JP6815394B2 - エッチング浴の処理 - Google Patents
エッチング浴の処理 Download PDFInfo
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- JP6815394B2 JP6815394B2 JP2018516118A JP2018516118A JP6815394B2 JP 6815394 B2 JP6815394 B2 JP 6815394B2 JP 2018516118 A JP2018516118 A JP 2018516118A JP 2018516118 A JP2018516118 A JP 2018516118A JP 6815394 B2 JP6815394 B2 JP 6815394B2
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- electrolytic solution
- sulfuric acid
- manganese
- ions
- solution
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- 238000005530 etching Methods 0.000 title description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 121
- 239000008151 electrolyte solution Substances 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 33
- -1 manganese (III) ions Chemical class 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 21
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical group [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims 2
- 238000012544 monitoring process Methods 0.000 claims 2
- 239000003570 air Substances 0.000 description 34
- 239000004033 plastic Substances 0.000 description 31
- 229920003023 plastic Polymers 0.000 description 31
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 17
- 239000011572 manganese Substances 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 12
- 229910001437 manganese ion Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 9
- 229940098779 methanesulfonic acid Drugs 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000010137 moulding (plastic) Methods 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
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001932 seasonal effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010003497 Asphyxia Diseases 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JOJPFQVZNUNZBO-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] JOJPFQVZNUNZBO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005441 electronic device fabrication Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910000471 manganese heptoxide Inorganic materials 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Chemically Coating (AREA)
- ing And Chemical Polishing (AREA)
Description
1)Mn(III)イオンが低電流密度で形成されるので、プロセスの所要動力が少ない。
2)アノードが非常に低い電流密度で動作するので、アノード面積との関係において小さなカソードを使用して、Mn(III)イオンのカソード還元を防ぐことができる。これによって、分割セルの必要がなくなり、エッチング液再生セルの加工がより簡単になる。
3)プロセスから過マンガン酸イオンが生成されないので、激しく爆発性であることから重大な安全上の問題である七酸化マンガン(manganese heptoxide)が溶液中で生成される可能性がない。
4)強硫酸中においてMn(III)イオンの安定性が高いことから、エッチング液を使用準備済みの状態で販売することができる。
5)他のエッチングプロセスは過マンガン酸塩に基づいているので、過マンガン酸塩とMn(II)イオンとの反応の結果、二酸化マンガンが急速に「スラッジング」し、エッチング液の寿命が非常に短くなる。経時的に若干不均化する可能性があるものの、Mn(III)ベースのエッチング液では問題にならない。
6)Mn(III)の電解生成では、毒性ガスが全く発生しない。カソードにおいて水素が若干生成されることがあるが、所要電流が低いので、多くのメッキプロセスによって生成されるよりも少ない。
a)前記電解液の一部分を電解セルから付加(annex)槽に移動させる工程と、
b)前記付加槽内の前記電解液の移動された部分を処理して、前記電解液の一部分から水分を除去する工程と、
c)前記電解液の処理された部分を前記電解セルに戻す工程と
を含み、
前記電解液の前記処理された部分における水分が除去又は低減される方法に関する。
a)前記電解液の一部分を電解セルから付加槽に移動させる工程と、
b)前記付加槽内の前記電解液の移動された部分を処理して除去する工程と、
c)前記電解液の処理された部分を前記電解セルに戻す工程と
を含み、
前記電解液の前記処理された部分における水分が除去又は低減される方法に関する。
Claims (16)
- 硫酸溶液中にマンガン(III)イオンを含む電解液における硫酸濃度を維持する方法であって、
前記マンガン(III)イオンが、準安定性錯体を形成し、
a)電解液における硫酸濃度を決定するために電解セルにおける電解液をモニタリングする工程と、
b)硫酸濃度が8Mの濃度未満に減少したときに前記電解液の一部分を前記電解セルから付加(annex)槽に移動させる工程と、
c)前記付加槽内の前記電解液の移動された部分を処理して、前記電解液の一部分から水分を除去し、硫酸濃度を12M〜13Mの濃度まで回復する工程と、
d)前記電解液の処理された部分を前記電解セルに戻す工程と
を含み、
前記電解液の前記処理された部分における水分が除去又は低減されること、及び硫酸濃度を回復させることを特徴とする方法。 - 前記付加槽が閉鎖式である請求項1に記載の方法。
- 前記付加槽内の前記電解液の表面上に乾燥ガスを通すことによって、前記電解液の前記除去された部分が処理される請求項1に記載の方法。
- 前記乾燥ガスが、乾燥空気注入口を通じて前記表面上に供給される請求項3に記載の方法。
- 前記付加槽がガス排出口を更に含み、前記乾燥ガスが前記電解液の前記表面上を通過し、水分を吸収し、水分を含んだガスを前記付加槽から除去することができる請求項3に記載の方法。
- 前記乾燥ガスが乾燥空気である請求項5に記載の方法。
- 前記乾燥ガスの温度が15℃〜30℃である請求項3に記載の方法。
- 前記付加槽内の前記電解液の表面上に乾燥ガスを通し、
前記乾燥ガスが、前記閉鎖式の付加槽に入った時点で15%未満の湿度を有する請求項2に記載の方法。 - 前記乾燥ガスが、前記閉鎖式の付加槽に入った時点で10%未満の湿度を有する請求項8に記載の方法。
- 工程b)が連続式で実施される請求項1に記載の方法。
- 工程b)がバッチ式で実施される請求項1に記載の方法。
- マンガン(III)イオンを含む前記電解液が、アノード及びカソードを含む電解セル内においてマンガン(II)イオンの少なくとも1つの酸溶液を含む電解液を酸化させることによって調製され、且つ前記電解液が、前記アノードと前記カソードとの間に電流を印加し、前記電解液を酸化させてマンガン(III)イオンを形成することによって調製される請求項1に記載の方法。
- 工程a)の前に、前記電解液中の前記硫酸の濃度をモニタリングする工程を更に含む請求項1に記載の方法。
- 工程b)が、前記電解液から水分を除去し、前記電解液中の前記硫酸濃度を回復させる時間実施される請求項1に記載の方法。
- 前記時間が1分間〜30分間の範囲である請求項14に記載の方法。
- 前記乾燥ガスが、前記閉鎖式の付加槽に入る前に乾燥剤チャンバを通過する請求項9に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US14/870,738 US20170088971A1 (en) | 2015-09-30 | 2015-09-30 | Treatment of Etch Baths |
US14/870,738 | 2015-09-30 | ||
PCT/US2016/054350 WO2017059019A1 (en) | 2015-09-30 | 2016-09-29 | Treatment of etch baths |
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JP2018530676A JP2018530676A (ja) | 2018-10-18 |
JP6815394B2 true JP6815394B2 (ja) | 2021-01-20 |
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MX (1) | MX2018004025A (ja) |
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US20190009185A1 (en) * | 2017-07-10 | 2019-01-10 | Srg Global, Inc. | Hexavalent chromium free etch manganese vacuum evaporation system |
JP2020526638A (ja) * | 2017-07-10 | 2020-08-31 | エスアールジー グローバル インコーポレイテッド | 六価クロムを含まないエッチングマンガン回収システム |
US10889905B2 (en) * | 2018-12-11 | 2021-01-12 | Rohm And Haas Electronic Materials Llc | Methods of generating manganese (III) ions in mixed aqueous acid solutions using ozone |
JP7336126B2 (ja) * | 2019-03-11 | 2023-08-31 | 国立研究開発法人産業技術総合研究所 | 高価数マンガンの製造方法、及び製造装置 |
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AT310285B (de) | 1966-02-22 | 1973-09-25 | Photocircuits Corp | Verfahren zur Herstellung eines Schichtkörpers für gedruckte Schaltungen |
US3663613A (en) * | 1969-02-18 | 1972-05-16 | American Cyanamid Co | Separation of organic acid products and water from catalysts after synthesis by reduced pressure distillation |
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US4948630A (en) | 1984-06-07 | 1990-08-14 | Enthone, Inc. | Three step process for treating plastics with alkaline permanganate solutions |
DE19521132C1 (de) * | 1995-06-09 | 1996-10-17 | Poligrat Holding Gmbh | Verfahren zum Entmetallisieren von hochsauren Bädern und Verwendung dieses Verfahrens beim Elektropolieren von Edelstahloberflächen |
US5648125A (en) | 1995-11-16 | 1997-07-15 | Cane; Frank N. | Electroless plating process for the manufacture of printed circuit boards |
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JP2004511803A (ja) | 2000-10-16 | 2004-04-15 | オーソ−マクニール・フアーマシユーチカル・インコーポレーテツド | バニロイド受容体についての改良リガンド結合アッセイ |
US7794573B2 (en) * | 2003-12-05 | 2010-09-14 | Semitool, Inc. | Systems and methods for electrochemically processing microfeature workpieces |
JP4393260B2 (ja) * | 2004-04-20 | 2010-01-06 | 株式会社東芝 | エッチング液管理方法 |
WO2007122869A1 (ja) | 2006-04-18 | 2007-11-01 | Okuno Chemical Industries Co., Ltd. | 樹脂成形体に対するエッチング処理用組成物 |
ATE445667T1 (de) | 2007-08-10 | 2009-10-15 | Enthone | Chromfreie beize für kunststoffoberflächen |
US9109295B2 (en) * | 2009-10-12 | 2015-08-18 | Novellus Systems, Inc. | Electrolyte concentration control system for high rate electroplating |
ES2643234T3 (es) * | 2010-03-30 | 2017-11-21 | Covestro Deutschland Ag | Procedimiento para la preparación de carbonatos de diarilo y policarbonatos |
US20110311433A1 (en) * | 2010-06-17 | 2011-12-22 | Mads Lykke | Process and system for production of concentrated sulphuric acid from off-gas |
JP5997130B2 (ja) * | 2011-03-08 | 2016-09-28 | デノラ・ペルメレック株式会社 | 硫酸電解装置及び硫酸電解方法 |
US10260000B2 (en) * | 2012-01-23 | 2019-04-16 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
US9534306B2 (en) * | 2012-01-23 | 2017-01-03 | Macdermid Acumen, Inc. | Electrolytic generation of manganese (III) ions in strong sulfuric acid |
US20140075985A1 (en) * | 2012-09-17 | 2014-03-20 | N. Wayne Mckay | Process for optimizing removal of condensable components from a fluid |
MY164331A (en) * | 2013-10-22 | 2017-12-15 | Okuno Chem Ind Co | Composition for etching treatment of resin material |
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MX2018004025A (es) | 2018-12-10 |
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BR112018006281A2 (pt) | 2018-10-16 |
TW201718826A (zh) | 2017-06-01 |
BR112018006281B1 (pt) | 2023-01-17 |
EP3356577A4 (en) | 2019-07-17 |
JP2018530676A (ja) | 2018-10-18 |
TWI636122B (zh) | 2018-09-21 |
KR102124453B1 (ko) | 2020-06-19 |
CN108350586A (zh) | 2018-07-31 |
EP3356577A1 (en) | 2018-08-08 |
CA3000659A1 (en) | 2017-04-06 |
EP3356577B1 (en) | 2022-08-17 |
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US20170088971A1 (en) | 2017-03-30 |
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