JP2006348324A - Corrosion inhibitor composition, acid purification solution, and acid purification method for metal - Google Patents
Corrosion inhibitor composition, acid purification solution, and acid purification method for metal Download PDFInfo
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- JP2006348324A JP2006348324A JP2005173316A JP2005173316A JP2006348324A JP 2006348324 A JP2006348324 A JP 2006348324A JP 2005173316 A JP2005173316 A JP 2005173316A JP 2005173316 A JP2005173316 A JP 2005173316A JP 2006348324 A JP2006348324 A JP 2006348324A
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- acid
- acid cleaning
- metal
- corrosion inhibitor
- nonionic surfactant
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- 239000002253 acid Substances 0.000 title claims abstract description 112
- 230000007797 corrosion Effects 0.000 title claims abstract description 95
- 238000005260 corrosion Methods 0.000 title claims abstract description 95
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000003112 inhibitor Substances 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000746 purification Methods 0.000 title abstract 7
- -1 acetylene alcohol Chemical compound 0.000 claims abstract description 61
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 43
- 230000005764 inhibitory process Effects 0.000 claims abstract description 32
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims description 98
- 239000007788 liquid Substances 0.000 claims description 44
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 11
- 239000004480 active ingredient Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 5
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- KXUSQYGLNZFMTE-UHFFFAOYSA-N hex-2-yne-1,1-diol Chemical compound CCCC#CC(O)O KXUSQYGLNZFMTE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000468 ketone group Chemical group 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 238000005554 pickling Methods 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- PBFKVYVGYHNCGT-UHFFFAOYSA-N 1-sulfanylpropane-1,2,3-triol Chemical compound OCC(O)C(O)S PBFKVYVGYHNCGT-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals 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
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
本発明は腐食抑制剤組成物、酸洗浄液組成物及び金属の酸洗浄方法に関する。更に詳しくは本発明は、金属表面に付着している錆や熱延スケール等の酸化物皮膜を除去するための酸洗浄液組成物と、これに添加される腐食抑制剤組成物と、前記酸洗浄液組成物を用いて金属を酸洗浄する金属の酸洗浄方法とに関する。 The present invention relates to a corrosion inhibitor composition, an acid cleaning solution composition, and a metal acid cleaning method. More specifically, the present invention relates to an acid cleaning liquid composition for removing oxide films such as rust and hot rolled scale adhering to the metal surface, a corrosion inhibitor composition added thereto, and the acid cleaning liquid. The present invention relates to a method for pickling a metal using a composition.
例えば鋼材等の熱間圧延工程では、金属材料の表面にいわゆる熱延スケールが発生する。又、多様な産業分野において、特に水との接触環境において利用される各種装置類を構成する鋼材等の金属材料の表面には、スケールや酸化皮膜が発生する。従来より、このような金属表面の錆やスケール等の酸化物皮膜を除去するために、酸洗浄液が使用されている。酸洗浄液としては、有機酸が使用される場合もあるが、主に塩酸、硫酸、硝酸等の無機酸が使用されている。 For example, in a hot rolling process of steel or the like, a so-called hot rolled scale is generated on the surface of a metal material. Further, in various industrial fields, scales and oxide films are generated on the surface of metal materials such as steel materials constituting various devices used particularly in contact environments with water. Conventionally, an acid cleaning liquid has been used to remove oxide films such as rust and scale on the metal surface. An organic acid may be used as the acid cleaning liquid, but inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid are mainly used.
ところで、酸洗浄プロセスにおいては「酸洗浄速度は大きく」、「金属の腐食は少なく」と言う要求を両立させる必要がある。しかし、これらの酸洗浄液は、錆やスケール等の酸化物皮膜を除去する一方で、金属素地も腐食させ、金属素地の色調が黒くなる等の品質低下を免れない。従って、酸洗浄時の金属素地の腐食を防止する目的で、腐食抑制剤が酸洗浄液に添加されている。従来の腐食抑制剤として、下記の特許文献１〜３に開示されたものを例示することができる。 By the way, in the acid cleaning process, it is necessary to satisfy both the requirements of “high acid cleaning rate” and “low metal corrosion”. However, these acid cleaning liquids cannot avoid the deterioration of quality, such as removing the oxide film such as rust and scale, but also corroding the metal substrate and blackening the color of the metal substrate. Therefore, a corrosion inhibitor is added to the acid cleaning liquid for the purpose of preventing corrosion of the metal substrate during the acid cleaning. Examples of conventional corrosion inhibitors include those disclosed in the following Patent Documents 1 to 3.
しかし、最近、金属の品質向上のため、酸洗浄時における金属素地の白色度の向上が特に強く求められている。本願発明者の研究によれば、上記特許文献１〜３に開示された窒素含有化合物を有効成分とする腐食抑制剤は、腐食抑制効果において必ずしも十分な効果を確保できないし、特に酸洗浄時の金属素地の白色度向上の面で、近年の高度な要求に対応できない。 However, recently, in order to improve the quality of metals, there is a strong demand for improving the whiteness of metal substrates during acid cleaning. According to the inventor's research, the corrosion inhibitor containing the nitrogen-containing compound disclosed in Patent Documents 1 to 3 as an active ingredient cannot always ensure a sufficient effect in the corrosion inhibition effect, and particularly during acid cleaning. In terms of improving the whiteness of metal substrates, it cannot meet the recent high demands.
更に、近年、河川や海域等の環境汚染物質（富栄養化物質）としての窒素源の削減が叫ばれている。上記の特許文献１〜特許文献３に開示された腐食抑制剤はアミン化合物やイミダゾリン化合物等の環境負荷が大きい窒素含有化合物を有効成分としており、この点でも好適な腐食抑制剤であるとは言い難い。 Furthermore, in recent years, reduction of nitrogen sources as environmental pollutants (eutrophication substances) in rivers and sea areas has been screamed. The corrosion inhibitors disclosed in the above Patent Documents 1 to 3 contain nitrogen-containing compounds having a large environmental load such as amine compounds and imidazoline compounds as active ingredients, and it is said that these are also suitable corrosion inhibitors. hard.
そこで本発明は、酸洗浄時の金属素地に対する良好な腐食抑制効果を維持したもとで、優れた白色度を実現できる（更に好ましくは、環境負荷も小さい）酸洗浄液組成物と、酸洗浄液組成物にこのような特性を与える腐食抑制剤組成物と、前記酸洗浄液組成物を用いて金属を酸洗浄する金属の酸洗浄方法とを提供することを、解決すべき技術的課題とする。 Therefore, the present invention is capable of realizing an excellent whiteness (more preferably with a low environmental load) and an acid cleaning liquid composition while maintaining a good corrosion inhibiting effect on the metal substrate during the acid cleaning. It is a technical problem to be solved to provide a corrosion inhibitor composition that gives such properties to a product and a metal acid cleaning method for acid cleaning a metal using the acid cleaning liquid composition.
（第１発明の構成）
上記課題を解決するための本願第１発明の構成は、有効成分としてアセチレンアルコールと非イオン界面活性剤とを含有する、腐食抑制剤組成物である。
(Configuration of the first invention)
The structure of the 1st invention of this application for solving the said subject is a corrosion inhibitor composition which contains acetylene alcohol and a nonionic surfactant as an active ingredient.
（第２発明の構成）
上記課題を解決するための本願第２発明の構成は、前記第１発明に係るアセチレンアルコールと非イオン界面活性剤とがノンチッソ型である、腐食抑制剤組成物である。ここにおいて、「ノンチッソ型のアセチレンアルコール」とは分子内にアミノ基その他の窒素含有基を含まないアセチレンアルコールを言い、「ノンチッソ型の非イオン界面活性剤」とは分子内又は構成単位であるモノマー内に窒素含有基を含まない非イオン界面活性剤を言う。
(Configuration of the second invention)
The configuration of the second invention of the present application for solving the above-mentioned problem is a corrosion inhibitor composition in which the acetylene alcohol and the nonionic surfactant according to the first invention are non-nitrous type. Here, “non-nitros type acetylene alcohol” means acetylene alcohol containing no amino group or other nitrogen-containing group in the molecule, and “non-nitros type nonionic surfactant” is a monomer that is an intramolecular or structural unit. This refers to a nonionic surfactant that does not contain a nitrogen-containing group.
（第３発明の構成）
上記課題を解決するための本願第３発明の構成は、前記第１発明又は第２発明に係るアセチレンアルコールが、プロパギルアルコール、メチルブチノール、ジメチルペンチノール、ブチンジオール及びヘキシンジオールから選ばれる１種以上である、腐食抑制剤組成物である。
(Configuration of the third invention)
According to the third aspect of the present invention for solving the above problem, the acetylene alcohol according to the first or second invention is selected from propargyl alcohol, methylbutynol, dimethylpentinol, butynediol and hexynediol. It is a corrosion inhibitor composition that is one or more.
（第４発明の構成）
上記課題を解決するための本願第４発明の構成は、前記第１発明〜第３発明のいずれかに係る非イオン界面活性剤が、分子内にエーテル基、水酸基、ケトン基、又はエステル基のいずれか１種以上を少なくとも２基以上有するものである、腐食抑制剤組成物である。
(Configuration of the fourth invention)
The structure of the fourth invention of the present application for solving the above problem is that the nonionic surfactant according to any one of the first to third inventions has an ether group, a hydroxyl group, a ketone group, or an ester group in the molecule. It is a corrosion inhibitor composition having at least two of any one or more.
（第５発明の構成）
上記課題を解決するための本願第５発明の構成は、前記第４発明に係る非イオン界面活性剤が、ポリオキシエチレン重合物、ポリオキシプロピレン重合物及びポリオキシエチレンポリオキシプロピレン重合物から選ばれる１種以上である、腐食抑制剤組成物である。
(Structure of the fifth invention)
In order to solve the above problems, the fifth aspect of the present invention is such that the nonionic surfactant according to the fourth aspect is selected from a polyoxyethylene polymer, a polyoxypropylene polymer, and a polyoxyethylene polyoxypropylene polymer. It is a corrosion inhibitor composition which is 1 or more types.
（第６発明の構成）
上記課題を解決するための本願第６発明の構成は、少なくとも、無機酸及び／又は有機酸からなる酸成分と、第１発明〜第５発明のいずれかに係る腐食抑制剤組成物とを含有する、酸洗浄液組成物である。
(Structure of the sixth invention)
The configuration of the sixth invention of the present application for solving the above-described problem contains at least an acid component composed of an inorganic acid and / or an organic acid and the corrosion inhibitor composition according to any one of the first to fifth inventions. This is an acid cleaning liquid composition.
（第７発明の構成）
上記課題を解決するための本願第７発明の構成は、前記第６発明に係る酸洗浄液組成物が、その１Ｌ当たり、アセチレンアルコールを２０〜２０００ｍｇ含有し、及び／又は、非イオン界面活性剤を５〜１０００ｍｇ含有する、酸洗浄液組成物である。
(Structure of the seventh invention)
The structure of the seventh invention of the present application for solving the above problem is that the acid cleaning liquid composition according to the sixth invention contains 20 to 2000 mg of acetylene alcohol per liter and / or a nonionic surfactant. It is an acid cleaning liquid composition containing 5-1000 mg.
（第８発明の構成）
上記課題を解決するための本願第８発明の構成は、前記第７発明に係るアセチレンアルコールの含有量が１００〜２００ｍｇであり、及び／又は、前記非イオン界面活性剤の含有量が１００〜２００ｍｇである、酸洗浄液組成物である。
(Configuration of the eighth invention)
The configuration of the eighth invention of the present application for solving the above problem is that the content of acetylene alcohol according to the seventh invention is 100 to 200 mg and / or the content of the nonionic surfactant is 100 to 200 mg. It is an acid cleaning liquid composition.
（第９発明の構成）
上記課題を解決するための本願第９発明の構成は、金属の酸洗浄時に第６発明〜第８発明のいずれかに係る酸洗浄液組成物を用いる、金属の酸洗浄方法である。
(Structure of the ninth invention)
The structure of the ninth invention of the present application for solving the above problem is a metal acid cleaning method using the acid cleaning liquid composition according to any one of the sixth to eighth inventions during metal acid cleaning.
（第１０発明の構成）
上記課題を解決するための本願第１０発明の構成は、前記第９発明に係る金属の酸洗浄方法により、酸洗浄後の金属素地表面において８８％以上の腐食抑制率を達成したもとで、７１度以上の白色度を得る、金属の酸洗浄方法である。
(Configuration of the tenth invention)
The structure of the present invention No. 10 for solving the above-mentioned problem is that the metal acid cleaning method according to the ninth invention achieves a corrosion inhibition rate of 88% or more on the metal substrate surface after the acid cleaning, This is a metal acid cleaning method for obtaining a whiteness of 71 degrees or more.
（第１発明の効果）
本願発明者は、前記した技術的課題の解決手段を追求する過程で、アセチレンアルコールと非イオン界面活性剤とを添加した酸洗浄液を使用すると、金属素地に対する良好な腐食抑制効果を維持したもとで、優れた白色度を実現できることを見出した。即ち、アセチレンアルコールによって主として優れた腐食抑制効果が確保される。又、これに併用する非イオン界面活性剤によって、優れた白色度の向上効果が得られると共に、腐食抑制効果も相乗的に補強される。その結果、従来の腐食抑制剤との比較において、次に述べる顕著な差異を生じる。
(Effect of the first invention)
The inventor of the present application maintained a good corrosion-inhibiting effect on the metal substrate by using an acid cleaning solution to which acetylene alcohol and a nonionic surfactant were added in the process of pursuing a solution to the technical problem described above. And found that excellent whiteness can be achieved. That is, acetylene alcohol ensures an excellent corrosion suppression effect mainly. In addition, the nonionic surfactant used in combination with this provides an excellent whiteness improvement effect and synergistically reinforces the corrosion inhibition effect. As a result, the following significant differences occur in comparison with conventional corrosion inhibitors.
第１発明の腐食抑制剤組成物は、例えば後述する実験例からも明らかなように、従来型の腐食抑制剤と比較して、酸洗浄時の金属の腐食抑制率及び白色度が、格段に高いレベルでバランス良く両立されている。即ち、窒素含有化合物を有効成分とする腐食抑制剤と比較して、酸洗浄時の金属の腐食抑制率において格段に優れ、白色度においても有意に優れている。一方、アセチレンアルコールのみを有効成分とする腐食抑制剤と比較すると、酸洗浄時の金属の白色度において格段に優れ、金属の腐食抑制率においても、酸洗浄液に対するアセチレンアルコールの同一添加量ベースで比較すると、有意に優れている。 The corrosion inhibitor composition of the first invention, as is clear from, for example, experimental examples described later, has a markedly higher corrosion inhibition rate and whiteness of the metal during acid cleaning than the conventional corrosion inhibitor. Both are balanced at a high level. That is, compared with the corrosion inhibitor which uses a nitrogen-containing compound as an active ingredient, it is remarkably excellent in the corrosion inhibition rate of the metal at the time of acid washing, and is also excellent in whiteness. On the other hand, compared with a corrosion inhibitor containing only acetylene alcohol as an active ingredient, the whiteness of the metal during acid cleaning is markedly superior, and the metal corrosion inhibition rate is also compared on the basis of the same amount of acetylene alcohol added to the acid cleaning solution. Then, it is significantly superior.
（第２発明の効果）
第２発明においては、アセチレンアルコールと非イオン界面活性剤とがノンチッソ型であるため、従来型の窒素含有化合物を有効成分とする腐食抑制剤とは異なり、廃水処理に伴い環境を窒素汚染しない。従って、環境負荷が小さい。しかも、上記した第１発明の効果が確保される。
(Effect of the second invention)
In the second invention, since the acetylene alcohol and the nonionic surfactant are non-chisto type, unlike the corrosion inhibitor containing a conventional nitrogen-containing compound as an active ingredient, the environment is not polluted with the waste water treatment. Therefore, the environmental load is small. In addition, the effect of the first invention is ensured.
（第３発明の効果）
上記したアセチレンアルコールとしては、第３発明に例示するように、プロパギルアルコール、メチルブチノール、ジメチルペンチノール、ブチンジオール及びヘキシンジオールから選ばれる１種以上であることが、特に好ましい。これらはいずれもノンチッソ型である。
(Effect of the third invention)
The acetylene alcohol is particularly preferably at least one selected from propargyl alcohol, methylbutynol, dimethylpentinol, butynediol and hexynediol, as exemplified in the third invention. These are all non-chisso types.
（第４発明の効果）
上記した非イオン界面活性剤としては、第４発明に例示するように、分子内にエーテル基、水酸基、ケトン基、又はエステル基のいずれか１種以上を少なくとも２基以上有するものであることが、特に好ましい。
(Effect of the fourth invention)
The nonionic surfactant described above has at least two or more of any one or more of an ether group, a hydroxyl group, a ketone group, or an ester group in the molecule, as exemplified in the fourth invention. Is particularly preferred.
（第５発明の効果）
非イオン界面活性剤としては、とりわけ、第５発明に例示するポリオキシエチレン重合物、ポリオキシプロピレン重合物及びポリオキシエチレンポリオキシプロピレン重合物から選ばれる１種以上であることが好ましい。これらはいずれもノンチッソ型である。
(Effect of the fifth invention)
The nonionic surfactant is preferably at least one selected from polyoxyethylene polymer, polyoxypropylene polymer and polyoxyethylene polyoxypropylene polymer exemplified in the fifth invention. These are all non-chisso types.
（第６発明の効果）
第６発明の酸洗浄液組成物は、無機酸や有機酸からなる酸成分と、第１発明〜第５発明のいずれかに係る腐食抑制剤組成物とを含有するので、酸洗浄プロセスにおける「酸洗浄速度は大きく」、「金属の腐食は少なく」と言う要求を両立させることができる。しかも「金属の腐食は少なく」と言う要求に対して、金属の腐食抑制率及び白色度が格段に高いレベルでバランス良く両立される。
(Effect of the sixth invention)
Since the acid cleaning liquid composition of the sixth invention contains an acid component comprising an inorganic acid or an organic acid and the corrosion inhibitor composition according to any one of the first to fifth inventions, the “acid” in the acid cleaning process It is possible to satisfy the requirements of “high cleaning speed” and “low metal corrosion”. In addition, the metal corrosion inhibition rate and the whiteness can be balanced at a remarkably high level in response to the requirement of “low metal corrosion”.
更に、腐食抑制剤組成物が第２発明に係るノンチッソ型のアセチレンアルコールとノンチッソ型の非イオン界面活性剤からなる場合、廃水処理に伴う環境負荷が小さい。 Furthermore, when the corrosion inhibitor composition comprises the non-nitrogen acetylene alcohol and the non-nitrogen nonionic surfactant according to the second invention, the environmental load associated with wastewater treatment is small.
（第７発明の効果）
上記の酸洗浄液組成物において、アセチレンアルコールと非イオン界面活性剤との含有量は必ずしも限定されないが、それぞれ第７発明に規定する含有量であることが特に好ましい。
(Effect of the seventh invention)
In the acid cleaning liquid composition described above, the contents of acetylene alcohol and nonionic surfactant are not necessarily limited, but are particularly preferably the contents specified in the seventh invention.
即ち、アセチレンアルコールの含有量が酸洗浄液組成物１Ｌ当たり２０ｍｇ未満（２０ｐｐｍ未満）であると、十分な腐食抑制効果を確保できず、逆に２０００ｍｇ（２０００ｐｐｍ）を超えても、腐食抑制効果が飽和し、それ以上の効果の上積みを期待できない。一方、非イオン界面活性剤の含有量が酸洗浄液組成物１Ｌ当たり５ｍｇ未満（５ｐｐｍ未満）であると、十分な白色度の向上効果を確保できず、腐食抑制に対する相乗効果も余り得られない。逆に、その含有量が１０００ｍｇ（１０００ｐｐｍ）を超えても、白色度の向上効果や腐食抑制に対する相乗効果が飽和し、それ以上の効果の上積みを期待できない。 That is, if the content of acetylene alcohol is less than 20 mg (less than 20 ppm) per liter of the acid cleaning liquid composition, a sufficient corrosion inhibiting effect cannot be ensured. Conversely, even if it exceeds 2000 mg (2000 ppm), the corrosion inhibiting effect is saturated. However, no further effect can be expected. On the other hand, when the content of the nonionic surfactant is less than 5 mg (less than 5 ppm) per liter of the acid cleaning liquid composition, a sufficient whiteness improvement effect cannot be ensured, and a synergistic effect on corrosion inhibition is hardly obtained. On the other hand, even if the content exceeds 1000 mg (1000 ppm), the synergistic effect on whiteness improvement and corrosion inhibition is saturated, and no further effect can be expected.
（第８発明の効果）
酸洗浄液組成物におけるアセチレンアルコールと非イオン界面活性剤との含有量が第８発明に規定する範囲内にあるとき、アセチレンアルコールによる腐食抑制効果と、非イオン界面活性剤による白色度向上効果及び腐食抑制に対する相乗効果とが、とりわけ効率的に発揮されるため、経済性にも優れる。
(Effect of the eighth invention)
When the content of the acetylene alcohol and the nonionic surfactant in the acid cleaning liquid composition is within the range specified in the eighth invention, the corrosion inhibition effect by the acetylene alcohol, the whiteness improvement effect by the nonionic surfactant, and the corrosion Since the synergistic effect on suppression is exhibited particularly efficiently, it is excellent in economic efficiency.
（第９発明の効果）
第９発明においては、金属の酸洗浄時に第６発明〜第８発明の酸洗浄液組成物を用いるので、実施例においても後述するように、従来の酸洗浄液組成物を用いる金属の酸洗浄に比較して、金属の腐食抑制率及び白色度を格段に高いレベルでバランス良く両立させることができる。
(Effect of the ninth invention)
In the ninth invention, since the acid cleaning liquid compositions of the sixth to eighth inventions are used at the time of acid pickling of the metal, as will be described later in the examples, it is compared with the metal acid cleaning using the conventional acid cleaning liquid composition. Thus, the corrosion inhibition rate and the whiteness of the metal can be made to be compatible with each other at a remarkably high level.
（第１０発明の効果）
上記の金属の酸洗浄方法においては、例えば第１０発明に示すように、酸洗浄後の金属素地表面において８８％以上の腐食抑制率を達成したもとで７１度以上の白色度を得るような良好な酸洗浄が可能となる。
(Effect of the tenth invention)
In the above-mentioned metal acid cleaning method, for example, as shown in the tenth invention, a whiteness of 71 degrees or more is obtained while achieving a corrosion inhibition rate of 88% or more on the surface of the metal substrate after the acid cleaning. Good acid cleaning is possible.
次に、第１発明〜第１０発明を実施するための形態を、その最良の形態を含めて説明する。以下において「本発明」と言うときは、本願の各発明を全体的に指している。 Next, modes for carrying out the first invention to the tenth invention will be described including the best mode. In the following, the term “present invention” refers to each invention of the present application as a whole.
〔腐食抑制剤組成物〕
本発明の腐食抑制剤組成物は、有効成分としてアセチレンアルコールと非イオン界面活性剤とを含有する点に特徴がある。
(Corrosion inhibitor composition)
The corrosion inhibitor composition of the present invention is characterized in that it contains acetylene alcohol and a nonionic surfactant as active ingredients.
この腐食抑制剤組成物は金属の酸洗浄時に酸洗浄液に添加して使用されるものであるが、予め腐食抑制剤組成物を準備しておいて酸洗浄液に添加すると言う使用法も可能であるし、酸洗浄液に対してアセチレンアルコールと非イオン界面活性剤とをそれぞれ添加して結果的に腐食抑制剤組成物を添加した状態になると言う使用法も可能である。 This corrosion inhibitor composition is used by being added to an acid cleaning solution at the time of acid cleaning of a metal. However, it is also possible to prepare a corrosion inhibitor composition in advance and add it to the acid cleaning solution. In addition, it is possible to use the acetylene alcohol and the nonionic surfactant to the acid cleaning solution, respectively, so that the corrosion inhibitor composition is added as a result.
前者のように予め腐食抑制剤組成物を準備しておく場合、その有効成分であるアセチレンアルコールと非イオン界面活性剤との使用時濃度は、酸洗浄液に対する腐食抑制剤組成物の添加割合によって調節される。従って、腐食抑制剤組成物におけるアセチレンアルコールと非イオン界面活性剤との絶対的な含有量は余り問題とならないが、両者の相対的な含有量比は、例えば前記第７発明で規定する両者の含有量の比率を満足するように調節されていることが好ましい。 When a corrosion inhibitor composition is prepared in advance as in the former, the concentration of acetylene alcohol, which is an active ingredient, and a nonionic surfactant during use is adjusted by the addition ratio of the corrosion inhibitor composition to the acid cleaning liquid. Is done. Therefore, the absolute content of the acetylene alcohol and the nonionic surfactant in the corrosion inhibitor composition is not so much of a problem, but the relative content ratio of the two is, for example, the two defined in the seventh invention. It is preferable to adjust so as to satisfy the content ratio.
〔アセチレンアルコール〕
アセチレンアルコールは、化学的定義に該当する限りにおいて、その種類は必ずしも限定されないが、ノンチッソ型のアセチレンアルコール、即ち、分子内にアミノ基その他の窒素含有基を含まないアセチレンアルコールが特に好ましい。このようなアセチレンアルコールとして、アセチレンモノアルコールやアセチレンジアルコールが例示され、より具体的には、プロパギルアルコール、メチルブチノール、ジメチルペンチノール、ブチンジオール及びヘキシンジオールから選ばれる１種以上を特に好ましく例示することができる。
[Acetylene alcohol]
The type of acetylene alcohol is not necessarily limited as long as it falls within the chemical definition, but non-nitrous acetylene alcohol, that is, acetylene alcohol containing no amino group or other nitrogen-containing group in the molecule is particularly preferred. Examples of such acetylene alcohol include acetylene monoalcohol and acetylene dialcohol, and more specifically, at least one selected from propargyl alcohol, methylbutynol, dimethylpentinol, butynediol and hexynediol. It can be illustrated preferably.
但し、廃水処理に伴う環境負荷を厳密に問題にしない場合には、優れた腐食抑制作用が確保されることを前提として、アミノ基その他の窒素含有基を含むアセチレンアルコール（例えば、上記に列挙した各種アセチレンアルコールのアミノ誘導体）を用いることもできる。 However, if the environmental load associated with wastewater treatment is not strictly a problem, acetylene alcohols containing amino groups or other nitrogen-containing groups (for example, listed above) on the premise that excellent corrosion inhibition is ensured. Various acetylene alcohol amino derivatives) can also be used.
〔非イオン界面活性剤〕
非イオン界面活性剤は、化学的定義に該当する限りにおいて、その種類は必ずしも限定されないが、ノンチッソ型の非イオン界面活性剤、即ち分子内又は構成単位であるモノマー内に窒素含有基を含まない非イオン界面活性剤が特に好ましい。このような非イオン界面活性剤として、ポリオキシエチレン重合物、ポリオキシプロピレン重合物及びポリオキシエチレンポリオキシプロピレン重合物から選ばれる１種以上を特に好ましく例示することができる。他にも、ポリオキシエチレンアルキルエステル、ポリオキシエチレンソルビタン脂肪酸エステル等の非イオン界面活性剤を用いることもできる。
[Nonionic surfactant]
The type of nonionic surfactant is not necessarily limited as long as it falls within the chemical definition. However, a non-nitrogen type nonionic surfactant, that is, a nitrogen-containing group is not included in a molecule or a monomer as a constituent unit. Nonionic surfactants are particularly preferred. As such a nonionic surfactant, one or more selected from polyoxyethylene polymer, polyoxypropylene polymer and polyoxyethylene polyoxypropylene polymer can be particularly preferably exemplified. In addition, nonionic surfactants such as polyoxyethylene alkyl esters and polyoxyethylene sorbitan fatty acid esters can also be used.
廃水処理に伴う環境負荷を厳密に問題にしない場合には、優れた白色度向上効果と腐食抑制に対する相乗効果が確保されることを前提として、分子内又は構成単位であるモノマー内に窒素含有基を含む非イオン界面活性剤を用いることも可能である。 In cases where the environmental burden associated with wastewater treatment is not strictly a problem, a nitrogen-containing group may be present in the molecule or constituent monomer, assuming that a superior synergistic effect on whiteness improvement and corrosion inhibition is ensured. It is also possible to use a nonionic surfactant containing.
一方、上記のノンチッソ型か否かの区別に関わらず、分子内にエーテル基、水酸基、ケトン基、又はエステル基のいずれか１種以上を少なくとも２基以上有する非イオン界面活性剤も好ましい。その内でも、とりわけ、ノンチッソ型のものが好ましい。 On the other hand, a nonionic surfactant having at least two of at least one of an ether group, a hydroxyl group, a ketone group, and an ester group in the molecule is also preferable regardless of whether or not it is the above-mentioned non-chisso type. Among them, the non-chisso type is particularly preferable.
〔酸洗浄液組成物〕
本発明の酸洗浄液組成物は、無機酸及び／又は有機酸からなる酸成分に加えて、上記いずれかの腐食抑制剤組成物を含有する点に特徴がある。酸洗浄液組成物は、予め使用時濃度に調節して準備しておいても良いし、高濃度の酸洗浄原液として準備して置き、使用時に適宜に希釈して用いても良い。
[Acid cleaning liquid composition]
The acid cleaning liquid composition of the present invention is characterized in that it contains any one of the above corrosion inhibitor compositions in addition to an acid component composed of an inorganic acid and / or an organic acid. The acid cleaning liquid composition may be prepared by adjusting the concentration at the time of use in advance, or may be prepared as a high concentration acid cleaning stock solution, and may be diluted as appropriate when used.
酸成分としては、この種の酸洗浄液組成物に用いられることがある無機酸及び／又は有機酸の１種以上を任意に含むことができるが、例えば無機酸としては、硫酸、塩酸、リン酸、硝酸、スルファミン酸、フッ酸等を例示することができる。有機酸としては、ギ酸、酢酸、シュウ酸、クエン酸、酒石酸、マロン酸、グリコール酸、アスコルビン酸、ＥＤＴＡ等を例示することができる。酸洗浄液の液相媒体の種類は限定されないが、水又は親水性媒体が好ましく利用される。 The acid component can optionally include one or more inorganic acids and / or organic acids that may be used in this type of acid cleaning liquid composition. Examples of inorganic acids include sulfuric acid, hydrochloric acid, and phosphoric acid. Nitric acid, sulfamic acid, hydrofluoric acid and the like can be exemplified. Examples of organic acids include formic acid, acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, glycolic acid, ascorbic acid, EDTA, and the like. The type of the liquid phase medium of the acid cleaning liquid is not limited, but water or a hydrophilic medium is preferably used.
本発明において、酸洗浄液組成物に添加される腐食抑制剤組成物たる上記アセチレンアルコール及び非イオン界面活性剤の添加量は必ずしも限定されないが、第８発明及び第９発明に関して前記した理由から、酸洗浄液組成物１Ｌ当たり、アセチレンアルコールを２０〜２０００ｍｇ（２０〜２０００ｐｐｍ）含有し、及び／又は非イオン界面活性剤を５〜１０００ｍｇ（５〜１０００ｐｐｍ）含有することが特に好ましい。とりわけ、アセチレンアルコールを１００〜２００ｍｇ（１００〜２００ｐｐｍ）含有し、及び／又は、前記非イオン界面活性剤を１００〜２００ｍｇ（１００〜２００ｐｐｍ）含有することが好ましい。 In the present invention, the addition amount of the acetylene alcohol and the nonionic surfactant as the corrosion inhibitor composition added to the acid cleaning liquid composition is not necessarily limited, but for the reasons described above with respect to the eighth and ninth inventions, It is particularly preferable that 20 to 2000 mg (20 to 2000 ppm) of acetylene alcohol and / or 5 to 1000 mg (5 to 1000 ppm) of nonionic surfactant is contained per liter of the cleaning liquid composition. In particular, it is preferable to contain 100 to 200 mg (100 to 200 ppm) of acetylene alcohol and / or 100 to 200 mg (100 to 200 ppm) of the nonionic surfactant.
本発明の酸洗浄液組成物は、以上の組成分以外にも、この種の酸洗浄液組成物に添加されることがある任意の組成分を含むことができる。例えば、亜硫酸塩、亜硝酸塩、ケイ酸塩、ポリリン酸塩等の無機酸塩類、メルカプトエタノール、メルカプトグリセロール等の含硫黄有機化合物、ベンゼン環のオルト−、メタ−又はパラ−の位置に含窒素置換基や含イオウ置換基を備えた芳香族化合物、界面活性剤等を任意に含有することができる。 The acid cleaning liquid composition of the present invention can contain any component that may be added to this type of acid cleaning liquid composition in addition to the above components. For example, inorganic acid salts such as sulfites, nitrites, silicates and polyphosphates, sulfur-containing organic compounds such as mercaptoethanol and mercaptoglycerol, nitrogen-containing substitution at the ortho-, meta- or para-positions of the benzene ring An aromatic compound having a group or a sulfur-containing substituent, a surfactant or the like can be optionally contained.
〔金属の酸洗浄方法〕
本発明に係る金属の酸洗浄方法は、任意の金属の酸洗浄時に、上記いずれかの酸洗浄液組成物を用いる点に特徴がある。
[Metal acid cleaning method]
The metal acid cleaning method according to the present invention is characterized in that any one of the above acid cleaning liquid compositions is used during the acid cleaning of any metal.
酸洗浄の適用対象となる金属の材質や形態は、限定されない。例えば、各種の加工中の金属材料や各種の装置類を構成する金属材料に対して広範囲に適用することができる。金属材料としては、鉄、炭素鋼、銅、真ちゅう等を例示できるが、鉄材が特に好ましく、とりわけステンレス等の鋼鉄材が好適である。適用対象たる装置類の１，２の例として、発電プラント、ボイラー等を好ましく例示することができる。又、一般論として、水との接触環境において利用される各種装置類も好ましく例示することができる。 The material and form of the metal to which the acid cleaning is applied are not limited. For example, the present invention can be widely applied to various metal materials being processed and metal materials constituting various devices. As the metal material, iron, carbon steel, copper, brass and the like can be exemplified, but an iron material is particularly preferable, and a steel material such as stainless steel is particularly preferable. As examples of the devices 1 and 2 as the application target, a power plant, a boiler, and the like can be preferably exemplified. Moreover, as a general theory, various devices used in a contact environment with water can be preferably exemplified.
酸洗浄液による洗浄処理の具体的な方法や、洗浄処理の条件及び処理時間等は、洗浄処理の適用対象等に応じて任意に設計されるものであり、全く限定されない。例えば、洗浄処理方法としては、処理対象物を酸洗浄液に浸漬する方法や、処理対象物に対して酸洗浄液をシャワーする方法等がある。処理対象物が熱延鋼板（ＳＰＨＣ材）である場合、例えば８０〜９５°Ｃ程度の酸洗浄液に１０秒〜１分ほど浸漬することができる。 The specific method of the cleaning process using the acid cleaning solution, the cleaning process conditions, the processing time, and the like are arbitrarily designed according to the application target of the cleaning process, and are not limited at all. For example, as the cleaning treatment method, there are a method of immersing the processing object in an acid cleaning liquid, a method of showering the acid cleaning liquid on the processing object, and the like. When the object to be treated is a hot-rolled steel plate (SPHC material), it can be immersed in an acid cleaning solution at about 80 to 95 ° C for about 10 seconds to 1 minute, for example.
本発明に係る金属の酸洗浄方法によれば、大きな酸洗浄速度と、少ない金属腐食と言う要求を両立できるだけでなく、金属の腐食抑制効果と白色度の向上効果とを高いレベルでバランス良く両立させることができる。例えば、酸洗浄後の金属素地表面において、８８％以上の腐食抑制率を達成したもとで、７１度以上の白色度を得ることも、容易に達成できる。 According to the metal acid cleaning method of the present invention, not only can a high acid cleaning rate and a low metal corrosion requirement be compatible, but also a high level balance between a metal corrosion inhibition effect and a whiteness improvement effect can be achieved. Can be made. For example, on the surface of the metal substrate after the acid cleaning, a whiteness of 71 degrees or more can be easily achieved while achieving a corrosion inhibition rate of 88% or more.
（実施例１：酸洗浄液組成物の調製）
まず１０％塩酸及び１００ｇ／ＬのＦｅ２＋を含有する酸洗浄液を８例分準備し、これらに対して、下記の表１の実施例１〜実施例４及び比較例５〜比較例７の欄における「成分」の項にそれぞれ示す腐食抑制剤を、併せて示すｐｐｍ単位の濃度となるように添加して（比較例８は腐食抑制剤を添加していない）、各例に係る酸洗浄液組成物を調製した。
(Example 1: Preparation of acid cleaning liquid composition)
First, 8 examples of acid cleaning solutions containing 10% hydrochloric acid and 100 g / L of Fe 2+ were prepared, and the columns of Examples 1 to 4 and Comparative Examples 5 to 7 in Table 1 below were prepared. In addition, the corrosion inhibitor shown in the “component” section of each is added so as to have a concentration of ppm unit shown together (Comparative Example 8 does not contain a corrosion inhibitor), and the acid cleaning solution composition according to each example A product was prepared.
（実施例２：酸洗浄液組成物の性能評価試験）
供試材として、５０×５０×２．３（ｍｍ）の熱延鋼板（ＳＰＨＣ材：いわゆる黒皮材）を使用した。このＳＰＨＣ材はＣ（０．０９％）、Ｍｎ（０．２６％）、Ｐ（０．０１７％）、Ｓ（０．０２１％）を含み、表面にはＦｅＯ、Ｆｅ２ Ｏ３ 及びＦｅ３ Ｏ４ の表面スケールが約４０ｇ／ｍ２ 付着した鋼板である。
(Example 2: Performance evaluation test of acid cleaning liquid composition)
A 50 × 50 × 2.3 (mm) hot-rolled steel plate (SPHC material: so-called black skin material) was used as a test material. This SPHC material contains C (0.09%), Mn (0.26%), P (0.017%), S (0.021%), and FeO, Fe 2 O 3 and Fe 3 are formed on the surface. It is a steel plate with an O 4 surface scale of about 40 g / m 2 attached.
性能評価試験としては、上記の各例に係る酸洗浄液組成物８００ｍＬを適宜な耐酸性容器に収容して恒温槽中で８５°Ｃに保ち、これらの酸洗浄液組成物中に上記供試材をそれぞれ２分間浸漬することにより、酸洗浄処理を行った。そして、各例に係る酸洗浄処理後の供試材について、下記のように腐食抑制率と白色度とを評価した。 As a performance evaluation test, 800 mL of the acid cleaning liquid composition according to each of the above examples is accommodated in an appropriate acid-resistant container and kept at 85 ° C. in a thermostatic bath, and the test material is put in these acid cleaning liquid compositions. The acid cleaning treatment was performed by immersing each for 2 minutes. And about the test material after the acid cleaning process which concerns on each example, the corrosion inhibition rate and the whiteness were evaluated as follows.
（実施例３：腐食抑制率の評価）
腐食抑制率の評価においては、腐食抑制剤を添加していない比較例８をスタンダードとして、まず、その場合の酸洗浄処理後の供試材の減重量（Ｘ）を測定した。次に、実施例１〜実施例４及び比較例５〜比較例７の場合における、酸洗浄処理後のそれぞれの供試材の減重量（Ｙ）を測定した。
(Example 3: Evaluation of corrosion inhibition rate)
In the evaluation of the corrosion inhibition rate, the weight loss (X) of the test material after the acid cleaning treatment in that case was first measured using Comparative Example 8 to which no corrosion inhibitor was added as a standard. Next, the weight loss (Y) of each test material after the acid cleaning treatment in Examples 1 to 4 and Comparative Examples 5 to 7 was measured.
そして実施例１〜実施例４及び比較例５〜比較例７における腐食抑制率（％）を「腐食抑制率（％）＝〔１−（Ｙ／Ｘ）〕×１００」の式により、実施例１〜実施例４及び比較例５〜比較例７の各例ごとに算出した。従って、腐食抑制率のパーセンテージの大きいもの程、酸洗浄液組成物（換言すれば、添加した腐食抑制剤）の腐食抑制効果が高い。 Then, the corrosion inhibition rate (%) in Examples 1 to 4 and Comparative Examples 5 to 7 is expressed by the formula “corrosion inhibition rate (%) = [1- (Y / X)] × 100”. The calculation was performed for each of Examples 1 to 4 and Comparative Examples 5 to 7. Therefore, the larger the percentage of the corrosion inhibition rate, the higher the corrosion inhibition effect of the acid cleaning liquid composition (in other words, the added corrosion inhibitor).
（実施例４：白色度の評価）
実施例１〜実施例４及び比較例５〜比較例７に係る上記酸洗浄処理後の供試材を水洗し、乾燥させた後の表面を分光測色計（ミノルタ製 CM2600d）を用いて測定し、「白色度＝１００−〔（１００−Ｌ）２ ＋ａ２ ＋ｂ２ 〕１／２ 」の式により、それぞれの白色度を求めた。上記の白色度の計算式において、「Ｌ」は明度、「ａ」は赤〜緑の色相（上記の分光測色計における赤〜緑の色相の読み値）を、「ｂ」は黄〜青の色相（上記の分光測色計における黄〜青の色相の読み値）を、それぞれ意味する。結局、白色度の数値の高いものほど鋼板表面の白さが優れ、好ましい品質を意味する。
(Example 4: Evaluation of whiteness)
The specimens after the acid washing treatment according to Examples 1 to 4 and Comparative Examples 5 to 7 were washed with water and dried, and the surface after drying was measured using a spectrocolorimeter (CM2600d manufactured by Minolta). Then, each whiteness was determined by the formula of “whiteness = 100 − [(100−L) 2 + a 2 + b 2 ] 1/2 ”. In the above formula for calculating the whiteness, “L” is lightness, “a” is a red to green hue (reading value of red to green hue in the above spectrocolorimeter), and “b” is yellow to blue. Are the hues (yellow to blue hue readings in the spectrocolorimeter). After all, the higher the whiteness value, the better the whiteness of the steel sheet surface, which means preferable quality.
（評価結果）
まず、スタンダードである比較例８においては、上記の計算式からして腐食抑制率が当然に０％であり、又、白色度も最も低い。
(Evaluation results)
First, in Comparative Example 8, which is a standard, the corrosion inhibition rate is naturally 0% from the above formula, and the whiteness is the lowest.
比較例５、６は腐食抑制剤としてプロパギルアルコールのみを各１００ｐｐｍ及び２００ｐｐｍ添加したものであり、比較例７は腐食抑制剤として従来型の窒素含有高分子化合物のみを２００ｐｐｍ添加したものである。これらの例において、比較例５、６は比較例７に対して相対的に高い腐食抑制率を示すが、白色度は劣る、と言う関係が見られる。即ち、「第１発明の効果」欄で前記したように、アセチレンアルコールが主として腐食抑制効果に優れ、非イオン界面活性剤が主として白色度の向上効果に優れる、と言う関係が認められる。 In Comparative Examples 5 and 6, only propagyl alcohol was added as a corrosion inhibitor at 100 ppm and 200 ppm, respectively, and Comparative Example 7 was added as a corrosion inhibitor only at a conventional nitrogen-containing polymer compound at 200 ppm. In these examples, Comparative Examples 5 and 6 show a relatively high corrosion inhibition rate as compared with Comparative Example 7, but a relationship that whiteness is inferior is seen. That is, as described above in the “Effects of the first invention” column, the relationship that acetylene alcohol is mainly excellent in corrosion inhibition effect and nonionic surfactant is mainly excellent in whiteness improvement effect is recognized.
そして、実施例１〜実施例４においては、腐食抑制率及び白色度が格段に高いレベルでバランス良く両立されている。腐食抑制率が、実施例３においてのみ、比較例６よりもわずかに劣るが、この点が本発明の効果を否定するものとは考えられない。何故なら、実施例１、２と実施例３、４との比較から「 Ploal」の腐食抑制効果が「Bdol」に比較して相対的に優れていることは明瞭であり、しかも実施例３における「Bdol」の添加量が１００ｐｐｍであるのに対して比較例６では「 Ploal」を２００ｐｐｍ添加しているからである。 In Examples 1 to 4, the corrosion inhibition rate and the whiteness are both balanced at a remarkably high level. Although the corrosion inhibition rate is slightly inferior to Comparative Example 6 only in Example 3, this point cannot be considered to deny the effect of the present invention. This is because it is clear from the comparison between Examples 1 and 2 and Examples 3 and 4 that the corrosion inhibition effect of “Ploal” is relatively superior to that of “Bdol”. This is because the amount of “Bdol” added is 100 ppm, whereas in Comparative Example 6, “Ploal” is added at 200 ppm.
むしろ、比較例６と実施例２との対比、あるいは比較例５と実施例１との対比から、アセチレンアルコールに対して非イオン界面活性剤を併せ添加することにより、白色度が向上するだけでなく、アセチレンアルコールの腐食抑制効果が相乗的に補強されていることが分かる。この点は、実施例１と実施例２との対比、あるいは実施例３と実施例４との対比によっても裏付けられている。 Rather, from the comparison between Comparative Example 6 and Example 2 or the comparison between Comparative Example 5 and Example 1, only adding a nonionic surfactant to acetylene alcohol improves whiteness. It can be seen that the corrosion inhibition effect of acetylene alcohol is synergistically reinforced. This point is supported by the comparison between Example 1 and Example 2 or the comparison between Example 3 and Example 4.
本発明によって、製鉄関連産業や金属材料を扱う各種産業において有効に利用され、優れた効果を得る腐食抑制剤組成物、酸洗浄液組成物、及び金属の酸洗浄方法が提供される。
INDUSTRIAL APPLICABILITY The present invention provides a corrosion inhibitor composition, an acid cleaning liquid composition, and a metal acid cleaning method that are effectively used in various industries dealing with iron making and metal materials and obtain excellent effects.
Claims (10)
The whiteness of 71 degrees or more is obtained by achieving a corrosion inhibition rate of 88% or more on the metal substrate surface after the acid cleaning by the acid cleaning method of the metal. Metal acid cleaning method.
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| JP2009037975A (en) * | 2007-08-03 | 2009-02-19 | Honda Motor Co Ltd | SEAL COMPOSITION FOR FUEL CELL, FUEL CELL SEAL, FUEL CELL HAVING FUEL CELL SEAL, AND METHOD FOR PRODUCING THE SAME |
| WO2009035341A1 (en) * | 2007-09-13 | 2009-03-19 | Borregaard Industries Limited Norge | Corrosion inhibitor |
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| JP2009037975A (en) * | 2007-08-03 | 2009-02-19 | Honda Motor Co Ltd | SEAL COMPOSITION FOR FUEL CELL, FUEL CELL SEAL, FUEL CELL HAVING FUEL CELL SEAL, AND METHOD FOR PRODUCING THE SAME |
| WO2009035341A1 (en) * | 2007-09-13 | 2009-03-19 | Borregaard Industries Limited Norge | Corrosion inhibitor |
| CN102976622A (en) * | 2011-09-06 | 2013-03-20 | 浩华科技实业有限公司 | Amorphous metal microfilament glass coating layer chemical removing method and corrosion liquid preparation method |
| CN102330099A (en) * | 2011-09-09 | 2012-01-25 | 北京星航机电设备厂 | Stainless steel pickling inhibitor |
| CN103882452A (en) * | 2014-03-13 | 2014-06-25 | 陕西省石油化工研究设计院 | Citric acid acid-pickling inhibitor |
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| US12018210B2 (en) | 2018-05-11 | 2024-06-25 | Dorf Ketal Chemicals Fze | Methods for stimulating a hydrocarbon-bearing formation by perforating a wellbore and introducing an acidic composition in the wellbore |
| US12241021B2 (en) | 2018-05-11 | 2025-03-04 | Dorf Ketal Chemicals Fze | Method for fracking of simulation of hydrocarbon bearing formation |
| US12497557B2 (en) | 2018-05-11 | 2025-12-16 | Dorf Ketal Chemicals Fze | Methods for stimulating a hydrocarbon-bearing formation by perforating a wellbore and introducing an acidic composition in the wellbore |
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