JPS62174386A - Treating solution for forming oxalate film and chemical conversion treatment of stainless steel material with said solution - Google Patents
Treating solution for forming oxalate film and chemical conversion treatment of stainless steel material with said solutionInfo
- Publication number
- JPS62174386A JPS62174386A JP1393486A JP1393486A JPS62174386A JP S62174386 A JPS62174386 A JP S62174386A JP 1393486 A JP1393486 A JP 1393486A JP 1393486 A JP1393486 A JP 1393486A JP S62174386 A JPS62174386 A JP S62174386A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- conversion treatment
- ions
- stainless steel
- film
- 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.)
- Pending
Links
- 239000000126 substance Substances 0.000 title claims abstract description 55
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 27
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 17
- 239000010935 stainless steel Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 13
- -1 nitrate ions Chemical class 0.000 claims abstract description 13
- 229920000620 organic polymer Polymers 0.000 claims abstract description 9
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 8
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005482 strain hardening Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 5
- 238000005491 wire drawing Methods 0.000 description 5
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 229960002799 stannous fluoride Drugs 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide 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
- 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、ステンレス鋼材の冷間加工用蓚酸塩皮膜化成
処理液並びに該化成処理液を用いて前記鋼材を化成処理
する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxalate coating chemical conversion treatment liquid for cold working of stainless steel materials, and a method of chemical conversion treatment of the steel materials using the chemical conversion treatment liquid.
従来ステンレス鋼材の冷間加工例えばステンレス鋼線を
線引加工する場合には、予め潤滑剤のべ−スとして線材
表面に蓚酸塩皮膜を形成させるのが通例である。蓚酸塩
皮膜化成処理液（以下、化成処理液という）としては蓚
酸を主成分としこれに弗化物、酸化剤等を含むもの、エ
ツチング剤として塩化物を含むもの、特公昭４６−６８
４８号公報に開示されている金ａイオンとして錫イオン
を含むものおよび特公昭５２−４２５５号公報に開示さ
れている錫イオン以外にさらにゼラチン、カゼイン等の
たんばく質を含むものなどが公知であるが、これ等の化
成処理液で皮膜化成を行なう場合に化成反応を促進させ
るためて酸化促進剤としてチオ硫酸塩例えばチオ硫酸ナ
トリウムを化成処理液に添加して行なわれるのが通例で
ある。Conventionally, when cold working stainless steel materials, such as drawing stainless steel wire, it is customary to form an oxalate film on the surface of the wire in advance as a lubricant base. Oxalate film chemical conversion treatment liquids (hereinafter referred to as chemical conversion treatment liquids) include those containing oxalic acid as a main component and fluoride, oxidizing agents, etc., those containing chloride as an etching agent, and those containing chloride as an etching agent.
There are known gold a ions that contain tin ions as disclosed in Japanese Patent Publication No. 48, and those that contain proteins such as gelatin and casein in addition to tin ions as disclosed in Japanese Patent Publication No. 52-4255. However, when performing film formation using these chemical conversion treatment solutions, it is customary to add a thiosulfate, such as sodium thiosulfate, to the chemical conversion treatment solution as an oxidation promoter in order to accelerate the chemical conversion reaction.
例えば市販されるステンレスヘッダ材の潤滑処理の現状
においては次の様なプロセスで処理したのち市販される
。即ち、酸洗−水洗一蓚酸塩処理−湯洗−乾燥一石憶潤
滑剤にてスキンパス−焼鈍−酸洗一水洗一蓚酸塩処理一
湯洗一乾燥一石鹸潤滑剤にてスキンパス−ヘッダ材とし
て市販以上の処理においては、化成処理液に字化物およ
び／またはチオ硫酸塩を含む場合に、蓚酸塩化成したヘ
ッダ材を湯洗しても結晶性蓚酸塩皮膜中に塩化物、チオ
硫酸塩等が微量存在し、これ等の何れもがスキンバス後
の焼鈍時においてステンレス材の肌荒れを引き起こしヘ
ッダ材の品質を損ねる問題を発生する。For example, the current state of lubricating treatment for commercially available stainless steel header materials is as follows. Namely, pickling, water washing, oxalate treatment, hot water washing, drying, skin pass with stone-memory lubricant, annealing, pickling, water washing, oxalate treatment, hot water washing, drying, soap lubricant, and skin pass.Commercially available as header material. In the above treatment, if the chemical conversion treatment solution contains curds and/or thiosulfates, chlorides, thiosulfates, etc. will remain in the crystalline oxalate film even if the oxalate-converted header material is washed with hot water. They are present in small amounts, and any of these causes the problem of roughening the surface of the stainless steel material during annealing after the skin bath, impairing the quality of the header material.
また、以上の化成処理液ではオーステナイト系ステンレ
ス鋼材に対しては冷間加工に適する優れた付着性を有す
る皮膜形成が可能であるが、フェライト系ステンレス鋼
材に対しては充分に満足な付着性を示す皮膜を形成させ
ることが困難である等の問題を有しており、更に処理液
の寿命が短くかつ形成皮膜の性能にバラツキを生ずる等
の問題も有しているのである。Furthermore, with the above chemical conversion treatment liquid, it is possible to form a film with excellent adhesion suitable for cold working on austenitic stainless steel materials, but it is not possible to form a film with sufficiently satisfactory adhesion on ferritic stainless steel materials. This method has problems such as difficulty in forming a film shown in the figure, and further problems such as the life of the treatment solution is short and the performance of the formed film varies.
本発明は、以上の問題点を解決することを目的としてな
され念ものであって、即ち、ステンレス鋼材特にフェラ
イト系ステンレス鋼材の化成処理に適用する蓚酸、金属
イオン、弗素化合物、硝酸イオン訃よび九んば〈質物質
以外の水溶性有機高分子化合物を含み塩素イオンを含ま
ない化成処理液、並びに実際の化成処理においては、前
記化成処理液に酸化促進剤であるチオ硫酸塩を添加しな
いで処理する方法を提供しようとするものである。The present invention has been made with the aim of solving the above-mentioned problems. Chemical conversion treatment solutions that contain water-soluble organic polymer compounds other than organic substances and do not contain chlorine ions, and in actual chemical conversion treatment, are treated without adding thiosulfate, which is an oxidation promoter, to the chemical conversion treatment solution. The aim is to provide a method to do so.
本発明の第１発明である化成処理液における蓚酸の濃度
は１０〜５０１！／ｌが好ましぐ、特に好ましくは３０
〜４０１１Ａである。１０９／ｌ未満では化成反応が遅
延するか又は不完全皮膜となシ易く、著しい低濃度では
全く皮膜を化成しなくなる等によシ好ましくない。５０
１！／ｌよシも多くしても化成効果の向上が余シ期待で
きず且つ処理液コストが高くなるので経済的に好ましく
ない。The concentration of oxalic acid in the chemical conversion treatment solution which is the first invention of the present invention is 10 to 501! /l is preferred, particularly preferably 30
~4011A. If the concentration is less than 109/l, the chemical conversion reaction is likely to be delayed or an incomplete film may be formed, and if the concentration is extremely low, the chemical formation of the film will not occur at all, which is undesirable. 50
1! Even if /l is increased, no further improvement in the chemical conversion effect can be expected and the cost of the treatment solution increases, which is economically unfavorable.
金属イオンとしては、錫、マンガン、ジルコニウム、ニ
ッケル、チタン、および亜鉛の１種又は２種以上が適用
され、その濃度は０．１〜１０９／ｌ、特に好ましくは
０．２〜２．０ Ｅ／ｌである。０．１辺未溝では皮膜
結晶の析出を早める効果並びに皮膜の付着性を高める効
果が不充分であり、 １０ ’ｊ／１を超えてもそれ等
の効果の向上が殆ど期待できない。As the metal ion, one or more of tin, manganese, zirconium, nickel, titanium, and zinc is used, and the concentration thereof is 0.1 to 109/l, particularly preferably 0.2 to 2.0 E /l. If the groove is not grooved on a side of 0.1, the effect of accelerating the precipitation of film crystals and the effect of increasing the adhesion of the film is insufficient, and even if it exceeds 10'j/1, hardly any improvement in these effects can be expected.
錫イオンとしては弗化第１聾、硫酸第１錫、蓚酸第１錫
等、マンガンイオンとしては炭酸マンガン、（６Ｈｌマ
ンガン等、シルコニウムイオントしテはフッ化ジルコニ
ウム酸（Ｈ３ＺｒＦａ ） ＋フッ化ジルコニウム（Ｚ
ｒＦ４ ） ’４、ニッケルイオンとしては炭酸ニッケ
ル、硝酸ニッケル、硫酸ニッケル等、チタンイオンとし
ては弗化チタン、蓚酸チタン、硫酸チタニール等、亜鉛
イオンとしては酸化亜鉛。Tin ions include stannous fluoride, stannous sulfate, stannous oxalate, etc. Manganese ions include manganese carbonate, (6Hl manganese, etc.), silconium ions include zirconium fluoride (H3ZrFa) + fluoride Zirconium (Z
rF4) '4. Nickel ions include nickel carbonate, nickel nitrate, nickel sulfate, etc. Titanium ions include titanium fluoride, titanium oxalate, titanyl sulfate, etc., and zinc ions include zinc oxide.
炭酸亜鉛、硝酸亜鉛等の化合物が処理液に配合される。Compounds such as zinc carbonate and zinc nitrate are added to the treatment liquid.
これ等の化合物は何れも塩化物を含まない事が必要であ
る以外は以上の如く特定するものではない。These compounds are not otherwise specified except that they must be chloride-free.
弗素化合物は皮膜化成反応を進行させるために素材を適
度にエツチングするのに好適なものであるので、弗素イ
オンとして０．１〜５ 、’；ｌ／ｌ 、特に好ましく
は０．５〜３．５．９７１存在する必要がある。０．１
Ｖ！未満でけ化成性を低下させるので好ましくなく、又
５ Ｑ／ｌよりも多くなると素材のエツチング作用が強
くなり粗雑な皮膜となるので好ましくない。Since the fluorine compound is suitable for etching the material appropriately in order to advance the film formation reaction, the fluorine ion is 0.1-5.l/l, particularly preferably 0.5-3.l/l. 5.971 must exist. 0.1
V! If it is less than 5 Q/l, it is undesirable because it lowers the chemical conversion properties, and if it is more than 5 Q/l, the etching effect on the material becomes strong, resulting in a rough film, which is not preferred.
また、硝酸イオンは皮膜化成反応を進行させる役割を持
つが、硝酸イオンの濃度が０．１ ｇ／ｌ以下ではその
効果が不充分となり、又３ ｇ／ｌ、１： ！Ｄも多く
なってもその効果の向上は余シ期待できず且つ処理液が
老化し易くなるので何れの場合も好ましくない。In addition, nitrate ions have the role of promoting film formation reactions, but if the concentration of nitrate ions is less than 0.1 g/l, the effect will be insufficient; Even if the amount of D is increased, no improvement in the effect can be expected and the processing solution tends to age, so either case is not preferable.
次に水溶性有機高分子化合物はたんばく質物質以外のも
とし、好ましくはポリビニルピロリドン、ポリエチレン
クリコール、ポリビニルアルコールおよびポリエチレン
オキザイドから選ばれ、これは化成反応で形成する蓚酸
塩結晶皮膜の結晶の粗大化を抑制して結晶密集度の高い
ち密な皮膜を形成させる効果と皮膜内に浸透して乾燥後
の皮膜の結合力を高める効果を付与する機能をもつ。た
だし前記高分子化合物の濃度がＩ ９７１未満ではその
効果が不充分となり、１０ Ｖｌよりも多くなると化成
反応を阻害するようになり、また化成処理液の粘変が高
くなるので被処理材による化成処理液の持出し量が多く
なり且つ処理液コスト自体も高くなるので経済的に好ま
しくない。Next, the water-soluble organic polymer compound is a substance other than a protein substance, preferably selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, and polyethylene oxide, which is a crystal of an oxalate crystal film formed by a chemical reaction. It has the effect of suppressing the coarsening of the crystals and forming a dense film with high crystal density, and the function of penetrating into the film and increasing the bonding strength of the film after drying. However, if the concentration of the polymer compound is less than I971, the effect will be insufficient, and if it exceeds 10 Vl, the chemical conversion reaction will be inhibited, and the viscosity of the chemical conversion treatment solution will increase, so that the chemical conversion by the material to be treated will be difficult. This is economically unfavorable because the amount of treatment liquid taken out increases and the cost of the treatment liquid itself increases.
本発明の第１発明の化成処理液は従来公知の方法即ち処
理液の温度を通常８０〜９０°Ｃに加熱しその中にスケ
ール、酸化膜等を除去したステンレス鋼材を通常１０〜
２０分浸漬する方法で適用されるが、前記の温度１時間
を特定するものではない。また例えばオーステナイト系
ステンレス鋼材の処理用としては前記化成処理液に故化
促進剤としてチオ硫酸塩を加えて処理することができる
。The chemical conversion treatment solution of the first aspect of the present invention is produced by a conventionally known method, that is, the temperature of the treatment solution is usually heated to 80 to 90°C, and the stainless steel material from which scale, oxide film, etc. have been removed is usually heated to 10 to
Although it is applied by a method of soaking for 20 minutes, the above-mentioned temperature for 1 hour is not specified. For example, for treating austenitic stainless steel materials, thiosulfate can be added to the chemical conversion treatment solution as a degradation accelerator.
これに対して本発明の第２発明の処理方法においては第
１発明の化成処理液にチオ硫酸塩（ｓｔｏｓ）を添加し
ないことを特定したものであって、従ってチオ硫酸塩（
ＳｚＯｓ）を含まない化成処理液で蓚酸塩皮膜を形成さ
せる方法である。On the other hand, in the treatment method of the second invention of the present invention, it is specified that thiosulfate (stos) is not added to the chemical conversion treatment liquid of the first invention, and therefore thiosulfate (stos) is not added to the chemical conversion treatment solution of the first invention.
This is a method in which an oxalate film is formed using a chemical conversion treatment solution that does not contain SzOs.
化成処理液中の蓚酸は弗化物のエツチング助成作用によ
り被処理材の表面から主として鉄その他クロム、ニッケ
ル等を溶出して被処理材の界面の−を上げる。酸化剤は
前記溶出の際に発生した水素イオンを水となし溶出を促
進する作用を営む。The oxalic acid in the chemical conversion treatment solution mainly elutes iron, chromium, nickel, etc. from the surface of the material to be treated due to the etching-assisting action of fluoride, thereby increasing the - level of the interface of the material to be treated. The oxidizing agent acts to promote elution by converting hydrogen ions generated during the elution into water.
鉄の反応を代表として次の様な反応式で説明できる。The following reaction formula can be used to explain the reaction of iron as a representative example.
Ｆｅ’−＋ Ｆｅ” ＋ ２ ｅ−（アノード反応）２
Ｈ＋＋ ２ｅ−−２Ｈ＋ ０ →ＨｔＯ（カンード反応
）前記界面における化成処理液の川向上により不溶性の
蓚酸鉄（ＦｅＣｔＯ４’）がアノード部に析出して結晶
核となシ同時に前記界面における化成処理液中の金属イ
オンも亦蓚酸塩となって析出するので結晶核の形成がそ
れだけ早められるのである。従ってそれだけ被処理材表
面のエツチング作用を少なくして消極作用を完了させる
ことができる。即ち密集度の高い結晶核が生長してち密
な蓚酸塩皮膜を形成するのであるが、この様にして得ら
れる皮膜は高い付着性を有しているのである。Fe'-+ Fe" + 2 e- (anodic reaction) 2
H++ 2e--2H+ 0 → HtO (Cando reaction) As the chemical conversion treatment liquid rises at the interface, insoluble iron oxalate (FeCtO4') precipitates on the anode part and becomes crystal nuclei, and at the same time, in the chemical conversion treatment liquid at the interface. Since the metal ions also precipitate as oxalate, the formation of crystal nuclei is accelerated accordingly. Therefore, the etching effect on the surface of the material to be treated can be reduced accordingly, and the passive effect can be completed. That is, highly dense crystal nuclei grow to form a dense oxalate film, and the film thus obtained has high adhesion.
水溶性有機高分子化合物は蓚酸塩皮膜の中に浸入するが
、これは次の工程で行なわれる水洗工程でも除去され難
く、次の乾燥の際に皮膜の結合力を高め、被処理材への
高付着性と相俟って冷間加工に優れた蓚酸塩皮膜となる
のである。The water-soluble organic polymer compound penetrates into the oxalate film, but it is difficult to remove even in the next step of washing with water, increasing the bonding strength of the film during the next drying process and attaching it to the treated material. Combined with high adhesion, this results in an oxalate film that is excellent in cold working.
以下に実施例を挙げ本発明の効果を具体的に説明する。EXAMPLES The effects of the present invention will be specifically explained below with reference to Examples.
実施例１〜７及び比較例１〜６
ステンレス線材として５ＵＳ４１０ ３．５ｓ＋φ×２
５０ｍ１と５ＵＳ４３４ ３．０＋ｍφＸ２５Ｏｎｏｎ
ＡＩの２種類を選び、それぞれ下記工程にて化成処理を
行なった。Examples 1 to 7 and Comparative Examples 1 to 6 5US410 3.5s+φ×2 as stainless steel wire
50m1 and 5US434 3.0+mφX25Onon
Two types of AI were selected and each was subjected to chemical conversion treatment in the following steps.
ただし皮膜化成に適用した化成処理液の実施例・比較例
は第１表の通りである。However, Table 1 shows examples and comparative examples of chemical conversion treatment liquids applied to film formation.
酸洗（ＨＮＯ，・ＨＦ系）−水洗−皮膜化成−湯洗−乾
燥（８０℃、５分）
試験方法：
ｆｉ＋皮膜重囮：（ＣＷ）
５％無水クロム酸水溶液を７５±１℃に加熱し、その中
に重？測定済みの化成処理線材を１５分間浸漬して皮膜
を完全にはく離する。Acid cleaning (HNO, HF system) - Water washing - Film formation - Hot water washing - Drying (80°C, 5 minutes) Test method: fi + Film decoy: (CW) 5% chromic anhydride aqueous solution heated to 75 ± 1°C Is there a heavy weight in it? The measured chemical conversion treated wire is immersed for 15 minutes to completely peel off the film.
次いで水洗したのち乾燥して再び線材の重量を測定して
両重貴差から皮膜重量（Ｖ、ｚ ）を求める。Next, the wire is washed with water and then dried, and the weight of the wire is measured again, and the coating weight (V, z) is determined from the weight difference between the two.
Ｃ２＋付着性
アムスラー引張試験機にて化成処理線材を破断させたの
ち、線材の破断部付近の蓚酸塩皮膜の残存状態を目視観
察する。After the chemically treated wire is broken using a C2+ adhesive Amsler tensile tester, the remaining state of the oxalate film near the broken part of the wire is visually observed.
○・・・破断部付近に完全に皮膜が残っているΔ・・・
〃 Ｉ の皮膜が僅かにはく離している
×・・・ 〃 〃 の皮膜が可成りにはく離している
実施例８および比較例７
ステンレス線材（ＳＵＳ４３４，５ｗφ）を夫々実施例
５の組成および比較例５の組成を有する各６０００ノ容
量の化成処理液で夫々８５℃の浴温で１５分間浸漬処理
した。処理プロセスは実施例１〜７および比較例１〜６
の場合と同様にして行なった。○...The film remains completely near the fracture Δ...
〃 The film of I is slightly peeled ×... The film of 〃 〃 is considerably peeled off Example 8 and Comparative Example 7 Stainless steel wire rod (SUS434, 5wφ) was compared with the composition of Example 5, respectively. Each sample was immersed in a 6000 volume chemical conversion solution having the composition of Example 5 at a bath temperature of 85° C. for 15 minutes. The treatment process is Examples 1 to 7 and Comparative Examples 1 to 6.
It was done in the same way as in the case of
実施例５の化成処理液で処理し念場合を実施例８とし、
比較例５の化成処理液で処理した場合を比較例７とし、
何れの場合にも１回当りの線材の処理量を５００ Ｋｙ
として処理を行なった。Example 8 is a case in which treatment is performed with the chemical conversion treatment solution of Example 5.
The case treated with the chemical conversion treatment liquid of Comparative Example 5 is referred to as Comparative Example 7,
In either case, the amount of wire rod processed per process is 500 Ky.
It was processed as follows.
処理した線材を夫々同一粉末石鹸を用いて同一条件のも
とに連続伸線をした結果、比較例７においては延べ約１
３０トン処理した時点で伸線不良を発生し念。その時点
における蓚酸塩皮膜は外観的に粗くまたスラッジ付着量
が多いので化成処理液を更新し再び比較例７と同様の条
件で処理をした処問題なく伸線することができ、延約１
２５トン処理した時点で＃記と同様の伸線不良が発生し
た。これに対し実施例８の場合には延べ約４５０トンの
線材の処理時のものでも最初の処理の場合と同様に良好
に伸線することができた。As a result of continuous wire drawing of the treated wire rods under the same conditions using the same powdered soap, in Comparative Example 7, a total of about 1
We apologized for the wire drawing failure that occurred when 30 tons were processed. At that point, the oxalate coating was rough in appearance and had a large amount of sludge attached, so the chemical conversion treatment solution was updated and the treatment was performed again under the same conditions as in Comparative Example 7. Wire drawing was possible without any problems, and the wire drawing was approximately 1
At the time of processing 25 tons, a wire drawing defect similar to # is observed. On the other hand, in the case of Example 8, even when a total of about 450 tons of wire rod was processed, it was possible to draw the wire as well as in the case of the first processing.
以上実施例並びに比較例で示される通シ、本第１発明の
化成処理液はフェライト系ステンレス鋼材に対し付着性
の優れた蓚酸塩皮膜を形成させるものである。ま念、実
施例には挙げていないが酸化促進剤を本発明の化成処理
液に併用することによってオーステナイト系ステンレス
鋼材にも優れた冷間加工用蓚酸塩皮膜を形成させること
ができるのである。As shown in the Examples and Comparative Examples above, the chemical conversion treatment liquid of the first invention forms an oxalate film with excellent adhesion on ferritic stainless steel materials. Although not mentioned in the examples, by using an oxidation promoter in combination with the chemical conversion treatment solution of the present invention, it is possible to form an excellent oxalate film for cold working even on austenitic stainless steel materials.
次に本発明の＠２発明の方法は、フェライト系ステンレ
ス鋼材に対して冷間加工性が最も優れたち密な皮膜を安
定して形成させることができるものであって、化成処理
液の寿命も長く処理液管理の面でも経済的にも優れた蓚
酸塩皮膜化成方法なのである。Next, the method of the present invention @2 is capable of stably forming a dense film with the best cold workability on ferritic stainless steel materials, and it also extends the lifespan of the chemical conversion treatment solution. It is an oxalate film formation method that has long been superior in terms of treatment solution management and economy.
Claims (5)
びたんぱく質物質以外の水溶性有機高分子化合物を含み
塩素イオンを含まないことを特徴とする蓚酸塩皮膜化成
処理液。(1) An oxalate film chemical conversion treatment solution, which contains oxalic acid, metal ions, fluorine compounds, nitrate ions, and water-soluble organic polymer compounds other than protein substances, and does not contain chlorine ions.
１０ｇ／ｌ、弗素化合物が弗素イオンとして０．１〜５
ｇ／ｌ、硝酸イオンが０．１〜３ｇ／ｌおよびたんぱく
質物質以外の水溶性有機高分子化合物が１〜１０ｇ／ｌ
である特許請求の範囲第１項記載の蓚酸塩皮膜化成処理
液。(2) Oxalic acid: 10 to 50 g/l, metal ions: 0.1 to 1
10g/l, fluorine compound is 0.1-5 as fluorine ion
g/l, nitrate ions from 0.1 to 3 g/l, and water-soluble organic polymer compounds other than protein substances from 1 to 10 g/l.
The oxalate film chemical conversion treatment liquid according to claim 1.
ケル、チタンおよび亜鉛の１種又は２種以上のイオンで
ある特許請求の範囲第１項または第２項記載の蓚酸塩皮
膜化成処理液。(3) The oxalate film chemical conversion treatment solution according to claim 1 or 2, wherein the metal ions are one or more ions of tin, manganese, zirconium, nickel, titanium, and zinc.
ポリビニルピロリドン、ポリエチレングリコール、ポリ
ビニルアルコールおよびポリエチレンオキサイドから選
ばれるものである特許請求の範囲第１項または第２項記
載の蓚酸塩皮膜化成処理液。(4) The oxalate film chemical conversion treatment solution according to claim 1 or 2, wherein the water-soluble organic polymer compound other than the protein substance is selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, and polyethylene oxide. .
びたんぱく質物質以外の水溶性有機高分子化合物を含み
塩素イオンを含まない蓚酸塩皮膜化成処理液でステンレ
ス鋼材を化成する際に、該化成処理液に酸化促進剤であ
るチオ硫酸塩を添加しないことを特徴とするステンレス
鋼材の化成処理方法。(5) When chemically converting stainless steel materials with an oxalate film chemical conversion treatment liquid that contains oxalic acid, metal ions, fluorine compounds, nitrate ions, and water-soluble organic polymer compounds other than protein substances and does not contain chlorine ions, the chemical conversion treatment liquid A method for chemical conversion treatment of stainless steel material, characterized in that thiosulfate, which is an oxidation promoter, is not added to the stainless steel material.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1393486A JPS62174386A (en) | 1986-01-27 | 1986-01-27 | Treating solution for forming oxalate film and chemical conversion treatment of stainless steel material with said solution |
| EP87100878A EP0233503A1 (en) | 1986-01-27 | 1987-01-22 | Process for applying oxalate coatings to stainless steel |
| DE19873701728 DE3701728A1 (en) | 1986-01-27 | 1987-01-22 | METHOD FOR APPLYING OXALATUE COATINGS ON STAINLESS STEEL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1393486A JPS62174386A (en) | 1986-01-27 | 1986-01-27 | Treating solution for forming oxalate film and chemical conversion treatment of stainless steel material with said solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62174386A true JPS62174386A (en) | 1987-07-31 |
Family
ID=11847021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1393486A Pending JPS62174386A (en) | 1986-01-27 | 1986-01-27 | Treating solution for forming oxalate film and chemical conversion treatment of stainless steel material with said solution |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0233503A1 (en) |
| JP (1) | JPS62174386A (en) |
| DE (1) | DE3701728A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5591275A (en) * | 1993-01-13 | 1997-01-07 | Henkel Corporation | Composition and process for surface treating metal prior to cold working |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4135524C2 (en) * | 1991-10-28 | 1995-01-26 | Gc Galvano Consult Gmbh | Method and means for chromating surfaces made of zinc or cadmium or alloys thereof |
| JP3193798B2 (en) * | 1993-01-13 | 2001-07-30 | 日本パーカライジング株式会社 | Metal surface treatment liquid for forming composite film for cold working of metal and method for forming composite film |
| EP1895023B1 (en) * | 2006-08-31 | 2013-05-01 | Takashi Arai | Agents for the surface treatment of zinc or zinc alloy products |
| WO2020165035A1 (en) * | 2019-02-14 | 2020-08-20 | Chemetall Gmbh | Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor |
| US20230091443A1 (en) | 2020-02-25 | 2023-03-23 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming |
| BR112022016684A2 (en) | 2020-02-25 | 2022-10-11 | Chemetall Gmbh | METHOD FOR PRETREATMENT OF A METALLIC SUBSTRATE, PRETREATED METALLIC SUBSTRATE, COLD FORMING PROCESS OF A METALLIC SUBSTRATE, AQUEOUS LUBRICANT COMPOSITION, AND, STANDARD MIXTURE |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5220967A (en) * | 1975-08-12 | 1977-02-17 | Nippon Shii Bii Kemikaru Kk | Composite lubrication coating for steel or alloy steel |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2759862A (en) * | 1952-03-11 | 1956-08-21 | Devex Corp | Coating compositions and method of treating ferrous surfaces therewith |
| BE561643A (en) * | 1957-01-30 | |||
| BE568437A (en) * | 1957-06-14 | |||
| NL275308A (en) * | 1961-03-07 | |||
| JPS524255B2 (en) * | 1972-08-26 | 1977-02-02 |
-
1986
- 1986-01-27 JP JP1393486A patent/JPS62174386A/en active Pending
-
1987
- 1987-01-22 DE DE19873701728 patent/DE3701728A1/en not_active Withdrawn
- 1987-01-22 EP EP87100878A patent/EP0233503A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5220967A (en) * | 1975-08-12 | 1977-02-17 | Nippon Shii Bii Kemikaru Kk | Composite lubrication coating for steel or alloy steel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5591275A (en) * | 1993-01-13 | 1997-01-07 | Henkel Corporation | Composition and process for surface treating metal prior to cold working |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0233503A1 (en) | 1987-08-26 |
| DE3701728A1 (en) | 1987-07-30 |
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