JP6589349B2 - Patina inhibitor and patina inhibitor method - Google Patents
Patina inhibitor and patina inhibitor method Download PDFInfo
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- JP6589349B2 JP6589349B2 JP2015083667A JP2015083667A JP6589349B2 JP 6589349 B2 JP6589349 B2 JP 6589349B2 JP 2015083667 A JP2015083667 A JP 2015083667A JP 2015083667 A JP2015083667 A JP 2015083667A JP 6589349 B2 JP6589349 B2 JP 6589349B2
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- 241001311547 Patina Species 0.000 title claims description 99
- 239000003112 inhibitor Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 25
- 230000002401 inhibitory effect Effects 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkali metal salts Chemical class 0.000 claims description 10
- AYWHENVLARCQQQ-UHFFFAOYSA-N copper;1h-pyrrole Chemical compound [Cu].C=1C=CNC=1 AYWHENVLARCQQQ-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- CYSFGVBLJIQAMD-UHFFFAOYSA-N carbamodithioic acid;piperazine Chemical compound NC(S)=S.NC(S)=S.C1CNCCN1 CYSFGVBLJIQAMD-UHFFFAOYSA-N 0.000 claims description 8
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 5
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 4
- XGIDEUICZZXBFQ-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol Chemical compound C1=CC=C2NC(CS)=NC2=C1 XGIDEUICZZXBFQ-UHFFFAOYSA-N 0.000 claims description 4
- UMZCLZPXPCNKML-UHFFFAOYSA-N 2h-imidazo[4,5-d][1,3]thiazole Chemical compound C1=NC2=NCSC2=N1 UMZCLZPXPCNKML-UHFFFAOYSA-N 0.000 claims description 4
- IXXAYKKRCMMEBY-UHFFFAOYSA-N 5h-pyrazolo[3,4-d][1,3]oxazole Chemical compound N1=NC2=NCOC2=C1 IXXAYKKRCMMEBY-UHFFFAOYSA-N 0.000 claims description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000003536 tetrazoles Chemical class 0.000 claims description 4
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 claims description 4
- 229960004546 thiabendazole Drugs 0.000 claims description 4
- 235000010296 thiabendazole Nutrition 0.000 claims description 4
- 239000004308 thiabendazole Substances 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- NYZGRSIYJUWVQM-UHFFFAOYSA-N C(N)(S)=S.NCCNCCNCCNCCN Chemical compound C(N)(S)=S.NCCNCCNCCNCCN NYZGRSIYJUWVQM-UHFFFAOYSA-N 0.000 claims description 3
- SZRLKIKBPASKQH-UHFFFAOYSA-N dibutyldithiocarbamic acid Chemical compound CCCCN(C(S)=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- IIAOJWVDGQZJOL-UHFFFAOYSA-N 4-trityl-2h-triazole Chemical compound N1N=NC(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 IIAOJWVDGQZJOL-UHFFFAOYSA-N 0.000 claims 2
- 239000010949 copper Substances 0.000 description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 43
- 229910052802 copper Inorganic materials 0.000 description 43
- 239000000498 cooling water Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000012990 dithiocarbamate Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- YBKBEKGVHFHCRI-UHFFFAOYSA-L zinc;piperidine-1-carbodithioate Chemical compound [Zn+2].[S-]C(=S)N1CCCCC1.[S-]C(=S)N1CCCCC1 YBKBEKGVHFHCRI-UHFFFAOYSA-L 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LYRDOGBAHPMIRB-UHFFFAOYSA-L [K+].C(N)([S-])=S.C(N)([S-])=S.N1CCNCC1.[K+] Chemical compound [K+].C(N)([S-])=S.C(N)([S-])=S.N1CCNCC1.[K+] LYRDOGBAHPMIRB-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- QNTARNCGFNQQRP-UHFFFAOYSA-N 5-carbamothioylsulfanylpentyl carbamodithioate Chemical compound NC(=S)SCCCCCSC(N)=S QNTARNCGFNQQRP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GWXMDJKGVWQLBZ-UHFFFAOYSA-N di(propan-2-yl)carbamodithioic acid Chemical compound CC(C)N(C(C)C)C(S)=S GWXMDJKGVWQLBZ-UHFFFAOYSA-N 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- BQCRLWBELMWYQA-UHFFFAOYSA-N dipropylcarbamodithioic acid Chemical compound CCCN(C(S)=S)CCC BQCRLWBELMWYQA-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- HUEQEOFKPWOYJN-UHFFFAOYSA-L disodium piperazine dicarbamodithioate Chemical compound [Na+].[Na+].NC([S-])=S.NC([S-])=S.C1CNCCN1 HUEQEOFKPWOYJN-UHFFFAOYSA-L 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent 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
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
本発明は、銅チューブ等の銅材質を含む冷却水系等の水処理に関し、特に、銅材質の表面における緑青の発生を阻止する緑青阻止剤及びこれを用いた緑青阻止方法に関する。 The present invention relates to a water treatment such as a cooling water system including a copper material such as a copper tube, and more particularly, to a patina-inhibiting agent that inhibits the generation of patina on the surface of the copper material and a patina-inhibiting method using the same.
銅は、耐食性や熱伝導性に優れ、加工しやすい等の利点を有している。このため、銅又は銅合金（以下、単に、銅とも言う。）として、空調機器や熱交換器、冷凍機等の冷却水系における銅チューブ等に多用されている。
このような銅チューブは、長時間使用すると孔食等の腐食が生じ、これは時間の経過とともに進行し、装置に重大な欠陥を与え、安全な運転を妨げる原因となる。
Copper has advantages such as excellent corrosion resistance and thermal conductivity, and easy processing. For this reason, it is frequently used as a copper tube or the like in a cooling water system such as an air conditioner, a heat exchanger, and a refrigerator as copper or a copper alloy (hereinafter also simply referred to as copper).
When such a copper tube is used for a long time, corrosion such as pitting corrosion occurs, which progresses with the passage of time, causes a serious defect in the apparatus and causes a safe operation.
銅の腐食生成物である緑青に対しては、従来、銅用防食剤を用いて発生を防止したり、薬剤を用いて化学的に緑青を除去することが行われている。
ここで、緑青とは、塩基性硫酸銅（ＣｕＳＯ４・３Ｃｕ（ＯＨ）２）や塩基性炭酸銅（ＣｕＣＯ３・Ｃｕ（ＯＨ）２）を主成分とする緑色の錆を言う。
Conventionally, the patina, which is a copper corrosion product, has been prevented by using a copper anticorrosive agent or chemically removed by using a chemical.
Here, patina refers to green rust mainly composed of basic copper sulfate (CuSO 4 .3Cu (OH) 2 ) or basic copper carbonate (CuCO 3 .Cu (OH) 2 ).
一般的な緑青の除去方法としては、塩酸等の強酸を用いることが知られている。また、特許文献１には、ヒドラジンと銅用防食剤を含む緑青除去剤が記載されている。
また、特許文献２には、銅用防食剤としてジチオカルバミン酸類又はその塩類を用いることが記載されている。
As a general method for removing patina, it is known to use a strong acid such as hydrochloric acid. Patent Document 1 describes a patina remover containing hydrazine and an anticorrosive for copper.
Patent Document 2 describes the use of dithiocarbamic acids or salts thereof as an anticorrosive for copper.
しかしながら、強酸は、銅地金に対しても腐食性を有しており、その取り扱いは危険を伴うものであった。その上、使用済みの酸性廃液を排出する際には中和処理が必要となり、多量の中和剤や水を使用して、緑青除去後の銅表面を十分にリンスする必要があった。 また、特許文献１に記載の緑青除去剤は、緑青除去効果には優れているものの、ヒドラジンは発がん性の疑いがあり、その使用を避けたいとの要望が強くなってきている。
一方、特許文献２には、ジチオカルバミン酸類又はその塩類が、銅表面に対して予め保護バリアー又は保護皮膜を形成することにより、銅の腐食を防止できることが記載されているが、該文献に記載の銅用防食剤が、銅表面における緑青の発生を阻止できること、さらに、発生した緑青を除去できることについては記載されていない。
However, strong acids are corrosive to copper bullion and their handling is dangerous. In addition, neutralization treatment is required when discharging the used acidic waste liquid, and it is necessary to sufficiently rinse the copper surface after removing the patina using a large amount of neutralizing agent and water. Moreover, although the patina remover described in Patent Document 1 is excellent in the patina removal effect, hydrazine is suspected to be carcinogenic and there is an increasing demand for avoiding its use.
On the other hand, Patent Document 2 describes that dithiocarbamic acids or salts thereof can prevent copper corrosion by forming a protective barrier or protective film on the copper surface in advance. It is not described that the anticorrosive agent for copper can prevent the generation of patina on the copper surface, and further can remove the generated patina.
本発明は、このような状況下でなされたものであり、銅表面に損傷を与えることなく、銅表面における緑青の発生を阻止し、さらに、発生した緑青を除去することができる緑青阻止剤及びこれを用いた緑青阻止方法を提供することを目的とする。 The present invention has been made under such circumstances, and prevents the generation of patina on the copper surface without damaging the copper surface, and further, the patina inhibitor capable of removing the generated patina. It aims at providing the patina prevention method using this.
本発明は、水溶性のジチオカルバミン酸類が、銅表面における緑青阻止効果に優れていることを見出したことに基づくものである。 The present invention is based on the discovery that water-soluble dithiocarbamic acids are excellent in the patina-inhibiting effect on the copper surface.
すなわち、本発明は、以下の［１］〜［７］を提供する。
［１］ジチオカルバミン酸及びその塩のうちから選ばれる少なくとも１種の水溶性化合物を含む、緑青阻止剤。
［２］アゾール系銅用防食剤を含む、上記［１］に記載の緑青阻止剤。
［３］前記アゾール系銅用防食剤が、イミダゾール、ピラゾール、オキサゾール、チアゾール、トリアゾール、テトラゾール、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾイソオキサゾール、ベンゾチアゾール、メルカプトベンゾイミダゾール、メルカプトメチルベンゾイミダゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール、トリルトリアゾール、インダゾール、プリン、イミダゾチアゾール、ピラゾロオキサゾール及びチアベンダゾール、並びにこれらの化合物の塩のうちから選ばれる少なくとも１種である、上記［２］に記載の緑青阻止剤。
［４］前記ジチオカルバミン酸が、ジエチルジチオカルバミン酸、ジブチルジチオカルバミン酸、ピペラジンビスジチオカルバミン酸、テトラエチレンペンタミンジチオカルバミン酸及びペンタメチレンジチオカルバミン酸のうちから選ばれる少なくとも１種である、上記［１］〜［３］のいずれかに記載の緑青阻止剤。
［５］前記水溶性化合物が、テトラエチレンペンタミンジチオカルバミン酸及びピペラジンビスジチオカルバミン酸、並びにこれらの化合物のアルカリ金属塩のうちから選ばれる少なくとも１種である、上記［１］〜［４］のいずれかに記載の緑青阻止剤。
That is, the present invention provides the following [1] to [7].
[1] A patina inhibitor comprising at least one water-soluble compound selected from dithiocarbamic acid and salts thereof.
[2] The patina inhibitor according to the above [1], which contains an azole copper anticorrosive.
[3] The anticorrosive for azole copper is imidazole, pyrazole, oxazole, thiazole, triazole, tetrazole, benzimidazole, benzoxazole, benzisoxazole, benzothiazole, mercaptobenzimidazole, mercaptomethylbenzimidazole, mercaptobenzothiazole, The patina inhibitor according to the above [2], which is at least one selected from benzotriazole, tolyltriazole, indazole, purine, imidazothiazole, pyrazolooxazole and thiabendazole, and salts of these compounds.
[4] The above [1] to [3], wherein the dithiocarbamic acid is at least one selected from diethyldithiocarbamic acid, dibutyldithiocarbamic acid, piperazine bisdithiocarbamic acid, tetraethylenepentaminedithiocarbamic acid and pentamethylenedithiocarbamic acid. ]. The patina inhibitor according to any one of the above.
[5] Any of the above [1] to [4], wherein the water-soluble compound is at least one selected from tetraethylenepentamine dithiocarbamic acid, piperazine bisdithiocarbamic acid, and alkali metal salts of these compounds. The patina of crab.
［６］上記［１］〜［５］のいずれかに記載の緑青阻止剤を用いる緑青阻止方法であって、水系において、前記緑青阻止剤を前記水溶性化合物の濃度が５〜１００００ｍｇ／Ｌとなるように調整して使用する、緑青阻止方法。
［７］緑青が発生している箇所に、前記緑青阻止剤を使用する、上記［６］に記載の緑青阻止方法。
[6] A patina treatment method using the patina inhibitor according to any one of [1] to [5], wherein in the aqueous system, the patina inhibitor has a concentration of the water-soluble compound of 5 to 10,000 mg / L. The patina prevention method that is adjusted and used.
[7] The patina-inhibiting method according to [6], wherein the patina-inhibiting agent is used at a site where patina is generated.
本発明の緑青阻止剤を用いれば、銅表面に損傷を与えることなく、銅表面における緑青の発生を阻止し、しかも、発生した緑青を除去することができる。したがって、本発明の緑青阻止剤は、空調機器や熱交換器、冷凍機等の冷却水系における銅チューブや、その他銅建材等の洗浄にも好適に用いることができる。
また、本発明の緑青阻止剤を用いた緑青阻止方法は、銅表面における緑青阻止効果を得るのに好適な方法であり、特に、冷却水系の銅チューブ等に発生した緑青の除去に好適に適用することができる。
If the patina of the present invention is used, the generation of patina on the copper surface can be prevented and the generated patina can be removed without damaging the copper surface. Therefore, the patina inhibitor of the present invention can be suitably used for cleaning copper tubes in cooling water systems such as air conditioners, heat exchangers, refrigerators, and other copper building materials.
Further, the patina treatment method using the patina inhibitor of the present invention is a suitable method for obtaining the patina treatment effect on the copper surface, and is particularly suitable for removing patina produced in a cooling water copper tube or the like. can do.
本発明の緑青阻止剤は、ジチオカルバミン酸及びその塩のうちから選ばれる少なくとも１種の水溶性化合物を有効成分として含むものである。このような水溶性のジチオカルバミン酸類は、銅表面における緑青の発生を阻止し、かつ、発生した緑青を除去する効果に優れている。 The patina inhibitor of the present invention contains at least one water-soluble compound selected from dithiocarbamic acid and salts thereof as an active ingredient. Such water-soluble dithiocarbamic acids are excellent in the effect of preventing the generation of patina on the copper surface and removing the generated patina.
（水溶性化合物）
本発明の緑青阻止剤の有効成分である水溶性化合物は、ジチオカルバミン酸又はその塩である。
なお、本発明で言う「水溶性」とは、薬剤としての実用性の観点から、２５℃の水１００ｇに対して５００ｍｇ以上溶解するものとする。
(Water-soluble compounds)
The water-soluble compound which is an active ingredient of the patina inhibitor of the present invention is dithiocarbamic acid or a salt thereof.
In the present invention, “water-soluble” means that 500 mg or more is dissolved in 100 g of water at 25 ° C. from the viewpoint of practicality as a drug.
前記ジチオカルバミン酸としては、水溶性のジチオカルバミン酸であれば、特に限定されるものではなく、例えば、ジメチルジチオカルバミン酸、ジエチルジチオカルバミン酸、ジプロピルジチオカルバミン酸、ジイソプロピルジチオカルバミン酸、ジブチルジチオカルバミン酸、ピペラジンビスジチオカルバミン酸、テトラエチレンペンタミンジチオカルバミン酸及びペンタメチレンジチオカルバミン酸等が挙げられ、これらの中でも、ジエチルジチオカルバミン酸、ピペラジンビスジチオカルバミン酸、テトラエチレンペンタミンジチオカルバミン酸及びペンタメチレンジチオカルバミン酸が好ましい。冷却水での使用においては、ピペラジンビスジチオカルバミン酸、テトラエチレンペンタミンジチオカルバミン酸及びペンタメチレンジチオカルバミン酸が好ましい。 The dithiocarbamic acid is not particularly limited as long as it is water-soluble dithiocarbamic acid. For example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dipropyldithiocarbamic acid, diisopropyldithiocarbamic acid, dibutyldithiocarbamic acid, piperazine bisdithiocarbamic acid Tetraethylenepentamine dithiocarbamic acid, pentamethylenedithiocarbamic acid and the like. Among these, diethyldithiocarbamic acid, piperazine bisdithiocarbamic acid, tetraethylenepentaminedithiocarbamic acid and pentamethylenedithiocarbamic acid are preferable. For use in cooling water, piperazine bisdithiocarbamic acid, tetraethylenepentamine dithiocarbamic acid and pentamethylenedithiocarbamic acid are preferred.
前記ジチオカルバミン酸の塩は、水溶性の塩であれば、特に限定されるものではなく、例えば、ナトリウム塩及びカリウム塩等のアルカリ金属塩、その他の金属塩、並びにアンモニウム塩等が挙げられる。これらの中でも、ジエチルジチオカルバミン酸、ピペラジンビスジチオカルバミン酸、テトラエチレンペンタミンジチオカルバミン酸及びペンタメチレンジチオカルバミン酸のアルカリ金属塩、また、ペンタメチレンジチオカルバミン酸亜鉛が好ましい。特に、テトラエチレンペンタミンジチオカルバミン酸ナトリウム、テトラエチレンペンタミンジチオカルバミン酸カリウム、ピペラジンビスジチオカルバミン酸ナトリウム、ピペラジンビスジチオカルバミン酸カリウム、ペンタメチレンジチオカルバミン酸ナトリウム及びペンタメチレンジチオカルバミン酸亜鉛が好ましい。 The salt of dithiocarbamic acid is not particularly limited as long as it is a water-soluble salt, and examples thereof include alkali metal salts such as sodium salt and potassium salt, other metal salts, and ammonium salt. Among these, diethyldithiocarbamic acid, piperazine bisdithiocarbamic acid, tetraethylenepentaminedithiocarbamic acid, alkali metal salts of pentamethylenedithiocarbamic acid, and zinc pentamethylenedithiocarbamate are preferable. In particular, sodium tetraethylenepentamine dithiocarbamate, potassium tetraethylenepentamine dithiocarbamate, sodium piperazine bisdithiocarbamate, potassium piperazine bisdithiocarbamate, sodium pentamethylenedithiocarbamate and zinc pentamethylenedithiocarbamate are preferred.
これらのジチオカルバミン酸及びその塩である水溶性化合物は、１種単独で用いても、２種以上を併用してもよい。
また、前記水溶性化合物は、十分な緑青阻止効果を発揮させるため、緑青阻止剤中、０．１〜１００質量％含有されていることが好ましい。前記含有量は、より好ましくは１〜５０質量％、さらに好ましくは５〜４０質量％である。
These water-soluble compounds which are dithiocarbamic acid and its salt may be used individually by 1 type, or may use 2 or more types together.
The water-soluble compound is preferably contained in an amount of 0.1 to 100% by mass in the patina inhibitor in order to exert a sufficient patina inhibitory effect. The content is more preferably 1 to 50% by mass, and still more preferably 5 to 40% by mass.
（アゾール系銅用防食剤）
本発明の緑青阻止剤は、アゾール系銅用防食剤を含んでいてもよい。これにより、緑青の除去時に銅表面に損傷を与えることがより防止され、また、前記水溶性化合物による緑青阻止効果に加えて、緑青が除去された銅表面の防食効果も得られる。
アゾール系銅用防食剤に用いられるアゾール系化合物は、ヘテロ原子を２個以上含み、そのうちの少なくとも１個が窒素原子である複素５員環を有する化合物である。具体的には、イミダゾール、ピラゾール、オキサゾール、チアゾール、トリアゾール及びテトラゾール等の単環式アゾール系化合物、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾイソオキサゾール、ベンゾチアゾール、メルカプトベンゾイミダゾール、メルカプトメチルベンゾイミダゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール、トリルトリアゾール、インダゾール、プリン、イミダゾチアゾール、ピラゾロオキサゾール及びチアベンダゾール等の縮合多環式アゾール系化合物、並びにこれらの塩等が挙げられる。これらのアゾール系化合物は、１種単独で用いても、２種以上を併用してもよい。これらのうち、ベンゾトリアゾール、トリルトリアゾール、及びメルカプトベンゾチアゾール等が好ましく、ベンゾトリアゾールがより好ましい。
アゾール系化合物の含有量は、緑青阻止剤中、０．０１〜５質量％であることが好ましい。より好ましくは０．０５〜４質量％、さらに好ましくは０．１〜２質量％である。
(Azole copper anticorrosive)
The patina inhibitor of the present invention may contain an azole copper anticorrosive. This further prevents damage to the copper surface during removal of patina, and also provides an anticorrosion effect on the copper surface from which patina has been removed in addition to the patina inhibition effect by the water-soluble compound.
An azole compound used for an azole copper anticorrosive agent is a compound having a hetero 5-membered ring containing two or more heteroatoms, at least one of which is a nitrogen atom. Specifically, monocyclic azole compounds such as imidazole, pyrazole, oxazole, thiazole, triazole and tetrazole, benzimidazole, benzoxazole, benzisoxazole, benzothiazole, mercaptobenzimidazole, mercaptomethylbenzimidazole, mercaptobenzothiazole , Condensed polycyclic azole compounds such as benzotriazole, tolyltriazole, indazole, purine, imidazothiazole, pyrazolooxazole and thiabendazole, and salts thereof. These azole compounds may be used alone or in combination of two or more. Of these, benzotriazole, tolyltriazole, mercaptobenzothiazole and the like are preferable, and benzotriazole is more preferable.
It is preferable that content of an azole type compound is 0.01-5 mass% in a patina inhibitor. More preferably, it is 0.05-4 mass%, More preferably, it is 0.1-2 mass%.
なお、前記緑青阻止剤は、緑青阻止効果を損なわず、かつ、銅表面に損傷を与えない範囲において、他の添加剤を含んでいてもよい。任意成分である添加剤としては、例えば、防腐剤、スケール防止剤、アルカリ剤、ｐＨ緩衝剤、スライムコントロール剤及び界面活性剤等が挙げられる。 The patina-inhibiting agent may contain other additives as long as the patina-inhibiting effect is not impaired and the copper surface is not damaged. Examples of additives that are optional components include preservatives, scale inhibitors, alkali agents, pH buffers, slime control agents, and surfactants.
前記緑青阻止剤の調製方法は、特に限定されるものではなく、必要に応じて、水等を溶媒として用い、前記緑青阻止剤の各構成成分を混合すればよい。前記水溶性化合物の濃度は、その使用用途に応じて、使用時に適宜調整される。 The method for preparing the patina inhibitor is not particularly limited, and if necessary, water or the like may be used as a solvent and the components of the patina inhibitor may be mixed. The concentration of the water-soluble compound is appropriately adjusted at the time of use according to the intended use.
（緑青阻止方法）
本発明の緑青阻止方法は、水系において、前記緑青阻止剤を前記水溶性化合物の濃度が５〜１００００ｍｇ／Ｌとなるように調整して使用するものである。
上記方法においては、前記緑青阻止剤を緑青が発生している箇所に使用してもよく、この場合には、銅表面に損傷を与えることなく、緑青を除去することができるという効果が得られる。
具体的な方法としては、例えば、以下のような処理方式が挙げられる。
（１）前記緑青阻止剤を必要に応じて水等で希釈して洗浄液を調製し、緑青の発生を阻止又は発生した緑青を除去したい箇所を該洗浄液に浸漬する、バッチ式。
（２）冷却水系の銅チューブ等の場合は、冷却水系の運転を中止し、緑青の発生を阻止又は発生した緑青を除去する必要がある銅チューブ等に、上記と同様に調製した洗浄液を循環供給する、バッチ式。
（３）冷却水系の銅チューブ等の場合、冷却水系の運転中に、緑青阻止剤を所定濃度で添加して循環させ、廃水（除去された緑青を含む場合もある。）をブロー水とともに系外に排出する、流通方式。
本発明の緑青阻止方法は、上記（１）〜（３）のいずれの方式にも適用することがきるが、処理廃水が緑青を含む場合には、バッチ式により行うことが好ましい。
(Green and blue prevention method)
The patina-inhibiting method of the present invention is used by adjusting the patina-inhibiting agent so that the concentration of the water-soluble compound is 5 to 10,000 mg / L in an aqueous system.
In the above-described method, the patina-inhibiting agent may be used in a place where patina is generated. In this case, the effect of removing patina without damaging the copper surface is obtained. .
Specific methods include the following processing methods, for example.
(1) A batch type in which the patina inhibitor is diluted with water or the like as necessary to prepare a cleaning liquid, and the portion where the patina that prevents or generates the patina is to be removed is immersed in the cleaning liquid.
(2) In the case of a cooling water system copper tube, etc., stop the operation of the cooling water system and circulate the cleaning liquid prepared in the same way as above to a copper tube that needs to prevent or remove the patina. Supply batch type.
(3) In the case of a cooling water system copper tube or the like, during operation of the cooling water system, a patina inhibitor is added and circulated at a predetermined concentration, and waste water (which may contain removed patina) may be combined with blow water. A distribution system that discharges outside.
The patina-inhibiting method of the present invention can be applied to any of the above methods (1) to (3). However, when the treated wastewater contains patina, it is preferably performed by a batch method.
前記緑青阻止方法における緑青阻止剤の使用濃度は、前記水溶性化合物の濃度が５〜１００００ｍｇ／Ｌとなるように調整される。
前記水溶性化合物の濃度が５ｍｇ／Ｌ未満では、十分な緑青阻止効果が得られない。また、前記濃度が１００００ｍｇ／Ｌを超える場合は、前記水溶性化合物の溶解性が低下し、水系が白濁する場合があり、また、処理コストが高くなるため好ましくない。
前記水溶性化合物の濃度は、１０〜３０００ｍｇ／Ｌであることが好ましく、より好ましくは５０〜１０００ｍｇ／Ｌである。
The use concentration of the patina inhibitor in the patina prevention method is adjusted so that the concentration of the water-soluble compound is 5 to 10,000 mg / L.
When the concentration of the water-soluble compound is less than 5 mg / L, a sufficient patina-inhibiting effect cannot be obtained. Moreover, when the said concentration exceeds 10,000 mg / L, the solubility of the said water-soluble compound falls, an aqueous system may become cloudy, and it is unpreferable since processing cost becomes high.
The concentration of the water-soluble compound is preferably 10 to 3000 mg / L, more preferably 50 to 1000 mg / L.
前記緑青阻止方法においては、本発明の緑青阻止剤以外に、緑青阻止効果を損なわず、かつ、銅表面に損傷を与えない範囲において、例えば、防腐剤、スケール防止剤、アルカリ剤、ｐＨ緩衝剤、スライムコントロール剤及び界面活性剤等の添加剤を用いてもよい。 In the patina-inhibiting method, in addition to the patina-inhibiting agent of the present invention, in the range that does not impair the patina-inhibiting effect and does not damage the copper surface, for example, preservatives, scale inhibitors, alkaline agents, pH buffering agents. Additives such as a slime control agent and a surfactant may be used.
以下、本発明をより詳細に説明するが、本発明は下記実施例により限定されるものではない。
下記実施例及び比較例に示すような緑青阻止剤（薬剤）を用いて、緑青阻止効果についての評価を行った。
Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the following examples.
Using the patina inhibitor (drug) as shown in the following examples and comparative examples, the patina inhibition effect was evaluated.
［評価方法］
緑青が発生した実機冷凍機の銅チューブ（直径１７ｍｍ）を長手方向に半割りし、長さ約３ｃｍに切断したものを試験片として用いた。また、試験水として、下記表１に示す２種類を準備した。
なお、表１における酸素消費量、全硬度及びカルシウム硬度は、いずれも、炭酸カルシウム換算の値である。また、ポリマレイン酸は、スケール防止剤として添加したものであり、ベルクレン２７２（ＢＷＡ社製）である。
[Evaluation methods]
A copper tube (diameter: 17 mm) of an actual refrigerator in which patina was generated was cut in half in the longitudinal direction and cut into a length of about 3 cm as a test piece. In addition, two types of test water shown in Table 1 below were prepared.
In addition, all the oxygen consumption, total hardness, and calcium hardness in Table 1 are values in terms of calcium carbonate. In addition, polymaleic acid is added as a scale inhibitor and is Berglen 272 (manufactured by BWA).
ビーカーに試験水と表２の各実施例及び比較例に示す薬剤成分を所定量入れ、試験片を懸吊してマグネットスターラーで緩撹拌した。１日後、試験片を取り出し、チューブ内表面の緑青の状態、及び緑青が除去された銅表面を目視観察により評価した。これらの評価結果を、表２にまとめて示す。 A predetermined amount of test water and the chemical components shown in each Example and Comparative Example in Table 2 were placed in a beaker, and the test piece was suspended and gently stirred with a magnetic stirrer. One day later, the test piece was taken out, and the state of patina on the inner surface of the tube and the copper surface from which patina was removed were evaluated by visual observation. These evaluation results are summarized in Table 2.
（実施例１〜３，５〜１０、比較例３、参考例１）
薬剤成分として表２に記載の各ジチオカルバミン酸塩を用いた。
（実施例４）
薬剤成分としてペンタメチレンジチオカルバミン酸亜鉛を用い、添加剤としてアルカリ剤（水酸化ナトリウム）１００ｍｇ／Ｌを添加した。
（実施例１１〜１４、比較例４）
薬剤成分として表２に記載の各ジチオカルバミン酸塩と、銅用防食剤であるベンゾトリアゾール５ｍｇ／Ｌを用いた。
（比較例１）
薬剤未添加の試験水のみのブランクである。
（比較例２）
銅用防食剤であるベンゾトリアゾールのみを添加した。
(Examples 1-3, 5-10, Comparative Example 3, Reference Example 1)
Each dithiocarbamate shown in Table 2 was used as a drug component.
Example 4
Zinc pentamethylenedithiocarbamate was used as a drug component, and 100 mg / L of an alkali agent (sodium hydroxide) was added as an additive.
(Examples 11-14, Comparative Example 4)
As the drug component, each dithiocarbamate shown in Table 2 and benzotriazole 5 mg / L which is an anticorrosive for copper were used.
(Comparative Example 1)
This is a blank containing only test water to which no drug is added.
(Comparative Example 2)
Only benzotriazole, an anticorrosive for copper, was added.
表２に示す評価基準は以下のとおりである。
緑青：緑青の状態を示す。○＝緑青がほぼ除去された；△＝緑青が一部除去された；×＝ほとんど変化なし
表面：緑青が除去された銅表面の状態を示す。○＝変化なし；△＝やや変色あり（損傷なし）；×＝損傷あり
評価：上記の緑青の状態、緑青が除去された銅表面の状態、及び試験水の状態を総合的に判断した緑青阻止効果の評価を示す。○＝良好；△＝やや良；×＝不良
The evaluation criteria shown in Table 2 are as follows.
Greenish blue: Indicates a greenish blue state. ○ = greenish blue was almost removed; Δ = partially greenish blue was removed; x = almost unchanged surface: the state of the copper surface from which greenish blue was removed. ○ = No change; △ = Slightly discolored (no damage); X = Damage evaluation: The above-mentioned patina state, the state of the copper surface from which the patina was removed, and the patina inhibition judging the state of the test water comprehensively The evaluation of the effect is shown. ○ = good; △ = slightly good; x = poor
表２に示した結果から分かるように、水溶性のジチオカルバミン酸塩を有効成分として含む緑青阻止剤を用いた場合（実施例）は、一般水道水及び模擬冷却水のいずれでも、優れた緑青阻止効果が得られ、銅表面に損傷を与えることなく、緑青が除去されることが認められた。
なお、ピペラジンビスジチオカルバミン酸カリウムを１００００ｍｇ／Ｌ含有する場合（実施例１０）は、一般水道水では、水がやや白濁したが、模擬冷却水では白濁は生じず、緑青除去効果はいずれも良好であった。
As can be seen from the results shown in Table 2, when a patina inhibitor containing a water-soluble dithiocarbamate as an active ingredient is used (Example), excellent patina prevention in both general tap water and simulated cooling water An effect was obtained, and it was observed that patina was removed without damaging the copper surface.
In addition, when the piperazine potassium bisdithiocarbamate potassium is contained at 10000 mg / L (Example 10), the water in the general tap water is slightly cloudy, but the simulated cooling water does not cause white turbidity, and the patina removal effect is good Met.
Claims (9)
前記ジチオカルバミン酸が、ピペラジンビスジチオカルバミン酸、テトラエチレンペンタミンジチオカルバミン酸及びペンタメチレンジチオカルバミン酸のうちから選ばれる少なくとも１種である、緑青阻止剤。 See contains at least one water soluble compound selected from among the dithiocarbamic acid and its salts,
The patina inhibitor, wherein the dithiocarbamic acid is at least one selected from piperazine bisdithiocarbamic acid, tetraethylenepentaminedithiocarbamic acid and pentamethylenedithiocarbamic acid .
水系において、前記緑青阻止剤を前記水溶性化合物の濃度が５〜１００００ｍｇ／Ｌとなるように調整して使用する、緑青阻止方法。 A patina treatment method using a patina inhibitor comprising at least one water-soluble compound selected from dithiocarbamic acid and salts thereof ,
In the aqueous system, the patina-inhibiting method wherein the patina-inhibiting agent is adjusted and used so that the concentration of the water-soluble compound is 5 to 10,000 mg / L.
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| JPH0581273U (en) * | 1992-04-01 | 1993-11-05 | 日産ディーゼル工業株式会社 | Engine cooling water filter device |
| JP4543502B2 (en) * | 2000-06-01 | 2010-09-15 | 栗田工業株式会社 | Determination method of required addition amount of chelating heavy metal scavenger, chemical injection control method and chemical injection control device |
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