JPH0335381B2 - - Google Patents
Info
- Publication number
- JPH0335381B2 JPH0335381B2 JP17598982A JP17598982A JPH0335381B2 JP H0335381 B2 JPH0335381 B2 JP H0335381B2 JP 17598982 A JP17598982 A JP 17598982A JP 17598982 A JP17598982 A JP 17598982A JP H0335381 B2 JPH0335381 B2 JP H0335381B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- iron
- hydrogen peroxide
- present
- chemical dissolution
- 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
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000004090 dissolution Methods 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 7
- 239000003929 acidic solution Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 20
- 230000002378 acidificating effect Effects 0.000 description 11
- 229960002050 hydrofluoric acid Drugs 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 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 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 4
- 229940044654 phenolsulfonic acid Drugs 0.000 description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GPFIZJURHXINSQ-UHFFFAOYSA-N acetic acid;nitric acid Chemical compound CC(O)=O.O[N+]([O-])=O GPFIZJURHXINSQ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrofluoric acid Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 description 1
- MYHXWQZHYLEHIU-UHFFFAOYSA-N oxalic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)C(O)=O MYHXWQZHYLEHIU-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Description
本発明は、浴の寿命が改善された過酸化水素と
フツ酸または重フツ酸イオンとを主成分とする化
学的溶解処理液に関する。
本発明の処理液は、鉄および鉄合金の化学溶解
処理に好適であり、特に、鉄および鉄−ニツケル
合金、鉄−ニツケル−コバルト合金など鉄合金等
の処理に極めて好適である。
これらの鉄合金は、集積回路や表示管等の電子
材料の導電性部品や耐食材料として利用されてい
るが、素材から製品への加工段階で、ロールによ
る引き抜き跡が付いたり、プレスや切断によるバ
リが発生したり、加熱処理による酸化スケールが
生成したり、保存中に錆が発生したりする等の現
象がある。この現象は、後処理工程のメツキ、ボ
ンデイングや樹脂封止等の処理における密着不良
の原因となる為、化学的溶解処理液で前処理が行
なわれている。
従来、これらの鉄および鉄合金の化学的溶解処
理液としては、硝酸−酢酸、硝酸−りん酸あるい
は硝酸−フツ酸などの混酸液が用いられて来た
が、これらの硝酸系の混酸液は、一般に70〜150
℃程度の比較的高温度で処理されることから、火
傷の危険があるとともに、濃厚な混酸であるので
有害なNOxガスやミストの発生があり、公害上
及び環境上好ましくないものであつた。またこれ
らの混酸からなる浴は溶解速度が非常に速いため
処理時間は一般に２〜６秒程度しか採れず、自動
化し難く、作業能率の低下を来たしている。
このため、硝酸を主成分とする混酸に替えて、
過酸化水素を主成分とする酸性液、たとえば、過
酸化水素−塩酸、過酸化水素−硫酸−フツ酸、過
酸化水素、しゆう酸−硫酸あるいは過酸化水素−
硫酸−酸性フツ化アンモニウムにセレン化合物を
添加した処理液などが種々提案され、実用化され
ているものもある。
しかしながら、これらの過酸化水素を主成分と
する酸性液からなる浴は、浴の寿命が短く長期間
の使用に耐えきれず、作業能率の低下を来たして
いるのが現状である。ここで、「浴の寿命」とは、
処理により浴液中に金属が多量に溶解して来ると
金属濃度が飽和点に達し、金属塩の結晶が析出
し、最早それ以上溶解処理しても良好な金属表面
が得られず、また溶解速度が著しく低下して来る
現象を言い、これを「寿命が来た」あるいは「老
化点に達した」と言う。
本発明者らは、過酸化水素とフツ酸または重フ
ツ酸イオンとを主成分とする酸性水溶液における
浴の寿命を延ばすべく種々検討を行つた結果、後
記する化合物を添加することにより顕著な効果が
あることが見い出された。
すなわち、本発明は、過酸化水素とフツ酸また
は重フツ酸イオンとを主成分として含有し、フツ
酸または重フツ酸イオンを少なくとも１ｇ／含
有する酸性溶液に、下記一般式で示されるフエノ
ール性水酸基を有する化合物の少なくとも一種
を、少なくとも0.1ｇ／含有させた鉄及び鉄合
金用化学的溶解処理液に関する。
一般式
The present invention relates to a chemical dissolution treatment liquid whose main components are hydrogen peroxide and hydrofluoric acid or difluoric acid ions, and which has an improved bath life. The treatment liquid of the present invention is suitable for chemically dissolving iron and iron alloys, and is particularly suitable for treating iron and iron alloys such as iron-nickel alloys and iron-nickel-cobalt alloys. These iron alloys are used as conductive parts and anti-corrosion materials for electronic materials such as integrated circuits and display tubes, but during the processing stage from material to product, there may be marks left by the rolls or marks caused by pressing or cutting. There are phenomena such as the formation of burrs, the formation of oxide scale due to heat treatment, and the formation of rust during storage. Since this phenomenon causes poor adhesion in post-processing processes such as plating, bonding, and resin sealing, pre-treatment is performed using a chemical dissolving treatment solution. Conventionally, mixed acid solutions such as nitric acid-acetic acid, nitric acid-phosphoric acid, or nitric acid-fluoric acid have been used as chemical dissolution treatment solutions for iron and iron alloys. , generally 70-150
Since it is processed at a relatively high temperature of about 0.9°C, there is a risk of burns, and since it is a concentrated mixed acid, it generates harmful NOx gas and mist, which is undesirable from a pollution and environmental standpoint. Furthermore, since the dissolution rate of baths made of these mixed acids is very fast, the processing time is generally only about 2 to 6 seconds, making it difficult to automate and reducing work efficiency. For this reason, instead of using a mixed acid whose main component is nitric acid,
Acidic liquids containing hydrogen peroxide as a main component, such as hydrogen peroxide-hydrochloric acid, hydrogen peroxide-sulfuric acid-fluoric acid, hydrogen peroxide, oxalic acid-sulfuric acid or hydrogen peroxide-
Various treatment solutions, such as sulfuric acid-acidic ammonium fluoride with selenium compounds added thereto, have been proposed, and some have been put into practical use. However, the current situation is that these baths made of acidic liquids containing hydrogen peroxide as a main component have a short bath life and cannot withstand long-term use, resulting in a decrease in work efficiency. Here, "bath life" means:
When a large amount of metal dissolves in the bath liquid during treatment, the metal concentration reaches a saturation point, and metal salt crystals precipitate, and it is no longer possible to obtain a good metal surface even with further dissolution treatment. A phenomenon in which the speed decreases significantly, and this is said to be ``reaching the end of its lifespan'' or ``reaching the aging point.'' The present inventors have conducted various studies to extend the life of a bath in an acidic aqueous solution containing hydrogen peroxide and hydrofluoric acid or difluoric acid ions as the main components, and have found that the addition of the compound described later has a remarkable effect. It was found that there is. That is, the present invention provides a solution containing hydrogen peroxide and hydrofluoric acid or difluoric acid ions as main components, and adding a phenolic compound represented by the following general formula to an acidic solution containing at least 1 g of hydrofluoric acid or difluoric acid ions. The present invention relates to a chemical dissolution treatment liquid for iron and iron alloys containing at least 0.1 g of at least one compound having a hydroxyl group. general formula
【式】
（式中Ｘは、Ｈまたは−COOHである。）
本発明の化学的溶解処理液によれば、金属表面
の仕上りは何んら劣化することなく、また溶解速
度も殆んど低下させないで工業的に有効なまでに
浴の寿命を延ばすことができ、自動化等も有効に
行なうことができる。すなわち、本発明の化学的
溶解処理液にて処理を行なうと、本発明の化合物
を添加しない化学的溶解処理液の処理作業時間に
比べて同条件（たとえば、同一溶解量、同一処理
速度等）で、２〜３倍の作業が出来る。したがつ
て、たとえば１日で浴を更新しているのであれ
ば、本発明の浴を用いると２〜３日で更新すれば
良い事となる。
本発明の化学的溶解処理液における過酸化水素
は、格別に制限はされず、従来の過酸化水素を主
成分として含有する酸性水溶液におけると同等で
よく、作業性、商業性等を考慮して、通常、１
ｇ／〜350ｇ／である。
フツ酸または重フツ酸イオンの濃度は、作業性
および商業性を考慮して、通常、１ｇ／〜350
ｇ／である。このフツ酸または重フツ酸イオン
は、任意のカチオンと塩または酸を形成している
もので、たとえば、フツ酸、酸性フツ化ナトリウ
ム、酸性フツ化カリウム、酸性フツ化アンモニウ
ムなどが例示され、これらのうち、作業性、溶解
性等を考慮すると、酸性フツ化アンモニウムが特
に好適である。
また、本発明の化学的溶解処理液において、浴
の寿命を延ばすために配合される先の一般式で示
される化合物の具体例を示すと、たとえばｏ−、
ｍ−、ｐ−フエノールスルホン酸、スルホサリチ
ル酸等が例示される。これらの化合物の濃度は、
広い範囲で使用可能であるが、作業性および経済
性を考慮し、一般的には0.01ｇ／〜100ｇ／
で使用され、好ましくは１ｇ／〜50ｇ／であ
る。
本発明の化学的溶解処理液には、鉄および鉄合
金を対象とする為実用性を考慮するとフツ酸また
は重フツ酸イオンが必須条件であるが、必要に応
じて少量の硫酸、硝酸、リン酸等の鉱酸を添加す
ることができる。又、アルコール、尿素、安息香
酸、アミノ安香酸等の安定剤、あるいは、界面活
性剤なども添加することができる。
本発明の化学的溶解処理液は、処理物の形状、
目的に応じて10〜80℃、好ましくは20〜60℃の温
度で、５秒〜30分、好ましくは10秒〜10分の処理
時間で使用される。又、操作法としては浸漬法、
スプレー法、回転バレル法のいずれの方法でも良
く、又、これらに限定される事はない。
以下に本発明を実施例にて具体的に説明する。
実施例 １
過酸化水素100ｇ／、酸性フツ化アンモニウ
ム40ｇ／と第１表に示す化合物を添加した化学
的溶解処理液に、純鉄を40℃で30ｇ／溶解し、
その後20℃で40時間放置し結晶を析出させ、上澄
液の鉄濃度を測定した。[Formula] (In the formula, X is H or -COOH.) According to the chemical dissolution treatment solution of the present invention, the finish of the metal surface does not deteriorate at all, and the dissolution rate almost decreases. The life of the bath can be extended to an industrially effective level without causing any damage, and automation can also be effectively carried out. That is, when processing with the chemical dissolution treatment solution of the present invention, the processing time is shorter under the same conditions (for example, the same amount of dissolution, the same processing speed, etc.) compared to the treatment time with the chemical dissolution treatment solution without the addition of the compound of the present invention. You can do 2 to 3 times as much work. Therefore, if the bath is renewed every day, for example, if the bath of the present invention is used, it can be renewed every two to three days. The hydrogen peroxide in the chemical dissolution treatment solution of the present invention is not particularly limited, and may be the same as that in conventional acidic aqueous solutions containing hydrogen peroxide as a main component. , usually 1
g/~350g/. The concentration of fluoric acid or difluoric acid ion is usually 1g/~350, considering workability and commercial efficiency.
g/. The hydrofluoric acid or difluoric acid ion forms a salt or acid with any cation, such as hydrofluoric acid, acidic sodium fluoride, acidic potassium fluoride, acidic ammonium fluoride, etc. Among them, acidic ammonium fluoride is particularly suitable in consideration of workability, solubility, etc. Further, in the chemical dissolution treatment solution of the present invention, specific examples of compounds represented by the above general formula that are blended in order to extend the life of the bath include, for example, o-,
Examples include m-, p-phenolsulfonic acid and sulfosalicylic acid. The concentration of these compounds is
It can be used in a wide range, but considering workability and economy, generally 0.01g/~100g/
The amount is preferably 1 g/~50 g/. Since the chemical dissolution treatment liquid of the present invention is intended for iron and iron alloys, hydrofluoric acid or difluoric acid ions are essential from a practical standpoint, but small amounts of sulfuric acid, nitric acid, phosphoric acid, and Mineral acids such as acids can be added. Furthermore, stabilizers such as alcohol, urea, benzoic acid, aminobenzoic acid, or surfactants can also be added. The chemical dissolution treatment liquid of the present invention has the shape of the object to be treated,
Depending on the purpose, it is used at a temperature of 10 to 80°C, preferably 20 to 60°C, and a treatment time of 5 seconds to 30 minutes, preferably 10 seconds to 10 minutes. In addition, the operation method is immersion method,
Either a spray method or a rotating barrel method may be used, and the method is not limited to these methods. The present invention will be specifically explained below with reference to Examples. Example 1 30 g of pure iron was dissolved at 40°C in a chemical dissolution treatment solution containing 100 g of hydrogen peroxide, 40 g of acidic ammonium fluoride, and the compounds listed in Table 1.
Thereafter, it was left at 20°C for 40 hours to precipitate crystals, and the iron concentration of the supernatant was measured.
【表】
この結果、本発明に係る化合物を添加すること
により、鉄の飽和溶解濃度は、およそ２〜３倍と
なる。
実施例 ２
過酸化水素80ｇ／、酸性フツ化アンモニウム
20ｇ／、硫酸１ｇ／、ｏ−アミノ安息香酸、
１ｇ／、フエノールスルホン酸20ｇ／からな
る化学的溶解処理液により、鉄−ニツケル合金
（鉄58％、ニツケル42％）を溶解し、液の寿命
（老化点）を測定した。尚、溶解に伴い液中の過
酸化水素、酸性弗化アンモニウム、硫酸、ｏ−ア
ミノ安息香酸、フエノールスルホン酸が減少して
来るので、消耗分を適宜追加し濃度を一定に保つ
た。
この結果を第１図に示した。第１図において、
１は上記した組成からなる本発明の化学的溶解処
理液、２はフエノールスルホン酸を加えない化学
的溶解処理液である。又、Ａは老化点（金属析
出）を示す、尚、処理温度は40℃である。
この結果より、老化点の金属析出濃度は、本発
明の処理液の場合35ｇ／（鉄換算）、フエノー
ルスルホン酸を加えない処理液の場合18ｇ／
（鉄換算）であつた。
実施例 ３
実施例２と同様の方法により鉄−ニツケル−コ
バルト合金（鉄52％、ニツケル22％、コバルト16
％）を溶解し、浴の寿命（老化点）を測定した。
処理温度は40℃である。
使用した化学的溶解処理液は第２表に示したも
のを用いた。尚、化学的溶解処理液１当りで、
老化点迄に出来る処理量（溶解量0.3ｇ／ｄm2と
した）、処理時間（処理速度0.5dm2／minとした）
並びに処理時間比率を並記した。
この結果、本発明の化合物により他の添加剤の
有無にかかわらず浴の寿命はおよそ２〜３倍とな
る。[Table] As a result, by adding the compound according to the present invention, the saturated dissolved concentration of iron increases approximately 2 to 3 times. Example 2 Hydrogen peroxide 80g/acidic ammonium fluoride
20g/, sulfuric acid 1g/, o-aminobenzoic acid,
An iron-nickel alloy (58% iron, 42% nickel) was dissolved using a chemical dissolution solution containing 1 g/20 g/phenolsulfonic acid, and the lifespan (aging point) of the solution was measured. Incidentally, as hydrogen peroxide, acidic ammonium fluoride, sulfuric acid, o-aminobenzoic acid, and phenolsulfonic acid in the solution decreased with dissolution, the consumables were added as appropriate to keep the concentration constant. The results are shown in FIG. In Figure 1,
1 is a chemical dissolution treatment solution of the present invention having the composition described above, and 2 is a chemical dissolution treatment solution to which phenolsulfonic acid is not added. Further, A indicates the aging point (metal precipitation), and the treatment temperature is 40°C. From this result, the metal precipitation concentration at the aging point is 35 g/(iron equivalent) for the treatment solution of the present invention and 18 g/(iron equivalent) for the treatment solution without phenolsulfonic acid.
(iron equivalent). Example 3 An iron-nickel-cobalt alloy (52% iron, 22% nickel, 16 cobalt) was prepared in the same manner as in Example 2.
%) was dissolved and the bath life (aging point) was measured.
The processing temperature is 40°C. The chemical dissolution treatment liquid used was shown in Table 2. In addition, per chemical dissolution treatment liquid,
Amount of processing that can be done up to the aging point (dissolution amount was set at 0.3 g/dm 2 ), processing time (processing speed was set at 0.5 dm 2 /min)
The processing time ratios are also listed. As a result, the life of the bath can be approximately 2-3 times longer with the compounds of the present invention, with or without other additives.
【表】【table】
図面は化学的溶解処理液の寿命（老化点）を示
すグラフである。被処理物は、鉄−ニツケル合金
（鉄58％、ニツケル42％）であり、図において１
は本発明の化学的溶解処理液、２は本発明に係る
添加剤の無添加の場合であり、Ａ点はそれぞれの
老化点（金属析出）を示す。
The drawing is a graph showing the life span (aging point) of the chemical dissolution treatment solution. The object to be treated is an iron-nickel alloy (58% iron, 42% nickel).
2 is the chemical dissolution treatment solution of the present invention, 2 is the case without the addition of the additive according to the present invention, and point A indicates the aging point (metal precipitation) of each.
Claims (1)
を主成分として含有し、フツ酸または重フツ酸イ
オンを少なくとも１ｇ／含有する酸性溶液に、
下記一般式で示されるフエノール性水酸基を有す
る化合物の少なくとも一種を、少なくも0.1ｇ／
含有させた鉄及び鉄合金用化学的溶解処理液。 一般式【式】 （式中Ｘは、Ｈまたは−COOHである。）[Scope of Claims] 1. An acidic solution containing hydrogen peroxide and hydrofluoric acid or difluoric acid ions as main components, and containing at least 1 g of hydrofluoric acid or difluoric acid ions,
At least one type of compound having a phenolic hydroxyl group represented by the following general formula, at least 0.1g/
Chemical dissolution treatment liquid for iron and iron alloys. General formula [Formula] (In the formula, X is H or -COOH.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17598982A JPS5967370A (en) | 1982-10-06 | 1982-10-06 | Chemical dissolving solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17598982A JPS5967370A (en) | 1982-10-06 | 1982-10-06 | Chemical dissolving solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5967370A JPS5967370A (en) | 1984-04-17 |
| JPH0335381B2 true JPH0335381B2 (en) | 1991-05-28 |
Family
ID=16005750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17598982A Granted JPS5967370A (en) | 1982-10-06 | 1982-10-06 | Chemical dissolving solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5967370A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8829253D0 (en) * | 1988-12-15 | 1989-01-25 | Imasa Ltd | Method of removing deposits of tin lead or tin/lead alloys from copper substrates and compositions for use therein |
| JPH09257067A (en) * | 1996-03-19 | 1997-09-30 | Komatsu Ltd | Vehicle brake wear detector |
| KR100248113B1 (en) * | 1997-01-21 | 2000-03-15 | 이기원 | Cleaning and Etching Compositions for Electronic Displays and Substrates |
-
1982
- 1982-10-06 JP JP17598982A patent/JPS5967370A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5967370A (en) | 1984-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3668131A (en) | Dissolution of metal with acidified hydrogen peroxide solutions | |
| JPH0242903B2 (en) | ||
| US3619390A (en) | Aqueous electrolytic stripping bath to remove metal coatings from bases of steel | |
| US4647347A (en) | Process and sealant compositions for sealing anodized aluminum | |
| US4040863A (en) | Method of treating surface of copper and its alloys | |
| CN102159752B (en) | Cyanide free electrolyte composition for the galvanic deposition of a copper layer | |
| JPS6043436B2 (en) | Composition for metal stripping and method thereof | |
| KR101286661B1 (en) | Silver-containing alloy plating bath and method for electrolytic plating using same | |
| CA1046387A (en) | Method and composition for cleaning the surface of ferrous metal | |
| JPH08253880A (en) | Chemical solution for iron-nickel alloy | |
| JPH0335381B2 (en) | ||
| JPS63286585A (en) | Chemical treating solution for titanium or alloy thereof and surface treatment of titanium or alloy thereof with said solution | |
| US3094489A (en) | Method and composition for brightening aluminum | |
| US3494839A (en) | Method of sealing chromic acid anodized aluminum surfaces | |
| JP3361680B2 (en) | Surface treatment solution for copper or copper alloy | |
| US3822156A (en) | Sealing and desmudging anodized aluminum | |
| KR20120051658A (en) | Tin-containing alloy plating bath, electroplating method using same, and base having electroplated material deposited thereon | |
| KR100453804B1 (en) | Surface Treatment Compositions And Method For Removing Si Component And Reduced Metal Salt On The Aluminum Dicast Substrate In Etching Process | |
| CN113860914A (en) | Soaking solution for removing white cobblestone rust macular and preparation method thereof, and method for removing white cobblestone rust macular | |
| EP0351771B1 (en) | Non-chrome cleaner/deoxidizer system | |
| US3410803A (en) | Novel process and composition for brightening aluminum | |
| JP3033455B2 (en) | Electroless nickel plating of aluminum | |
| US2871172A (en) | Electro-plating of metals | |
| CN115323364A (en) | A kind of preparation method and application of high temperature zinc-manganese phosphating solution | |
| JPH01215993A (en) | Additive for pickling acid solution |