JPH02101174A - Treatment with zinc phosphate for cold working - Google Patents
Treatment with zinc phosphate for cold workingInfo
- Publication number
- JPH02101174A JPH02101174A JP63252435A JP25243588A JPH02101174A JP H02101174 A JPH02101174 A JP H02101174A JP 63252435 A JP63252435 A JP 63252435A JP 25243588 A JP25243588 A JP 25243588A JP H02101174 A JPH02101174 A JP H02101174A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- acid
- treatment
- phosphate
- contg
- 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
- 238000005482 strain hardening Methods 0.000 title claims abstract description 9
- 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 title claims description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims description 8
- -1 etc. Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 230000003750 conditioning effect Effects 0.000 claims abstract description 15
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 13
- 239000010959 steel Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940005657 pyrophosphoric acid Drugs 0.000 claims abstract description 6
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229940085991 phosphate ion Drugs 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010802 sludge Substances 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004202 carbamide Substances 0.000 abstract description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 abstract description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005491 wire drawing Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 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
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 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
- C23C22/23—Condensed phosphates
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、鉄鋼材を冷間加工する場合に施される冷間加
工潤滑処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a cold working lubrication treatment method applied when cold working steel materials.
（従来の技術）
従来、鉄鋼材を冷間加工する場合、被加工材と工具との
金属表面の摩擦を防止するために被加工材に金属石ケン
のキャリアーとして働く表面処理を施すのが普通である
。(Conventional technology) Conventionally, when cold working steel materials, it is common to apply a surface treatment to the workpiece that acts as a carrier for metal soap in order to prevent friction between the metal surface of the workpiece and the tool. It is.
この表面処理として亜鉛イオン、鉄イオン、リン酸イオ
ン、硝酸イオンを含む処理液を用いることが行なわれて
いたが、この場合処理温度が８５℃〜９９℃と高く、し
かも処理時間り月０〜４０分と長い。また、鉄の酸塩と
思われるスラッジが発生し、処理浴槽に堆積し頻繁に清
掃が必要であった。This surface treatment has been carried out by using a treatment solution containing zinc ions, iron ions, phosphate ions, and nitrate ions, but in this case, the treatment temperature is as high as 85℃ to 99℃, and the treatment time is 0 to 100℃. It's 40 minutes long. In addition, sludge, believed to be iron salts, was generated and accumulated in the treatment bath, requiring frequent cleaning.
これを改善するために酸化剤として亜硝酸塩を処理液中
に配合する方法が提案され、処理時間の短縮や低温化が
やや可能になったものの、いまだ十分でない。さらにス
ラッジも少なくなったものの、やはり処理浴槽の掃除が
多かった。In order to improve this problem, a method has been proposed in which nitrite is added to the treatment solution as an oxidizing agent, and although it has become possible to shorten the treatment time and lower the temperature to some extent, it is still not sufficient. Furthermore, although there was less sludge, the treatment bath still required a lot of cleaning.
処理浴槽中に発生ずるスラッジを減少させる手法とし特
開昭５７−８２４７８号公報ではリン酸塩を主成分とし
チタン化合物と塩素酸塩を含む表面調整液で処理後、亜
硝酸イオンを促進剤とするリン酸亜鉛処理を実施する。As a method for reducing sludge generated in a treatment bath, JP-A No. 57-82478 discloses a method in which nitrite ions are used as an accelerator after treatment with a surface conditioning liquid containing phosphate as a main component and a titanium compound and chlorate. Perform zinc phosphate treatment.
特開昭５８−２５４８０号公報では、リン酸亜Ａ１
鉛処理浴に酸化剤として亜硝酸の外に過塩素酸塩を加え
ている。In Japanese Unexamined Patent Publication No. 58-25480, perchlorate is added in addition to nitrous acid as an oxidizing agent to the A1 lead phosphate treatment bath.
特開昭６１−７９７８２号公報ではチタンイオンを含む
表面調整液で処理後、浴中に３価の鉄イオンを含み浴中
ｐｌ−Ｔを３．３〜４，５に調整し、温度をＩＯ〜／１
０℃にしたリン酸亜鉛処理を実施する。ごれら公開さね
ている技術では浴中スラッジの減少は不充分で、八尾す
る結果を得ていない。In JP-A-61-79782, after treatment with a surface conditioning liquid containing titanium ions, the bath contains trivalent iron ions, the pl-T in the bath is adjusted to 3.3 to 4.5, and the temperature is adjusted to IO. ~/1
Perform zinc phosphate treatment at 0°C. The technology that we have published is insufficient to reduce sludge in the bath, and has not yielded satisfactory results.
（課題を解決するための手段）
本発明者らは、スラッジをほとんど発生しないで、短時
間に処理しうる冷間加工用の処理方法を検月の結果、本
発明をなすに至った。ずなわぢ、本発明は、鉄鋼材料を
チタンイオン１〜２０ｐｐｍを含み、ｐｒ−ｒｓ〜ＩＩ
に調整した表面調整液で処理し、次いで亜鉛イオン１〜
２０ｇ／ｌ、リン酸イオン５９／ρ以上、リン酸イオン
／硝酸イオンの比１／３以上、ピロリン酸あるいはトリ
ポリリン酸０．２〜２２／ｌ、鉄（ＩＴ）イオン０．１
〜２０ｇ／ｌ、該鉄０１）イオンを酸化上ず亜硝酸イオ
ンを分解する物質０．０５ｙ／ρ以」−含有する化成液
で処理す塩、トリポリリン酸、トリポリリン酸のアルカ
リ塩またはアンモニウム塩等が挙げられる。リン酸イオ
ンの濃度は特に限定的ではないが、０．５〜１０ｇ／ｌ
、好ましくは１〜４９／Ｑである。０．５ｇ／ρ以下で
あると、チタンイオンを安定的に浴中に維持できなくな
る。Ｉ０９／ρを越えると添加量に比例する効果がみら
れない。(Means for Solving the Problems) The present inventors have conducted extensive research into a cold working treatment method that can be processed in a short period of time without generating much sludge, and as a result, have arrived at the present invention. Zunawaji, the present invention is characterized in that the steel material contains 1 to 20 ppm of titanium ions and has pr-rs to II
treated with a surface conditioning liquid adjusted to
20g/l, phosphate ion 59/ρ or more, phosphate ion/nitrate ion ratio 1/3 or more, pyrophosphoric acid or tripolyphosphoric acid 0.2-22/l, iron (IT) ion 0.1
~20g/l, a substance that oxidizes iron 01) ions and decomposes nitrite ions, 0.05y/ρ or more - treated with a chemical solution containing salts, tripolyphosphoric acid, alkali salts or ammonium salts of tripolyphosphoric acid, etc. can be mentioned. The concentration of phosphate ions is not particularly limited, but is 0.5 to 10 g/l.
, preferably 1 to 49/Q. If it is less than 0.5 g/ρ, titanium ions cannot be stably maintained in the bath. When I09/ρ is exceeded, no effect proportional to the amount added is observed.
本発明の次の工程は特定の組成の化成液で前記表面調整
した鉄鋼材料を処理することである。化成液は亜鉛イオ
ンを１〜２０ｇ、Ｑ、好ましくは２〜１０ｇ／１２含む
。Ｉ ｇ／ｃ以下では皮膜形成が不十分となる。２０９
／ρ以Ｆでは経済性が悪い。亜鉛イオンは亜鉛化合物を
オルトリン酸および硝酸で溶解し、化成処理剤とする。The next step of the present invention is to treat the surface-conditioned steel material with a chemical liquid of a specific composition. The chemical conversion solution contains zinc ions in an amount of 1 to 20 g/12, preferably 2 to 10 g/12. If it is less than I g/c, film formation will be insufficient. 209
/ρ or more F is not economical. Zinc ions dissolve zinc compounds with orthophosphoric acid and nitric acid to form a chemical conversion treatment agent.
亜鉛化合物の例としては酸化亜鉛、金属亜鉛、炭酸亜鉛
、水酸化亜鉛、硝酸亜鉛等が挙げられる。Examples of zinc compounds include zinc oxide, zinc metal, zinc carbonate, zinc hydroxide, zinc nitrate, and the like.
リン酸イオンは−に述の表面調整剤で述へたリン酸イオ
ンの供給源を用いる。リン酸イオンの濃度は５ ｇ／Ｑ
以−ｈ、好ましくはＩ０９／ρ０９／ρる。As for the phosphate ions, the sources of phosphate ions mentioned above in connection with the surface conditioner mentioned in - are used. The concentration of phosphate ion is 5 g/Q
-h, preferably I09/ρ09/ρ.
５ｇ／ρ以下であると、皮膜形成が不十分となる。If it is less than 5 g/ρ, film formation will be insufficient.
ることを特徴とする冷間加工用リン酸亜鉛処理方法を提
供する。A method for treating zinc phosphate for cold working is provided.
本発明の最初の工程は表面調整液で鉄鋼材料を処理する
ことである。表面調整液はチタンイオンを１〜２０ｐｐ
ｍを含む。チタンイオンは硫酸チタン、硫酸ヂタニル、
酸化チタン等により供給される。チタンイオンカ月ｐｐ
ｍ以下であると、皮膜形成が不十分になり、スケ、ムラ
、錆が発生ずることがある。２０ｐｐｍを越えると、効
果の向」―が見られず経済的でない。この表面調整液の
ｐＨは、８〜ＩＩ、好ましくはｐＨ約９である。ｐ Ｉ
−（が８以下であるとチタンイオンが不安定となり、表
面調整効果が損なわれる。ｐＨ１１以上になるとアルカ
リが強すぎ、化成浴の中和が進みすぎ、浴のバランスを
くずす。Ｉ）Ｈを調整するために通常炭酸ソーダや第三
リン酸ソーダ等を加える。The first step of the invention is to treat the steel material with a surface conditioning fluid. Surface conditioning liquid contains 1-20pp of titanium ions.
Contains m. Titanium ions include titanium sulfate, ditanyl sulfate,
Supplied by titanium oxide, etc. titanium ion ka month pp
If it is less than m, the film formation will be insufficient, and scratches, unevenness, and rust may occur. If it exceeds 20 ppm, no improvement in effectiveness can be seen and it is not economical. The pH of this surface conditioning liquid is 8 to II, preferably about pH 9. p I
If -( is less than 8, titanium ions will become unstable and the surface conditioning effect will be impaired. If the pH is more than 11, the alkali will be too strong and the chemical bath will be neutralized too much, destroying the balance of the bath.I) H To make adjustments, soda carbonate, tribasic sodium phosphate, etc. are usually added.
表面調整液はリン酸イオンが主成分であり、リン酸イオ
ンの供給源はオルトリン酸、オルトリン酸のアルカリ塩
またはアンモニウム塩、ピロリン酸、ピロリン酸のアル
カリ塩またはアンモニウム上記イオンのほかに硝酸イオ
ンが金属イオン保持を保持するために添加される。硝酸
イオンは種々の硝酸塩または硝酸そのものの形として添
加される。硝酸イオンの添加量はリン酸イオン／硝酸イ
オンの比として表され、この比り月／３以上、好ましく
はＩ／］以上である。１／３より少ないと皮膜形成が不
足する。The main component of the surface conditioning liquid is phosphate ions, and the sources of phosphate ions are orthophosphoric acid, alkali salts or ammonium salts of orthophosphoric acid, pyrophosphoric acid, alkali salts of pyrophosphoric acid, or ammonium.In addition to the above ions, nitrate ions are also used. Added to maintain metal ion retention. Nitrate ions are added in the form of various nitrates or nitric acid itself. The amount of nitrate ion added is expressed as a ratio of phosphate ion/nitrate ion, and this ratio is 1/3 or more, preferably I/] or more. If it is less than 1/3, film formation will be insufficient.
本発明の化成液にはピロリン酸あるいはトリポリリン酸
が０２〜２ｇ／Ｑ、好ましくは０２〜１９／ρ添加され
る。これらのピロリン酸またはトリポリリン酸は鉄イオ
ンが蓄積すると皮膜結晶の粗大化、皮膜量の上昇が起こ
るのを抑制する。０２９／Ｑ以下であるとその抑制効果
が低い。２ｇ／Ｉ２を越えると抑制効果が大きくなりす
ぎる。Pyrophosphoric acid or tripolyphosphoric acid is added to the chemical solution of the present invention in an amount of 02 to 2 g/Q, preferably 02 to 19/ρ. These pyrophosphoric acids or tripolyphosphoric acids suppress the occurrence of coarsening of the film crystals and increase in the amount of the film when iron ions accumulate. If it is less than 029/Q, the suppressing effect will be low. If it exceeds 2 g/I2, the suppressing effect becomes too large.
本発明の化成液中には素材より溶解した第１鉄イオン（
Ｆｅ（ＩＩ））０．１〜２０ｇ／Ｃを含有する。０．１
ｇ／ρ程度は鉄の溶解によりずぐに生成する量である。The chemical solution of the present invention contains ferrous ions (
Contains 0.1 to 20 g/C of Fe(II)). 0.1
The amount of about g/ρ is the amount that is quickly generated by dissolving iron.
２０ｇ／ρを越えると鉄のエツチングが抑制され、処理
時間が長くなる。If it exceeds 20 g/ρ, iron etching will be suppressed and the processing time will become longer.
本発明の化成液中には上記第１鉄イオンを酸化せず亜硝
酸イオンを分解する物質を００５ｇ／Ｑ。The chemical solution of the present invention contains 0.05 g/Q of a substance that does not oxidize the ferrous ions but decomposes the nitrite ions.
以、Ｆ、添加する。このような物質の例としては尿素、
スルファミン酸、ヂオ硫酸、亜硫酸等が挙げられる。亜
硝酸イオンは鉄イオンの酸化により硝酸イオンが還元さ
れて生成する。この還元生成した亜硝酸イオンは第）鉄
イオンを酸化し、スラッジの発生を促進する。したがっ
て、この亜硝酸イオンの発生を防ぐ化合物を添加する必
要がある。００５ｇ／ρより少ないとその亜硝酸イオン
の発生を抑制することは困難である。Hereafter, F is added. Examples of such substances are urea,
Examples include sulfamic acid, diosulfuric acid, sulfurous acid, and the like. Nitrite ions are generated by reducing nitrate ions through the oxidation of iron ions. The nitrite ions produced by this reduction oxidize the ferrous ions and promote the generation of sludge. Therefore, it is necessary to add a compound that prevents the generation of nitrite ions. If the amount is less than 0.005 g/ρ, it is difficult to suppress the generation of nitrite ions.
化成浴中に１−記イオンの他にニッケルイオン、銅イオ
ン、フッ素化合物等の添加が可能である。In addition to the ions described in 1- above, nickel ions, copper ions, fluorine compounds, etc. can be added to the chemical conversion bath.
ニッケルイオンは水酸化ニッケル、炭酸ニッケル、酸化
ニッケル、硝酸ニッケル等を供給源をとし、銅イオン等
は水酸化銅、炭酸銅、酸化銅、硝酸ニッケルを供給源と
ケる。フッ素化合物の例としてはフッ酸、ケイフッ酸、
ポウフッ酸等が挙げられる。Nickel ions are supplied from nickel hydroxide, nickel carbonate, nickel oxide, nickel nitrate, etc., and copper ions are supplied from copper hydroxide, copper carbonate, copper oxide, nickel nitrate, etc. Examples of fluorine compounds include hydrofluoric acid, hydrofluorosilicic acid,
Examples include porhydrofluoric acid.
ニッケルイオンの添加量は００２〜ｌ ｇ／Ｑが好適で
ある。また、銅イオンの添加量は０．０１〜０ 、２
（ｙ／Ｃ）が好適である。The amount of nickel ions added is preferably 0.02 to 1 g/Q. In addition, the amount of copper ions added is 0.01 to 0.2
(y/C) is preferred.
本発明の処理液の処理温度は特に限定的ではないが３０
〜６０℃、好ましくは４０〜５０℃が好ましい。また処
理時間は」１記処理温度により変化しうるが、好適には
４〜ｌＯ分である。Although the processing temperature of the processing liquid of the present invention is not particularly limited,
~60°C, preferably 40-50°C is preferred. Although the treatment time may vary depending on the treatment temperature described in 1., it is preferably 4 to 10 minutes.
本発明の化成液を用いた場合、その皮膜量は５〜１５９
／ＩＩ＋２．８〜１２ｇ／Ｒ’程度が好適である。When the chemical liquid of the present invention is used, the film amount is 5 to 159
/II+2.8 to 12 g/R' is suitable.
（発明の効果）
本発明によればスラッジの生成が従来の亜硝酸イオンを
使用するタイプに比較し１１５〜１１５０に減少する。(Effects of the Invention) According to the present invention, the generation of sludge is reduced to 115 to 1150 compared to the conventional type using nitrite ions.
これにより処理浴槽のスラッジ清掃に頻度が大幅に減少
あわせてこれにともなう薬品、エネルギー、労力等の節
約が可能になった。This has made it possible to significantly reduce the frequency of cleaning sludge in the treatment bath and to save on chemicals, energy, labor, etc.
（実施例） 本発明を実施例ににりさらに詳細に説明する。(Example) The present invention will be explained in more detail with reference to Examples.
実施例１
硬鋼線（ＳＷＲＩ−Ｉ６２）を下記工程でリン酸亜鉛処
理し、さらに潤滑剤（ニーシンＡ、共栄社４１１脂製）
を使用し伸線加工を行なった。伸線機は貯線型伸線機を
用い、ダイスは８枚使用し、伸線スピ一１・は８００ｍ
／分で３ｍｍφを９５１ｍφに伸線し、その時の減面率
は９０％であった。Example 1 A hard steel wire (SWRI-I62) was treated with zinc phosphate in the following process, and then a lubricant (Nishin A, manufactured by Kyoeisha 411 Seki) was added.
The wire drawing process was performed using. The wire drawing machine uses a storage type wire drawing machine, 8 dies are used, and the wire drawing speed is 800 m.
The wire was drawn from 3 mmφ to 951 mφ at a rate of 951 mφ, and the area reduction rate at that time was 90%.
リン酸亜鉛工程 酸洗−・水洗−表面調整＝化成処理−
＝水洗−・中和−＝乾燥
酸洗、塩酸１５％、鉄イオン１〜ＩＯ％を含む溶液中で
室温で３０分処理した。Zinc phosphate process Pickling - Water washing - Surface conditioning = Chemical conversion treatment -
= Water washing - Neutralization - Dry pickling, treated in a solution containing 15% hydrochloric acid and 1 to IO% iron ions at room temperature for 30 minutes.
表面調整 日本ペイント社製フィキソジン５Ｎ５（チタ
ンイオンを含む）を約０２％を水に溶解して使用し、室
温で１０秒間浸漬した。この表面調整剤の組成は表−１
に示す通りである。Surface Conditioning About 0.2% of Fixozin 5N5 (containing titanium ions) manufactured by Nippon Paint Co., Ltd. was dissolved in water and immersed for 10 seconds at room temperature. The composition of this surface conditioning agent is shown in Table 1.
As shown.
化成液、化成処理剤Ｉ（酸化亜鉛１０％、リン酸３０％
、硝酸８％で溶解したもの）に対し、添加剤（ピロリン
酸ナトリウム、尿素）で水溶液を作り、５０℃に昇温し
、スチールウールを用いて鉄を溶解させた。第１鉄以外
のイオン組成は硝酸亜鉛、リン酸、硝酸等で表−１に示
すように補正を行なった。Chemical liquid, chemical conversion treatment agent I (zinc oxide 10%, phosphoric acid 30%
, dissolved in 8% nitric acid), an aqueous solution was prepared with additives (sodium pyrophosphate, urea), the temperature was raised to 50°C, and iron was dissolved using steel wool. The ion composition other than ferrous iron was corrected using zinc nitrate, phosphoric acid, nitric acid, etc. as shown in Table 1.
中和・日本ペイント社（Ｎｌ）フープＮｏ、６）を使用
した。１％の溶液中で８０６０３分間処理を行なっ実施
例２〜７
実施例１と同様に処理を行なったが、表−１に示すよう
に、表面調整剤および化成液を調整した。Neutral Nippon Paint Co., Ltd. (Nl) Hoop No. 6) was used. Examples 2 to 7 A treatment was carried out for 80603 minutes in a 1% solution.The treatment was carried out in the same manner as in Example 1, but the surface conditioner and chemical solution were adjusted as shown in Table 1.
比較例１〜６
実施例１に準じて表面調整、化成浴を調整して実施した
。ただし、実施例５は化成浴凋整の途中、浴中にスラッ
ジが発生してきたため、処理は行なっていない。比較例
７の場合、現在法〈実施されているタラノドロウＩＯＮ
、トーナー３０１（（＋−１本ペイント社製）を用い実
施した。Comparative Examples 1 to 6 Comparative Examples 1 to 6 were carried out in accordance with Example 1, with surface conditioning and chemical conversion baths adjusted. However, in Example 5, sludge was generated in the chemical bath during conditioning, so no treatment was performed. In the case of Comparative Example 7, the current method
, was carried out using Toner 301 (manufactured by +-1 Paint Co., Ltd.).
評価方法 Ｉ 処理外観は肉眼で判定した。Evaluation method I: The appearance of the treatment was determined visually.
２゜皮膜量はクロム酸水溶液剥離による重量法で測定し
た。処理線を７５℃に加熱した５％クロム酸水溶液に１
０分間浸漬し、皮膜を剥離する。The amount of the 2° film was measured gravimetrically by stripping with an aqueous chromic acid solution. 1 in a 5% chromic acid aqueous solution heated to 75°C.
Immerse for 0 minutes and peel off the film.
処理線の剥離後の重量差を測定し、皮膜量を算出する。The weight difference after peeling off the treated line is measured and the amount of film is calculated.
４、伸線性は最終ダイスでの伸線でできた線材数量を伸
線性とした。4. Wire drawability was defined as the number of wires drawn in the final die.
特許出願人 日本ペイント株式会社
代 理 人 弁理士 前出 葆 ほか２名［式中、Ｗｏ
−剥離前の重量（ｇ）、Ｗｌは剥離後の重量（＋？）、
Ｓは処理線表面積（Ｍ２）を示す。］で求めノこ。Patent applicant: Nippon Paint Co., Ltd. Representative: Patent attorney: Mr. Maeda and two others [During the ceremony, Mr.
- Weight before peeling (g), Wl is weight after peeling (+?),
S represents the treated line surface area (M2). ] So search for it.
３、スラッジ発生は肉眼で測定した。ただし比較例７は
化成浴を十分撹拌し、１００好のザンプルをスラッジ濾
過して乾燥し、重量を測定した。3. Sludge generation was measured visually. However, in Comparative Example 7, the chemical conversion bath was thoroughly stirred, and 100 samples were filtered through sludge, dried, and weighed.
スラッジ発成量は
Ｗ Ｖ
１００ Ａ
１式中、Ｗはスラッジ量（ｇ）、■は処理浴の大きさＣ
ｆｆ＆）、Ａは処理面積（Ｍ２）を示す。］から求めた
。The amount of sludge generated is W V 100 A In the formula, W is the amount of sludge (g), ■ is the size of the treatment bath C
ff&), A indicates the processing area (M2). ].
事件の表示 昭和 ６３年特許願第 発明の名称 てテ 冷間加工用リン酸亜鉛処理方法 補正をする者 事件との関係Display of incidents 1986 Patent Application No. name of invention Tete Zinc phosphate treatment method for cold working person who makes corrections Relationship with the incident
Claims (1)
Ｈ８〜１１に調整した表面調整液で処理し、次いで亜鉛
イオン１〜２０ｇ／ｌ、リン酸イオン５ｇ／ｌ以上、リ
ン酸イオン／硝酸イオンの比１／３以上、ピロリン酸あ
るいはトリポリリン酸０．２〜２ｇ／ｌ、鉄（II）イオ
ン０．１〜２０ｇ／ｌ、該鉄（II）イオンを酸化せず亜
硝酸イオンを分解する物質０．０５ｇ／ｌ以上含有する
化成液で処理することを特徴とする冷間加工用リン酸亜
鉛処理方法。1. Steel materials containing 1 to 20 ppm of titanium ions, p
It is treated with a surface conditioning liquid adjusted to H8-11, and then treated with zinc ions of 1-20 g/l, phosphate ions of 5 g/l or more, a phosphate ion/nitrate ion ratio of 1/3 or more, and pyrophosphoric acid or tripolyphosphoric acid of 0. Treat with a chemical solution containing 2 to 2 g/l, iron (II) ions 0.1 to 20 g/l, and 0.05 g/l or more of a substance that does not oxidize the iron (II) ions and decomposes nitrite ions. A zinc phosphate treatment method for cold working, characterized by:
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252435A JPH02101174A (en) | 1988-10-06 | 1988-10-06 | Treatment with zinc phosphate for cold working |
| EP89310196A EP0363200A3 (en) | 1988-10-06 | 1989-10-05 | Improvement of zinc phosphate treatment for cold working |
| KR1019890014407A KR900006033A (en) | 1988-10-06 | 1989-10-06 | Zinc Phosphate Treatment for Cold Processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252435A JPH02101174A (en) | 1988-10-06 | 1988-10-06 | Treatment with zinc phosphate for cold working |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02101174A true JPH02101174A (en) | 1990-04-12 |
Family
ID=17237332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63252435A Pending JPH02101174A (en) | 1988-10-06 | 1988-10-06 | Treatment with zinc phosphate for cold working |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0363200A3 (en) |
| JP (1) | JPH02101174A (en) |
| KR (1) | KR900006033A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE116694T1 (en) * | 1990-06-19 | 1995-01-15 | Henkel Corp | TREATMENT METHOD OF ALUMINUM OR SHEET CANS TO INCREASE THE CORROSION RESISTANCE AND TO REDUCE THE COEFFICIENT OF FRICTION AND COMPOSITION OF THE TREATMENT LIQUID. |
| US5370909A (en) * | 1990-06-19 | 1994-12-06 | Henkel Corporation | Liquid composition and process for treating aluminum or tin cans to impart corrosion resistance and mobility thereto |
| DE4326388A1 (en) * | 1993-08-06 | 1995-02-09 | Metallgesellschaft Ag | Process for the phosphating treatment of one-sided galvanized steel strip |
| JP3072757B2 (en) * | 1996-01-10 | 2000-08-07 | 日本ペイント株式会社 | High durability surface conditioner |
| CA2271730A1 (en) * | 1996-11-27 | 1998-06-04 | Henkel Corporation | Aqueous composition and process for preparing metal substrate for cold forming |
| JP3973323B2 (en) * | 1998-08-13 | 2007-09-12 | 日本ペイント株式会社 | Non-chromium treatment with sulfur-containing and phosphorus-containing compounds |
| KR20030062305A (en) * | 2003-07-10 | 2003-07-23 | (주)제이엔씨인더스트리 | Automatic welding system for tank |
| US11566330B2 (en) * | 2019-04-16 | 2023-01-31 | Ppg Industries Ohio, Inc. | Systems and methods for maintaining pretreatment baths |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6179782A (en) * | 1984-09-27 | 1986-04-23 | Nippon Parkerizing Co Ltd | Treatment of phosphate |
| JPS63130781A (en) * | 1986-11-21 | 1988-06-02 | Nippon Paint Co Ltd | Phosphate film treating agent |
| JPS63190178A (en) * | 1986-10-25 | 1988-08-05 | メタルゲゼルシャフト アクチェンゲゼルシャフト | Formation of phosphate film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1062082B (en) * | 1956-02-10 | 1959-07-23 | Metallgesellschaft Ag | Phosphating process |
| US3671332A (en) * | 1969-07-15 | 1972-06-20 | Hooker Chemical Corp | Metal treating process |
| US3923554A (en) * | 1974-02-07 | 1975-12-02 | Detrex Chem Ind | Phosphate coating composition and method |
| DE2540684A1 (en) * | 1975-09-12 | 1977-03-17 | Metallgesellschaft Ag | PROCESS FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
| GB2080835B (en) * | 1980-07-25 | 1984-08-30 | Pyrene Chemical Services Ltd | Prevention of sludge in phosphating baths |
-
1988
- 1988-10-06 JP JP63252435A patent/JPH02101174A/en active Pending
-
1989
- 1989-10-05 EP EP89310196A patent/EP0363200A3/en not_active Withdrawn
- 1989-10-06 KR KR1019890014407A patent/KR900006033A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6179782A (en) * | 1984-09-27 | 1986-04-23 | Nippon Parkerizing Co Ltd | Treatment of phosphate |
| JPS63190178A (en) * | 1986-10-25 | 1988-08-05 | メタルゲゼルシャフト アクチェンゲゼルシャフト | Formation of phosphate film |
| JPS63130781A (en) * | 1986-11-21 | 1988-06-02 | Nippon Paint Co Ltd | Phosphate film treating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0363200A2 (en) | 1990-04-11 |
| EP0363200A3 (en) | 1990-07-18 |
| KR900006033A (en) | 1990-05-07 |
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