JPS619580A - Blackening phosphate treatment method - Google Patents
Blackening phosphate treatment methodInfo
- Publication number
- JPS619580A JPS619580A JP13027084A JP13027084A JPS619580A JP S619580 A JPS619580 A JP S619580A JP 13027084 A JP13027084 A JP 13027084A JP 13027084 A JP13027084 A JP 13027084A JP S619580 A JPS619580 A JP S619580A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- phosphate
- blackening
- treatment solution
- zinc
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 21
- 229910019142 PO4 Inorganic materials 0.000 title claims description 17
- 239000010452 phosphate Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 title description 2
- -1 chlorate ions Chemical class 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 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 claims description 9
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 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 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 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 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940005989 chlorate ion Drugs 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic 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-QWKBTXIPSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000008 nickel(II) carbonate 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- OSKILZSXDKESQH-UHFFFAOYSA-K zinc;iron(2+);phosphate Chemical compound [Fe+2].[Zn+2].[O-]P([O-])([O-])=O OSKILZSXDKESQH-UHFFFAOYSA-K 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
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
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、鉄鋼材料の表面処理に適用され、鉄鋼表面を
黒色化するリン酸塩皮膜処理液に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a phosphate film treatment liquid that is applied to surface treatment of steel materials and blackens the surface of steel.
［従来例］
従来、鉄鋼材料の表面を黒色化する方法としては、黒染
、リン酸マンガン系皮膜、リン酸亜鉛系皮膜剤及び、塗
装を行うことは公知の技術である。[Conventional Example] Conventionally, methods for blackening the surface of steel materials include black dyeing, manganese phosphate coating, zinc phosphate coating, and painting.
まず黒染はアルカリ性溶液で１４０〜１５０℃で２０〜
５０分浸漬処理して酸化鉄皮膜を作るものである。これ
は、外観は青黒色〜茶褐色〜黒色まで色々あり、表面が
滑らかで光沢があるけれども耐蝕性及び作業性が悪い。First, black dyeing is done with an alkaline solution at 140-150℃ for 20~
An iron oxide film is created by immersion treatment for 50 minutes. The appearance varies from blue-black to brownish-brown to black, and although the surface is smooth and glossy, corrosion resistance and workability are poor.
リン酸マンガン系皮膜は９５〜沸騰状態で２０〜３０分
処理してリン酸マンガン皮膜を作る。これは外観は灰黒
色〜黒色であり、耐摩耗性及び耐蝕性は良いが、皮膜が
粗く作業性も悪い。リン酸亜鉛系皮膜は９０〜沸騰状態
で２０〜３０分間処理づることによりリン酸亜鉛鉄皮膜
を作る。これは外観は灰黒色〜黒色であり、耐蝕性は良
いが、皮膜が粗い。又処理液中には酸化剤としてＮｏｘ
を含んでいる。塗装は外観は良好であるが、密着性や作
業性に問題がある。A manganese phosphate film is formed by processing at a boiling temperature of 95°C for 20 to 30 minutes. This has a grayish-black to black appearance and has good wear resistance and corrosion resistance, but the coating is rough and has poor workability. Zinc phosphate-based coatings are treated at 90 to boiling temperature for 20 to 30 minutes to form zinc iron phosphate coatings. This has a grayish-black to black appearance and has good corrosion resistance, but the film is rough. In addition, the processing liquid contains Nox as an oxidizing agent.
Contains. Although the paint looks good, there are problems with adhesion and workability.
特に塗装及び乾燥等の作業性並びに各種性能を十分満足
することができないのが現、状である。In particular, the current situation is that workability such as painting and drying, as well as various performances, cannot be fully satisfied.
［発明の目的］
本発明は従来例における欠点を除去し、作業性が良好で
あると共に、皮膜の外観は黒色緻密で耐蝕性に優れたリ
ン酸塩皮膜を鉄鋼材料表面に形成させることができるリ
ン酸塩処理液を提供することを目的とするものである。[Object of the invention] The present invention eliminates the drawbacks of the conventional method, and can form a phosphate film on the surface of a steel material that has good workability, has a dense black appearance, and has excellent corrosion resistance. The purpose is to provide a phosphate treatment solution.
［発明の構成］
上記目的を達成させるためになされた本発明は、硝酸イ
オン及び亜硝酸イオンを含まないリン酸亜鉛処理液に、
ニッケルイオン０．０５〜！Ｍ＃。[Structure of the Invention] The present invention, which has been made to achieve the above object, includes a zinc phosphate treatment solution that does not contain nitrate ions and nitrite ions.
Nickel ion 0.05 ~! M#.
塩素酸イオン０．５〜８ｇ／ｌ及び鉄イオン０．０２〜
４ｇ／９を含むと共に、前記リン酸亜鉛処理液中の亜鉛
イオン／リン酸イオンの重量比が０．０７〜０．２５で
あり、更に少量のキレート剤を添加した鉄鋼材料の黒色
化リン酸塩皮膜処理液である。Chlorate ion 0.5~8g/l and iron ion 0.02~
4g/9, the weight ratio of zinc ions/phosphate ions in the zinc phosphate treatment solution is 0.07 to 0.25, and a small amount of chelating agent is added. This is a salt film treatment liquid.
本発明の処理液においては、リン酸亜鉛処理液にニッケ
ルイオン、塩素酸イオン及び鉄イオンを共存させたもの
であって、被処理物から溶出してくる鉄分をすばやく３
価鉄イオンにして沈澱させ反応系外の成分にしてしまう
硝酸イオン及び亜硝酸イオンを実質的に含有させない点
に特徴が存するのである。そして、リン酸亜鉛処理液中
の亜鉛イオン／リン酸イオンの重量比を限定することに
よって黒色化を一段と助長させ黒色化の優れた皮膜が得
られるのである。In the treatment solution of the present invention, nickel ions, chlorate ions, and iron ions are made to coexist in the zinc phosphate treatment solution, and the iron content eluted from the object to be treated can be quickly removed.
It is characterized in that it does not substantially contain nitrate ions and nitrite ions, which are converted into valent iron ions and precipitated and become components outside the reaction system. By limiting the weight ratio of zinc ions/phosphate ions in the zinc phosphate treatment solution, blackening is further promoted and a film with excellent blackening can be obtained.
次に各イオン濃度の限定理由を述べる。Next, the reason for limiting each ion concentration will be described.
ニッケルイオンが、０．０５９／Ｉ以下になるとリン酸
塩皮膜の黒色化が不充分となり、５７／」以上になると
経済的に不利である。If the nickel ion content is less than 0.059/I, the blackening of the phosphate film will be insufficient, and if it is more than 57/I, it will be economically disadvantageous.
塩素酸イオンが、０．５ｇ／ｆＪ以下になるとリン酸塩
皮膜の化成性および黒色化が不充分であり、８１勺以上
になると酸化力が強すぎて処理液中に鉄イオンを維持さ
せるのが困難になる。If the chlorate ion is less than 0.5 g/fJ, the chemical formation and blackening of the phosphate film will be insufficient, and if it is more than 81 g/fJ, the oxidizing power will be too strong and it will be difficult to maintain iron ions in the processing solution. becomes difficult.
鉄イオンが、０．０２ｇ／４１以下になると、リン酸塩
皮膜の黒色化が不充分となり、４ｇ／、ｌ１以上になる
とリン酸塩皮膜結晶が粗くなり耐蝕性が劣化する。If the iron ion content is less than 0.02 g/41, the blackening of the phosphate film will be insufficient, and if it is more than 4 g/11, the phosphate film crystals will become coarse and the corrosion resistance will deteriorate.
リン酸亜鉛処理液中の亜鉛イオン／リン酸イオンの重量
比が、０．０７以下にな、ると化成されるリン酸塩皮膜
中の鉄分が多くなり耐蝕性が悪くなり、反対に０．２５
以上になるとリン酸塩皮膜の黒色化が不充分となる。If the weight ratio of zinc ions/phosphate ions in the zinc phosphate treatment solution is less than 0.07, the iron content in the phosphate film that is chemically formed will increase, resulting in poor corrosion resistance; 25
If it is more than that, the blackening of the phosphate film will be insufficient.
本発明の黒色化リン酸塩皮膜処理液の好ましい成分範囲
は、亜鉛イオン２〜５グ／ρ、リン酸イオン２０〜３０
ｇ／ｌニッケルイオン０．５〜２、（１／４１、塩素酸
イオン１．５〜５ｇ／、０及び鉄イオン０．０５〜２．
（１／ｆＪである。The preferable component range of the blackening phosphate film treatment solution of the present invention is 2 to 5 g/ρ of zinc ion, 20 to 30 g/ρ of phosphate ion,
g/l nickel ions 0.5-2, (1/41, chlorate ions 1.5-5 g/l, 0 and iron ions 0.05-2.
(1/fJ.
被処理物が焼入材等で表面硬度か高いものについては、
処理液にエツチング剤を添加すると良い。If the object to be treated has a high surface hardness such as quenched material,
It is recommended to add an etching agent to the processing solution.
そのエツチング剤としては、硫酸イオン、塩素イオン及
びフッ素イオンであり、最適添加量は０．２〜１．５ｇ
／ｆＪである。The etching agents are sulfate ions, chloride ions, and fluorine ions, and the optimum amount to add is 0.2 to 1.5 g.
/fJ.
本発明の処理液に、鉄イオンを維持し易くするために有
機キレート剤を添加する。その有機キレート剤としては
、クエン酸、酒石酸、グルコン酸、ＥＤＴＡ、ＮＴＡ、
コハク酸、タンニン酸及びリンゴ酸とその化合物や誘導
体である。この中で特に効果のあるものは、クエン酸、
酒石酸、ＥＤＴＡｌ”アリ、そ］１ＨＪ０．０５〜２．
０ｇ／ｌ である。An organic chelating agent is added to the treatment solution of the present invention in order to facilitate the maintenance of iron ions. The organic chelating agents include citric acid, tartaric acid, gluconic acid, EDTA, NTA,
Succinic acid, tannic acid and malic acid and their compounds and derivatives. Among these, the most effective ones are citric acid,
Tartaric acid, EDTA1, So] 1HJ0.05-2.
It is 0g/l.
本発明に於ける黒色化リン酸塩皮膜処理液に含有させる
ニッケルイオンはリン酸第−ニッケル、炭酸ニッケル、
酸化ニッケル等の可溶性塩によって供給されてよく、塩
素酸イオンはＮ、ａＣ，ＱＯ３、ＫＣｌ０ 、ＨＣｇ０
３等の可溶性塩及び／又は酸の形で供給されてよく、鉄
イオンは処理物又はスチールウールのような鉄材料、酸
化第一・鉄、リン酸第−・鉄のような可溶性塩によって
供給されて良い。The nickel ions contained in the blackening phosphate film treatment solution in the present invention include ferrous nickel phosphate, nickel carbonate,
Chlorate ions may be supplied by soluble salts such as nickel oxide, N, aC, QO3, KCl0, HCg0
Iron ions may be supplied in the form of soluble salts and/or acids such as ferrous salts such as ferrous oxides, ferrous oxides, ferrous phosphates, ferrous materials such as treated products or steel wool, etc. It's good to be done.
［実施例］
冷延鋼板（材質５ｔ）ＣＣ−１，７０Ｘ１５０Ｘ０．８
”）をアルカリ脱脂→水洗→酸洗（１３％塩酸、常温）
→水洗→皮膜化成処理→水洗→熱風乾燥→防錆油塗布（
パーカー興産、Ｎ０Ｘ−Ｒｕｓｔ−７７０１稀釈油で２
５％に稀釈する）→案内乾燥の工程で処理し、耐蝕性試
験を行う。なお、処理外観、皮膜付着量の試験は防錆油
塗布は行わない板について実施する。[Example] Cold rolled steel plate (material 5t) CC-1, 70X150X0.8
”), alkaline degreasing → water washing → pickling (13% hydrochloric acid, room temperature)
→ Water washing → Film chemical conversion treatment → Water washing → Hot air drying → Anti-rust oil application (
Parker Kosan, N0X-Rust-7701 diluted oil 2
(Dilute to 5%) → Treat with guided drying process and conduct corrosion resistance test. The treated appearance and film adhesion tests are conducted on boards that are not coated with anti-rust oil.
その結果を第１表に示す。The results are shown in Table 1.
尚、耐蝕性試験は、室内乾燥１週間後に塩水噴霧試験器
にてＪ Ｉｓ−に−２２４６に準拠して発錆までの時間
を調べる。In the corrosion resistance test, after one week of indoor drying, the time until rusting is determined using a salt spray tester in accordance with JIS-2246.
処理外観は、肉眼にて色調の状態を観察する。The treated appearance is determined by observing the color tone with the naked eye.
（以下余白）
［発明の効果］
以上説明したように本発明に係る黒色化リン酸塩皮膜処
ｙＪ！液で鉄鋼材料の表面処理に適用すれば、従来の黒
色化処理に比べて処理液の温度が７７〜８３℃と低温で
処理することができると共に、処理時間も１０分程度で
あって短時間で処理することができ、経済性及び作業性
に優れるばかりでなく、鉄鋼表面に形成された皮膜は耐
蝕性、密着性及び外観においても優れたものとなる等の
種々の優れた効果を発する。(The following is a blank space) [Effects of the Invention] As explained above, the blackening phosphate film treatment according to the present invention yJ! If the liquid is applied to surface treatment of steel materials, the temperature of the treatment liquid can be lowered to 77-83℃ compared to conventional blackening treatment, and the treatment time is about 10 minutes, which is a short time. Not only is it excellent in economy and workability, but the film formed on the steel surface has various excellent effects such as excellent corrosion resistance, adhesion, and appearance.
Claims (3)
鉛処理液に、ニッケルイオン０．０５〜５ｇ／ｌ、塩素
酸イオン０．５〜８ｇ／ｌ及び鉄イオン０．０２〜４ｇ
／ｌを含むことを特徴とする鉄鋼材料の黒色化リン酸塩
皮膜処理液。(1) Add 0.05 to 5 g/l of nickel ions, 0.5 to 8 g/l of chlorate ions, and 0.02 to 4 g of iron ions to a zinc phosphate treatment solution that does not contain nitrate ions or nitrite ions.
A blackening phosphate film treatment solution for steel materials, characterized by containing /l.
の重量比が０．０７〜０．２５であることを特徴とする
前記（１）項記載の黒色化リン酸塩皮膜処理液。(2) The blackening phosphate film treatment solution according to item (1) above, wherein the weight ratio of zinc ions/phosphate ions in the zinc phosphate treatment solution is 0.07 to 0.25.
記（１）（２）項記載の黒色化リン酸塩皮膜処理液。(3) The blackening phosphate coating treatment solution described in items (1) and (2) above, characterized in that a small amount of a chelating agent is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13027084A JPS619580A (en) | 1984-06-25 | 1984-06-25 | Blackening phosphate treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13027084A JPS619580A (en) | 1984-06-25 | 1984-06-25 | Blackening phosphate treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS619580A true JPS619580A (en) | 1986-01-17 |
| JPS635471B2 JPS635471B2 (en) | 1988-02-03 |
Family
ID=15030276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13027084A Granted JPS619580A (en) | 1984-06-25 | 1984-06-25 | Blackening phosphate treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS619580A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4855898A (en) * | 1971-11-18 | 1973-08-06 | ||
| JPS57152473A (en) * | 1981-03-06 | 1982-09-20 | Metallgesellschaft Ag | Manufacture of phosphate film on metal surface |
-
1984
- 1984-06-25 JP JP13027084A patent/JPS619580A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4855898A (en) * | 1971-11-18 | 1973-08-06 | ||
| JPS57152473A (en) * | 1981-03-06 | 1982-09-20 | Metallgesellschaft Ag | Manufacture of phosphate film on metal surface |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS635471B2 (en) | 1988-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2312855A (en) | Method of coating aluminum | |
| US4278477A (en) | Metal treatment | |
| JP2806531B2 (en) | Zinc phosphate aqueous solution for surface treatment of iron or iron alloy material and treatment method | |
| US4168983A (en) | Phosphate coating composition | |
| JP2680618B2 (en) | Metal phosphate treatment method | |
| JPS6315991B2 (en) | ||
| US4486241A (en) | Composition and process for treating steel | |
| US4670066A (en) | Process for the treatment by chemical conversion of substrates of zinc or of one of its alloys, concentrate and bath used for performing this process | |
| US4600447A (en) | After-passivation of phosphated metal surfaces | |
| US4963198A (en) | Composition and process for treating metal surfaces | |
| US4705576A (en) | Acidic chromium containing coating solution for zinc or cadmium surfaces | |
| JPS63190178A (en) | Formation of phosphate film | |
| GB2072225A (en) | Process and composition for coating metal surfaces | |
| US4140551A (en) | Low temperature microcrystalline zinc phosphate coatings, compositions, and processes for using and preparing the same | |
| US4490185A (en) | Phosphating solutions and process | |
| US4897129A (en) | Corrosion resistant coating | |
| EP0056675B1 (en) | Pretreatment composition for phosphatising ferrous metals, and method of preparing the same | |
| US3338755A (en) | Production of phosphate coatings on metals | |
| US4749417A (en) | Corrosion resistant coating | |
| US3767476A (en) | Method and composition for phosphatizing steel under pressure | |
| JPH0411629B2 (en) | ||
| US4643778A (en) | Composition and process for treating steel | |
| US3372064A (en) | Method for producing black coatings on metal surfaces | |
| JPH0730454B2 (en) | Chemical conversion method of metal substrate | |
| US5888315A (en) | Composition and process for forming an underpaint coating on metals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |