JP6266930B2 - Granular sludge generation inhibitor - Google Patents
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- JP6266930B2 JP6266930B2 JP2013185958A JP2013185958A JP6266930B2 JP 6266930 B2 JP6266930 B2 JP 6266930B2 JP 2013185958 A JP2013185958 A JP 2013185958A JP 2013185958 A JP2013185958 A JP 2013185958A JP 6266930 B2 JP6266930 B2 JP 6266930B2
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- 239000010802 sludge Substances 0.000 title claims description 95
- 239000003112 inhibitor Substances 0.000 title claims description 65
- 239000000126 substance Substances 0.000 claims description 94
- 239000002253 acid Substances 0.000 claims description 82
- 238000004140 cleaning Methods 0.000 claims description 74
- 150000001875 compounds Chemical class 0.000 claims description 41
- 230000007797 corrosion Effects 0.000 claims description 41
- 238000005260 corrosion Methods 0.000 claims description 41
- 238000005554 pickling Methods 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 34
- 239000007769 metal material Substances 0.000 description 31
- 229910000831 Steel Inorganic materials 0.000 description 25
- 239000010959 steel Substances 0.000 description 25
- 239000011230 binding agent Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000002923 metal particle Substances 0.000 description 7
- 230000001629 suppression Effects 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- -1 alkyne compound Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- GBTLTMCERWNPFD-UHFFFAOYSA-N 3,3-dimethylpent-1-yn-1-ol Chemical compound CCC(C)(C)C#CO GBTLTMCERWNPFD-UHFFFAOYSA-N 0.000 description 1
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KXUSQYGLNZFMTE-UHFFFAOYSA-N hex-2-yne-1,1-diol Chemical compound CCCC#CC(O)O KXUSQYGLNZFMTE-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
本願が開示する発明は、鋼材等の金属材料表面の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に添加して使用する粒状スラッジ発生抑制剤に関する。 The invention disclosed by the present application relates to a granular sludge generation inhibitor used by being added to an acid cleaning solution for removing an oxide film such as a hot-rolled scale on the surface of a metal material such as a steel material.
例えば鋼材等の熱間圧延(熱延とも称する)工程では、金属材料の表面にいわゆる熱延スケール等の酸化物皮膜が付着しており、メッキや冷間圧延(冷延とも称する)等の後工程に供するために、この酸化物皮膜を金属材の表面から除去する必要がある。 For example, in a hot rolling (also referred to as hot rolling) process for steel materials or the like, an oxide film such as a so-called hot rolling scale adheres to the surface of a metal material, and after plating or cold rolling (also referred to as cold rolling). In order to use for a process, it is necessary to remove this oxide film from the surface of a metal material.
このような酸化物皮膜の化学的な除去手段としては、一般的に酸洗浄液(無機酸を含む場合が多い)が用いられる。 As a means for chemically removing such an oxide film, an acid cleaning solution (which often contains an inorganic acid) is generally used.
ところが、酸洗浄液は酸化物皮膜を除去すると同時に、金属材料の表面を腐食する。仮に金属材料の表面が完全に均一な状態であるとすれば、論理的には、金属材料の表面において緩徐な速度で均一に進行する一般腐食が起こり、その被害は比較的少ないと考えられる。 However, the acid cleaning solution removes the oxide film and simultaneously corrodes the surface of the metal material. If the surface of the metal material is completely uniform, logically, general corrosion that proceeds uniformly at a slow rate occurs on the surface of the metal material, and the damage is considered to be relatively small.
しかし、金属材料の表面には酸化物皮膜の割れや粒界析出物等の不均一性要因が見られるのが普通である。酸洗浄時における酸洗浄液の濃度や流速の局所的な不均一性という要因も作用する。その結果、実際には、非常に腐食進行速度の大きい孔食が発生し、金属の品質が劣化する。このような金属品質の劣化は、例えば金属の加工工程においてはその後の冷間圧延、メッキ、伸線等の工程に悪影響を及ぼすし、装置等を構成する金属材料においては、装置等の機能保全を危うくする原因となる。 However, non-uniformity factors such as oxide film cracks and grain boundary precipitates are usually found on the surface of the metal material. Factors such as local non-uniformity in the concentration and flow rate of the acid cleaning solution during acid cleaning also act. As a result, in reality, pitting corrosion having a very high corrosion progress rate occurs, and the quality of the metal deteriorates. Such deterioration of the metal quality adversely affects the subsequent processes such as cold rolling, plating, and wire drawing in the metal processing step, and the functional maintenance of the device etc. in the metal material constituting the device etc. It will cause the danger.
このため、従来、金属材料表面の酸化物皮膜を酸洗浄液によって除去する際には、腐食防止剤を併用することが提案されている。そして、腐食防止剤の有効成分として、有機アミン系化合物が提案されている。 For this reason, it has been conventionally proposed to use a corrosion inhibitor together when removing the oxide film on the surface of the metal material with an acid cleaning solution. And the organic amine type compound is proposed as an active ingredient of a corrosion inhibitor.
下記特許文献1では、所定のポリアミン群から選ばれた2種類のポリアミンを有効成分とする腐食抑制剤と、これを含有する酸洗浄液が提案されている。 In the following Patent Document 1, a corrosion inhibitor having two types of polyamines selected from a predetermined polyamine group as active ingredients and an acid cleaning solution containing the same are proposed.
下記特許文献2では、有機含窒素化合物と、アルキン化合物と、ポリオール系化合物との3成分系からなる金属腐食防止剤を提案することによって下記特許文献1で提案されているものより更に良好な腐食防止効果を得ている。 In the following patent document 2, corrosion is further improved than that proposed in the following patent document 1 by proposing a metal corrosion inhibitor composed of a three-component system of an organic nitrogen-containing compound, an alkyne compound, and a polyol compound. The prevention effect is obtained.
下記特許文献3では、特定の含窒素化合物及び特定の酸素含有化合物を含む金属素地の腐食抑制剤組成物が提案されている。当該腐食抑制剤組成物によれば、腐食を抑制し、孔食を防止し、かつ白色度も改善できるとされている。 Patent Document 3 below proposes a corrosion inhibitor composition for a metal substrate containing a specific nitrogen-containing compound and a specific oxygen-containing compound. According to the corrosion inhibitor composition, it is said that corrosion can be suppressed, pitting corrosion can be prevented, and whiteness can be improved.
下記特許文献4には、イミダゾリウム系4級アンモニウム塩、ポリアミン化合物及び有機硫黄化合物を含み、金属用酸洗浄液に添加される腐食抑制剤が提案されている。当該腐食抑制剤は、高酸濃度(好ましくは硫酸濃度として15〜30重量%)及び高温(好ましくは液温90〜98℃)という過酷な酸洗条件下でも好適に使用可能とされている。 Patent Document 4 below proposes a corrosion inhibitor that contains an imidazolium-based quaternary ammonium salt, a polyamine compound, and an organic sulfur compound and is added to a metal acid cleaning solution. The corrosion inhibitor can be suitably used even under severe pickling conditions of high acid concentration (preferably 15 to 30% by weight as sulfuric acid concentration) and high temperature (preferably liquid temperature 90 to 98 ° C.).
以上の通り、従来、腐食抑制効果と酸洗浄効果の並立に着目した発明が開示されてきた。しかし、このような効果を有する腐食防止剤や腐食防止剤含有酸洗浄液において、その含有成分によっては、以下の不具合が発生する場合があった。 As mentioned above, the invention which paid its attention to the parallel of the corrosion inhibitory effect and the acid cleaning effect conventionally has been disclosed. However, in the corrosion inhibitor and the corrosion inhibitor-containing acid cleaning liquid having such an effect, the following problems may occur depending on the components contained therein.
特定の腐食防止剤を使用した酸洗浄液を連続使用すると、大粒径の粒状スラッジが発生する場合があることが見出された。次に、当該粒状スラッジが鋼板等の金属材料表面に付着することで表面欠陥(100μm程度の疵)を多数発生させると考えられた。 It has been found that the continuous use of an acid cleaning solution with a specific corrosion inhibitor can result in the formation of large particle size granular sludge. Next, it was considered that the granular sludge adheres to the surface of a metal material such as a steel plate to generate many surface defects (soot of about 100 μm).
概念図である図1を用いてより具体的に説明すると、酸洗出側に設置したリンガーロール3を使用する場合と使用しない場合とで欠陥混入率を比較した結果、リンガーロール3使用時に欠陥(100μm程度の疵)混入率が高くなることがわかった(図1、図2)。よって、リンガーロール3が、酸洗槽内で発生した粒状スラッジ1を鋼板等の金属材料表面に押し付けている可能性が高いと考えられた。 Describing more specifically with reference to FIG. 1 which is a conceptual diagram, as a result of comparing the defect mixing rate when the ringer roll 3 installed on the pickling side is used and when not used, the defect is found when the ringer roll 3 is used. It was found that the contamination rate was increased (FIG. 1 and FIG. 2). Therefore, it was considered that the ringer roll 3 is likely to press the granular sludge 1 generated in the pickling tank against the surface of a metal material such as a steel plate.
本願発明者は上記粒状スラッジの発生に基づく不具合を抑制するため鋭意研究を重ねた結果、以下の知見を得て、本願が開示する発明を完成するに至った。 The inventor of the present application has earnestly studied in order to suppress the problems due to the generation of the granular sludge. As a result, the inventors have obtained the following knowledge and completed the invention disclosed by the present application.
(1)腐食防止剤には、粒状スラッジを発生させるものと粒状スラッジを発生しにくいものがあった。 (1) Some corrosion inhibitors generate granular sludge and others do not easily generate granular sludge.
(2)次に、粒状スラッジを発生させる腐食防止剤に含まれる成分と粒状スラッジを発生しにくい腐食防止剤に含まれる成分の構造に着目して比較検討した。その結果、以下の推測を得るに至った。
粒状スラッジを発生させる腐食防止剤に含まれていた成分には、以下の(2−1)や(2−2)の特徴があった。
(2) Next, a comparative study was conducted focusing on the structure of components contained in the corrosion inhibitor that generates granular sludge and components contained in the corrosion inhibitor that hardly generates granular sludge. As a result, the following estimation was obtained.
The components contained in the corrosion inhibitor that generates granular sludge have the following characteristics (2-1) and (2-2).
(2−1)SO2基やチオール基等のS原子を含む電子吸引性基を含むか、又は、ポリエチレングリコール等のポリオール重合体(分子量100〜10000)の様な、指向性を持たずに集積可能と考えられる構造を含むと考えられる骨格を有していた。 (2-1) It contains an electron-withdrawing group containing S atoms such as SO 2 group and thiol group, or has no directivity like polyol polymer (molecular weight 100 to 10,000) such as polyethylene glycol. It had a skeleton that was thought to contain structures that could be integrated.
(2−2)ヘキサメチレンテトラミン等の低分子量アミン(分子量200以下)、又は、三重結合を有する分子量が小さいアセチレンアルコール(分子量200以下)。 (2-2) Low molecular weight amines (molecular weight 200 or less) such as hexamethylenetetramine, or acetylene alcohols having a triple bond and a small molecular weight (molecular weight 200 or less).
金属材料から剥離または溶出する金属粒子、その酸化物粒子及びその水酸化物系粒子等が核となり、上記成分がバインダーとなって粒状スラッジが発生すると推測された(図3)。よって、以下、粒状スラッジを発生させる成分を「バインダー成分」と呼ぶ。 It was speculated that the metal particles exfoliated or eluted from the metal material, the oxide particles thereof, the hydroxide particles thereof, and the like serve as nuclei, and the above components serve as a binder to generate granular sludge (FIG. 3). Therefore, hereinafter, a component that generates granular sludge is referred to as a “binder component”.
一方、粒状スラッジを発生しにくい腐食防止剤に含まれる成分は、その骨格に比較的大きな分岐鎖を持つ場合が多く、かつ、上記(2−1)及び(2−2)の特徴を持たなかった。よって、金属材料から剥離または溶出する金属粒子、その酸化物粒子及びその水酸化物系粒子等と粒を形成するような結合・凝集・会合等が起こりにくく、粒状スラッジが発生しにくいと推測された(図4)。 On the other hand, the component contained in the corrosion inhibitor that hardly generates granular sludge often has a relatively large branched chain in its skeleton, and does not have the characteristics of (2-1) and (2-2) above. It was. Therefore, it is presumed that binding, aggregation, association, etc. that form particles with metal particles that peel or elute from the metal material, their oxide particles and their hydroxide-based particles are unlikely to occur, and granular sludge is unlikely to occur. (FIG. 4).
(3)上記粒状スラッジが発生しにくい成分を使用すれば、一定量のバインダー成分を含んでいても粒状スラッジが発生しにくいことを見出した。即ち、上記粒状スラッジが発生しにくい成分は、バインダー成分の機能を抑制できることを見出した。 (3) It has been found that if the above-mentioned components that do not easily generate granular sludge are used, it is difficult for granular sludge to be generated even if a certain amount of binder component is included. That is, the present inventors have found that the above-mentioned component that hardly generates granular sludge can suppress the function of the binder component.
金属材料の酸洗浄時において、酸洗槽内には腐食抑制剤を入れる必要がある。上記粒状スラッジが発生しにくい成分は様々な腐食抑制剤の使用を可能にしつつ、粒状スラッジの発生を抑制できることを見出した。 When pickling metal materials, it is necessary to put a corrosion inhibitor in the pickling tank. It has been found that the above-mentioned components that hardly generate granular sludge can suppress the generation of granular sludge while enabling the use of various corrosion inhibitors.
よって、優れた粒状スラッジ発生抑制剤、酸洗浄用添加剤セット及び酸洗方法を提供することを、本願が開示する発明が解決すべき課題とする。 Accordingly, it is an object of the present invention to solve the problem to provide an excellent granular sludge generation inhibitor, an acid cleaning additive set, and a pickling method.
(第1発明)
上記課題を解決するための本願第1発明の構成は、
下記「化1」〜「化8」のいずれかの一般式に該当する化合物から選ばれる1種又は2種以上を含有する粒状スラッジ発生抑制剤である。
(First invention)
The configuration of the first invention of the present application for solving the above problems is as follows.
It is a granular sludge generation inhibitor containing one or more selected from compounds corresponding to any one of the following general formulas of “Chemical Formula 1” to “Chemical Formula 8”.
(第2発明)
上記課題を解決するための本願第2発明の構成は、
金属材料を酸洗浄するための酸洗浄液に、上記「化1」〜「化8」のいずれかの一般式に該当する化合物の1種又は2種以上を1〜50,000(mg/L)の濃度で添加して使用する第1発明に記載の粒状スラッジ発生抑制剤である。
(Second invention)
The configuration of the second invention of the present application for solving the above problem is as follows.
1 to 50,000 (mg / L) of one or more compounds corresponding to the general formula of any one of the above “Chemical Formula 1” to “Chemical Formula 8” in an acid cleaning solution for acid cleaning a metal material It is a granular sludge generation | occurrence | production inhibitor as described in 1st invention used by adding with the density | concentration.
濃度について説明すると、仮に、粒状スラッジ発生抑制剤が上記一般式「化1」に該当する化合物のみを含む場合は、当該化合物の濃度が1〜50,000(mg/L)という意味である。上記一般式「化1」〜「化8」に該当する化合物を含む場合は、これらの各化合物の濃度の合計が1〜50,000(mg/L)という意味である。 Describing the concentration, if the granular sludge generation inhibitor contains only a compound corresponding to the general formula “Chemical Formula 1”, it means that the concentration of the compound is 1 to 50,000 (mg / L). When the compounds corresponding to the above general formulas “Chemical Formula 1” to “Chemical Formula 8” are included, the total concentration of these compounds means 1 to 50,000 (mg / L).
(第3発明)
上記課題を解決するための本願第3発明の構成は、
金属材料を酸洗浄するための酸洗浄液に、バインダー成分を2000(mg/L)以下の濃度で添加して使用する第1発明又は第2発明に記載の粒状スラッジ発生抑制剤である。
(Third invention)
The configuration of the third invention of the present application for solving the above problem is as follows.
The granular sludge generation inhibitor according to the first invention or the second invention, which is used by adding a binder component at a concentration of 2000 (mg / L) or less to an acid cleaning solution for acid cleaning of a metal material.
当該バインダー成分は粒状スラッジ発生抑制剤に含まれても良い。また、粒状スラッジ発生抑制剤とは別途に調製されて酸洗浄液に添加されても良い。 The binder component may be included in the granular sludge generation inhibitor. Further, it may be prepared separately from the granular sludge generation inhibitor and added to the acid cleaning liquid.
(第4発明)
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発明のいずれかに記載した粒状スラッジ発生抑制剤と、
腐食抑制剤、スケール除去促進剤、消泡剤、発泡剤、着色剤、及び香料から選ばれる1つ又は2つ以上と、
を構成に含む酸洗浄用添加剤セットである。
(Fourth invention)
The configuration of the fourth invention of the present application for solving the above problem is as follows.
The granular sludge generation inhibitor described in any one of the first to third inventions,
One or more selected from a corrosion inhibitor, a descaling accelerator, an antifoaming agent, a foaming agent, a colorant, and a fragrance, and
Is an acid cleaning additive set.
ここで、腐食抑制剤、スケール除去促進剤、消泡剤、発泡剤、着色剤、香料として、種々の腐食抑制剤、スケール除去促進剤、消泡剤、発泡剤、着色剤、香料を採用することができる。 Here, various corrosion inhibitors, scale removal accelerators, antifoaming agents, foaming agents, colorants, and fragrances are employed as corrosion inhibitors, scale removal accelerators, antifoaming agents, foaming agents, coloring agents, and fragrances. be able to.
(第5発明)
上記課題を解決するための本願第5発明は、
金属材料を酸洗浄するための酸洗浄液に、上記「化1」〜「化8」のいずれかの一般式に該当する化合物の1種又は2種以上を1〜50,000(mg/L)の濃度で添加して行う酸洗方法である。
(Fifth invention)
The fifth invention of the present application for solving the above-mentioned problems is
1 to 50,000 (mg / L) of one or more compounds corresponding to the general formula of any one of the above “Chemical Formula 1” to “Chemical Formula 8” in an acid cleaning solution for acid cleaning a metal material It is the pickling method performed by adding at the density | concentration of.
(第6発明)
上記課題を解決するための本願第6発明の構成は、
金属材料を酸洗浄するための酸洗浄液に、バインダー成分を2000(mg/L)以下の濃度で添加して行う第5発明に記載の酸洗方法である。
(Sixth invention)
The configuration of the sixth invention of the present application for solving the above-described problems is as follows.
The pickling method according to the fifth aspect, wherein the binder component is added at a concentration of 2000 (mg / L) or less to an acid cleaning solution for acid cleaning of a metal material.
本願が開示する粒状スラッジ発生抑制剤は、鋼板等の金属材料の酸洗浄時に粒状スラッジが発生することを良好に抑制する。酸洗浄液中に金属材料中から剥離または溶出する金属粒子、その酸化物粒子及びその水酸化物系粒子が分散していても、良好に粒状スラッジの発生を抑制できる。また、当該粒状スラッジ発生抑制剤は、様々な腐食抑制剤と併用することも可能である。 The granular sludge generation inhibitor disclosed in the present application favorably suppresses the generation of granular sludge during acid cleaning of a metal material such as a steel plate. Even if the metal particles peeled or eluted from the metal material, the oxide particles thereof, and the hydroxide particles thereof are dispersed in the acid cleaning liquid, the generation of granular sludge can be satisfactorily suppressed. Moreover, the said granular sludge generation | occurrence | production inhibitor can also be used together with various corrosion inhibitors.
1 粒状スラッジ
2 リンガーロール3によって鋼板4に押し付けられた粒状スラッジ
3 リンガーロール
4 鋼板
5 酸洗槽第1槽
6 酸洗槽第2槽
7 酸洗槽第3槽
8 酸洗槽第4槽
31 金属粒子
32 バインダー成分
41 金属粒子
42 粒状スラッジを発生しにくい腐食防止剤に含まれる成分
51 鋼板
52 リンガーロール
53 第1槽(温水槽)
54 第2槽
55 第3槽
56 第4槽
57 第5槽
DESCRIPTION OF SYMBOLS 1 Granular sludge 2 Granular sludge pressed against steel plate 4 by Ringer roll 3 3 Ringer roll 4 Steel plate 5 Pickling tank 1st tank 6 Pickling tank 2nd tank 7 Pickling tank 3rd tank 8 Pickling tank 4th tank 31 Metal particle 32 Binder component 41 Metal particle 42 Component contained in corrosion inhibitor that hardly generates granular sludge 51 Steel plate 52 Ringer roll 53 First tank (hot water tank)
54 2nd tank 55 3rd tank 56 4th tank 57 5th tank
以下、本願が開示する発明をその最良の形態を含めて説明する。 Hereinafter, the invention disclosed by the present application will be described including the best mode.
〔粒状スラッジ発生抑制剤〕
本願が開示する発明において、「粒状スラッジ発生抑制」とは、粒状スラッジの発生の抑制を意味する。酸洗浄液中に微細な金属粒子、その酸化物粒子、及び、その水酸化物粒子等が分散している場合は、良好な分散状態の維持をも含む概念である。
[Granular sludge generation inhibitor]
In the invention disclosed in the present application, “inhibition of granular sludge generation” means suppression of generation of granular sludge. When fine metal particles, their oxide particles, their hydroxide particles, and the like are dispersed in the acid cleaning liquid, this is a concept including maintaining a good dispersion state.
なお、粒状スラッジは、酸洗浄液の上面に浮く場合もあるし、沈殿する場合もある。粒状スラッジが金属材料等の表面に付着したまま酸洗浄の後工程が行われると、例えば上記した孔食が生じた場合と同等程度の不具合等、種々の不具合が起こる可能性がある。 The granular sludge may float on the upper surface of the acid cleaning solution or may precipitate. When the post-process of acid cleaning is performed with the granular sludge attached to the surface of a metal material or the like, various problems such as a problem equivalent to the case where the pitting corrosion described above occurs may occur.
酸洗浄の後工程は種々考えられる。よって、酸洗浄の後工程にあわせて、本願が開示する発明によって発生が抑制されるべき粒状スラッジの大きさは適宜決定される。
後述の試験結果から、金属材料の表面に粒状スラッジが付着した状態でリンガーロールを使用すると、当該粒状スラッジの存在が原因で、100μm程度の疵が多数生じると本願発明者は考えている。よって、粒子径が100μm以上の粒状スラッジの発生を抑制することが好ましい。
Various post-processes for acid cleaning are conceivable. Therefore, the size of the granular sludge that should be suppressed by the invention disclosed in the present application is appropriately determined in accordance with the subsequent step of the acid cleaning.
From the test results described later, the present inventor believes that when a ringer roll is used in a state where granular sludge is adhered to the surface of the metal material, a large number of wrinkles of about 100 μm are generated due to the presence of the granular sludge. Therefore, it is preferable to suppress the generation of granular sludge having a particle diameter of 100 μm or more.
本願が開示する粒状スラッジ発生抑制剤は、上記「化1」〜「化8」のいずれかの一般式に該当する化合物から選ばれる1種又は2種以上を含有する。 The granular sludge generation inhibitor disclosed in the present application contains one or more selected from compounds corresponding to the general formulas of any one of the above “Chemical Formula 1” to “Chemical Formula 8”.
粒状スラッジ発生抑制剤は、好ましくは、「化1」〜「化7」のいずれかの一般式に該当する化合物から選ばれる1種又は2種以上を含有する。粒状スラッジ発生抑制効果の観点から、より好ましくは、「化1」〜「化4」のいずれかの一般式に該当する化合物から選ばれる1種又は2種以上を含有する。更に好ましくは、「化1」の一般式に該当する化合物から選ばれる1種又は2種以上を含有する。 The granular sludge generation inhibitor preferably contains one or more selected from compounds corresponding to any one of the general formulas of “Chemical Formula 1” to “Chemical Formula 7”. From the viewpoint of the effect of suppressing the generation of granular sludge, more preferably, one or more selected from compounds corresponding to any one of the general formulas of “Chemical Formula 1” to “Chemical Formula 4” are contained. More preferably, it contains one or more selected from compounds corresponding to the general formula of “Chemical Formula 1”.
上記「化1」に示す一般式において、nの上限は特に限定されない。上記「化1」に示す一般式においてnは、分子量が500〜2000となる数が好ましく、800〜1500となる数がより好ましい。Rは1個のアルキレン基が好ましい。XはClが好ましい。 In the general formula shown in the above “Chemical Formula 1”, the upper limit of n is not particularly limited. In the general formula shown in the above “Chemical Formula 1”, n is preferably a number having a molecular weight of 500 to 2000, and more preferably 800 to 1500. R is preferably one alkylene group. X is preferably Cl.
上記「化2」に示す一般式において、nの上限は特に限定されない。上記「化2」に示す一般式においてnは、分子量が1000〜50000となる数が好ましく、2000〜10000となる数がより好ましい。 In the general formula shown in the above “Chemical Formula 2”, the upper limit of n is not particularly limited. In the general formula shown in the above “Chemical Formula 2”, n is preferably a number having a molecular weight of 1000 to 50000, more preferably 2000 to 10,000.
上記「化3」に示す一般式において、nの上限は特に限定されない。上記「化3」に示す一般式においてnは、分子量が1000〜50000となる数が好ましく、2000〜20000となる数がより好ましい。 In the general formula shown in the above “Chemical Formula 3”, the upper limit of n is not particularly limited. In the general formula shown in the above “Chemical Formula 3”, n is preferably a number with a molecular weight of 1000 to 50000, more preferably 2000 to 20000.
上記「化4」に示す一般式において、nの上限は特に限定されない。上記「化4」に示す一般式においてnは、分子量が2000〜50000となる数が好ましく、3000〜20000となる数がより好ましい。R1とR2はそれぞれ水素が好ましい。R3はアルケニル基が好ましい。XはClが好ましい。 In the general formula shown in the above “Chemical Formula 4”, the upper limit of n is not particularly limited. In the general formula shown in the above “chemical formula 4”, n is preferably a number with a molecular weight of 2000 to 50000, more preferably 3000 to 20000. R 1 and R 2 are each preferably hydrogen. R 3 is preferably an alkenyl group. X is preferably Cl.
上記「化5」に示す一般式において、nの上限は特に限定されない。上記「化5」に示す一般式においてnは、分子量が500〜5000となる数が好ましく、700〜3000となる数がより好ましい。Rは1個のアルキレン基が好ましい。 In the general formula shown in the above “Chemical Formula 5”, the upper limit of n is not particularly limited. In the general formula shown in the above “chemical formula 5”, n is preferably a number having a molecular weight of 500 to 5,000, more preferably 700 to 3,000. R is preferably one alkylene group.
上記「化6」に示す一般式において、nの上限は特に限定されない。上記「化6」に示す一般式においてnは、分子量が300〜200000となる数が好ましく、500〜50000となる数がより好ましい。Rは1個のアルキレン基が好ましい。 In the general formula shown in the above “Chemical Formula 6”, the upper limit of n is not particularly limited. In the general formula shown in the above “chemical formula 6”, n is preferably a number having a molecular weight of 300 to 200,000, more preferably 500 to 50,000. R is preferably one alkylene group.
上記「化7」に示す一般式において、nの上限は特に限定されない。上記「化7」に示す一般式においてnは、分子量が2000〜50000となる数が好ましく、3500〜20000となる数がより好ましい。XはClが好ましい。 In the general formula shown in the above “Chemical Formula 7”, the upper limit of n is not particularly limited. In the general formula shown in the above “chemical formula 7”, n is preferably a number having a molecular weight of 2000 to 50000, more preferably 3500 to 20000. X is preferably Cl.
上記「化8」に示す一般式において、nの上限は特に限定されない。上記「化8」に示す一般式においてnは、分子量が300〜50000となる数が好ましく、1000〜30000となる数がより好ましい。 In the general formula shown in the above “Chemical Formula 8”, the upper limit of n is not particularly limited. In the general formula shown in the above “Chemical Formula 8”, n is preferably a number having a molecular weight of 300 to 50,000, more preferably 1000 to 30,000.
上記「化1〜化8」に示す一般式に該当する化合物は、その末端が明示されている場合を除き、各一般式の括弧で示した単位が粒状スラッジの発生抑制の観点から重要であると考えられる。よって、その末端が明示されていない場合は、粒状スラッジの発生抑制機能が認められる限り、末端の基は限定されない。通常、重合体の形成反応等により、適宜末端の基は決定される。但し、本願発明者に知見によれば、当該末端の基はSO2基やチオール基等のS原子を含む電子吸引性基でない。 In the compounds corresponding to the general formulas shown in the above “Chemical Formula 1 to Chemical Formula 8”, the units shown in parentheses of the general formulas are important from the viewpoint of suppressing the generation of granular sludge, unless the terminal is clearly indicated. it is conceivable that. Therefore, when the terminal is not specified, the terminal group is not limited as long as the function of suppressing the generation of granular sludge is recognized. Usually, the terminal group is appropriately determined by a polymer formation reaction or the like. However, according to the knowledge of the inventor of the present application, the terminal group is not an electron-withdrawing group containing an S atom such as an SO 2 group or a thiol group.
上記バインダー成分として、例えば、(i)スルホニル基(−SO2−)及び/又はチオール基(−SH)を有する成分、(ii)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、ブチレンジオール、及びヘキシンジオール等のアセチレンアルコール、(iii)ヘキサメチレンテトラミン、並びに、(iv)ポリエチレングリコール等のポリオール重合体が挙げられる。バインダー成分には、腐食抑制剤として使用可能の成分もある。 Examples of the binder component include (i) a component having a sulfonyl group (—SO 2 —) and / or a thiol group (—SH), (ii) propargyl alcohol, methylbutynol, dimethylpentynol, butylenediol, and Examples include acetylene alcohols such as hexynediol, (iii) hexamethylenetetramine, and (iv) polyol polymers such as polyethylene glycol. Some binder components can also be used as corrosion inhibitors.
上記バインダー成分に該当する、上記チオール基を有する化合物として、下記一般式「化9」〜一般式「化11」に示す化合物が例示される。 Examples of the compound having a thiol group corresponding to the binder component include compounds represented by the following general formulas “Chemical Formula 9” to “Chemical Formula 11”.
上記バインダー成分に該当する、上記スルホニル基を有する化合物として、下記一般式「化12」〜一般式「化14」に示す化合物が例示される。 Examples of the compound having a sulfonyl group corresponding to the binder component include compounds represented by the following general formulas “Chemical Formula 12” to “Chemical Formula 14”.
本願が開示する発明において、上記バインダー成分に該当するポリエチレングリコール等のポリオールは、単量体及び重合体は分子量が100〜10000とする。 In the invention disclosed in the present application, the monomer and the polymer of the polyol such as polyethylene glycol corresponding to the binder component have a molecular weight of 100 to 10,000.
本願発明者の知見によれば、上記「化1」〜「化8」のいずれかの一般式に該当する化合物は、バインダー成分のバインダー機能を抑制できると考えられる。即ち、粒状スラッジを発生させる腐食防止剤と粒状スラッジ発生抑制剤の併用が可能である。これを別の視点から捉えると、粒状スラッジ発生抑制剤は腐食防止剤に使用できる成分を含んでいても良い。 According to the knowledge of the present inventor, it is considered that a compound corresponding to any one of the general formulas of “Chemical Formula 1” to “Chemical Formula 8” can suppress the binder function of the binder component. That is, a corrosion inhibitor that generates granular sludge and a granular sludge generation inhibitor can be used in combination. From another viewpoint, the granular sludge generation inhibitor may contain a component that can be used as a corrosion inhibitor.
本願が開示する粒状スラッジ発生抑制剤は、通常、金属材料を酸洗浄するための酸洗浄液に添加して使用される。そして、酸洗浄の条件に応じて粒状スラッジ発生抑制剤の使用量は適宜決定される。よって、上記「化1」〜「化8」の一般式に該当する化合物の酸洗浄液への添加濃度は特に限定されない。本願発明者の知見によれば、バインダー成分を含まず上記「化1」〜「化8」の一般式に該当する化合物のみを酸洗浄液に添加する場合は、これらの化合物の濃度の合計が0.1〜50000(mg/L)となることが好ましく、0.1〜8000(mg/L)となることが好ましく、0.1〜1800(mg/L)となることが更に好ましく、0.1〜800(mg/L)となることが特に好ましい。上記「化1」〜「化8」の一般式に該当する化合物と、バインダー成分を併用する場合は、上記「化1」〜「化8」の一般式に該当する化合物の濃度の合計が1〜50,000(mg/L)であることが好ましく、10〜5000(mg/L)であることがより好ましい。 The granular sludge generation inhibitor disclosed in the present application is usually used by being added to an acid cleaning solution for acid cleaning of a metal material. And the usage-amount of granular sludge generation | occurrence | production inhibitor is suitably determined according to the conditions of acid cleaning. Therefore, the concentration of the compound corresponding to the general formulas of “Chemical Formula 1” to “Chemical Formula 8” to the acid cleaning solution is not particularly limited. According to the knowledge of the inventor of the present application, when only the compounds corresponding to the general formulas of “Chemical Formula 1” to “Chemical Formula 8” are added to the acid cleaning solution without including the binder component, the total concentration of these compounds is 0. 0.1 to 50000 (mg / L), preferably 0.1 to 8000 (mg / L), more preferably 0.1 to 1800 (mg / L), It is particularly preferably 1 to 800 (mg / L). When the compound corresponding to the general formulas of “Chemical Formula 1” to “Chemical Formula 8” and the binder component are used in combination, the total concentration of the compounds corresponding to the general formulas of “Chemical Formula 1” to “Chemical Formula 8” is 1. It is preferable that it is -50,000 (mg / L), and it is more preferable that it is 10-5000 (mg / L).
また、バインダー成分の酸洗浄液への添加は2000(mg/L)以下とすることが好ましく、700(mg/L)以下とすることがより好ましく、300(mg/L)以下とすることが更に好ましい。酸洗浄液がバインダー成分を含有しないことも好ましい。本願が開示する粒状スラッジ発生抑制剤は、このような条件を参考にして、バインダー成分を含有しても良い。 The addition of the binder component to the acid cleaning solution is preferably 2000 (mg / L) or less, more preferably 700 (mg / L) or less, and further 300 (mg / L) or less. preferable. It is also preferred that the acid cleaning liquid does not contain a binder component. The granular sludge generation inhibitor disclosed in the present application may contain a binder component with reference to such conditions.
本願が開示する粒状スラッジ発生抑制剤は上記「化1」〜「化8」の一般式に該当する化合物のみからなっても良く、これら以外の成分を含んで構成されても良い。粒状スラッジ発生抑制機能が発揮される限り、腐食抑制成分や上記バインダー成分等の他の任意成分を粒状スラッジ発生抑制剤に含有することができる。 The granular sludge generation inhibitor disclosed in the present application may be composed only of a compound corresponding to the general formulas of the above-mentioned “Chemical Formula 1” to “Chemical Formula 8”, or may include other components. As long as the particulate sludge generation suppressing function is exhibited, other optional components such as a corrosion suppressing component and the binder component can be contained in the granular sludge generation suppressing agent.
粒状スラッジ発生抑制剤の剤型は特に限定されないが、例えば、液状とすることができる。粒状スラッジ発生抑制剤は、任意の手法により製造可能である。 Although the dosage form of a granular sludge generation | occurrence | production inhibitor is not specifically limited, For example, it can be set as a liquid form. The granular sludge generation inhibitor can be produced by any method.
本願が開示する粒状スラッジ発生抑制剤が添加される酸洗浄液は、鋼材等の金属材料を酸洗浄するためのものである。酸としては有機酸、無機酸のいずれも使用可能である。本願が開示する粒状スラッジ発生抑制剤は、好ましくは、無機酸を主な酸として使用する(無機酸の濃度0.1〜30質量%)場面で酸洗浄液に添加される。当該無機酸として、例えば、塩酸、硫酸、硝酸、リン酸、スルファミン酸およびフッ酸から選ばれる1種または2種以上がある。塩酸又は硫酸を主な酸として使用する酸洗浄液に粒状スラッジ発生抑制剤を添加することが好ましい。 The acid cleaning liquid to which the granular sludge generation inhibitor disclosed in the present application is added is for acid cleaning of metal materials such as steel. As the acid, either an organic acid or an inorganic acid can be used. The granular sludge generation inhibitor disclosed in the present application is preferably added to the acid cleaning liquid when an inorganic acid is used as a main acid (inorganic acid concentration of 0.1 to 30% by mass). Examples of the inorganic acid include one or more selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, and hydrofluoric acid. It is preferable to add a granular sludge generation inhibitor to an acid cleaning liquid that uses hydrochloric acid or sulfuric acid as the main acid.
以上のとおり、本願は、粒状スラッジの発生が抑制された酸洗浄液をも開示する。 As described above, the present application also discloses an acid cleaning liquid in which the generation of granular sludge is suppressed.
上記酸洗浄の形態は特に限定されない。例えば、浸漬、吹付、塗布が挙げられる。好ましくは、圧延工程を経た金属材料の浸漬による酸洗浄である。 The form of the acid washing is not particularly limited. For example, immersion, spraying, application | coating is mentioned. Preferably, acid cleaning is performed by dipping a metal material that has undergone a rolling process.
浸漬法により酸洗浄をする場合、酸洗槽の形態は特に限定されない。あえて好ましい一例を挙げると幅1〜3m、長さ10〜100m、深さ0.3〜2mである。 When pickling by the dipping method, the form of the pickling tank is not particularly limited. A preferred example is a width of 1 to 3 m, a length of 10 to 100 m, and a depth of 0.3 to 2 m.
酸洗浄工程において浸漬法を採用し、複数の酸洗槽が存在する場合、粒状スラッジ発生抑制剤はいずれの酸洗槽に添加しても良い。好ましくは、少なくとも、酸洗浄工程に続く後工程に最も近い酸洗槽に粒状スラッジ発生抑制剤を添加する。 When the dipping method is employed in the pickling process and there are a plurality of pickling tanks, the granular sludge generation inhibitor may be added to any pickling tank. Preferably, a granular sludge generation inhibitor is added to at least the pickling tank closest to the subsequent step following the pickling step.
酸洗浄時の温度は特に限定されない。酸洗浄の形態や金属材料に合わせて酸洗浄時の温度を適宜選択可能である。後述する粒状スラッジ発生抑制試験では、10℃という低温においても粒状スラッジの発生抑制に成功している。よって、10〜100℃の温度で行う酸洗浄にも、粒状スラッジ発生抑制剤は好ましく使用できると合理的に推測される。酸洗浄時の温度は、より好ましくは、60〜100℃である。 The temperature at the time of acid cleaning is not particularly limited. The temperature during acid cleaning can be appropriately selected according to the form of acid cleaning and the metal material. In the granular sludge generation suppression test described later, the generation of granular sludge has been successfully suppressed even at a low temperature of 10 ° C. Therefore, it is reasonably estimated that the granular sludge generation inhibitor can be preferably used for acid cleaning performed at a temperature of 10 to 100 ° C. The temperature at the time of acid cleaning is more preferably 60 to 100 ° C.
粒状スラッジは、一旦発生してしまうと再度金属の微粒子状に分解することは難しいと考えられる。よって、粒状スラッジが発生していない、又は、粒状スラッジ量が少ない酸洗浄液に対して粒状スラッジ発生抑制剤を添加することが好ましい。また、金属材料の酸洗開始前又は開始直後に酸洗浄液に対して粒状スラッジ発生抑制剤を添加することが好ましい。 Once the granular sludge is generated, it is considered difficult to decompose it again into fine metal particles. Therefore, it is preferable to add a granular sludge generation inhibitor to the acid cleaning liquid in which no granular sludge is generated or the amount of granular sludge is small. In addition, it is preferable to add a particulate sludge generation inhibitor to the acid cleaning liquid before or immediately after the start of pickling of the metal material.
酸洗浄の対象となる金属材料は特に限定されない。例えば、酸洗浄を受ける金属として、鉄及び/又は銅を含む金属(合金を含む)が挙げられる。好ましくは、鉄を含む金属(合金をも含む)、鉄鋼が挙げられる。鉄鋼には普通鋼、特殊鋼などがあり、それぞれの鋼について熱間圧延製品、冷間圧延製品、電磁鋼板、鋳造品、鍛造品などがある。鉄合金としては、たとえば、高張力鋼、高速度鋼、刃物鋼、ステンレス鋼、などが挙げられる。 There are no particular limitations on the metal material to be subjected to acid cleaning. For example, as a metal subjected to acid cleaning, a metal (including an alloy) containing iron and / or copper can be given. Preferably, iron-containing metals (including alloys) and steel are used. Iron and steel include ordinary steel and special steel, and each steel includes hot rolled products, cold rolled products, electromagnetic steel sheets, cast products, forged products, and the like. Examples of the iron alloy include high-tensile steel, high-speed steel, blade steel, and stainless steel.
以上の通り、本願は、酸洗浄液における粒状スラッジの発生抑制方法、並びに、粒状スラッジの発生を抑制した酸洗方法をも開示する。 As described above, the present application also discloses a method of suppressing the generation of granular sludge in the acid cleaning liquid and a method of pickling that suppresses the generation of granular sludge.
〔リンガーロールの使用による疵の発生の確認〕
酸洗ラインは、幅2500mm、長さ20m、深さ1200mmの酸洗槽を4槽有するディープディップ型の酸洗槽を使用した。本試験で使用した酸洗槽の概要を図5に示す。なお、図5では、第1槽53(温水層)における温水、並びに、第2〜5槽(酸洗槽:54〜57)における酸洗浄液の図示は省略する。
[Confirmation of generation of wrinkles by using Ringer Roll]
The pickling line used was a deep dip type pickling tank having four tanks having a width of 2500 mm, a length of 20 m, and a depth of 1200 mm. An outline of the pickling tank used in this test is shown in FIG. In addition, in FIG. 5, illustration of the warm water in the 1st tank 53 (warm water layer) and the acid cleaning liquid in the 2nd-5th tank (pickling tank: 54-57) is abbreviate | omitted.
鋼板51は軟鋼である。酸洗浄液の温度は85℃とした。酸洗浄液は、酸として塩酸を使用し、腐食抑制剤は後述の実施例における(J)成分、ポリエチレングリコール((M)成分)、及び、プロパギルアルコール((K)成分)を合わせて500(mg/L)で使用した。 The steel plate 51 is mild steel. The temperature of the acid cleaning solution was 85 ° C. The acid cleaning solution uses hydrochloric acid as the acid, and the corrosion inhibitor is a combination of (J) component, polyethylene glycol ((M) component), and propargyl alcohol ((K) component) in the examples described later. mg / L).
最終槽(第5槽)57の鋼板出側から酸洗浄液を供給し、酸洗浄液は第2槽54から流出させた。最終槽57の塩酸濃度は10.0〜13.0質量%に管理した。鋼板51は第2槽54、第3槽55、第4槽56、第5槽57に順次搬送して各酸洗槽内の酸洗浄液に浸漬され、次の工程に搬送されることとした。鋼板51の搬送速度は100〜200m/minとした。 The acid cleaning liquid was supplied from the steel plate outlet side of the final tank (fifth tank) 57, and the acid cleaning liquid was allowed to flow out of the second tank 54. The hydrochloric acid concentration in the final tank 57 was controlled to 10.0 to 13.0% by mass. The steel plate 51 was sequentially transferred to the second tank 54, the third tank 55, the fourth tank 56, and the fifth tank 57, immersed in the acid cleaning solution in each of the acid cleaning tanks, and transferred to the next step. The conveyance speed of the steel plate 51 was 100 to 200 m / min.
以上の条件の酸洗浄の後、リンガーロール52を使用する場合とリンガーロール52を使用しない場合の欠陥(100μm程度の疵)混入率を求めた。本試験において、欠陥混入率は以下の式で求めた。
欠陥混入率(%)=鋼板疵混入数/鋼板長(m)×100
After the acid cleaning under the above conditions, the defect (flaw of about 100 μm) contamination rate when the Ringer roll 52 was used and when the Ringer roll 52 was not used was determined. In this test, the defect mixing rate was determined by the following formula.
Defect mixing rate (%) = Number of steel plate defects / Steel length (m) × 100
リンガーロール52を使用した場合の欠陥混入率は、リンガーロール52を使用しなかった場合の欠陥混入率の3倍程度と高かった。 The defect mixing rate when the Ringer roll 52 was used was as high as about three times the defect mixing rate when the Ringer roll 52 was not used.
酸洗槽内の酸洗浄液を分析した結果、酸洗浄液中から粒子径が300μm程度の粒状スラッジが検出された。よって、酸洗槽内で発生し鋼板表面に付着していた粒状スラッジをリンガーロールが鋼板に押し付けている可能性が高いと考えられた。 As a result of analyzing the acid cleaning liquid in the pickling tank, granular sludge having a particle size of about 300 μm was detected in the acid cleaning liquid. Therefore, it was considered that there was a high possibility that the ringer roll pressed the granular sludge generated in the pickling tank and adhering to the steel plate surface against the steel plate.
以下に実施例を説明する。本願が開示する発明の技術的範囲は以下の実施例に限定されない。 Examples will be described below. The technical scope of the invention disclosed in the present application is not limited to the following examples.
〔粒状スラッジ発生抑制試験〕
−試験に使用する成分−
以下の(A)〜(M)の化合物を添加成分として使用して試験した。
(A):上記一般式「化1」であらわされる化合物であり、Rは1個のアルキレン基であり、Xは塩素であり、数平均分子量が約1000である。
(B):上記一般式「化2」であらわされる化合物であり、数平均分子量が約3000である。
(C):上記一般式「化3」であらわされる化合物であり、数平均分子量が約3000である。
(D):上記一般式「化4」であらわされる化合物であり、R1は水素であり、R2は水素であり、R3は1個のアルキレン基であり、Xは塩素であり、数平均分子量が約5000である。
(E):上記一般式「化5」であらわされる化合物であり、mは1であり、Rは1個のアルキレン基であり、数平均分子量が約1000である。
(F):上記一般式「化6」であらわされる化合物であり、Rは1個のアルキレン基であり、数平均分子量が約10000である。
(G):上記一般式「化7」であらわされる化合物であり、Xは塩素であり、数平均分子量が約5000である。
(H):上記一般式「化8」であらわされる化合物であり、数平均分子量が約2000である。
(I):上記一般式「化9」であらわされる化合物であり、R1は炭素数1のアルキル基であり、R2は炭素数1のアルキル基であり、数平均分子量が約5000である。
(J):上記一般式「化12」であらわされる化合物であり、R1は炭素数1のアルキル基であり、R2は炭素数1のアルキル基であり、nは1であり、数平均分子量が約5000である。
(K):プロパギルアルコール
(L):下記一般式「化15」に示す化合物。
-Components used in the test-
The following compounds (A) to (M) were tested using as additive components.
(A): A compound represented by the above general formula “Chemical Formula 1”, R is one alkylene group, X is chlorine, and the number average molecular weight is about 1000.
(B): A compound represented by the above general formula “Chemical Formula 2”, and has a number average molecular weight of about 3000.
(C): A compound represented by the above general formula “Chemical Formula 3”, having a number average molecular weight of about 3000.
(D): a compound represented by the above general formula “Chemical Formula 4”, R 1 is hydrogen, R 2 is hydrogen, R 3 is one alkylene group, X is chlorine, The average molecular weight is about 5000.
(E): A compound represented by the above general formula “Chemical Formula 5”, m is 1, R is one alkylene group, and the number average molecular weight is about 1000.
(F): A compound represented by the above general formula “Chemical Formula 6”, R is one alkylene group, and the number average molecular weight is about 10,000.
(G): a compound represented by the above general formula “Chemical Formula 7”, X is chlorine, and the number average molecular weight is about 5000.
(H): a compound represented by the above general formula “Chemical Formula 8”, having a number average molecular weight of about 2000.
(I): a compound represented by the above general formula “Chemical Formula 9”, R 1 is an alkyl group having 1 carbon atom, R 2 is an alkyl group having 1 carbon atom, and has a number average molecular weight of about 5000. .
(J): a compound represented by the above general formula “Chemical Formula 12”, R 1 is an alkyl group having 1 carbon atom, R 2 is an alkyl group having 1 carbon atom, n is 1, and the number average The molecular weight is about 5000.
(K): Propagyl alcohol (L): Compound represented by the following general formula “Chemical Formula 15”.
−試験−
試験容器(高さ100mm×底面φ35mmの筒型容器)に、水道水28mlを入れ、次いで鉄酸化物粒子分散液5mlを入れ、次いで上記添加成分を含む添加剤2mlを添加した。この時点で、液面は試験容器の底から30mm程度である。
-Test-
In a test container (cylindrical container having a height of 100 mm and a bottom surface of φ35 mm), 28 ml of tap water was placed, then 5 ml of an iron oxide particle dispersion was placed, and then 2 ml of the additive containing the above-mentioned additive components was added. At this point, the liquid level is about 30 mm from the bottom of the test container.
ここで、添加剤は、
(1)上記(A)〜(M)成分をそれぞれ単独で含有するもの、
(2)上記(A)成分、並びに、(I)〜(M)成分のいずれかを併用したもの、
(3)上記(G)成分、並びに、(I)〜(M)成分のいずれかを併用したもの、を使用した。
Here, the additive is
(1) Those containing the above components (A) to (M) each independently,
(2) The above-mentioned component (A) and any of the components (I) to (M) in combination,
(3) The said (G) component and what used any of (I)-(M) component together were used.
試験容器中の上記(1)における添加成分の試験時濃度(上記水道水、鉄酸化物粒子分散液及び添加剤混合後の、各添加成分の濃度)は0.1(mg/L)、1(mg/L)、10(mg/L)、50(mg/L)、100(mg/L)、300(mg/L)、500(mg/L)、1000(mg/L)、2000(mg/L)、5000(mg/L)、10000(mg/L)、又は50000(mg/L)とした。 The concentration at the time of test of the additive component in (1) in the test container (the concentration of each additive component after mixing the tap water, the iron oxide particle dispersion and the additive) is 0.1 (mg / L), 1 (Mg / L), 10 (mg / L), 50 (mg / L), 100 (mg / L), 300 (mg / L), 500 (mg / L), 1000 (mg / L), 2000 ( mg / L), 5000 (mg / L), 10000 (mg / L), or 50000 (mg / L).
試験容器中の上記(2)、(3)の添加成分の試験時濃度は、(A)成分及び(G)成分は、上記(1)と同様とした。(I)〜(M)成分の濃度は100(mg/L)、500(mg/L)、1000(mg/L)、又は2000(mg/L)とした。 Concentrations at the time of testing of the additive components (2) and (3) in the test container were the same as those for the component (A) and the component (G). The concentrations of the components (I) to (M) were 100 (mg / L), 500 (mg / L), 1000 (mg / L), or 2000 (mg / L).
酸洗浄液には、金属材料から剥離または溶出するスケールや鉄系粒子が通常含まれる。よって、鉄酸化物粒子分散液を添加して酸洗浄中の酸洗浄液の状態に近付けて試験を行った。 The acid cleaning liquid usually contains scales and iron-based particles that are peeled off or eluted from the metal material. Therefore, the iron oxide particle dispersion liquid was added and the test was conducted in a state close to the state of the acid cleaning liquid during acid cleaning.
水道水、鉄酸化物粒子分散液及び添加剤が入った試験容器は、液面が試験容器の底から70〜80mm位に振れる力で、約40回転振とうした(所要時間は約10秒間)。振とう操作直後の試験容器内には沈殿がないことを確認した後、10℃に設定した恒温槽中に24時間試験容器を静置した。 The test container containing the tap water, the iron oxide particle dispersion and the additive was shaken for about 40 rotations with a force that the liquid level was swung to about 70 to 80 mm from the bottom of the test container (the required time was about 10 seconds). . After confirming that there was no precipitation in the test container immediately after the shaking operation, the test container was allowed to stand for 24 hours in a thermostat set at 10 ° C.
その後、下記評価基準に基づき、目視による評価を行った。評価結果は、各成分とその試験時濃度の組合せに応じて、表1〜3に記載した。表2において「A濃度」とは、上記(A)成分の試験時濃度を意味する。表3において「G濃度」とは、上記(G)成分の試験時濃度を意味する。表2及び表3において、「IJKLM濃度」とは、各(I)〜(M)成分の試験時濃度を意味する。 Thereafter, visual evaluation was performed based on the following evaluation criteria. The evaluation results are shown in Tables 1 to 3 in accordance with the combination of each component and the test concentration. In Table 2, “A concentration” means the concentration of the component (A) at the time of testing. In Table 3, “G concentration” means the concentration during the test of the component (G). In Tables 2 and 3, “IJKLM concentration” means the test concentration of each of the components (I) to (M).
−評価基準−
本願発明者の知見によれば、粒状スラッジが発生しない状態、言いかえれば、鉄酸化物粒子が試験容器中に分散した状態が維持されることが好ましい。一方、試験容器内が透明になると、鉄酸化物粒子が沈殿もしくは添加成分と結合・凝集・会合等してしまったことを意味すると考えられる。よって、下記の基準とした。
-Evaluation criteria-
According to the inventor's knowledge, it is preferable to maintain a state in which no granular sludge is generated, in other words, a state in which iron oxide particles are dispersed in a test container. On the other hand, when the inside of the test container becomes transparent, it is considered that the iron oxide particles are precipitated or bound / aggregated / associated with the added components. Therefore, the following standards were used.
5:試験容器中の上層下層で濁り度合いにかたよりがなく、濁り状態が継続している。
4:試験容器中に沈殿物(非常に細かい)が認められるが、試験容器中の上層下層で濁り度合いにかたよりがなく濁りが継続している。
3:試験容器中に沈殿物が認められ、試験容器の上層下層で濁り度合いに差が認められる。(下層の方が濁っている。)
2:試験容器中に沈殿物が認められ、液には若干の濁りがある。
1:(イ)粒子はほとんど沈殿しており、液には濁りがみられない場合、(ロ)液に凝集固着物が認められる場合(沈殿もしくは液表面にミリ単位の凝集物が認められる。)。この場合、液は濁っていても評価は1とする。
以上の評価結果の一例(見本)を、表4に示す。
5: There is no turbidity in the upper and lower layers in the test container, and the turbid state continues.
4: Precipitates (very fine) are observed in the test container, but the turbidity is continued in the upper and lower layers in the test container without depending on the degree of turbidity.
3: Precipitates are observed in the test container, and a difference in turbidity is observed between the upper and lower layers of the test container. (The lower layer is cloudy.)
2: A precipitate is observed in the test container, and the liquid is slightly turbid.
1: (I) Particles are almost precipitated, and when the liquid is not turbid, (b) When agglomerated fixed matter is observed in the liquid (precipitation or agglomerates in millimeters are observed on the liquid surface. ). In this case, the evaluation is 1 even if the liquid is cloudy.
An example (sample) of the above evaluation results is shown in Table 4.
〔表1〕
[Table 1]
〔表2〕
[Table 2]
〔表3〕
[Table 3]
〔表4〕
[Table 4]
〔実施例品を使用したリンガーロール試験〕
本試験では、上記(J)成分に代わり、上記(D)成分を使用した。酸洗浄液に当該(D)成分、ポリエチレングリコール((M)成分)、及び、プロパギルアルコール((K)成分)を合わせて500(mg/L)添加した点以外は、上記「リンガーロールの使用による疵の発生の確認」と同様の条件で酸洗を行った。その結果、上記(D)成分の添加により、リンガーロール52を使用した場合の欠陥混入率は、(J)成分を用いた場合の1/3程度まで低減された。酸洗槽内の酸洗浄液を分析した結果、酸洗浄液中から粒状スラッジは検出されなかった。(粒子径が50μm以下の小さなスラッジ形態を維持していた。)
[Ringer Roll Test Using Example Products]
In this test, the component (D) was used instead of the component (J). Except for adding (D) component, polyethylene glycol (component (M)), and propargyl alcohol (component (K)) to the acid washing solution in a combined amount of 500 (mg / L), the above “Use of Ringer Roll” Pickling was performed under the same conditions as in “Confirmation of generation of wrinkles by”. As a result, due to the addition of the component (D), the defect mixing rate when the Ringer roll 52 was used was reduced to about 1/3 that when the component (J) was used. As a result of analyzing the acid cleaning liquid in the pickling tank, no granular sludge was detected in the acid cleaning liquid. (The small sludge form with a particle size of 50 μm or less was maintained.)
本試験に使用した上記(D)成分は粒状スラッジ発生抑制試験でも良好な評価を得ている。よって、粒状スラッジ発生抑制試験で良好な評価を得た上記(A)〜(H)成分は、いずれも、粒状スラッジの発生を抑制する有効成分であると合理的に推測された。 The said (D) component used for this test has also received favorable evaluation also in the granular sludge generation | occurrence | production suppression test. Therefore, it was reasonably presumed that the components (A) to (H), which were favorably evaluated in the granular sludge generation suppression test, were all effective ingredients for suppressing the generation of granular sludge.
上記(A)〜(M)成分は、酸洗浄液に添加される腐食抑制剤として使用可能である。粒状スラッジ発生抑制試験の結果から、上記(A)〜(H)成分と粒状スラッジを発生させてしまう腐食抑制成分との併用により、酸洗浄液中に粒状スラッジが発生することを抑制できると合理的に推測された。よって、本願が開示する粒状スラッジ発生抑制剤を他の腐食抑制剤と併用して、様々な金属材料において良好な酸洗浄が実現可能であると考えられた。 The above components (A) to (M) can be used as a corrosion inhibitor added to the acid cleaning liquid. From the results of the granular sludge generation suppression test, it is reasonable that the generation of granular sludge in the acid cleaning liquid can be suppressed by the combined use of the above components (A) to (H) and the corrosion suppression component that generates granular sludge. Was guessed. Therefore, it was thought that good acid cleaning can be realized in various metal materials by using the granular sludge generation inhibitor disclosed in the present application in combination with other corrosion inhibitors.
上記(A)〜(H)成分は、腐食抑制剤としても使用可能である。よって、酸洗浄液に上記一般式「化1」〜「化8」で表される成分を添加して、良好な粒状スラッジ発生の抑制と良好な金属材料の酸洗浄が可能であると考えられた。 The above components (A) to (H) can also be used as a corrosion inhibitor. Therefore, it was considered that the components represented by the above general formulas “Chemical Formula 1” to “Chemical Formula 8” were added to the acid cleaning liquid, so that it was possible to suppress the generation of fine granular sludge and to perform a good acid cleaning of the metal material. .
本願が開示する発明により、優れた粒状スラッジ発生抑制剤、酸洗浄用添加剤セット及び酸洗方法が提供される。 By the invention which this application discloses, the outstanding granular sludge generation | occurrence | production inhibitor, the additive set for acid cleaning, and the pickling method are provided.
Claims (1)
下記「化1」、「化2」、「化6」〜「化8」のいずれかの一般式に該当する化合物から選ばれる1種又は2種以上を、1〜50000mg/Lの濃度で添加して使用する粒状スラッジ発生抑制剤。
(上記「化1」の一般式において、nは3以上の整数を示し、Rは1〜3個のアルキレン基であり、XはF、Cl、Br、またはIである。)
(上記「化2」の一般式において、nは3以上の整数を示す。)
(上記「化6」において、Rは1〜3個のアルキレン基であり、nは10以上の整数である。)
(上記「化7」において、nは3以上の整数であり、XはF、Cl、Br、又はIである。)
(上記「化8」において、nは1以上の整数である。)
(上記「化9」の一般式で示される末端にチオール基を有するアリルアミン類重合体において、R1、R2は水素又は炭素数1〜10のアルキル基を示し、R1とR2は同一の基であっても異なる基であってもよい。nは1以上の整数を示す。)
(上記「化10」の一般式で示される末端にチオール基を有するアリルアミン類重合体において、Rは水素又は水酸基を有しても良い炭素数1〜10のアルキル基を示し、nは1以上の整数を示す。)
(上記「化11」の一般式で示される末端にチオール基を有するアリルアミン類重合体において、Rは水素又は水酸基を有しても良い炭素数1〜10のアルキル基を示し、nは1以上の整数を示す。)
(上記「化12」の一般式において、R1、R2は水素又は炭素数1〜4のアルキル基を示し、R1とR2は同一の基であっても異なる基であってもよい。nは1〜4整数を示し、pは1以上の整数を示す。)
(上記「化13」の一般式において、R1、R2は水素又は炭素数1〜4のアルキル基を示し、R1とR2は同一の基であっても異なる基であってもよい。nは1〜4整数を示し、pは1以上の整数を示す。)
(上記「化14」の一般式において、nは1以上の整数を示し、R1とR2はそれぞれ水素、メチル基、又はエチル基であって、R1とR2は同一の基であっても異なる基であってもよい。XはF、Cl、Br、又はIを示す。) In the acid washing step in which a ringer roll is disposed on the exit side of the pickling tank, one or more types of corrosion selected from compounds corresponding to any one of the following general formulas of “Chemical 9” to “Chemical 14” A granular sludge generation inhibitor used by adding to an acid cleaning solution containing an inhibitor at a concentration of 10 to 2000 mg / L ,
One or more selected from compounds corresponding to any one of the following general formulas of “Chemical Formula 1”, “Chemical Formula 2”, “Chemical Formula 6” to “Chemical Formula 8” are added at a concentration of 1 to 50000 mg / L granular sludge inhibiting agent used in.
(In the general formula of “Chemical Formula 1”, n represents an integer of 3 or more, R represents 1 to 3 alkylene groups, and X represents F, Cl, Br, or I.)
(In the general formula of “Chemical Formula 2”, n represents an integer of 3 or more.)
(In the above “Chemical Formula 6”, R is 1 to 3 alkylene groups, and n is an integer of 10 or more.)
(In the above “chemical formula 7”, n is an integer of 3 or more, and X is F, Cl, Br, or I.)
(In the above “Chemical Formula 8”, n is an integer of 1 or more.)
(In the allylamine polymer having a thiol group at the terminal represented by the general formula of “Chemical Formula 9”, R 1 and R 2 represent hydrogen or an alkyl group having 1 to 10 carbon atoms, and R 1 and R 2 are the same. Or a different group, n represents an integer of 1 or more.)
(In the allylamine polymer having a thiol group at the terminal represented by the general formula of “Chemical Formula 10”, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, and n is 1 or more. Indicates an integer.)
(In the allylamine polymer having a thiol group at the terminal represented by the general formula of “Chemical Formula 11”, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, and n is 1 or more. Indicates an integer.)
(In the general formula of “Chemical Formula 12”, R 1 and R 2 represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 1 and R 2 may be the same group or different groups. N represents an integer of 1 to 4, and p represents an integer of 1 or more.)
(In the general formula of “Chemical Formula 13”, R 1 and R 2 represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 1 and R 2 may be the same group or different groups. N represents an integer of 1 to 4, and p represents an integer of 1 or more.)
(In the general formula of “Chemical Formula 14”, n represents an integer of 1 or more, R 1 and R 2 are each hydrogen, methyl group, or ethyl group, and R 1 and R 2 are the same group. X may be F, Cl, Br, or I.)
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JPS48103032A (en) * | 1972-04-14 | 1973-12-24 | ||
US4069225A (en) * | 1972-05-11 | 1978-01-17 | Vasily Efimovich Privalov | 3-(1-Hydroxyethyl)imino-1,2,4-dithiazolidine-5-thione |
JPS61195983A (en) * | 1985-02-26 | 1986-08-30 | Sumitomo Metal Ind Ltd | Preventing method of discoloration of steel sheet in pickling line |
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JP2001207281A (en) * | 2000-01-26 | 2001-07-31 | Asahi Kagaku Kogyo Co Ltd | Corrosion inhibitor for acid cleaning, cleaning liquid composition containing the same and cleaning method for metallic surface |
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