JPH0564717B2 - - Google Patents
Info
- Publication number
- JPH0564717B2 JPH0564717B2 JP4079688A JP4079688A JPH0564717B2 JP H0564717 B2 JPH0564717 B2 JP H0564717B2 JP 4079688 A JP4079688 A JP 4079688A JP 4079688 A JP4079688 A JP 4079688A JP H0564717 B2 JPH0564717 B2 JP H0564717B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- pickling
- solution
- metal
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 35
- 238000005554 pickling Methods 0.000 claims description 32
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 21
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 description 42
- 239000002184 metal Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 238000004090 dissolution Methods 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 18
- 238000004381 surface treatment Methods 0.000 description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 239000012085 test solution Substances 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000002401 inhibitory effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- VQGBPCIONNQYIL-UHFFFAOYSA-N 1-benzylquinolin-1-ium Chemical compound C=1C=CC2=CC=CC=C2[N+]=1CC1=CC=CC=C1 VQGBPCIONNQYIL-UHFFFAOYSA-N 0.000 description 1
- HRDCVMSNCBAMAM-UHFFFAOYSA-N 3-prop-2-ynoxyprop-1-yne Chemical compound C#CCOCC#C HRDCVMSNCBAMAM-UHFFFAOYSA-N 0.000 description 1
- XPTMJJIPRSWBDK-UHFFFAOYSA-N 3-prop-2-ynylsulfanylprop-1-yne Chemical compound C#CCSCC#C XPTMJJIPRSWBDK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
〔産業上の利用分野〕
本発明は、酸洗いの酸液用添加剤に関し、詳し
くは酸洗いの酸液における金属の溶解を抑制する
添加剤に関し、さらに詳しくは、金属製品の酸洗
いの酸液において金属の表面に発生した金属塩ま
たは金属の酸化物のスケールおよび錆を除去する
が、金属そのものの溶解を抑制する酸洗いの酸液
用添加剤に関する。
本発明の酸洗いの酸液用添加剤は、金属製品の
表面処理のための酸洗いの酸液に対する添加物と
して利用することができ、また本発明の酸洗いの
酸液用添加剤を使用した酸洗いの酸液は、金属製
品またはその材料の塗装、ホウロウ掛け、メツ
キ、リン酸塩処理または冷間圧延処理などの金属
の表面処理における金属表面の清浄化処理に利用
することができる。
〔技術の背景および従来技術の説明〕
金属の表面処理において、金属表面の研磨や成
形を、薬液による金属の化学溶解を利用して行な
うことは、金属表面の化学研磨として古くから知
られており、アルミニウム、鉄、銅、亜鉛または
カドミウムなどの金属を、リン酸、硝酸、クロム
酸、塩酸、フツ酸または硫酸を基本浴成分とする
薬液に浸漬して、その表面を清浄化することが知
られている。（「化学便覧」丸善株式会社発行第
1150頁〜「金属表面処理」）
これらの金沿の表面処理において、薬液中の酸
は、金属表面のスケールおよび錆を溶解し、除去
するが、清浄化された表面の金属をさらに溶解し
て、金属表面を浸食、溶解するだけでなく、金属
の溶解により生成した金属塩濃度の増加により薬
液の使用寿命を短縮する。この金属表面の浸食、
溶解を抑制するための添加物を薬液に加えること
が知られている。塩酸による鉄または鋼の表面処
理において、塩酸にアルキルアミン、ベンジルキ
ノリニウム、アルキルベンジルキノリニウムハラ
イド、ｎ−アルキルトリメチルアンモニウム、ｎ
−アルキルピリジニウム、ｎ−アルキルキノリニ
ウム、ヘキサメチレンテトラミン（ウロトロピ
ン）などの含窒素化合物、ヒドロキシアセチレ
ン、プロパルギルアルコール、プロパルギルエー
テル、プロパルギルチオエーテル、メルカプタ
ン、スルホニウム化合物、スルホキシド、チオシ
アネート、チオ尿素およびチアゾールに属する化
合物を加えて、鉄や鋼の浸食、溶解を抑制するこ
とが提案され、またこれらの抑制剤の中には、ア
ルミニウム、その合金、ニツケル、チタンまたは
その合金などの浸食および溶解の抑制に有効なも
ののあることも知られており、さらに硫酸、硝
酸、フツ酸およびリン酸による金属の溶解および
浸食の抑制に有効な抑制物質のあることも知られ
ている。〔ジー・シユミツト：抑制剤に対する浸
食作業部会のヨーロツパ会議のために作成された
報告（G.Schmidt：Report prepared for the
European Federation of Corrosion Working
Party on Inhibitor）、酸浴のための抑制剤の適
用（Application of Inhibtor fot Acid
Media）〕
さらに金属表面のスケールやサビを除去するた
めの酸洗いの酸液に第４級アンモニウム化合物、
またはアンモニウム化合物および第４級アンモニ
ウム化合物以外の有機窒素化合物を添加し、それ
によつて脱スケール効果、腐食抑制効果および水
素脆性抑制効果を向上し、また酸洗い液の濁り、
沈デン物、油状物質の生成および廃酸処理におけ
る泡立ちを抑制することが提案されている。（特
開昭61−37988号公報）
本発明者らは、金属製品の表面処理における酸
洗いの研究において、塩酸に対するヘキサメチレ
ンテトラミンの鉄の溶解抑制効果が、ポリビニル
アルコールの添加により向上することを見出し、
この知見に基づいて本発明に到達した。
〔発明の目的および発明の要約〕
本発明の目的は、酸洗いの酸液における金属の
溶解を抑制する添加剤を提供することにあり、詳
しくは、酸洗いの酸液において、金属の表面に発
生した金属塩または金属酸化物のスケールおよび
錆を除去するが、勤続そのものの溶解を抑制する
酸洗いの酸液における添加剤を提供することにあ
る。
本発明のもう一つの目的は、金属の表面処理に
おいて、金属表面のスケールおよび錆を除去する
が、金属そのものを浸食および溶解することな
く、金属表面を清浄化することができる酸洗いの
酸液を提供することにある。
本発明は、ヘキサメチレンテトラミンおよびポ
リビニルアルコールからなることを特徴とする酸
洗いの酸液用添加剤である。
本発明の酸洗いの酸液用添加剤は、ヘキサメチ
レンテトラミンおよびポリビニルアルコールにジ
エチレングリコールを加えて、金属の溶解、浸食
抑制効果を向上することができる。
本発明の酸洗いの酸液用添加剤は、塩酸、硫
酸、リン酸、フツ化水素酸などの金属の表面処理
における酸洗いにおいて通常使用する酸液に対す
る添加物として使用することができるが、塩酸と
リン酸、および硫酸とリン酸の混合酸に添加する
と、その錆落しおよびスケール除去の効果を向上
し、金属の表面処理において、金属の溶解を抑制
するとともに、きれいで清浄化された表面を造出
することができる。
〔発明の具体的な説明〕
本発明の酸洗いの酸液用添加剤は、ヘキサメチ
レンテトラミン100重量部に対して4000〜20000重
量部のポリビニルアルコールを配合する。ヘキサ
メチレンテトラミンおよびポリビニルアルコール
は、粉状または水溶液のどのような形態において
も配合することができるが、水溶液の状態におい
て配合するのが好ましい。ヘキサメチレンテトラ
ミンおよびポリビニルアルコールを水溶液の状態
で配合することによつて、酸洗いの酸液に添加し
た時に、良好な溶解状態を保持することが容易に
なる、という利点、効果がある。
本発明のヘキサメチレンテトラミンおよびポリ
ビニルアルコールからなる酸洗いの酸液用添加剤
にジエチレングリコールを添加する場合は、ヘキ
サメチレンテトラミン100重量部に対して4000〜
20000重量部のポリビニルアルコールおよび2000
〜20000重量部のジエチレングリコールを配合す
るが、これらのものは酸洗いの酸液に添加した時
に、良好な溶解状態を維持するために、水溶液の
状態で配合するのが好ましい。
本発明の酸洗いの酸液用添加剤におけるヘキサ
メチレンテトラミン、ポリビニルアルコールおよ
びジエチレングリコールは、それぞれの水溶液を
酸洗いの酸液に加えて、配合することもできる。
本発明の酸洗いの酸液用添加剤は、塩酸、硫
酸、リン酸、フツ化水素酸またはその他の酸洗い
に通常用いられる酸液に添加することができる
が、塩酸およびリン酸の混合酸液または硫酸およ
びリン酸の混合酸液に添加することもできる。こ
れらの混合酸液に本発明の酸洗いの酸液用添加剤
を添加すると、酸洗いにおける金属表面における
錆取り反応を促進し、仕上りのきれいな金属表面
を形成することができる。
本発明の酸洗いの酸液用添加剤は、酸液100重
量部に対してヘキサメチレンテトラミン0.005〜
0.2重量部（好ましくは0.05〜0.1重量部）の量に
おいて酸液に添加される。
次に実施例の代りうる試験例により本発明をさ
らに詳しく説明する。
試験例 １
ヘキサメチレンテトラミン（ウロトロピン、ヘ
キサミン）が塩酸による鉄の溶解を抑制する効果
に対するポリビニルアルコールおよびジエチレン
グリコールの影響について試験を行なつた。
(1) 試験溶液の調製
20.0mlの4M塩酸に、0.5％ヘキサメチレンテ
トラミン水溶液0.5mlを加え、これに第１表に
示す量の２％ポリビニルアルコール（重合度：
500）水溶液および２％ジエチレングリコール
水溶液を加え、さらに水を加えて総量を40.0ml
にして、試験溶液を調製した。
(2) 試験方法
鉄片（10mm×10mm×１mm）の重量を精秤し、
この鉄片を試験溶液に浸漬し、常温において２
時間放置した後、鉄片を試験溶液から取り出
し、充分に水洗した。風乾後、鉄片の重量を精
秤し、浸漬中の重量損失から試験溶液による鉄
片の溶解量（mg／cm2）を算出した。
(3) 試験の結果
第１表に示すとおりであつた。
[Industrial Application Field] The present invention relates to an additive for an acid solution for pickling, and more particularly, to an additive for suppressing the dissolution of metal in an acid solution for pickling. This invention relates to an additive for pickling acid solutions that removes scale and rust of metal salts or metal oxides generated on the surface of metals in the solution, but suppresses dissolution of the metals themselves. The pickling acid solution additive of the present invention can be used as an additive for pickling acid solution for surface treatment of metal products, and the pickling acid solution additive of the present invention can be used as an additive for pickling acid solution for surface treatment of metal products. The pickling acid solution can be used for cleaning metal surfaces in metal surface treatments such as painting, enameling, plating, phosphating, or cold rolling treatments of metal products or their materials. [Technical Background and Description of Prior Art] In metal surface treatment, polishing and shaping of the metal surface using chemical dissolution of the metal using a chemical solution has long been known as chemical polishing of the metal surface. It is known that the surface of metals such as aluminum, iron, copper, zinc, or cadmium can be cleaned by immersing them in a chemical solution whose basic bath components are phosphoric acid, nitric acid, chromic acid, hydrochloric acid, hydrofluoric acid, or sulfuric acid. It is being (“Chemistry Handbook” published by Maruzen Co., Ltd.
(page 1150 - "Metal Surface Treatment") In these metal surface treatments, the acid in the chemical solution dissolves and removes scale and rust on the metal surface, but it also dissolves and removes the metal on the cleaned surface. , not only erodes and dissolves the metal surface, but also shortens the service life of the chemical solution due to an increase in the concentration of metal salts generated by dissolving the metal. This erosion of the metal surface,
It is known to add additives to drug solutions to inhibit dissolution. In surface treatment of iron or steel with hydrochloric acid, alkylamine, benzylquinolinium, alkylbenzylquinolinium halide, n-alkyltrimethylammonium, n-
- belongs to nitrogen-containing compounds such as alkylpyridinium, n-alkylquinolinium, hexamethylenetetramine (urotropin), hydroxyacetylene, propargyl alcohol, propargyl ether, propargyl thioether, mercaptan, sulfonium compounds, sulfoxide, thiocyanate, thiourea and thiazole The addition of compounds has been proposed to inhibit the erosion and dissolution of iron and steel, and some of these inhibitors have been shown to be effective in inhibiting the erosion and dissolution of aluminum, its alloys, nickel, titanium, and its alloys. It is also known that there are inhibitors that are effective in inhibiting the dissolution and erosion of metals by sulfuric, nitric, hydrofluoric, and phosphoric acids. [G. Schmidt: Report prepared for the European Conference of the Erosion Working Group on Inhibitors
European Federation of Corrosion Working
Party on Inhibitor), Application of Inhibtor fot Acid
Media)] In addition, quaternary ammonium compounds are added to the pickling acid solution to remove scale and rust from metal surfaces.
Alternatively, organic nitrogen compounds other than ammonium compounds and quaternary ammonium compounds are added, thereby improving the descaling effect, corrosion inhibiting effect, and hydrogen embrittlement inhibiting effect, and also reducing the turbidity of the pickling solution.
It has been proposed to suppress the formation of sediments, oily substances and foaming in waste acid treatment. (Japanese Unexamined Patent Publication No. 61-37988) In research on pickling in surface treatment of metal products, the present inventors found that the effect of inhibiting iron dissolution of hexamethylenetetramine against hydrochloric acid was improved by the addition of polyvinyl alcohol. heading,
The present invention was achieved based on this knowledge. [Objective of the Invention and Summary of the Invention] An object of the present invention is to provide an additive that suppresses the dissolution of metal in an acid solution for pickling. An object of the present invention is to provide an additive in an acid solution for pickling that removes scale and rust of generated metal salts or metal oxides, but inhibits the dissolution of the rust itself. Another object of the present invention is that in metal surface treatment, a pickling acid solution can remove scale and rust on the metal surface, but can clean the metal surface without eroding and dissolving the metal itself. Our goal is to provide the following. The present invention is an additive for an acid solution for pickling, characterized by comprising hexamethylenetetramine and polyvinyl alcohol. The acid solution additive for pickling of the present invention can improve metal dissolution and corrosion inhibition effects by adding diethylene glycol to hexamethylenetetramine and polyvinyl alcohol. The additive for pickling acid solutions of the present invention can be used as an additive for acid solutions commonly used in pickling in metal surface treatment such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrofluoric acid. When added to hydrochloric acid and phosphoric acid, or mixed acids of sulfuric acid and phosphoric acid, it improves the rust removal and scale removal effects, suppresses metal dissolution in metal surface treatment, and creates a clean and purified surface. can be created. [Detailed Description of the Invention] The acid solution additive for pickling of the present invention contains 4,000 to 20,000 parts by weight of polyvinyl alcohol per 100 parts by weight of hexamethylenetetramine. Hexamethylenetetramine and polyvinyl alcohol can be blended in any form, powder or aqueous solution, but preferably in the form of an aqueous solution. By blending hexamethylenetetramine and polyvinyl alcohol in the form of an aqueous solution, there is an advantage that a good dissolution state can be easily maintained when added to the acid solution for pickling. When diethylene glycol is added to the acid solution additive for pickling consisting of hexamethylenetetramine and polyvinyl alcohol of the present invention, the amount of diethylene glycol is 4000 to 100 parts by weight per 100 parts by weight of hexamethylenetetramine.
20000 parts by weight of polyvinyl alcohol and 2000 parts by weight
~20,000 parts by weight of diethylene glycol is blended, but these are preferably blended in the form of an aqueous solution in order to maintain a good dissolution state when added to the acid solution for pickling. Hexamethylenetetramine, polyvinyl alcohol, and diethylene glycol in the additive for the pickling acid solution of the present invention can also be blended by adding aqueous solutions of each to the pickling acid solution. The acid solution additive for pickling of the present invention can be added to hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid or other acid solutions commonly used for pickling. It can also be added to a mixed acid solution of sulfuric acid and phosphoric acid. When the acid solution additive for pickling of the present invention is added to these mixed acid solutions, it is possible to promote the rust removal reaction on the metal surface during pickling and form a metal surface with a clean finish. The additive for acid solution for pickling of the present invention is 0.005 to 0.005 hexamethylenetetramine per 100 parts by weight of acid solution.
It is added to the acid solution in an amount of 0.2 parts by weight (preferably 0.05-0.1 parts by weight). Next, the present invention will be explained in more detail using test examples that can be substituted for the examples. Test Example 1 A test was conducted on the influence of polyvinyl alcohol and diethylene glycol on the effect of hexamethylenetetramine (urotropin, hexamine) on inhibiting the dissolution of iron by hydrochloric acid. (1) Preparation of test solution Add 0.5 ml of 0.5% hexamethylenetetramine aqueous solution to 20.0 ml of 4M hydrochloric acid, and add 2% polyvinyl alcohol (degree of polymerization:
500) Add the aqueous solution and 2% diethylene glycol aqueous solution, then add water to make a total volume of 40.0ml.
A test solution was prepared. (2) Test method Accurately weigh the iron piece (10mm x 10mm x 1mm),
This iron piece was immersed in the test solution, and 2
After standing for a period of time, the iron piece was removed from the test solution and thoroughly washed with water. After air drying, the weight of the iron piece was accurately weighed, and the amount of iron piece dissolved by the test solution (mg/cm 2 ) was calculated from the weight loss during immersion. (3) Test results The results were as shown in Table 1.
【表】【table】
【表】
(4) 考察
ヘキサメチレンテトラミンの塩酸のよる鉄の
溶解の抑制効果は、ポリビニルアルコールの添
加により増大するが、ジエチレングリコールの
添加では、それ程顕著に増大しない。しかしな
がらポリビニルアルコールおよびジエチレング
リコールの両者を添加すると、ヘキサメチレン
テトラミンの塩酸による鉄の溶解の抑制効果
は、顕著に増大し、それはポリビニルアルコー
ルの単独を添加したときよりも大きい。
試験例 ２
ヘキサメチレンテトラミン（ウロトロピン、ヘ
キサミン）が塩酸による鉄の溶解を抑制する効果
に対するポリビニルアルコールの影響をリン酸の
共存する系について試験を行なつた。
(1) 試験溶液の調製
20.0mlの4M塩酸に、0.5％ヘキサメチレンテ
トラミン水溶液0.5mlを加え、これに第２表に
示す量のリン酸（１：２）および２％ポリビニ
ルアルコール（重合度：500）水溶液を加え、
さらに水を加えて総量を40.0mlにして、試験溶
液を調製した。
(2) 試験方法
表面に赤錆を生じた鉄片（10mm×10mm×１
mm）の重量を精秤し、この鉄片を試験溶液に浸
漬し、常温において２時間放置した後、鉄片を
試験溶液から取り出し、充分に水洗した。風乾
後、鉄片の重量を精秤し、浸漬中の重量損失か
ら試験溶液による錆の除去量および鉄片の溶解
量（mg／cm2）を算出した。
(3) 試験の結果
第２表に示すとおりであつた。[Table] (4) Discussion The inhibitory effect of hexamethylenetetramine on the dissolution of iron by hydrochloric acid increases with the addition of polyvinyl alcohol, but does not increase significantly with the addition of diethylene glycol. However, when both polyvinyl alcohol and diethylene glycol are added, the inhibitory effect of hexamethylenetetramine on iron dissolution by hydrochloric acid increases significantly, which is greater than when polyvinyl alcohol alone is added. Test Example 2 The effect of polyvinyl alcohol on the effect of hexamethylenetetramine (urotropin, hexamine) on inhibiting the dissolution of iron by hydrochloric acid was tested in a system in which phosphoric acid coexisted. (1) Preparation of test solution Add 0.5 ml of 0.5% hexamethylenetetramine aqueous solution to 20.0 ml of 4M hydrochloric acid, and add phosphoric acid (1:2) in the amount shown in Table 2 and 2% polyvinyl alcohol (degree of polymerization: 500) Add aqueous solution,
Further water was added to make the total volume 40.0 ml to prepare a test solution. (2) Test method Iron piece with red rust on the surface (10mm x 10mm x 1
mm), the iron piece was immersed in the test solution and left at room temperature for 2 hours, then the iron piece was taken out from the test solution and thoroughly washed with water. After air-drying, the weight of the iron pieces was accurately weighed, and the amount of rust removed by the test solution and the amount of iron pieces dissolved (mg/cm 2 ) were calculated from the weight loss during immersion. (3) Test results The results were as shown in Table 2.
【表】【table】
金属の表面処理における酸洗いにおいて、金属
の溶解、浸食を抑制することができ、その金属の
溶解、浸食の抑制効果は、リン酸の共存により錆
の除去を促進しても減少することなく、持続す
る。
金属の表面処理において、仕上りのきれいな金
属表面を形成することができる。
In pickling for metal surface treatment, metal dissolution and corrosion can be suppressed, and the effect of suppressing metal dissolution and corrosion does not decrease even if rust removal is promoted by the coexistence of phosphoric acid. last. In metal surface treatment, it is possible to form a metal surface with a clean finish.
Claims (1)
アルコールからなることを特徴とする酸洗いの酸
液用添加剤。 ２ ヘキサメチレンテトラミン、ポリビニルアル
コールおよびジエチレングリコールからなること
を特徴とする酸洗いの酸液用添加剤。[Scope of Claims] 1. An additive for acid solutions for pickling, characterized by comprising hexamethylenetetramine and polyvinyl alcohol. 2. An additive for acid solutions for pickling, characterized by comprising hexamethylenetetramine, polyvinyl alcohol and diethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4079688A JPH01215991A (en) | 1988-02-25 | 1988-02-25 | Additive for pickling acid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4079688A JPH01215991A (en) | 1988-02-25 | 1988-02-25 | Additive for pickling acid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01215991A JPH01215991A (en) | 1989-08-29 |
| JPH0564717B2 true JPH0564717B2 (en) | 1993-09-16 |
Family
ID=12590584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4079688A Granted JPH01215991A (en) | 1988-02-25 | 1988-02-25 | Additive for pickling acid solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01215991A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100311853B1 (en) * | 1999-09-18 | 2001-10-18 | 명 섭 한 | Corrosion Inhibitor Composition for Acid Cleaning |
| CN101786732A (en) * | 2010-03-22 | 2010-07-28 | 许昌东方化工有限公司 | Scale remover and preparation method thereof |
| AU2015249410B2 (en) * | 2014-04-22 | 2017-02-16 | Tal Or Ecology Ltd. | Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process |
| CN107326370A (en) * | 2017-05-31 | 2017-11-07 | 成都振中电气有限公司 | Electric Appliance Cabinet surface rust removal liquid |
-
1988
- 1988-02-25 JP JP4079688A patent/JPH01215991A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01215991A (en) | 1989-08-29 |
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