JPH02197581A - Lubrication treatment for cold plastic working of steel - Google Patents
Lubrication treatment for cold plastic working of steelInfo
- Publication number
- JPH02197581A JPH02197581A JP1015128A JP1512889A JPH02197581A JP H02197581 A JPH02197581 A JP H02197581A JP 1015128 A JP1015128 A JP 1015128A JP 1512889 A JP1512889 A JP 1512889A JP H02197581 A JPH02197581 A JP H02197581A
- Authority
- JP
- Japan
- Prior art keywords
- phosphate
- steel
- film
- treatment
- ions
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 25
- 239000010959 steel Substances 0.000 title claims abstract description 25
- 238000005461 lubrication Methods 0.000 title claims description 16
- 229920003023 plastic Polymers 0.000 title claims description 11
- 239000004033 plastic Substances 0.000 title claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 41
- 239000010452 phosphate Substances 0.000 claims abstract description 35
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 125000001174 sulfone group Chemical group 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 19
- 230000001050 lubricating effect Effects 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 nitrate ions Chemical class 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229940085991 phosphate ion Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 21
- 239000010802 sludge Substances 0.000 abstract description 12
- 238000005482 strain hardening Methods 0.000 abstract description 12
- 229910000165 zinc phosphate Inorganic materials 0.000 abstract description 10
- 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 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 239000007788 liquid Substances 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 4
- JIAMRSLGASIQPE-UHFFFAOYSA-N 1,6-dimethyl-5-nitrocyclohexa-2,4-diene-1-sulfonic acid Chemical class [N+](=O)([O-])C=1C(C(C=CC1)(C)S(=O)(=O)O)C JIAMRSLGASIQPE-UHFFFAOYSA-N 0.000 description 3
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical class OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- IZJVVXCHJIQVOL-UHFFFAOYSA-N nitro(phenyl)methanesulfonic acid Chemical class OS(=O)(=O)C([N+]([O-])=O)C1=CC=CC=C1 IZJVVXCHJIQVOL-UHFFFAOYSA-N 0.000 description 3
- CUYDQRGVPLSZQI-UHFFFAOYSA-N nitro(phenyl)sulfamic acid Chemical class OS(=O)(=O)N([N+]([O-])=O)C1=CC=CC=C1 CUYDQRGVPLSZQI-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000005069 Extreme pressure additive Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- DPUZPWAFXJXHBN-UHFFFAOYSA-N tetrasodium dioxidoboranyloxy(dioxido)borane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]B([O-])OB([O-])[O-] DPUZPWAFXJXHBN-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- 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
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)
- Lubricants (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、低炭素鋼、高炭素鋼および低合金鋼などの鉄
鋼材料（本明細書では単に鉄鋼と称す）の表面に冷間塑
性加工すなわち冷間で行われる伸線。[Detailed Description of the Invention] [Industrial Application Field] The present invention applies cold plastic processing to the surface of steel materials such as low carbon steel, high carbon steel, and low alloy steel (herein simply referred to as steel). In other words, cold wire drawing.
伸管、鍛造、ヘッダー加工などに適する潤滑皮膜を形成
させるための処理方法に関する。This invention relates to a processing method for forming a lubricating film suitable for pipe drawing, forging, header processing, etc.
［従来の技術］
鉄鋼を冷間塑性加工（以下冷間加工という）する場合に
、工具の摩耗の低減および被加工材の工具への焼付の抑
制のために被加工材の表面をあらがじめ潤滑処理するこ
とがなされる。比較的に冷間加工度が低いときは潤滑処
理として例えば極圧添加剤や油性向上剤が配合された油
を被加工材の表面に塗布する方法が行われ、高冷間加工
の場合は例えば促進剤として亜硝酸ナトリウムを含むり
ん酸亜鉛系化成処理液を７０〜８０℃に加熱して浸漬処
理しその後例えばステアリン酸ナトリウムを主成分とす
る金属石鹸液（例えば１日本パー力ライジング（株）製
バルーブ２３５）を７０〜７５℃に加熱しその溶液で浸
漬処理してりん酸亜鉛系皮膜上にステアリン酸亜鉛潤滑
層とさらにその上にステアリン酸ナトリウム層とを形成
させる方法が広く行われている。また、この潤滑処理皮
膜の性能を向上させることを目的として下地皮膜の改良
研究がなされ、その成果が特公昭６０−２０４６３号公
報に開示されている。この発明における化成処理は成分
濃度を特定したりん酸亜鉛カルシウムタイプ処理液で約
８０℃の温度条件でなされるものである。[Prior art] When performing cold plastic working (hereinafter referred to as cold working) on steel, the surface of the workpiece is roughened to reduce tool wear and prevent the workpiece from seizing on the tool. Therefore, lubrication treatment is performed. When the degree of cold working is relatively low, a method of applying oil containing extreme pressure additives or oiliness improvers to the surface of the workpiece is used as a lubrication treatment, and in the case of high cold working, for example, A zinc phosphate-based chemical conversion treatment solution containing sodium nitrite as an accelerator is heated to 70 to 80°C for immersion treatment, and then, for example, a metal soap solution containing sodium stearate as a main component (for example, 1 Nippon Parriki Rising Co., Ltd.) is applied. A widely used method is to heat a manufactured valve 235) to 70 to 75°C and immerse it in the solution to form a zinc stearate lubricating layer on the zinc phosphate film and a sodium stearate layer thereon. There is. In addition, research has been conducted to improve the base film in order to improve the performance of this lubricating film, and the results are disclosed in Japanese Patent Publication No. 60-20463. The chemical conversion treatment in this invention is carried out at a temperature of about 80° C. using a zinc calcium phosphate type treatment solution with a specified component concentration.
以上の２つのタイプの下地処理について検討してみると
、共通して化成処理温度が比較的に高く。When considering the above two types of surface treatment, the chemical conversion treatment temperature is relatively high in common.
また処理液中に発生するスラッジ生成量が比較的に多い
といった問題を有しているのである。Another problem is that the amount of sludge generated in the processing liquid is relatively large.
［発明が解決しようとする課Ｍ１
本発明は前述の２種類のタイプのりん酸塩処理液即ちり
ん酸亜鉛系処理液とりん酸亜鉛カルシウム系処理液につ
いて、それぞれ処理温度の低温化と低スラッジ化さらに
形成される皮膜の冷間加工下地としてのより高品質化を
目的とする鉄鋼の冷間塑性加工用潤滑処理方法である。[Problem to be solved by the invention M1 The present invention aims at lowering the treatment temperature and reducing sludge with respect to the two types of phosphate treatment liquids mentioned above, namely, the zinc phosphate treatment liquid and the zinc calcium phosphate treatment liquid. This is a lubrication treatment method for cold plastic working of steel, which aims to improve the quality of the film formed as a base for cold working.
［課題を解決するための手段］
本発明者等は何れのタイプの処理液の場合においても、
処理温度を下げることに加えて処理液中に第１鉄イオン
の存在を許容できるようにすること、換言すれば処理液
中に第１鉄イオンおよび亜鉛イオンやカルシウムイオン
の一部をりん酸塩として析出させスラッジ化する作用を
持つ亜硝酸塩、過酸化水素などの促進剤を殆どもしくは
全く添加する必要がないようにして低温処理化すること
を目標として検討した結果、第１鉄イオンを有するりん
酸塩処理液に適度の酸化作用を有するニトロベンゼンス
ルフォン酸、ニトロアニリンスルフォン酸、ニトロトル
エンスルフォン酸、ニトロキシレンスルフォン酸のアル
カリ金属塩等のニトロ基及びスルフォン基を有する水溶
性芳香族化合物を特定量含有させ、かつ前述のような手
段と併行して処理液中の他の成分濃度を特定することに
よって、処理液の処理温度を３５〜６５℃の範囲迄に低
下させることができると共に発生するスラッジ生成量を
大幅に低減させることができかつ従来技術によるよりも
優れた耐冷間加工性を持つ潤滑皮膜を形成し得ることを
見出したのである。[Means for solving the problem] The present inventors have solved the problem in the case of any type of processing liquid.
In addition to lowering the processing temperature, it is necessary to allow the presence of ferrous ions in the processing solution. As a result of our study, we aimed to achieve low-temperature treatment with little or no need to add promoters such as nitrite and hydrogen peroxide, which have the effect of precipitating as sludge and forming sludge. Contains a specific amount of water-soluble aromatic compounds with nitro and sulfone groups, such as alkali metal salts of nitrobenzenesulfonic acid, nitroaniline sulfonic acid, nitrotoluenesulfonic acid, and nitroxylenesulfonic acid, which have a moderate oxidizing effect on acid salt treatment solutions. By specifying the concentration of other components in the treatment liquid in parallel with the above-mentioned measures, the treatment temperature of the treatment liquid can be lowered to a range of 35 to 65°C, and the sludge formation that occurs can be reduced. It has been discovered that it is possible to form a lubricating film that has superior cold work resistance than that achieved by the prior art.
即ち本発明は、第１発明として鉄鋼の冷間塑性加工用潤
滑処理方法において、鉄鋼を亜鉛イオン０゜３〜２．５
％、第１鉄イオン０．Ｏ１〜２．０％、りん酸イオン０
．５〜５．０％、硝酸イオン０．７〜１２．０％および
ニトロ基及びスルフォン基を有する水溶性芳香族化合物
０．０２〜０．２５％を含有しかつ亜鉛イオンに対する
第１鉄イオンの重量比が０．００５〜３．０であるりん
酸塩処理液に３５〜６５℃の温度で３〜２０分間浸漬し
て該鉄鋼表面にりん酸塩皮膜を形成させることおよび該
りん酸塩皮膜上に潤滑皮膜を形成させることから成るこ
とを特徴とする鉄鋼の冷間塑性加工用潤滑処理方法であ
り、第２発明として鉄鋼の冷間塑性加工用潤滑処理方法
において、鉄鋼を亜鉛イオン０．３〜２．５％、カルシ
ウムイオン０゜２〜２．０％、第１鉄イオン０．０１〜
２．０％、りん酸イオン０．５〜５．０％、硝酸イオン
０．７〜１２．０％およびニトロ基及びスルフォン基を
有する水溶性芳香族化合物０．０２〜０．２５％を含有
し、亜鉛イオンに対する第１鉄イオンの重量比が０．０
０５〜３．０でありかつ亜鉛イオンに対するカルシウム
イオンの重量比が０．７〜４．０であるりん酸塩処理液
に３５〜６５℃の温度で３〜２０分間浸漬して該鉄鋼表
面にりん酸塩皮膜を形成させることおよび該りん酸塩皮
膜上に潤滑皮膜を形成させることから成ることを特徴と
する鉄鋼の冷間塑性加工用潤滑処理方法である。That is, the present invention provides, as a first invention, a lubrication treatment method for cold plastic working of steel, in which the steel is treated with zinc ions of 0°3 to 2.5°.
%, ferrous ion 0. O1-2.0%, phosphate ion 0
．． 5-5.0%, nitrate ion 0.7-12.0% and water-soluble aromatic compound having nitro group and sulfone group 0.02-0.25%, and ferrous ion relative to zinc ion. Forming a phosphate film on the steel surface by immersing it in a phosphate treatment solution having a weight ratio of 0.005 to 3.0 at a temperature of 35 to 65°C for 3 to 20 minutes; and the phosphate film. A lubrication treatment method for cold plastic working of steel, which is characterized by forming a lubricating film on the steel. 3-2.5%, calcium ion 0°2-2.0%, ferrous ion 0.01-
Contains 2.0%, 0.5-5.0% phosphate ions, 0.7-12.0% nitrate ions, and 0.02-0.25% water-soluble aromatic compounds having nitro and sulfone groups. and the weight ratio of ferrous ions to zinc ions is 0.0
05 to 3.0 and the weight ratio of calcium ions to zinc ions is 0.7 to 4.0. A lubrication treatment method for cold plastic working of steel, characterized by forming a phosphate film and forming a lubricant film on the phosphate film.
［作用］
先ず第１発明について説明する。この発明は改良された
りん酸亜鉛系処理液による処理と潤滑処理液による処理
とにより鉄鋼表面に優れた潤滑皮股を形成させる方法に
関するものである。この改良りん酸亜鉛系処理液の成分
構成について先ず説明する。この処理液は必須のカチオ
ン成分として亜鉛イオンと第１鉄イオンとを含有するも
のである。亜鉛イオンは０．３〜２．５％であって０．
３％未満では冷間加工に適する皮膜の形成がなされにく
くなる傾向を示し、２．５％を越えても化成処理性が向
上せずむしろ処理液の管理が悪くなりかつ経済的にも好
ましくない。[Operation] First, the first invention will be explained. This invention relates to a method for forming an excellent lubricating skin on a steel surface by treatment with an improved zinc phosphate treatment liquid and treatment with a lubricating treatment liquid. First, the composition of the improved zinc phosphate treatment liquid will be explained. This treatment liquid contains zinc ions and ferrous ions as essential cation components. Zinc ion is 0.3 to 2.5% and 0.3% to 2.5%.
If it is less than 3%, it tends to be difficult to form a film suitable for cold working, and if it exceeds 2.5%, the chemical conversion treatment properties will not improve, and the management of the treatment liquid will become worse, and it is not economically preferable. .
第１鉄イオンは０．０１〜２．０％含有するが、このイ
オンは亜鉛イオンに対する第１鉄イオンの重量比（Ｆｅ
／Ｚｎ ）を０．００５〜３．０の範囲とするこ
とによって更に律せられる。即ち、亜鉛イオン濃度が下
限値０．３％のときは前記重量比から許容し得る第１鉄
イオンは０．０００１５〜０．９％と計算されるが前記
第１鉄イオンの下限値は０．０１％であるから含有量は
０．０１〜０．９％と限定される。逆に亜鉛イオンの上
限値即ち２．５％のときは第１鉄イオンは０．０１２５
〜７．５％と計算されるがそのイオンの上限値から０．
０１２５〜２．０％とする必要が起るのである。The ferrous ion content is 0.01 to 2.0%, and the weight ratio of ferrous ion to zinc ion (Fe
/Zn) within the range of 0.005 to 3.0. That is, when the zinc ion concentration is the lower limit of 0.3%, the allowable ferrous ion is calculated from the weight ratio to be 0.00015 to 0.9%, but the lower limit of the ferrous ion is 0. Since it is .01%, the content is limited to 0.01 to 0.9%. Conversely, when the upper limit of zinc ion is 2.5%, ferrous ion is 0.0125
It is calculated to be ~7.5%, but from the upper limit of that ion, it is 0.
Therefore, it becomes necessary to set the content to 0.0125% to 2.0%.
この事は、処理液中の亜鉛イオン濃度が低いときは、許
容される第１鉄イオン濃度の上限を低目に抑える必要が
あること、その逆の場合には第１鉄イオンを低い値から
上限まで維持し得ることを示している。This means that when the zinc ion concentration in the treatment solution is low, it is necessary to keep the upper limit of the allowable ferrous ion concentration low, and vice versa, the ferrous ion concentration must be lowered to a lower value. This shows that it can be maintained up to the upper limit.
第１鉄イオン濃度が０．０１％未満では形成されるりん
酸塩皮膜の潤滑下地としての効果が不十分でありかつこ
の様に鉄分濃度を抑えるには処理液に促進剤（ＮａＮＯ
，、Ｈ，Ｏ□）等を頻発的に添加して鉄分を析出させる
必要があるのでスラッジ生成量が増大する。逆に第１鉄
イオン、これは鉄鋼のりん酸塩処理の際に鉄鋼から溶出
して増加するのであるが、この濃度が２％を越えると、
粗い不完全な皮膜を形成し易くまた鉄分により置換され
て亜鉛成分が激減してくるので皮膜化成性が悪くなる０
以上説明したことから亜鉛イオンに対する第１鉄イオン
の重量比を前述のように限定する必要が生ずるのである
。If the ferrous ion concentration is less than 0.01%, the effect of the phosphate film formed as a lubricating base is insufficient, and in order to suppress the iron concentration in this way, an accelerator (NaNO
, H, O□) etc. must be added frequently to precipitate iron, which increases the amount of sludge produced. Conversely, ferrous ions, which are eluted from steel during phosphate treatment and increase in concentration, exceed 2%.
It tends to form a rough and incomplete film, and the zinc content is drastically reduced by being replaced by iron, resulting in poor film formation properties.
From the above explanation, it becomes necessary to limit the weight ratio of ferrous ions to zinc ions as described above.
次にりん酸イオン（ｐｏ、”）は０．５〜５．０％の範
囲であって、この濃度は前記金属イオンの量と比例的な
関係によって概ね位置づけられる。０．５％未満では皮
膜化成性が悪くなり、逆に５．０％より多く加えること
は可能であるが単に濃度が高くなるだけで化成性は向上
しない１次に硝酸イオン（ＮＯｌ−）は０．７〜１２．
０％を必要とするが、０．７未満では皮膜化成速度が遅
くなるので処理に時間を要し、また形成される皮膜は粗
い密着力の劣った状態となる。Next, phosphate ions (po,'') are in the range of 0.5 to 5.0%, and this concentration is roughly determined by a proportional relationship with the amount of metal ions. On the contrary, it is possible to add more than 5.0%, but the concentration will simply increase and the chemical formation property will not improve.The primary nitrate ion (NOl-) is 0.7 to 12%.
0% is required, but if it is less than 0.7, the rate of film formation will be slow and the treatment will take time, and the formed film will be rough and have poor adhesion.
１２．０％を越えると処理液中のＺｎ（Ｎｏ、）、の濃
度が多くなりＺ ｎ （ＮＯ３）２に対するＺｎ（Ｉｌ
ｚＰＯ４）ｔの比が小さくなる傾向となるので皮膜化成
に必要なＺｎ（１！□ｐｏ、）ｚの濃度が不足して皮膜
化成性（つきまわり性即ちスローイングパワー）が低下
する。When it exceeds 12.0%, the concentration of Zn(No,) in the treatment solution increases and the Zn(Il) relative to Zn(NO3)2 increases.
Since the ratio of zPO4)t tends to become smaller, the concentration of Zn(1!□po,)z required for film formation becomes insufficient, resulting in a decrease in film formation properties (throwing power, that is, throwing power).
次に本発明に適用するりん酸塩処理液には前記以外の必
須成分としてニトロベンゼンスルフォン酸。Next, the phosphate treatment solution used in the present invention contains nitrobenzenesulfonic acid as an essential component other than the above.
ニトロアニリンスルフォン酸、ニトロトルエンスルフォ
ン酸、ニトロキシレンスルフォン酸等のニトロ基及びス
ルフォン基を有する水溶性芳香族化合物を０．０２〜０
．２５％含有する。これらの化合物は、何れも鉄分含有
りん酸亜鉛処理液による処理の低温化に役立つと共に結
晶粒子の比較的に細かい緻密なりん酸塩皮膜を形成させ
る作用を有する。このような組成を持つ本発明処理液は
鉄分を含んでいても３５〜６５℃という比較的に低い温
度（中低温）で３〜２０分間の浸漬により鉄鋼表面に皮
膜重量が７〜１２に／ ｍ ”の結晶粒子の比較的に小
さな緻密な皮膜を形成させることができ、このような皮
膜は高度の冷間加工に適する下地なのである。また、こ
のりん酸亜鉛系処理液は鉄分（Ｆｅ ）を含むもので
あり、従ってＮＯｌ−または１１，０．などの促進剤を
殆どもしくは全く必要とするものではないので処理液か
らのスラッジ（ＦｅＰＯ４，Ｚｎ、 （ＰＯ４）ｚ ）
の析出が比較的に少ないのも効果の１つとして挙げるこ
とができる。A water-soluble aromatic compound having a nitro group and a sulfone group such as nitroaniline sulfonic acid, nitrotoluenesulfonic acid, nitroxylene sulfonic acid, etc.
．． Contains 25%. All of these compounds are useful in lowering the temperature of the treatment with the iron-containing zinc phosphate treatment solution and have the effect of forming a dense phosphate film with relatively fine crystal grains. Although the treatment solution of the present invention having such a composition contains iron, it can be applied to the steel surface by immersion for 3 to 20 minutes at a relatively low temperature of 35 to 65°C (medium-low temperature) to a coating weight of 7 to 12%. It is possible to form a dense film with comparatively small crystal grains of 1.5 m'', and such a film is a suitable base for advanced cold working. sludge from the processing solution (FePO4, Zn, (PO4)z), and therefore requires little or no promoters such as NOl- or 11,0.
One of the effects is that the amount of precipitation is relatively small.
以上の前記化合物の添加量が０．０２％未満ではその添
加の効果が小さいかあるいは全く認められないかの何れ
かであり、逆に０．２５％より多く加えても処理温度の
低下、りん酸塩皮膜の緻密化などの効果の向上は望めず
、多量の添加によりむしろ皮膜化成性を損ねるといった
傾向を示す。If the amount of the above-mentioned compounds added is less than 0.02%, the effect of the addition is small or not observed at all, and conversely, if more than 0.25% is added, the processing temperature decreases and the phosphorus No improvement in effects such as densification of the acid salt film can be expected, and addition of a large amount tends to impair film formation properties.
これらの化合物のうち代表的に用いられるものはメタニ
トロベンゼンスルフォン酸である。りん酸塩処理液は必
要に応じてその中低温における化成速度を速める（化成
性の向上に寄与する）ためにキレート化剤として蓚酸、
くえん酸、グリセロリン酸、尿素、ポリビニルアルコー
ルまたはポリビニルピロリドンを０．０１〜０．０５％
含有させることができる。また、本発明に適用するりん
酸塩処理液は、さらに酸化剤として塩素酸塩例えばＮａ
ＣＱ Ｏ，、ニッケル、コバルトまたは銅などの重金属
イオン等を含有させることを拒むものではない、前述の
ごとく本発明の方法においては１表面清浄な鉄鋼を以上
のごとく成分を特定したりん酸塩処理液に３５〜６５℃
の温度で３〜２０分浸漬してりん酸塩皮膜を形成させる
が、このプロセスには皮膜化成後の水洗−乾燥もしくは
水洗−中和の工程が含まれる。Among these compounds, the one typically used is metanitrobenzenesulfonic acid. If necessary, the phosphate treatment solution may contain oxalic acid or
0.01-0.05% citric acid, glycerophosphoric acid, urea, polyvinyl alcohol or polyvinylpyrrolidone
It can be included. In addition, the phosphate treatment solution applied to the present invention further contains a chlorate such as Na as an oxidizing agent.
As mentioned above, the method of the present invention does not exclude the inclusion of heavy metal ions such as CQ O, nickel, cobalt, or copper. 35-65℃ for liquid
A phosphate film is formed by immersion at a temperature of 3 to 20 minutes, and this process includes a water washing-drying or water washing-neutralization step after film formation.
水洗−乾燥後の潤滑処理としては、例えば２硫化モリブ
デン、２硫化タングステン、グラファイトまたはふっ素
樹脂などを含む潤滑剤または極圧添加剤を含む油性潤滑
剤などを適用してりん酸塩皮膜上に潤滑皮膜を形成させ
る。For lubrication treatment after water washing and drying, for example, a lubricant containing molybdenum disulfide, tungsten disulfide, graphite or fluororesin, or an oil-based lubricant containing an extreme pressure additive is applied to lubricate the phosphate film. Forms a film.
水洗−中和後の潤滑処理として、広く適用される方法即
ちＣ１６〜Ｃ，。の飽和または不飽和脂肪酸のアルカリ
金属塩１適常ステアリン酸ナトリウムを主成分とする弱
アルカリ性金属石鹸水溶液を７０〜７５℃に加熱しその
中に浸漬処理してりん酸塩皮膜上に脂肪酸亜鉛皮膜と脂
肪酸アルカリ金属皮膜を層状に形成させる方法が一般的
であり特に好ましい潤滑処理方法である。Water washing - A method widely applied as a lubrication treatment after neutralization, namely C16-C. Alkali metal salts of saturated or unsaturated fatty acids (1) A weakly alkaline metal soap aqueous solution containing suitable sodium stearate as a main component is heated to 70-75°C and immersed in it to form a fatty acid zinc film on a phosphate film. A method of forming a layered layer of a fatty acid alkali metal film is a common and particularly preferred lubrication treatment method.
この潤滑皮膜形成法には最終工程として潤滑皮膜の乾燥
が含まれる。This lubricant film forming method includes drying the lubricant film as a final step.
次に第２発明について説明する。この発明の第１発明と
相違する点は、潤滑下地処理に適用するりん酸塩処理液
が金属イオンとして亜鉛イオン、第１鉄イオン以外にカ
ルシウムイオンを０．２〜２．０％含有することそして
、亜鉛イオンに対するカルシウムイオンの重量比が０．
７〜４．０であることである。Next, the second invention will be explained. This invention is different from the first invention in that the phosphate treatment liquid used for lubricating base treatment contains 0.2 to 2.0% calcium ions in addition to zinc ions and ferrous ions as metal ions. The weight ratio of calcium ions to zinc ions is 0.
7 to 4.0.
従って他の面では第１発明と全く同じである。故に本第
２発明で適用するりん酸塩処理液は第１発明の方法にお
いて適用するりん酸亜鉛系処理液の処理液構成にカルシ
ウムイオンを前述の如き限定をもって加えたものである
。Therefore, in other respects, this invention is completely the same as the first invention. Therefore, the phosphate treatment solution applied in the second invention is one in which calcium ions are added to the treatment solution composition of the zinc phosphate treatment solution used in the method of the first invention, with the above-mentioned limitations.
このような処理液を用いる以外は第１発明と全く同様に
行う方法が第２発明である０本第１発明の方法にて使用
するりん酸亜鉛系処理液、厳密にはりん酸亜鉛・鉄処理
液からはｐｈｏｓｐｈｏｐｈｙｌｌｉｔａ結晶（ＺｎＪ
ｅ（ＰＯ４）ｚ−４１１，ｏ）を主成分とする均質皮膜
が形成されるが、この処理液に前述のような限定された
量のカルシウムイオンを含有させると５ｃｈｏｌｚｉ−
ｔｅ（Ｚｎ、Ｃａ（ＰＯ４）２−２１１．０）が主体と
なり、これに副成分としてＺｎ、Ｆｅ（ＰＯ４）、 ・
４１１２０ならびにｈｏｐｅｉｔ（Ｚｎ、 （ＰＯ４）
、４１１ｔＯ）が共析しこれらが略一体化した均質微細
な粒状皮膜を構成するのである。The second invention is a method that is carried out in exactly the same manner as the first invention except for using such a treatment liquid.Zinc phosphate treatment liquid used in the method of the first invention, strictly speaking, zinc/iron phosphate. Phosphophyllita crystals (ZnJ
A homogeneous film containing e(PO4)z-411,o) as the main component is formed, but if this treatment solution contains a limited amount of calcium ions as described above,
te(Zn, Ca(PO4)2-211.0) is the main component, and Zn, Fe(PO4), as subcomponents.
41120 and hopeit (Zn, (PO4)
, 411tO) are eutectoid to form a homogeneous fine granular film that is substantially integrated.
しかしながら、カルシウムイオン含有量が０．２％未満
または亜鉛イオンに対する重量比が０．７未満では、前
記の微細な結晶群の中に主成分としてｐｈｏｓｐｈｏｐ
ｈｙｌｌｉｔｅと断定される５ｃｈｏｌｚｉｔｅ系より
も大きな結晶が散在するようになり前記重量比が小さく
なるにつれて ｐｈｏｓｐｈｏｐｈｙｌｌｉｔａ系結晶
が増加するようになるので結晶構造的に不均一な皮膜と
なる。特に強い冷間加工の際はミクロ的に均一皮膜を要
件とするので、このような不均一な皮膜は強い冷間加工
下地として望ましいものではない。However, if the calcium ion content is less than 0.2% or the weight ratio to zinc ions is less than 0.7, phosphophosph is present as a main component in the fine crystal group.
Crystals larger than the 5cholzite type, which is determined to be hyllite, are scattered, and as the weight ratio decreases, the number of phosphophyllita type crystals increases, resulting in a film that is non-uniform in terms of crystal structure. In particular, since a microscopically uniform film is required during strong cold working, such a non-uniform film is not desirable as a base for strong cold working.
逆にＣａイオンが２．０％超またはＣａ”／Ｚｎ”＋が
４゜０超では、前記の微細な粒状結晶群の間に比較的に
軟質のｍｏｎｅｔｉｔｅ （ＣａＨＰＯ４）が析出する
ようになり、冷間加工性を低下させる。りん酸塩処理液
中のＺｎイオン濃度は０．３〜２．５％が好ましく０．
３未満では形成皮膜中に比較的に軟質のｍｏｎｅｔｉｔ
ｅを共析し易くなり、逆に２．５超では前記微細な結晶
群にｈｏｐｅｉｔ（Ｚｎｉ （ＰＯ４）２ ”４Ｈ２０
）とｐｈｏｓｐｈｏｐｈｙｌｌｉｔｅとの共析結晶が散
在し易くなるので結晶構造的に不均一な皮膜となり易い
、従って、何れにしても好ましくない、また、第１鉄イ
オンは０．０１〜２．０％が好ましく ｏ、ｏｔ％未満
またはＦｅ”／Ｚｎ”＋が０．００５未滴では強冷間加
工に適する潤滑下地としては不十分な皮膜を形成し易い
。On the other hand, if the Ca ion content exceeds 2.0% or the Ca''/Zn''+ exceeds 4°0, relatively soft monetite (CaHPO4) will precipitate between the fine granular crystal groups. Decreases cold workability. The Zn ion concentration in the phosphate treatment solution is preferably 0.3 to 2.5%.
If it is less than 3, relatively soft monetitol is present in the formed film.
If it exceeds 2.5, hopeeit (Zni (PO4)2 ''4H20
) and phosphophyllite are likely to be scattered, resulting in a film with a non-uniform crystal structure. Preferably, if less than 0.0% or less than 0.005 drops of Fe''/Zn''+ are present, a film is likely to be formed that is insufficient as a lubricating base suitable for intense cold working.
また処理液中の第１鉄イオンを０．０１％未満とするに
は処理液に促進剤（ＮａＮＯ，、ｌｌ＊ｏ＊等）を頻発
的に添加して第１鉄イオンを析出除去させる必要がある
のでスラッジ生成量が増大する。In addition, in order to keep the ferrous ions in the processing solution to less than 0.01%, it is necessary to frequently add accelerators (NaNO, ll*o*, etc.) to the processing solution to precipitate and remove ferrous ions. Because of this, the amount of sludge produced increases.
逆に、第１鉄イオンが２．０％超またはＦｅ ／Ｚｎ
が３．０超では処理液中の鉄分過多により逆に亜鉛
やカルシウム分の低下を紹来し、Ｆｅ−１１ｕｒｅａｕ
ｌｉｔｈ （Ｆｅｓ Ｉｔ、 （ＰＯ４）４−４１１．
Ｏ）を含む５ｃｈｏｌｚｉｔｅ系の粗雑皮膜の形成も
しくは化成不良をもたらす、故にＦｅ ／Ｚｎ！＋比
は０．００５〜３．０と限定される。Conversely, if ferrous ions exceed 2.0% or Fe/Zn
If it exceeds 3.0, the iron content in the treatment solution is too high, which leads to a decrease in zinc and calcium content, and Fe-11ureau
lith (Fes It, (PO4)4-411.
Fe/Zn! The + ratio is limited to 0.005 to 3.0.
次に、リン酸イオン濃度は０．５〜５．０％の範囲が好
ましく、Ｏ，Ｓ％未満では皮膜化成性が悪くなり、５゜
０％より多くしても単に濃度が高くなるだけで化成性の
向上に寄与しない０次に硝酸イオン濃度は０．７〜１２
．０％が好ましく、０．７％未満では皮膜化成速度が遅
くなるので長時間の処理を要しまた形成される皮膜は粗
い密着力の劣った状態となる。１２゜０％を越えると処
理液中のＺｎ（Ｎｏ、）、やＣａ （Ｎｏ、 ）ｓの濃
度が高くなり、従ってそれだけ皮膜形成に必要なｚｎ（
ｎ＊ｐｏ４）ｓ並びにＣａ （Ｉｆ、 ＰＯ，）、の濃
度が低下して皮膜化成性（つきまわり性）が低下する。Next, the phosphate ion concentration is preferably in the range of 0.5 to 5.0%; if it is less than O, S%, the film formation properties will be poor, and if it is more than 5.0%, the concentration will simply increase. The zero-order nitrate ion concentration that does not contribute to improving chemical formation is 0.7 to 12.
．． 0% is preferable; if it is less than 0.7%, the rate of film formation will be slow, requiring a long treatment time, and the formed film will be rough and have poor adhesion. When it exceeds 12°0%, the concentration of Zn(No, ) and Ca(No, )s in the treatment solution increases, and therefore the Zn(No, )s necessary for film formation increases.
The concentration of n*po4)s and Ca (If, PO,) decreases, and the film formation property (throwing property) decreases.
また、本第２発明で使用するりん酸塩処理液には第１発
明の場合と同様にニトロベンゼンスルフォン酸、ニトロ
アニリンスルフォン酸、ニトロトルエンスルフォン酸、
ニトロキシレンスルフォン酸等のニトロ基を有する水溶
性芳香族化合物を０．０２〜０．２５％含有するが、こ
の添加理由はりん酸塩処理の低温化（３５〜６５℃の処
理温度）にあり、処理液が鉄分を含んでいても低温化を
可能ならしめるのである。前記化合物の濃度が０．０２
％未満ではその効果が期待し難く、０．２５％超加えて
もその効果の向上は望めず、多量の添加によりむしろ、
皮膜化成性を損ねる作用を示す、これらの化合物のうち
代表的に用いられのはメタニトロベンゼンスルフォン酸
である０本りん酸塩処理液は第１発明におけるそれと同
様に第１鉄イオンを含有するものであるから、ＮａＮ０
．又は＋１，０．などの促進剤の使用を殆ど又は全く回
避できるのでスラッジ析出量が比較的に少ないという効
果も付与するものである。In addition, the phosphate treatment solution used in the second invention also includes nitrobenzenesulfonic acid, nitroaniline sulfonic acid, nitrotoluenesulfonic acid, as in the case of the first invention.
Contains 0.02 to 0.25% of water-soluble aromatic compounds with nitro groups such as nitroxylene sulfonic acid, and the reason for this addition is to lower the temperature of the phosphate treatment (35 to 65°C treatment temperature). This makes it possible to lower the temperature even if the processing liquid contains iron. The concentration of the compound is 0.02
If it is less than 0.25%, it is difficult to expect the effect, and even if it is added in excess of 0.25%, no improvement in the effect can be expected;
Among these compounds that have the effect of impairing film formation properties, metanitrobenzene sulfonic acid is typically used.The phosphate treatment solution contains ferrous ions as in the first invention. Therefore, NaN0
．． Or +1,0. This also provides the effect that the amount of sludge deposited is relatively small since the use of accelerators such as the like can be avoided at all or little.
また１本第２発明において使用されるりん酸塩処理液に
１本第１発明におけるそれの場合と同様に必要に応じて
キレート化剤として蓚酸、酒石酸。In addition, one bottle of the phosphate treatment solution used in the second invention may contain oxalic acid or tartaric acid as a chelating agent, if necessary, as in the case of the first invention.
くえん酸、グリセロリン酸、尿素、ポリビニルアルコー
ルまたはポリビニルピロリドンを０．０１〜０゜０５％
添加してその処理液の中低温（３５〜６５℃）における
化成速度を速めることができる。なお、この処理液は、
さらに酸化剤として塩素酸塩例えばＮａＣｎ Ｏｊ、ニ
ッケル、コバルトまたは銅などの重金属イオン等を含有
させることを拒むものではない。Citric acid, glycerophosphoric acid, urea, polyvinyl alcohol or polyvinylpyrrolidone 0.01-0°05%
By adding it, it is possible to accelerate the chemical conversion rate of the treatment liquid at medium to low temperatures (35 to 65°C). In addition, this treatment liquid is
Furthermore, it is possible to include chlorate, for example, NaCn Oj, heavy metal ions such as nickel, cobalt, or copper as an oxidizing agent.
次に、りん酸塩処理に続いて行われる処理ならびにその
皮膜上に形成させるために適用する潤滑剤およびその処
理は本第１発明におけると全く同様である。Next, the treatment performed subsequent to the phosphate treatment, the lubricant applied to form the film, and the treatment thereof are exactly the same as in the first invention.
以下に本発明の効果をさらに具体的に説明するために実
施例を挙げ比較例と共に示す。Examples will be given below along with comparative examples in order to more specifically explain the effects of the present invention.
［実施例１〜４］
８３５Ｇの円筒形試験片を酸洗、水洗し、表１のりん酸
塩処理液でそれぞれ処理し、次いで石けん潤滑剤バルー
ブー２３５（商品名、日本パー力うイジング■社製、主
成分ニステアリン酸ナトリウム。[Examples 1 to 4] A cylindrical test piece of 835G was pickled, washed with water, and treated with the phosphate treatment solution shown in Table 1, respectively, and then soap lubricant Ballubu 235 (trade name, manufactured by Nippon Parr Ising Co., Ltd.) was used. The main ingredient is sodium nistearate.
副成分ニホウ酸ナトリウムおよび亜硝酸ナトリウム）７
０ｇ／ Ｑ 、７５℃で５分間浸漬し乾燥後下記条件に
より後方穿孔押出し加工法により潤滑性の評価を表
１りん酸塩皮股処理液組成
表
生成した皮膜重量及び金属石けん量
行った。Subcomponents sodium diborate and sodium nitrite)7
0g/Q, immersed for 5 minutes at 75°C, dried, and then evaluated for lubricity using the backward perforation extrusion process under the following conditions.
試験条件
（株）豊田中央研究所の団野らが１ｍ性と加工ＪＶｏｌ
２４．Ｎｏ、２６５に発表した後方穿孔押出し加工法
により焼付発生限界穿孔深さを求めた。即ちその加工法
は以下の通りである。Test conditions Danno et al. of Toyota Central Research Institute Co., Ltd.
24. The critical drilling depth for seizure occurrence was determined using the backward drilling extrusion method published in No. 265. That is, the processing method is as follows.
使用機器及び試験条件
福井機械（株）製：２００Ｔｏｎ冷間鍛造用クランクプ
レス
ストローク回数：３０ｓｐｍ
試験金型： ダイ３０ｓ＋ｍφ ５ＫＤＩＩ、パンチ２
１．２１ｍｍφ１日立金属粉末ハイス（ＨＡ Ｐ ４０
、 Ｃ＝１．３ Ｃｒ＝４．０ Ｍ＝６．０ Ｍｏ
＝５．０ｖ＝３．０ＣＯ＝８．０）。Equipment used and test conditions Manufactured by Fukui Machinery Co., Ltd.: 200Ton cold forging crank press Stroke count: 30spm Test mold: Die 30s + mφ 5KDII, punch 2
1.21mmφ1 Hitachi Metal Powder High Speed Steel (HA P 40
, C=1.3 Cr=4.0 M=6.0 Mo
=5.0v=3.0CO=8.0).
断面減少率：５０％（ブランク底部１０＋ｕ＋残し）前
記表２．及び第１図から明らかなように実施例１〜４は
充分な皮膜重量、金属石けん量が得られており後方穿孔
押出し試験の結果、実施例は比較例よりも焼き付き発生
限界深さが深く潤滑性に優れている。Section reduction rate: 50% (blank bottom 10+u+remaining) Table 2 above. As is clear from Figure 1, Examples 1 to 4 had sufficient coating weight and amount of metal soap, and as a result of the rear hole extrusion test, the Examples had a deeper seizure occurrence limit depth than the Comparative Example, and the lubrication Excellent in sex.
［実施例５〜８］
Ｓ−４５０の線材（１０ｍ震φＸ １００ｍｍ）を酸洗
、水洗し、表３のりん酸塩処理液でそれぞれ処理し、次
いで水洗してから石鹸潤滑剤バルーブ２３５（商品名１
日本パー力うイジング■社Ｉ！り７０ｇ／ｆｆ、７５℃
で５分間浸漬し、乾燥後バウデン式摩擦摩耗試験機（Ｅ
ｌ”Ｍ−４、東洋ボールドウィン社製）で１表４の条件
により焼付（摩擦係数０．２以上）までの摺動１ｉ１１
数を測定した。その結果は表５及び表６に示す通りであ
った。前記表５，６から明らかな通り実施例５〜８は充
分な皮膜重量、金属石鹸量が得られ、パウデン試験結果
も耐焼付き性において、比較例５〜８よりも著しく優れ
ていることが明らかである。[Examples 5 to 8] S-450 wire rod (10 m earthquake φ Name 1
Japanese Parr Ising ■ Company I! 70g/ff, 75℃
After soaking for 5 minutes in
1"M-4, manufactured by Toyo Baldwin Co., Ltd.) under the conditions in Table 4. Sliding 1i11 until seizing (coefficient of friction 0.2 or more)
The number was measured. The results were as shown in Tables 5 and 6. As is clear from Tables 5 and 6 above, Examples 5 to 8 obtained sufficient film weight and amount of metal soap, and the Powden test results clearly showed that they were significantly superior to Comparative Examples 5 to 8 in terms of seizure resistance. It is.
「発明の効果ゴ
以」−説明したように、本発明の潤滑処理方法は何れも
（第１発明も第２発明も）鉄鋼の冷間加工に適した優れ
た潤滑皮膜を形成させるものであって。"Effects of the Invention" - As explained, both the lubrication treatment methods of the present invention (both the first invention and the second invention) form an excellent lubricating film suitable for cold working of steel. hand.
次のような効果をもたらすものである。This brings about the following effects.
１、本発明において適用するりん酸塩処理上の効表
りん酸塩皮膜処理液組成
表
バウデン試験条件
ａ、比較的に低い温度（３５〜６５℃）で効率的に処理
できる（処理時間３〜２０分浸漬）
ｂ、処理の際に促進剤（ＮａＮＯ，，１１，０，など）
の使用が殆ど又は全く回避できる。従って処理液の管理
がそれだけ容易である。1. Efficacy of phosphate treatment applied in the present invention Phosphate film treatment liquid composition table Bowden test condition a, efficient treatment at relatively low temperature (35-65°C) (treatment time 3-65°C) b. Accelerator (NaNO, 11, 0, etc.) during treatment
little or no use of Therefore, management of the processing liquid is that much easier.
ｃ、ｆｉ密なりん酸塩皮膜（何れの処理液の場合も７〜
１２ｇ／ｍ”の皮膜重量）を形成し強冷間加工に適する
下地皮膜が得られる。c, fi dense phosphate film (7~ for any treatment solution)
A base film having a coating weight of 12 g/m'' is formed and is suitable for intense cold working.
ｄ、処理液からのスラッジ生成量が少ない２、本発明の
実施により得られる潤滑皮膜は優れた冷間加工性を示す
ものであり、潤滑処理液としてＣｔａ〜Ｃ８，の飽和又
は不飽和脂肪酸のアルカリ金属塩、特にステアリン酸ナ
トリウムを主成分とする水系潤滑処理液を適用してりん
酸塩皮膜の上に金属石鹸皮膜層を形成させたものは特に
優れた性能を発揮する。d. The amount of sludge generated from the treatment liquid is small. 2. The lubricating film obtained by implementing the present invention exhibits excellent cold workability. Particularly excellent performance is achieved when a metal soap film layer is formed on a phosphate film by applying an aqueous lubricating treatment liquid containing an alkali metal salt, particularly sodium stearate, as a main component.
第１図は［実施例１〜４］の後方穿孔押出しの焼付き限
界穿孔深さを示す図。
第２ｒｓは、後方穿孔押出加工の試験装置の概略図。
第３図は、後方穿孔押出加工の工具形状を示す図、であ
る。FIG. 1 is a diagram showing the seizure limit perforation depth of backward perforation extrusion in [Examples 1 to 4]. 2nd rs is a schematic diagram of a test device for backward perforation extrusion processing. FIG. 3 is a diagram illustrating the shape of a tool for backward perforation extrusion processing.
Claims (2)
鋼を亜鉛イオン０．３〜２．５％（重量％以下同じ）、
第１鉄イオン０．０１〜２．０％、りん酸イオン０．５
〜５．０％、硝酸イオン０．７〜１２．０％およびニト
ロ基及びスルフォン基を有する水溶性芳香族化合物０．
０２〜０．２５％を含有しかつ亜鉛イオンに対する第１
鉄イオンの重量比が０．００５〜３．０であるりん酸塩
処理液に３５〜６５℃の温度で３〜２０分間浸漬して該
鉄鋼表面にりん酸塩皮膜を形成させることおよび該りん
酸塩皮膜上に潤滑皮膜を形成させることから成ることを
特徴とする鉄鋼の冷間塑性加工用潤滑処理方法(1) In the lubrication treatment method for cold plastic working of steel, the steel is treated with 0.3 to 2.5% zinc ions (the same below weight%),
Ferrous ion 0.01-2.0%, phosphate ion 0.5
5.0%, 0.7-12.0% nitrate ions and 0.0% water-soluble aromatic compounds having nitro and sulfone groups.
02-0.25% and the first for zinc ions
Forming a phosphate film on the surface of the steel by immersing it in a phosphate treatment solution having an iron ion weight ratio of 0.005 to 3.0 at a temperature of 35 to 65°C for 3 to 20 minutes; and A lubrication treatment method for cold plastic working of steel, characterized by forming a lubricating film on an acid salt film.
鋼を亜鉛イオン０．３〜２．５％、カルシウムイオン０
．２〜２．０％、第１鉄イオン０．０１〜２．０％、り
ん酸イオン０．５〜５．０％、硝酸イオン０．７〜１２
．０％およびニトロ基及びスルフォン基を有する水溶性
芳香族化合物０．０２〜０．２５％を含有し、亜鉛イオ
ンに対する第１鉄イオンの重量比が０．００５〜３．０
でありかつ亜鉛イオンに対するカルシウムイオンの重量
比が０．７〜４．０であるりん酸塩処理液に３５〜６５
℃の温度で３〜２０分間浸漬して該鉄鋼表面にりん酸塩
皮膜を形成させることおよび該りん酸塩皮膜上に潤滑皮
膜を形成させることから成ることを特徴とする鉄鋼の冷
間塑性加工用潤滑処理方法(2) In the lubrication treatment method for cold plastic working of steel, the steel is treated with 0.3 to 2.5% zinc ions and 0 calcium ions.
．． 2-2.0%, ferrous ion 0.01-2.0%, phosphate ion 0.5-5.0%, nitrate ion 0.7-12
．． 0% and 0.02 to 0.25% of water-soluble aromatic compounds having nitro and sulfone groups, and the weight ratio of ferrous ions to zinc ions is 0.005 to 3.0.
and the weight ratio of calcium ions to zinc ions is 0.7 to 4.0.
Cold plastic working of steel, characterized by forming a phosphate film on the surface of the steel by immersing it at a temperature of °C for 3 to 20 minutes, and forming a lubricant film on the phosphate film. lubrication treatment method
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1015128A JP2636919B2 (en) | 1989-01-26 | 1989-01-26 | Lubrication treatment method for cold plastic working of steel |
| ZA90305A ZA90305B (en) | 1989-01-26 | 1990-01-16 | Lubrication treatment method for the cold plastic-working or iron and steel |
| DK90101350.8T DK0380067T3 (en) | 1989-01-26 | 1990-01-24 | Method for lubricating iron and steel before cold working |
| DE90101350T DE69001680T2 (en) | 1989-01-26 | 1990-01-24 | Method of greasing iron and steel before cold processing. |
| EP90101350A EP0380067B1 (en) | 1989-01-26 | 1990-01-24 | Improved method of lubricating iron and steel before cold working |
| AT90101350T ATE89875T1 (en) | 1989-01-26 | 1990-01-24 | METHOD FOR LUBRICATION OF IRON AND STEEL BEFORE COLD WORKING. |
| ES199090101350T ES2042082T3 (en) | 1989-01-26 | 1990-01-24 | PERFECTED METHOD FOR LUBRICATING IRON AND STEEL BEFORE COLD MACHINING. |
| BR909000328A BR9000328A (en) | 1989-01-26 | 1990-01-25 | PROCESS TO APPLY A LUBRICANT LAYER TO THE SURFACE OF IRON AND STEEL OBJECTS |
| CA002008551A CA2008551A1 (en) | 1989-01-26 | 1990-01-25 | Improved method of lubricating iron and steel before cold working |
| AU48736/90A AU621977B2 (en) | 1989-01-26 | 1990-01-25 | Improved method of lubricating iron and steel before cold working |
| AR90316014A AR244117A1 (en) | 1989-01-26 | 1990-01-25 | Method for lubricating iron and steel before they are cold- worked. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1015128A JP2636919B2 (en) | 1989-01-26 | 1989-01-26 | Lubrication treatment method for cold plastic working of steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02197581A true JPH02197581A (en) | 1990-08-06 |
| JP2636919B2 JP2636919B2 (en) | 1997-08-06 |
Family
ID=11880186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1015128A Expired - Lifetime JP2636919B2 (en) | 1989-01-26 | 1989-01-26 | Lubrication treatment method for cold plastic working of steel |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0380067B1 (en) |
| JP (1) | JP2636919B2 (en) |
| AR (1) | AR244117A1 (en) |
| AT (1) | ATE89875T1 (en) |
| AU (1) | AU621977B2 (en) |
| BR (1) | BR9000328A (en) |
| CA (1) | CA2008551A1 (en) |
| DE (1) | DE69001680T2 (en) |
| DK (1) | DK0380067T3 (en) |
| ES (1) | ES2042082T3 (en) |
| ZA (1) | ZA90305B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2111949T3 (en) * | 1993-09-06 | 1998-03-16 | Henkel Kgaa | NICKEL-FREE PHOSPHATE PROCEDURE. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58213880A (en) * | 1982-06-04 | 1983-12-12 | Nippon Parkerizing Co Ltd | Lubricating treatment of steel material before cold working |
| JPS64277A (en) * | 1987-04-11 | 1989-01-05 | Metallges Ag | Phosphation as treatment before electrodeposition coating |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3407513A1 (en) * | 1984-03-01 | 1985-09-05 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR ZINC-CALCIUM PHOSPHATION OF METAL SURFACES AT LOW TREATMENT TEMPERATURE |
| DE3408577A1 (en) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS |
| AU592671B2 (en) * | 1986-09-26 | 1990-01-18 | Ppg Industries Ohio, Inc. | Phosphate coating composition and method of applying a zinc-nickel phosphate coating |
-
1989
- 1989-01-26 JP JP1015128A patent/JP2636919B2/en not_active Expired - Lifetime
-
1990
- 1990-01-16 ZA ZA90305A patent/ZA90305B/en unknown
- 1990-01-24 DE DE90101350T patent/DE69001680T2/en not_active Expired - Fee Related
- 1990-01-24 EP EP90101350A patent/EP0380067B1/en not_active Expired - Lifetime
- 1990-01-24 ES ES199090101350T patent/ES2042082T3/en not_active Expired - Lifetime
- 1990-01-24 DK DK90101350.8T patent/DK0380067T3/en active
- 1990-01-24 AT AT90101350T patent/ATE89875T1/en active
- 1990-01-25 CA CA002008551A patent/CA2008551A1/en not_active Abandoned
- 1990-01-25 AR AR90316014A patent/AR244117A1/en active
- 1990-01-25 AU AU48736/90A patent/AU621977B2/en not_active Ceased
- 1990-01-25 BR BR909000328A patent/BR9000328A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58213880A (en) * | 1982-06-04 | 1983-12-12 | Nippon Parkerizing Co Ltd | Lubricating treatment of steel material before cold working |
| JPS64277A (en) * | 1987-04-11 | 1989-01-05 | Metallges Ag | Phosphation as treatment before electrodeposition coating |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0380067B1 (en) | 1993-05-26 |
| ATE89875T1 (en) | 1993-06-15 |
| AR244117A1 (en) | 1993-10-29 |
| AU4873690A (en) | 1990-08-02 |
| JP2636919B2 (en) | 1997-08-06 |
| CA2008551A1 (en) | 1990-07-26 |
| EP0380067A1 (en) | 1990-08-01 |
| ZA90305B (en) | 1991-03-27 |
| DK0380067T3 (en) | 1993-06-21 |
| ES2042082T3 (en) | 1993-12-01 |
| AU621977B2 (en) | 1992-03-26 |
| DE69001680D1 (en) | 1993-07-01 |
| DE69001680T2 (en) | 1993-09-30 |
| BR9000328A (en) | 1990-11-27 |
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