JP4595096B2 - Method for forming fine through holes in aluminum foil, corrosion solution for the method, and aluminum foil having fine through holes - Google Patents
Method for forming fine through holes in aluminum foil, corrosion solution for the method, and aluminum foil having fine through holes Download PDFInfo
- Publication number
- JP4595096B2 JP4595096B2 JP01968499A JP1968499A JP4595096B2 JP 4595096 B2 JP4595096 B2 JP 4595096B2 JP 01968499 A JP01968499 A JP 01968499A JP 1968499 A JP1968499 A JP 1968499A JP 4595096 B2 JP4595096 B2 JP 4595096B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum foil
- holes
- micro
- corrosion
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims description 83
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 82
- 239000011888 foil Substances 0.000 title claims description 77
- 238000000034 method Methods 0.000 title claims description 28
- 238000005260 corrosion Methods 0.000 title claims description 23
- 230000007797 corrosion Effects 0.000 title claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 239000003518 caustics Substances 0.000 claims 1
- 230000004580 weight loss Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 chlorine ions Chemical class 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Landscapes
- ing And Chemical Polishing (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、アルミニウム箔に微小貫通孔を形成させる方法、該方法のための腐食用液及び微小貫通孔を有するアルミニウム箔に関する。
【0002】
【従来の技術】
従来より、アルミニウム箔に多数の微小貫通孔を形成させ、得られるアルミニウム箔を各種粉末等の担持体等として利用する試みはなされている。この微小貫通孔を形成させる方法としては、化学的手段や機械的手段が知られている。化学的手段としては、金属アルミニウムが酸及びアルカリ水溶液によって腐食される性質を利用して、例えば酸及びアルカリに耐え得るフォトレジストにてアルミニウム箔表面を被覆し、該マスクを介して露光、現像し、次いで酸又はアルカリ処理して、非マスク部分を腐食させて所望の貫通孔を形成させ、最終的にレジストを剥離する手段が知られている。機械的手段としては、パンチングやレーザー光線照射等による穿孔が知られている。
【0003】
しかしながら、従来の化学的及び機械的手段は、いずれも高価な装置を要したり、煩雑な操作を要する不利がある。しかも、之等方法により形成される貫通孔は、通常、アルミニウム箔に対して垂直方向に貫通しており、同一径を有しており、しかも規則正しく配列される。かかる規則正しく配列された同一孔径の直線上貫通孔を有するアルミニウム箔は、ある種の用途には有効であるが、用途によっては必ずしもかかる貫通孔は要求されず、むしろ各種粉末等を担持するための担持体としての用途等では、不規則、不均一な孔径、形状の多数の微小貫通孔を有する、空隙密度の高いものが要求される。
【0004】
【発明が解決しようとする課題】
本発明の目的は、上記従来の化学的手段及び機械的手段によっては、形成できない不規則不均一な孔径、形状の多数の微小貫通孔を設けたアルミニウム箔及びその製造技術を提供することにある。
【0005】
【課題を解決するための手段】
本発明者らは上記目的より鋭意研究を重ねる過程において、アルミニウム箔の酸による腐食は、本来アルミニウム箔全体に亘って区別なく同時に進行するが、かかる腐食をアルミニウム箔を構成する金属成分に対して部分的に行なうことができれば、上記目的に合致する微小貫通孔が形成できるとの着想から、更に引き続き研究を重ねた。その結果、上記腐食を行なわせる酸液にある種の界面活性剤を添加存在させるときには、該腐食用液との接触によってアルミニウム箔が不規則不均一に部分的に腐食され、かくして目的とする微小貫通孔が形成されるという事実を見出した。本発明はかかる知見を基礎として完成されたものである。
【0006】
本発明によれば、アルミニウム箔に微小貫通孔を形成させるための腐食用液であって、無機酸及び有機酸から選択される少なくとも1種の酸、無機塩素化合物及びノニオン系界面活性剤を有効成分として含有することを特徴とするアルミニウム箔腐食用液が提供される。
【0007】
本発明に係わるアルミニウム箔腐食用液は、より好ましくは、酸の含有量が1.0重量%以上、無機塩素化合物の含有量が塩素イオン濃度換算で3.5〜70g/l及びノニオン系界面活性剤の含有量が0.05〜10g/lである。
【0008】
また、本発明によれば、アルミニウム箔を上記アルミニウム箔腐食用液と接触させることを特徴とするアルミニウム箔に微小貫通孔を形成させる方法、より好適には、アルミニウム箔がJISH4160に規定される合金番号1085から8079に属するものである上記方法及び接触が、アルミニウム箔を40〜70℃程度の温度条件下、10〜120秒間程度腐食用液中に浸漬することにより行なわれる上記方法が提供される。
【0009】
更に、本発明によれば、上記方法により得られ、不均一な多数の微小貫通孔が形成されており且つ該微小貫通孔の形成による重量減少が10〜60重量%である微小貫通孔を有するアルミニウム箔が提供される。
【0010】
【発明の実施の形態】
本発明に係わる微小貫通孔を有するアルミニウム箔は、従来例を見ない特有の構造、即ち不均一な孔径、形状の多数の微小貫通孔を有する形態、より具体的には不規則な孔径、形状の網目を有するいわゆるメッシュ状形態を有している。従って、これは、例えば各種粉末等の担持体として有効である。
【0011】
該微小貫通孔を有するアルミニウム箔は、本発明に係わるアルミニウム箔腐食用液の利用により容易に製造できる。以下この腐食用液につき詳述する。
【0012】
本発明腐食用液において、第一の有効成分とする酸は、無機酸及び有機酸から選択することができる。かかる酸はアルミニウムの腐食し得ること、即ち金属アルミニウムに作用してこれをイオン化できることを前提として、特に限定されるものではなく、現在知られているおよそ全ての酸がこれに包含される。
【0013】
好ましく利用できる無機酸の具体例としては、例えば硫酸、硝酸、塩酸、リン酸等を挙げることができる。之等の無機酸は、比較的少量の使用で、短時間に目的とする腐食を速やかに行なうことができ、コスト的にも安価であるため好ましい。特にかかる無機酸の内では、硫酸、リン酸等が、使用される条件下において気化等による損失や環境問題を伴うおそれが少ないため、より好ましい。また、有機酸の好ましい具体例としては、例えば蟻酸、酢酸、蓚酸、クエン酸、メタンスルホン酸、フェノールスルホン酸等のカルボン酸類及びスルホン酸類を挙げることができる。上記酸は通常その1種を単独で用いられるが、勿論、2種以上を併用することも可能である。之等の酸は水溶液形態で本発明腐食用液に用いられる。
【0014】
その使用量(濃度)は、これが上記アルミニウム箔の腐食作用を発揮できる限り特に限定されない。上記濃度の下限は、通常約1重量%とされるのがよい。該濃度の上限は、飽和濃度であり、これは利用する酸の種類に応じてそれぞれ異なっている。取扱性や気化による環境に対する危険性等を考慮すると、上記濃度の上限は、硫酸では45重量%、リン酸では50重量%、塩酸では28重量%、硝酸では35重量%、各種有機酸では40重量%程度(又はそれ以下の飽和濃度を有するものではその飽和濃度)とするのが好ましい。
【0015】
本発明腐食用液において、第2の有効成分とする無機塩素化合物は、その塩素イオンが、上記酸によるアルミニウム箔の腐食によって生じるアルミニウムイオンを液中に安定に保持(溶液化)し、該液中にアルミニウム沈殿物の析出を防止する作用を奏し得る。かかる無機塩化合物には、例えば塩化リチウム、塩化ナトリウム、塩化カリウム等のアルカリ金属の塩化物;塩化バリウム、塩化マグネシウム、塩化カルシウム等のアルカリ土類金属の塩化物;塩化鉄等が包含される。但し、之等の無機塩素化合物は、第一の必須成分とする酸との併用によっても沈殿を生じるおそれのないものから選択される必要がある。このことを考慮すると、特に上記の内でも塩化ナトリウム、塩化カリウム等の利用が好ましい。
【0016】
上記無機塩素化合物の使用量は、塩素イオン濃度換算で3.5〜70g/lの範囲、より好ましくは10〜50g/lの範囲から選ばれるのが適当である。これはモル濃度では約0.1〜2.0モル/lの範囲に相当する。該使用量範囲を下回る使用量では、アルミニウム箔の腐食速度が遅くなりすぎて、実用的でなくなる不利がある。逆に上回る使用量では液中に不溶解物が析出して、アルミニウム箔の腐食が停止する不具合が生じるおそれがある。
【0017】
第3の有効成分とするノニオン系界面活性剤は、アルミニウム箔のある部分のみを腐食させ、微小貫通孔を形成させるために必須のものである。このノニオン系界面活性剤の利用によって、本発明所期の微小貫通孔が形成される理由は、明らかではないが、おそらく該界面活性剤がアルミニウム箔表面の特定部分に吸着し、該部分の上記酸による腐食を抑制するためと考えられる。
【0018】
上記ノニオン系界面活性剤は、本発明腐食用液中でも安定な、適当な耐酸性を有するものから選ばれる。該界面活性剤には、例えばアルキルポリオキシエチレンエーテル型、アルキルポリオキシエチレンポリオキシプロピレンエーテル型のものが包含される。之等の内では特にアルキルフェノールや高級アルコールのエチレンオキサイド及び/又はプロピレンオキサイド付加物が好適である。また、好ましい界面活性剤は、アルミニウム箔を処理する温度条件に応じて適宜選択することができ、通常60℃以上の雲点、より好ましくは80℃以上の雲点を有しているのがよい。
【0019】
上記界面活性剤の使用量は、0.05〜10g/l、より好ましくは0.1〜5g/lの範囲から選択できる。該範囲を下回る量の利用では、本発明の目的とする選択的腐食による微小貫通孔の形成は困難となり、アルミニウム箔全体が均一に腐食される結果となる。逆に上記範囲を上回る量で用いる場合は、腐食速度を遅延させるだけでなく、アルミニウム箔全体が徐々に腐食され、同様に微小貫通孔の形成は困難となる。
【0020】
本発明腐食用液は、上記特定の3成分を混合、又は更に水を配合することにより容易に調製できる。
【0021】
かくして得られる本発明腐食用液は、これとアルミニウム箔とを接触させることによって、アルミニウム箔に所望の微小貫通孔を形成させ得る。本発明はかかる方法をも提供するものである。以下、本発明方法につき詳述する。
【0022】
本発明方法において被処理対象とするアルミニウム箔は、通常のアルミニウム箔であることができる。その具体例としては、例えばJISH4160に規定されている合金番号1085から8079に属するものを例示できる。特に被処理対象として好ましいアルミニウム箔は、比較的鉄成分含量の多い例えば合金番号8021や8079のものである。之等アルミニウム箔の厚さは、特に限定されるものではないが、通常0.005〜0.1mm程度であるのが普通である。本発明方法の適用できる特に好ましい厚さとしては、0.01〜0.05mm程度を挙げることができる。
【0023】
本発明方法は、本発明腐食用液とアルミニウム箔とが接触する限り、特にその接触方法に限定はない。該方法は、単に本発明腐食用液中にアルミニウム箔を浸漬する方法によることもでき、また、例えばアルミニウム箔に本発明腐食用液を噴霧、塗布する方法によることもできる。上記浸漬法も、バッチ法及び連続法のいずれによってもよい。尚、バッチ法の場合、予め本発明腐食用液中の各成分濃度を比較的高めに設定した液を用いるのが好ましく、連続法では、同各成分濃度を比較的低めに設定して、連続運転中適宜各成分を補給するのが好ましい。
【0024】
上記接触時の条件は、本発明腐食用液を構成する各成分の種類や濃度、接触時間、被処理対象とするアルミニウム箔の厚さ等に応じて、適宜決定することができる。好ましい接触時の温度及び時間条件としては、例えば厚さ0.02mmのアルミニウム箔を例にとれば、該アルミニウム箔を、本発明腐食用液中に、液温40〜70℃程度下で約10〜120秒間浸漬する条件を採用することができる。上記条件はまた、浸漬時に本発明腐食用液を攪拌したり、アルミニウム箔を揺動する操作等を採用することによって、適宜変更(緩和)することができる。本発明方法では勿論かかる液の攪拌操作や被処理アルミニウム箔の揺動操作を適宜採用することができる。
【0025】
かくして、本発明所期の微小貫通孔を有するアルミニウム箔を製造することができる。
【0026】
得られる処理アルミニウム箔は、不均一な多数の微小貫通孔が形成された構造を有しており、該貫通孔の直径は、一般には約20〜200μmの範囲にある。また、該処理アルミニウム箔は、処理前の重量より10〜60%の重量減少が認められる。即ち、該アルミニウム箔は重量でその10〜60%の部分が微小貫通孔となっている。
【0027】
上記処理アルミニウム箔に認められる微小貫通孔は、従来知られているレジスト法や機械的加工によって得られるそれらと比較して、各孔の径が不均一であること、各孔がアルミニウム箔に対して垂直方向に直線的に形成されるのではなくて、アルミニウム箔全般にわたって迷走的に形成されていることによって特徴付けられる。本発明はかかる特有の微小貫通孔を有するアルミニウム箔をも提供するものである。
【0028】
本発明に係わるアルミニウム箔は、上記特有の微小貫通孔を有する特徴を利用して、通常の各種粉体の担持体として利用することができる。特にこれはアルミニウム箔であることより、導電性の担持体として利用できる。また、これを常法に従いアルマイト処理すれば、非導電性の担持体として利用することもできる。
【0029】
【実施例】
以下、本発明を更に詳しく説明するため、実施例を挙げる。
実施例1〜6及び比較例1〜2
JISH4160に規定される合金番号8079のアルミニウム箔(厚さ0.02mm)を、10cm×10cm切り取って試料とした。
【0030】
予め上記試料の重量を測定し、その後、前処理として該試料を硫酸100ml/l中に「トップアルクリーンSO−4」(奥野製薬工業株式会社製、界面活性剤系脱脂剤)を20ml/l添加した液中に30℃下に5分間浸漬して脱脂し、その後水洗した。
【0031】
次いで、上記試料を表1に示す組成の本発明腐食用液中に、表1に示した所定温度条件下に所定時間浸漬処理した。
【0032】
尚、本発明腐食用液に用いた各薬品は全て試薬級のものであり、ノニオン界面活性剤としてはそれぞれ次のものを用いた。
界面活性剤a…「エマルゲン911」(花王株式会社製、ノニルフェノールのエチレンオキサイド付加物、雲点:74℃)
界面活性剤b…「アデカトールLA−875」(旭電化工業株式会社製、ラウリルアルコールのエチレンオキサイド付加物、雲点:70℃)
かくして、本発明の微小貫通孔を有するアルミニウム箔を得た。
【0033】
得られた処理アルミニウム箔について、その微小貫通孔の形状を目視観察し、微小貫通孔が形成されているものを○、微小貫通孔が形成できないもの又はアルミニウム箔全体が腐食溶出したものを×として評価した結果、及びその重量減少率を測定、算出した結果を、表1に併記する。
【0034】
【表1】
【0035】
また、得られた本発明アルミニウム箔の顕微鏡写真(倍率:×50)を、図1に示す。該図において、黒色部分が形成された微小貫通孔を示している。
【0036】
上記表1及び図1より、本発明処理アルミニウム箔は、不均一な孔径の多数の微小貫通孔が迷走的に形成された特有の構造を有することが明らかであり、このことから各種粉体等の担持体として有用であることが判る。
【図面の簡単な説明】
【図1】本発明に係わる微小貫通孔を有するアルミニウム箔(金属組織)を撮影した図面に代わる顕微鏡写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming fine through holes in an aluminum foil, a corrosive solution for the method, and an aluminum foil having fine through holes.
[0002]
[Prior art]
Conventionally, attempts have been made to form a large number of fine through holes in an aluminum foil and to use the obtained aluminum foil as a carrier for various powders. Chemical means and mechanical means are known as methods for forming these micro through-holes. As a chemical means, utilizing the property that metal aluminum is corroded by an acid and alkali aqueous solution, for example, the surface of the aluminum foil is coated with a photoresist that can withstand acid and alkali, and then exposed and developed through the mask. Then, an acid or alkali treatment is performed to corrode the non-mask portion to form a desired through hole, and finally a means for stripping the resist is known. As mechanical means, punching by punching or laser beam irradiation is known.
[0003]
However, the conventional chemical and mechanical means both have the disadvantage of requiring expensive equipment and complicated operations. Moreover, the through holes formed by this method usually penetrate in the vertical direction with respect to the aluminum foil, have the same diameter, and are regularly arranged. Such an aluminum foil having regularly arranged through-holes with the same hole diameter is effective for certain applications, but is not necessarily required for some applications, but rather for supporting various powders and the like. For use as a carrier, a material having a large void density having a large number of minute through-holes having irregular, non-uniform pore diameters and shapes is required.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an aluminum foil provided with a large number of micro through-holes having irregular and nonuniform pore diameters and shapes that cannot be formed by the conventional chemical means and mechanical means, and a manufacturing technique thereof. .
[0005]
[Means for Solving the Problems]
In the process in which the present inventors have conducted earnest research for the above purpose, the corrosion of the aluminum foil by acid proceeds simultaneously without distinction over the entire aluminum foil, but such corrosion is applied to the metal components constituting the aluminum foil. The research continued further from the idea that if it can be performed partially, a micro through hole meeting the above purpose can be formed. As a result, when a certain type of surfactant is added to the acid solution that causes the corrosion, the aluminum foil is irregularly and unevenly partially corroded by contact with the corrosive solution, and thus the desired microscopic amount is obtained. We have found the fact that through holes are formed. The present invention has been completed based on such knowledge.
[0006]
According to the present invention, a corrosion liquid for forming micro through-holes in an aluminum foil, which is effective at least one acid selected from inorganic acids and organic acids, inorganic chlorine compounds, and nonionic surfactants An aluminum foil corrosive liquid characterized by containing as a component is provided.
[0007]
More preferably, the aluminum foil corrosion solution according to the present invention has an acid content of 1.0% by weight or more, an inorganic chlorine compound content of 3.5 to 70 g / l in terms of chloride ion concentration, and a nonionic interface. The activator content is 0.05 to 10 g / l.
[0008]
Further, according to the present invention, the aluminum foil is brought into contact with the above-mentioned solution for corroding the aluminum foil, and the method for forming fine through holes in the aluminum foil, more preferably, the aluminum foil is an alloy specified in JISH4160. The above method and the contact belonging to the numbers 1085 to 8079 are provided by immersing the aluminum foil in a corrosive solution for about 10 to 120 seconds under a temperature condition of about 40 to 70 ° C. .
[0009]
Furthermore, according to the present invention, there are a plurality of non-uniform micro through-holes obtained by the above method, and the micro through-holes having a weight reduction of 10 to 60% by weight due to the formation of the micro through-holes. An aluminum foil is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The aluminum foil having minute through holes according to the present invention has a unique structure not seen in the prior art, that is, a form having a large number of minute through holes having a nonuniform hole diameter and shape, more specifically, an irregular hole diameter and shape. It has what is called a mesh-like form having a mesh. Therefore, this is effective as a carrier for various powders, for example.
[0011]
The aluminum foil having the minute through holes can be easily produced by using the aluminum foil corroding liquid according to the present invention. The corrosive liquid will be described in detail below.
[0012]
In the corrosion solution of the present invention, the acid as the first active ingredient can be selected from inorganic acids and organic acids. Such an acid is not particularly limited, provided that it can corrode aluminum, that is, it can act on metal aluminum and ionize it, and includes almost all acids currently known.
[0013]
Specific examples of inorganic acids that can be preferably used include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and the like. These inorganic acids are preferred because they can be used in a relatively short amount of time and can rapidly perform the desired corrosion in a short time, and are inexpensive. Among such inorganic acids, sulfuric acid, phosphoric acid and the like are more preferable because they are less likely to cause loss due to vaporization and environmental problems under the conditions used. Specific examples of the organic acid include carboxylic acids such as formic acid, acetic acid, succinic acid, citric acid, methanesulfonic acid, and phenolsulfonic acid, and sulfonic acids. The above acids are usually used alone, but of course, two or more can be used in combination. These acids are used in the corrosive liquid of the present invention in the form of an aqueous solution.
[0014]
The amount used (concentration) is not particularly limited as long as it can exert the corrosive action of the aluminum foil. The lower limit of the concentration is usually about 1% by weight. The upper limit of the concentration is a saturated concentration, which varies depending on the type of acid used. Considering the handling properties and environmental hazards due to vaporization, the upper limit of the concentration is 45% by weight for sulfuric acid, 50% by weight for phosphoric acid, 28% by weight for hydrochloric acid, 35% by weight for nitric acid, and 40% for various organic acids. It is preferable that the concentration be about% by weight (or the saturation concentration in the case of having a saturation concentration below that).
[0015]
In the corrosive liquid of the present invention, the inorganic chlorine compound as the second active ingredient is such that the chlorine ions stably hold (solution) the aluminum ions generated by the corrosion of the aluminum foil by the acid. The effect | action which prevents precipitation of an aluminum precipitate inside can be show | played. Such inorganic salt compounds include, for example, alkali metal chlorides such as lithium chloride, sodium chloride and potassium chloride; alkaline earth metal chlorides such as barium chloride, magnesium chloride and calcium chloride; iron chloride and the like. However, these inorganic chlorine compounds need to be selected from those which do not cause precipitation even when used in combination with an acid as the first essential component. Considering this, it is particularly preferable to use sodium chloride, potassium chloride and the like among the above.
[0016]
The amount of the inorganic chlorine compound used is suitably selected from the range of 3.5 to 70 g / l, more preferably 10 to 50 g / l in terms of chlorine ion concentration. This corresponds to a range of about 0.1 to 2.0 mol / l in molar concentration. If the amount is less than the above range, the corrosion rate of the aluminum foil becomes too slow, which is disadvantageous in that it is not practical. On the other hand, when the amount used is larger than that, insoluble substances may be deposited in the liquid, which may cause a problem that the corrosion of the aluminum foil stops.
[0017]
The nonionic surfactant as the third active ingredient is indispensable for corroding only a certain portion of the aluminum foil and forming micro through holes. The reason for the formation of the micro through hole of the present invention is not clear by the use of this nonionic surfactant, but the surfactant probably adsorbs to a specific part of the surface of the aluminum foil and This is considered to suppress acid corrosion.
[0018]
The nonionic surfactant is selected from those having suitable acid resistance that is stable even in the corrosive liquid of the present invention. Examples of the surfactant include alkyl polyoxyethylene ether type and alkyl polyoxyethylene polyoxypropylene ether type. Among these, alkylphenols and higher alcohol ethylene oxide and / or propylene oxide adducts are particularly suitable. Further, a preferable surfactant can be appropriately selected according to the temperature condition for treating the aluminum foil, and usually has a cloud point of 60 ° C. or higher, more preferably a cloud point of 80 ° C. or higher. .
[0019]
The amount of the surfactant used can be selected from the range of 0.05 to 10 g / l, more preferably 0.1 to 5 g / l. If the amount is less than the above range, it is difficult to form micro through-holes by the selective corrosion targeted by the present invention, resulting in uniform corrosion of the entire aluminum foil. Conversely, when used in an amount exceeding the above range, not only the corrosion rate is delayed, but also the entire aluminum foil is gradually corroded, and it is difficult to form micro through holes.
[0020]
The corrosive liquid of the present invention can be easily prepared by mixing the above three specific components or further blending water.
[0021]
The corrosive liquid of the present invention thus obtained can form desired micro through-holes in the aluminum foil by bringing it into contact with the aluminum foil. The present invention also provides such a method. Hereinafter, the method of the present invention will be described in detail.
[0022]
The aluminum foil to be treated in the method of the present invention can be a normal aluminum foil. Specific examples thereof include those belonging to alloy numbers 1085 to 8079 defined in JISH4160. Particularly preferable aluminum foils to be treated are those having relatively high iron content, for example, alloy numbers 8021 and 8079. The thickness of the aluminum foil is not particularly limited, but is usually about 0.005 to 0.1 mm. A particularly preferable thickness to which the method of the present invention can be applied is about 0.01 to 0.05 mm.
[0023]
The method of the present invention is not particularly limited as long as the corrosion solution of the present invention and the aluminum foil are in contact with each other. The method may be simply a method of immersing the aluminum foil in the corrosive liquid of the present invention, or may be a method of spraying and applying the corrosive liquid of the present invention to an aluminum foil, for example. The immersion method may be either a batch method or a continuous method. In the case of the batch method, it is preferable to use a solution in which the concentration of each component in the corrosion liquid of the present invention is set to be relatively high in advance. In the continuous method, the concentration of each component is set to be relatively low, and It is preferable to replenish each component as appropriate during operation.
[0024]
The contact conditions can be appropriately determined according to the type and concentration of each component constituting the corrosion solution of the present invention, the contact time, the thickness of the aluminum foil to be treated, and the like. As a preferable temperature and time condition at the time of contact, for example, when an aluminum foil having a thickness of 0.02 mm is taken as an example, the aluminum foil is about 10 to 10 at a liquid temperature of about 40 to 70 ° C. in the corrosion solution of the present invention. Conditions for immersing for ˜120 seconds can be employed. The above conditions can also be changed (relaxed) as appropriate by stirring the corrosive liquid of the present invention at the time of immersion or adopting an operation of swinging the aluminum foil. In the method of the present invention, of course, such a liquid stirring operation and a swinging operation of the aluminum foil to be treated can be appropriately employed.
[0025]
Thus, an aluminum foil having the minute through-holes according to the present invention can be manufactured.
[0026]
The obtained treated aluminum foil has a structure in which a large number of non-uniform micro through holes are formed, and the diameter of the through holes is generally in the range of about 20 to 200 μm. In addition, the treated aluminum foil has a weight reduction of 10 to 60% compared to the weight before the treatment. That is, the aluminum foil has 10 to 60% by weight of fine through holes.
[0027]
The fine through-holes recognized in the treated aluminum foil have a non-uniform diameter of each hole compared to those obtained by a conventionally known resist method or mechanical processing, and each hole is in comparison with the aluminum foil. Rather than being linearly formed in the vertical direction, it is characterized by being staggered over the entire aluminum foil. The present invention also provides an aluminum foil having such unique micro through holes.
[0028]
The aluminum foil according to the present invention can be used as a carrier for ordinary various powders by utilizing the characteristic features of the above-described minute through holes. In particular, since it is an aluminum foil, it can be used as a conductive carrier. Moreover, if this is anodized according to a conventional method, it can be used as a non-conductive carrier.
[0029]
【Example】
Examples are given below to illustrate the present invention in more detail.
Examples 1-6 and Comparative Examples 1-2
An aluminum foil (thickness: 0.02 mm) having an alloy number of 8079 as defined in JISH4160 was cut out as a sample by cutting 10 cm × 10 cm.
[0030]
The weight of the sample is measured in advance, and then, as a pretreatment, the sample is subjected to 20 ml / l of “Top Alclean SO-4” (manufactured by Okuno Pharmaceutical Co., Ltd., surfactant-based degreasing agent) in 100 ml / l of sulfuric acid. It was degreased by dipping in the added solution at 30 ° C. for 5 minutes, and then washed with water.
[0031]
Next, the sample was immersed in the corrosion solution of the present invention having the composition shown in Table 1 for a predetermined time under the predetermined temperature conditions shown in Table 1.
[0032]
The chemicals used in the corrosive liquid of the present invention are all reagent grade, and the following nonionic surfactants were used.
Surfactant a ... “Emulgen 911” (manufactured by Kao Corporation, nonylphenol ethylene oxide adduct, cloud point: 74 ° C.)
Surfactant b ... “Adecatol LA-875” (Asahi Denka Kogyo Co., Ltd., ethylene oxide adduct of lauryl alcohol, cloud point: 70 ° C.)
Thus, an aluminum foil having fine through holes of the present invention was obtained.
[0033]
Regarding the obtained treated aluminum foil, visually observe the shape of the micro through hole, ○ if the micro through hole is formed, x if the micro aluminum through hole cannot be formed or the aluminum foil as a whole is corroded and eluted The results of evaluation and the results of measuring and calculating the weight reduction rate are also shown in Table 1.
[0034]
[Table 1]
[0035]
Moreover, the microscope picture (magnification: x50) of the obtained aluminum foil of the present invention is shown in FIG. In the figure, a micro through-hole in which a black portion is formed is shown.
[0036]
From the above Table 1 and FIG. 1, it is clear that the treated aluminum foil of the present invention has a unique structure in which a large number of micro through-holes having non-uniform pore diameters are strayed. It can be seen that it is useful as a carrier.
[Brief description of the drawings]
FIG. 1 is a photomicrograph in place of a drawing of an aluminum foil (metal structure) having fine through holes according to the present invention.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01968499A JP4595096B2 (en) | 1999-01-28 | 1999-01-28 | Method for forming fine through holes in aluminum foil, corrosion solution for the method, and aluminum foil having fine through holes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01968499A JP4595096B2 (en) | 1999-01-28 | 1999-01-28 | Method for forming fine through holes in aluminum foil, corrosion solution for the method, and aluminum foil having fine through holes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000219978A JP2000219978A (en) | 2000-08-08 |
| JP4595096B2 true JP4595096B2 (en) | 2010-12-08 |
Family
ID=12006074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01968499A Expired - Fee Related JP4595096B2 (en) | 1999-01-28 | 1999-01-28 | Method for forming fine through holes in aluminum foil, corrosion solution for the method, and aluminum foil having fine through holes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4595096B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011124142A (en) * | 2009-12-11 | 2011-06-23 | Nippon Light Metal Co Ltd | Aluminum/resin/copper composite article, its manufacturing method, and lid member for sealed battery |
| JP5726466B2 (en) * | 2010-09-10 | 2015-06-03 | 国立大学法人東京農工大学 | Catalyst carrier, catalyst body and method for producing them |
| KR20140107467A (en) * | 2011-12-20 | 2014-09-04 | 솔베이 (차이나) 컴퍼니, 리미티드 | Use of phenol compounds as activator for metal surface corrosion |
| CN110887779A (en) * | 2019-11-28 | 2020-03-17 | 新疆众和股份有限公司 | Method for detecting initial corrosion state of high-voltage anode aluminum foil |
| TW202528241A (en) * | 2023-10-31 | 2025-07-16 | 日商三菱瓦斯化學股份有限公司 | Aluminum perforated foil manufacturing method |
-
1999
- 1999-01-28 JP JP01968499A patent/JP4595096B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000219978A (en) | 2000-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4895739A (en) | Pretreatment for electroplating process | |
| US5007990A (en) | Electroplating process | |
| US5147692A (en) | Electroless plating of nickel onto surfaces such as copper or fused tungston | |
| JP4605409B2 (en) | Surface treatment method of aluminum or aluminum alloy | |
| US4952286A (en) | Electroplating process | |
| JPH01268896A (en) | Electroplating apparatus | |
| JP6142408B2 (en) | Electrolytic stripper for jigs | |
| TW200949016A (en) | Etching solution, etching pre-treating solution and etching process for copper or copper alloy | |
| EP0520195B1 (en) | Electroplating process and composition | |
| US5484518A (en) | Electroplating process | |
| CN101098989A (en) | Copper etching solution and etching method | |
| JP4595096B2 (en) | Method for forming fine through holes in aluminum foil, corrosion solution for the method, and aluminum foil having fine through holes | |
| EP0418333A1 (en) | Composition and method for stripping tin or tin-lead alloy from copper surfaces. | |
| CN1222636C (en) | Pretreatment solution and pretreatment process of chemical nickle plating | |
| US5238550A (en) | Electroplating process | |
| US5425873A (en) | Electroplating process | |
| US5419829A (en) | Electroplating process | |
| JPS6231070B2 (en) | ||
| KR100535977B1 (en) | Electroless Plating Method Using Additive for Electroplating | |
| JP2021139015A (en) | Composition for electroless gold plating | |
| SU1763434A1 (en) | Method for treatment of dielectric before chemical copper-plating | |
| JPH03214689A (en) | Group of reduced processes for manufacturing printed circuit and composite for executing the same | |
| US6017967A (en) | Electroplating process and composition | |
| JPH05311484A (en) | Reflow tin or tin alloy plating bath | |
| KR100213470B1 (en) | Surface treatment composition of aluminum and its alloy and its treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051019 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060703 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080618 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080811 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20081203 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100831 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131001 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |