JP2016089210A - Composition for copper corrosion protection, and copper corrosion protection method - Google Patents
Composition for copper corrosion protection, and copper corrosion protection method Download PDFInfo
- Publication number
- JP2016089210A JP2016089210A JP2014223682A JP2014223682A JP2016089210A JP 2016089210 A JP2016089210 A JP 2016089210A JP 2014223682 A JP2014223682 A JP 2014223682A JP 2014223682 A JP2014223682 A JP 2014223682A JP 2016089210 A JP2016089210 A JP 2016089210A
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- Prior art keywords
- copper
- acid
- corrosion protection
- salt
- composition
- 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.)
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000005260 corrosion Methods 0.000 title abstract description 30
- 230000007797 corrosion Effects 0.000 title abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 150000001851 cinnamic acid derivatives Chemical class 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
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- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 1
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、水に接する銅系材料の防食技術、及び防食方法に関する。詳しくは、銅系材料を用いた設備内を循環する各種工業用水系、排水系、冷却水系などの水系に添加して用いられる銅防食用組成物、及び、銅防食方法に関する。 The present invention relates to an anticorrosion technique for a copper-based material in contact with water, and an anticorrosion method. More specifically, the present invention relates to a copper anticorrosive composition and a copper anticorrosion method used by adding to various water systems such as various industrial water systems, drainage systems, and cooling water systems that circulate in facilities using copper-based materials.
各種工業用水系、排水系、冷却水系等に、銅あるいは銅合金など銅系材料からなる各種機器、配管などが用いられるが、これら機器、配管等の水系と接触する部位に腐食、孔食が発生して問題となっている。 Various industrial water systems, drainage systems, cooling water systems, etc., use various equipment and pipes made of copper-based materials such as copper or copper alloys. Has occurred and has become a problem.
このような銅の腐食や孔食を防止するために、銅系材料を含む機器や配管と接触する水系に防食剤を添加することが行われており、ベンゾトリアゾール、トリルトリアゾール、メルカプトベンゾチアゾール、イミダゾール（例えば、特許文献１，２）、フィチン酸（例えば、特許文献３）等が公知である。しかしながら、これらの従来使用されている防食剤では短期間で効果が無くなったり、孔食には十分な効果が得られないという問題があった。特に循環冷却水系ではアゾール系の銅用防食剤が汎用されているが、使用条件によっては腐食の発生及び進行を十分に抑制できない場合がある。例えば、酸化剤の過剰添加など、何らかの原因によりアゾール系防食剤等よりなる防食皮膜が局所で破壊され、皮膜の破壊された部分からの銅の溶出をアゾール系防食剤が抑えきれずに局部的な腐食が進行して孔食が発生する場合がある。更に、フィチン酸は対象となる水系のｐＨによっては逆に銅の溶解を加速するので低濃度での使用が必要となる場合がある。 In order to prevent such corrosion and pitting corrosion of copper, an anticorrosive agent is added to an aqueous system that comes into contact with equipment and piping containing a copper-based material, and benzotriazole, tolyltriazole, mercaptobenzothiazole, Imidazole (for example, Patent Documents 1 and 2), phytic acid (for example, Patent Document 3) and the like are known. However, these conventionally used anticorrosives have a problem that they are not effective in a short period of time, and sufficient effects cannot be obtained for pitting corrosion. In particular, azole-type anticorrosive agents for copper are widely used in circulating cooling water systems, but depending on the use conditions, the occurrence and progression of corrosion may not be sufficiently suppressed. For example, an anti-corrosion film composed of an azole anti-corrosive agent is locally destroyed for some reason, such as excessive addition of an oxidizing agent, and the elution of copper from the damaged part of the film cannot be controlled by the azole anti-corrosive agent locally. Corrosion may occur and pitting corrosion may occur. Furthermore, phytic acid may accelerate the dissolution of copper depending on the pH of the target aqueous system, so it may be necessary to use it at a low concentration.
また、特開平１０−２６５９７９公報（特許文献４）にはアクリル系共重合体等を対象水系に添加する防食方法が提案されているが、銅系材料の腐食、孔食に対して充分な防食効果が得られない。 Japanese Patent Laid-Open No. 10-265979 (Patent Document 4) proposes an anticorrosion method in which an acrylic copolymer or the like is added to the target aqueous system. However, the anticorrosion sufficient for corrosion and pitting corrosion of a copper-based material. The effect is not obtained.
本発明は、毒性が低く、かつ、環境汚染を引き起こすおそれがなく、銅に対して高い防食特性を有し、孔食防止にも効果が得られる優れた銅用防食剤及び防食方法を提供することを目的とする。 The present invention provides an excellent anticorrosive agent for copper and an anticorrosion method that has low toxicity, does not cause environmental pollution, has high anticorrosive properties with respect to copper, and is effective in preventing pitting corrosion. For the purpose.
１）本発明の銅防食用組成物は、下記の一般式（１）で示される桂皮酸誘導体、またはその塩の少なくとも１種を含有することを特徴とする。 1) The copper anticorrosive composition of the present invention is characterized by containing at least one of a cinnamic acid derivative represented by the following general formula (1) or a salt thereof.
式中のＲ１、Ｒ２及びＲ３の内の何れか１つは水素原子、残り２つの内の１つはアルコキシ基、残りの１つは水素原子、水酸基及びアルコキシ基の内から選ばれる何れか１つである。
In the formula, any one of R1, R2, and R3 is a hydrogen atom, one of the remaining two is an alkoxy group, and the other is any one selected from a hydrogen atom, a hydroxyl group, and an alkoxy group. One.
２）本発明の銅防食用組成物は、前記桂皮酸誘導体、またはその塩が、フェルラ酸、イソフェルラ酸、またはそれらの塩であることを特徴とする。 2) The copper anticorrosive composition of the present invention is characterized in that the cinnamic acid derivative or a salt thereof is ferulic acid, isoferulic acid, or a salt thereof.
３）本発明の銅防食方法は、１）又は２）に記載の銅防食用組成物を処理対象水系に添加することを特徴とする。 3) The copper anticorrosion method of the present invention is characterized in that the composition for copper anticorrosion described in 1) or 2) is added to the water system to be treated.
本発明の銅防食用組成物によれば、低い濃度での使用でも効果的に銅の防食、及び孔食防止が得られ、本発明の銅防食方法により、環境汚染を引き起こす恐れがなく、装置の保守管理に関する負担が軽減される効果がある。 According to the copper anticorrosive composition of the present invention, copper anticorrosion and pitting corrosion prevention can be effectively obtained even when used at a low concentration, and the copper anticorrosion method of the present invention does not cause environmental pollution, and the apparatus. This has the effect of reducing the burden on maintenance management.
本発明においては下記一般式（１）で示される桂皮酸誘導体、またはその塩が用いられる。 In the present invention, a cinnamic acid derivative represented by the following general formula (1) or a salt thereof is used.
式中のＲ１、Ｒ２及びＲ３の内の何れか１つは水素原子、残り２つの内の１つはアルコキシ基、残りの１つは水素原子、水酸基及びアルコキシ基の内から選ばれる何れか１つである。
In the formula, any one of R1, R2, and R3 is a hydrogen atom, one of the remaining two is an alkoxy group, and the other is any one selected from a hydrogen atom, a hydroxyl group, and an alkoxy group. One.
本発明の一般式（１）で示される桂皮酸誘導体の塩としては、好ましくはアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩が用いられ、特にナトリウム、カリウム、リチウム、マグネシウム、カルシウム、及びアンモニウムの何れかの塩が好ましく用いられる。 As the salt of the cinnamic acid derivative represented by the general formula (1) of the present invention, an alkali metal salt, an alkaline earth metal salt, or an ammonium salt is preferably used, particularly sodium, potassium, lithium, magnesium, calcium, and ammonium. Any of these salts is preferably used.
本発明の一般式（１）の桂皮酸誘導体の化合物としては、フェルラ酸、イソフェルラ酸、３−エトキシ−４−ヒドロキシ桂皮酸、４−エトキシ−３−ヒドロキシ桂皮酸、３−メトキシ−５−ヒドロキシ桂皮酸、３−エトキシ−５−ヒドロキシ桂皮酸、３，４−ジメトキシ桂皮酸、３，４−ジエトキシ桂皮酸、３，５−ジメトキシ桂皮酸、３，５−ジエトキシ桂皮酸等、が挙げられ、アルコシキ基としてはメトキシ基、エトキシ基が好ましい。好ましくはフェルラ酸、またはイソフェルラ酸であり、特に孔食抑制効果が高く、食品添加物であり安全性も高い点からフェルラ酸が好ましく用いられる。 As the compound of the cinnamic acid derivative of the general formula (1) of the present invention, ferulic acid, isoferulic acid, 3-ethoxy-4-hydroxycinnamic acid, 4-ethoxy-3-hydroxy cinnamic acid, 3-methoxy-5-hydroxy Cinnamic acid, 3-ethoxy-5-hydroxycinnamic acid, 3,4-dimethoxy cinnamic acid, 3,4-diethoxy cinnamic acid, 3,5-dimethoxy cinnamic acid, 3,5-diethoxy cinnamic acid and the like, As the alkoxy group, a methoxy group and an ethoxy group are preferable. Ferulic acid or isoferulic acid is preferable, and ferulic acid is preferably used because it has a particularly high pitting corrosion inhibiting effect, is a food additive, and has high safety.
本発明の一般式（１）で示される桂皮酸誘導体、またはその塩は、対象水系での濃度が合計で０．１ｍｇ／Ｌ以上、１０００ｍｇ／Ｌ以下となるように添加することが好ましく、より好ましい濃度は、０．２ｍｇ／Ｌ以上、１００ｍｇ／Ｌ以下である。濃度が０．１ｍｇ／Ｌより低いと防食効果が十分に得られず、１０００ｍｇ／Ｌより高くしても添加量に見合った防食効果が得られにくい。 The cinnamic acid derivative represented by the general formula (1) of the present invention or a salt thereof is preferably added so that the total concentration in the target aqueous system is 0.1 mg / L or more and 1000 mg / L or less. A preferred concentration is 0.2 mg / L or more and 100 mg / L or less. When the concentration is lower than 0.1 mg / L, the anticorrosive effect is not sufficiently obtained, and even when the concentration is higher than 1000 mg / L, it is difficult to obtain the anticorrosive effect commensurate with the added amount.
本発明の一般式（１）で示される桂皮酸誘導体、またはその塩は、そのまま適切な濃度となるように対象水系に添加しても良く、場合により予め水などの溶剤に溶解した液剤として、必要時にその液剤を対象水系に添加しても良い。 The cinnamic acid derivative represented by the general formula (1) of the present invention, or a salt thereof, may be added to the target aqueous system so as to have an appropriate concentration as it is, and in some cases as a liquid agent previously dissolved in a solvent such as water, The liquid agent may be added to the target aqueous system when necessary.
本発明の一般式（１）で示される桂皮酸誘導体の低級アルコールのエステルである、フェルラ酸メチル、フェルラ酸エチル、イソフェルラ酸メチル、イソフェルラ酸エチル等も良好な銅系金属の防食、孔食防止効果が得られる。更に、本発明の一般式（１）の桂皮酸誘導体やその塩、およびエステル化物を単独重合または他のモノマーと共重合させたオリゴマーないしポリマーは、熱安定性が高いために、特に熱負荷の高い加熱冷却循環水系等における銅系金属の防食剤として有用である。 Anticorrosion and pitting corrosion prevention of copper-based metals, such as methyl ferulate, ethyl ferulate, methyl isofellrate, and ethyl isofellrate, which are esters of lower alcohols of cinnamic acid derivatives represented by the general formula (1) of the present invention An effect is obtained. Furthermore, the cinnamic acid derivative of the general formula (1) of the present invention, its salt, and the oligomer or polymer obtained by homopolymerization or copolymerization with other monomers have high thermal stability, so that the heat load is particularly high. It is useful as a corrosion inhibitor for copper-based metals in high heating / cooling circulating water systems.
本発明の銅防食用組成物には、桂皮酸誘導体またはその塩の安定化のために酸化防止剤を含有させてもよい。好ましくは食品添加物であるアスコルビン酸、エリソルビン酸やそれらの誘導体、及びそれらの塩の少なくとも１種が使用される。それらの誘導体としては、アスコルビン酸エステル、エリソルビン酸エステル、アスコルビン酸−２−-グリコシド、エリソルビン酸−２−グリコシド、及びアスコルビン酸エーテル、エリソルビン酸エーテル等が挙げられ、それらの塩としてはアルカリ金属塩、アルカリ土類金属塩、アルミニウム塩及びアンモニウム塩等が挙げられる。 The copper anticorrosive composition of the present invention may contain an antioxidant for stabilizing the cinnamic acid derivative or a salt thereof. Preferably, at least one of ascorbic acid, erythorbic acid and derivatives thereof, and salts thereof, which are food additives, is used. Examples of these derivatives include ascorbic acid esters, erythorbic acid esters, ascorbic acid-2-glycosides, erythorbic acid-2-glycosides, ascorbic acid ethers, erythorbic acid ethers, etc., and their salts include alkali metal salts. , Alkaline earth metal salts, aluminum salts and ammonium salts.
本発明の銅防食用組成物にアスコルビン酸、エリソルビン酸やそれらの誘導体、及びそれらの塩を含有させる場合の含有量は、本発明の一般式（１）で示される桂皮酸誘導体、またはその塩に対して、通常0.1〜200質量％、好ましくは1〜100質量％である。 Ascorbic acid, erythorbic acid, their derivatives, and salts thereof in the copper anticorrosive composition of the present invention, the cinnamic acid derivative represented by the general formula (1) of the present invention, or a salt thereof Is usually 0.1 to 200% by mass, preferably 1 to 100% by mass.
本発明の銅防食用組成物は、前記の有効成分の他、例えば亜硝酸、リン酸、珪酸、モリブデン酸、タングステン酸、アルミン酸、硼酸、オキシ酸、アミノ酸、脂肪族有機酸、芳香族カルボン酸、リグニンスルホン酸、或いはこれらの塩などや、タンニン、リグニン亜鉛塩、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等のアゾール類などの従来公知の金属防食剤を含有していてもよい。 The copper anticorrosive composition of the present invention includes, in addition to the above active ingredients, for example, nitrous acid, phosphoric acid, silicic acid, molybdic acid, tungstic acid, aluminate, boric acid, oxyacid, amino acid, aliphatic organic acid, aromatic carboxyl A conventionally known metal anticorrosive agent such as acid, lignin sulfonic acid, or a salt thereof, and azoles such as tannin, lignin zinc salt, tolyltriazole, benzotriazole, and mercaptobenzothiazole may be contained.
さらに、本発明の銅防食用組成物を使用するに当たっては、例えば本発明に含まれないアクリル酸系重合体、リン酸系重合体、イタコン酸系重合体、イソブチレン系重合体、例えば、１−ヒドロキシエチリデン−１,１−ジホスホン酸、２−ホスホノブタン−１,２,４−トリカルボン酸、ヒドロキシホスホノ酢酸、アミノトリメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸等のホスホン酸、有機ホスフィン酸、ホスフィノポリカルボン酸、あるいはこれらの水溶性塩などのスケール防止剤、例えば５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、１，２−ベンゾイソチアゾリン−３−オン等のイソチアゾロン系化合物、例えばグルタルアルデヒド、フタルアルデヒド等のアルデヒド類、例えば過酸化水素、次亜塩素酸ナトリウム、ハロゲン化イソシアヌル酸、ハロゲン化ヒダントイン、クロラミン、ブロラミン、ハロゲン化スルファミン酸等の酸化性物質、更にジチオール系化合物、メチレンビスチオシアネート等のチオシアネート系化合物、ジブロモニトリロプロピオンアミド、２−ブロモ−２−ニトロプロパン−１，３−ジオール等の有機臭素系化合物、ヨーネンポリマー、四級アンモニウム塩系化合物、ピリジニウム塩系化合物などのスライム防止剤、例えばエチレンジアミン、ジエチレントリアミン等のアミン系化合物、例えばニトリロ三酢酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸等のアミノカルボン酸系化合物、例えばグルコン酸、クエン酸、シュウ酸、ギ酸、酒石酸、フィチン酸、琥珀酸、乳酸等の有機カルボン酸など、各種の水処理剤を併用することができ、場合によっては予め本発明の銅防食用組成物にこれらの水処理剤を配合したものを用いてもよい。 Further, when using the copper anticorrosive composition of the present invention, for example, an acrylic acid polymer, a phosphoric acid polymer, an itaconic acid polymer, an isobutylene polymer, such as 1- Phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, hydroxyphosphonoacetic acid, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, organic phosphinic acid, phosphino Scale inhibitors such as polycarboxylic acids or their water-soluble salts, such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzo Isothiazolone compounds such as isothiazoline-3-one, such as glutaraldehyde, phthalaldehyde Aldehydes such as hydrogen peroxide, sodium hypochlorite, halogenated isocyanuric acid, halogenated hydantoin, chloramine, bromoamine, halogenated sulfamic acid and other oxidizing substances, dithiol compounds, methylene bis thiocyanate, etc. Anti-slime agents such as thiocyanate compounds, organic bromine compounds such as dibromonitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol, ionene polymers, quaternary ammonium salt compounds, pyridinium salt compounds Amine compounds such as ethylenediamine and diethylenetriamine, aminocarboxylic acid compounds such as nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, such as gluconic acid, citric acid, oxalic acid, formic acid, tartaric acid, Various water treatment agents such as organic carboxylic acids such as butyric acid, succinic acid, and lactic acid can be used in combination. In some cases, these water treatment agents are used in combination with the copper anticorrosive composition of the present invention in advance. May be.
以下に本発明の腐食防止用組成物を用いた実施例について具体的に説明する。 Examples of using the composition for preventing corrosion according to the present invention will be specifically described below.
［実施例１~６、比較例１~７、参考例１〜４］
つくば市水に塩化物イオン、硫酸イオン各５００mg／Lを添加し、銅材質に対する腐食性を高めた試験水と、表１に記載の薬剤Ａ〜Ｇとを用意した。
[Examples 1 to 6, Comparative Examples 1 to 7, Reference Examples 1 to 4]
Test water in which 500 mg / L each of chloride ions and sulfate ions were added to Tsukuba city water to enhance the corrosiveness to the copper material, and the drugs A to G shown in Table 1 were prepared.
開放容器に入れた試験用水１０００ｍＬに、Ａ〜Ｇの薬剤をそれぞれ表２に示す濃度（
ｍｇ／Ｌ）となるよう添加し、その中に２０ｍｍ×６０ｍｍ×２ｍｍの大きさの研磨銅試験片（Ｃ１２２０Ｐ）を浸漬して、３００ｒｐｍで攪拌しながら３５℃で３日間の腐食試験を行った。３日後に銅板の腐食減量を測定して腐食速度（ｍｇ／ｄｍ２／日（ｍｄｄ））を算出し、目視で評価した銅板の孔食数とともに、その結果を表２に示した。
The concentration of each of the drugs A to G shown in Table 2 is added to 1000 mL of test water in an open container.
In addition, a polished copper test piece (C1220P) having a size of 20 mm × 60 mm × 2 mm was immersed therein, and a corrosion test was conducted at 35 ° C. for 3 days while stirring at 300 rpm. . The corrosion weight loss of the copper plate was measured after 3 days, and the corrosion rate (mg / dm 2 / day (mdd)) was calculated. The results are shown in Table 2 together with the number of pitting corrosion of the copper plate evaluated visually.
表２の結果から、本発明の桂皮酸誘導体であるフェルラ酸、イソフェルラ酸の何れかを含有する銅防食用組成物が、その他の化合物と比べて、銅を主成分とする金属に対する優れた防食性、及び孔食防止性を有していること、および参考例で挙げた桂皮酸誘導体であるシナピン酸やカフェ酸についても特に低濃度の添加で公知のフィチン酸よりも良好な防食性、孔食防止性を示すことがわかる。 From the results of Table 2, the anticorrosive composition containing either ferulic acid or isoferulic acid, which is a cinnamic acid derivative of the present invention, is superior in anticorrosion to metals mainly composed of copper as compared with other compounds. And cinnamic acid derivatives, such as sinapinic acid and caffeic acid, mentioned in the reference examples, especially with a low concentration, better anticorrosion and pores than known phytic acid. It turns out that it shows food-proofing property.
［実施例７、８、比較例８〜１０］
つくば市水に塩素を各１０mg／Lを添加し、銅材質に対する腐食性を高めた試験水と、表１に記載の薬剤Ａ、Ｆ、Ｇとを用意した。
[Examples 7 and 8, Comparative Examples 8 to 10]
Test water in which 10 mg / L of chlorine was added to Tsukuba city water to increase the corrosiveness to the copper material, and chemicals A, F and G shown in Table 1 were prepared.
開放容器に入れた試験用水１０００ｍＬに、Ａ、Ｆ、Ｇの薬剤をそれぞれ表３に示す濃度（ｍｇ／Ｌ）となるよう添加し、その中に２０ｍｍ×６０ｍｍ×２ｍｍの大きさの研磨銅試験片（Ｃ１２２０Ｐ）を浸漬して、３００ｒｐｍで攪拌しながら３５℃で３日間の腐食試験を行った。３日後に銅板の腐食減量を測定して腐食速度（ｍｇ／ｄｍ２／日（ｍｄｄ））を算出し、目視で評価した銅板の孔食数とともに、その結果を表３に示した。 Add the chemicals of A, F, and G to 1000 mL of test water in an open container so that each of the concentrations (mg / L) shown in Table 3 is obtained, and a polished copper test of 20 mm × 60 mm × 2 mm in it. The piece (C1220P) was immersed, and a corrosion test was conducted at 35 ° C. for 3 days while stirring at 300 rpm. Three days later, the corrosion weight loss of the copper plate was measured to calculate the corrosion rate (mg / dm 2 / day (mdd)), and the results are shown in Table 3 together with the number of pitting corrosion of the copper plate evaluated visually.
表３の結果から、酸化剤として塩素を含有する試験水を用いた試験では、本発明の桂皮酸誘導体であるフェルラ酸を含有する銅防食用組成物は、ベンゾトリアゾール、トリルトリアゾールと比べて、腐食速度はほぼ同程度であるが、優れた孔食防止性を示すことがわかる。 From the results of Table 3, in the test using test water containing chlorine as an oxidizing agent, the copper anticorrosive composition containing ferulic acid, which is a cinnamic acid derivative of the present invention, is compared with benzotriazole and tolyltriazole, Although the corrosion rate is almost the same, it can be seen that the pitting corrosion resistance is excellent.
本発明は、各種工業用水系、排水系、冷却水系、ボイラ水系等の銅系材料を用いた金属で構成された設備内を循環する水系などに添加して用いられる銅防食用組成物、及び、銅防食方法であり、銅に対して高い防食特性を有し、孔食防止にも効果が得られる。本発明の桂皮酸誘導体は安全性が高く、特にフェルラ酸は食品添加物であり、食品工場や医療機関等の高い安全性が要求される冷却水系等にも好適に用いることができ、かつ、環境汚染を引き起こす恐れがなく、装置の保守管理に関する負担が軽減される効果が得られる。 The present invention relates to a copper anticorrosive composition used by adding to an aqueous system circulating in facilities composed of metals using copper-based materials such as various industrial water systems, drainage systems, cooling water systems, boiler water systems, and the like, and It is a copper anticorrosion method, has high anticorrosion properties with respect to copper, and is effective in preventing pitting corrosion. The cinnamic acid derivative of the present invention is highly safe, in particular ferulic acid is a food additive, can be suitably used for cooling water systems and the like that require high safety such as food factories and medical institutions, and There is no risk of causing environmental pollution, and an effect of reducing the burden on the maintenance and management of the apparatus can be obtained.
Claims (3)
式中のＲ１、Ｒ２及びＲ３の内の何れか１つは水素原子、残り２つの内の１つはアルコキシ基、残りの１つは水素原子、水酸基及びアルコキシ基の内から選ばれる何れか１つである。 A copper anticorrosive composition comprising at least one of a cinnamic acid derivative represented by the following general formula (1) or a salt thereof.
In the formula, any one of R1, R2, and R3 is a hydrogen atom, one of the remaining two is an alkoxy group, and the other is any one selected from a hydrogen atom, a hydroxyl group, and an alkoxy group. One.
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| CN114916545A (en) * | 2022-06-02 | 2022-08-19 | 合肥天帆医药科技有限公司 | Low-grey-dyeing o-phthalaldehyde disinfectant and preparation method and application thereof |
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