JP2016211058A - Porous metal plate and manufacturing method therefor - Google Patents
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 169
- 239000002184 metal Substances 0.000 title claims abstract description 169
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 27
- 230000001681 protective effect Effects 0.000 claims abstract description 24
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 238000005530 etching Methods 0.000 claims description 90
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 59
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 36
- 239000010936 titanium Substances 0.000 claims description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000007639 printing Methods 0.000 claims description 5
- 230000004075 alteration Effects 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 3
- 238000003486 chemical etching Methods 0.000 abstract description 36
- 230000007850 degeneration Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 47
- 230000008569 process Effects 0.000 description 16
- 238000004090 dissolution Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000007943 implant Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002341 toxic gas Substances 0.000 description 4
- 238000000866 electrolytic etching Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000008952 bacterial invasion Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003495 flagella Anatomy 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Abstract
Description
本発明は、多孔金属板及びその製造方法に関する。 The present invention relates to a porous metal plate and a method for producing the same.
近年、金属板（金属プレート）に多数の微細な貫通孔を形成したものが、医療用バリアメンブレンや生体情報計測のためのインプラント(埋入)用デバイス、化学プラント用フィルター、電池用フィルター等、医療、電池、化学、航空宇宙等の各種分野で注目されている。なかでも、チタニウムやチタニウム合金は生体親和性や耐食性に優れるとともに軽量かつ高強度であるため、医療用インプラント(埋入)材料、化学機器やフィルター用材料、航空宇宙用材料等として広い分野で注目を集めている。しかしながら、チタニウムやチタニウム合金は難加工性材料として知られており、特に微細加工が困難である。チタニウムやチタニウム合金等の金属材料に微細な貫通孔を形成する方法としては、軸径の非常に細いパンチで貫通孔をあける方法（特許文献１）、レーザー光の照射による方法（特許文献２）、エチレングリコールとアルカリ金属塩又はアルカリ土類金属塩を含む電解液を用いた電解エッチングによる方法（特許文献３）等が提案されているが、これらの方法には以下の問題があった。 In recent years, a metal plate (metal plate) with a number of fine through-holes has been developed into medical barrier membranes, implant devices for biological information measurement, chemical plant filters, battery filters, etc. It is attracting attention in various fields such as medicine, batteries, chemistry, and aerospace. In particular, titanium and titanium alloys have excellent biocompatibility and corrosion resistance, and are lightweight and strong, so they are attracting attention in a wide range of fields as medical implant (embedding) materials, chemical equipment, filter materials, aerospace materials, etc. Collecting. However, titanium and titanium alloys are known as difficult-to-process materials and are particularly difficult to finely process. As a method of forming a fine through hole in a metal material such as titanium or a titanium alloy, a method of forming a through hole with a punch having a very thin shaft diameter (Patent Document 1), or a method using laser light irradiation (Patent Document 2) In addition, a method by electrolytic etching using an electrolytic solution containing ethylene glycol and an alkali metal salt or an alkaline earth metal salt (Patent Document 3) has been proposed. However, these methods have the following problems.
機械加工である微細パンチによる精密プレス加工は金型の作製自体が非常に困難であり、貫通孔の縁にささくれが生じやすい。同じく機械加工であるマイクロドリル等の微細加工用切削工具を使用する方法は、一孔ずつ貫通孔を開けるため非常に時間がかかるとともに、貫通孔の縁にささくれが生じやすい。さらに切削工具の作製自体が非常に困難であるだけでなく、加工対象金属が切削工具へ溶着するため切削工具の寿命が短く、金属板への貫通孔の安定的な作製は困難であり、貫通孔の作製に関するコストも大きい。また、機械的な加工方法は、加工時に加えた力により金属板に残留応力が発生するため、加工後に時間経過に伴う多孔金属板の形状変化や耐食性の低下が生じる。レーザー、電子ビーム、プラズマ等を使用するドライエッチングによる方法は、熱による金属板の変質を完全に防ぐことができないため、加工により金属材料の特性が劣化し、多孔金属板の耐食性が悪化する。また、これらドライエッチングによる方法も高価な製造設備が必要となり生産コスト及び生産時間が増大する。電解エッチングによる方法は、保護膜による多孔パターンを金属板表面に形成して、保護膜のない部分（孔部）を電解エッチングして貫通孔を形成する方法であるが、金属露出面積が小さいため高電圧が必要となり多孔パターン保護膜の破壊が生じやすいほか、超音波を付与して電解液を攪拌する必要があるため、超音波の付与により電解液温度の制御が困難となる。
さらに、電解液に高濃度のエチレングリコールを含むため、保護膜にレジストを使用した場合、保護膜が溶解してしまい、高精度の加工が困難である。一方、金属材料に対する他の加工方法として化学エッチングによる方法があるが、化学エッチングでチタニウムやチタニウム合金をはじめとする様々な金属に、１００μｍ以下の微細な貫通孔を高密度で形成することは難しかった。
The precision press working by the fine punch, which is a machining process, is very difficult to manufacture the mold itself, and the edge of the through-hole is easily raised. The method using a micro-machining cutting tool such as micro drill, which is also machined, takes a very long time to open through holes one by one, and is likely to be crushed at the edges of the through holes. In addition, it is not only difficult to manufacture the cutting tool itself, but also because the metal to be processed is welded to the cutting tool, the life of the cutting tool is short, and it is difficult to stably manufacture the through hole in the metal plate. The costs associated with producing the holes are also high. Further, in the mechanical processing method, since a residual stress is generated in the metal plate due to the force applied during processing, the shape change of the porous metal plate and the corrosion resistance decrease with time after processing. The dry etching method using laser, electron beam, plasma, or the like cannot completely prevent the deterioration of the metal plate due to heat. Therefore, the properties of the metal material are deteriorated by processing, and the corrosion resistance of the porous metal plate is deteriorated. In addition, these dry etching methods also require expensive manufacturing equipment, which increases production cost and production time. The electrolytic etching method is a method of forming a through-hole by forming a porous pattern with a protective film on the surface of the metal plate and electrolytically etching a portion (hole) without the protective film, but the exposed metal area is small. Since a high voltage is required and the porous pattern protective film is easily broken, and it is necessary to stir the electrolytic solution by applying ultrasonic waves, it becomes difficult to control the temperature of the electrolytic solution by applying ultrasonic waves.
Furthermore, since a high concentration of ethylene glycol is included in the electrolytic solution, when a resist is used for the protective film, the protective film is dissolved, and high-precision processing is difficult. On the other hand, as another processing method for metal materials, there is a chemical etching method. However, it is difficult to form fine through holes of 100 μm or less at high density in various metals such as titanium and titanium alloys by chemical etching. It was.
本発明の課題は、ミクロンオーダーの貫通孔を、必要とされる配列パターンに応じて高密度に形成でき、金属板の変質及び生産コストを抑制して大面積の金属板へ貫通孔を形成できる多孔金属板の製造方法を提供することにある。また、ミクロンオーダーの貫通孔が高密度に形成され、貫通孔形成に伴う金属板の変質が抑制された多孔金属板を提供することにある。 The problem of the present invention is that micron-order through-holes can be formed with high density according to the required arrangement pattern, and through-holes can be formed on a large-area metal plate while suppressing deterioration and production costs of the metal plate. It is providing the manufacturing method of a perforated metal plate. Another object of the present invention is to provide a porous metal plate in which micron-order through-holes are formed with high density, and the metal plate is prevented from being altered due to the formation of the through-holes.
本発明者らは、金属板に孔径が１〜１００μｍというミクロンオーダーの貫通孔を高密度で安価に金属板の特性を損なうことなく形成することを目指して検討を開始した。本発明者らは、従来、金属板の表面部分の洗浄や凹凸形成のためのエッチングに使用されることが多く、ミクロンオーダーの貫通孔の形成への検討が行われていなかった化学エッチングについて検討を進めたところ、金属板の表面に、耐酸性保護膜の多孔パターンを形成し、前記多孔パターンが形成された金属板を、無機酸を含むエッチング液で化学エッチング処理することにより、化学エッチングであってもミクロンオーダーの微細な貫通孔を高密度で金属板に形成できることを見いだし、さらに難加工性材料であるチタニウム又はチタニウム合金に対しても適用可能であることを見い出したものである。 The inventors of the present invention have started investigations aiming at forming micron-order through-holes having a hole diameter of 1 to 100 μm in a metal plate at high density and low cost without impairing the properties of the metal plate. The inventors of the present invention have studied chemical etching, which has been conventionally used for etching for cleaning the surface portion of a metal plate and forming irregularities, and has not been studied for formation of micron-order through holes. As a result, a porous pattern of an acid-resistant protective film was formed on the surface of the metal plate, and the metal plate on which the porous pattern was formed was chemically etched with an etchant containing an inorganic acid. It has been found that fine through-holes on the order of microns can be formed in a metal plate at a high density, and that it can also be applied to titanium or titanium alloys that are difficult to process materials.
すなわち、本発明は以下に示す事項により特定されるものである。
（１）金属板の表面に、耐酸性保護膜の多孔パターンを形成し、無機酸を含むエッチング液で前記多孔パターンが形成された金属板を化学エッチング処理することにより、前記金属板に孔径が１〜１００μｍの貫通孔を形成することを特徴とする多孔金属板の製造方法。
（２）金属板が、チタニウム製又はチタニウム合金製の金属板であることを特徴とする上記（１）記載の多孔金属板の製造方法。
（３）エッチング液が、リン酸及び硫酸から選ばれる少なくとも一種、フッ酸並びに硝酸を含むことを特徴とする上記（１）又は（２）記載の多孔金属板の製造方法。
（４）エッチング液が、塩酸を含むことを特徴とする上記（３）記載の多孔金属板の製造方法。
（５）エッチング液が、エッチング液全体に対する重量比で、フッ酸を３〜１５％、硝酸を５〜２５％含み、リン酸及び硫酸のどちらか一方を含む場合は、リン酸又は硫酸を３０〜７０％含み、リン酸及び硫酸の両方を含む場合は、リン酸と硫酸を合計で３０〜７０％含むことを特徴とする上記（３）記載の多孔金属板の製造方法。
（６）エッチング液が、エッチング液全体に対する重量比で、塩酸を０．０１〜１５％含むことを特徴とする上記（４）又は（５）記載の多孔金属板の製造方法。
（７）多孔パターンが、フォトリソグラフ法、インクジェット法、スーパーインクジェット法、ナノインプリント法又は印刷法により形成されることを特徴とする上記（１）〜（６）のいずれか記載の多孔金属板の製造方法。
（８）隣接する貫通孔の中心間距離が４〜３００μｍである貫通孔を形成することを特徴とする上記（１）〜（７）のいずれか記載の多孔金属板の製造方法。
（９）複数の貫通孔が形成された多孔金属板であって、前記貫通孔は、耐酸性保護膜の多孔パターンを表面に形成した金属板を、無機酸を含むエッチング液で化学エッチング処理することにより形成され、孔径が１〜１００μｍであり、隣接する前記貫通孔の中心間距離が４〜３００μｍであることを特徴とする多孔金属板。
（１０）金属板が、チタニウム製又はチタニウム合金製の金属板であることを特徴とする上記（９）記載の多孔金属板の製造方法。
（１１）貫通孔の孔径が金属板の一方の面から他方の面に向けて漸減していることを特徴とする上記（９）又は（１０）記載の多孔金属板。
（１２）貫通孔の形成に伴う残留応力及び熱による変質がないことを特徴とする上記（９）〜（１１）のいずれか記載の多孔金属板。
（１３）厚さが２〜１００μｍであることを特徴とする上記（９）〜（１２）のいずれか記載の多孔金属板。
That is, the present invention is specified by the following items.
(1) By forming a porous pattern of an acid-resistant protective film on the surface of the metal plate and chemically etching the metal plate on which the porous pattern is formed with an etching solution containing an inorganic acid, the pore size of the metal plate is reduced. A method for producing a perforated metal plate, comprising forming a through hole of 1 to 100 μm.
(2) The method for producing a porous metal plate according to (1), wherein the metal plate is a metal plate made of titanium or a titanium alloy.
(3) The method for producing a porous metal plate as described in (1) or (2) above, wherein the etching solution contains at least one selected from phosphoric acid and sulfuric acid, hydrofluoric acid and nitric acid.
(4) The method for producing a porous metal plate according to the above (3), wherein the etching solution contains hydrochloric acid.
(5) When the etching solution contains 3 to 15% hydrofluoric acid, 5 to 25% nitric acid, and contains either phosphoric acid or sulfuric acid in a weight ratio to the whole etching solution, 30 phosphoric acid or sulfuric acid is added. The method for producing a perforated metal sheet according to (3) above, wherein when containing both phosphoric acid and sulfuric acid, the total content of phosphoric acid and sulfuric acid is 30 to 70%.
(6) The method for producing a porous metal plate as described in (4) or (5) above, wherein the etching solution contains 0.01 to 15% hydrochloric acid in a weight ratio with respect to the whole etching solution.
(7) The porous metal plate according to any one of (1) to (6), wherein the porous pattern is formed by a photolithographic method, an ink jet method, a super ink jet method, a nanoimprint method, or a printing method. Method.
(8) The method for producing a porous metal plate according to any one of the above (1) to (7), wherein a through-hole having a distance between centers of adjacent through-holes of 4 to 300 μm is formed.
(9) A porous metal plate in which a plurality of through holes are formed, and the through holes chemically etch a metal plate on the surface of which a porous pattern of an acid resistant protective film is formed with an etching solution containing an inorganic acid. A perforated metal plate, wherein the hole diameter is 1 to 100 μm, and the distance between the centers of the adjacent through holes is 4 to 300 μm.
(10) The method for producing a porous metal plate according to (9), wherein the metal plate is a metal plate made of titanium or a titanium alloy.
(11) The porous metal plate according to (9) or (10) above, wherein the diameter of the through hole is gradually reduced from one surface of the metal plate to the other surface.
(12) The porous metal plate according to any one of the above (9) to (11), wherein there is no alteration due to residual stress and heat accompanying the formation of the through hole.
(13) The porous metal plate according to any one of (9) to (12), wherein the thickness is 2 to 100 μm.
本発明によると、孔径が１〜１００μｍというミクロンオーダーの貫通孔を、金属板に残留応力の発生や熱の影響を与えずに、必要とされる配列パターンに応じて高密度に金属板に形成することができ、生産コストを抑制して大面積の金属板への適用が可能である多孔金属板の製造方法を提供することができる。また、本発明によると、孔径が１〜１００μｍというミクロンオーダーの貫通孔が、高密度に金属板に形成され、貫通孔の形成に伴う残留応力や熱による変質のない多孔金属板を提供することができる。 According to the present invention, micron-order through-holes having a hole diameter of 1 to 100 μm are formed on a metal plate at a high density according to a required arrangement pattern without generating residual stress or heat on the metal plate. It is possible to provide a method for producing a porous metal plate that can be applied to a large-area metal plate while suppressing production costs. In addition, according to the present invention, there is provided a perforated metal plate in which micron-order through holes having a hole diameter of 1 to 100 μm are formed in a metal plate at a high density, and there is no deterioration due to residual stress or heat accompanying the formation of the through holes. Can do.
本発明の多孔金属板の製造方法は、金属板の表面に、耐酸性保護膜の多孔パターンを形成し、無機酸を含むエッチング液で前記多孔パターンが形成された金属板を化学エッチング処理することにより、前記金属板に孔径が１〜１００μｍの貫通孔を形成することを特徴とする。本発明の製造方法における金属板は、特に限定されるものではないが、金属板を構成する金属としては、例えば、鉄、ステンレス、アルミニウム、銅、チタニウム、ニッケル、ジルコニウム、ニオブ、モリブデン、銀、タンタル、これらの合金等を挙げることができる。金属板の厚さは、特に限定されるものではないが、本発明の製造方法によると、例えば、厚さが２〜１００μｍ、あるいは２〜５０μｍ、あるいは２〜３０μｍという薄い金属板に孔径が１〜１００μｍというミクロンサイズの微細な貫通孔を高密度に形成することができ、孔径が１〜５０μｍ、あるいは１〜３０μｍという微細な貫通孔を高密度に形成することができる。本発明の製造方法は、生体親和性及び耐食性に優れ、生体インプラント（埋入）デバイス等の医療用途や化学プラント用フィルター等の化学用途など様々な用途への利用が可能であるが、難加工性の金属材料でありミクロンサイズの貫通孔の形成が難しいチタニウム又はチタニウム合金製の金属板においても、例えば、厚さが２〜１００μｍ、あるいは２〜５０μｍ、あるいは２〜３０μｍという厚さのチタニウム又はチタニウム合金製の金属板に、孔径が１〜１００μｍ、あるいは１〜５０μｍ、あるいは１〜３０μｍというミクロンサイズの微細な貫通孔を高密度に形成することができる。ここで、本発明における貫通孔の孔径とは、貫通孔の開口部が円である場合は、その直径のことであり、貫通孔の開口部が円と異なる形状の場合は、開口部の面積と同じ面積を有する円の直径（円に換算した直径）のことであり、貫通孔の一方の面の開口部と他方の面の開口部との孔径が異なる場合は、小さい方の開口部の孔径をいう。また、本発明の製造方法は、孔径が１〜１００μｍというミクロンサイズの微細な貫通孔を、例えば、その中心間距離が４〜３００μｍの間隔で、あるいは４〜１５０μｍの間隔で、あるいは４〜９０μｍの間隔で金属板に形成することができ、高密度に形成できる。そのため、例えば、１ｍｍ２あたり１５０個以上の貫通孔を形成することができる。 In the method for producing a porous metal plate of the present invention, a porous pattern of an acid-resistant protective film is formed on the surface of the metal plate, and the metal plate on which the porous pattern is formed is chemically etched with an etchant containing an inorganic acid. Thus, a through hole having a hole diameter of 1 to 100 μm is formed in the metal plate. The metal plate in the production method of the present invention is not particularly limited. Examples of the metal constituting the metal plate include iron, stainless steel, aluminum, copper, titanium, nickel, zirconium, niobium, molybdenum, silver, Examples thereof include tantalum and alloys thereof. The thickness of the metal plate is not particularly limited, but according to the manufacturing method of the present invention, for example, the hole diameter is 1 on a thin metal plate having a thickness of 2 to 100 μm, alternatively 2 to 50 μm, or 2 to 30 μm. Fine through holes having a micron size of ˜100 μm can be formed with high density, and fine through holes with a hole diameter of 1 to 50 μm or 1 to 30 μm can be formed with high density. The production method of the present invention is excellent in biocompatibility and corrosion resistance, and can be used for various applications such as medical applications such as biological implant (implantation) devices and chemical applications such as filters for chemical plants. In a metal plate made of titanium or a titanium alloy that is difficult to form a micron-sized through hole, for example, titanium or titanium having a thickness of 2 to 100 μm, or 2 to 50 μm, or 2 to 30 μm. Fine through holes having a micron size of 1 to 100 μm, 1 to 50 μm, or 1 to 30 μm can be formed in a titanium alloy metal plate at high density. Here, the hole diameter of the through hole in the present invention is the diameter when the opening of the through hole is a circle, and the area of the opening when the opening of the through hole is different from the circle. The diameter of a circle having the same area as (the diameter converted to a circle), and when the hole diameter of the opening on one surface of the through hole is different from the opening on the other surface, Refers to the pore size. In addition, the manufacturing method of the present invention allows fine through-holes having a micron size of 1 to 100 μm, for example, a center-to-center distance of 4 to 300 μm, or 4 to 150 μm, or 4 to 90 μm. It can form in a metal plate by the space | interval of, and can form in high density. Therefore, for example, 150 or more through holes can be formed per 1 mm 2 .
本発明の製造方法における耐酸性保護膜を形成する材料は、金属板の表面に多孔パターンを形成でき、酸を含むエッチング液で化学エッチングされ難いものであれば特に限定されないが、例えば、フォトレジスト等の光硬化性樹脂、ポリメタクリル酸メチル等の熱可塑性樹脂などの有機化合物、ファインセラミックス等の絶縁酸化物、カーボンナノチューブ、カーボンブラック等の炭素及び炭化物微粒固体などを挙げることができる。本発明における多孔パターンの形成方法は、特に限定されないが、例えば、フォトリソグラフ法をはじめ、インクジェット法、スーパーインクジェット法、ナノインプリント法や各種印刷法等を挙げることができ、印刷法としては、オフセット印刷法、活版印刷法等を挙げることができる。フォトリソグラフ法、インクジェット法、スーパーインクジェット法及びナノインプリント法は、孔径が１〜２０μｍの貫通孔を形成する場合に特に好適であり、印刷法は、孔径が１０〜１００μｍの貫通孔を低コストで形成する場合に特に好適である。本発明の製造方法では、金属板の表面に、耐酸性保護膜からなる多孔パターンを形成し、無機酸を含むエッチング液で、多孔パターンが形成された金属板を化学エッチング処理して、耐酸性保護膜で覆われていない金属板の露出部分（多孔パターンの孔部分）を溶解させることにより、金属板に貫通孔が形成される。 The material for forming the acid-resistant protective film in the production method of the present invention is not particularly limited as long as it can form a porous pattern on the surface of the metal plate and is difficult to be chemically etched with an acid-containing etchant. Examples thereof include organic compounds such as photocurable resins such as thermoplastic resins such as polymethyl methacrylate, insulating oxides such as fine ceramics, carbon and carbide fine solids such as carbon nanotubes and carbon black, and the like. The method for forming a porous pattern in the present invention is not particularly limited, and examples thereof include a photolithographic method, an ink jet method, a super ink jet method, a nanoimprint method, and various printing methods, and the printing method includes offset printing. Method, letterpress printing method and the like. The photolithographic method, the ink jet method, the super ink jet method, and the nanoimprint method are particularly suitable for forming a through hole having a hole diameter of 1 to 20 μm, and the printing method forms a through hole having a hole diameter of 10 to 100 μm at a low cost. This is particularly preferable. In the production method of the present invention, a porous pattern made of an acid-resistant protective film is formed on the surface of the metal plate, and the metal plate on which the porous pattern is formed is chemically etched with an etching solution containing an inorganic acid, thereby being acid-resistant. A through hole is formed in the metal plate by dissolving the exposed portion of the metal plate that is not covered with the protective film (the hole portion of the porous pattern).
本発明におけるエッチング液は、無機酸を含む。本発明における無機酸としては、特に限定されないが、例えば、塩酸、フッ酸、硫酸、硝酸、リン酸、過塩素酸等を挙げることができる。なかでも、ミクロンオーダーの貫通孔を高密度に安定して形成する観点から、リン酸及び硫酸から選ばれる少なくとも一種と、フッ酸並びに硝酸を含むことが好ましく、リン酸、硫酸、フッ酸及び硝酸を含むことがより好ましい。さらに金属板の材質によっては塩酸を加えることがより望ましい。リン酸及び硫酸は、エッチング液の比重を高め、エッチング液の粘度を増加させることができる。粘度が高いと溶解した金属イオンが液中に拡散することを阻害し、金属表面近傍に滞留する。これにより局所的に酸の濃度が低下することで過剰な金属の溶解反応が抑制される。またこれらの酸を混合することで界面活性作用も生じることから、金属溶解時に発生する水素ガスのエッチング面からの円滑な排出がしやすくなる。フッ酸及び塩酸は、各種の金属を溶解させることができ、特に、フッ酸はチタニウムやチタニウム合金を溶解させることができる。硝酸は、フッ酸と共に各種金属を溶解させることができるが、チタニウムやチタニウム合金の場合、チタニウムやチタニウム合金の表面を不動態化させることができる。この作用により、硝酸はフッ酸によるチタニウムの溶解反応を抑制し、反応を制御することができる。本発明における無機酸のエッチング液中の含有量は、特に限定されないが、リン酸及び硫酸から選ばれる少なくとも一種と、フッ酸並びに硝酸を含む場合は、エッチング液全体に対する重量比で、リン酸及び硫酸のどちらか一方を含む場合は、リン酸又は硫酸を３０〜７０％、リン酸及び硫酸の両方を含む場合は、リン酸と硫酸を合計で３０〜７０％、フッ酸を３〜１５％、硝酸を５〜２５％を含むことが好ましい。また、エッチング液の残部は水とすることができる。リン酸及び硫酸については、エッチング液の粘度が高すぎると、金属の溶解反応が極度に抑制され、処理時間が長くなるおそれがあるので、リン酸又は硫酸のエッチング液中の含有割合は、リン酸及び硫酸のどちらか一方を含む場合は、リン酸又は硫酸の含有割合として、リン酸及び硫酸の両方を含む場合は、リン酸及び硫酸の合計の含有割合として、重量比で３０〜７０％であることが好ましく、３０〜６０％であることがより好ましく、４０〜６０％であることが更に好ましい。また、リン酸と硫酸の両方を含む場合、片方の酸を１％以上含有し、合計で前記含有割合となることが好ましいが、リン酸と硫酸の両方を含む場合のリン酸のエッチング液中の含有割合は、３０％以上であることが好ましく、３５％以上であることがより好ましい。さらに、リン酸と硫酸との配合割合は、重量比でリン酸：硫酸が６９：１〜５：２であることが好ましい。基材の厚さが極端に薄い場合、反応を抑制するためにリン酸及び／又は硫酸を７０％により近い配合で含有させることも可能である。フッ酸については、フッ酸の濃度が高ければ金属の溶解速度が大きくなり処理時間の短縮につながるが、反応の制御が困難になり、貫通孔の径のばらつきが発生するおそれがある。また、フッ酸は揮発性であるため、高濃度であると有毒ガスが発生しやすくなるとともにエッチング液中のフッ酸濃度が時間とともに変化してしまい、安定した溶解速度を保つことができなくなる。一方、極端に濃度が低いと溶解反応の進行が遅くなりすぎてしまい、処理時間が長くなってしまうことから、フッ酸のエッチング液中での含有割合は、重量比で３〜１５％であることが好ましく、５〜１２％であることがより好ましい。硝酸については、硝酸の濃度が高ければ溶解反応はより抑制されるが、高すぎると処理時間が長くなってしまうこと、及び揮発性であるため有毒ガスが発生しやすくなるとともに、エッチング液中の硝酸濃度が時間とともに変化してしまい、エッチング液の安定性を保つことが困難となることから、硝酸のエッチング液中での含有割合は、重量比で５〜２５％が好ましく、５〜２２％がより好ましく、８〜１８％であることが更に好ましい。塩酸については、塩酸の濃度が高ければ金属の溶解速度が大きくなり処理時間の短縮につながるが、反応の制御が困難になり、貫通孔の径のばらつきが発生するおそれがある。また、塩酸は揮発性であるため、高濃度であると有毒ガスが発生しやすくなるとともにエッチング液中の塩酸濃度が時間とともに変化してしまい、安定した溶解速度を保つことができなくなる。一方、極端に濃度が低いと溶解反応の進行が遅くなりすぎてしまい、処理時間が長くなってしまうことから、塩酸を含む場合は、塩酸のエッチング液中での含有割合は、重量比で０．０１〜１５％であることが好ましく、２〜１３％であることがより好ましく、５〜１０％であることが更に好ましい。また、本発明におけるリン酸、硫酸、フッ酸、硝酸及び塩酸には、水に溶解して、リン酸イオン、硫酸イオン、フッ素イオン、硝酸イオン又は塩素イオンを生成するこれらの塩も含まれる。これらの塩としては、例えば、リン酸一ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム、ピロリン酸ナトリウム、リン酸二水素ナトリウム、メタリン酸ナトリウム、硫酸銅、硫酸銀、フッ化アンモニウム、フッ化水素アンモニウム、硝酸ナトリウム、亜硝酸ナトリウム、硝酸銅、硝酸銀、塩化亜鉛等を挙げることができる。エッチング液中でのこれらの塩の含有割合は、前記各イオン濃度が、リン酸、硫酸、フッ酸、硝酸及び塩酸を用いた場合における各イオン濃度と同じになることが好ましい。 The etching solution in the present invention contains an inorganic acid. Although it does not specifically limit as an inorganic acid in this invention, For example, hydrochloric acid, hydrofluoric acid, a sulfuric acid, nitric acid, phosphoric acid, perchloric acid etc. can be mentioned. Among these, from the viewpoint of stably forming micron-order through holes with high density, it is preferable to include at least one selected from phosphoric acid and sulfuric acid, hydrofluoric acid and nitric acid, and phosphoric acid, sulfuric acid, hydrofluoric acid and nitric acid. It is more preferable to contain. Furthermore, it is more desirable to add hydrochloric acid depending on the material of the metal plate. Phosphoric acid and sulfuric acid can increase the specific gravity of the etchant and increase the viscosity of the etchant. When the viscosity is high, the dissolved metal ions are prevented from diffusing into the liquid and stay in the vicinity of the metal surface. As a result, the acid concentration locally decreases, so that excessive metal dissolution reaction is suppressed. In addition, the mixing of these acids also causes a surface active action, so that it is easy to smoothly discharge the hydrogen gas generated during metal dissolution from the etching surface. Hydrofluoric acid and hydrochloric acid can dissolve various metals. In particular, hydrofluoric acid can dissolve titanium or a titanium alloy. Nitric acid can dissolve various metals together with hydrofluoric acid, but in the case of titanium or a titanium alloy, the surface of the titanium or titanium alloy can be passivated. By this action, nitric acid can suppress the titanium dissolution reaction by hydrofluoric acid and control the reaction. The content of the inorganic acid in the etching solution in the present invention is not particularly limited, but when it contains at least one selected from phosphoric acid and sulfuric acid, and hydrofluoric acid and nitric acid, phosphoric acid and When either one of sulfuric acid is included, phosphoric acid or sulfuric acid is 30 to 70%. When both phosphoric acid and sulfuric acid are included, phosphoric acid and sulfuric acid are 30 to 70% in total, and hydrofluoric acid is 3 to 15%. Nitric acid is preferably contained in an amount of 5 to 25%. The remainder of the etchant can be water. Regarding phosphoric acid and sulfuric acid, if the viscosity of the etching solution is too high, the dissolution reaction of the metal is extremely suppressed, and the treatment time may be prolonged. When either one of acid or sulfuric acid is included, the content ratio of phosphoric acid or sulfuric acid, and when both phosphoric acid and sulfuric acid are included, the total content ratio of phosphoric acid and sulfuric acid is 30 to 70% by weight. It is preferable that it is 30 to 60%, and it is still more preferable that it is 40 to 60%. Further, when both phosphoric acid and sulfuric acid are contained, it is preferable that one acid is contained at 1% or more, and the total content is as described above, but in the phosphoric acid etching solution when both phosphoric acid and sulfuric acid are contained. The content ratio is preferably 30% or more, and more preferably 35% or more. Furthermore, the mixing ratio of phosphoric acid and sulfuric acid is preferably 69: 1 to 5: 2 in terms of weight ratio of phosphoric acid: sulfuric acid. When the thickness of the substrate is extremely thin, phosphoric acid and / or sulfuric acid can be contained in a formulation closer to 70% in order to suppress the reaction. As for hydrofluoric acid, if the concentration of hydrofluoric acid is high, the dissolution rate of the metal increases and the treatment time is shortened. However, the control of the reaction becomes difficult, and the diameter of the through-holes may vary. Further, since hydrofluoric acid is volatile, a toxic gas is likely to be generated at a high concentration, and the hydrofluoric acid concentration in the etching solution changes with time, so that a stable dissolution rate cannot be maintained. On the other hand, if the concentration is extremely low, the progress of the dissolution reaction becomes too slow and the treatment time becomes long, so the content ratio of hydrofluoric acid in the etching solution is 3 to 15% by weight. It is preferably 5 to 12%. As for nitric acid, the dissolution reaction is further suppressed if the concentration of nitric acid is high, but if it is too high, the processing time will be long, and since it is volatile, toxic gas is likely to be generated, and in the etching solution. Since the nitric acid concentration changes with time and it becomes difficult to maintain the stability of the etching solution, the content ratio of nitric acid in the etching solution is preferably 5 to 25% by weight, and 5 to 22%. Is more preferable, and it is still more preferable that it is 8 to 18%. As for hydrochloric acid, if the concentration of hydrochloric acid is high, the dissolution rate of the metal is increased and the treatment time is shortened. However, the control of the reaction becomes difficult, and the diameter of the through-holes may be varied. Further, since hydrochloric acid is volatile, a toxic gas is likely to be generated at a high concentration, and the hydrochloric acid concentration in the etching solution changes with time, so that a stable dissolution rate cannot be maintained. On the other hand, if the concentration is extremely low, the progress of the dissolution reaction becomes too slow and the treatment time becomes long. Therefore, when hydrochloric acid is included, the content ratio of hydrochloric acid in the etching solution is 0 by weight. 0.01 to 15% is preferable, 2 to 13% is more preferable, and 5 to 10% is still more preferable. Further, the phosphoric acid, sulfuric acid, hydrofluoric acid, nitric acid and hydrochloric acid in the present invention include those salts which are dissolved in water to produce phosphate ion, sulfate ion, fluorine ion, nitrate ion or chlorine ion. Examples of these salts include monosodium phosphate, disodium phosphate, trisodium phosphate, sodium pyrophosphate, sodium dihydrogen phosphate, sodium metaphosphate, copper sulfate, silver sulfate, ammonium fluoride, hydrogen fluoride. Examples include ammonium, sodium nitrate, sodium nitrite, copper nitrate, silver nitrate, and zinc chloride. The content ratio of these salts in the etching solution is preferably the same as each ion concentration when phosphoric acid, sulfuric acid, hydrofluoric acid, nitric acid and hydrochloric acid are used.
本発明における化学エッチング処理は、金属板の表面をエッチング液で化学エッチングできれば特に限定されず通常の処理方法を用いることができ、例えば、表面に多孔パターンが形成された金属板を、エッチング液中に浸漬して化学エッチングを行うことができる。以下に本発明の製造方法により、多孔金属板を製造する場合の一実施形態を示す（図１）。まず、（１）金属板（基材）を用意し、必要に応じて基材の洗浄を行う。基材の洗浄は、通常行われている方法で行うことができる。次に、（２）金属板の一方の面（表の面）の表面にレジストを塗布する。その後、（３）レジストを定着させるために、必要に応じてプリベーキングを行う。次に、（４）多孔パターンが形成されたフォトマスクをレジスト膜上に設置して、露光する。露光後、（５）フォトマスクをはずして、現像を行い、露光部のレジストを除去する。これにより、貫通孔を形成する箇所のレジストが除去される。次に、（６）金属板の他方の面（多孔パターンを形成した面と反対の面：裏面）がエッチングされるのを防ぐために、金属板の他方の面にレジストを塗布する。（７）必要に応じてポストベーキングを行う。こうして得られた表面に多孔パターンが形成された金属板をエッチング液に浸漬して化学エッチング処理を行う。金属板を所定の時間エッチング液に浸漬することにより、多孔パターンの孔部に、貫通孔が形成される。浸漬処理を行った後は、過剰なエッチング反応を防ぐために、金属板をエッチング液から取り出して、エッチング液を水により洗い流し、さらに残留している微量なエッチング液をアルカリ溶液によって中和させる。その後、レジストはく離液、アセトン等の有機溶媒、アルカリ溶液などでレジストを除去して多孔金属板を得ることができる。また、本発明の製造方法における多孔パターンの形成及び化学エッチング処理は、金属板の片方の面に限られるものではない。一方の面からの化学エッチング処理により貫通孔を形成した後、他方の面から再度同様の化学エッチング処理を行ってもよく、図２に示すように、一方の面からの化学エッチング処理により途中まで孔を形成した後、他方の面から同様の化学エッチング処理を行って、孔を貫通させて貫通孔を形成してもよい。図２に示す実施形態では、図１の場合と同様に、金属板の一方の面（表の面）に耐酸性保護膜の多孔パターンを形成し（［工程１］）、化学エッチング処理を行うが、化学エッチング処理を途中で終了し（［工程２］）、他方の面（裏面）の表面に、表裏対称となるように同じ多孔パターンをレジスト塗布、プリベーキング、露光、現像により耐酸性保護膜で形成し、表の面にエッチングを防ぐためのレジストを塗布、ポストベーキングを行ってから（［工程３］）、化学エッチング処理（［工程４］）を行うことにより、両表面から形成される孔を貫通させて貫通孔を形成している。また、表の面及び裏面に多孔パターンを形成してから、表裏同時に化学エッチングを行うこともできる。片面から化学エッチングした場合、金属露出部が深さ方向に溶解するとともに横方向へも溶解が進行することによって孔径が一方の面から他方の面に向かって漸減した貫通孔を得ることができ、表裏両表面からエッチングした場合、孔径の変化の少ない貫通孔を得ることができる。 The chemical etching treatment in the present invention is not particularly limited as long as the surface of the metal plate can be chemically etched with an etching solution, and a normal treatment method can be used. For example, a metal plate having a porous pattern formed on the surface can be used in the etching solution. Chemical etching can be performed by immersing the film in the substrate. One embodiment in the case of manufacturing a porous metal plate by the manufacturing method of the present invention is shown below (FIG. 1). First, (1) a metal plate (base material) is prepared, and the base material is washed as necessary. The substrate can be washed by a commonly used method. Next, (2) a resist is applied to the surface of one surface (front surface) of the metal plate. Thereafter, (3) pre-baking is performed as necessary to fix the resist. Next, (4) a photomask having a porous pattern formed thereon is placed on the resist film and exposed. After the exposure, (5) the photomask is removed, development is performed, and the resist in the exposed portion is removed. Thereby, the resist of the location which forms a through-hole is removed. Next, (6) a resist is applied to the other surface of the metal plate in order to prevent the other surface of the metal plate (the surface opposite to the surface on which the porous pattern is formed: the back surface) from being etched. (7) Post-bake as necessary. A chemical etching process is performed by immersing a metal plate having a porous pattern formed on the surface thus obtained in an etching solution. By immersing the metal plate in an etching solution for a predetermined time, through holes are formed in the holes of the porous pattern. After the immersion treatment, in order to prevent an excessive etching reaction, the metal plate is taken out from the etching solution, the etching solution is washed away with water, and the remaining trace etching solution is neutralized with an alkali solution. Thereafter, the resist can be removed with a resist stripping solution, an organic solvent such as acetone, an alkaline solution or the like to obtain a porous metal plate. Moreover, the formation of the porous pattern and the chemical etching treatment in the production method of the present invention are not limited to one surface of the metal plate. After the through hole is formed by the chemical etching process from one surface, the same chemical etching process may be performed again from the other surface, and as shown in FIG. After forming the hole, the same chemical etching treatment may be performed from the other surface to penetrate the hole to form a through hole. In the embodiment shown in FIG. 2, as in the case of FIG. 1, a porous pattern of an acid-resistant protective film is formed on one surface (front surface) of a metal plate ([Step 1]), and chemical etching treatment is performed. However, the chemical etching process is terminated in the middle ([Step 2]), and the same porous pattern is applied to the surface of the other side (back side) so as to be front and back symmetrical by applying resist, pre-baking, exposing and developing to protect against acid. It is formed from both surfaces by applying a resist to prevent etching on the front surface, applying post-baking ([Step 3]), and performing chemical etching ([Step 4]). Through holes are formed. Moreover, after forming a porous pattern in the front surface and the back surface, it is also possible to perform chemical etching simultaneously with the front and back surfaces. When chemical etching is performed from one side, a through-hole in which the hole diameter gradually decreases from one side to the other side can be obtained by dissolving the metal exposed portion in the depth direction and proceeding in the lateral direction, When etching is performed from both the front and back surfaces, through-holes with little change in hole diameter can be obtained.
本発明における化学エッチング処理は、処理時間や処理温度は、特に限定されず、使用する金属板の材質、厚さ、形成する貫通孔の孔径や貫通孔間の間隔に応じて選択することができる。化学エッチング処理を行う際のエッチング液の温度は、例えば、常温程度とすることができ、液温を上げるとエッチング速度を速めることができるが、過度にエッチング液の温度を上げると溶解反応の制御が困難になり貫通孔径のばらつきが生じるおそれがあるほか、含まれる酸の揮発によるエッチング液の配合率変化や有毒ガスの発生が顕著になるおそれがあるため、２０〜４０℃程度が好ましい。また、本発明における化学エッチング処理は、金属板の厚さを考慮して、金属の溶解速度が毎分０．３〜１０μｍとなるように各種条件を設定することが好ましい。本発明の製造方法によると、深さ方向のエッチングが横方向のエッチングに対して優位な異方性の化学エッチングが実現できるので、孔の横方向の広がりを抑えることができるため貫通孔間の間隔を狭くすることができ、高密度に貫通孔を形成できる。また、深さ方向のエッチングが横方向のエッチングに対して優位なことから、耐酸性保護膜の多孔パターンにほぼ近い形状及び配列の貫通孔を形成できるので、必要とされる配列パターンに適合した貫通孔を形成できる。さらに、本発明の製造方法は、貫通孔の形成時に、機械的な力や熱を加えないため、金属板に残留応力が発生せず、熱による金属板の形状変化や特性の劣化も生じない。このため、本発明の製造方法により製造された多孔金属板は、貫通孔の形成加工後も高い耐食性を有する。本発明の製造方法によれば、貫通孔形成時に変形や変質することが問題となる厚さの薄い金属板、例えば、２〜１００μｍ、あるいは２〜５０μｍ、あるいは２〜３０μｍといった厚さの金属板であっても、変形や特性の劣化がない多孔金属板を製造することができる。また、深さ方向のエッチングが横方向のエッチングに対して優位な異方性の化学エッチングが行えるので、厚さの厚い金属板、例えば、前記範囲の中で比較的厚みのある５０〜１００μｍといった厚さの金属板であっても、貫通孔間の間隔を狭くして高密度に貫通孔を形成できる。本発明の製造方法は、電解エッチング法のように電圧を印加する必要がなく、金属板をエッチング液に浸漬することにより貫通孔の形成ができるので、多孔パターンを形成する耐酸性保護膜の破壊や、金属板における印加電圧のばらつきが生じず、小面積の金属板から大面積の金属板まで、金属板の面積にかかわらず均一な貫通孔を形成することができ、コストも抑制できる。さらに、本発明の製造方法によると、機械加工による貫通孔の孔縁部でのささくれ（バリ）の発生や、レーザー加工による貫通孔の孔縁部でのドロス（溶融物の付着）の発生がないため、均一な貫通孔を形成することができると共に、バリやドロスの除去工程を必要とせず、工程を簡略化できる。 In the chemical etching treatment in the present invention, the treatment time and treatment temperature are not particularly limited, and can be selected according to the material and thickness of the metal plate to be used, the diameter of the through holes to be formed, and the interval between the through holes. . The temperature of the etching solution when performing the chemical etching process can be, for example, about room temperature, and the etching rate can be increased by increasing the solution temperature, but the dissolution reaction can be controlled by increasing the temperature of the etching solution excessively. The temperature is preferably 20 to 40 ° C., because there is a risk that variations in the through-hole diameter may occur and the change in the mixing ratio of the etching solution and the generation of toxic gas due to volatilization of the contained acid may be significant. In the chemical etching treatment according to the present invention, it is preferable to set various conditions so that the metal dissolution rate is 0.3 to 10 μm per minute in consideration of the thickness of the metal plate. According to the manufacturing method of the present invention, anisotropic chemical etching in which etching in the depth direction is superior to etching in the lateral direction can be realized. A space | interval can be narrowed and a through-hole can be formed in high density. In addition, since the etching in the depth direction is superior to the etching in the lateral direction, it is possible to form through holes having a shape and arrangement almost similar to the porous pattern of the acid-resistant protective film, so that it conforms to the required arrangement pattern. A through hole can be formed. Furthermore, since the manufacturing method of the present invention does not apply mechanical force or heat when forming the through-holes, no residual stress is generated on the metal plate, and neither the shape change of the metal plate nor the deterioration of characteristics due to heat occurs. . For this reason, the porous metal plate manufactured by the manufacturing method of the present invention has high corrosion resistance even after the formation of the through holes. According to the manufacturing method of the present invention, a thin metal plate having a problem of deformation or alteration during formation of a through hole, for example, a metal plate having a thickness of 2 to 100 μm, 2 to 50 μm, or 2 to 30 μm. Even so, it is possible to produce a porous metal plate free from deformation and deterioration of characteristics. Further, since anisotropic chemical etching can be performed in which the etching in the depth direction is superior to the etching in the lateral direction, a thick metal plate, for example, 50 to 100 μm having a relatively thick thickness within the above range. Even if it is a metal plate of thickness, a space | interval between through-holes can be narrowed and a through-hole can be formed in high density. The manufacturing method of the present invention does not need to be applied with a voltage unlike the electrolytic etching method and can form a through hole by immersing a metal plate in an etching solution, so that the acid-resistant protective film that forms a porous pattern is destroyed. In addition, the applied voltage does not vary in the metal plate, and a uniform through hole can be formed from a small area metal plate to a large area metal plate regardless of the area of the metal plate, and the cost can be suppressed. Furthermore, according to the manufacturing method of the present invention, the occurrence of burr at the hole edge of the through hole due to machining and the occurrence of dross (adhesion of melt) at the hole edge of the through hole due to laser processing. Therefore, a uniform through hole can be formed, and a burr and dross removal process is not required, and the process can be simplified.
本発明の多孔金属板は、複数の貫通孔が形成された多孔金属板であって、前記貫通孔は、耐酸性保護膜の多孔パターンを表面に形成した金属板を、無機酸を含むエッチング液で化学エッチング処理することにより形成され、孔径が１〜１００μｍであり、隣接する前記貫通孔の中心間距離が４〜３００μｍであることを特徴とする。本発明の多孔金属板における耐酸性保護膜を形成する材料、多孔パターンの形成方法、エッチング液に含まれる酸の種類、化学エッチングの方法は、本発明の多孔金属板の製造方法における場合と同様である。本発明の多孔金属板は、耐酸性保護膜の多孔パターンを表面に形成した金属板を、無機酸を含むエッチング液で化学エッチング処理することにより形成されているので、貫通孔の形成時に機械的な力を受けておらず、熱の影響も受けていないので、残留応力や熱的変質のない多孔金属板であり機械的加工方法やドライエッチング等の熱の発生を伴う加工方法で貫通孔が形成された多孔金属板とは多孔金属板として異なる。本発明の多孔金属板における金属板は、特に限定されるものではないが、金属板を構成する金属としては、例えば、鉄、ステンレス、アルミニウム、銅、チタニウム、ニッケル、ジルコニウム、ニオブ、モリブデン、銀、タンタル、これらの合金等を挙げることができる。なかでも、生体親和性及び耐食性に優れ、医療用バリアメンブレンや生体情報計測のためのインプラント(埋入)用デバイス、化学プラント用フィルター、電池用フィルター等、医療、電池、化学、航空宇宙等の各種用途に好適に使用できるので、チタニウム又はチタニウム合金が好ましい。貫通孔の孔径は、医療用のバリアメンブレンやインプラントでは細菌侵入阻害や生体適合促進の観点から、化学プラント用等のフィルターでは微粒塵捕捉の観点から、１〜５０μｍが好ましく、１〜３０μｍがより好ましい。また、金属板の厚さは、特に限定されるものではないが、化学プラントや電池用フィルターでは腐食による減厚など耐食性の観点から、２〜１００μｍが好ましい。また、医療用バリアメンブレンやインプラントでは生体埋入の観点から、２〜１００μｍが好ましく、２〜５０μｍがより好ましく、２〜３０μｍが更に好ましい。本発明の多孔金属板における貫通孔は、その孔径が金属板の一方の面から反対側の他方の面に向けて漸減していることが好ましい。貫通孔がこのような形状をしていると、医療用のバリアメンブレンでは鞭毛を持つ細菌や細長い細菌の侵入を防御でき、また化学プラントや電池用フィルターでは細長い形状や複雑な形状を持つ塵を有効に捕捉できる。 The porous metal plate of the present invention is a porous metal plate in which a plurality of through-holes are formed, and the through-hole is an etching solution containing an inorganic acid on a metal plate having a porous pattern of an acid-resistant protective film formed on the surface. The hole diameter is 1 to 100 μm, and the distance between the centers of adjacent through holes is 4 to 300 μm. The material for forming the acid-resistant protective film in the porous metal plate of the present invention, the method of forming the porous pattern, the type of acid contained in the etching solution, and the method of chemical etching are the same as in the method of manufacturing the porous metal plate of the present invention. It is. The porous metal plate of the present invention is formed by chemically etching a metal plate having a porous pattern of an acid-resistant protective film on its surface with an etching solution containing an inorganic acid. It is a porous metal plate that has no residual stress or thermal alteration, and is not affected by heat. The formed porous metal plate is different as a porous metal plate. The metal plate in the porous metal plate of the present invention is not particularly limited. Examples of the metal constituting the metal plate include iron, stainless steel, aluminum, copper, titanium, nickel, zirconium, niobium, molybdenum, and silver. , Tantalum, and alloys thereof. Among them, it has excellent biocompatibility and corrosion resistance, medical barrier membranes, implant devices for biological information measurement, chemical plant filters, battery filters, medical, battery, chemical, aerospace, etc. Titanium or a titanium alloy is preferable because it can be suitably used for various applications. The diameter of the through hole is preferably 1 to 50 μm, more preferably 1 to 30 μm from the viewpoint of inhibiting bacterial invasion and promoting biocompatibility in medical barrier membranes and implants, and from the viewpoint of capturing fine dust in filters for chemical plants and the like. preferable. The thickness of the metal plate is not particularly limited, but is preferably 2 to 100 μm from the viewpoint of corrosion resistance such as thickness reduction due to corrosion in chemical plants and battery filters. Moreover, 2-100 micrometers is preferable from a viewpoint of biological implantation in a medical barrier membrane or an implant, 2-50 micrometers is more preferable, and 2-30 micrometers is still more preferable. It is preferable that the through-hole in the porous metal plate of the present invention gradually decreases in diameter from one surface of the metal plate to the other surface on the opposite side. If the through-hole has such a shape, the barrier membrane for medical use can prevent the invasion of bacteria with flagella and elongated bacteria, and the chemical plant and battery filter can remove dust with elongated and complex shapes. It can be captured effectively.
以下、本発明を実施例に基づき更に説明する。但し、本発明は実施例に示す様態に限定されるものではない。 Hereinafter, the present invention will be further described based on examples. However, the present invention is not limited to the modes shown in the examples.
金属基材として、高い生体親和性と耐食性を有するＪＩＳ１種の純チタニウム（ＴＲ２７０Ｃ）板（１０ｍｍ×１０ｍｍ、厚さ２０μｍ）を用い、このチタニウム板に、貫通孔を形成した。図１に本発明の多孔金属板の製造工程を示す。製造工程は、工程１の金属板の表面に耐酸性保護膜による多孔パターンを形成する工程と、工程２の化学エッチング処理工程から構成される。以下に実施例について工程毎に説明する。 As a metal substrate, a JIS type 1 pure titanium (TR270C) plate (10 mm × 10 mm, thickness 20 μm) having high biocompatibility and corrosion resistance was used, and through holes were formed in the titanium plate. FIG. 1 shows the production process of the porous metal plate of the present invention. The manufacturing process includes a process of forming a porous pattern with an acid-resistant protective film on the surface of the metal plate in process 1 and a chemical etching process in process 2. Examples will be described below for each process.
［工程１］耐酸性保護膜による多孔パターンの形成工程（フォトレジスト法）
（１）基材の洗浄：超音波洗浄機を用いてチタニウム板をアセトンで５分間、アルカリ溶液５５分間洗浄した。
（２）レジスト塗布：スピンコーターを用いてチタニウム板を回転させ、チタニウム板上（表の面上）にレジスト溶液Ｓ１８１８Ｇ（ロームアンドハース社）を滴下し、厚さ２μｍのレジスト膜を塗布した。なお、厚さ２０μｍのチタニウム板に多数の微小孔を精度よく開けるにはレジスト膜厚が１〜２μｍの範囲が好適であった。
（３）プリベーキング：残留している有機溶媒の除去とレジスト膜の基材への密着性を向上させるため、９０℃で３０分間のベーキングを行った。なお、種々のベーキング温度で試行した結果、最適なプリベーキング条件は、ベーキング時間が３０分間では８０〜１２０℃であった。
（４）露光：塗布したレジストにマスクアライナーを用いて多孔パターンを形成した。形成したパターンは、孔径２０μｍ、周期７０μｍである。なお、種々のパターン孔径で試行した結果、貫通孔のチタニウム板裏面（上記（２）でレジストを塗布した面と反対の面）での孔径を２０μｍとする場合、レジストパターンの孔径の範囲は５〜２０μｍであった。
（５）レジスト除去：レジストパターンを形成したチタニウム板を現像液ＭＦ−ＣＤ−２６（ロームアンドハース社)に浸漬し、レジストの露光部（孔部）を除去して、レジストによる多孔パターンを形成した。
（６）裏面へのレジスト塗布：裏面の化学エッチングを防止するために、チタニウム板の裏面にレジストを塗布した。
（７）ポストベーキング：表の面と裏面に形成されたレジスト膜とチタニウム板の密着性を向上させるために、１２０℃で３０分間のベーキングを行った。なお、種々のベーキング温度を試行した結果、最適なポストベーキング条件はベーキング時間が３０分間では９０〜１４０℃であった。
[Step 1] Formation of porous pattern with acid-resistant protective film (photoresist method)
(1) Cleaning of substrate: The titanium plate was cleaned with acetone for 5 minutes and the alkaline solution for 55 minutes using an ultrasonic cleaner.
(2) Resist application: The titanium plate was rotated using a spin coater, and a resist solution S1818G (Rohm and Haas) was dropped onto the titanium plate (on the front surface) to apply a 2 μm thick resist film. It should be noted that the resist film thickness in the range of 1 to 2 μm was suitable for accurately opening a large number of micro holes in a 20 μm thick titanium plate.
(3) Pre-baking: Baking was performed at 90 ° C. for 30 minutes in order to remove the remaining organic solvent and improve the adhesion of the resist film to the substrate. As a result of trials at various baking temperatures, the optimum pre-baking conditions were 80 to 120 ° C. when the baking time was 30 minutes.
(4) Exposure: A porous pattern was formed on the applied resist using a mask aligner. The formed pattern has a hole diameter of 20 μm and a period of 70 μm. In addition, as a result of trials with various pattern hole diameters, when the hole diameter on the back surface of the titanium plate of the through hole (the surface opposite to the surface coated with the resist in (2) above) is 20 μm, the range of the hole diameter of the resist pattern is 5 ˜20 μm.
(5) Resist removal: The titanium plate on which the resist pattern is formed is dipped in the developer MF-CD-26 (Rohm and Haas) to remove the exposed portion (hole) of the resist to form a porous pattern by the resist. did.
(6) Resist application to the back surface: In order to prevent chemical etching of the back surface, a resist was applied to the back surface of the titanium plate.
(7) Post-baking: Baking was performed at 120 ° C. for 30 minutes in order to improve the adhesion between the resist film formed on the front and back surfaces and the titanium plate. As a result of trying various baking temperatures, the optimum post-baking conditions were 90 to 140 ° C. when the baking time was 30 minutes.
［工程２］化学エッチング
リン酸（８９重量パーセント）を１．５Ｌ、硫酸（７５重量パーセント）を０．５Ｌ、フッ酸（５５重量パーセント）を１Ｌ及び硝酸（６７．５重量パーセント）を１Ｌ混合したものをエッチング液とした。エッチング液の各成分の濃度は重量比でリン酸３８％、硫酸１０％、フッ酸１１％、硝酸１６％及び残部は水である。エッチング液を入れた容器を湯煎し、３０℃に保った状態で［工程１］で得られた多孔パターンを表面に形成したチタニウム板（以下、試料という。）を容器に浸漬して、化学エッチングを行った。化学エッチング時間は５分間とした。
[Step 2] Chemical etching 1.5 L of phosphoric acid (89 weight percent), 0.5 L of sulfuric acid (75 weight percent), 1 L of hydrofluoric acid (55 weight percent) and 1 L of nitric acid (67.5 weight percent) This was used as an etching solution. The concentration of each component of the etchant is 38% phosphoric acid, 10% sulfuric acid, 11% hydrofluoric acid, 16% nitric acid, and the balance is water. Chemical etching is performed by immersing a titanium plate (hereinafter referred to as a sample) on which the porous pattern obtained in [Step 1] is immersed in a water bath in an etching solution container and maintaining the temperature at 30 ° C. in the container. Went. The chemical etching time was 5 minutes.
実施例１と同じ金属基材に同様の工程で耐酸性保護膜による多孔パターンを形成し、組成の異なるエッチング液で化学エッチングを行った。
［工程２］化学エッチング
リン酸（８９重量パーセント）を２Ｌ、フッ酸（５５重量パーセント）を１．５Ｌ及び硝酸（６７．５重量パーセント）を２Ｌ、水を０．５Ｌ混合したものをエッチング液とした。エッチング液の各成分の濃度は重量比でリン酸３６％、フッ酸１２％、硝酸２２％及び残部は水である。エッチング液を入れた容器を湯煎し、３０℃に保った状態で［工程１］で得られた試料を容器に浸漬して、化学エッチングを行った。化学エッチング時間は３分間とした。
A porous pattern made of an acid-resistant protective film was formed on the same metal substrate as in Example 1 by the same process, and chemical etching was performed using etching solutions having different compositions.
[Step 2] Chemical etching 2 L of phosphoric acid (89 weight percent), 1.5 L of hydrofluoric acid (55 weight percent), 2 L of nitric acid (67.5 weight percent), and 0.5 L of water are mixed into an etching solution. It was. The concentration of each component of the etching solution is 36% phosphoric acid, 12% hydrofluoric acid, 22% nitric acid, and the balance is water. The container containing the etching solution was bathed in water, and the sample obtained in [Step 1] was immersed in the container while being kept at 30 ° C. to perform chemical etching. The chemical etching time was 3 minutes.
［評価方法］
試料は、孔を形成する過程で深さ方向のエッチングが横方向のエッチングに対して優位な異方性エッチングが進行しているか調べるために、孔が貫通していない３段階のエッチング深さの多孔を形成した試料と、貫通孔について調べるために裏面孔径が２０μｍの貫通孔が形成された試料の合計４種類を作製した。化学エッチング後の試料の評価は、開孔径やエッチング深さはレーザー顕微鏡（キーエンス社製VK９７００）で評価し、表面形態および貫通孔径は走査電子顕微鏡ＳＵ３５００（日立ハイテクノロジーズ社製）でチタニウム板の表裏を観察し評価した。
[Evaluation method]
In order to investigate whether or not the anisotropic etching in which the etching in the depth direction is superior to the etching in the lateral direction is progressing in the process of forming the hole, the sample has a three-stage etching depth in which the hole does not penetrate. A total of four types were prepared: a sample in which a hole was formed, and a sample in which a through hole having a back hole diameter of 20 μm was formed in order to investigate the through hole. Evaluation of the sample after chemical etching is performed by evaluating the hole diameter and etching depth with a laser microscope (VK9700 manufactured by Keyence Corporation), and the surface morphology and through hole diameter with the scanning electron microscope SU3500 (manufactured by Hitachi High-Technologies Corporation). Were observed and evaluated.
表１に、実施例１の工程１の後、実施例１で使用したエッチング液でエッチング時間を変更することで３段階のエッチング度合でエッチングした試料の深さ方向のエッチング量と横方向のエッチング量を示す。ここで横方向のエッチング量は開口部の孔径からレジストパターン膜の開孔径を差し引いた値の半値とした。いずれのエッチング度合においても深さ方向のエッチング量が横方向のエッチング量の２倍程度であることがわかる。すなわち「深さ方向のエッチング量」／「横方向のエッチング量」が１より大である。これは、本発明の多孔金属板の孔形成過程において横方向のエッチングに対して深さ方向のエッチングが優位な異方性エッチングが実現できていることを示している。貫通孔が形成された試料は、５分間エッチング液に浸漬したものである。 In Table 1, the etching amount in the depth direction and the etching in the lateral direction of the sample etched in three stages of etching by changing the etching time with the etching solution used in Example 1 after Step 1 of Example 1 Indicates the amount. Here, the amount of etching in the horizontal direction was half the value obtained by subtracting the hole diameter of the resist pattern film from the hole diameter of the opening. It can be seen that the etching amount in the depth direction is about twice the etching amount in the lateral direction at any etching degree. That is, “the etching amount in the depth direction” / “the etching amount in the lateral direction” is larger than 1. This indicates that anisotropic etching in which etching in the depth direction is superior to etching in the lateral direction can be realized in the hole forming process of the porous metal plate of the present invention. The sample in which the through hole is formed is immersed in an etching solution for 5 minutes.
実施例１で作製した多孔チタニウム板を、エッチング面（表の面）から観察した走査電子顕微鏡像を図３に、裏面から観察した走査電子顕微鏡像を図４に示す。表側の開孔径が４５μｍ、裏側の開孔径が２０μｍであり、孔径が表から裏にかけて漸減している貫通孔が得られた。また、隣接する貫通孔との中心間距離は、７０μｍであり、貫通孔が１ｍｍ２あたり２００穴を超える高密度で形成されていることが確認された。 A scanning electron microscope image of the porous titanium plate produced in Example 1 observed from the etching surface (front surface) is shown in FIG. 3, and a scanning electron microscope image observed from the back surface is shown in FIG. A through-hole having an opening diameter of 45 μm on the front side and an opening diameter of 20 μm on the back side and gradually decreasing from the front to the back was obtained. Further, the distance between the centers of the adjacent through holes was 70 μm, and it was confirmed that the through holes were formed at a high density exceeding 200 holes per 1 mm 2 .
実施例２で作製した多孔チタニウム板を、エッチング面（表の面）から観察した走査電子顕微鏡像を図５に、裏面から観察した走査電子顕微鏡像を図６に示す。表側の開孔径が５０μｍ、裏側の開孔径が２２μｍであり、孔径が表から裏にかけて漸減している貫通孔が得られた。また、隣接する貫通孔との中心間距離は、７０μｍであり、貫通孔が１ｍｍ２あたり２００穴を超える高密度で形成されていることが確認された。 FIG. 5 shows a scanning electron microscope image of the porous titanium plate produced in Example 2 observed from the etching surface (front surface), and FIG. 6 shows a scanning electron microscope image observed from the back surface. A through-hole having an opening diameter of 50 μm on the front side and an opening diameter of 22 μm on the back side and gradually decreasing from the front to the back was obtained. Further, the distance between the centers of the adjacent through holes was 70 μm, and it was confirmed that the through holes were formed at a high density exceeding 200 holes per 1 mm 2 .
本発明の多孔金属板の製造方法は、医療用バリアメンブレンや生体情報計測のためのインプラント(埋入)用デバイス、化学プラント用フィルター、電池用フィルター等、医療、電池、化学、航空宇宙等の各種分野での様々な用途に利用できる多孔金属板を製造することができ、本発明の多孔金属板は、医療用バリアメンブレンや生体情報計測のためのインプラント(埋入)用デバイス、化学プラント用フィルター、電池用フィルター等、医療、電池、化学、航空宇宙等の各種分野での様々な用途に利用できる。 The method for producing a porous metal plate of the present invention includes a medical barrier membrane, an implant device for biological information measurement, a filter for a chemical plant, a filter for a battery, a medical, a battery, a chemical, an aerospace, etc. It is possible to produce a porous metal plate that can be used for various applications in various fields. The porous metal plate of the present invention is used for medical barrier membranes, implant devices for biological information measurement, for chemical plants. It can be used for various uses in various fields such as filters, filters for batteries, medical treatment, batteries, chemistry, and aerospace.
Claims (13)
Thickness is 2-100 micrometers, The porous metal plate in any one of Claims 9-12 characterized by the above-mentioned.
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| CN115029701B (en) * | 2022-07-08 | 2023-02-21 | 四川新远宏机械设备有限公司 | Zirconium alloy metal plate etching processing method and formed plate |
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