０μｍ）からなる櫛歯電極を形成した。次いで、銅による導体回路層の形成されたフィルムを、５０℃に設定した３質量％の水酸化ナトリウム水溶液に浸漬することによって、パターンレジストを剥離し、櫛歯電極（線間隔２０μｍ）を形成したポリイミドフィルムを得た。Next, an electrolytic plating solution containing copper sulfate (copper sulfate 70 g / L, sulfuric acid 200 g / L, chlorine ion 50 mg / L, additive (Okuno Pharmaceutical Co., Ltd.), with the silver layer set as the cathode and phosphorus-containing copper as the anode. By electroplating at a current density of 2.5 A / dm 2 for 20 minutes using the company's "Top Lucina SF-M"), a conductor circuit layer (thickness 10 μm) by electrolytic copper plating is applied to the pattern part from which the resist has been removed. A comb tooth electrode made of copper was formed. Next, the pattern resist was peeled off by immersing the film on which the conductor circuit layer made of copper was formed in a 3% by mass sodium hydroxide aqueous solution set at 50 ° C., and the comb tooth was formed. A polyimide film on which electrodes (line spacing 20 μm) were formed was obtained.
［作製例３：ポリフェニレンスルフィド（ＰＰＳ）基材上の櫛歯電極（線間隔２０μｍ）の作製］
作製例１で得られたＰＰＳ基材を用い、製造例１で得られたプライマー（Ｂ−１）に１０秒間浸漬した後、ＰＰＳ基材を引き揚げ、１分間静置した後、熱風乾燥機を用いて２００℃で５分間乾燥して、ＰＰＳ基材上にプライマー層（厚さ１３０ｎｍ）を形成した。[Production Example 3: Preparation of comb-tooth electrode (line spacing 20 μm) on a polyphenylene sulfide (PPS) substrate]
Using the PPS base material obtained in Production Example 1, the PPS base material was immersed in the primer (B-1) obtained in Production Example 1 for 10 seconds, the PPS base material was withdrawn, allowed to stand for 1 minute, and then a hot air dryer was installed. It was dried at 200 ° C. for 5 minutes to form a primer layer (thickness 130 nm) on the PPS substrate.
次いで、このプライマー層を形成したＰＰＳ基材を、調製例１で得られた銀粒子分散液に１０秒間浸漬した。その後、基材を引き揚げ、１分間静置した後、熱風乾燥機を用いて２００℃で５分間乾燥して、プライマー層上に銀粒子を含有する１００ｎｍ厚の銀層を形成した。 Next, the PPS substrate on which this primer layer was formed was immersed in the silver particle dispersion obtained in Preparation Example 1 for 10 seconds. Then, the base material was lifted and allowed to stand for 1 minute, and then dried at 200 ° C. for 5 minutes using a hot air dryer to form a 100 nm-thick silver layer containing silver particles on the primer layer.
銀層の上に、ドライフィルムレジスト（日立化成株式会社製「フォテックＲＤ−１２２５」；レジスト膜厚２５μｍ）を、真空ラミネーターを用いて１００℃で圧着することで、ＰＰＳ基材上に、プライマー層、銀粒子を含有する銀層、感光性樹脂層が積層された積層体を作製した。 A dry film resist (“Fortec RD-1225” manufactured by Hitachi Kasei Co., Ltd .; resist film thickness 25 μm) is pressure-bonded onto the silver layer at 100 ° C. using a vacuum laminator to form a primer layer on the PPS substrate. , A laminated body in which a silver layer containing silver particles and a photosensitive resin layer were laminated was prepared.
上記で得られた積層体を用い、実施例１と同様に、レジスト上にＬ／Ｓ＝２０／２０μｍの櫛歯パターンを露光し、１質量％炭酸ナトリウム水溶液を用いて現像を行うことによって、銀層上に櫛歯電極パターン部が除去されたパターンレジストを形成した。 Using the laminate obtained above, the comb tooth pattern of L / S = 20/20 μm is exposed on the resist in the same manner as in Example 1, and development is performed using a 1 mass% sodium carbonate aqueous solution. A pattern resist from which the comb tooth electrode pattern portion was removed was formed on the silver layer.
次いで、銀層をカソードに設定し、含リン銅をアノードとして、硫酸銅を含有する電解めっき液（硫酸銅７０ｇ／Ｌ、硫酸２００ｇ／Ｌ、塩素イオン５０ｍｇ／Ｌ、添加剤（奥野製薬工業株式会社製「トップルチナＳＦ−Ｍ」）を用いて電流密度２．５Ａ／ｄｍ２で２０分間電解めっきを行うことによって、レジストの除去されたパターン部に電解銅めっきによる導体回路層（膜厚１０μｍ）を形成した。次いで、銅による導体回路層の形成されたＰＰＳ基材を、５０℃に設定した３質量％の水酸化ナトリウム水溶液に浸漬することによって、パターンレジストを剥離し、櫛歯電極（線間隔２０μｍ）を形成したＰＰＳ基材を得た。Next, an electrolytic plating solution containing copper sulfate (copper sulfate 70 g / L, sulfate 200 g / L, chlorine ion 50 mg / L, additives (Okuno Pharmaceutical Co., Ltd.), with the silver layer set as the cathode and phosphorus-containing copper as the anode. By electroplating at a current density of 2.5 A / dm 2 for 20 minutes using the company's "Top Lucina SF-M"), a conductor circuit layer (thickness 10 μm) by electrolytic copper plating is applied to the pattern part from which the resist has been removed. Next, the PPS substrate on which the conductor circuit layer made of copper was formed was immersed in a 3% by mass sodium hydroxide aqueous solution set at 50 ° C. to peel off the pattern resist, and the comb tooth electrode (wire) was formed. A PPS substrate having an interval of 20 μm) was obtained.
［作製例４：ポリイミドフィルム上の櫛歯電極（線間隔５０μｍ）の作製］
レジスト上に作製する櫛歯パターンのＬ／Ｓを２０／５０μｍにした以外は、作製例１と同様にして、櫛歯電極（線間隔５０μｍ）を形成したポリイミドフィルムを得た。[Production Example 4: Fabrication of comb tooth electrode (line spacing 50 μm) on polyimide film]
A polyimide film having comb tooth electrodes (line spacing 50 μm) formed was obtained in the same manner as in Production Example 1 except that the L / S of the comb tooth pattern produced on the resist was set to 20/50 μm.
［作製例５：ポリイミドフィルム上の櫛歯電極（線間隔１０μｍ）の作製］
ジスト上に作製する櫛歯パターンのＬ／Ｓを２０／１０μｍにした以外は、作製例１と同様にして櫛歯電極（線間隔１０μｍ）を形成したポリイミドフィルムを得た。[Production Example 5: Fabrication of comb tooth electrode (line spacing 10 μm) on polyimide film]
A polyimide film having comb tooth electrodes (line spacing 10 μm) formed in the same manner as in Production Example 1 was obtained in the same manner as in Production Example 1 except that the L / S of the comb tooth pattern produced on the gist was set to 20/10 μm.
（実施例１）
水２７質量部に、酢酸３質量部及び２−プロパノール（以下、「ＩＰＡ」と略記する。）２０質量部を加え、さらに、３１質量％過酸化水素水５０質量部を加えて、均一に混合し銀用エッチング液（１）を調製した。(Example 1)
To 27 parts by mass of water, 3 parts by mass of acetic acid and 20 parts by mass of 2-propanol (hereinafter abbreviated as "IPA") are added, and further, 50 parts by mass of 31% by mass hydrogen peroxide solution is added and mixed uniformly. An etching solution (1) for silver was prepared.
（実施例２）
水２７質量部に、酢酸３質量部及びエタノール２０質量部を加え、さらに、３１質量％過酸化水素水５０質量部を加えて、均一に混合し銀用エッチング液（２）を調製した。(Example 2)
To 27 parts by mass of water, 3 parts by mass of acetic acid and 20 parts by mass of ethanol were added, and 50 parts by mass of 31% by mass hydrogen peroxide solution was added and mixed uniformly to prepare an etching solution for silver (2).
（実施例３）
水６０質量部に、酢酸１０質量部及びエタノール２０質量部を加え、さらに、３１質量％過酸化水素水１０質量部を加えて、均一に混合し銀用エッチング液（３）を調製した。(Example 3)
To 60 parts by mass of water, 10 parts by mass of acetic acid and 20 parts by mass of ethanol were added, and 10 parts by mass of 31% by mass hydrogen peroxide solution was added and mixed uniformly to prepare an etching solution for silver (3).
（実施例４）
水３７質量部に、酢酸３質量部及び２−ブトキシエタノール１０質量部を加え、さらに、３１質量％過酸化水素水５０質量部を加えて、均一に混合し銀用エッチング液（４）を調製した。(Example 4)
To 37 parts by mass of water, 3 parts by mass of acetic acid and 10 parts by mass of 2-butoxyethanol were added, and 50 parts by mass of 31% by mass hydrogen peroxide solution was added and mixed uniformly to prepare an etching solution for silver (4). did.
（実施例５）
水３７質量部に、１−プロピオン酸３質量部及び２−ブトキシエタノール１０質量部を加え、さらに、３１質量％過酸化水素水５０質量部を加えて、均一に混合し銀用エッチング液（５）を調製した。(Example 5)
To 37 parts by mass of water, 3 parts by mass of 1-propionic acid and 10 parts by mass of 2-butoxyethanol were added, and 50 parts by mass of 31% by mass hydrogen peroxide solution was added and mixed uniformly to an etching solution for silver (5). ) Was prepared.
（実施例６）
水３８質量部に、ギ酸２質量部、ＩＰＡ１８質量部及び２−ブトキシエタノール２質量部を加え、さらに、３１質量％過酸化水素水４０質量部を加えて、均一に混合し銀用エッチング液（６）を調製した。(Example 6)
To 38 parts by mass of water, 2 parts by mass of formic acid, 18 parts by mass of IPA and 2 parts by mass of 2-butoxyethanol were added, and 40 parts by mass of 31% by mass hydrogen peroxide solution was added and mixed uniformly. 6) was prepared.
（実施例７）
水５２質量部に、酢酸２．９質量部、モノクロロ酢酸０．１質量部及びＩＰＡ５質量部を加え、さらに、３１質量％過酸化水素水４０質量部を加えて、均一に混合し銀用エッチング液（７）を調製した。(Example 7)
To 52 parts by mass of water, 2.9 parts by mass of acetic acid, 0.1 part by mass of monochloroacetic acid and 5 parts by mass of IPA were added, and 40 parts by mass of 31 mass% hydrogen peroxide solution was added, and the mixture was uniformly mixed and etched for silver. Liquid (7) was prepared.
（実施例８）
水４７質量部に、酢酸５質量部及びＩＰＡ８質量部を加え、さらに、３１質量％過酸化水素水４０質量部を加えて、均一に混合し銀用エッチング液（８）を調製した。(Example 8)
To 47 parts by mass of water, 5 parts by mass of acetic acid and 8 parts by mass of IPA were added, and 40 parts by mass of 31% by mass hydrogen peroxide solution was added and mixed uniformly to prepare an etching solution for silver (8).
（比較例１）
水４７質量部に、酢酸３質量部を加え、さらに、３１質量％過酸化水素水５０質量部を加えて、銀用エッチング液（Ｒ１）を調製した。(Comparative Example 1)
3 parts by mass of acetic acid was added to 47 parts by mass of water, and 50 parts by mass of 31% by mass hydrogen peroxide solution was further added to prepare an etching solution for silver (R1).
（比較例２）
水４０質量部に、硫酸１質量部及び２−ブトキシエタノール１０質量部を加え、さらに、３１質量％過酸化水素水４９質量部を加えて、銀用エッチング液（Ｒ２）を調製した。(Comparative Example 2)
To 40 parts by mass of water, 1 part by mass of sulfuric acid and 10 parts by mass of 2-butoxyethanol were added, and 49 parts by mass of 31% by mass hydrogen peroxide solution was added to prepare an etching solution for silver (R2).
上記の実施例１〜８、比較例１及び２で得られた銀用エッチング液の組成について、表１にまとめた。 The compositions of the etching solutions for silver obtained in Examples 1 to 8 and Comparative Examples 1 and 2 are summarized in Table 1.
（実施例９）
作製例２で得られたポリイミドフィルムを２質量％２−ブトキシエタノールと３質量％酢酸の混合水溶液に３０秒間浸漬後、実施例１で得られた銀用エッチング液（１）に、２５℃で３０秒間浸漬して櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 9)
The polyimide film obtained in Production Example 2 is immersed in a mixed aqueous solution of 2% by mass 2-butoxyethanol and 3% by mass acetic acid for 30 seconds, and then immersed in the silver etching solution (1) obtained in Example 1 at 25 ° C. A printed wiring board was obtained by immersing for 30 seconds to remove the silver layer other than the comb tooth electrode portion.
（実施例１０）
実施例１で得られた銀用エッチング液（１）に、作製例５で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 10)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 5 is used for the silver etching solution (1) obtained in Example 1. So I got a printed wiring board.
（実施例１１）
実施例２で得られた銀用エッチング液（２）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 11)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used for the silver etching solution (2) obtained in Example 2. So I got a printed wiring board.
（実施例１２）
実施例３で得られた銀用エッチング液（３）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 12)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used for the silver etching solution (3) obtained in Example 3. So I got a printed wiring board.
（実施例１３）
実施例４で得られた銀用エッチング液（４）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 13)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used in the silver etching solution (4) obtained in Example 4. So I got a printed wiring board.
（実施例１４）
実施例５で得られた銀用エッチング液（５）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 14)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used in the silver etching solution (5) obtained in Example 5. So I got a printed wiring board.
（実施例１５）
実施例６で得られた銀用エッチング液（６）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 15)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used in the silver etching solution (6) obtained in Example 6. So I got a printed wiring board.
（実施例１６）
実施例７で得られた銀用エッチング液（７）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 16)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used in the silver etching solution (7) obtained in Example 7. So I got a printed wiring board.
（実施例１７）
実施例８で得られた銀用エッチング液（８）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 17)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used in the silver etching solution (8) obtained in Example 8. So I got a printed wiring board.
（実施例１８）
実施例１で得られた銀用エッチング液（１）に、作製例３で得られたＰＰＳ基材を用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 18)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the PPS substrate obtained in Production Example 3 is used in the silver etching solution (1) obtained in Example 1. As a result, a printed wiring board was obtained.
（実施例１９）
作製例５で得られたポリイミドフィルムを２−ブトキシエタノール２質量％と酢酸３質量％とを含有する混合水溶液に３０秒間浸漬後、実施例４で得られた銀用エッチング液（４）に、２５℃で３０秒間浸漬した。さらに、１質量％過酸化水素水（２５℃）に２分間浸漬洗浄後、エアブローを用いて基材表面に付着している洗浄液を除去し、７０℃のホットプレートを用いて３分間乾燥を行った。次いで、０．５Ｍチオ硫酸ナトリウム水溶液（２５℃）に３０秒間浸漬洗浄後、窒素ブローを用いて基材表面に付着している洗浄液を除去し、イオン交換水を用いて洗浄後、７０℃のホットプレートを用いて３分間乾燥して櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 19)
The polyimide film obtained in Production Example 5 was immersed in a mixed aqueous solution containing 2% by mass of 2-butoxyethanol and 3% by mass of acetic acid for 30 seconds, and then immersed in the etching solution for silver (4) obtained in Example 4. It was immersed at 25 ° C. for 30 seconds. Further, after immersing and cleaning in 1 mass% hydrogen peroxide solution (25 ° C.) for 2 minutes, the cleaning liquid adhering to the surface of the substrate is removed by using an air blow, and drying is performed for 3 minutes using a hot plate at 70 ° C. It was. Next, after immersing and cleaning in a 0.5 M sodium thiosulfate aqueous solution (25 ° C.) for 30 seconds, the cleaning liquid adhering to the surface of the substrate is removed using a nitrogen blow, and after cleaning with ion-exchanged water, the temperature is 70 ° C. A printed wiring board was obtained by drying for 3 minutes using a hot plate to remove the silver layer other than the comb tooth electrode portion.
（実施例２０）
作製例５で得られたポリイミドフィルムを２−ブトキシエタノール２質量％と酢酸３質量％とを含有する混合水溶液に３０秒間浸漬後、実施例４で得られた銀用エッチング液（４）に、２５℃で３０秒間浸漬した。さらに、１質量％過酸化水素水（２５℃）に２分間浸漬洗浄後、エアブローを用いて基材表面に付着している洗浄液を除去し、７０℃のホットプレートを用いて３分間乾燥を行った。次いで、過マンガン酸カリウム５質量％と水酸化ナトリウム４質量％とを含有する混合水溶液（５０℃）に１分間浸漬洗浄後、イオン交換水を用いて洗浄液を十分にすすぎ洗浄した後、１質量％過酸化水素水（２５℃）に２分間浸漬洗浄後、１０質量％酢酸と１質量％過酸化水素の混合水溶液（２５℃）で中和した。さらに、３０質量％エタノール水溶液に２分間浸漬洗浄し、７０℃のホットプレートを用いて３分間乾燥して櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 20)
The polyimide film obtained in Production Example 5 was immersed in a mixed aqueous solution containing 2% by mass of 2-butoxyethanol and 3% by mass of acetic acid for 30 seconds, and then immersed in the etching solution for silver (4) obtained in Example 4. It was immersed at 25 ° C. for 30 seconds. Further, after immersing and cleaning in 1 mass% hydrogen peroxide solution (25 ° C.) for 2 minutes, the cleaning liquid adhering to the surface of the substrate is removed by using an air blow, and drying is performed for 3 minutes using a hot plate at 70 ° C. It was. Then, after immersing and washing in a mixed aqueous solution (50 ° C.) containing 5% by mass of potassium permanganate and 4% by mass of sodium hydroxide for 1 minute, the washing solution was thoroughly rinsed and washed with ion-exchanged water, and then 1 mass. After immersing and washing in% hydrogen peroxide solution (25 ° C.) for 2 minutes, the mixture was neutralized with a mixed aqueous solution (25 ° C.) of 10% by mass acetic acid and 1% by mass hydrogen peroxide. Further, the printed wiring board was obtained by immersing and washing in a 30 mass% ethanol aqueous solution for 2 minutes and drying for 3 minutes using a hot plate at 70 ° C. to remove the silver layer other than the comb tooth electrode portion.
（実施例２１）
作製例５で得られたポリイミドフィルムを２−ブトキシエタノール２質量％と酢酸３質量％とを含有する混合水溶液に３０秒間浸漬後、実施例４で得られた銀用エッチング液（４）に、２５℃で３０秒間浸漬した。さらに、１質量％過酸化水素水（２５℃）に２分間浸漬洗浄後、エアブローを用いて基材表面に付着している洗浄液を除去し、７０℃のホットプレートを用いて３分間乾燥を行った。次いで０．５Ｍチオ硫酸ナトリウム水溶液（２５℃）に３０秒間浸漬洗浄後、窒素ブローを用いて基材表面に付着している洗浄液を除去し、イオン交換水を用いて洗浄後、７０℃のホットプレートを用いて３分乾燥を行った。さらに、５質量％過マンガン酸カリウムと４質量％水酸化ナトリウム混合水溶液（５０℃）に６０秒間浸漬洗浄後、イオン交換水を用いて洗浄液を十分にすすぎ洗浄した後、１質量％過酸化水素水（２５℃）に２分間浸漬洗浄後、１０質量％酢酸と１質量％過酸化水素の混合水溶液（２５℃）で中和した。さらに、３０質量％エタノール水溶液に２分間浸漬洗浄し、７０℃のホットプレートを用いて３分間乾燥して櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Example 21)
The polyimide film obtained in Production Example 5 was immersed in a mixed aqueous solution containing 2% by mass of 2-butoxyethanol and 3% by mass of acetic acid for 30 seconds, and then immersed in the etching solution for silver (4) obtained in Example 4. It was immersed at 25 ° C. for 30 seconds. Further, after immersing and cleaning in 1 mass% hydrogen peroxide solution (25 ° C.) for 2 minutes, the cleaning liquid adhering to the surface of the substrate is removed by using an air blow, and drying is performed for 3 minutes using a hot plate at 70 ° C. It was. Next, after immersing and cleaning in a 0.5 M sodium thiosulfate aqueous solution (25 ° C.) for 30 seconds, the cleaning liquid adhering to the surface of the substrate is removed using a nitrogen blow, cleaning is performed using ion-exchanged water, and then hot at 70 ° C. Drying was performed for 3 minutes using a plate. Further, after immersing and washing in a mixed aqueous solution of 5% by mass potassium permanganate and 4% by mass sodium hydroxide (50 ° C.) for 60 seconds, the washing solution is thoroughly rinsed and washed with ion-exchanged water, and then 1% by mass hydrogen peroxide is used. After immersing and washing in water (25 ° C.) for 2 minutes, the mixture was neutralized with a mixed aqueous solution (25 ° C.) of 10% by mass acetic acid and 1% by mass hydrogen peroxide. Further, the printed wiring board was obtained by immersing and washing in a 30 mass% ethanol aqueous solution for 2 minutes and drying for 3 minutes using a hot plate at 70 ° C. to remove the silver layer other than the comb tooth electrode portion.
（比較例３）
比較例１で得られた銀用エッチング液（Ｒ１）に、作製例４で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Comparative Example 3)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 4 is used for the silver etching solution (R1) obtained in Comparative Example 1. So I got a printed wiring board.
（比較例４）
比較例１で得られた銀用エッチング液（Ｒ１）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Comparative Example 4)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used for the silver etching solution (R1) obtained in Comparative Example 1. So I got a printed wiring board.
（比較例５）
比較例１で得られた銀用エッチング液（Ｒ１）に、作製例５で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Comparative Example 5)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 5 is used for the silver etching solution (R1) obtained in Comparative Example 1. So I got a printed wiring board.
（比較例６）
比較例２で得られた銀用エッチング液（Ｒ２）に、作製例２で得られたポリイミドフィルムを用いた以外は実施例９と同じ方法で、櫛歯電極部以外の銀層を除去することで、プリント配線板を得た。(Comparative Example 6)
The silver layer other than the comb tooth electrode portion is removed by the same method as in Example 9 except that the polyimide film obtained in Production Example 2 is used for the silver etching solution (R2) obtained in Comparative Example 2. So I got a printed wiring board.
上記の実施例９〜１８及び比較例３〜６で得られたプリント配線板について、下記の方法により、配線間のテスターによる導通確認、絶縁抵抗の測定、非配線部の絶縁抵抗の測定、アンダーカットの有無及び配線部の断面形状の確認を行った。 With respect to the printed wiring boards obtained in Examples 9 to 18 and Comparative Examples 3 to 6 above, continuity confirmation by a tester between wirings, measurement of insulation resistance, measurement of insulation resistance of non-wiring portions, under The presence or absence of a cut and the cross-sectional shape of the wiring part were confirmed.
［配線間の絶縁抵抗の測定］
上記で得られたプリント配線板について、対向櫛歯電極間の導通の有無をテスター（ＦＬＵＫＥ社製「２３３リモート・ディスプレイ・デジタル・マルチメーター）で確認した。この結果、銀層の除去が不十分で、導通が確認されたものを「短絡」とし、銀層が充分に除去され、導通しなかったものを「絶縁」とした。次いで、導通しなかったものについて、日置電機株式会社製の超絶縁計「ＳＭ−８２１３」を用いて、同様に２０μｍスペースの電極間の抵抗値を測定した。ここで、抵抗値が１０６Ωを超えるものは、配線間の絶縁が十分だといえる。めっき下地層（銀層）の除去性の評価として、同条件で行った試験１０回のうち、導通確認で短絡又は電極間抵抗値が１０６Ωを超えなかった場合を「不合格」として、その数を示した。[Measurement of insulation resistance between wiring]
With respect to the printed wiring board obtained above, the presence or absence of continuity between the facing comb tooth electrodes was confirmed with a tester (“233 Remote Display Digital Multimeter” manufactured by FLUKE). As a result, the removal of the silver layer was insufficient. Then, the one in which continuity was confirmed was defined as "short circuit", and the one in which the silver layer was sufficiently removed and did not conduct was defined as "insulation". Next, for those that did not conduct, the resistance value between the electrodes in a 20 μm space was similarly measured using a super insulation meter “SM-8213” manufactured by Hioki Electric Co., Ltd. Here, what resistance value exceeds 10 6 Omega, said insulation between wiring is enough. As the evaluation of the removal of the plating base layer (silver layer), of performing the test 10 times under the same conditions, a case where the resistance value between the short-circuit or electrode with continuity test does not exceed the 10 6 Omega as "fail", The number is shown.
［非配線部の絶縁抵抗の測定］
上記で得られたプリント配線板の非配線部（配線部以外の銀除去領域）について、株式会社三菱ケミカルアナリティック製のハイレスタ−ＵＰ（ＭＣＰ−ＨＴ４５０型）を用いて、１００Ｖ印加での抵抗値を測定した。なお、抵抗値が「オーバーレンジ」となった場合は、測定装置の仕様から９．９９×１０１３Ω以上の抵抗値であることを示す。[Measurement of insulation resistance of non-wiring part]
For the non-wiring part (silver removal area other than the wiring part) of the printed wiring board obtained above, the resistance value at 100 V application using High Restor-UP (MCP-HT450 type) manufactured by Mitsubishi Chemical Analytical Co., Ltd. Was measured. When the resistance value becomes "overrange", it indicates that the resistance value is 9.99 × 10 13 Ω or more according to the specifications of the measuring device.
［アンダーカットの有無及び配線部の断面形状の確認］
上記で得られたプリント配線板の配線部の断面を走査型電子顕微鏡（日本電子株式会社製「ＪＳＭ７８００」）で５００〜１０，０００倍に拡大し観察して、アンダーカットの有無及び配線部の断面形状から、サイドエッチの有無を確認した。サイドエッチが起こる場合には、断面形状が「矩形」を保持できず、「非矩形」となる。[Check for undercut and cross-sectional shape of wiring]
The cross section of the wiring part of the printed wiring board obtained above was magnified 500 to 10,000 times with a scanning electron microscope (“JSM7800” manufactured by JEOL Ltd.) and observed, and the presence or absence of undercut and the wiring part were observed. The presence or absence of side etching was confirmed from the cross-sectional shape. When side etching occurs, the cross-sectional shape cannot hold the "rectangular" and becomes "non-rectangular".
実施例９〜１８及び比較例３〜７で得られたプリント配線板の評価結果をまとめたものを、表２及び３に示す。 Tables 2 and 3 show a summary of the evaluation results of the printed wiring boards obtained in Examples 9 to 18 and Comparative Examples 3 to 7.
表２に示した実施例９〜２１で得られたプリント配線板の評価結果から、本発明の銀用エッチング液（１）〜（８）を用いることにより、非配線部の銀層が十分に除去できることが確認できた。 From the evaluation results of the printed wiring boards obtained in Examples 9 to 21 shown in Table 2, by using the etching solutions for silver (1) to (8) of the present invention, the silver layer of the non-wiring portion is sufficiently sufficient. It was confirmed that it could be removed.
一方、表３に示した比較例３〜５で得られたプリント配線板の評価結果から、アルコールを含有していないエッチング液（Ｒ１）を用いた場合は、非配線部の銀層が十分に除去できないことが確認できた。 On the other hand, from the evaluation results of the printed wiring boards obtained in Comparative Examples 3 to 5 shown in Table 3, when the etching solution (R1) containing no alcohol was used, the silver layer in the non-wiring portion was sufficiently sufficient. It was confirmed that it could not be removed.
また、比較例６で得られたプリント配線板の評価結果から、カルボン酸の代わりに硫酸を含有するエッチング液（Ｒ２）を用いた場合は、非配線部の銀層が十分に除去できないだけでなく、配線部の銅が溶解して断面形状が非矩形となることが確認できた。 Further, from the evaluation results of the printed wiring board obtained in Comparative Example 6, when the etching solution (R2) containing sulfuric acid was used instead of the carboxylic acid, the silver layer in the non-wiring portion could not be sufficiently removed. It was confirmed that the copper in the wiring portion was melted and the cross-sectional shape became non-rectangular.
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| JP2009162727A (en) * | 2008-01-10 | 2009-07-23 | Yazaki Corp | Method for analyzing poisonous metal in silver-plated layer |
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| WO2015029478A1 (en) * | 2013-08-29 | 2015-03-05 | 日立金属株式会社 | Method for manufacturing ceramic circuit board |
| CN108048842A (en) * | 2017-12-13 | 2018-05-18 | 天津宝兴威科技股份有限公司 | A kind of etching liquid and its application method of nano silver wire conductive film |
| KR20190017473A (en) * | 2017-08-11 | 2019-02-20 | 동우 화인켐 주식회사 | Etchant composition for etching metal layer and method of forming conductive pattern using the same |
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| JP2012194024A (en) * | 2011-03-16 | 2012-10-11 | Sumiko Techno-Research Co Ltd | Silver-plated layer dissolution solution, silver-plated layer dissolution method, and quantitative method of silver-plated layer-contained element |
| WO2015029478A1 (en) * | 2013-08-29 | 2015-03-05 | 日立金属株式会社 | Method for manufacturing ceramic circuit board |
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