JP2017066515A - Steel wire excellent in corrosion resistance and appearance after working - Google Patents
Steel wire excellent in corrosion resistance and appearance after working Download PDFInfo
- Publication number
- JP2017066515A JP2017066515A JP2016121490A JP2016121490A JP2017066515A JP 2017066515 A JP2017066515 A JP 2017066515A JP 2016121490 A JP2016121490 A JP 2016121490A JP 2016121490 A JP2016121490 A JP 2016121490A JP 2017066515 A JP2017066515 A JP 2017066515A
- Authority
- JP
- Japan
- Prior art keywords
- film
- steel wire
- water
- lubricant
- lubricating film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000010959 steel Substances 0.000 title claims abstract description 101
- 238000005260 corrosion Methods 0.000 title abstract description 43
- 230000007797 corrosion Effects 0.000 title abstract description 43
- 230000001050 lubricating effect Effects 0.000 claims abstract description 98
- -1 fatty acid alkali metal salt Chemical class 0.000 claims abstract description 50
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 45
- 239000000194 fatty acid Substances 0.000 claims abstract description 45
- 229930195729 fatty acid Natural products 0.000 claims abstract description 45
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 43
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 22
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- 239000007769 metal material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
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- 150000001340 alkali metals Chemical class 0.000 description 4
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- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- VJJBJJBTUXPNEO-UHFFFAOYSA-N docosanamide;ethene Chemical compound C=C.CCCCCCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCCCCCC(N)=O VJJBJJBTUXPNEO-UHFFFAOYSA-N 0.000 description 1
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- FPLIHVCWSXLMPX-UHFFFAOYSA-M lithium 12-hydroxystearate Chemical compound [Li+].CCCCCCC(O)CCCCCCCCCCC([O-])=O FPLIHVCWSXLMPX-UHFFFAOYSA-M 0.000 description 1
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- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 238000005554 pickling Methods 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- IFQCEOKSFPQHTD-UHFFFAOYSA-M potassium;12-hydroxyoctadecanoate Chemical compound [K+].CCCCCCC(O)CCCCCCCCCCC([O-])=O IFQCEOKSFPQHTD-UHFFFAOYSA-M 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- PYJBVGYZXWPIKK-UHFFFAOYSA-M potassium;tetradecanoate Chemical compound [K+].CCCCCCCCCCCCCC([O-])=O PYJBVGYZXWPIKK-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/22—Carboxylic acids or their salts
- C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/146—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies to metallic pipes or tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/06—Metal compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/22—Compounds containing sulfur, selenium or tellurium
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- C—CHEMISTRY; METALLURGY
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- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/02—Polyethene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
- C10M145/08—Vinyl esters of a saturated carboxylic or carbonic acid
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
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Abstract
Description
本発明は、リンを含まない潤滑皮膜を表面に有する鋼線材に関する。 The present invention relates to a steel wire having a lubricating film containing no phosphorus on its surface.
鋼線および鋼線材の塑性加工において、金属表面同士（特にダイスと被加工材）が激しく擦れ合う際に生じる摩擦は、加工エネルギーの増大、発熱、焼付き現象などの原因となるため摩擦力低減を目指した様々な潤滑剤が用いられてきた。潤滑剤としては、古くから油や石けん類などが用いられ、摩擦面に供給することで流体潤滑膜として摩擦力を低減してきたが、表面積拡大による大きな発熱を伴い高面圧下で摺動する塑性加工では潤滑性不足や、潤滑膜切れなどにより焼付き現象が発生し易くなる。そのため充分な皮膜強度を有し、高面圧下でもダイスと被加工材の界面に介在することで潤滑膜切れを起こしにくく金属同士の直接接触を回避できるホウ酸塩皮膜、リン酸塩結晶皮膜等の無機皮膜等の固体皮膜で予め金属材料表面を被覆しておく技術が一般化されている。特にリン酸亜鉛皮膜と石鹸層からなる複合皮膜（以下、化成処理皮膜と呼ぶ場合がある）は高い加工性と耐食性を有しており、広く用いられている。 In plastic processing of steel wires and steel wires, friction generated when metal surfaces (especially dies and workpieces) rub against each other violently increases processing energy, generates heat, and causes seizure. Various targeted lubricants have been used. Oil and soap have been used for a long time as lubricants, and by supplying them to the friction surface, the frictional force has been reduced as a fluid lubrication film, but plasticity that slides under high surface pressure with large heat generation due to surface area expansion In processing, seizure phenomenon is likely to occur due to lack of lubricity or running out of the lubricating film. For this reason, borate films, phosphate crystal films, etc. that have sufficient film strength and that are less likely to cause lubrication film breakage due to being present at the interface between the die and the workpiece even under high surface pressure, and avoid direct contact between metals A technique of previously coating a metal material surface with a solid film such as an inorganic film has been generalized. In particular, a composite film composed of a zinc phosphate film and a soap layer (hereinafter sometimes referred to as a chemical conversion film) has high processability and corrosion resistance and is widely used.
一方、近年、加工エネルギーの更なる低減化や強加工度化、難加工材への対応、皮膜プロセスの環境保全性（例えばリン酸塩処理はスラッジ等の産業廃棄物を多量に生じさせるので環境保全上問題がある）、ボルト等の浸リン（高強度ボルトのヘッダー加工後に皮膜成分のリンが残存すると熱処理時にリンが鋼中に進入し脆性破壊の起因となる）対策など、固体皮膜への要求は多岐に亘り急速に高まりつつあり、これらの要求に対して環境保全を考慮する一方、高度な潤滑性を有する固体皮膜が開発されつつある。この技術は被加工材の表面に水系の塑性加工潤滑剤を塗布し乾燥するだけの簡便な工程によって高度な潤滑性を有する皮膜を形成させるものである。 On the other hand, in recent years, the processing energy has been further reduced, the degree of processing has been increased, difficult-to-process materials can be handled, and the environmental protection of the coating process (for example, phosphating has caused a large amount of industrial waste such as sludge. There is a problem in terms of maintenance), and immersion of phosphorus such as bolts (if phosphorus of the coating component remains after header processing of high-strength bolts, phosphorus enters the steel during heat treatment and causes brittle fracture). The demands are increasing rapidly in various fields, and while considering environmental protection for these demands, solid coatings having high lubricity are being developed. This technique is to form a film having high lubricity by a simple process of applying a water-based plastic processing lubricant to the surface of a workpiece and drying it.
特許文献１には（Ａ）水溶性無機塩と（Ｂ）ワックスを水に溶解または分散させた組成物で、固形分重量比（Ｂ）／（Ａ）が０．３〜１．５の範囲内にあることを特徴とする金属材料塑性加工用水系潤滑皮膜処理剤とその皮膜形成方法が開示されている。 Patent Document 1 discloses a composition in which (A) a water-soluble inorganic salt and (B) wax are dissolved or dispersed in water, and the solid content weight ratio (B) / (A) is in the range of 0.3 to 1.5. An aqueous lubricating film treating agent for plastic working of metal materials and a method for forming the film are disclosed.
特許文献２にはアルカリ金属ホウ酸塩（Ａ）を含有する水系潤滑皮膜処理剤において、アルカリ金属ホウ酸塩（Ａ）にホウ酸リチウムを含み、アルカリ金属ホウ酸塩（Ａ）における全アルカリ金属に対するリチウムのモル比率が０．１〜１．０であって、かつ、アルカリ金属ホウ酸塩（Ａ）のホウ酸Ｂとアルカリ金属Ｍとのモル比率（Ｂ／Ｍ）が１．５〜４．０であることを特徴とする金属材料塑性加工用水系潤滑皮膜処理剤とその皮膜形成方法が開示されている。この技術は皮膜が吸湿することによって発生する皮膜の結晶化を抑制することで加工性のみならず、高い耐食性を有する皮膜を形成することができるとされている。 Patent Document 2 discloses an aqueous lubricant film treatment agent containing an alkali metal borate (A), wherein the alkali metal borate (A) contains lithium borate, and the alkali metal borate (A) contains all alkali metals. The molar ratio of lithium to 0.1 to 1.0 and the molar ratio (B / M) of boric acid B and alkali metal M of the alkali metal borate (A) to 1.5 to 4 0.0, a water-based lubricating film treating agent for plastic working of metal materials and a method for forming the film are disclosed. This technique is said to be able to form a film having not only workability but also high corrosion resistance by suppressing the crystallization of the film that occurs when the film absorbs moisture.
特許文献３にはＡ成分：無機系固体潤滑剤と、Ｂ成分：ワックスと、Ｃ成分：水溶性無機金属塩とを含有し、Ａ成分とＢ成分の固形分乾燥質量比（Ａ成分／Ｂ成分）が０．１〜５であり、Ａ成分、Ｂ成分、およびＣ成分の合計量に対するＣ成分の固形分乾燥質量比率（Ｃ成分／（Ａ成分＋Ｂ成分＋Ｃ成分））が１〜３０％であることを特徴とする非リン系塑性加工用水溶性潤滑剤が開示されている。この技術はリンを含有しない潤滑剤であり、且つ化成処理皮膜と同等の耐食性が実現できるとされている。 Patent Document 3 contains an A component: an inorganic solid lubricant, a B component: a wax, and a C component: a water-soluble inorganic metal salt, and a solid content dry mass ratio of the A component and the B component (A component / B Component) is 0.1 to 5, and the solid content dry mass ratio of the C component to the total amount of the A component, the B component, and the C component (C component / (A component + B component + C component)) is 1 to 30% A water-soluble lubricant for non-phosphorus plastic processing is disclosed. This technique is a lubricant that does not contain phosphorus, and is said to be able to realize corrosion resistance equivalent to that of a chemical conversion coating.
特許文献４には、水溶性無機塩（Ａ）と、二硫化モリブデン、およびグラファイトから選ばれる１種以上の滑剤（Ｂ）と、ワックス（Ｃ）とを含有し、かつこれらを水に溶解または分散しており、（Ｂ）／（Ａ）が固形分重量比で１．０〜５．０、（Ｃ）／（Ａ）が固形分重量比で０．１〜１．０である水系潤滑皮膜処理剤とその皮膜形成方法が開示されている。この技術は従来の水系潤滑皮膜処理剤に二硫化モリブデンやグラファイトを配合することで、化成処理皮膜と同等レベルの高い加工性を実現できるとされている。 Patent Document 4 contains a water-soluble inorganic salt (A), one or more lubricants (B) selected from molybdenum disulfide and graphite, and a wax (C), and these are dissolved in water or Aqueous lubrication in which (B) / (A) is 1.0 to 5.0 in terms of solids weight ratio and (C) / (A) is 0.1 to 1.0 in terms of solids weight ratio. A film treatment agent and a method for forming the film are disclosed. This technology is said to be able to realize high workability equivalent to that of a chemical conversion treatment film by blending molybdenum disulfide or graphite with a conventional water-based lubricating film treatment agent.
特許文献５には、珪酸塩（Ａ）と、ポリカルボン酸塩（Ｂ）と、水親和性ポリマー及び／又は水親和性有機ラメラ構造体（Ｃ）と、モリブデン酸塩及び／又はタングステン酸塩（Ｄ）とを含有し、前記各成分の乾燥質量比が所定の比率である皮膜形成剤が開示されている。 Patent Document 5 discloses silicate (A), polycarboxylate (B), water-compatible polymer and / or water-compatible organic lamellar structure (C), molybdate and / or tungstate. (D) and the film formation agent whose dry mass ratio of each said component is a predetermined ratio is disclosed.
特許文献１〜５にも記載されるように水溶性無機塩は水系潤滑皮膜処理剤の固体皮膜における必須成分である。その理由は水溶性無機塩で構成される潤滑皮膜は充分な皮膜強度を有し、前述のように高面圧下でもダイスと被加工材の界面に介在して潤滑膜切れを起こしにくく金属同士の直接接触を回避することができるためである。よって水系潤滑皮膜処理剤では水溶性無機塩や水溶性樹脂から成る固体皮膜に摩擦係数を低減可能な適切な滑剤を組み合わせることで塑性加工時に良好な潤滑状態を維持することができる。 As described in Patent Documents 1 to 5, the water-soluble inorganic salt is an essential component in the solid film of the aqueous lubricant film treating agent. The reason is that a lubricating film composed of a water-soluble inorganic salt has a sufficient film strength, and as described above, it is difficult to cause the lubricating film to break by intervening at the interface between the die and the workpiece even under high surface pressure. This is because direct contact can be avoided. Therefore, in the case of a water-based lubricating film treatment agent, a good lubricating state can be maintained during plastic processing by combining a solid film made of a water-soluble inorganic salt or a water-soluble resin with an appropriate lubricant capable of reducing the friction coefficient.
水溶性成分で構成される水系潤滑皮膜の皮膜形成メカニズムについて説明する。水溶性成分の水溶性無機塩は潤滑剤処理液中で水に溶解した状態であって金属材料表面に潤滑剤を塗布して乾燥させると溶媒の水が蒸発して潤滑皮膜が形成される。その際に水溶性無機塩は金属材料表面で固形物として析出して固体皮膜を形成する。このように形成された固体皮膜は塑性加工に耐え得る皮膜強度を備えており、摩擦係数を低減させる適当な滑剤を配合させることで塑性加工時に良好な潤滑性を示す。 The film formation mechanism of the water-based lubricating film composed of water-soluble components will be described. The water-soluble inorganic salt of the water-soluble component is in a state of being dissolved in water in the lubricant treatment liquid. When the lubricant is applied to the surface of the metal material and dried, the solvent water evaporates to form a lubricating film. At that time, the water-soluble inorganic salt is deposited as a solid on the surface of the metal material to form a solid film. The solid coating formed in this way has a coating strength that can withstand plastic processing, and exhibits good lubricity during plastic processing by incorporating an appropriate lubricant that reduces the friction coefficient.
しかし、特許文献１〜５の潤滑皮膜では上記の化成処理皮膜と比較して２ヶ月以上の長期防錆性が著しく劣っており、実用レベルまで高めることができていない。これは皮膜の主成分が水溶性成分であるため、大気中の水分を容易に吸収あるいは透過し、鋼材と水分の接触が容易であることが原因となっている。特許文献２では吸湿による皮膜の結晶化を抑制することで耐食性が向上しているが、吸湿そのものを抑制している訳ではなく、十分な耐食性が得られていない。また、特許文献３に記載されている水系潤滑皮膜は、恒温恒湿器を用いて発錆を促進したラボでの耐食性試験において、化成処理皮膜と同等以上の耐食性を示したと記載されている。しかし、実際に潤滑皮膜を使用する環境はホコリや粉塵、酸洗薬剤のミストが付着し得るような状態にあるのが普通であり、そのような過酷な環境においては化成処理皮膜よりも耐食性が劣っているのが実状である。このように、リンを含有していない水系潤滑皮膜において、化成処理皮膜と同等以上の防錆性を有するものは過去に存在しなかった。 However, the lubricating films of Patent Documents 1 to 5 are significantly inferior in long-term rust prevention for 2 months or more as compared with the chemical conversion film, and cannot be increased to a practical level. This is because the main component of the film is a water-soluble component, so that moisture in the atmosphere can be easily absorbed or permeated, and the steel material can easily come into contact with moisture. In Patent Document 2, although corrosion resistance is improved by suppressing crystallization of the film due to moisture absorption, moisture absorption itself is not suppressed, and sufficient corrosion resistance is not obtained. Moreover, it is described that the water-based lubricating film described in Patent Document 3 exhibited a corrosion resistance equivalent to or higher than that of the chemical conversion coating film in a corrosion resistance test in a laboratory in which rusting was accelerated using a thermo-hygrostat. However, the actual environment in which the lubricant film is used is usually in a state where dust, dust, and pickling chemical mist can adhere, and in such a harsh environment, the corrosion resistance is better than the chemical conversion film. The actual situation is inferior. As described above, there has been no water-based lubricating film that does not contain phosphorus that has a rust prevention property equal to or higher than that of the chemical conversion film.
比較的高い耐食性が得られる水溶性無機塩としては、ケイ酸塩のアルカリ金属塩（以下、ケイ酸塩と記載する場合がある）とタングステン酸塩のアルカリ金属塩および／またはアンモニウム塩（以下、タングステン酸塩と記載する場合がある）が挙げられる。これら水溶性無機塩は特許文献１や特許文献４や特許文献５にも記載されている。しかし、それらも実用上の耐食性は、化成処理皮膜と比較すると大きく劣るものである。 Examples of water-soluble inorganic salts that can provide relatively high corrosion resistance include alkali metal salts of silicates (hereinafter sometimes referred to as silicates), alkali metal salts of tungstates and / or ammonium salts (hereinafter referred to as May be described as tungstate). These water-soluble inorganic salts are also described in Patent Document 1, Patent Document 4 and Patent Document 5. However, they also have a practically inferior corrosion resistance compared to the chemical conversion coating.
水溶性ケイ酸塩は水溶性無機塩の中では水分を透過しにくく、且つ素材との密着性が非常に高い性質がある。この性質のため、化成処理皮膜ほどではないが、比較的高い耐食性を発現することができる材料である。これは潤滑剤の溶媒である水が揮発する皮膜生成過程において水溶性ケイ酸塩が架橋し、ネットワーク構造をとるためである。しかし、このネットワーク構造であるが故に、水溶性ケイ酸塩の皮膜は潤滑皮膜としては脆すぎる。このため基材が加工された際には皮膜が割れて、十分に追従できず、加工部位の皮膜残存量低下につながる場合がある。 The water-soluble silicate has a property that it hardly permeates moisture in the water-soluble inorganic salt and has very high adhesion to the material. Because of this property, it is a material that can exhibit relatively high corrosion resistance, although not as much as the chemical conversion coating. This is because the water-soluble silicate is crosslinked and forms a network structure in the process of forming a film in which water as a solvent of the lubricant volatilizes. However, because of this network structure, the water-soluble silicate film is too brittle as a lubricating film. For this reason, when a base material is processed, a film | membrane cracks and it cannot follow enough, and may lead to the film residual amount fall of a process site | part.
水溶性タングステン酸塩は皮膜を形成させた際に外気の水分を吸収しにくい。これは水溶性タングステン酸塩が皮膜を形成する際、粒子状の結晶を形成するためである。さらに水溶性タングステン酸塩は鋼材表面に自己修復機能を有する不動態膜を形成させる性質があり、皮膜成分として用いることで高耐食性の皮膜形成が期待できる。しかし、水溶性タングステン酸塩は結晶質であるが故に素材との密着性が乏しい上、均一な皮膜を形成することができないため、期待通りの耐食性や加工性を得ることができない。例えば潤滑剤中に合成樹脂成分を加えることで皮膜の密着性、均一性を高めることができるが、それでも耐食性は化成処理皮膜と比較して著しく劣るものである。 A water-soluble tungstate hardly absorbs moisture from the outside air when a film is formed. This is because when the water-soluble tungstate forms a film, it forms particulate crystals. Furthermore, water-soluble tungstate has the property of forming a passive film having a self-repairing function on the surface of the steel material, and it can be expected to form a highly corrosion-resistant film by using it as a film component. However, since the water-soluble tungstate is crystalline, it has poor adhesion to the material and cannot form a uniform film, so that the expected corrosion resistance and workability cannot be obtained. For example, the adhesion and uniformity of the film can be improved by adding a synthetic resin component to the lubricant, but the corrosion resistance is still inferior to that of the chemical conversion film.
特許文献４に掲載された水系潤滑皮膜処理剤は、二硫化モリブデンやグラファイトを含有することで、強加工時も化成処理皮膜と同等以上の加工性を得ることができる。しかし、特許文献１〜３の潤滑皮膜と比較して耐食性が劣るものである。 By containing molybdenum disulfide and graphite, the water-based lubricating film treating agent described in Patent Document 4 can obtain workability equivalent to or better than that of the chemical conversion film even during strong working. However, the corrosion resistance is inferior to that of the lubricating film of Patent Documents 1 to 3.
特許文献５では、珪酸塩（Ａ）を主成分として含有し、耐食剤（Ｄ）などが多すぎたりする皮膜処理材では、押出荷重が高い場合、焼付が発生する等して、潤滑性が劣るため安定した作業が困難となり、また、長期防錆性も十分ではない。 In Patent Document 5, a coating material containing silicate (A) as a main component and containing too much corrosion-resistant agent (D) or the like has seizure when the extrusion load is high. Since it is inferior, stable work becomes difficult, and long-term rust prevention is not sufficient.
さらに、特許文献１〜５に記載の潤滑皮膜を有する鋼材を圧造加工すると、圧造加工の方法や圧造加工後の形状等によっては、鋼材に対する皮膜の押し込みが発生して製品の外観不良が発生する。これらの潤滑皮膜は皮膜中における滑剤成分の分布が疎らになりやすく、滑剤が多い箇所と、滑剤が少ない箇所との間で、圧造加工時に局所的に摩擦状態の差が生まれてしまう。その結果、鋼材を加工した際の変形量が局所的に異なって所謂スティックスリップ現象と類似する現象が生じ、特に摩擦が局所的に高くなっている箇所で皮膜の押し込みが発生して鱗状の模様が生じるなどの外観不良を招く。また、潤滑皮膜中に配合される無機塩は比較的硬質なため、圧造加工時の面圧で鋼材に押し込み痕が発生しやすい。これらの模様や押し込み痕は目視で容易に確認できるため、製品の外観を著しく損ねるものとなっていた。 Furthermore, when the steel material having the lubricating film described in Patent Documents 1 to 5 is forged, depending on the forging method and the shape after forging, the indentation of the film against the steel material occurs, resulting in poor appearance of the product. . In these lubricating coatings, the distribution of the lubricant component in the coating tends to be sparse, and a difference in the frictional state is locally produced during the forging process between the portion where the lubricant is large and the portion where the lubricant is small. As a result, the amount of deformation when the steel material is processed is locally different, resulting in a phenomenon similar to the so-called stick-slip phenomenon. Cause appearance defects such as In addition, since the inorganic salt blended in the lubricating film is relatively hard, indentation marks are likely to occur in the steel material due to the surface pressure during forging. Since these patterns and indentation marks can be easily confirmed visually, the appearance of the product has been significantly impaired.
このように水系潤滑皮膜では、実用環境でも化成処理皮膜に匹敵するような、約２ヶ月以上の長期間にわたる高い耐食性を有し、且つ、圧造加工後も優れた外観を同時に兼ね備えることはできなかった。 In this way, the water-based lubricant film has high corrosion resistance over a long period of about two months or more, comparable to the chemical conversion film even in a practical environment, and cannot have an excellent appearance at the same time after forging. It was.
そこで、本発明の課題は、長期防錆性等の耐食性と、圧造加工後の優れた外観と、を両立することができる潤滑皮膜を有する鋼線材を提供することにある。 Then, the subject of this invention is providing the steel wire which has a lubricous film which can make corrosion resistance, such as long-term rust prevention property, and the outstanding external appearance after forging process compatible.
本発明者らは、リンを含まない潤滑皮膜を表面に有する鋼線材について、上記課題を解決するために鋭意研究を行ってきた。その結果、水溶性ケイ酸塩などに由来するケイ素と、水溶性タングステン酸塩などに由来するタングステンとの比率、すなわちタングステン／ケイ素の乾燥質量比を所定比率に制御した潤滑皮膜に、滑剤として用いられる種々の化合物のなかでも脂肪酸のアルカリ金属塩を所定の比率で配合することにより、それら成分単体では決して成し得なかった高い耐食性と、ワックスなどの滑剤を配合したときには決して得られなかった圧造加工後の優れた外観が同時に得られることを見出し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a steel wire having a lubricating film containing no phosphorus on its surface. As a result, the ratio of silicon derived from water-soluble silicates and tungsten derived from water-soluble tungstates, that is, a lubricant film in which the dry mass ratio of tungsten / silicon is controlled to a predetermined ratio, is used as a lubricant. Among these various compounds, by blending a certain proportion of alkali metal salts of fatty acids, high corrosion resistance that could never be achieved with these components alone, and forging that was never obtained when a lubricant such as wax was blended It was found that an excellent appearance after processing was obtained at the same time, and the present invention was completed.
本発明の鋼線材は、上記課題を解決するために、以下のように構成されている。 The steel wire rod of the present invention is configured as follows in order to solve the above problems.
本発明の鋼線材は、ケイ素（Ａ）とタングステン（Ｂ）と脂肪酸のアルカリ金属塩（Ｃ）を含み、（Ｂ）／（Ａ）の乾燥質量比が１．３〜１８の範囲であり、（Ｃ）／{（Ａ）＋（Ｂ）}の乾燥質量比が０．１４〜２．０の範囲であり、リンを含まない潤滑皮膜を表面に有するものである。 The steel wire rod of the present invention contains silicon (A), tungsten (B) and an alkali metal salt of fatty acid (C), and the dry mass ratio of (B) / (A) is in the range of 1.3 to 18, The dry mass ratio of (C) / {(A) + (B)} is in the range of 0.14 to 2.0, and has a lubricating film containing no phosphorus on the surface.
前記ケイ素が水溶性ケイ酸塩由来であり、且つ、前記タングステンが水溶性タングステン酸塩由来であることが好ましい。 It is preferable that the silicon is derived from a water-soluble silicate and the tungsten is derived from a water-soluble tungstate.
前記ケイ素がケイ酸リチウム、ケイ酸ナトリウム、及びケイ酸カリウムよりなる群から選ばれる少なくとも１種以上に由来し、且つ、前記タングステンがタングステン酸リチウム、タングステン酸ナトリウム、タングステン酸カリウム、及びタングステン酸アンモニウムよりなる群から選ばれる少なくとも１種以上に由来することが好ましい。 The silicon is derived from at least one selected from the group consisting of lithium silicate, sodium silicate, and potassium silicate, and the tungsten is lithium tungstate, sodium tungstate, potassium tungstate, and ammonium tungstate. It is preferably derived from at least one selected from the group consisting of:
前記潤滑皮膜が前記脂肪酸のアルカリ金属塩（Ｃ）以外の滑剤（Ｄ）を更に含み、｛（Ｃ）＋（Ｄ）｝／｛（Ａ）＋（Ｂ）｝の乾燥質量比が０．１４〜２．０であることが好ましい。 The lubricating coating further contains a lubricant (D) other than the alkali metal salt (C) of the fatty acid, and the dry mass ratio of {(C) + (D)} / {(A) + (B)} is 0.14. It is preferable that it is -2.0.
前記滑剤（Ｄ）がワックス、ポリテトラフルオロエチレン、脂肪酸金属石鹸、脂肪酸アマイド、二硫化モリブデン、二硫化タングステン、グラファイト、及びメラミンシアヌレートよりなる群から選ばれる少なくとも１種以上であることが好ましい。 The lubricant (D) is preferably at least one selected from the group consisting of wax, polytetrafluoroethylene, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, and melamine cyanurate.
前記潤滑皮膜が樹脂（Ｅ）を更に含み、（Ｅ）／{（Ａ）＋（Ｂ）}の乾燥質量比が０超１．４以下であることが好ましい。 It is preferable that the lubricating film further contains a resin (E), and the dry mass ratio of (E) / {(A) + (B)} is more than 0 and 1.4 or less.
前記樹脂（Ｅ）がビニル樹脂、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、フェノール樹脂、セルロース誘導体、ポリマレイン酸、及びポリエステル樹脂よりなる群から選ばれる少なくとも１種以上であることが好ましい。 The resin (E) is preferably at least one selected from the group consisting of vinyl resin, acrylic resin, epoxy resin, urethane resin, phenol resin, cellulose derivative, polymaleic acid, and polyester resin.
前記潤滑皮膜の単位面積当たりの皮膜質量が１．０〜２０ｇ／ｍ2であることが好ましい。 The coating mass per unit area of the lubricating coating is preferably 1.0 to 20 g / m 2 .
本発明の鋼線材は潤滑皮膜を上記のように構成されているため、長期防錆性等の耐食性に優れ、且つ、圧造加工後の外観も良好な鋼線材が得られる。これらの性能は全て、化成処理皮膜を有する鋼線材と同等以上の水準である点が従来の水系潤滑皮膜と比べて大きく優れている点である。 Since the steel wire of the present invention has the lubricating coating as described above, a steel wire having excellent corrosion resistance such as long-term rust prevention and excellent appearance after forging is obtained. All of these performances are greatly superior to conventional water-based lubricating coatings in that they are at or above the level of a steel wire having a chemical conversion coating.
本発明の鋼線材は、ケイ素（Ａ）とタングステン（Ｂ）と脂肪酸のアルカリ金属塩（Ｃ）を含み、（Ｂ）／（Ａ）の乾燥質量比が１．３〜１８の範囲であり、（Ｃ）／{（Ａ）＋（Ｂ）}の乾燥質量比が０．１４〜２．０の範囲であり、リンを含まない潤滑皮膜を表面に有するところに特徴がある。 The steel wire rod of the present invention contains silicon (A), tungsten (B) and an alkali metal salt of fatty acid (C), and the dry mass ratio of (B) / (A) is in the range of 1.3 to 18, The dry mass ratio of (C) / {(A) + (B)} is in the range of 0.14 to 2.0, and is characterized by having a lubricating film containing no phosphorus on the surface.
本発明の鋼線材に使用される鋼は、炭素鋼、合金鋼、特殊鋼等が含まれる。かかる鋼としては、炭素含有量が０．２質量％以下（０質量％を含まない）の軟鋼から０．２質量％超１．５質量％以下程度の炭素鋼、及び軟鋼もしくは炭素鋼の用途に応じてシリコン、マンガン、リン、硫黄、ニッケル、クロム、銅、アルミニウム、モリブデン、バナジウム、コバルト、チタン、ジルコニウム等から選ばれる少なくとも１種を含有する合金鋼又は特殊鋼等が挙げられる。 The steel used for the steel wire of the present invention includes carbon steel, alloy steel, special steel and the like. As such steel, carbon steel having a carbon content of 0.2% by mass or less (excluding 0% by mass) to carbon steel having a carbon content of more than 0.2% by mass and not more than 1.5% by mass, and uses of mild steel or carbon steel Depending on the above, alloy steel or special steel containing at least one selected from silicon, manganese, phosphorus, sulfur, nickel, chromium, copper, aluminum, molybdenum, vanadium, cobalt, titanium, zirconium and the like can be mentioned.
本発明において鋼線材とは、一般的には鋼を熱間加工により線材に加工したものをいう。本発明の鋼線材には鋼線も含まれる。鋼線とは上記の鋼線材をさらに加工処理したものであり、上記加工処理には、伸線加工処理、圧造加工処理、鍛造加工処理等が挙げられる。具体的には例えば、上記の鋼線材を規定サイズ（線径や真円度等）に伸線加工したもの、伸線加工後に圧造加工したもの、上記の鋼線材を鍛造加工したもの等が挙げられる。また、上記鋼線には、上記加工処理後の製品に対して熱処理；メッキ処理などの表面処理等を更に施したものも含まれる。具体的には例えば、上記圧造加工または鍛造加工の後、機械加工を行なって製品にした後、熱処理を施したもの、上記熱処理の後にメッキ処理を更に施したもの等が挙げられる。 In the present invention, the steel wire generally refers to steel processed into a wire by hot working. The steel wire material of the present invention includes a steel wire. The steel wire is obtained by further processing the steel wire, and examples of the processing include wire drawing processing, forging processing, forging processing, and the like. Specifically, for example, those obtained by drawing the above steel wire to a specified size (wire diameter, roundness, etc.), those forged after drawing, those forged from the above steel wire, etc. It is done. The steel wire includes those obtained by further subjecting the processed product to heat treatment; surface treatment such as plating. Specifically, for example, after the above forging or forging, machining is performed to obtain a product, heat treatment is performed, and after the heat treatment, plating is further performed.
本発明の鋼線材は、後述する潤滑皮膜を有することで耐食性と圧造加工後の外観に優れるものであれば、特に限定されないが、鋼線材の表面と潤滑皮膜との間にさらなる皮膜、すなわち下地皮膜が形成されていてもよい。これらの皮膜は、いずれも一層または二層以上の層であってもよい。 The steel wire material of the present invention is not particularly limited as long as it has a lubricating film described later and has excellent corrosion resistance and appearance after forging, but a further film between the surface of the steel wire and the lubricating film, that is, the base A film may be formed. Any of these films may be a single layer or two or more layers.
本発明に用いられる上記潤滑皮膜及び下地皮膜はいずれも、リンを含まないものである。よって、潤滑皮膜の形成に使用される潤滑皮膜処理剤にはリンを含む成分は含まれない。しかしながら、本発明において、操業過程等でリンを含む成分が鋼線材表面の皮膜に不可避的に混入されることを排除するものではない。すなわち、実際の操業では不可避的不純物としてリンがコンタミする場合があるが、リンの含有量が１質量％以下程度であれば、かかるリンにより鋼線材が脆性破壊される可能性は低く、浸リンは起こらないとみなすことができる。 Both the lubricating coating and the base coating used in the present invention do not contain phosphorus. Therefore, the lubricating film treating agent used for forming the lubricating film does not contain a component containing phosphorus. However, in the present invention, it is not excluded that a component containing phosphorus is inevitably mixed in the coating on the surface of the steel wire in the operation process or the like. In other words, phosphorus may be contaminated as an inevitable impurity in actual operation. However, if the phosphorus content is about 1% by mass or less, the steel wire is not likely to be brittlely broken by such phosphorus. Can be considered not to happen.
以下、本発明の鋼線材における潤滑皮膜の各成分、組成等から順に説明する。 Hereinafter, each component, composition, etc. of the lubricating film in the steel wire of the present invention will be described in order.
本発明の鋼線材は、ケイ素（Ａ）、タングステン（Ｂ）、および脂肪酸のアルカリ金属塩（Ｃ）を含み、（Ｂ）／（Ａ）が１．３〜１８の範囲内にあり、（Ｃ）／｛（Ａ）＋（Ｂ）｝が０．１４〜２．０の範囲で含有する潤滑皮膜を表面に有する。上記成分を含み、且つ、それらの比率を上記範囲に制御した、潤滑皮膜を鋼線材の表面に形成することにより、高い耐食性と圧造加工後の優れた外観を同時に達成することができる。 The steel wire rod of the present invention contains silicon (A), tungsten (B), and an alkali metal salt (C) of a fatty acid, and (B) / (A) is in the range of 1.3 to 18, ) / {(A) + (B)} has a lubricating film on the surface in the range of 0.14 to 2.0. By forming a lubricating film on the surface of the steel wire containing the above components and controlling their ratio within the above range, high corrosion resistance and excellent appearance after forging can be achieved at the same time.
例えば後述される水溶性ケイ酸塩と水溶性タングステン酸塩とを複合して潤滑皮膜とした場合、水溶性ケイ酸塩が形成するネットワーク構造の中に水溶性タングステン酸塩が取り込まれることとなる。上述の通り、水溶性タングステン酸塩は結晶質の皮膜を形成するという欠点を有するが、水溶性ケイ酸塩のネットワーク構造に取り込まれることにより、水溶性タングステン酸塩が均一且つ微細に存在することができるようになる。これにより、水溶性ケイ酸塩の水分を透過しにくい性質と水溶性タングステン酸塩の自己修復機能を有する不動態膜が両立され、耐食性が著しく向上する。 For example, when a water-soluble silicate and a water-soluble tungstate described later are combined to form a lubricating film, the water-soluble tungstate is incorporated into the network structure formed by the water-soluble silicate. . As described above, water-soluble tungstate has the disadvantage of forming a crystalline film. However, water-soluble tungstate is present uniformly and finely by being incorporated into the network structure of water-soluble silicate. Will be able to. As a result, the properties of the water-soluble silicate that hardly permeate moisture and the passive film having the self-healing function of the water-soluble tungstate are compatible, and the corrosion resistance is remarkably improved.
また、水溶性タングステン酸塩が水溶性ケイ酸塩に与える影響として皮膜追従性の改善に伴う、加工部位の皮膜残存量の増加が挙げられる。上述の通り、水溶性ケイ酸塩の皮膜追従性が劣る原因は水溶性ケイ酸塩の高分子化によって強固な連続皮膜を形成することによるものであるが、複合している水溶性タングステン酸塩が水溶性ケイ酸塩のネットワーク構造中に介在することで強固なネットワーク構造の形成を適度に阻害し、皮膜追従性が向上することにより皮膜残存量を増加させることができる。 Further, as an influence of the water-soluble tungstate on the water-soluble silicate, there is an increase in the remaining amount of the film at the processing site due to the improvement of the film followability. As described above, the reason why the water-soluble silicate film is inferior is due to the formation of a strong continuous film by polymerizing the water-soluble silicate. Intervening in the network structure of the water-soluble silicate moderately inhibits the formation of a strong network structure and increases the film followability, thereby increasing the film residual amount.
特に良好な耐食性を確保するため、タングステン（Ｂ）／ケイ素（Ａ）の乾燥質量比は１．３以上であり、好ましくは１．８以上、より好ましくは２．０以上である。また、上記乾燥質量比は１８以下であり、好ましくは１０以下、より好ましくは５．４以下である。Ｂ／Ａの乾燥質量比が１．３を下回ると十分な耐食性が得られない他、加工部の皮膜残存量が低下する。これは相対的に前記タングステン酸塩の量が減ることにより、不動態膜が十分に形成されないこと、前記ケイ酸塩量が相対的に増えることで強固なネットワーク構造を形成してしまうことに起因する。タングステン／ケイ素の乾燥質量比が１８を上回ると十分な耐食性が得られない皮膜となる。これは、相対的にケイ酸塩量が少なくなることで水分が透過しやすくなること、前記タングステン酸塩の結晶が析出し、皮膜の密着性、均一性が低下することに起因する。なお、本発明において、タングステン／ケイ素の乾燥質量比は、皮膜中の水溶性タングステン酸塩由来のタングステン元素と、水溶性ケイ酸塩由来のケイ素元素との比率に基づくものであり、後述の通りにして算出することができる。 In order to ensure particularly good corrosion resistance, the dry mass ratio of tungsten (B) / silicon (A) is 1.3 or more, preferably 1.8 or more, more preferably 2.0 or more. The dry mass ratio is 18 or less, preferably 10 or less, more preferably 5.4 or less. When the dry mass ratio of B / A is less than 1.3, sufficient corrosion resistance cannot be obtained, and the remaining amount of the film in the processed portion is reduced. This is because the amount of the tungstate is relatively reduced, the passive film is not sufficiently formed, and the amount of the silicate is relatively increased to form a strong network structure. To do. When the dry mass ratio of tungsten / silicon exceeds 18, a film in which sufficient corrosion resistance cannot be obtained. This is due to the fact that the amount of silicate becomes relatively small and moisture can easily permeate, the crystals of the tungstate precipitate, and the adhesion and uniformity of the film are lowered. In the present invention, the dry mass ratio of tungsten / silicon is based on the ratio of the tungsten element derived from the water-soluble tungstate and the silicon element derived from the water-soluble silicate in the film, as described later. Can be calculated as follows.
本発明において、ケイ素（Ａ）は水溶性ケイ酸塩由来であり、タングステン（Ｂ）は水溶性タングステン酸塩由来であることが好適である。後記する実施例における、タングステン（Ｂ）／ケイ素（Ａ）の乾燥質量比は、潤滑皮膜中の水溶性タングステン酸塩由来のタングステン元素と、潤滑皮膜中の水溶性ケイ酸塩由来のケイ素元素との乾燥質量比率に基づくものであり、例えば誘導結合プラズマまたは蛍光Ｘ線分析を用いて算出することができる。 In the present invention, silicon (A) is preferably derived from a water-soluble silicate, and tungsten (B) is preferably derived from a water-soluble tungstate. In the examples described later, the dry mass ratio of tungsten (B) / silicon (A) is as follows: the tungsten element derived from the water-soluble tungstate in the lubricating film, and the silicon element derived from the water-soluble silicate in the lubricating film. Based on the dry mass ratio, it can be calculated using, for example, inductively coupled plasma or fluorescent X-ray analysis.
また、上記ケイ素（Ａ）が水溶性ケイ酸塩（ａ）由来であり、タングステン（Ｂ）が水溶性タングステン酸塩（ｂ）由来である場合、それらの乾燥質量比（ｂ）／（ａ）は０．７以上であり、好ましくは０．９以上、より好ましくは１．１以上である。当該乾燥質量比は１０以下であり、好ましくは６．０、より好ましくは３．０以下である。 When the silicon (A) is derived from a water-soluble silicate (a) and the tungsten (B) is derived from a water-soluble tungstate (b), their dry mass ratio (b) / (a) Is 0.7 or more, preferably 0.9 or more, more preferably 1.1 or more. The dry mass ratio is 10 or less, preferably 6.0, and more preferably 3.0 or less.
前記水溶性ケイ酸塩の種類は例えばケイ酸リチウム、ケイ酸ナトリウム、ケイ酸カリウムが挙げられる。これらは、単独で用いてもよいし、二種以上組み合わせて用いてもよい。 Examples of the water-soluble silicate include lithium silicate, sodium silicate, and potassium silicate. These may be used alone or in combination of two or more.
前記水溶性タングステン酸塩の種類は、例えばタングステン酸リチウム、タングステン酸ナトリウム、タングステン酸カリウム、タングステン酸アンモニウムが挙げられる。これらは、単独で用いてもよいし、二種以上組み合わせて用いてもよい。 Examples of the water-soluble tungstate include lithium tungstate, sodium tungstate, potassium tungstate, and ammonium tungstate. These may be used alone or in combination of two or more.
次に脂肪酸のアルカリ金属塩（Ｃ）について説明する。脂肪酸のアルカリ金属塩（Ｃ）は、潤滑皮膜の摩擦低減と圧造加工後の外観不良防止のために配合される。脂肪酸のアルカリ金属塩（Ｃ）は僅かであるが水溶性を有しており、潤滑皮膜の形成過程において、溶解していた脂肪酸のアルカリ金属塩（Ｃ）が微細かつ均一に析出してくる。前述したように、従来の潤滑皮膜は皮膜中における滑剤成分の分布が疎らになりやすく、滑剤が多い箇所と、滑剤が少ない箇所との間で、圧造加工時に局所的に摩擦状態の差が生じるが、脂肪酸のアルカリ金属塩（Ｃ）は他の滑剤成分と異なり、皮膜中に微細かつ均一に存在できるため局所的な摩擦状態の差が生じにくく、圧造加工後に良好な外観（圧造外観）が得られる。また、脂肪酸のアルカリ金属塩（Ｃ）の配合により、潤滑皮膜が軟質化して、鋼線材に潤滑皮膜が押し込まれ難くなるという効果もある。 Next, the alkali metal salt (C) of the fatty acid will be described. The alkali metal salt (C) of the fatty acid is blended for reducing friction of the lubricating film and preventing appearance defects after the forging process. Although the alkali metal salt (C) of the fatty acid is slight, it has water solubility, and the dissolved alkali metal salt (C) of the fatty acid precipitates finely and uniformly during the formation of the lubricating film. As described above, in the conventional lubricating film, the distribution of the lubricant component in the film tends to be sparse, and a local frictional state difference is produced during the forging process between the portion with a large amount of lubricant and the portion with a small amount of lubricant. However, unlike other lubricant components, fatty acid alkali metal salts (C) can exist finely and evenly in the film, so there is little difference in the local frictional state, and a good appearance after forging (forging appearance). can get. Further, the blending of the fatty acid alkali metal salt (C) has an effect that the lubricating film is softened and the lubricating film is hardly pushed into the steel wire.
上述した脂肪酸のアルカリ金属塩（Ｃ）による添加効果を有効に発揮させるため、ケイ素（Ａ）、タングステン（Ｂ）、脂肪酸のアルカリ金属塩（Ｃ）の乾燥質量比である（Ｃ）／｛（Ａ）＋（Ｂ）｝は０．１４以上であり、好ましくは０．２以上であり、より好ましくは０．４以上である。上記乾燥質量比は２．０以下であり、好ましくは１．５以下である。上記乾燥質量比が０．１４を下回ると良好な圧造外観が得られなくなる。一方、上記乾燥質量比が２．０を超える場合はケイ素（Ａ）とタングステン（Ｂ）の量が相対的に少なくなってしまい、耐食性の低下や、圧造加工時における皮膜の耐焼付き性の低下、それに伴う金型寿命の低下を招く。 In order to effectively exert the effect of addition of the above-described fatty acid alkali metal salt (C), the dry mass ratio of silicon (A), tungsten (B), and fatty acid alkali metal salt (C) is (C) / {( A) + (B)} is 0.14 or more, preferably 0.2 or more, and more preferably 0.4 or more. The dry mass ratio is 2.0 or less, preferably 1.5 or less. When the dry mass ratio is less than 0.14, a good forged appearance cannot be obtained. On the other hand, when the dry mass ratio exceeds 2.0, the amounts of silicon (A) and tungsten (B) are relatively small, resulting in a decrease in corrosion resistance and a decrease in seizure resistance of the film during forging. This leads to a decrease in mold life.
また、上記ケイ素（Ａ）が水溶性ケイ酸塩（ａ）由来であり、タングステン（Ｂ）が水溶性タングステン酸塩（ｂ）由来である場合、乾燥質量比（Ｃ）／{（ａ）+（ｂ）}は０．０４３以上であり、好ましくは０．０６２以上であり、より好ましくは０．０９以上である。当該乾燥質量比は０．９５以下であり、より好ましくは０．８以下である。 When the silicon (A) is derived from the water-soluble silicate (a) and the tungsten (B) is derived from the water-soluble tungstate (b), the dry mass ratio (C) / {(a) + (B)} is 0.043 or more, preferably 0.062 or more, more preferably 0.09 or more. The dry mass ratio is 0.95 or less, more preferably 0.8 or less.
本発明に用いられる脂肪酸のアルカリ金属塩（Ｃ）は、炭素数１２個以上の長鎖脂肪酸（高級脂肪酸）のアルカリ金属塩（例えばナトリウム塩、カリウム塩、リチウム塩）を意味する。脂肪酸を構成する炭化水素基は、直鎖状でも分岐鎖状でも構わない。上記脂肪酸のアルカリ金属塩（Ｃ）は、ミリスチン酸ナトリウム、ミリスチン酸カリウム、ミリスチン酸リチウム、パルミチン酸ナトリウム、パルミチン酸カリウム、パルミチン酸リチウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸リチウム、１２-ヒドロキシステアリン酸ナトリウム、１２-ヒドロキシステアリン酸カリウム、１２-ヒドロキシステアリン酸リチウムなどが挙げられる。これらは、単独で用いてもよいし、二種以上組み合わせて用いてもよい。 The alkali metal salt (C) of a fatty acid used in the present invention means an alkali metal salt (for example, sodium salt, potassium salt, lithium salt) of a long chain fatty acid (higher fatty acid) having 12 or more carbon atoms. The hydrocarbon group constituting the fatty acid may be linear or branched. The alkali metal salt (C) of the fatty acid is sodium myristate, potassium myristate, lithium myristate, sodium palmitate, potassium palmitate, lithium palmitate, sodium stearate, potassium stearate, lithium stearate, 12-hydroxy Examples include sodium stearate, potassium 12-hydroxystearate, and lithium 12-hydroxystearate. These may be used alone or in combination of two or more.
以上、本発明の鋼線材を構成する潤滑皮膜の基本成分について説明した。 In the above, the basic component of the lubricating film which comprises the steel wire material of this invention was demonstrated.
本発明の鋼線材は、更に脂肪酸アルカリ金属塩（Ｃ）以外の滑剤（Ｄ）、樹脂（Ｅ）を潤滑皮膜に含有しても良い。 The steel wire of the present invention may further contain a lubricant (D) other than the fatty acid alkali metal salt (C) and a resin (E) in the lubricating film.
これらのうち滑剤（Ｄ）は、それ自体にすべり性があり、摩擦力を低減させる機能を有する。一般に塑性加工時に摩擦力が増大すると加工エネルギーの増大や発熱、焼付き等が発生するが、上記滑剤（Ｄ）を本発明に係る鋼線材の潤滑皮膜中に含有させると、潤滑皮膜中で固体の形で存在して摩擦力の増大が抑制されることになる。そのような機能および性質を有する滑剤（Ｄ）として、ワックス、ポリテトラフルオロエチレン、脂肪酸金属石鹸、脂肪酸アマイド、二硫化モリブデン、二硫化タングステン、グラファイト、及びメラミンシアヌレートが挙げられる。これらは単独で用いてもよいし、二種類以上組み合わせて用いてもよい。 Among these, the lubricant (D) is slippery in itself and has a function of reducing the frictional force. In general, when the frictional force is increased during plastic processing, processing energy increases, heat generation, seizure, etc. occur. However, when the lubricant (D) is contained in the lubricating film of the steel wire according to the present invention, the lubricating film is solid. Therefore, the increase in frictional force is suppressed. Examples of the lubricant (D) having such functions and properties include wax, polytetrafluoroethylene, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, and melamine cyanurate. These may be used alone or in combination of two or more.
上記ワックスは、具体例としてポリエチレンワックス、パラフィンワックス、マイクロクリスタリンワックス、ポリプロピレンワックス、カルナバワックスなどが挙げられる。上記脂肪酸金属石鹸は、具体例としてステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸バリウム、ステアリン酸マグネシウムなどが挙げられる。上記脂肪酸アマイドは脂肪酸を２つ有するアミド化合物であり、具体例としてエチレンビスラウリン酸アマイド、エチレンビスステアリン酸アマイド、エチレンビスベヘン酸アマイド、Ｎ−Ｎ’−ジステアリルアジピン酸アマイド、エチレンビスオレイン酸アマイド、エチレンビスエルカ酸アマイド、ヘキサメチレンビスオレイン酸アマイド、Ｎ−Ｎ’−ジオレイルアジピン酸アマイドが挙げられる。 Specific examples of the wax include polyethylene wax, paraffin wax, microcrystalline wax, polypropylene wax, and carnauba wax. Specific examples of the fatty acid metal soap include calcium stearate, zinc stearate, barium stearate, magnesium stearate and the like. The fatty acid amide is an amide compound having two fatty acids, and specific examples include ethylene bislauric acid amide, ethylene bis stearic acid amide, ethylene bisbehenic acid amide, NN′-distearyl adipic acid amide, ethylene bis oleic acid. Amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, NN′-dioleyl adipic acid amide may be mentioned.
本発明における潤滑皮膜が滑剤（Ｄ）を更に含む場合、上記滑剤（Ｄ）の添加効果を有効に発揮させるため、｛（Ｃ）＋（Ｄ）｝／｛（Ａ）＋（Ｂ）｝の乾燥質量比は０．１４以上であることが好ましく、０．２以上であることがより好ましく、更に好ましくは０．４以上である。上記乾燥質量比は２．０以下であることが好ましく、より好ましくは１．５以下である。上記乾燥質量比が０．１４未満では、上記滑剤（Ｄ）の含有量が少なすぎるために、上記の性能を発揮できない。一方、上記乾燥質量比が２．０を超える場合はケイ素とタングステンの量が相対的に少なくなってしまい、耐食性が低下する。 When the lubricating film in the present invention further contains a lubricant (D), in order to effectively exhibit the effect of adding the lubricant (D), {(C) + (D)} / {(A) + (B)} The dry mass ratio is preferably 0.14 or more, more preferably 0.2 or more, and still more preferably 0.4 or more. The dry mass ratio is preferably 2.0 or less, more preferably 1.5 or less. When the dry mass ratio is less than 0.14, the content of the lubricant (D) is too small, so that the above performance cannot be exhibited. On the other hand, when the said dry mass ratio exceeds 2.0, the quantity of silicon and tungsten will become relatively small, and corrosion resistance will fall.
また、樹脂（Ｅ）はバインダー作用、基材と皮膜の密着性向上、増粘作用によるレベリング性の付与、分散成分の安定化作用を有する。そのような機能および性質を有する樹脂として、例えばビニル樹脂、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、フェノール樹脂、セルロース誘導体、ポリマレイン酸、ポリエステル樹脂などが挙げられる。なお、アクリル樹脂には、メタクリル樹脂も含まれる。また、これらの樹脂は重合体であっても共重合体であってもよい。共重合体としては、例えば、ビニル−アクリル酸の共重合体、ビニル−エポキシの共重合体、ビニル−ウレタンの共重合体、ビニル−フェノールの共重合体、ビニル−（無水）マレイン酸の共重合体、アクリル酸−エポキシの共重合体、アクリル酸−ウレタンの共重合体、アクリル酸−フェノールの共重合体、アクリル酸−（無水）マレイン酸の共重合体、エポキシ−ウレタンの共重合体、エポキシ−フェノールの共重合体、エポキシ−（無水）マレイン酸の共重合体、ウレタン−フェノールの共重合体、ウレタン−（無水）マレイン酸の共重合体、フェノール−（無水）マレイン酸の共重合体、オレフィン−アクリル酸の共重合体、オレフィン−エポキシの共重合体、オレフィン−ウレタンの共重合体、オレフィン−フェノールの共重合体、オレフィン−（無水）マレイン酸の共重合体などが挙げられる。これらは単独で用いてもよいし、二種類以上組み合わせて用いてもよい。 Further, the resin (E) has a binder action, an improvement in adhesion between the base material and the film, a leveling property imparted by a thickening action, and a stabilizing action of the dispersed component. Examples of the resin having such functions and properties include vinyl resin, acrylic resin, epoxy resin, urethane resin, phenol resin, cellulose derivative, polymaleic acid, and polyester resin. The acrylic resin includes methacrylic resin. These resins may be a polymer or a copolymer. Examples of the copolymer include a vinyl-acrylic acid copolymer, a vinyl-epoxy copolymer, a vinyl-urethane copolymer, a vinyl-phenol copolymer, and a vinyl- (maleic anhydride) copolymer. Polymer, acrylic acid-epoxy copolymer, acrylic acid-urethane copolymer, acrylic acid-phenol copolymer, acrylic acid- (anhydrous) maleic acid copolymer, epoxy-urethane copolymer , Epoxy-phenol copolymer, epoxy- (anhydride) maleic acid copolymer, urethane-phenol copolymer, urethane- (anhydride) maleic acid copolymer, phenol- (anhydride) maleic acid copolymer Polymer, olefin-acrylic acid copolymer, olefin-epoxy copolymer, olefin-urethane copolymer, olefin-phenol copolymer Olefin - (anhydrous) and a copolymer of maleic acid. These may be used alone or in combination of two or more.
上記潤滑皮膜中に上記樹脂（Ｅ）を更に含む場合、上記樹脂（Ｅ）の添加効果を有効に発揮させるため、（Ｅ）／｛（Ａ）＋（Ｂ）｝の乾燥質量比は０．０１以上であることが好ましく、より好ましくは０．０５以上である。上記乾燥質量比は１．４以下であることが好ましく、より好ましくは０．９以下である。上記乾燥質量比が０．０１未満の場合、上記の作用が十分に発揮されない。一方、上記乾燥質量比が１．４を超える場合、圧造加工後の外観不良が発生しやすくなる。 When the resin (E) is further contained in the lubricating film, the dry mass ratio of (E) / {(A) + (B)} is 0. 0 in order to effectively exhibit the effect of adding the resin (E). It is preferably 01 or more, more preferably 0.05 or more. The dry mass ratio is preferably 1.4 or less, and more preferably 0.9 or less. When the dry mass ratio is less than 0.01, the above-described effect is not sufficiently exhibited. On the other hand, when the said dry mass ratio exceeds 1.4, the external appearance defect after forging process will generate | occur | produce easily.
更に本発明を構成する潤滑皮膜は、上記の基本成分（ケイ素、タングステン、脂肪酸のアルカリ金属塩）および選択成分（樹脂、脂肪酸のアルカリ金属塩以外の滑剤）の他、粘度調整剤を更に配合することができる。これにより、加工処理を施す鋼線材（加工処理を必要とする鋼線材、すなわち、加工処理前の鋼線材を意味する。）に潤滑皮膜処理剤を塗布した際にレベリング性とチクソ性を付与されて、均一な塗布状態を確保することができる。そのような粘度調整剤は、具体例としてモンモリロナイト、ソーコナイト、バイデライト、ヘクトライト、ノントロナイト、サポナイト、鉄サポナイト、スチブンサイト等のスメクタイト系粘土鉱物；微粉シリカ、ベントナイト、カオリン等の無機系の増粘剤などが挙げられる。 Furthermore, the lubricating film constituting the present invention further contains a viscosity modifier in addition to the above basic components (silicon, tungsten, fatty acid alkali metal salt) and selective components (resin, lubricant other than alkali metal salt of fatty acid). be able to. As a result, leveling properties and thixotropy are imparted when a lubricating film treatment agent is applied to a steel wire material to be processed (meaning a steel wire material that requires processing, that is, a steel wire material before processing). Thus, a uniform application state can be ensured. Specific examples of such viscosity modifiers include smectite clay minerals such as montmorillonite, sauconite, beidellite, hectorite, nontronite, saponite, iron saponite, and stevensite; inorganic thickeners such as finely divided silica, bentonite, and kaolin Agents and the like.
また、上記潤滑皮膜は、密着性などを向上させるため、水溶性塩を更に含んでいてもよい。水溶性塩の種類は特に限定されず、無機塩及び有機塩のいずれか又は両方を用いることができる。無機塩としては、硫酸ナトリウム、硫酸カリウム等の硫酸塩；メタホウ酸ナトリウム、メタホウ酸カリウム、メタホウ酸アンモニウム等のホウ酸塩等が挙げられる。有機塩としては、蟻酸、酢酸、酪酸、シュウ酸、コハク酸、乳酸、アスコルビン酸、酒石酸、クエン酸、リンゴ酸、マロン酸、マレイン酸、フタル酸等の酸と、アルカリ金属、アルカリ土類金属等との塩等が挙げられる。 In addition, the lubricating film may further contain a water-soluble salt in order to improve adhesion and the like. The kind of water-soluble salt is not particularly limited, and either or both of an inorganic salt and an organic salt can be used. Examples of inorganic salts include sulfates such as sodium sulfate and potassium sulfate; borate salts such as sodium metaborate, potassium metaborate, and ammonium metaborate. Organic salts include acids such as formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, ascorbic acid, tartaric acid, citric acid, malic acid, malonic acid, maleic acid, phthalic acid, alkali metals, alkaline earth metals And the like.
本発明の鋼線材の潤滑皮膜は伸線加工前後における高い耐食性を付与することができるが、さらに耐食性を向上させる目的で、他の水溶性防錆剤やインヒビターを配合しても良い。これらは公知のものを用いることができ、例えばオレイン酸、ダイマー酸、酒石酸、クエン酸等の各種有機酸；ＥＤＴＡ、ＮＴＡ、ＨＥＤＴＡ、ＤＴＰＡ等の各種キレート剤；トリエタノールアミンなどのアルカノールアミンの混合成分；ｐ−ｔ−ブチル安息香酸のアミン塩類；カルボン酸アミン塩、２塩基酸アミン塩、アルケニルコハク酸及びその水溶性塩；アミノテトラゾール及びその水溶性塩が挙げられる。これらは単独で用いてもよいし、二種類以上組み合わせて用いてもよい。 Although the lubricating film of the steel wire material of the present invention can provide high corrosion resistance before and after wire drawing, other water-soluble rust preventives and inhibitors may be blended for the purpose of further improving the corrosion resistance. These may be known ones, for example, various organic acids such as oleic acid, dimer acid, tartaric acid and citric acid; various chelating agents such as EDTA, NTA, HEDTA and DTPA; and a mixture of alkanolamines such as triethanolamine Ingredients: amine salts of pt-butylbenzoic acid; carboxylic acid amine salts, dibasic amine salts, alkenyl succinic acid and water-soluble salts thereof; aminotetrazole and water-soluble salts thereof. These may be used alone or in combination of two or more.
本発明の鋼線材を構成する上記潤滑皮膜は、上記成分（ケイ素の代表的な供給源である水溶性ケイ酸塩、タングステンの代表的な供給源である水溶性タングステン酸塩、脂肪酸のアルカリ金属塩の必須成分；必要に応じて脂肪酸のアルカリ金属塩以外の滑剤、樹脂、粘土調整剤、水溶性塩など）を液体媒体に添加して混合することにより潤滑皮膜処理剤を調製し、加工処理を施す鋼線材の表面に塗布して作製することができる。 The lubricating film constituting the steel wire of the present invention comprises the above components (water-soluble silicate which is a typical source of silicon, water-soluble tungstate which is a typical source of tungsten, alkali metal of fatty acid) An essential component of the salt; if necessary, lubricants other than alkali metal salts of fatty acids, resins, clay modifiers, water-soluble salts, etc.) are added to the liquid medium and mixed to prepare a lubricating film treatment agent and processed. It can apply and produce on the surface of the steel wire which gives.
上記水溶性ケイ酸塩は、潤滑皮膜処理剤中のａ成分、ｂ成分、Ｃ成分、Ｄ成分、Ｅ成分の乾燥質量での合計量１００質量％中、５質量％超であることが好ましく、より好ましくは１０質量％以上、さらに好ましくは１５質量％以上であり、５８質量％以下であることが好ましく、より好ましくは５２質量％以下、さらに好ましくは４５質量％以下である。 The water-soluble silicate is preferably more than 5% by mass in the total amount of 100% by mass in dry mass of component a, b component, C component, D component and E component in the lubricant coating treatment agent, More preferably, it is 10 mass% or more, More preferably, it is 15 mass% or more, It is preferable that it is 58 mass% or less, More preferably, it is 52 mass% or less, More preferably, it is 45 mass% or less.
上記水溶性タングステン酸塩は、潤滑皮膜処理剤中のａ成分、ｂ成分、Ｃ成分、Ｄ成分、Ｅ成分の乾燥質量での合計量１００質量％中、１０質量％以上であることが好ましく、より好ましくは１５質量％以上、さらに好ましくは２０質量％以上であり、８８質量％未満であることが好ましく、より好ましくは８５質量％以下、さらに好ましくは８０質量％以下である。 The water-soluble tungstate is preferably 10% by mass or more in a total amount of 100% by mass in dry mass of component a, b, C, D, and E in the lubricant film treatment agent. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more, It is preferable that it is less than 88 mass%, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less.
上記脂肪酸のアルカリ金属塩は、潤滑皮膜処理剤中のａ成分、ｂ成分、Ｃ成分、Ｄ成分、Ｅ成分の乾燥質量での合計量１００質量％中、３質量％超であることが好ましく、７質量％超であることがより好ましく、更に好ましくは１２質量％以上、特に好ましくは１６質量％以上であり、５０質量％以下であることが好ましく、より好ましくは４０質量％以下、さらに好ましくは３０質量％以下である。 The alkali metal salt of the fatty acid is preferably more than 3% by mass in a total amount of 100% by mass in dry mass of component a, b, C, D, and E in the lubricating film treating agent, More preferably, it is more than 7% by mass, more preferably 12% by mass or more, particularly preferably 16% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably. 30% by mass or less.
ここで上記水溶性ケイ酸塩の量が５質量％以下、上記水溶性タングステン酸塩の量が８８質量％以上である場合、十分な長期防錆性が得られない他、圧造加工後の外観不良が生じる。これは、相対的に水溶性ケイ酸塩量が少なくなることで水分が透過しやすくなること、タングステン酸塩の結晶が析出し、皮膜の密着性、均一性が低下することに起因する。一方、上記水溶性ケイ酸塩の量が５８質量％超、上記水溶性タングステン酸塩の量が１０質量％未満であると十分な耐食性、圧造加工後の良好な外観が得られない。これは相対的にタングステンの量が減ることにより、不動態膜が十分に形成されないこと、水溶性ケイ酸塩量が相対的に増えることで強固なネットワーク構造を形成してしまうことに起因する。 Here, when the amount of the water-soluble silicate is 5% by mass or less and the amount of the water-soluble tungstate is 88% by mass or more, sufficient long-term rust preventive property cannot be obtained, and appearance after forging Defects occur. This is due to the fact that the amount of water-soluble silicate becomes relatively small, so that moisture can easily permeate, and the crystals of tungstate precipitate and the adhesion and uniformity of the film are reduced. On the other hand, if the amount of the water-soluble silicate exceeds 58% by mass and the amount of the water-soluble tungstate is less than 10% by mass, sufficient corrosion resistance and a good appearance after forging cannot be obtained. This is because a relatively thin passive film is not formed due to a relatively small amount of tungsten, and a strong network structure is formed due to a relatively large amount of water-soluble silicate.
また、上記脂肪酸のアルカリ金属塩の量が５０質量％超の場合、ケイ素（Ａ）とタングステン（Ｂ）の量が相対的に少なくなってしまい、耐食性が低下する。一方、上記脂肪酸のアルカリ金属塩の量が３質量％以下の場合、圧造加工後に外観不良を生じやすくなる。 Moreover, when the amount of the alkali metal salt of the fatty acid is more than 50% by mass, the amounts of silicon (A) and tungsten (B) are relatively decreased, and the corrosion resistance is lowered. On the other hand, when the amount of the alkali metal salt of the fatty acid is 3% by mass or less, poor appearance tends to occur after the forging process.
上記潤滑皮膜上に、潤滑性、耐焼付き性、耐食性等を一層向上させるために、乾式潤滑剤を付着させてもよい。乾式潤滑剤の種類は特に限定されないが、例えば高級脂肪酸石鹸、ボラックス、石灰、二硫化モリブデン等を主成分とするような一般的な潤滑パウダーや伸線パウダーが使用できる。 In order to further improve the lubricity, seizure resistance, corrosion resistance, etc., a dry lubricant may be adhered on the lubricating film. The type of dry lubricant is not particularly limited, and general lubricating powders and wire drawing powders mainly composed of higher fatty acid soap, borax, lime, molybdenum disulfide, etc. can be used.
本発明において、潤滑皮膜を形成させるための潤滑皮膜処理剤における液体媒体（溶媒、分散媒体）は水である。なお、乾燥工程での潤滑皮膜処理剤の乾燥時間短縮化のために水よりも低沸点のアルコールを配合してもよい。 In the present invention, the liquid medium (solvent, dispersion medium) in the lubricant film treatment agent for forming the lubricant film is water. In addition, you may mix | blend alcohol with a boiling point lower than water in order to shorten the drying time of the lubricating film processing agent in a drying process.
上記潤滑皮膜処理剤はその液の安定性を高めるため、水溶性の強アルカリ成分を含んでいても良い。具体例として、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどが挙げられる。これらは単独で用いてもよいし、二種類以上組み合わせて用いてもよい。 The lubricating film treating agent may contain a water-soluble strong alkali component in order to improve the stability of the liquid. Specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. These may be used alone or in combination of two or more.
次に、本発明に係る鋼線材の製造方法を説明する。上記製造方法は、加工処理を施す鋼線材の清浄化工程、潤滑皮膜の製造（処理）工程、乾燥工程、及び加工工程を含む。加工工程の後、必要に応じて熱処理、表面処理などの工程を更に行なっても良い。以下、各工程を説明する。 Next, the manufacturing method of the steel wire concerning the present invention is explained. The manufacturing method includes a cleaning process of a steel wire to be processed, a manufacturing (processing) process of a lubricating film, a drying process, and a processing process. After the processing step, steps such as heat treatment and surface treatment may be further performed as necessary. Hereinafter, each process will be described.
・清浄化工程（前処理工程）
鋼線材に潤滑皮膜を形成させる前に、ショットブラスト、サンドブラスト、ウェットブラスト、ピーリング、アルカリ脱脂および酸洗浄よりなる群から選ばれる少なくとも一種類の清浄化処理を行うことが好ましい。ここでの清浄化は、焼鈍等により成長した酸化スケールや各種の汚れ（油など）を除去することを目的とするものである。
・ Cleaning process (pretreatment process)
Before forming the lubricating film on the steel wire, it is preferable to perform at least one type of cleaning treatment selected from the group consisting of shot blasting, sand blasting, wet blasting, peeling, alkali degreasing and acid cleaning. The purpose of cleaning here is to remove oxide scales and various types of dirt (oil, etc.) grown by annealing or the like.
・潤滑皮膜製造工程
本発明において、潤滑皮膜を、加工処理を施す鋼線材に製造する工程は、特に限定されないが、浸漬法、フローコート法、スプレー法などの塗布を用いることができる。塗布の程度は、表面が充分に本発明に用いられる潤滑皮膜処理剤に覆われればよく、塗布する時間も特に制限されない。ここで、塗布時の乾燥性を高めるために鋼線材を６０〜８０℃に加温してから、潤滑皮膜処理剤と接触させてもよい。また、４０〜７０℃に加温した潤滑皮膜処理剤を鋼線材と接触させてもよい。これらの方法により、乾燥性が大幅に向上して乾燥が常温で可能になる場合もあり、熱エネルギーのロスを少なくすることもできる。
-Lubricant film manufacturing process In this invention, although the process which manufactures a lubricating film to the steel wire which performs a process is not specifically limited, Application | coating, such as a dipping method, a flow coat method, a spray method, can be used. The degree of application is not particularly limited as long as the surface is sufficiently covered with the lubricant treatment agent used in the present invention. Here, in order to improve the drying property at the time of application, the steel wire may be heated to 60 to 80 ° C. and then brought into contact with the lubricant coating agent. Moreover, you may make the lubricating film processing agent heated at 40-70 degreeC contact with a steel wire. By these methods, the drying property may be greatly improved and drying may be possible at room temperature, and loss of heat energy can be reduced.
・乾燥工程
次に、前記潤滑皮膜処理剤を乾燥する必要がある。乾燥は常温放置でも構わないが、６０〜１５０℃で１〜３０分行ってもよい。
-Drying process Next, it is necessary to dry the said lubricating film processing agent. Drying may be performed at room temperature, but may be performed at 60 to 150 ° C. for 1 to 30 minutes.
・加工工程
上記潤滑皮膜製造工程及び乾燥工程を行うことによって得られた、潤滑皮膜を有する鋼線材は、本発明に係る鋼線材の範囲に含まれるが、加工工程によって潤滑皮膜を有する鋼線材に加工処理を施したものであっても、潤滑皮膜を有するものであれば、本発明に係る鋼線材の範囲に含まれる。上記加工処理には、前述したように伸線加工処理、圧造加工処理、鍛造加工処理等が挙げられる。
-Machining process The steel wire having a lubricating film obtained by performing the lubricating film manufacturing process and the drying process is included in the scope of the steel wire according to the present invention. Even if it has been subjected to processing, it is included in the scope of the steel wire according to the present invention as long as it has a lubricating film. Examples of the processing include wire drawing, forging, and forging as described above.
ここで、鋼線材に形成される潤滑皮膜の皮膜質量は、その後の加工の程度により適宜コントロールされるが、皮膜質量は１．０ｇ／ｍ2以上であることが好ましく、より好ましくは２．０ｇ／ｍ2以上であり、２０ｇ／ｍ2以下であることが好ましく、より好ましくは１５ｇ／ｍ2以下である。なお、皮膜質量は処理前後の鋼線材の質量差および表面積より計算することができる。前述の皮膜質量範囲になるようにコントロールするためには、潤滑皮膜処理剤の固形分質量（濃度）を適宜調節する。実際には、高濃度の潤滑皮膜処理剤を水で希釈し、その希釈液にて使用する場合が多い。希釈調整する水は特に限定されないが、例えば純水、脱イオン水、水道水、地下水、工業用水等を使用できる。 Here, the film mass of the lubricating film formed on the steel wire is appropriately controlled by the degree of subsequent processing, but the film mass is preferably 1.0 g / m 2 or more, more preferably 2.0 g. / M 2 or more, preferably 20 g / m 2 or less, more preferably 15 g / m 2 or less. The film mass can be calculated from the mass difference and surface area of the steel wire before and after the treatment. In order to control so that it may become the above-mentioned film mass range, solid content mass (concentration) of a lubricating film processing agent is adjusted suitably. In practice, a lubricant film treatment agent having a high concentration is often diluted with water and used in the diluted solution. The water to be diluted is not particularly limited. For example, pure water, deionized water, tap water, ground water, industrial water, and the like can be used.
・加工工程後の工程
上記加工工程の後、本発明の鋼線材に、熱処理；メッキ処理等の表面処理；等の工程を更に施すことができる。上記熱処理は、加工工程によって得られた鋼線材を硬くして、強度や靭性等を付与する目的で行なわれる。熱処理の方法は特に限定されず、一般的な方法を採用でき、例えば焼入れ、焼戻し等の一般熱処理；浸炭焼入れ、窒化等の表面熱処理等が挙げられる。また、メッキ処理は、耐食性を付与する目的で行なわれるものであり、主に熱処理後のものに対して行なわれる。メッキ処理の方法は特に限定されず、一般的な方法を採用でき、例えば電気メッキ、溶融メッキ等が挙げられる。メッキの種類も特に限定されず、一般的なメッキを行なうことができ、例えば亜鉛メッキ、クロムメッキ、ニッケルメッキ等が挙げられる。
-Process after a process process After the said process process, processes, such as heat treatment; surface treatments, such as a plating process, can further be given to the steel wire rod of this invention. The said heat processing is performed in order to harden the steel wire obtained by the process, and to provide intensity | strength, toughness, etc. The heat treatment method is not particularly limited, and a general method can be adopted, and examples thereof include general heat treatment such as quenching and tempering; surface heat treatment such as carburizing and quenching and nitriding. The plating process is performed for the purpose of imparting corrosion resistance, and is mainly performed on the heat-treated product. The method of the plating treatment is not particularly limited, and a general method can be adopted, and examples thereof include electroplating and hot dipping. The type of plating is not particularly limited, and general plating can be performed. Examples thereof include zinc plating, chromium plating, and nickel plating.
・脱膜方法
本発明において、潤滑皮膜処理剤により形成された前記潤滑皮膜は水系のアルカリ洗浄剤に浸漬するかスプレー洗浄することによって脱膜可能である。アルカリ洗浄剤は水に水酸化ナトリウム、水酸化カリウム等の一般的なアルカリ成分を溶解させた液であり、これに前記潤滑皮膜を接触させると、前記潤滑皮膜が洗浄液中に溶解するので容易に脱膜することができる。また、加工後の熱処理によって脱落しやすい皮膜とすることができる。よって、上述したアルカリ洗浄や熱処理により、脱膜不良による後工程での汚染やメッキ不良を未然に防ぐことができる。
-Film removal method In the present invention, the lubricant film formed by the lubricant film treatment agent can be removed by dipping in a water-based alkaline cleaner or by spray cleaning. Alkaline cleaner is a solution in which common alkaline components such as sodium hydroxide and potassium hydroxide are dissolved in water. When the lubricant film is brought into contact with this, the lubricant film dissolves in the cleaning solution. The film can be removed. Moreover, it can be set as the film | membrane which is easy to drop off by the heat processing after a process. Therefore, the above-described alkali cleaning and heat treatment can prevent contamination in the subsequent process and defective plating due to defective film removal.
以下、鋼線材を対象とした場合について、実施例を比較例と共に挙げることによって、本発明の効果とともにさらに具体的な説明をする。なお、本発明はこれらの実施例によって制限されるものではない。 Hereinafter, about the case where steel wire material is made into a target, by giving an example with a comparative example, it explains still more concretely with the effect of the present invention. In addition, this invention is not restrict | limited by these Examples.
（１−１）水系潤滑皮膜処理剤の調製
以下に示す各成分を用いて、表１に示す固形分質量比となるようにそれぞれを水に混合し、実施例１〜１９及び比較例１〜７の鋼線材あるいは冷間圧延鋼板（ＳＰＣＣ-ＳＤ）に浸漬させる各潤滑皮膜処理剤を調製した。なお、各成分を混合した水の量は、形成される潤滑皮膜が表１に示す皮膜質量となるように適宜調整した。また、これらの潤滑皮膜処理剤には、水酸化リチウムを０．５質量％で配合した。また、比較例８（従来例）の鋼線材あるいは冷間圧延鋼板（ＳＰＣＣ-ＳＤ）に浸漬させる潤滑皮膜処理剤として、市販の反応石けん潤滑剤を使用した。
(1-1) Preparation of Aqueous Lubricating Film Treatment Agent Each of the components shown below was mixed with water so that the solid content mass ratio shown in Table 1 was obtained, and Examples 1 to 19 and Comparative Examples 1 to 1 were mixed. Each lubricant film treatment agent to be immersed in steel wire rod No. 7 or cold rolled steel plate (SPCC-SD) was prepared. The amount of water in which each component was mixed was appropriately adjusted so that the formed lubricating film had the film mass shown in Table 1. Moreover, lithium hydroxide was mix | blended with these lubricating film processing agents at 0.5 mass%. Moreover, the commercially available reaction soap lubricant was used as a lubricating film processing agent immersed in the steel wire of the comparative example 8 (conventional example) or a cold-rolled steel plate (SPCC-SD).
＜水溶性ケイ酸塩＞
（ａ−１）３号ケイ酸ナトリウム（Ｎａ2Ｏ・ｎＳｉＯ2 ｎ＝３）
（ａ−２）ケイ酸リチウム（Ｌｉ2Ｏ・ｎＳｉＯ2 ｎ＝３．５）
＜水溶性タングステン酸塩＞
（ｂ−１）タングステン酸ナトリウム
（ｂ−２）タングステン酸カリウム
＜脂肪酸のアルカリ金属塩＞
（Ｃ−１）１２−ヒドロキシステアリン酸リチウム
（Ｃ−２）イソヘキサデカン酸（分岐パルミチン酸）ナトリウム
＜滑剤＞
（Ｄ−１）アニオン性ポリエチレンワックス（平均粒子径５μｍ）
（Ｄ−２）ステアリン酸カルシウム（平均粒子径８μｍ）
＜樹脂＞
（Ｅ−１）イソブチレン・無水マレイン酸共重合体（重量平均分子量１６０，０００〜１７０，０００）のナトリウム中和塩
<Water-soluble silicate>
(A-1) No. 3 sodium silicate (Na 2 O · nSiO 2 n = 3)
(A-2) Lithium silicate (Li 2 O.nSiO 2 n = 3.5)
<Water-soluble tungstate>
(B-1) Sodium tungstate (b-2) Potassium tungstate <alkali metal salt of fatty acid>
(C-1) 12-hydroxy lithium stearate (C-2) sodium isohexadecanoate (branched palmitate) <lubricant>
(D-1) Anionic polyethylene wax (average particle size 5 μm)
(D-2) Calcium stearate (average particle size 8 μm)
<Resin>
(E-1) Sodium neutralized salt of isobutylene / maleic anhydride copolymer (weight average molecular weight 160,000 to 170,000)
（１−２）前処理、潤滑皮膜処理、及び乾燥処理
前処理、潤滑皮膜処理、及び乾燥処理は、φ１２．５ｍｍの鋼線材（鋼種：ＳＣＭ４３５）表面を対象に以下の工程で実施した。
(1-2) Pretreatment, lubricating film treatment, and drying treatment Pretreatment, lubricating film treatment, and drying treatment were performed on the surface of a steel wire (steel type: SCM435) with a diameter of 12.5 mm in the following steps.
＜実施例１〜１９及び比較例１〜７の鋼線材あるいは冷間圧延鋼板を製造するための、前処理、潤滑皮膜処理、及び乾燥処理＞
（ａ）脱脂：市販の脱脂剤（ファインクリーナーＥ６４００、日本パーカライジング（株）製）濃度２０ｇ／Ｌ、温度６０℃、浸漬１０分
（ｂ）水洗：水道水、常温、浸漬３０秒
（ｃ）酸洗：１７．５％塩酸、常温、浸漬２０分
（ｄ）水洗：水道水、常温、浸漬３０秒
（ｅ）中和：市販の中和剤（プレパレン２７、日本パーカライジング（株）製）
（ｆ）潤滑皮膜処理：（１−１）で調製した各潤滑皮膜処理剤 温度６０℃、浸漬１分
（ｇ）乾燥：１００℃、１０分
（ｈ）皮膜質量は、処理前後の鋼線材の質量差および表面積より算出
<Pretreatment, Lubricating Film Treatment, and Drying Treatment for Manufacturing Steel Wire Materials or Cold Rolled Steel Plates of Examples 1-19 and Comparative Examples 1-7>
(A) Degreasing: Commercially available degreasing agent (Fine Cleaner E6400, manufactured by Nihon Parkerizing Co., Ltd.), concentration 20 g / L, temperature 60 ° C., immersion 10 minutes (b) water washing: tap water, room temperature, immersion 30 seconds (c) acid Washing: 17.5% hydrochloric acid, normal temperature, immersion 20 minutes (d) Washing: tap water, normal temperature, immersion 30 seconds (e) Neutralization: Commercial neutralizer (preparene 27, manufactured by Nippon Parkerizing Co., Ltd.)
(F) Lubricant film treatment: Each lubricant film treatment agent prepared in (1-1) Temperature 60 ° C., immersion 1 minute (g) Drying: 100 ° C., 10 minutes (h) The film mass is the steel wire before and after treatment. Calculated from mass difference and surface area
＜比較例８の鋼線材あるいは冷間圧延鋼板を製造するための、前処理、潤滑皮膜処理、及び乾燥処理＞
（ａ）脱脂：市販の脱脂剤（ファインクリーナーＥ６４００、日本パーカライジング（株）製）濃度２０ｇ／Ｌ、温度６０℃、浸漬１０分
（ｂ）水洗：水道水、常温、浸漬３０秒
（ｃ）酸洗：塩酸、濃度１７．５％、常温、浸漬２０分
（ｄ）水洗：水道水、常温、浸漬３０秒
（ｅ）化成処理：市販のリン酸亜鉛化成処理剤（パルボンド３６９６Ｘ、日本パーカライジング（株）製）濃度７５ｇ／Ｌ、温度８０℃、浸漬１０分
（ｆ）水洗：水道水、常温、浸漬３０秒
（ｇ）石けん処理：市販の反応石けん潤滑剤（パルーブ２３５、日本パーカライジング（株）製）濃度７０ｇ／Ｌ、温度８５℃、浸漬３分
（ｈ）乾燥：１００℃、１０分
（ｉ）皮膜量：１０ｇ／ｍ2
<Pretreatment, Lubricating Film Treatment, and Drying Treatment for Manufacturing Steel Wire of Comparative Example 8 or Cold Rolled Steel Plate>
(A) Degreasing: Commercially available degreasing agent (Fine Cleaner E6400, manufactured by Nihon Parkerizing Co., Ltd.), concentration 20 g / L, temperature 60 ° C., immersion 10 minutes (b) water washing: tap water, room temperature, immersion 30 seconds (c) acid Washing: hydrochloric acid, concentration 17.5%, normal temperature, immersion 20 minutes (d) Water washing: tap water, normal temperature, immersion 30 seconds (e) Chemical conversion treatment: commercial zinc phosphate chemical conversion treatment agent (Palbond 3696X, Nippon Parkerizing Co., Ltd. )) Concentration: 75 g / L, temperature: 80 ° C., immersion: 10 minutes (f) Water washing: tap water, room temperature, immersion: 30 seconds (g) Soap treatment: commercially available reaction soap lubricant (Palube 235, manufactured by Nippon Parkerizing Co., Ltd.) ) Concentration 70 g / L, temperature 85 ° C., immersion 3 minutes (h) drying: 100 ° C., 10 minutes (i) coating amount: 10 g / m 2
（１−３）評価試験
（１−３−１）圧造加工試験
上記（１−２）の各処理を行なったφ１２．５ｍｍ×４ｍの鋼線材を用い、図１に示す手順で圧造加工を行った。まず、上記鋼線材をφ１１．０５のダイスに通して引抜くことでφ１１．０５の鋼線材を作製した。その後、圧造フォーマーにて二段階の圧造加工を実施した。詳細には、まず図１の左図に示すように鋼線材を適当な長さに切断し、一段目で図１の中央図に示すサイズに加工した後、二段目で図１の右図に示すようにφ７．２ｍｍまで加工した。上記圧造加工試験では、全ての水準で、圧造の直前にフォーマー油（関西油脂興業（株）製のダイヤプレス Ｎｏ．１７Ｂ）を塗油した。
(1-3) Evaluation test (1-3-1) Forging processing test Using the φ12.5 mm × 4 m steel wire material subjected to each of the above (1-2), forging processing is performed according to the procedure shown in FIG. It was. First, the steel wire rod of φ11.05 was produced by drawing the steel wire rod through a φ11.05 die. After that, two-step forging process was carried out with a forging former. In detail, first, as shown in the left figure of FIG. 1, the steel wire is cut into an appropriate length, processed into the size shown in the central view of FIG. 1 at the first stage, and then the right figure of FIG. 1 at the second stage. To φ7.2 mm as shown in FIG. In the forging process test, former oil (Diapress No. 17B manufactured by Kansai Yushi Kogyo Co., Ltd.) was applied immediately before forging at all levels.
圧造加工後の鋼線材の皮膜残存量、および外観不良の有無を以下のようにして評価した。 The remaining amount of the steel wire rod after forging and the presence or absence of poor appearance were evaluated as follows.
（圧造加工後の皮膜残存量）
圧造加工後の皮膜残存量は下記の方法で皮膜を剥離（脱膜）し、剥離前後の、圧造加工後の鋼線材重量から算出した。
・皮膜剥離剤：市販のアルカリ性剥離剤（日本パーカライジング（株）製のＦＣ−Ｅ６４６３）、２０ｇ／Ｌ
・脱膜方法：上記皮膜剥離剤を液温６０℃に加温して、上記圧造加工後の鋼線材を６０分間浸漬した後、スポンジで擦って皮膜を剥離した。その後、脱イオン水による洗浄を行い、圧縮エアで水気を完全に飛ばした。
・評価基準：皮膜残存量を下記のようにして算出し、下記基準で残膜性を評価した。皮膜残存量が多い程、圧造加工後の耐焼付き性が良好であることを意味する。本実施例では皮膜残存量が０．８ｇ／ｍ2以上を合格とした。
皮膜残存量（ｇ／ｍ2）＝（脱膜前の試験片重量−脱膜後の試験片重量）／試験片の表面積
〇：皮膜残存量１．８ｇ／ｍ2以上
△：皮膜残存量０．８ｇ／ｍ2以上、１．８ｇ／ｍ2未満
×：皮膜残存量０．８ｇ／ｍ2未満
(Residual amount of film after forging)
The remaining amount of the film after the forging process was calculated from the weight of the steel wire after the forging process before and after peeling after the film was peeled off (de-filming) by the following method.
Film release agent: Commercially available alkaline release agent (FC-E6463 manufactured by Nippon Parkerizing Co., Ltd.), 20 g / L
-Film removal method: The above-mentioned film remover was heated to a liquid temperature of 60 ° C., the steel wire after the above forging process was immersed for 60 minutes, and then the film was peeled off by rubbing with a sponge. Thereafter, washing with deionized water was performed, and water was completely blown away with compressed air.
Evaluation criteria: The remaining film amount was calculated as follows, and the remaining film property was evaluated according to the following criteria. It means that the seizure resistance after the forging process is better as the remaining amount of the film is larger. In this example, the remaining film amount was 0.8 g / m 2 or more as acceptable.
Residual amount of film (g / m 2 ) = (weight of test piece before film removal−weight of test piece after film removal) / surface area of test piece ○: remaining amount of film 1.8 g / m 2 or more Δ: remaining amount of film 0 0.8 g / m 2 or more and less than 1.8 g / m 2 ×: film remaining amount less than 0.8 g / m 2
（圧造加工後の外観不良の評価基準）
○：外観不良が発生しない。
×：圧造加工部の全面に外観不良が発生する。
(Evaluation criteria for appearance defects after forging)
○: Appearance defect does not occur.
X: Appearance defects occur on the entire surface of the forged portion.
（１−３−２）耐食性（長期防錆性）試験
上記圧造加工後の鋼線材では、耐食性試験の評価が困難であることから、各潤滑皮膜処理剤により潤滑皮膜を形成させた鋼材を用いて、耐食性試験を行った。具体的には、パルテック社製のＳＰＣＣ-ＳＤ（７５ｍｍ×３５ｍｍ×０．８ｍｍ）に上記（１−２）の各処理を施し、夏場に２ヶ月間屋内に曝露して錆を発生させ、錆の発生具合を観察した。発錆面積が大きい程、耐食性（長期防錆性）に劣ると判断した。
（評価基準）
◎：比較例８のＳＰＣＣ-ＳＤにおける潤滑皮膜の性能より著しく優れる（錆面積３％以下）
○：比較例８のＳＰＣＣ-ＳＤにおける潤滑皮膜の性能より優れる（錆面積３％超、１０％以下）
△：比較例８のＳＰＣＣ-ＳＤにおける潤滑皮膜の性能と同等（錆面積１０％超、２０％以下）
×：比較例８のＳＰＣＣ-ＳＤにおける潤滑皮膜の性能より劣る（錆面積２０％超、３０％以下）
(1-3-2) Corrosion resistance (long-term rust prevention) test In the steel wire after the above forging process, it is difficult to evaluate the corrosion resistance test, so a steel material in which a lubricant film is formed with each lubricant film treatment agent is used. The corrosion resistance test was conducted. Specifically, SPCC-SD (75 mm x 35 mm x 0.8 mm) manufactured by Partec Co., Ltd. is subjected to the above treatment (1-2) and exposed indoors for two months in summer to generate rust. The occurrence of was observed. It was judged that the larger the rusting area, the poorer the corrosion resistance (long-term rust prevention).
(Evaluation criteria)
A: Remarkably superior to the performance of the lubricating film in SPCC-SD of Comparative Example 8 (rust area 3% or less)
○: superior to the performance of the lubricating film in SPCC-SD of Comparative Example 8 (rust area over 3%, 10% or less)
Δ: Equivalent to the performance of the lubricating film in SPCC-SD of Comparative Example 8 (rust area over 10%, 20% or less)
×: Inferior to the performance of the lubricating film in SPCC-SD of Comparative Example 8 (rust area over 20%, 30% or less)
これらの試験結果を表２に示す。 These test results are shown in Table 2.
まず、表２の実施例１〜１９はいずれも、本発明の構成要件を満足する潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤであり、圧造加工後の外観が良好であり、且つ、高い耐食性を有していた。また、圧造加工後の皮膜残存量も多いため、焼付きなども発生せず、金型寿命に優れる。 First, each of Examples 1 to 19 in Table 2 is a steel wire or SPCC-SD having a lubricating film that satisfies the structural requirements of the present invention, has a good appearance after forging, and has high corrosion resistance. Had. In addition, since the remaining amount of the film after forging is large, seizure does not occur and the mold life is excellent.
これに対し、本発明の構成要件を満足しない比較例は以下の不具合を有している。 On the other hand, the comparative example that does not satisfy the constituent requirements of the present invention has the following problems.
まず、比較例１はケイ素（Ａ）の供給源である水溶性ケイ酸塩を含まない潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤ、比較例２はタングステン（Ｂ）の供給源である水溶性タングステン酸塩を含まない潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤ、比較例３は上記ＡとＢの乾燥質量比（Ｂ）／（Ａ）が高い潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤ、比較例４は上記ＡとＢの乾燥質量比（Ｂ）／（Ａ）が低い潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤであり、いずれも、耐食性が劣っていた。 First, Comparative Example 1 is a steel wire or SPCC-SD having a lubricating film not containing a water-soluble silicate that is a supply source of silicon (A), and Comparative Example 2 is a water-soluble tungsten that is a supply source of tungsten (B). Steel wire rod or SPCC-SD having a lubricant film not containing acid salt, Comparative Example 3 is a steel wire rod or SPCC-SD having a lubricant film having a high dry mass ratio (B) / (A) of A and B above, Comparative Example 4 is a steel wire or SPCC-SD having a lubricating film having a low dry mass ratio (B) / (A) of A and B, both of which were inferior in corrosion resistance.
また、比較例５〜７は上記（Ｃ）／{（Ａ）＋（Ｂ）}の乾燥質量比が本発明の範囲を満足しない潤滑皮膜を有する鋼線材若しくはＳＰＣＣ-ＳＤ、あるいは、該乾燥質量比が本発明の範囲を満足せず、かつ、脂肪酸のアルカリ金属塩（Ｃ）を含まない潤滑皮膜を有する鋼線材若しくはＳＰＣＣ-ＳＤである。 In Comparative Examples 5 to 7, the above-mentioned (C) / {(A) + (B)} dry mass ratio is a steel wire or SPCC-SD having a lubricating film that does not satisfy the scope of the present invention, or the dry mass. The steel wire rod or SPCC-SD having a lubricating film whose ratio does not satisfy the scope of the present invention and does not contain an alkali metal salt (C) of a fatty acid.
これらのうち比較例５は、脂肪酸のアルカリ金属塩（Ｃ）を含まず、滑剤としてワックス（Ｄ）のみを含む潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤであり、圧造外観が劣っていた。この実験結果より、圧造加工後の優れた外観を得るためには、潤滑皮膜中に脂肪酸のアルカリ金属塩（Ｃ）が含まれていることが不可欠であり、代表的な滑剤であるワックスを添加しても所望とする効果が得られないことが分かる。 Of these, Comparative Example 5 was a steel wire or SPCC-SD that did not contain the fatty acid alkali metal salt (C) and had a lubricating film containing only the wax (D) as a lubricant, and had a poor forged appearance. From this experimental result, in order to obtain an excellent appearance after forging, it is indispensable that the lubricating film contains an alkali metal salt (C) of a fatty acid, and a wax that is a representative lubricant is added. It can be seen that the desired effect cannot be obtained.
また、比較例６は、上記（Ｃ）／｛（Ａ）＋（Ｂ）｝の乾燥質量比が本発明の範囲より低い潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤであり、脂肪酸のアルカリ金属塩（Ｃ）の添加効果が有効に発揮されないため、圧造外観が劣っていた。 Comparative Example 6 is a steel wire or SPCC-SD having a lubricating film having a dry mass ratio of (C) / {(A) + (B)} lower than the range of the present invention, and an alkali metal salt of a fatty acid. Since the additive effect of (C) is not exhibited effectively, the forged appearance was inferior.
比較例７は、上記（Ｃ）／｛（Ａ）＋（Ｂ）｝の乾燥質量比が本発明の範囲より高い潤滑皮膜を有する鋼線材又はＳＰＣＣ-ＳＤであり、脂肪酸のアルカリ金属塩（Ｃ）の添加効果により圧造加工後の外観は良好であったが、脂肪酸のアルカリ金属塩の量が多すぎるため、圧造加工後の皮膜残存量が低下して微小な焼付きが生じた。 Comparative Example 7 is a steel wire or SPCC-SD having a lubricating film having a dry mass ratio of (C) / {(A) + (B)} higher than the range of the present invention, and an alkali metal salt of fatty acid (C ), The appearance after the pressing process was good, but the amount of the alkali metal salt of the fatty acid was too large, so that the remaining amount of the film after the pressing process was reduced, resulting in minute seizure.
比較例８は、反応石けん処理を行って形成させたリン酸塩皮膜を有する鋼線材又はＳＰＣＣ-ＳＤ（従来例）であり、焼入れ焼戻しなどの熱処理を行う際に浸リンを起こして鋼線材が脆弱となる虞がある。 Comparative Example 8 is a steel wire material or SPCC-SD (conventional example) having a phosphate film formed by a reactive soap treatment, and the steel wire material is subjected to immersion phosphorus when performing heat treatment such as quenching and tempering. There is a risk of becoming vulnerable.
以上の説明から明らかなように本発明の鋼線材は、潤滑皮膜中にリンを含まないため浸リン性がなく、且つ、従来のリン酸塩と石けん処理材と同等以上の良好な長期間耐食性を有し、しかも圧造加工後の外観不良も生じない。よって、本発明の鋼線材は、産業上の利用価値が極めて大きいものである。 As is clear from the above description, the steel wire rod of the present invention does not contain phosphorus in the lubricating film, so it has no phosphorus immersion property, and has good long-term corrosion resistance equivalent to or better than conventional phosphate and soap treatment materials. In addition, there is no appearance defect after forging. Therefore, the steel wire rod of the present invention has a very high industrial utility value.
Claims (8)
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| KR1020187008815A KR102105304B1 (en) | 2015-09-30 | 2016-09-27 | Steel wire with excellent corrosion resistance and appearance after processing |
| CN201680056590.7A CN108138327B (en) | 2015-09-30 | 2016-09-27 | Steel wire rod excellent in corrosion resistance and appearance after working |
| PCT/JP2016/078500 WO2017057385A1 (en) | 2015-09-30 | 2016-09-27 | Steel wire with excellent corrosion resistance and appearance after processing |
| US15/763,975 US20180273869A1 (en) | 2015-09-30 | 2016-09-27 | Steel wire with excellent corrosion resistance and appearance after processing |
| MX2018003548A MX2018003548A (en) | 2015-09-30 | 2016-09-27 | Steel wire with excellent corrosion resistance and appearance after processing. |
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| CN113399483A (en) * | 2021-06-07 | 2021-09-17 | 威海银兴预应力线材有限公司 | Environment-friendly lubricating coating agent for cold-drawn steel wire and preparation method and application thereof |
| WO2024048598A1 (en) * | 2022-09-02 | 2024-03-07 | 日本パーカライジング株式会社 | Metal surface treatment agent, and metal material having coating film and manufacturing method for same |
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| CN113118234B (en) * | 2021-04-16 | 2022-09-27 | 江西富鸿金属有限公司 | Production process of tinned alloy wire for medical equipment |
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| JP2000309793A (en) * | 1999-04-27 | 2000-11-07 | Nippon Parkerizing Co Ltd | Water-based lubricant for plastic working of metallic material |
| JP3984158B2 (en) | 2000-08-07 | 2007-10-03 | 日本パーカライジング株式会社 | Water-based lubricant for metal material plastic working and method for treating lubricating film |
| TW588108B (en) | 2000-08-07 | 2004-05-21 | Nihon Parkerizing | Aqueous lubricant for plastic working of metallic material and method for forming lubricant film |
| JP4031213B2 (en) * | 2001-06-07 | 2008-01-09 | 株式会社神戸製鋼所 | Film forming agent and film |
| US7884058B2 (en) * | 2003-09-30 | 2011-02-08 | Chevron Oronite Company Llc | Stable colloidal suspensions and lubricating oil compositions containing same |
| JP5181393B2 (en) * | 2008-11-20 | 2013-04-10 | 日本パーカライジング株式会社 | Steel wire rod for fastening parts |
| KR101411199B1 (en) * | 2009-06-29 | 2014-06-23 | 니혼 파커라이징 가부시키가이샤 | Water-based lubricant for plastic processing having excellent corrosion resistance and metal material having excellent plastic processability |
| JP5682021B2 (en) | 2010-05-25 | 2015-03-11 | 日本パーカライジング株式会社 | Metallic material with poor crystallinity and excellent moisture absorption, corrosion resistance and workability Water-based lubricant for plastic working and metal material with its lubricating film formed |
| JP2013209625A (en) | 2012-02-27 | 2013-10-10 | Kobe Steel Ltd | Water-soluble lubricating agent for plastic working, metal material for plastic working, and worked metal article |
| JP2015189952A (en) * | 2014-03-28 | 2015-11-02 | 株式会社神戸製鋼所 | Steel wire material having lubrication coating excellent in corrosion resistance and processability |
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| CN113399483A (en) * | 2021-06-07 | 2021-09-17 | 威海银兴预应力线材有限公司 | Environment-friendly lubricating coating agent for cold-drawn steel wire and preparation method and application thereof |
| WO2024048598A1 (en) * | 2022-09-02 | 2024-03-07 | 日本パーカライジング株式会社 | Metal surface treatment agent, and metal material having coating film and manufacturing method for same |
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| CN108138327B (en) | 2020-07-21 |
| US20180273869A1 (en) | 2018-09-27 |
| JP6694769B2 (en) | 2020-05-20 |
| KR102105304B1 (en) | 2020-04-28 |
| CN108138327A (en) | 2018-06-08 |
| MX2018003548A (en) | 2018-06-19 |
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