JP4290621B2 - Electroless copper plating method for multilayer flexible printed circuit board - Google Patents
Electroless copper plating method for multilayer flexible printed circuit board Download PDFInfo
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- JP4290621B2 JP4290621B2 JP2004254743A JP2004254743A JP4290621B2 JP 4290621 B2 JP4290621 B2 JP 4290621B2 JP 2004254743 A JP2004254743 A JP 2004254743A JP 2004254743 A JP2004254743 A JP 2004254743A JP 4290621 B2 JP4290621 B2 JP 4290621B2
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- 238000000034 method Methods 0.000 title claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 7
- 229910052802 copper Inorganic materials 0.000 title description 6
- 239000010949 copper Substances 0.000 title description 6
- 238000007747 plating Methods 0.000 title description 6
- 230000003750 conditioning effect Effects 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 150000002009 diols Chemical class 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 238000007772 electroless plating Methods 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000000945 filler Substances 0.000 description 15
- 229910002677 Pd–Sn Inorganic materials 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000010168 coupling process Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- -1 phosphorus compound salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 241001343369 Aegle <moth> Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は、電子機器に使用されるフレキシブルプリント基板の製造方法に関わり、とくにスルーホールの導電化処理方法に関する。 The present invention relates to a method for manufacturing a flexible printed circuit board used in an electronic device, and more particularly to a method for conducting through holes.
多層フレキシブルプリント基板における層間接続は、スルーホールの内壁面に導電膜を形成して行なうことが多い。そして、プリント基板のスルーホール内壁への導電化処理方法については、従来から無電解銅メッキが広く使用されており、Pd−Snコロイドを用いた導電化処理が行われる。この導電化処理において0.1〜1.0μmの銅析出層を形成し、次に電解メッキによって15〜25μmの銅メッキ層が形成される。 Interlayer connection in a multilayer flexible printed circuit board is often performed by forming a conductive film on the inner wall surface of the through hole. And as for the conductive treatment method for the inner wall of the through hole of the printed circuit board, electroless copper plating has been widely used so far, and conductive treatment using Pd—Sn colloid is performed. In this conductive treatment, a copper deposit layer of 0.1 to 1.0 μm is formed, and then a copper plating layer of 15 to 25 μm is formed by electrolytic plating.
多層フレキシブルプリント基板において、積層に使用される接着剤には耐熱性を有する各種フィラーが充填されている。主に添加される物質としては、ガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物があるが、これらのフィラー物質は粒子界面が疎水性を有し、Pd−Snコロイドが吸着し難いという問題点がある。 In a multilayer flexible printed board, the adhesive used for lamination is filled with various heat-resistant fillers. Mainly added substances include glass bodies and metal oxides such as aluminum oxide and magnesium oxide, but these filler substances have a hydrophobic particle interface and are difficult to adsorb Pd—Sn colloids. There is a point.
従来のコンディショニング工程で使用されているコンディショナーは、トリエタノールアミンなどのアミン系界面活性剤からなり、親水性を付与する効能およびスルーホール内の基材をプラス側に帯電させる効能を有している。 The conditioner used in the conventional conditioning process is made of an amine surfactant such as triethanolamine, and has the effect of imparting hydrophilicity and the effect of charging the substrate in the through hole to the plus side. .
しかし、ガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物の粒子界面を完全に親水性にするほどの効能はない。このため、従来のコンディショニング工程よりもさらに有効な親水化処理を行なう方法が望まれていた。 However, it is not effective to make the particle interface of glass oxide or metal oxide such as aluminum oxide and magnesium oxide completely hydrophilic. For this reason, the method of performing a hydrophilic treatment more effective than the conventional conditioning process was desired.
また、ガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物の粒子界面を親水性にする方法として、シランカップリング処理を行なうものがある。シランカップリングの方法としては、例えば特許文献1に示されるようなガラス基板表面の親水化処理などの方法が知られている。 In addition, as a method for making the particle interface of a metal body such as a glass body or aluminum oxide / magnesium oxide hydrophilic, there is a method of performing a silane coupling treatment. As a silane coupling method, for example, a method of hydrophilizing the surface of a glass substrate as disclosed in Patent Document 1 is known.
この方法は、表面に親水基を付与し、親水性を向上させる有効な手段であるが、反応中に脱水結合させる過程があり、一般的には強アルカリ液中で処理しなければならない。 This method is an effective means for imparting a hydrophilic group to the surface and improving the hydrophilicity, but there is a process of dehydration bonding during the reaction, and generally it must be treated in a strong alkaline solution.
しかし、強アルカリ液中にプリント基板を浸漬すると、絶縁層主成分であるポリイミドが溶解するという問題がある。
本発明は、上述の点を考慮してなされたもので、フィラー物質の表面を改質し、スルーホール壁面にボイドが生じない無電解銅メッキプロセスを持つプリント基板の製造方法を提供することを目的とする。 The present invention has been made in view of the above points, and provides a method for manufacturing a printed circuit board having an electroless copper plating process in which the surface of a filler material is modified and voids are not generated on the wall surface of the through hole. Objective.
本発明は、絶縁層を形成するポリイミドと、フィラー物質であるガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物の粒子界面を親水性にする方法を提供することをより具体的な目的とする。 It is a more specific object of the present invention to provide a method for making the particle interface between polyimide forming an insulating layer and a filler metal such as glass body or aluminum oxide / magnesium oxide hydrophilic. .
上記目的達成のため、本発明では、
多層フレキシブルプリント基板のスルーホールに、無電解メッキを施して層間接続用金属導体を形成するプリント基板の製造方法において、前処理となるコンディショニング工程を、アミン系界面活性剤を主成分とする水溶液に被処理物を浸漬する第1コンディショニング工程と、ジオール類を主成分とする水溶液に被処理物を浸漬する第2コンディショニング工程との2段階で行なうことを特徴とする、プリント基板の製造方法、
を提供するものである。
In order to achieve the above object, in the present invention,
In the method of manufacturing a printed circuit board in which through-holes of a multilayer flexible printed circuit board are subjected to electroless plating to form a metal conductor for interlayer connection, a conditioning process as a pretreatment is performed with an aqueous solution mainly composed of an amine-based surfactant. A method for producing a printed circuit board, characterized in that it is performed in two stages: a first conditioning step for immersing the object to be processed and a second conditioning step for immersing the object to be processed in an aqueous solution containing diols as a main component,
Is to provide.
本発明は上述のように、第1、第2の2段階に別けて被処理物をコンディショニングすることによって、従来のアミン系界面活性剤だけで被処理物をコンディショニングしていたときは2〜3ppm位の頻度でボイドが発生していたが、全くボイドが発生しなくなった。このことから、本発明による2段階でコンディショニングする方法の優位性が確認できた。 In the present invention, as described above, the object to be treated is conditioned in two stages, the first and second stages, so that when the object to be treated is conditioned only with a conventional amine surfactant, 2 to 3 ppm. Voids were generated with a frequency of approximately 5%, but no voids were generated at all. This confirms the superiority of the two-stage conditioning method according to the present invention.
以下、本発明の実施例に到る経緯および実施例を説明する。被処理物であるプリント基板のスルーホール内壁の導電化処理は、一般に、次の7工程、すなわち
(1)脱脂:未硬化樹脂成分などの非水溶性物質の除去。
(2)コンディショニング:触媒であるPd−Snコロイドがマイナスの電荷を有しているので、スルーホール内の基材をプラス側に帯電させる。
(3)ソフトエッチング:銅箔表面の酸化膜除去と、凹凸を付与してメッキ剥離を抑止する。
(4)プレディップ:Pd−Snコロイドの溶媒と同じ成分に浸漬し、Pd−Snコロイドとの親和性を持たせる。
(5)アクチベーター:Pd−Snコロイドを吸着させる。
(6)アクセレレーター:Pd−SnコロイドからSnを除去し、Pd単体を析出させる。
(7)無電解メッキ:Pdを核として銅イオンを還元して析出させる。
によって行なわれる。
Hereinafter, the background to the embodiments of the present invention and the embodiments will be described. The conductive treatment of the inner wall of the through hole of the printed circuit board that is the object to be processed is generally the following seven steps:
(1) Degreasing: Removal of water-insoluble substances such as uncured resin components.
(2) Conditioning: Since the Pd—Sn colloid as a catalyst has a negative charge, the substrate in the through hole is charged to the positive side.
(3) Soft etching: The removal of the oxide film on the surface of the copper foil and the provision of irregularities to suppress plating peeling.
(4) Pre-dip: Immerse in the same component as the solvent of the Pd—Sn colloid to give affinity to the Pd—Sn colloid.
(5) Activator: Pd-Sn colloid is adsorbed.
(6) Accelerator: Removes Sn from the Pd—Sn colloid and precipitates Pd alone.
(7) Electroless plating: Copper ions are reduced and deposited using Pd as a nucleus.
Is done by.
多層フレキシブルプリント基板において、積層に使用される接着剤には耐熱性を有する各種フィラーが充填されている。フィラーとして主に添加される物質としては、ガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物であるが、これらのフィラー物質は粒子界面が疎水性を有し、Pd−Snコロイドが吸着し難いという特性がある。ただし、これらフィラー物質は、スルーホール穴明け時には、接着剤樹脂に埋没しているか、ごく一部が穴壁表面に露出しているに過ぎない(図3)から、とくに問題がない。 In a multilayer flexible printed board, the adhesive used for lamination is filled with various heat-resistant fillers. Substances that are mainly added as fillers are glass oxides and metal oxides such as aluminum oxide and magnesium oxide. These filler substances have hydrophobic particle interfaces and are difficult to adsorb Pd—Sn colloids. There is a characteristic. However, since these filler substances are buried in the adhesive resin at the time of through-hole drilling or only a part is exposed on the hole wall surface (FIG. 3), there is no particular problem.
しかし、多層基板に欠かせないデスミア処理の後に問題が生じる。このデスミア処理によって、接着剤樹脂がより多く除去されて、フィラー物質がスルーホール穴壁に露出して疎水性が強くなる(図4(a),(b))。このため、「ボイド(図5(a),(b))」と呼ばれる無電解銅メッキが付かない箇所が生じ易くなる。 However, problems arise after desmear processing, which is essential for multilayer substrates. By this desmear treatment, more adhesive resin is removed, and the filler material is exposed to the through-hole hole wall, so that the hydrophobicity becomes strong (FIGS. 4A and 4B). For this reason, a portion called “void (FIGS. 5A and 5B)” that is not attached with electroless copper plating tends to occur.
デスミア処理によって、樹脂成分であるポリイミドがより多く除去されてフィラー物質がスルーホール穴壁に露出するが、シランカップリング処理を行なうとさらに穴壁がエッチングされ、エグレが生じる(図6)。このエグレは、マイグレーションを引き起こす要因となるため、シランカップリングのような親水化処理は不適当である。 By the desmear treatment, more polyimide as a resin component is removed and the filler material is exposed to the through-hole hole wall. However, when the silane coupling treatment is performed, the hole wall is further etched to cause an egress (FIG. 6). Since this aggression causes migration, a hydrophilic treatment such as silane coupling is inappropriate.
他方、前述したような強アルカリ溶液の問題を避けるものとして、弱アルカリ溶液のような穏やかな条件下で親水化処理を行なう方法があり、側鎖アルキル基や水酸基、カルボキシル基、アミノ基などを有する変性ポリビニルアルコールを粗水物質表面にカップリングする方法が知られている。 On the other hand, as a method for avoiding the problem of the strong alkali solution as described above, there is a method of performing a hydrophilization treatment under a mild condition such as a weak alkali solution, and a side chain alkyl group, a hydroxyl group, a carboxyl group, an amino group, etc. There is known a method of coupling the modified polyvinyl alcohol having a surface of a crude water substance.
しかし、通常、ポリビニルアルコールは増粘剤にも使用されるもので、水溶液にした場合でも一般的に粘度が高いものが多いため、使用する変性ポリビニルアルコールの架橋度、プリント基板のスルーホール内径、このスルーホール内径と基板厚みとの比率によっては、プリント基板に適用しようとすると、処理溶液がスルーホール内に浸透していかない場合がある。 However, usually polyvinyl alcohol is also used as a thickener, and even when it is made into an aqueous solution, since there are many generally high viscosity, the degree of crosslinking of the modified polyvinyl alcohol used, the through-hole inner diameter of the printed circuit board, Depending on the ratio between the inner diameter of the through hole and the thickness of the substrate, the treatment solution may not penetrate into the through hole when applied to a printed circuit board.
数々のコンディショナー・親水化処理の方法を試みた結果、フィラー物質であるガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物の粒子界面を親水性にする方法として、変性ポリビニルアルコールを使用する代りに、プロピレングリコール、トリメチレングリコールなどのジオール類をフィラー物質とカップリングする方法によって親水性付与の効果が得られることを突き止めた。 As a result of a number of conditioner / hydrophilization treatment methods, instead of using modified polyvinyl alcohol as a method to make the particle interface of fillers such as glass bodies and metal oxides such as aluminum oxide and magnesium oxide hydrophilic. It has been found that the effect of imparting hydrophilicity can be obtained by a method of coupling diols such as propylene glycol and trimethylene glycol with a filler substance.
これらのジオール類は、水に溶解した状態で表面張力を低下させ、プリント基板のスルーホール内に容易に浸透していく性質を有する。したがって、プリント基板のスルーホール内に露出したフィラー物質であるガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物の粒子界面を親水性にする手段として有効である。 These diols have the property of reducing the surface tension in a state dissolved in water and easily penetrating into the through holes of the printed circuit board. Therefore, it is effective as a means for making the particle interface of a glass body or metal oxide such as aluminum oxide / magnesium oxide, which is a filler material exposed in the through hole of the printed circuit board, hydrophilic.
カップリング剤として、Ca,Mgなどのリン化合物塩もしくはホウ素化合物塩を添加することが行なわれるが、リンを含む化合物は排水処理に難があり、ホウ素化合物塩を使用することが好ましい。例えば、ホウ素酸ナトリウム、ホウフッ酸ナトリウム、ホウフッ酸マグネシウムなどが挙げられる。 As a coupling agent, phosphorus compound salts such as Ca and Mg or boron compound salts are added. However, phosphorus-containing compounds have difficulty in wastewater treatment, and boron compound salts are preferably used. For example, sodium borate, sodium borofluoride, magnesium borofluoride and the like can be mentioned.
但し、上記方法は、ガラス体や酸化アルミニウム・酸化マグネシウムなどの金属酸化物の粒子界面のみを親水性にする効果しか得られず、これだけではポリイミド等の樹脂を親水化してプラス側に帯電させることはできない。 However, the above method can only obtain the effect of making only the particle interface of glass oxide or metal oxide such as aluminum oxide / magnesium oxide hydrophilic, and this only makes the resin such as polyimide hydrophilic and charges it to the plus side. I can't.
そこで、従来のコンディショナーであるトリエタノールアミンなどのアミン系界面活性剤を併用すれば、スルーホール内すべての組成物質をPd−Snコロイドが吸着できる表面状態にすることができる。 Thus, when an amine surfactant such as triethanolamine, which is a conventional conditioner, is used in combination, all the composition substances in the through hole can be brought into a surface state on which the Pd—Sn colloid can be adsorbed.
すなわち、アミン系界面活性剤を主成分とするコンディショニング工程を、ジオール類を主成分とするコンディショニング工程に組み合わせることにより、Pd−Snコロイドを吸着し易い処理を行なうことができる。
このことから、
1) まず、従来のコンディショナーであるアミン系界面活性剤による第1のコンディショニング工程で、ポリイミド等の樹脂を親水化しプラス側に帯電させる。
That is, by combining the conditioning step mainly containing an amine surfactant with the conditioning step mainly containing a diol, a treatment that easily adsorbs the Pd—Sn colloid can be performed.
From this,
1) First, in a first conditioning process using an amine surfactant, which is a conventional conditioner, a resin such as polyimide is made hydrophilic and charged positively.
2) 次いで水洗の後、ジオール類の水溶液による第2のコンディショニング工程で、フィラー物質の親水化を行なう。 2) Next, after washing with water, the filler material is hydrophilized in a second conditioning step with an aqueous solution of diols.
3) この2段階のコンディショニング工程の後、従来方法にしたがって無電解メッキまでの工程を行なう。 3) After the two-stage conditioning process, the process up to electroless plating is performed according to the conventional method.
なお、アミン系界面活性剤とジオール類とを混ぜて、一度にコンディショニングを行なうこともできなくはないが、アミン系界面活性剤が効率よく反応するためのpHが12〜13であるのに対して、ジオール類での親水化の有効pH領域が9〜11であるため、好ましくない。また、先にジオール類の親水化を行なうと、アミン系界面活性剤によってジオール類が除去されてしまうため、上記順序で別々に行なうことが好ましい。 In addition, although it is not impossible to mix amine surfactant and diol and perform conditioning at once, the pH for amine surfactant to react efficiently is 12-13. In addition, the effective pH range for hydrophilization with diols is 9 to 11, which is not preferable. In addition, if the diols are hydrophilized first, the diols are removed by the amine-based surfactant.
上記の知見の結果、第1および第2のコンディショニング工程を下記のように行なうことが最適であることが分った。 As a result of the above findings, it has been found that it is optimal to perform the first and second conditioning steps as follows.
第1のコンディショニング工程は、アミン系界面活性剤を用いて処理を行なう。この第1のコンディショニング工程で使用されるアミン系界面活性剤には、トリエタノールアミン、2−アミノエタノールなどのうちのどれか一つ、あるいは2種類が使用され、アミン系界面活性剤水溶液としての濃度は0.04〜0.16モル/リットルで管理される。液温は50〜60℃が好ましく、この溶液中に被処理物が60〜300秒浸漬される。 In the first conditioning step, treatment is performed using an amine surfactant. As the amine surfactant used in the first conditioning step, one or two of triethanolamine, 2-aminoethanol and the like are used, and the amine surfactant aqueous solution is used as the amine surfactant aqueous solution. The concentration is controlled at 0.04 to 0.16 mol / liter . The liquid temperature is preferably 50 to 60 ° C., and the object to be treated is immersed in this solution for 60 to 300 seconds.
水洗の後、ジオール類を用いる第2のコンディショニング工程となる。この第2のコンディショニング工程で使用されるジオール類には、プロピレングリコール、トリメチレングリコール、ジメチレングリコールなどのうちのどれか一つ、あるいは2種類以上が使用され、水溶液としての濃度は0.05〜0.20モル/リットルで管理される。さらにこの中に、ホウ酸ナトリウムを0.01〜0.04g/リットルになるように添加する。液温は40〜50℃が好ましく、この溶液中に被処理物が60〜720秒浸漬される。 After the water washing, the second conditioning process using diols is performed. As the diol used in the second conditioning step, one or more of propylene glycol, trimethylene glycol, dimethylene glycol and the like are used, and the concentration as an aqueous solution is 0.05. Managed at ~ 0.20 mol / liter . Furthermore, sodium borate is added to this so that it may become 0.01-0.04 g / liter. The liquid temperature is preferably 40 to 50 ° C., and the object to be treated is immersed in this solution for 60 to 720 seconds.
そして水洗の後、従来通りの無電解メッキ工程を経て、プリント基板のスルーホール導通を得ることができる。その際、パラジウム(Pd)、スズ(Sn)コロイド触媒をより効率的に吸着させることができる。 After washing with water, through-hole conduction of the printed circuit board can be obtained through a conventional electroless plating process. At that time, palladium (Pd) and tin (Sn) colloidal catalyst can be adsorbed more efficiently.
このような2段階のコンディショニング処理を行ってから、2年以上に亘り1日当り3000シート処理のモニタリング期間中、一度もボイドが発生しなかった。 No void was generated during the monitoring period of 3000 sheets per day for 2 years or more after the two-stage conditioning process.
図1におけるスルーホールの壁面11、図2におけるスルーホールの壁面12は、図3のそれと対比すれば分るように、ともに一様に滑らかであり、ボイドのない状態を示している。このように、本発明によるコンディショニング処理方法はスルーホールの壁面処理に有効性である。 The wall surface 11 of the through hole in FIG. 1 and the wall surface 12 of the through hole in FIG. 2 are both uniformly smooth and free of voids, as can be seen from the comparison with that in FIG. As described above, the conditioning method according to the present invention is effective for the wall treatment of the through hole.
1 ボイド発生箇所、2 ポリイミド樹脂部分、3 ガラス体、
4 フィラー物質、5 エグレ発生箇所、
11,12 スルーホール壁面。
1 Void generation place 2 Polyimide resin part 3 Glass body
4 Filler substance, 5 Aegle occurrence point,
11, 12 Through hole wall surface.
Claims (7)
前処理となる被処理物のコンディショニング工程を、
アミン系界面活性剤を主成分とする水溶液に被処理物を浸漬する第1コンディショニング工程と、
ジオール類を主成分とする水溶液に被処理物を浸漬する第2コンディショニング工程と
の2段階で行なうことを特徴とする、プリント基板の製造方法。 In the method for manufacturing a printed circuit board, in which a metal conductor for interlayer connection is formed by performing electroless plating on the through hole of the multilayer flexible printed circuit board,
The conditioning process for the pre-treatment object
A first conditioning step of immersing the object to be treated in an aqueous solution containing an amine-based surfactant as a main component;
A method for producing a printed circuit board, comprising: a second conditioning step in which an object to be treated is immersed in an aqueous solution containing diol as a main component.
前記アミン系界面活性剤には、トリエタノールアミン、2−アミノエタノールのうちの1または2種類を用いることを特徴とするプリント基板の製造方法。 In the manufacturing method of the printed circuit board of Claim 1,
1 or 2 types of triethanolamine and 2-aminoethanol are used for the said amine type surfactant, The manufacturing method of the printed circuit board characterized by the above-mentioned.
前記アミン系界面活性剤の水溶液としての濃度は、0.04〜0.16モル/リットルであることを特徴とするプリント基板の製造方法。 In the manufacturing method of the printed circuit board of Claim 2,
The method for producing a printed circuit board, wherein the concentration of the amine surfactant as an aqueous solution is 0.04 to 0.16 mol / liter .
前記アミン系界面活性剤の水溶液の液温は50〜60℃とし、この水溶液中に60〜300秒浸漬することを特徴とするプリント基板の製造方法。 In the manufacturing method of the printed circuit board of Claim 2,
The method for producing a printed circuit board, wherein the temperature of the aqueous solution of the amine surfactant is 50 to 60 ° C., and the aqueous solution is immersed in the aqueous solution for 60 to 300 seconds.
前記ジオール類には、プロピレングリコール、トリメチレングリコール、ジメチレングリコールのうちの少なくとも1種類を用いるとともに、ジオール類水溶液にはホウ酸ナトリウムを添加することを特徴とするプリント基板の製造方法。 In the manufacturing method of the printed circuit board of Claim 1,
A method for producing a printed circuit board, wherein at least one of propylene glycol, trimethylene glycol, and dimethylene glycol is used as the diol, and sodium borate is added to the aqueous diol solution .
前記ジオール類の水溶液としての濃度は、0.05〜0.20モル/リットルであり、ホウ酸ナトリウムの濃度は0.01〜0.04g/リットルであることを特徴とするプリント基板の製造方法。 In the manufacturing method of the printed circuit board of Claim 5,
The concentration of the diol as an aqueous solution is 0.05 to 0.20 mol / liter , and the concentration of sodium borate is 0.01 to 0.04 g / liter. .
前記ジオール類の水溶液の液温は40〜50℃とし、この水溶液中に60〜720秒浸漬することを特徴とするプリント基板の製造方法。 In the manufacturing method of the printed circuit board of Claim 5,
The method for producing a printed circuit board, wherein the temperature of the aqueous solution of the diol is 40 to 50 ° C., and the solution is immersed in the aqueous solution for 60 to 720 seconds.
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JP6327463B2 (en) * | 2013-10-09 | 2018-05-23 | 日立化成株式会社 | Manufacturing method of multilayer wiring board |
JP6350064B2 (en) * | 2013-10-09 | 2018-07-04 | 日立化成株式会社 | Manufacturing method of multilayer wiring board |
JP6350062B2 (en) * | 2013-10-09 | 2018-07-04 | 日立化成株式会社 | Manufacturing method of multilayer wiring board |
JP2015088710A (en) * | 2013-11-01 | 2015-05-07 | 日本酢ビ・ポバール株式会社 | Etchant, liquid additive agent for etchant, uneven substrate and method for manufacturing uneven substrate, and solar battery |
CN105430927B (en) * | 2015-12-29 | 2017-12-26 | 潍坊学院 | A kind of method and apparatus of printed circuit board chemical palladium-plating |
JP7387326B2 (en) | 2019-08-02 | 2023-11-28 | 上村工業株式会社 | Pretreatment method for electroless plating and pretreatment solution for electroless plating |
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CN105517348B (en) * | 2015-11-27 | 2018-04-06 | 上海英内物联网科技股份有限公司 | The preparation method of copper facing aluminium base FPC |
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