JP4921001B2 - How to remove patina - Google Patents
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- JP4921001B2 JP4921001B2 JP2006070908A JP2006070908A JP4921001B2 JP 4921001 B2 JP4921001 B2 JP 4921001B2 JP 2006070908 A JP2006070908 A JP 2006070908A JP 2006070908 A JP2006070908 A JP 2006070908A JP 4921001 B2 JP4921001 B2 JP 4921001B2
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- 241001311547 Patina Species 0.000 title claims description 56
- FAUOSXUSCVJWAY-UHFFFAOYSA-N tetrakis(hydroxymethyl)phosphanium Chemical class OC[P+](CO)(CO)CO FAUOSXUSCVJWAY-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910000881 Cu alloy Inorganic materials 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Cleaning By Liquid Or Steam (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
本発明は、空調機、冷凍機等の熱交換器や配管などの、水系水に接する銅製機器を初めとする、銅製物品や銅合金製物品（部材を含む）に発生した緑青の除去に関する。 The present invention relates to the removal of patina generated in copper articles and copper alloy articles (including members) such as heat exchangers and pipes such as air conditioners and refrigerators, including copper equipment in contact with aqueous water.
冷却水系等の各種水系に使用される銅または銅合金よりなる配管、熱交換器、その他の部材では、銅の酸化による緑青（塩基性炭酸銅ＣｕＣＯ３・Ｃｕ（ＯＨ）２や塩基性硫酸銅ＣｕＳＯ４・３Ｃｕ（ＯＨ）２を中心とした塩基性化合物）の発生が問題となっている。 For pipes, heat exchangers and other parts made of copper or copper alloys used in various water systems such as cooling water systems, patina (basic copper carbonate CuCO 3 · Cu (OH) 2 or basic copper sulfate by oxidation of copper) The generation of basic compounds centering on CuSO 4 .3Cu (OH) 2 is a problem.
緑青はこれら銅・銅合金機器表面に、点状や斑点状、あるいは面状に発生するが、これら緑青はさらなる腐食や孔食の原因になったり、また、これら緑青には水系水内に発生するスケールや生物のスライムが付着しやすいので熱交換機器の場合には熱交換効率を低下させたり、生物腐食等の問題の原因となる。このため、これら機器に緑青が発生した場合、可及的速やかに除去することが望ましい。 The patinas appear on the surface of these copper and copper alloy equipment in the form of spots, spots, or planes, but these patinas cause further corrosion and pitting corrosion, and these patinas occur in aqueous water. In the case of a heat exchange device, the heat exchange efficiency is reduced and problems such as biological corrosion are caused. For this reason, when patina is generated in these devices, it is desirable to remove them as soon as possible.
しかしながら、銅材質表面に生成する酸化銅を含む腐食生成物を除去する方法としては、従来、塩酸あるいはスルファミン酸を用いた酸洗浄が行われてきた。しかし、酸洗浄を行った場合、酸が残存した場合、その場所から孔食が生じるおそれがあり、緑青除去処理後には充分洗浄し、酸を完全に洗い流さなければならず、また、排出される洗浄廃液は強酸性溶液であることから、適正なｐＨになるように処理を行わなければならない。 However, acid cleaning using hydrochloric acid or sulfamic acid has been conventionally performed as a method for removing corrosion products including copper oxide formed on the surface of a copper material. However, when acid cleaning is performed, if the acid remains, pitting corrosion may occur from the place, and after removing the patina, the acid must be thoroughly washed out and discharged. Since the washing waste liquid is a strongly acidic solution, it must be treated so as to have an appropriate pH.
また、ヒドラジンによる緑青除去方法も提案されているが（特開昭６１−２７２３９２号公報（特許文献１））、ヒドラジンは発がん性等、安全性の疑いがある。 Further, although a method for removing patina with hydrazine has been proposed (Japanese Patent Laid-Open No. 61-272392 (Patent Document 1)), hydrazine is suspected of safety such as carcinogenicity.
なお、銅材質に対する防食剤としては、トリルトリアゾール、ベンゾトリアゾール、メルカプトベンゾチアゾールが主に使用されている。しかしながら、これらの防食剤はすでに発生した緑青を除去することはできないので、銅表面を清浄に回復させることは難しく、緑青による新たな腐食の発生・進行のおそれを払拭することができない。
本発明は、上記した従来の問題点を改善する、すなわち、ヒドラジンなどの安全性に疑いのある薬品を用いることなく、処理後の腐食の恐れも「やせ」発生の恐れもない、迅速な緑青除去処理が可能な緑青除去方法を提供することを目的とする。 The present invention improves the above-mentioned conventional problems, that is, without using a chemical with a suspected safety such as hydrazine, and does not cause the risk of corrosion after processing or the occurrence of “fading”. It is an object of the present invention to provide a patina removal method that can be removed.
また、本発明の緑青除去方法は上記課題を解決するため、請求項１に記載の通り、テトラキス（ヒドロキシメチル）ホスホニウム塩を５０ｍｇ／Ｌ以上５００ｍｇ／Ｌ以下含む薬液に、緑青が発生した物品を３０分以上４８時間以下の処理時間で接触させる緑青除去方法である。 In addition, in order to solve the above-mentioned problem, the method for removing patina of the present invention provides an article in which patina is generated in a chemical solution containing 50 mg / L or more and 500 mg / L or less of tetrakis (hydroxymethyl) phosphonium salt as described in claim 1. This is a patina removal method in which contact is made for a treatment time of 30 minutes to 48 hours .
本発明の緑青除去剤によれば、テトラキス（ヒドロキシメチル）ホスホニウム塩を用いることで低濃度での使用であっても短時間で緑青を効果的に除去でき、延いては腐食を効果的に防止することができる。 According to the patina remover of the present invention, by using a tetrakis (hydroxymethyl) phosphonium salt, it is possible to effectively remove patina in a short time even when used at a low concentration, thereby effectively preventing corrosion. can do.
本発明では緑青除去剤の有効成分として、テトラキス（ヒドロキシメチル）ホスホニウム塩を用いる。テトラキス（ヒドロキシメチル）ホスホニウム塩としては、緑青除去効果が得られる濃度で水に溶解すれば、無機酸との塩であっても、有機酸との塩であっても良いが、硫酸塩が入手しやすい（入手先：ローディアジャパン社等）。 In the present invention, tetrakis (hydroxymethyl) phosphonium salt is used as the active ingredient of the patina removing agent. The tetrakis (hydroxymethyl) phosphonium salt may be a salt with an inorganic acid or a salt with an organic acid as long as it dissolves in water at a concentration that provides a patina removal effect. Easy to obtain (source: Rhodia Japan, etc.).
テトラキス（ヒドロキシメチル）ホスホニウム塩の水溶液は緑青除去用途として用いる通常の濃度であれば、特別な処理なしに廃棄できる。ただし、緑青除去処理に使用した後の水溶液には緑青由来の、銅などの成分が含まれているので、その種類及び含有量に従って適正に処理する必要がある。 The aqueous solution of tetrakis (hydroxymethyl) phosphonium salt can be discarded without special treatment if it is a normal concentration used for removing patina. However, since the aqueous solution after being used for the patina removal treatment contains components such as copper derived from patina, it is necessary to treat it appropriately according to its type and content.
本発明の緑青除去剤ではテトラキス（ヒドロキシメチル）ホスホニウム塩の濃度を通常、２０ｍｇ／Ｌ以上１０００ｍｇ／Ｌ以下の範囲の水溶液として、緑青除去対象の機器・配管に接触させる。このとき２０ｍｇ／Ｌ未満であると充分な緑青除去処理効果が得られない場合があり、また１０００ｍｇ／Ｌ超添加しても添加量の増加に見合う緑青除去効果の増加が見られないので無駄となることがある。テトラキス（ヒドロキシメチル）ホスホニウム塩の濃度のより好ましい範囲としては５０ｍｇ／Ｌ以上５００ｍｇ／Ｌ以下の範囲である。 In the patina-removing agent of the present invention, the concentration of the tetrakis (hydroxymethyl) phosphonium salt is usually brought into contact with the device / pipe to be removed with patina as an aqueous solution in the range of 20 mg / L to 1000 mg / L. At this time, if it is less than 20 mg / L, a sufficient patina removal effect may not be obtained, and even if added over 1000 mg / L, an increase in the patina removal effect commensurate with the increase in the amount added is not seen, which is wasteful. May be. A more preferable range of the concentration of the tetrakis (hydroxymethyl) phosphonium salt is a range of 50 mg / L to 500 mg / L.
テトラキス（ヒドロキシメチル）ホスホニウム硫酸塩を用いた場合、一般的な冷却水、冷温水、工業用水などに上記範囲で溶解させた場合、そのｐＨは中性域（ｐＨ６〜９程度）である。 When tetrakis (hydroxymethyl) phosphonium sulfate is used, the pH is in the neutral range (about pH 6 to 9) when dissolved in general cooling water, cold / warm water, industrial water or the like in the above range.
ここで、本発明の緑青除去剤の使用方法としては、例えば冷暖房などの用途に用いられる機器や配管などの場合には、それら機器や配管に接する水系水を一旦すべて排水した後に、銅・銅合金製の機器・配管等の緑青除去目的物に適切な濃度のテトラキス（ヒドロキシメチル）ホスホニウム塩を有する溶液を接触させてもよいが、使用していた水系水にそのままテトラキス（ヒドロキシメチル）ホスホニウム塩を添加して適切な濃度として用いても良い。 Here, as a method of using the patina remover of the present invention, for example, in the case of equipment and piping used for applications such as cooling and heating, after draining all the aqueous water in contact with the equipment and piping, A solution having an appropriate concentration of tetrakis (hydroxymethyl) phosphonium salt may be brought into contact with the target object for removing patina, such as alloy equipment and piping. Tetrakis (hydroxymethyl) phosphonium salt is used as it is in the aqueous water used May be used as an appropriate concentration.
なお、緑青除去処理を行った後は、例えば冷暖房などの用途に用いられる機器や配管などの場合には、通常は、処理廃水を全部排水して、必要に応じて適宜洗浄し、次いで、再度水系の運転に適した水を補充した後、その水系水の運転を行う。ただし、除去された緑青による銅濃度が高くない場合には、水系水の全交換はしなくても、少量ずつ水を入れ替えながら運転を継続することができる。 In addition, after performing the patina removal process, for example, in the case of equipment or piping used for applications such as air conditioning, usually drain all the processing wastewater, wash it as necessary, and then again After replenishing water suitable for the operation of the water system, the water system is operated. However, when the copper concentration by the removed patina is not high, the operation can be continued while replacing the water little by little, without completely replacing the aqueous water.
ここで上述のようにテトラキス（ヒドロキシメチル）ホスホニウム塩の水溶液は中性域であるため、テトラキス（ヒドロキシメチル）ホスホニウム塩が水系内に多少残留した場合であっても、新たな腐食を引き起こす恐れはない。 Here, since the aqueous solution of tetrakis (hydroxymethyl) phosphonium salt is in the neutral range as described above, even if the tetrakis (hydroxymethyl) phosphonium salt remains somewhat in the aqueous system, there is a risk of causing new corrosion. Absent.
冷暖房などの用途に用いられる機器や配管などの場合以外での、テトラキス（ヒドロキシメチル）ホスホニウム塩を有する溶液を接触させる方法としては、例えば、直接操作可能な面の場合には溶液のシャワーや噴霧による接触、あるいは溶液への浸漬、あるいは、溶液を保持できるスポンジ・繊維体などの併用による接触等が挙げられるが、本発明はこれらに限定されず、緑青が発生した部分に本発明の緑青除去剤が接触できれば良い。なお、テトラキス（ヒドロキシメチル）ホスホニウム塩を有する溶液との接触の後には、適当な手段で洗浄を行い、テトラキス（ヒドロキシメチル）ホスホニウム塩を除去する。 As a method of bringing a solution having a tetrakis (hydroxymethyl) phosphonium salt into contact with a device other than equipment or piping used for applications such as air conditioning, for example, in the case of a directly operable surface, a solution shower or spray Contact by immersion, immersion in a solution, or contact by combined use of a sponge / fiber body capable of holding the solution, etc., but the present invention is not limited thereto, and the patina removal of the present invention is applied to a portion where patina is generated. What is necessary is just to be able to contact the agent. In addition, after contact with the solution having a tetrakis (hydroxymethyl) phosphonium salt, washing is performed by an appropriate means to remove the tetrakis (hydroxymethyl) phosphonium salt.
緑青除去処理時間としては、水温（処理温度）、使用濃度、あるいは、緑青の発生状況を勘案して決定するが、通常３０分以上４８時間以下である。 The patina removal treatment time is determined in consideration of the water temperature (treatment temperature), the use concentration, or the occurrence of patina, but it is usually 30 minutes to 48 hours.
本発明の緑青除去剤にはテトラキス（ヒドロキシメチル）ホスホニウム塩の他にテトラキス（ヒドロキシメチル）ホスホニウム塩の効果を妨げない範囲で他の補助成分が添加されていても良い。このようなものとしては、ｐＨ緩衝剤、アゾール類などの銅防食剤、ポリマレイン酸、ポリアクリル酸、ホスホン酸等の分散剤などが挙げられる。 In addition to the tetrakis (hydroxymethyl) phosphonium salt, other auxiliary components may be added to the patina removing agent of the present invention as long as the effect of the tetrakis (hydroxymethyl) phosphonium salt is not hindered. Examples thereof include pH buffering agents, copper anticorrosives such as azoles, and dispersants such as polymaleic acid, polyacrylic acid, and phosphonic acid.
以下に本発明の緑青除去剤の実施例について具体的に説明する。
つくば市水（各種成分分析結果を表１に示す）にテトラキス（ヒドロキシメチル）ホスホニウム硫酸塩を所定濃度（０ｍｇ／Ｌ（添加なし）、２０ｍｇ／Ｌ、３０ｍｇ／Ｌ、５０ｍｇ／Ｌ、７５ｍｇ／Ｌ、２２５ｍｇ／Ｌ、３７５ｍｇ／Ｌ）添加して溶解し、これらそれぞれ１０００ｍＬに緑青が発生しているテストピース（ＴＣｕＰ。大きさ：２ｃｍ×６ｃｍ×２ｍｍ。緑青はテストピース表面に島状に発生している。なお、テストピースは、同程度の面積に緑青が発生しているものを目視で選択して用いた）をそれぞれ１枚ずつ浸漬し、３００ｒｐｍ、３５℃で放置し、その後の緑青の除去状態を観察した。
Examples of the patina removing agent of the present invention will be specifically described below.
Tsukuba city water (various component analysis results are shown in Table 1) with tetrakis (hydroxymethyl) phosphonium sulfate at a predetermined concentration (0 mg / L (no addition), 20 mg / L, 30 mg / L, 50 mg / L, 75 mg / L) 225 mg / L, 375 mg / L) added and dissolved, and each of these 1000 mL of test pieces (TCuP. Size: 2 cm × 6 cm × 2 mm). In addition, the test pieces were used by selecting one piece each having a patina of the same area by visual observation) and letting it stand at 300 rpm and 35 ° C. The removal state was observed.
また、比較として、銅の防食剤であるベンゾトリアゾールの１００ｍｇ／Ｌ水溶液（水としてはつくば市水を使用）１０００ｍＬにも上記同様に緑青が付着したテストピースを浸漬した（従来例）。 For comparison, a test piece with patina adhering to 1000 mL of a 100 mg / L aqueous solution of benzotriazole, which is a copper anticorrosive (uses Tsukuba city water as water), was also immersed (conventional example).
緑青除去効果の判定は目視で行った。変化がない場合は「×」、若干除去された場合は「△」、緑青の痕跡は残ったものの、ほぼ除去されている場合には「○」、さらに痕跡も残さずに緑青が除去できた場合には「◎」として、それぞれ評価した。 Judgment of the effect of removing patina was made visually. “X” when there is no change, “△” when it is slightly removed, “○” when it is almost removed, but patina can be removed without leaving any trace. In some cases, each was evaluated as “◎”.
また、これら目視判定に加えて、質量変化（減量）を調べた。結果は（）内に併せて示した。 In addition to these visual determinations, mass changes (weight loss) were examined. The results are shown in parentheses.
ここで、緑青除去処理によって、緑青が除去されるとテストピースの質量はある程度失われるが、同時に、テストピースの緑青発生部分以外の場所からの銅の溶出が大きいと、テストピースの質量は大きく失われ、銅・銅合金機器の肉厚の「やせ」が発生する。 Here, when the patina is removed by the patina removal process, the mass of the test piece is lost to some extent, but at the same time, if the elution of copper from a place other than the portion of the test piece where the patina is generated is large, the mass of the test piece becomes large. Lost, resulting in a “thin” thickness of copper / copper alloy equipment.
後者、すなわち、銅・銅合金機器の緑青発生部分以外の場所からの銅の溶出の大小は、緑青が発生していないテストピースを用いて、テトラキス（ヒドロキシメチル）ホスホニウム硫酸塩水溶液に浸漬した比較例により判断することができるので、緑青発生のない（新品の）テストピースについて、上記同様に調製した３７５ｍｇ／Ｌのテトラキス（ヒドロキシメチル）ホスホニウム硫酸塩水溶液１０００ｍＬに浸漬する比較例も行った。その結果を表２に併せて記載した。 The latter, that is, the amount of copper leaching from places other than the patina area of the copper / copper alloy equipment was compared with the test piece that did not generate patina and immersed in an aqueous solution of tetrakis (hydroxymethyl) phosphonium sulfate. Since it can be judged by an example, a comparative example in which a test piece having no patina (new article) was immersed in 1000 mL of a 375 mg / L tetrakis (hydroxymethyl) phosphonium sulfate aqueous solution prepared in the same manner as described above was also performed. The results are also shown in Table 2.
表２よりテトラキス（ヒドロキシメチル）ホスホニウム硫酸塩の添加量が２０ｍｇ／Ｌ以上の水溶液による処理で緑青を除去できること、及び、添加量が５０ｍｇ／Ｌ以上で、より短い時間で緑青を効果的に除去できることが判る。 Table 2 shows that patina can be removed by treatment with an aqueous solution of tetrakis (hydroxymethyl) phosphonium sulfate with an addition amount of 20 mg / L or more, and patina is effectively removed in a shorter time with an addition amount of 50 mg / L or more. I understand that I can do it.
また、緑青が発生していないテストピースをテトラキス（ヒドロキシメチル）ホスホニウム硫酸塩の添加量が３７５ｍｇ／Ｌの溶液に浸漬した比較例と、同濃度の溶液に緑青が発生しているサンプルを浸漬した実施例とを比較すると、本発明の緑青除去剤では、２時間と云う短い処理時間で極めて高い緑青除去性能が得られる濃度の添加であっても、緑青の発生していない部分からの銅の溶出は極めて少なく、２４時間接触させた場合であっても、銅・銅合金機器の肉厚の「やせ」が発生するような大きい銅の溶出の懸念がないことが確認された。 In addition, a test piece in which patina was not generated was immersed in a solution having an addition amount of tetrakis (hydroxymethyl) phosphonium sulfate of 375 mg / L, and a sample in which patina was generated was immersed in a solution having the same concentration. Comparing with the examples, with the patina removing agent of the present invention, even when the concentration is such that extremely high patina removing performance is obtained in a short processing time of 2 hours, the copper from the portion where no patina is generated is compared. It was confirmed that there was no fear of large copper elution that would cause a thinness of the thickness of the copper / copper alloy device even when contacted for 24 hours.
一方、一般的な銅の防食剤であるベンゾトリアゾールでは、一旦発生した緑青を除去することができないことも確認された。 On the other hand, it was also confirmed that benzotriazole, which is a general copper anticorrosive, cannot remove the patina once generated.
本発明は、空調機、冷凍機などの熱交換器や配管などの、水系水に接する銅製機器を初めとする、銅製物品や銅合金製物品に発生した緑青の除去に利用でき、安全性に疑いのある薬品を用いず、処理後の腐食の恐れもない、迅速な緑青除去処理が可能な緑青除去剤である。 INDUSTRIAL APPLICABILITY The present invention can be used for removing patina generated in copper articles and copper alloy articles, including copper equipment that comes into contact with aqueous water, such as heat exchangers and pipes such as air conditioners and refrigerators, for safety. It is a patina-removing agent that does not use suspected chemicals and does not cause the risk of corrosion after the treatment and can be quickly removed.
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