JPS63235483A - Surface regulating solution for chemical treatment of steel material - Google Patents
Surface regulating solution for chemical treatment of steel materialInfo
- Publication number
- JPS63235483A JPS63235483A JP6807987A JP6807987A JPS63235483A JP S63235483 A JPS63235483 A JP S63235483A JP 6807987 A JP6807987 A JP 6807987A JP 6807987 A JP6807987 A JP 6807987A JP S63235483 A JPS63235483 A JP S63235483A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- surface conditioning
- chelating agent
- steel material
- oxalic acid
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 30
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 29
- 239000010959 steel Substances 0.000 title claims abstract description 29
- 238000011282 treatment Methods 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 title claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 title abstract 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 19
- 239000002738 chelating agent Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 230000003750 conditioning effect Effects 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 238000010422 painting Methods 0.000 abstract description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 abstract description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 abstract description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001447 alkali salts Chemical class 0.000 abstract description 2
- 239000000174 gluconic acid Substances 0.000 abstract description 2
- 235000012208 gluconic acid Nutrition 0.000 abstract description 2
- 235000002906 tartaric acid Nutrition 0.000 abstract description 2
- 239000011975 tartaric acid Substances 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005554 pickling Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 aromatic carboxylic acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000007654 immersion Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 238000011179 visual inspection Methods 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、鉄鋼材料の化成処理のための表面調整液に関
するものであり、さらに詳しく述べるならば、化成被膜
の性質を改良し、また酸洗等の予備処理を十分に行なっ
た後に表面調整を行なっても十分な表面調整機能を実現
することが難しい、溶接部のある鉄鋼材料の塗装下地用
皮膜処理前に使用するのに好適な表面調整液に関するも
のである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a surface conditioning liquid for chemical conversion treatment of steel materials. Suitable surface for use before coating coating for steel materials with welded parts, where it is difficult to achieve sufficient surface conditioning function even after thorough pretreatment such as washing and surface conditioning. This relates to adjustment liquid.
鉄鋼材料を化成処理する前の表面調整法としては、Ｔｉ
コロイドによる方法と蓚酸による方法がある。主として
、前者は非酸洗鋼材に、また後者は酸洗鋼材に、適用さ
れている。As a surface conditioning method before chemical conversion treatment of steel materials, Ti
There are methods using colloids and methods using oxalic acid. The former is mainly applied to non-pickled steel, and the latter to pickled steel.
溶接箇所がある鉄鋼材料を表面調整する場合は、酸洗（
兼脱脂）→水洗→中和→水洗→表面調整→水洗→皮膜化
成→水洗→乾燥の工程で処理し塗装性能を向上させる。When surface-conditioning steel materials with welded areas, pickling (
The coating performance is improved through the process of (combination and degreasing) → water washing → neutralization → water washing → surface conditioning → water washing → film formation → water washing → drying.
この工程における酸洗は、溶接部のフラックス、スケー
ル等の除去及び付着油の除去を目的とし、通常、硫酸酸
洗で行なわれる。The pickling in this step is generally carried out with sulfuric acid pickling for the purpose of removing flux, scale, etc. and adhering oil from the welded parts.
なお、硫酸には脱脂のための界面活性剤が添加される。Note that a surfactant for degreasing is added to the sulfuric acid.
中和は主に苛性ソーダ系を使用し、鉄鋼材料表面の酸を
中和する０表面調整は、蓚酸等の蓚酸を使用し、前工程
より持込まれる中和液の除去及び次工程である皮膜化成
工程での処理液のバランス壊れの防止および皮膜化成を
スムーズに行なわせる為の皮膜の形成を主目的とする。Neutralization mainly uses caustic soda, and oxalic acid such as oxalic acid is used for zero surface adjustment to neutralize the acid on the surface of steel materials, and the removal of the neutralizing liquid brought in from the previous process and the subsequent process of film formation. The main purpose is to prevent the balance of the processing liquid from being disrupted during the process and to form a film to ensure smooth film formation.
なお、表面調整に使用される酸による若干の除錆効果も
あるので、酸洗後の水洗工程で形成される薄い酸化膜は
除去される。Note that since the acid used for surface conditioning has a slight rust removal effect, the thin oxide film formed in the water washing step after pickling is removed.
近年、塗装外観に対する消費者の要求がますます高級化
しかつ多様化するにつれて、塗装下地処理としての化成
処理の性能が一層厳しく要求され、その結果化成処理の
ための表面調整に対する要求も厳しくなりつつある。In recent years, as consumer demands for paint appearance have become more sophisticated and diversified, the performance of chemical conversion treatment as a base treatment for painting has become more demanding, and as a result, requirements for surface preparation for chemical treatment have also become stricter. be.
特に、溶接部を有する鉄鋼材料では溶接部に存在する微
量のフラックス、酸化物などの溶接時の副生成物、なら
びに溶接治具と被溶接材との接触による付着油汚染など
が表面調整液の作用を妨害する。このために、次工程の
皮膜化成では油付着箇所は化成不良となり、その後の塗
装外観ムラおよび塗装性能劣化を引き起し、製品価値の
低落を招く、この防止対策として、表面調整の前工程に
おいて、酸洗や界面活性剤による処理が行なわれていた
が、その効果は十分ではなかった。特に、溶接部の近傍
で被溶接材に焼付いた油については酸洗（兼脱脂）工程
では完全に除去出来ないし、また酸洗により除去された
油が酸洗液中に蓄積し、油分濃度が増えると油が鋼板に
再付着するため溶接部を有する鉄鋼材料の表面調整前処
理には困難性があった。In particular, in the case of steel materials that have welded parts, the surface conditioning liquid may be contaminated by trace amounts of flux, oxides, and other welding by-products that exist in the welded parts, as well as oil contamination caused by contact between the welding jig and the workpiece. interfere with the action. For this reason, in the next process of film formation, oil adhesion areas become defective, causing subsequent uneven coating appearance and deterioration of coating performance, leading to a decline in product value.As a preventive measure, in the process before surface conditioning, Previously, pickling and treatment with surfactants have been carried out, but the effects were not sufficient. In particular, oil baked on the welded material near the weld cannot be completely removed by the pickling (and degreasing) process, and the oil removed by pickling accumulates in the pickling solution, causing the oil concentration to increase. If the oil increases, the oil will re-adhere to the steel plate, making it difficult to pre-treat the surface of steel materials with welded parts.
本発明は、鉄鋼材料の化成処理用表面調整において、溶
接部を有する材料についてはその塗装品質を溶接部がな
い材料とほぼ同等程度まで近づけることができ、また溶
接部を有しない材料についてはその塗装品質を従来のも
の以上とすることができる表面調整液を提供することを
目的とする。In surface preparation for chemical conversion treatment of steel materials, the present invention makes it possible to bring the coating quality of materials with welds to almost the same level as materials without welds, and to improve the coating quality of materials without welds. The purpose of the present invention is to provide a surface conditioning liquid that can improve coating quality to a level higher than that of conventional ones.
本発明に係る鉄鋼材料の化成処理用表面調整液は、蓚酸
もしくはその塩を主成分とする表面調整液に、有機キレ
ート剤を添加したことを特徴とする。この有機キレート
剤としては、グルコン酸などのポリオキシカルボン酸；
クエン酸、酒石酸などのオキシ酸： （ＣＨｚ）ｎ（Ｃ
ＯＯＩＩ）ｚ 、 ｎ≧２のジカルボン酸、例えばコハ
ク酸、 ＥＤＴ＾、ＮＴＡ、安息香酸などの芳香族カル
ボン酸；グリシンなどのアミノ酸；タンニン酸；および
、これらの有機酸のアルカリ塩などがある。有機キレー
ト剤は表面調整後に行なわれる化成処理の均質性を高め
る。すなわち、鉄のエツチング作用が強く、表面調整作
用を有する蓚酸と、鉄のエツチング作用が弱く、表面調
整作用をもたない有機キレート剤を併用すると蓚酸が、
鉄鋼材料表面に均一に作用して、その効果が高められる
。エツチング作用が弱い有機キレート剤を単独で使用し
ても表面調整効果は生じず、併用により表面調整効果が
高められ、溶接部・非溶接部（母材）に関係なく均質な
化成処理が可能になり、また溶接部がない鉄鋼材料につ
いては化成処理皮膜の特性を直接測定してその性能向上
評価はできないが、塗装性能を測定すると、その性能向
上が認められ、これは化成皮膜下地の性能向上によるこ
とが分かる。このような効果をもたらす蓚酸とキレート
剤の表面調整液中の濃度は、蓚酸もしくはその塩１〜２
０ｇ／ｌ、有機キレート剤０．１−１５ｇ７１更に好ま
しくは１〜１０ｇ／ｅが好ましい、それぞれの濃度の下
限未満では、効果が少なく、一方、蓚酸濃度の上限を越
えると、素材に蓚酸塩皮膜が形成される為、リン酸亜鉛
の皮膜化成が阻害されることとなり、また有機キレート
剤の上限を越えると、リン酸亜鉛皮膜化成で肌荒れを起
し、その後の塗装の耐蝕性が悪くなるので、好ましくな
い。The surface conditioning liquid for chemical conversion treatment of steel materials according to the present invention is characterized in that an organic chelating agent is added to the surface conditioning liquid containing oxalic acid or its salt as a main component. This organic chelating agent includes polyoxycarboxylic acids such as gluconic acid;
Oxyacids such as citric acid and tartaric acid: (CHz)n(C
OOII) Z, dicarboxylic acids with n≧2, such as aromatic carboxylic acids such as succinic acid, EDT^, NTA, benzoic acid; amino acids such as glycine; tannic acid; and alkali salts of these organic acids. The organic chelating agent improves the homogeneity of the chemical conversion treatment performed after surface conditioning. That is, when oxalic acid, which has a strong iron etching effect and surface conditioning effect, is used in combination with an organic chelating agent, which has a weak iron etching effect and no surface conditioning effect, oxalic acid becomes
It acts uniformly on the surface of the steel material, increasing its effectiveness. Even if an organic chelating agent with a weak etching effect is used alone, it will not produce a surface conditioning effect, but when used in combination, the surface conditioning effect will be enhanced, making it possible to perform homogeneous chemical conversion treatment regardless of welded or non-welded areas (base metal). Furthermore, for steel materials without welds, it is not possible to directly measure the characteristics of the chemical conversion coating and evaluate its performance improvement, but when the coating performance is measured, an improvement in performance is observed, which is due to the improvement in the performance of the chemical conversion coating base. It can be seen that this is due to The concentration of oxalic acid and chelating agent in the surface conditioning solution that produces this effect is 1 to 2 oxalic acid or its salt.
0 g/l, organic chelating agent 0.1-15 g/e71, more preferably 1-10 g/e. Below the lower limit of each concentration, there is little effect; on the other hand, when the upper limit of oxalic acid concentration is exceeded, an oxalate film is formed on the material. is formed, which inhibits the formation of the zinc phosphate film, and if the upper limit of the organic chelating agent is exceeded, the formation of the zinc phosphate film will cause roughness and the corrosion resistance of subsequent coatings will deteriorate. , undesirable.
上記した表面調Ｍ′ａにさらに界面活性剤を添加すると
、油等が除去し易くなり、蓚酸によるエツチング作用が
均一になる。界面活性剤としては通常の活性剤が使用で
きるが、好ましくは低発泡性の非イオン界面活性剤及び
両性界面活性剤を使用する。界面活性剤の濃度は、添加
の効果および経済性の面から１０ｇ／ｌ以下であり、好
ましくは０．２〜１０ｇ／ｌ’、より好ましくは０．５
〜５ｇ／ｌである。When a surfactant is further added to the above-mentioned surface condition M'a, oil etc. can be easily removed and the etching action by oxalic acid can be made uniform. As the surfactant, conventional surfactants can be used, but low foaming nonionic surfactants and amphoteric surfactants are preferably used. The concentration of the surfactant is 10 g/l or less, preferably 0.2 to 10 g/l', more preferably 0.5 g/l' from the viewpoint of the effect of addition and economical efficiency.
~5g/l.
上記した表面調整液は通常の方法で使用される。The surface conditioning liquid described above is used in a conventional manner.
溶接部を有する鉄鋼材料の場合は、酸洗（兼脱脂）およ
び中和処理された材料を本発明の表面調整液で表面調整
する。この場合、中和後に脱脂だけの目的のための工程
により付着油を除去する必要はなく、表面調整と脱脂が
一工程で実施される。In the case of a steel material having a welded part, the surface of the pickled (and degreased) and neutralized material is adjusted using the surface conditioning liquid of the present invention. In this case, there is no need to remove the adhered oil by a step for the sole purpose of degreasing after neutralization, and surface conditioning and degreasing are performed in one step.
また溶接部を有しない鉄鋼材料の場合も酸洗（必要によ
り脱脂）および中和処理された材料を本発明の表面調整
液でスプレー処理する０通常、処理温度は室温でよく処
理時間は０．５〜３分である。In addition, in the case of steel materials that do not have welded parts, the material that has been pickled (degreased if necessary) and neutralized is spray treated with the surface conditioning liquid of the present invention.Usually, the treatment temperature is room temperature and the treatment time is 0. It takes 5 to 3 minutes.
以下、実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
実施例１゜
普通鋼、クロムモリブデン鋼、ハイテン計３種類の自転
車フレーム用に溶接されたパイプを用いて、酸洗兼脱脂
を行ない（硫酸２０％士界面活性剤０．２％、８０℃、
１５分浸漬）、次いで、水洗、中和（苛性ソーダ０．１
％、２０℃、３分浸漬）、水洗を行なった後、蓚酸７ｇ
／ｌ、グルコン酸ソーダ５ｇ／ｌを含有するｐＨ＝２、
液温２０℃の酸性水溶液で３０秒間スプレー処理し＃＃
請衣表面調整行ない、水洗、リン酸塩処理〔エナレス”
２０、日本バー力ライジング（株）製〕を２０℃で２分
間スプレー法により実施し、水洗後乾燥した。Example 1 Pickling and degreasing were carried out using pipes welded for three types of bicycle frames: ordinary steel, chromium molybdenum steel, and high tensile steel (20% sulfuric acid, 0.2% surfactant, 80°C,
15 minutes soaking), then washing with water, neutralization (caustic soda 0.1
%, 20℃, 3 minutes immersion), after washing with water, 7g of oxalic acid
/l, pH=2 containing 5g/l of sodium gluconate,
Spray for 30 seconds with an acidic aqueous solution at a liquid temperature of 20℃.
Surface adjustment, water washing, phosphate treatment [Enares]
No. 20, manufactured by Nippon Bar Chikara Rising Co., Ltd.] was sprayed at 20° C. for 2 minutes, washed with water, and then dried.
比較例１゜
上記実施例の除錆兼表面調整を蓚酸７ｇ／Ｖとした以外
は全て実施例１と同じ条件の処理を行３つな。Comparative Example 1 Three treatments were carried out under the same conditions as in Example 1, except that 7 g/V of oxalic acid was used for rust removal and surface conditioning in the above example.
実施例２〜７
除錆兼表面調整を蓚酸キレート剤、および界面活性剤、
さらに消泡剤サンノプコ社製の非イオン系活性剤を含有
する液を用いた他は実施例１と同様の条件で処理を行な
った。次に上記化成処理パイプにメラミン系下塗り塗料
（２０μ）、メラミン系中塗り塗料（２０μ）、メラミ
ン系上塗り塗料（２０μ）計６０μを３コート３ベーク
（焼付温度１６０℃）の条件で塗装し、塗膜密着性及び
耐食性試験を行なった。Examples 2 to 7 Rust removal and surface conditioning using oxalic acid chelating agent and surfactant,
Further, the treatment was carried out under the same conditions as in Example 1 except that a liquid containing a nonionic activator made by Sannopco, an antifoaming agent, was used. Next, apply a total of 60μ of melamine base coat (20μ), melamine intermediate coat (20μ), and melamine topcoat (20μ) to the chemical conversion treatment pipe under the conditions of 3 coats and 3 bakes (baking temperature 160 ° C.). Paint film adhesion and corrosion resistance tests were conducted.
実施例結果は表−１に示す。The results of the examples are shown in Table-1.
以下余白 皮膜特性および塗装特性は次の基準で評価した。Margin below Film characteristics and coating characteristics were evaluated using the following criteria.
（１）皮膜外観二目視にて判定する。(1) Film appearance is determined by second visual inspection.
〇−均一
△−溶接部と溶接部以外とで外観上のムラ・スケあり
×−溶接部、母材部を問わず外観上のムラ・スケあり
（２）皮膜付着量：皮膜化成した品物の重量を測定した
後５％クロム酸液中７５℃
で１５分間浸漬し皮膜のみ除去
する、水洗、乾燥後重量を測定
して前後の差より算出する。ｇ
／輸２で示す。〇 - Uniform △ - Appearance unevenness and sagging between welded and non-welded areas × - Appearance unevenness and sagging both in welded and base metal parts After measuring the weight, it is immersed in a 5% chromic acid solution at 75°C for 15 minutes to remove only the film. After washing and drying, the weight is measured and calculated from the difference between before and after. It is expressed as g/export 2.
（３）塗装密着性：塗膜面に２Ｘ２ｍｍのゴバン目２５
個をカミソリの刃を用いて
切り込みこの部分にセロテープ
（住友３Ｍ製）を貼りつけた後、
急激にはがし取る。この時の塗
膜残存状況をチェックする。(3) Paint adhesion: 25 2x2mm goblets on the paint surface
Cut the piece with a razor blade, apply cellophane tape (manufactured by Sumitomo 3M) to this area, and then quickly peel it off. Check the remaining status of the paint film at this time.
Ｏ：異常なし
０：点状に数ケ所（特に溶接部）ハクリ、又は面積とし
て１０％以下
△：バクリ面積１１〜３０％
×：ハ、クリ面積３０％以上
（４）塗装後の耐蝕性：塗膜面にカミソリの刃で傷を入
れＪＩＳ−Ｚ−２３７１に準じ
て、５ＳＴ２４０時間実施す
る。判定は片側最大フクレ
巾とする。O: No abnormality 0: Peeling in several spots (especially welded parts) or 10% or less in area △: Peeling area 11-30% ×: C, Peeling area 30% or more (4) Corrosion resistance after painting: The coating surface is scratched with a razor blade and subjected to 5ST for 240 hours in accordance with JIS-Z-2371. Judgment is based on the maximum bulge width on one side.
０：１＋ａ−以下
◎：１〜４ＩＩＩＩＩ
△ ： ４〜７ｓ＋ｍ
×ニア１以上
表１の比較例１と実施例１を対比すると、キレート剤の
添加により外観および耐食性が１ランク向上し、溶接部
による化成ムラが緩和されることが分かる。0: 1+a- or less ◎: 1-4III △: 4-7s+m It can be seen that the formation unevenness is alleviated.
比較例１と２を対比すると、界面活性剤は溶接部による
化成ムラ緩和に効果がないことが分かる。Comparing Comparative Examples 1 and 2, it can be seen that the surfactant is not effective in alleviating the formation unevenness caused by the weld.
ところが、界面活性剤をキレート剤と併用すると、格段
の効果が現われる。However, when a surfactant is used in combination with a chelating agent, a remarkable effect appears.
なお、溶接部を有しない鉄鋼材料の皮膜特性および塗装
特性を、上記実施例および比較例について比較すると、
皮膜特性の差はなかったが塗装後の耐食性、密着性につ
いて差が認められた。In addition, when comparing the film characteristics and coating characteristics of steel materials without welds for the above examples and comparative examples,
Although there was no difference in film properties, differences were observed in corrosion resistance and adhesion after painting.
以上のごとく、本発明によって、鉄鋼材料の表面調整後
の皮膜化成性及び塗装性能を向上することができる。As described above, according to the present invention, it is possible to improve the film formation properties and coating performance of steel materials after surface conditioning.
Claims (1)
有機キレート剤を添加したことを特徴とする鉄鋼材料の
化成処理用表面調整液。 ２．１〜２０ｇ／ｌの蓚酸もしくはその塩および０．１
〜１５ｇ／ｌの有機キレート剤を含有することを特徴と
する特許請求の範囲第１項記載の化成処理用表面調整液
。 ３、溶接部を有する鉄鋼材料の表面調整に用いることを
特徴とする特許請求の範囲第１項または第２項記載の化
成処理用表面調整液。 ４、蓚酸もしくはその塩を主成分とする表面調整液に、
有機キレート剤および界面活性剤を添加したことを特徴
とする化成表面処理用表面調整液。 ５．１〜２０ｇ／ｌの蓚酸もしくはその塩、０．１〜１
５ｇ／ｌの有機キレート剤、および１０ｇ／ｌ以下の界
面活性剤を含有することを特徴とする特許請求の範囲第
４項記載の化成処理用表面調整液。 ６、溶接部を有する鉄鋼材料の表面調整に用いることを
特徴とする特許請求の範囲第４項または第５項記載の化
成処理用表面調整液。[Claims] 1. A surface conditioning liquid containing oxalic acid or its salt as a main component,
A surface conditioning liquid for chemical conversion treatment of steel materials, characterized by the addition of an organic chelating agent. 2.1-20g/l oxalic acid or its salt and 0.1
The surface conditioning liquid for chemical conversion treatment according to claim 1, characterized in that it contains 15 g/l of an organic chelating agent. 3. The surface conditioning liquid for chemical conversion treatment according to claim 1 or 2, which is used for surface conditioning of steel materials having welded parts. 4. Surface conditioning liquid whose main component is oxalic acid or its salt,
A surface conditioning liquid for chemical surface treatment characterized by adding an organic chelating agent and a surfactant. 5.1-20g/l oxalic acid or its salt, 0.1-1
5. The surface conditioning liquid for chemical conversion treatment according to claim 4, which contains 5 g/l of an organic chelating agent and 10 g/l or less of a surfactant. 6. The surface conditioning liquid for chemical conversion treatment according to claim 4 or 5, which is used for surface conditioning of steel materials having welded parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6807987A JPS63235483A (en) | 1987-03-24 | 1987-03-24 | Surface regulating solution for chemical treatment of steel material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6807987A JPS63235483A (en) | 1987-03-24 | 1987-03-24 | Surface regulating solution for chemical treatment of steel material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63235483A true JPS63235483A (en) | 1988-09-30 |
| JPH0149790B2 JPH0149790B2 (en) | 1989-10-26 |
Family
ID=13363392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6807987A Granted JPS63235483A (en) | 1987-03-24 | 1987-03-24 | Surface regulating solution for chemical treatment of steel material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63235483A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003239078A (en) * | 2001-12-12 | 2003-08-27 | Nippon Parkerizing Co Ltd | Surface treatment method for lead-containing copper alloy and member in contact with water made of the same copper alloy |
| JP2012162762A (en) * | 2011-02-04 | 2012-08-30 | Jfe Steel Corp | Chemical conversion treatment method of steel member, method for manufacturing coated steel member having electrodeposition coating and coated steel member |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036473A (en) * | 1983-06-29 | 1985-02-25 | バスフ アクチェン ゲゼルシャフト | Manufacture of oxirane |
-
1987
- 1987-03-24 JP JP6807987A patent/JPS63235483A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036473A (en) * | 1983-06-29 | 1985-02-25 | バスフ アクチェン ゲゼルシャフト | Manufacture of oxirane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003239078A (en) * | 2001-12-12 | 2003-08-27 | Nippon Parkerizing Co Ltd | Surface treatment method for lead-containing copper alloy and member in contact with water made of the same copper alloy |
| JP2012162762A (en) * | 2011-02-04 | 2012-08-30 | Jfe Steel Corp | Chemical conversion treatment method of steel member, method for manufacturing coated steel member having electrodeposition coating and coated steel member |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0149790B2 (en) | 1989-10-26 |
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