JPS635471B2 - - Google Patents
Info
- Publication number
- JPS635471B2 JPS635471B2 JP59130270A JP13027084A JPS635471B2 JP S635471 B2 JPS635471 B2 JP S635471B2 JP 59130270 A JP59130270 A JP 59130270A JP 13027084 A JP13027084 A JP 13027084A JP S635471 B2 JPS635471 B2 JP S635471B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- phosphate
- ion
- film
- blackening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 iron ion Chemical class 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 32
- 229910019142 PO4 Inorganic materials 0.000 claims description 24
- 239000010452 phosphate Substances 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229940005989 chlorate ion Drugs 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000003449 preventive effect Effects 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229940085991 phosphate ion Drugs 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 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 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 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
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000047 product 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
- 238000005406 washing Methods 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
- 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
- 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
- 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
- 239000013522 chelant Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940116007 ferrous phosphate Drugs 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
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 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
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 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)
Description
［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処理方法に関するも
のである。
［従来例］
従来、鉄鋼材料の表面を黒色にする方法として
は、黒染法、リン酸マンガン系化成法、リン酸亜
鉛系化成法及び、塗装法があることは公知の技術
である。まず黒染法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。リン酸マンガン系化成
法は95〜沸騰状態で20〜30分処理してリン酸マン
ガン系皮膜を作る。これは耐摩耗性及び耐蝕性は
良いが、皮膜が粗く又高温で長時間処理しなけれ
ばならないので作業性も悪い。リン酸亜鉛系化成
法により得られる皮膜は、通常灰色の皮膜が得ら
れるが、亜硝酸イオンや塩素酸イオンを含まない
リン酸亜鉛系皮膜処理液に２価鉄イオンを含有さ
せると90〜沸騰状態で20〜30分間処理することに
よりリン酸亜鉛鉄皮膜が化成され、外観が黒色に
近い灰色を得ることが出来、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
含んでおり公害上好ましくない塗装法は外観は良
好であるが、密着性に問題があり塗装コストが高
い。
［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
させた後、防錆油を塗布して皮膜を形成させる方
法を提供することを目的とするものである。
［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、鉄鋼材料に、亜鉛イオン５ｇ／以下、リン
酸イオン20〜30ｇ／、ニツケルイオン0.5〜５
ｇ／、塩素酸イオン1.5〜５ｇ／、有機キレ
ート剤0.05〜2.0ｇ／、および鉄イオン0.05〜２
ｇ／を含み、亜鉛イオン／リン酸イオンの重量
比が0.07超〜0.25未満であつて硝酸イオンおよび
亜硝酸イオンを含まないリン酸塩皮膜処理液にて
黒色皮膜を化成させた後、防錆油を塗布すること
を特徴とする黒色化リン酸塩処理方法である。
本発明における処理液は、リン酸亜鉛処理液に
ニツケルイオン、塩素酸イオン及び鉄イオンを共
存させたものであつて、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、リン酸塩皮膜処理液中の亜鉛
イオン／リン酸イオンの重量比を限定することに
よつ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。
次に各イオン濃度の限定理由を述べる。
亜鉛イオンは５ｇ／以下が適切であり、５
ｇ／よりも多くなると化成皮膜の黒色化が不完
全となるので好ましくない。
リン酸イオンの濃度は20ｇ／未満だと化成さ
れるリン酸塩皮膜の耐食性が弱くなるので好まし
くない。又30ｇ／よりも多くすることは経済的
に好ましくない。
ニツケルイオンは、0.5ｇ／未満になるとリ
ン酸塩皮膜の黒色化が不充分となり、５ｇ／以
上になると経済的に不利である。
塩素酸イオンは、0.5ｇ／未満になるとリン
酸塩皮膜の化成性および黒色化が不充分であり、
５ｇ／を超え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。
鉄イオンは、0.05ｇ／未満になると、リン酸
塩皮膜の黒色化が不充分であり、２ｇ／を超え
るとリン酸塩皮膜結晶が粗くなり耐蝕性が劣化す
る。
リン酸塩皮膜処理液中の亜鉛イオン／リン酸イ
オンの重量比は、0.07以下だ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、
0.25以上だとリン酸塩皮膜の黒色化が不充分とな
る。
本発明の黒色化リン酸塩皮膜処理液の好ましい
亜鉛イオンの成分範囲は、２〜５ｇ／である。
被処理物が焼入材等で表面硬度が高いものにつ
いては、処理液にエツチング剤を添加すると良
い。そのエツチング剤としては、硫酸イオン、塩
素イオン及びフツ素イオンであり、それから選ば
れる１種又は２種以上のエツチング剤の適切な添
加量は0.2〜1.5ｇ／である。
本発明におけるリン酸塩皮膜処理液には酸化剤
である塩素酸イオンが含まれるので、Fe2+→
Fe3+の反応により鉄イオンを0.05〜２ｇ／の範
囲で処理液中に維持するのが困難となる。よつて
発明における処理液に、鉄イオンを維持し易くす
るために鉄イオンとキレート結合可能な有機キレ
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、EDTAであり、
その量は0.05〜2.0ｇ／である。
従来塩素酸イオン又は亜硝酸イオン存在下で
は、リン酸塩皮膜処理液中に鉄イオンを0.05〜２
ｇ／含有させることが不可能とされていたが、
本発明においては、リン酸塩皮膜処理液中の亜鉛
イオン濃度を低めとし、リン酸イオン濃度を高め
とし、亜硝酸イオン及び硝酸イオンを含有させ
ず、鉄イオンとキレート結合可能な有機キレート
剤を含有させることによつて前記不可能を可能と
なした。
本発明に於ける黒色化リン酸塩皮膜処理液に含
有させるニツケルイオンはリン酸第一ニツケル、
炭酸ニツケル、酸化ニツケル等の可溶性塩によつ
て供給されてよく、塩素酸イオンはNaClO3、
KClO3、HClO3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、リン酸第一
鉄のような可溶性塩によつて供給されて良い。
［実施例］
冷延鋼板（材質Spcc−１、70×150×0.8mm）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、Nox−Rust−7701稀釈油で
25％に稀釈する）→室内乾燥の工程で処理し、耐
蝕性試験を行う。なお、処理皮膜外観、皮膜重量
の試験は防錆油塗布は行わない板について実施す
る。
その結果を第１表に示す。
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JIS―Ｋ―2246に準拠して発錆まで
の時間を調べる。
処理皮膜外観は、肉眼にて色調の状態を観察す
る。
[Industrial Application Field] The present invention relates to a phosphate treatment method that is applied to the surface treatment of steel materials and blackens the steel surface. [Conventional Example] Conventionally, methods for blackening the surface of steel materials include a black dyeing method, a manganese phosphate-based chemical conversion method, a zinc phosphate-based chemical conversion method, and a painting method. First, the black dyeing method uses an alkaline solution at 140 to 150
An iron oxide film is created by immersion treatment at ℃ for 20 to 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. In the manganese phosphate chemical conversion method, a manganese phosphate film is created by treating at a boiling temperature of 95 to 20 minutes for 20 to 30 minutes. Although this has good wear resistance and corrosion resistance, it has a rough coating and has poor workability because it must be treated at high temperatures for a long time. The film obtained by the zinc phosphate chemical conversion method is usually a gray film, but when divalent iron ions are added to the zinc phosphate film treatment solution that does not contain nitrite ions or chlorate ions, the temperature rises from 90 to 100% boiling. By treating the product for 20 to 30 minutes in this state, the zinc iron phosphate film is chemically converted, giving it a gray appearance close to black.Although the corrosion resistance is good, the film is rough. Furthermore, the treatment liquid contains NOx as an oxidizing agent, which is undesirable in terms of pollution. Although the coating method has a good appearance, it has problems with adhesion and is expensive. [Object of the invention] The present invention eliminates the drawbacks of the conventional example, and after forming a phosphate film on the surface of a steel material, which has good workability, has a dense black appearance, and has excellent corrosion resistance, The object of the present invention is to provide a method for forming a film by applying rust preventive oil. [Structure of the Invention] The present invention, which has been made to achieve the above object, contains zinc ions of 5g/or less, phosphate ions of 20 to 30g/, and nickel ions of 0.5 to 5g/.
g/, chlorate ion 1.5-5 g/, organic chelating agent 0.05-2.0 g/, and iron ion 0.05-2
After chemically converting a black film with a phosphate film treatment solution containing g/, the weight ratio of zinc ions / phosphate ions is more than 0.07 to less than 0.25, and does not contain nitrate ions or nitrite ions, rust prevention This is a blackening phosphate treatment method characterized by applying oil. The treatment solution in the present invention is a zinc phosphate treatment solution in which nickel ions, chlorate ions, and iron ions coexist, and it quickly converts iron eluted from the object to be treated into trivalent iron ions and precipitates them. It is characterized in that it does not substantially contain nitrate ions and nitrite ions, which would otherwise become components outside the reaction system. By limiting the weight ratio of zinc ions/phosphate ions in the phosphate coating treatment solution, blackening is further promoted and a coating with excellent blackening can be obtained. Next, the reason for limiting each ion concentration will be described. The appropriate amount of zinc ion is 5g/or less;
If it exceeds g/, the blackening of the chemical conversion coating will be incomplete, which is not preferable. If the concentration of phosphate ions is less than 20 g/min, the corrosion resistance of the chemically formed phosphate film will be weakened, which is not preferable. Moreover, it is economically unfavorable to increase the amount more than 30g/. If the amount of nickel ion is less than 0.5 g/l, the blackening of the phosphate film will be insufficient, and if it is more than 5 g/l, it will be economically disadvantageous. When the amount of chlorate ion is less than 0.5g/concentration, the chemical formation and blackening of the phosphate film are insufficient.
If the amount exceeds 5 g, the oxidizing power will be too strong and it will be difficult to maintain iron ions in the treatment liquid. If the amount of iron ions is less than 0.05 g, the blackening of the phosphate film will be insufficient, and if it exceeds 2 g, the crystals of the phosphate film will become coarse and the corrosion resistance will deteriorate. If the weight ratio of zinc ions/phosphate ions in the phosphate film 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.
If it is more than 0.25, the blackening of the phosphate film will be insufficient. The preferable range of zinc ions in the blackening phosphate film treatment solution of the present invention is 2 to 5 g/g. If the object to be treated has a high surface hardness, such as a hardened material, it is preferable to add an etching agent to the treatment liquid. The etching agents include sulfate ions, chlorine ions, and fluoride ions, and the appropriate amount of one or more etching agents selected from them is 0.2 to 1.5 g. Since the phosphate coating treatment solution in the present invention contains chlorate ions, which are oxidizing agents, Fe 2+ →
Due to the Fe 3+ reaction, it becomes difficult to maintain iron ions in the treatment solution in a range of 0.05 to 2 g/. Therefore, an organic chelating agent capable of forming a chelate bond with iron ions is added to the treatment liquid in the 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 are citric acid, tartaric acid, and EDTA.
The amount is 0.05-2.0g/. Conventionally, in the presence of chlorate ions or nitrite ions, iron ions were added to the phosphate film treatment solution by 0.05 to 2
g/Although it was considered impossible to contain it,
In the present invention, the concentration of zinc ions in the phosphate film treatment solution is kept low, the concentration of phosphate ions is made high, nitrite ions and nitrate ions are not contained, and an organic chelating agent capable of chelating with iron ions is used. The above-mentioned impossibility has been made possible by incorporating the above. The nickel ions contained in the blackening phosphate coating treatment solution in the present invention include nickel phosphate,
The chlorate ions may be supplied by soluble salts such as nickel carbonate, nickel oxide , etc.
It may be supplied in the form of soluble salts and/or acids such as KClO 3 , HClO 3 , and iron ions may be supplied in the form of treated products or iron materials such as steel wool, soluble salts such as ferrous oxide, ferrous phosphate, etc. Powered by OK. [Example] Cold-rolled steel plate (material Spcc-1, 70 x 150 x 0.8 mm) was degreased with alkaline → washed with water → pickled (13% hydrochloric acid, room temperature) →
Water washing → Film chemical conversion treatment → Water washing → Hot air drying → Anti-rust oil application (Parker Kosan, Nox-Rust-7701 diluted oil)
(diluted to 25%) → Treated with an indoor drying process and conducted a corrosion resistance test. Note that tests for the treated film appearance and film weight are conducted on boards that are not coated with anti-rust oil. The results are shown in Table 1. 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-K-2246. The appearance of the treated film is determined by observing the color tone with the naked eye.
【表】
［発明の効果］
以上説明したように本発明の黒色化リン酸塩処
理方法を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リン酸塩皮膜処理液の温度
を77〜83℃と低温に維持して処理することができ
ると共に、処理時間も10分程度であつて短時間で
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。[Table] [Effects of the Invention] As explained above, if the blackening phosphate treatment method of the present invention is applied to the surface treatment of steel materials, the temperature of the phosphate film treatment solution will be lower than that of the conventional blackening treatment. The process can be maintained at a low temperature of 77 to 83℃, and the processing time is about 10 minutes, making it possible to process in a short period of time. The formed film exhibits various excellent effects such as excellent corrosion resistance, adhesion, and appearance.
Claims (1)
30ｇ／、ニツケルイオン0.5〜５ｇ／、塩素
酸イオン1.5〜５ｇ／、鉄イオンとキレート結
合可能な有機キレート剤0.05〜2.0ｇ／、およ
び鉄イオン0.05〜２ｇ／を含み、亜鉛イオン／
リン酸イオンの重量比が0.07超〜0.25未満であつ
て硝酸イオンおよび亜硝酸イオンを含まないリン
酸塩皮膜処理液にて黒色皮膜を化成させた後、防
錆油を塗布することを特徴とする黒色化リン酸塩
処理方法。 ２ リン酸塩皮膜処理液に、硫酸イオン、塩素イ
オンおよびフツ素イオンから選ばれる１種又は２
種以上のイオンを0.2〜1.5ｇ／含むものである
特許請求の範囲第１項記載の黒色化リン酸塩処理
方法。[Claims] 1. Zinc ion 5g/or less, phosphate ion 20~
30g/, nickel ion 0.5-5g/, chlorate ion 1.5-5g/, organic chelating agent capable of chelating with iron ion 0.05-2.0g/, and iron ion 0.05-2g/, zinc ion/
A black film is formed using a phosphate film treatment solution with a weight ratio of phosphate ions of more than 0.07 to less than 0.25 and does not contain nitrate ions or nitrite ions, and then a rust preventive oil is applied. Blackening phosphate treatment method. 2 One or two selected from sulfate ions, chlorine ions, and fluorine ions are added to the phosphate film treatment solution.
The blackening phosphate treatment method according to claim 1, which contains 0.2 to 1.5 g of ions of different species or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13027084A JPS619580A (en) | 1984-06-25 | 1984-06-25 | Treating solution for blackened phosphate film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13027084A JPS619580A (en) | 1984-06-25 | 1984-06-25 | Treating solution for blackened phosphate film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS619580A JPS619580A (en) | 1986-01-17 |
| JPS635471B2 true 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 | Treating solution for blackened phosphate film |
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 |
|---|---|
| JPS619580A (en) | 1986-01-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |