JP6255424B2 - Lubricating coating agent for metal plastic working and metal material for metal plastic working - Google Patents
Lubricating coating agent for metal plastic working and metal material for metal plastic working Download PDFInfo
- Publication number
- JP6255424B2 JP6255424B2 JP2015560869A JP2015560869A JP6255424B2 JP 6255424 B2 JP6255424 B2 JP 6255424B2 JP 2015560869 A JP2015560869 A JP 2015560869A JP 2015560869 A JP2015560869 A JP 2015560869A JP 6255424 B2 JP6255424 B2 JP 6255424B2
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- JP
- Japan
- Prior art keywords
- lithium
- component
- plastic working
- metal
- 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.)
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- 229910052751 metal Inorganic materials 0.000 title claims description 119
- 239000002184 metal Substances 0.000 title claims description 119
- 229920003023 plastic Polymers 0.000 title claims description 115
- 239000004033 plastic Substances 0.000 title claims description 115
- 230000001050 lubricating effect Effects 0.000 title claims description 113
- 239000007769 metal material Substances 0.000 title claims description 49
- 239000011248 coating agent Substances 0.000 title claims description 45
- 239000008207 working material Substances 0.000 title 1
- 239000000314 lubricant Substances 0.000 claims description 86
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 inorganic compound lithium salt Chemical class 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 3
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 claims description 3
- 230000003245 working effect Effects 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 42
- 238000000576 coating method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 18
- 238000012545 processing Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000005242 forging Methods 0.000 description 11
- 239000001993 wax Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000007373 indentation Methods 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 239000012184 mineral wax Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012170 montan wax Substances 0.000 description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 102200082816 rs34868397 Human genes 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VZGOTNLOZGRSJA-ZZEZOPTASA-N (z)-n-octadecyloctadec-9-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC VZGOTNLOZGRSJA-ZZEZOPTASA-N 0.000 description 1
- RDYWHMBYTHVOKZ-UHFFFAOYSA-N 18-hydroxyoctadecanamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCO RDYWHMBYTHVOKZ-UHFFFAOYSA-N 0.000 description 1
- KHTJRKQAETUUQH-UHFFFAOYSA-N 2-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCC(CO)C(N)=O KHTJRKQAETUUQH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- FVUKYCZRWSQGAS-UHFFFAOYSA-N 3-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=CC(C(O)=O)=C1 FVUKYCZRWSQGAS-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
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- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
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- PECBPCUKEFYARY-ZPHPHTNESA-N n-[(z)-octadec-9-enyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC PECBPCUKEFYARY-ZPHPHTNESA-N 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- DJWFNQUDPJTSAD-UHFFFAOYSA-N n-octadecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC DJWFNQUDPJTSAD-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- WRMXOVHLRUVREB-UHFFFAOYSA-N phosphono phosphate;tributylazanium Chemical compound OP(O)(=O)OP([O-])([O-])=O.CCCC[NH+](CCCC)CCCC.CCCC[NH+](CCCC)CCCC WRMXOVHLRUVREB-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 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
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000012176 shellac wax Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000004711 α-olefin Substances 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
- C10M173/00—Lubricating compositions containing more than 10% water
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/081—Inorganic acids or salts thereof containing halogen
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/082—Inorganic acids or salts thereof containing nitrogen
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
-
- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
-
- 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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
本願が開示する発明は、金属塑性加工用潤滑皮膜剤及び金属塑性加工用金属材料に関する。詳しくは、潤滑性に優れ、高皮膜追随性を有する潤滑皮膜を形成できる金属塑性加工用潤滑皮膜剤、並びに、当該金属塑性加工用潤滑皮膜剤を使用して潤滑皮膜をコーティングさせた金属塑性加工用金属材料に関する。 The invention disclosed by the present application relates to a lubricating coating agent for metal plastic working and a metal material for metal plastic working. Specifically, a lubricating film agent for metal plastic working that can form a lubricating film having excellent lubricity and high film followability, and metal plastic working in which a lubricating film is coated using the lubricating film agent for metal plastic working It relates to a metal material.
金属材料の塑性加工において、金属材料の表面に形成させる潤滑皮膜は、大別して反応型潤滑皮膜と塗布型潤滑皮膜が存在する。 In the plastic processing of a metal material, the lubricant film formed on the surface of the metal material is roughly classified into a reactive lubricant film and a coating lubricant film.
前記反応型潤滑皮膜については、一般に、化学反応により金属材料の表面に化成処理皮膜を生成させた後に潤滑剤を付与して潤滑皮膜を得る。反応型潤滑皮膜の形成には、リン酸亜鉛のようなリン酸塩やシュウ酸塩が使用されることが多い。反応型潤滑皮膜は潤滑性に優れるが、一方で反応型潤滑皮膜の形成には複雑な処理液管理や多くの工程を必要とし、膜厚の制御が難しく、更に薄膜化が困難である。また、反応型潤滑皮膜の形成には多くの工程が必要で、多量の廃水及び廃棄物の発生、エネルギー使用量の増大等による環境負荷が大きいという問題もある。 In general, the reactive lubricating film is obtained by forming a chemical conversion film on the surface of a metal material by a chemical reaction and then applying a lubricant to obtain the lubricating film. In order to form a reactive lubricant film, phosphates and oxalates such as zinc phosphate are often used. A reactive lubricant film is excellent in lubricity. On the other hand, formation of a reactive lubricant film requires complicated treatment liquid management and many processes, and it is difficult to control the film thickness, and it is difficult to reduce the film thickness. In addition, the formation of a reactive lubricant film requires many steps, and there is also a problem that the environmental load is large due to the generation of a large amount of waste water and waste and the increase in energy consumption.
前記塗布型潤滑皮膜については、金属材料表面に金属塑性加工用潤滑皮膜剤を塗布等により接触させ乾燥することで潤滑皮膜を得る。潤滑皮膜の形成工程が簡便であり、環境負荷を抑制できる。また、金属塑性加工用潤滑皮膜剤を１剤式にすることができるという利点がある。更に、薄膜化が容易であるという利点がある。一方で、塑性加工後の切削工程を除いている精密鍛造加工では、塗布型潤滑皮膜が十分な性能を発揮しないという問題があった。また、加工後の金型内に金属材料から欠落した皮膜残渣が堆積して、成形不良が発生する、機械稼働ができなくなる等の問題があった。 About the said application | coating type lubricating film, a lubricating film is obtained by contacting the metal material surface with the lubricating film agent for metal plastic working by application | coating etc., and drying. The formation process of the lubricating film is simple and the environmental load can be suppressed. Further, there is an advantage that the lubricant coating agent for metal plastic working can be made into one agent type. Furthermore, there is an advantage that thinning is easy. On the other hand, in the precision forging process excluding the cutting process after the plastic working, there is a problem that the coating type lubricating film does not exhibit sufficient performance. In addition, film residues missing from the metal material accumulate in the mold after processing, resulting in problems such as forming defects and inability to operate the machine.
塗布型潤滑皮膜として、下記特許文献１及び特許文献２に記載のもの等が知られている。下記特許文献１は、水溶性無機塩と、スメクタイト系粘土鉱物とを含有し、これらの質量比が一定の範囲内にある塗布型潤滑皮膜形成用の水性組成物を開示する。下記特許文献２は、水溶性無機塩と、Ｎε−モノアシル塩基性アミノ酸塩類とを含有し、これらの質量比が一定の範囲内にある塗布型潤滑皮膜形成用の水性組成物を開示する。 As the application-type lubricating film, those described in Patent Document 1 and Patent Document 2 below are known. Patent Document 1 below discloses an aqueous composition for forming a coating-type lubricating film, which contains a water-soluble inorganic salt and a smectite clay mineral, and has a mass ratio within a certain range. Patent Document 2 listed below discloses an aqueous composition for forming a coating-type lubricating film, which contains a water-soluble inorganic salt and Nε-monoacyl basic amino acid salts and has a mass ratio within a certain range.
なお、下記非特許文献１は様々な潤滑皮膜の試験方法をレビューしている。下記非特許文献１では、試験方法の一つとして、スパイク高さと成形荷重との関係を確認するスパイク試験が紹介されている。非特許文献１Ｆｉｇ．９（ａ）には一般的なスパイク試験のイラストが記載されている。Ｆｉｇ．９（ａ）左側は加工前の状態（テストピースがセットされた状態）を図示しており、Ｆｉｇ．９（ａ）右側は加工後の状態を図示している。 The following non-patent document 1 reviews various test methods for lubricating films. Non-Patent Document 1 below introduces a spike test for confirming the relationship between spike height and forming load as one of test methods. Non-Patent Document 1 FIG. 9 (a) shows a typical spike test illustration. FIG. 9 (a) on the left side shows a state before processing (a state in which a test piece is set), and FIG. 9 (a) shows the state after processing on the right side.
上記特許文献２に開示されているように、近年、切削工程を必要とせず複雑形状部品を完成品に鍛造加工する精密鍛造加工を目指す流れが進んでいる。 As disclosed in Patent Document 2 above, in recent years, there has been a trend toward precision forging processing that forges complex-shaped parts into a finished product without requiring a cutting process.
精密鍛造加工では反応型潤滑皮膜が採用されることが多いが、上述の通り環境負荷の問題があり、また、処理が複雑でコスト高となる問題もあった。 In the precision forging process, a reactive lubricant film is often employed. However, as described above, there is a problem of environmental load, and there is also a problem that the process is complicated and expensive.
そこで、精密鍛造加工において塗布型潤滑皮膜の採用が検討されているものの、従来知られている塗布型潤滑皮膜はその性能が十分ではなかった。 Then, although adoption of the coating type lubricating film is being studied in precision forging, the performance of the conventionally known coating type lubricating film is not sufficient.
「スパイク高さと最大押込み荷重との関係を確認するスパイク試験（以下、単にスパイク試験とも称する。）ではリン酸塩を使用する反応型潤滑皮膜と同等程度の良好な結果が得られるものの、実際の塑性加工現場では（ａ）金属材料の塑性変形が不十分になる、及び／又は、（ｂ）皮膜の追随性が低いために金型と金属材料との直接接触によるかじりや焼き付きが発生する」という不具合が、従来知られている塗布型潤滑皮膜では起こっていた。 “The spike test to confirm the relationship between the spike height and the maximum indentation load (hereinafter also simply referred to as the spike test) gives good results comparable to the reactive lubricant film using phosphate, At the plastic working site, (a) the plastic deformation of the metal material is insufficient, and / or (b) the low followability of the film causes galling and seizure due to direct contact between the mold and the metal material. This problem occurred in the conventionally known coating-type lubricant film.
以上のような背景から、反応型潤滑皮膜から１剤式にできる塗布型潤滑皮膜への転換が進んでいなかった。よって、塗布型潤滑皮膜の利点を生かし、その上で反応型潤滑皮膜と同等程度の性能を備えた塗布型潤滑皮膜の実現が要望されていた。 From the background as described above, the conversion from a reactive lubricant film to a coating-type lubricant film that can be made into a single agent type has not progressed. Therefore, there has been a demand for the realization of a coating-type lubricating film that takes advantage of the coating-type lubricating film and has the same performance as that of the reactive lubricating film.
しかし、同等程度の性能といっても、それを実現するための要素は無数に存在すると考えられる。本願発明者は、リン酸塩を使用する反応型潤滑皮膜と従来の塗布型潤滑皮膜のスパイク試験での挙動の違いを注意深く調べたところ、潤滑皮膜の追随性において著しい差があることを見出した。従来の塗布型潤滑皮膜の多くは、潤滑性は良好な結果が得られるが潤滑皮膜の追随性は不十分となった（即ち、試験後のテストピースにおける新生面へ潤滑皮膜が追随しにくかった）。結果として良好な潤滑性及び良好な潤滑皮膜の追随性を両立する塗布型潤滑皮膜は見当たらなかった。 However, even if the performance is comparable, there are innumerable elements for realizing it. The inventor of the present application carefully examined the difference in behavior in the spike test between the reactive lubricant film using phosphate and the conventional coating-type lubricant film, and found that there was a significant difference in the followability of the lubricant film. . Many of the conventional coating-type lubrication films have good lubricity results, but the followability of the lubrication film is insufficient (that is, it is difficult for the lubricant film to follow the new surface of the test piece after the test). . As a result, there was no coating-type lubricant film that achieved both good lubricity and good followability of the lubricant film.
また、上記特許文献１ではスパイク高さと最大押込み荷重との関係に着目したスパイク試験が行われていない。一方、上記特許文献２ではスパイク試験における潤滑皮膜の追随性が確認されていない。以上より、スパイク試験で確認される、潤滑性と潤滑皮膜の追随性との関連性は、従来は重視されていなかったと考えられる。 Moreover, in the said patent document 1, the spike test which paid its attention to the relationship between spike height and the maximum indentation load is not performed. On the other hand, in Patent Document 2, the followability of the lubricant film in the spike test is not confirmed. From the above, it is considered that the relationship between the lubricity and the followability of the lubricating film confirmed by the spike test has not been emphasized conventionally.
本願発明者は鋭意研究を重ねた結果、（Ａ）滑剤から選ばれる１種又は２種以上、（Ｂ１）リン酸アルカリ金属塩（但し、リン酸リチウム塩を除く。）から選ばれる１種又は２種以上、（Ｂ２）無機化合物リチウム塩から選ばれる１種又は２種以上、及び（Ｃ）水を併用することで、リン酸塩を使用する反応型潤滑皮膜と同等程度又はそれを超える性能を有する塗布型潤滑皮膜を形成できることをスパイク試験において見出した。 As a result of extensive research, the inventor of the present application has (A) one or more selected from lubricants, and (B1) one or more selected from alkali metal phosphates (excluding lithium phosphates). 2 or more types, (B2) 1 type or 2 types or more selected from inorganic compound lithium salts, and (C) performance equivalent to or exceeding that of a reactive lubricant film using phosphate by using water together It was found in the spike test that a coating-type lubricating film having the following can be formed.
よって、潤滑性に優れ、高皮膜追随性を有する潤滑皮膜を形成でき、環境への負荷を低減した金属塑性加工用潤滑皮膜剤を提供することを、本願が解決すべき課題とする。また、当該金属塑性加工用潤滑皮膜剤を使用して潤滑皮膜をコーティングさせた金属塑性加工用金属材料を提供することを、本願が解決すべき課題とする。 Therefore, it is an object of the present application to provide a lubricating coating agent for metal plastic working that can form a lubricating coating having excellent lubricity and high coating followability and that reduces the environmental load. It is another object of the present application to provide a metal material for metal plastic working in which a lubricant film is coated using the metal plastic working lubricant film agent.
（Ｂ１）成分と（Ｂ２）成分とはイオン交換反応が可能であると考えられ、これが優れた潤滑性及び高皮膜追随性の発揮に重要であると本願発明者は推測している。 It is considered that the component (B1) and the component (B2) can undergo an ion exchange reaction, and the inventors of the present application speculate that this is important for exhibiting excellent lubricity and high film followability.
なお、上述のとおり、本願が開示する金属塑性加工用潤滑皮膜剤は、潤滑性に優れ、高皮膜追随性を有する潤滑皮膜を形成できる。よって、従来知られている塗布型潤滑皮膜より膜厚を薄くしても、良好に金属材料を加工できる。即ち、合理的に潤滑皮膜を薄くでき、これにより加工後の金型内の皮膜残渣を低減できる。 As described above, the lubricating film agent for metal plastic working disclosed in the present application is excellent in lubricity and can form a lubricating film having high film followability. Therefore, a metal material can be processed satisfactorily even if the film thickness is made thinner than a conventionally known coating-type lubricating film. That is, the lubricating coating can be made reasonably thin, thereby reducing the coating residue in the mold after processing.
（第１発明）
上記課題を解決するための本願第１発明は、
下記（Ａ）成分、（Ｂ１）成分、（Ｂ２）成分、及び（Ｃ）成分を含有する金属塑性加工用潤滑皮膜剤である。
（Ａ）滑剤から選ばれる１種又は２種以上。
（Ｂ１）リン酸アルカリ金属塩（但し、リン酸リチウム塩を除く。）から選ばれる１種又は２種以上。
（Ｂ２）無機化合物リチウム塩から選ばれる１種又は２種以上。
（Ｃ）水。(First invention)
The first invention of the present application for solving the above-described problems is as follows.
It is a lubricating film agent for metal plastic working containing the following component (A), component (B1), component (B2), and component (C).
(A) One or more selected from lubricants.
(B1) One or more selected from alkali metal phosphates (excluding lithium phosphate).
(B2) One or more selected from inorganic compound lithium salts.
(C) Water.
本願が開示する金属塑性加工用潤滑皮膜剤は水を必須成分として含有する。よって、本願が開示する金属塑性加工用潤滑皮膜剤はいわゆる水系である。また、塗布型潤滑皮膜を形成するために使用される。 The lubricating film agent for metal plastic working disclosed in the present application contains water as an essential component. Therefore, the lubricating film agent for metal plastic working disclosed in the present application is a so-called aqueous system. It is also used to form a coating type lubricating film.
（第２発明）
上記課題を解決するための本願第２発明は、
前記金属塑性加工用潤滑皮膜剤が、更に下記（Ｄ）成分を含有する第１発明に記載の金属塑性加工用潤滑皮膜剤である。
（Ｄ）水溶性樹脂及び水分散性樹脂から選ばれる１種又は２種以上。(Second invention)
The second invention of the present application for solving the above-described problems is as follows.
The lubricating coating agent for metal plastic working is the lubricating coating agent for metal plastic working according to the first aspect of the present invention, which further contains the following component (D).
(D) One or more selected from water-soluble resins and water-dispersible resins.
（第３発明）
上記課題を解決するための本願第３発明は、
前記金属塑性加工用潤滑皮膜剤が、更に下記（Ｅ）成分を含有する第１発明又は第２発明に記載の金属塑性加工用潤滑皮膜剤である。
（Ｅ）シランカップリング剤から選ばれる１種又は２種以上。(Third invention)
The third invention of the present application for solving the above problem is
The lubricant film for metal plastic working is the lubricant film for metal plastic working according to the first invention or the second invention, further comprising the following component (E).
(E) One or more selected from silane coupling agents.
（第４発明）
上記課題を解決するための本願第４発明は、
前記（Ａ）成分が、ワックス、金属石鹸、脂肪酸アマイド、ポリテトラフルオロエチレン、二硫化モリブデン、及び黒鉛から選ばれる１種又は２種以上である第１発明〜第３発明のいずれかに記載の金属塑性加工用潤滑皮膜剤である。(Fourth invention)
In order to solve the above problems, the fourth invention of the present application is:
The component (A) according to any one of the first to third inventions, wherein the component (A) is one or more selected from wax, metal soap, fatty acid amide, polytetrafluoroethylene, molybdenum disulfide, and graphite. It is a lubricant film agent for metal plastic working.
（第５発明）
上記課題を解決するための本願第５発明は、
前記（Ｂ１）成分が、リン酸、ピロリン酸、トリポリリン酸、テトラポリリン酸、ペンタポリリン酸、及びヘキサメタリン酸のアルカリ金属塩から選ばれる１種又は２種以上である第１発明〜第４発明のいずれかに記載の金属塑性加工用潤滑皮膜剤である。(Fifth invention)
The fifth invention of the present application for solving the above-mentioned problems is
The first to fourth inventions wherein the component (B1) is one or more selected from phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, and alkali metal salts of hexametaphosphoric acid. The lubricant film for metal plastic working according to any one of the above.
（第６発明）
上記課題を解決するための本願第６発明は、
前記（Ｂ２）成分が、塩化リチウム、硝酸リチウム、硫酸リチウム、及び水酸化リチウムから選ばれる１種又は２種以上である第１発明〜第５発明のいずれかに記載の金属塑性加工用潤滑皮膜剤である。(Sixth invention)
The sixth invention of the present application for solving the above-described problems is as follows.
The lubricating film for metal plastic working according to any one of the first to fifth inventions, wherein the component (B2) is one or more selected from lithium chloride, lithium nitrate, lithium sulfate, and lithium hydroxide. It is an agent.
（第７発明）
上記課題を解決するための本願第７発明は、
第１発明〜第６発明のいずれかに記載した金属塑性加工用潤滑皮膜剤を金属材料の表面に接触させ、次いで乾燥して当該金属材料の表面に潤滑皮膜をコーティングさせた金属塑性加工用金属材料である。(Seventh invention)
The seventh invention of the present application for solving the above-mentioned problems is
Metallic plastic working metal according to any one of the first to sixth inventions, wherein the metal plastic working lubricant film agent is brought into contact with the surface of the metal material and then dried to coat the surface of the metal material with the lubricant film Material.
本願が開示する金属塑性加工用潤滑皮膜剤は、潤滑性に優れ、高皮膜追随性を有する潤滑皮膜を形成できる。よって、金属材料の表面に形成させる潤滑皮膜を合理的に薄くでき、これにより加工後の金型内の皮膜残渣を低減できる。更に、いわゆる塗布型潤滑皮膜剤であることから、潤滑皮膜の形成工程が簡便であり、環境負荷を抑制できる。 The lubricating film agent for metal plastic working disclosed in the present application is excellent in lubricity and can form a lubricating film having high film followability. Therefore, the lubricating film formed on the surface of the metal material can be made reasonably thin, thereby reducing the film residue in the mold after processing. Furthermore, since it is a so-called coating-type lubricating film agent, the lubricating film forming process is simple and the environmental load can be suppressed.
本願が開示する金属塑性加工用潤滑皮膜剤は、リン酸塩やシュウ酸塩等を使用する反応型潤滑皮膜と同等程度又はそれを超える加工性を有する潤滑皮膜を形成可能と考えられる。 The lubricating film agent for metal plastic working disclosed in the present application is considered to be capable of forming a lubricating film having workability equivalent to or exceeding that of a reactive lubricating film using phosphate, oxalate, or the like.
本願が開示する金属塑性加工用潤滑皮膜剤を表面にコーティングさせた金属塑性加工用金属材料は、精密鍛造加工、引抜加工、伸線加工、プレス加工等の塑性加工に好適である。 The metal material for metal plastic working having the surface coated with the lubricant film for metal plastic working disclosed in the present application is suitable for plastic working such as precision forging, drawing, wire drawing, and press working.
以下、本願が開示する発明の実施形態をその最良の形態も含めて説明する。 Hereinafter, embodiments of the invention disclosed in the present application will be described including the best mode.
本願は、下記（Ａ）成分、（Ｂ１）成分、（Ｂ２）成分、及び（Ｃ）成分を含有する金属塑性加工用潤滑皮膜剤を開示する。
（Ａ）滑剤から選ばれる１種又は２種以上。
（Ｂ１）リン酸アルカリ金属塩（但し、リン酸リチウム塩を除く。）から選ばれる１種又は２種以上。
（Ｂ２）無機化合物リチウム塩から選ばれる１種又は２種以上。
（Ｃ）水。This application discloses the lubricant film agent for metal plastic working containing the following component (A), component (B1), component (B2), and component (C).
(A) One or more selected from lubricants.
(B1) One or more selected from alkali metal phosphates (excluding lithium phosphate).
(B2) One or more selected from inorganic compound lithium salts.
(C) Water.
当該金属塑性加工用潤滑皮膜剤は、そのまま金属材料に接触させてもよいし、更に水で希釈してから金属材料に接触させてもよい。一般的には、濃縮状態の金属塑性加工用潤滑皮膜剤で保存・流通させ、接触前に水で希釈し、その後金属材料表面に接触させることが多い。 The lubricant film for metal plastic working may be brought into contact with the metal material as it is, or further diluted with water and then brought into contact with the metal material. In general, it is often stored and distributed in a concentrated metal plastic working lubricant film, diluted with water before contact, and then contacted with the surface of the metal material.
以下の各成分の説明において、金属材料表面への接触時は「使用時」として説明する。 In the following description of each component, it will be described as “in use” when in contact with the surface of a metal material.
〔（Ａ）成分〕
（Ａ）成分は、滑剤から選ばれる１種又は２種以上である。[Component (A)]
(A) A component is 1 type, or 2 or more types chosen from a lubricant.
当該滑剤は、金属塑性加工分野で使用可能のものであれば特に限定されない。滑剤の具体例として、例えば、ワックス、金属石鹸、脂肪酸アマイド、ポリテトラフルオロエチレン（ＰＴＦＥ）、二硫化モリブデン、黒鉛、メラミンシアヌール酸（ＭＣＡ）、窒化ホウ素、雲母、植物油、鉱物油、合成油等がある。 The lubricant is not particularly limited as long as it can be used in the metal plastic working field. Specific examples of the lubricant include, for example, wax, metal soap, fatty acid amide, polytetrafluoroethylene (PTFE), molybdenum disulfide, graphite, melamine cyanuric acid (MCA), boron nitride, mica, vegetable oil, mineral oil, and synthetic oil. Etc.
好ましくは、ワックス、金属石鹸、脂肪酸アマイド、ポリテトラフルオロエチレン、二硫化モリブデン、及び黒鉛から選ばれる１種又は２種以上である。 Preferably, it is one or more selected from wax, metal soap, fatty acid amide, polytetrafluoroethylene, molybdenum disulfide, and graphite.
上記ワックスとして、例えば、ポリエチレンワックス、ポリプロピレンワックス等の合成ワックス、カルナバワックス等の植物系ワックス、パラフィンワックス、モンタンワックス等の鉱物系ワックス、ミツロウ、シェラックワックス等の動物系ワックス等がある。上記ワックスとして、潤滑性の観点から好ましくは、合成ワックス、鉱物系ワックスであり、より好ましくは、ポリエチレンワックス、ポリプロピレンワックス、モンタンワックスである。 Examples of the wax include synthetic waxes such as polyethylene wax and polypropylene wax, plant waxes such as carnauba wax, mineral waxes such as paraffin wax and montan wax, and animal waxes such as beeswax and shellac wax. From the viewpoint of lubricity, the wax is preferably a synthetic wax or a mineral wax, and more preferably a polyethylene wax, a polypropylene wax, or a montan wax.
上記金属石鹸として、例えば、脂肪酸のナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、リチウム塩等がある。好ましくは、脂肪酸のナトリウム塩である。上記脂肪酸として、例えば、ステアリン酸、パルミチン酸、オレイン酸、モンタン酸等がある。 Examples of the metal soap include fatty acid sodium salt, potassium salt, magnesium salt, calcium salt, and lithium salt. Preferably, it is a sodium salt of a fatty acid. Examples of the fatty acid include stearic acid, palmitic acid, oleic acid, and montanic acid.
上記脂肪酸アマイドとして、例えばラウリン酸アマイド、パルミチン酸アマイド、ステアリン酸アマイド、ベヘン酸アマイド、ヒドロキシステアリン酸アマイド、オレイン酸アマイド、エルカ酸アマイド、Ｎ−オレイルパルミチン酸アマイド、Ｎ−ステアリルステアリン酸アマイド、Ｎ−ステアリルオレイン酸アマイド、Ｎ−オレイルステアリン酸アマイド、Ｎ−ステアリルエルカ酸アマイド、メチロールステアリン酸アマイド、メチレンビスステアリン酸アマイド、エチレンビスステアリン酸アマイド、エチレンビスオレイン酸アマイド、エチレンビスエルカ酸アマイド、Ｎ，Ｎ’−システアリルイソフタル酸アマイド、ステアロアマイドエチルステアレート等がある。 Examples of the fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide, N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N -Stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, methylol stearic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, N , N′-cysteallyl isophthalic acid amide, stearoamide ethyl stearate and the like.
金属塑性加工用潤滑皮膜剤における（Ａ）成分の含有量は特に限定されない。あえて例を挙げると、０．２〜４０質量％として良く、１〜３０質量％として良く、１〜１５質量％としてよい。 The content of the component (A) in the lubricant film for metal plastic working is not particularly limited. For example, it may be 0.2 to 40% by mass, 1 to 30% by mass, or 1 to 15% by mass.
また、（Ａ）成分の使用時の含有量は金属塑性加工の条件等を考慮して適宜決定可能である。あえて例を挙げると、０．５〜３０質量％としてよく、１〜１５質量％としてよい。 Moreover, content at the time of use of (A) component can be suitably determined in consideration of the conditions of metal plastic working. For example, it may be 0.5 to 30% by mass or 1 to 15% by mass.
〔（Ｂ１）成分〕
（Ｂ１）成分は、リン酸アルカリ金属塩（但し、リン酸リチウム塩を除く。）から選ばれる１種又は２種以上である。[(B1) component]
The component (B1) is one or more selected from alkali metal phosphates (excluding lithium phosphates).
本願において、当該「リン酸」はリン酸及び縮合リン酸である。リン酸として、皮膜追随性の観点から好ましくは、リン酸、ピロリン酸、トリポリリン酸、テトラポリリン酸、ペンタポリリン酸、ヘキサメタリン酸であり、より好ましくはピロリン酸、トリポリリン酸、テトラポリリン酸、ペンタポリリン酸、ヘキサメタリン酸である。優れた皮膜追随性を確保しつつより優れた潤滑性を得る観点から、更に好ましくはトリポリリン酸、テトラポリリン酸、ペンタポリリン酸、ヘキサメタリン酸である。 In the present application, the “phosphoric acid” is phosphoric acid and condensed phosphoric acid. Phosphoric acid is preferably phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexametaphosphoric acid, more preferably pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid from the viewpoint of film followability. Acid, hexametaphosphoric acid. Tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, and hexametaphosphoric acid are more preferred from the viewpoint of obtaining superior lubricity while ensuring excellent film followability.
上記リン酸と塩を形成するアルカリ金属として、皮膜追随性の観点から好ましくは、ナトリウムイオン、カリウムイオンであり、より好ましくはナトリウムイオンである。 The alkali metal that forms a salt with the phosphoric acid is preferably a sodium ion or a potassium ion, more preferably a sodium ion, from the viewpoint of film followability.
なお（Ｂ１）成分において、上記リン酸における全てのマイナス電荷部位がアルカリ金属と塩を形成しているものを使用してもよいし（例えば、ピロリン酸ナトリウム： Ｎａ４Ｐ２Ｏ７等）、マイナス電荷部位の一部がアルカリ金属と塩を形成しているもの（例えば、酸性ピロリン酸二水素ナトリウム：Ｎａ２Ｈ２Ｐ２Ｏ７等）を使用してもよい。In the component (B1), all of the negatively charged sites in the phosphoric acid may form a salt with an alkali metal (for example, sodium pyrophosphate: Na 4 P 2 O 7 etc.) A material in which a part of the negative charge site forms a salt with an alkali metal (for example, sodium dihydrogen pyrophosphate: Na 2 H 2 P 2 O 7 or the like) may be used.
金属塑性加工用潤滑皮膜剤における（Ｂ１）成分の含有量は特に限定されない。あえて例を挙げると、０．３〜１５質量％として良く、１〜１０質量％としてよい。 The content of the component (B1) in the lubricant film for metal plastic working is not particularly limited. For example, it may be 0.3 to 15% by mass or 1 to 10% by mass.
また、（Ｂ１）成分の使用時の含有量は金属塑性加工の条件等を考慮して適宜決定可能である。あえて例を挙げると、０．２〜１２質量％としてよく、０．５〜１０質量％としてよい。 Moreover, content at the time of use of (B1) component can be suitably determined in consideration of the conditions of metal plastic working and the like. For example, it may be 0.2 to 12% by mass or 0.5 to 10% by mass.
〔（Ｂ２）成分〕
（Ｂ２）成分は、無機化合物リチウム塩から選ばれる１種又は２種以上である。[(B2) component]
The component (B2) is one or more selected from inorganic compound lithium salts.
（Ｂ２）成分の具体例として、例えば、塩化リチウム、硝酸リチウム、亜硝酸リチウム、硫酸リチウム、水酸化リチウム、臭化リチウム、モリブデン酸リチウム、珪酸リチウム、フッ化リチウム、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、チタン酸リチウム等がある。潤滑性及び皮膜追随性をバランスよく向上する観点から、塩化リチウム、硝酸リチウム、硫酸リチウム、水酸化リチウムが好ましく、硝酸リチウム、硫酸リチウム、水酸化リチウムがより好ましく、硫酸リチウム、水酸化リチウムが更に好ましく、硫酸リチウムが特に好ましい。 Specific examples of the component (B2) include, for example, lithium chloride, lithium nitrate, lithium nitrite, lithium sulfate, lithium hydroxide, lithium bromide, lithium molybdate, lithium silicate, lithium fluoride, lithium cobaltate, and lithium nickelate. , Lithium manganate and lithium titanate. From the viewpoint of improving the lubricity and film followability in a balanced manner, lithium chloride, lithium nitrate, lithium sulfate, and lithium hydroxide are preferable, lithium nitrate, lithium sulfate, and lithium hydroxide are more preferable, and lithium sulfate and lithium hydroxide are further included. Lithium sulfate is preferable and lithium sulfate is particularly preferable.
なお、（Ｂ２）成分を含有することにより、形成した潤滑皮膜の吸湿を抑制できる。 In addition, the moisture absorption of the formed lubricating film can be suppressed by containing (B2) component.
金属塑性加工用潤滑皮膜剤における（Ｂ２）成分の含有量は特に限定されない。あえて例を挙げると、０．３〜１５質量％として良く、１〜１０質量％としてよい。 The content of the component (B2) in the lubricating film agent for metal plastic working is not particularly limited. For example, it may be 0.3 to 15% by mass or 1 to 10% by mass.
また、（Ｂ２）成分の使用時の含有量は金属塑性加工の条件等を考慮して適宜決定可能である。あえて例を挙げると、０．２〜１２質量％としてよく、０．５〜１０質量％としてよい。 Moreover, content at the time of use of (B2) component can be suitably determined in consideration of conditions of metal plastic working. For example, it may be 0.2 to 12% by mass or 0.5 to 10% by mass.
〔（Ｂ１）成分と（Ｂ２）成分の相互作用の推測〕
本願が開示する金属塑性加工用潤滑皮膜剤の効果が発揮される化学的な要因は必ずしも明らかではない。しかし、（Ｂ１）成分と（Ｂ２）成分とはイオン交換反応が可能であると考えられ、これが優れた潤滑性及び高皮膜追随性の発揮に重要であると本願発明者は推測している。[Estimation of interaction between component (B1) and component (B2)]
The chemical factor that exerts the effect of the lubricating coating agent for metal plastic working disclosed in the present application is not necessarily clear. However, it is considered that the component (B1) and the component (B2) can undergo an ion exchange reaction, and the inventor of the present application speculates that this is important for exhibiting excellent lubricity and high film followability.
金属塑性加工時に摺動面に加わる鍛造圧力及び塑性変形熱により上記イオン交換反応が機能することで、潤滑性の向上が発揮されるとともに、潤滑皮膜の追随性が高まると本願発明者は考えている。 The present inventor believes that the ion exchange reaction functions by the forging pressure and the plastic deformation heat applied to the sliding surface during metal plastic processing, thereby improving lubricity and increasing the followability of the lubricating film. Yes.
金属塑性加工用潤滑皮膜剤は、（Ｂ１）成分及び（Ｂ２）成分の両者を含有することが重要である。 It is important that the lubricating coating agent for metal plastic working contains both the component (B1) and the component (B2).
〔（Ａ）成分と、（Ｂ１）成分及び（Ｂ２）成分の合計との含有比〕
金属塑性加工用潤滑皮膜剤における、（Ａ）成分と、（Ｂ１）成分及び（Ｂ２）成分の合計との質量基準の含有比は特に限定されないが、〔（Ａ）成分／（Ｂ１＋Ｂ２）成分〕＝０．０１〜１０が好ましい。優れた潤滑性及び皮膜追随性を得る観点から、当該比率は０．０６〜３が好ましく、０．２〜２．５がより好ましく、０．５〜２．５が更に好ましい。使用時においても、当該比率の好ましい範囲は同様である。[Content Ratio of Component (A) and Total of Component (B1) and Component (B2)]
The mass-based content ratio of the component (A) and the sum of the components (B1) and (B2) in the lubricant film for metal plastic working is not particularly limited, but [(A) component / (B1 + B2) component] = 0.01-10 is preferable. From the viewpoint of obtaining excellent lubricity and film followability, the ratio is preferably 0.06 to 3, more preferably 0.2 to 2.5, and still more preferably 0.5 to 2.5. The preferred range of the ratio is the same when in use.
本願発明者の知見によれば、（Ａ）成分、（Ｂ１）成分及び（Ｂ２）成分の合計の両者の質量基準の含有比を好ましい範囲内とすることで、より優れた潤滑性及び皮膜追随性が実現する。 According to the knowledge of the inventor of the present application, more excellent lubricity and follow-up of the film can be obtained by setting the mass-based content ratios of the total of the component (A), the component (B1) and the component (B2) within the preferred range. Realize.
〔（Ｃ）成分〕
（Ｃ）成分は水である。水として、例えば、水道水、蒸留水、イオン交換水、純水、工業用水等を適宜使用可能である。金属塑性加工用潤滑皮膜剤はいわゆる水系である。金属材料の表面に良好な均一性を有する潤滑皮膜を形成するために、水は必要である。[Component (C)]
Component (C) is water. As water, for example, tap water, distilled water, ion exchange water, pure water, industrial water and the like can be used as appropriate. The lubricating coating agent for metal plastic working is a so-called aqueous system. Water is necessary to form a lubricating film having good uniformity on the surface of the metal material.
金属塑性加工用潤滑皮膜剤における（Ｃ）成分の含有量は特に限定されない。あえて例を挙げると、５０質量％以上として良く、５０〜９８質量％としてよい。（Ｃ）成分の含有量を、他の成分の含有量との関係で比較的少なく抑えると、流通段階の容積を小さくできて有利である。 The content of the component (C) in the lubricant film for metal plastic working is not particularly limited. For example, it may be 50% by mass or more, or 50 to 98% by mass. If the content of the component (C) is suppressed to a relatively low level in relation to the content of other components, it is advantageous in that the volume at the distribution stage can be reduced.
（Ｃ）成分の使用時の含有量は金属塑性加工の条件等を考慮して適宜決定可能である。あえて例を挙げると、７０質量％以上としてよく、８０〜９５質量％としてよい。 (C) Content at the time of use of a component can be suitably determined in consideration of the conditions of metal plastic working. If an example is given, it may be 70 mass% or more, and may be 80-95 mass%.
〔（Ｄ）成分〕
（Ｄ）成分は、水溶性樹脂及び水分散性樹脂から選ばれる１種又は２種以上である。当該「水分散性」とは、水中に良好に分散できることの他、エマルジョン、コロイド状となれることを含む概念である。[Component (D)]
(D) A component is 1 type, or 2 or more types chosen from water-soluble resin and water-dispersible resin. The “water dispersibility” is a concept including not only being able to be dispersed well in water but also being able to become an emulsion or a colloid.
金属塑性加工用潤滑皮膜剤は、上記（Ａ）成分〜（Ｃ）成分に加え、更に（Ｄ）成分を含有することが好ましい。形成した潤滑皮膜の潤滑性がより優れる。また、潤滑皮膜の吸湿を抑制できる。 The lubricating film agent for metal plastic working preferably further contains a component (D) in addition to the components (A) to (C). The lubricity of the formed lubricating film is more excellent. Moreover, moisture absorption of the lubricating film can be suppressed.
上記水溶性樹脂及び水分散性樹脂は、金属塑性加工分野で使用可能のものであれば特に限定されない。水溶性樹脂及び水分散性樹脂の具体例として、例えば、アクリル樹脂、ウレタン樹脂、ポリビニルアルコール、ポリビニルピロリドン、酢酸ビニル樹脂、エポキシ樹脂、フェノール樹脂、イソブチレン−無水マレイン酸共重合体に代表されるα−オレフィンとカルボキシル基を有するエチレン性単量体からなる共重合体等がある。水溶性樹脂及び水分散性樹脂として、アクリル樹脂、ウレタン樹脂、α−オレフィンとカルボキシル基を有するエチレン性単量体からなる共重合体が好ましく、アクリル樹脂、ウレタン樹脂がより好ましく、アクリル樹脂が更に好ましい。水溶性樹脂及び水分散性樹脂の選択においては、例えば、特開２０００−６３８８０号公報等を参照することもできる。 The water-soluble resin and water-dispersible resin are not particularly limited as long as they can be used in the field of metal plastic processing. Specific examples of water-soluble resins and water-dispersible resins include, for example, acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl pyrrolidone, vinyl acetate resins, epoxy resins, phenol resins, and isobutylene-maleic anhydride copolymers. -A copolymer composed of an ethylenic monomer having an olefin and a carboxyl group. As the water-soluble resin and water-dispersible resin, an acrylic resin, a urethane resin, a copolymer composed of an α-olefin and an ethylenic monomer having a carboxyl group is preferable, an acrylic resin and a urethane resin are more preferable, and an acrylic resin is further preferable. In selecting a water-soluble resin and a water-dispersible resin, for example, JP-A-2000-63880 can be referred to.
金属塑性加工用潤滑皮膜剤における（Ｄ）成分の含有量は特に限定されない。あえて例を挙げると、０．１〜１０質量％として良く、０．２〜５質量％としてよい。 The content of the component (D) in the metal plastic working lubricant film agent is not particularly limited. If an example is given, it may be 0.1-10 mass%, and may be 0.2-5 mass%.
また、（Ｄ）成分の使用時の含有量は金属塑性加工の条件等を考慮して適宜決定可能である。あえて例を挙げると、０．０５〜１０質量％としてよく、０．１〜５質量％としてよい。 Moreover, content at the time of use of (D) component can be suitably determined in consideration of the conditions of metal plastic working. To give an example, it may be 0.05 to 10% by mass or 0.1 to 5% by mass.
〔（Ｅ）成分〕
（Ｅ）成分は、シランカップリング剤から選ばれる１種又は２種以上である。[(E) component]
(E) A component is 1 type, or 2 or more types chosen from a silane coupling agent.
金属塑性加工用潤滑皮膜剤は、上記（Ａ）成分〜（Ｃ）成分に加え、更に（Ｅ）成分を含有することが好ましい。形成した潤滑皮膜の潤滑性がより優れる。また、金属塑性加工用潤滑皮膜剤は、上記（Ａ）成分〜（Ｄ）成分に加え、更に（Ｅ）成分を含有することも好ましい。形成した潤滑皮膜について、更に優れた潤滑性を得ることができる。 It is preferable that the lubricating film agent for metal plastic working further contains the component (E) in addition to the components (A) to (C). The lubricity of the formed lubricating film is more excellent. In addition to the components (A) to (D), the lubricating coating agent for metal plastic working preferably further contains a component (E). Further excellent lubricity can be obtained for the formed lubricating film.
上記シランカップリング剤は、金属塑性加工分野で使用可能のものであれば特に限定されない。シランカップリング剤の具体例として、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、ｐ−スリチルトリメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルメチルジメトキシシラン等がある。シランカップリング剤として、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランが好ましく、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランがより好ましい。 The silane coupling agent is not particularly limited as long as it can be used in the metal plastic working field. Specific examples of the silane coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, p-stilt. Limethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , 3-Merka There are bets propyl methyl dimethoxy silane. As silane coupling agents, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane are preferred, and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane are preferred. More preferred.
金属塑性加工用潤滑皮膜剤における（Ｅ）成分の含有量は特に限定されない。あえて例を挙げると、０．１〜５質量％として良く、０．５〜３質量％としてよい。 The content of the component (E) in the lubricant film for metal plastic working is not particularly limited. If an example is given, it may be 0.1-5 mass%, and may be 0.5-3 mass%.
また、（Ｅ）成分の使用時の含有量は金属塑性加工の条件等を考慮して適宜決定可能である。あえて例を挙げると、０．０３〜５質量％としてよく、０．０５〜１質量％としてよい。 Moreover, content at the time of use of (E) component can be suitably determined in consideration of the conditions etc. of metal plastic working. If an example is given, it may be 0.03-5 mass%, and may be 0.05-1 mass%.
〔その他の任意成分〕
金属塑性加工用潤滑皮膜剤は、上記（Ａ）成分〜（Ｅ）成分の他に、任意の成分を適宜含有してよい。当該任意成分として、例えば、上記（Ｂ１）成分及び（Ｂ２）成分に該当しない無機塩、セルロース等の多糖類、カルボキシメチルセルロース等の多糖類誘導体、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール−ポリプロピレングリコールコポリマー、ソルビン酸塩等の防腐剤、染料、顔料、香料、界面活性剤、消泡剤、ｐＨ調整剤、防錆剤、極圧添加剤、レベリング剤等がある。[Other optional ingredients]
The lubricating film agent for metal plastic working may appropriately contain any component in addition to the components (A) to (E). Examples of the optional component include inorganic salts not corresponding to the above components (B1) and (B2), polysaccharides such as cellulose, polysaccharide derivatives such as carboxymethylcellulose, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, There are antiseptics such as sorbates, dyes, pigments, fragrances, surfactants, antifoaming agents, pH adjusters, rust inhibitors, extreme pressure additives, leveling agents and the like.
〔製造方法、使用方法等〕
金属塑性加工用潤滑皮膜剤は、周知の方法により製造可能である。金属塑性加工用潤滑皮膜剤の剤型は特に限定されない。金属塑性加工用潤滑皮膜剤は、通常、２５℃で液状である。金属塑性加工用潤滑皮膜剤は、１剤式でも２剤式以上の多剤式でもよい。好ましくは、金属塑性加工用潤滑皮膜剤は、１剤式である。[Production method, usage, etc.]
The lubricating coating agent for metal plastic working can be produced by a known method. The dosage form of the lubricating film agent for metal plastic working is not particularly limited. The lubricating coating agent for metal plastic working is usually liquid at 25 ° C. The lubricant coating agent for metal plastic working may be a single agent type or a multi-agent type having two or more agents. Preferably, the lubricating film agent for metal plastic working is a one-agent type.
金属塑性加工用潤滑皮膜剤は塗布型潤滑皮膜を形成するために使用される。金属塑性加工用潤滑皮膜剤は周知の方法により使用できる。通常、脱脂、酸洗、ショットブラスト、ウェットブラスト等常法によって前処理された金属材料に対して塗布等により金属塑性加工用潤滑皮膜剤を接触させる。その後、乾燥させて金属材料表面に潤滑皮膜を形成させる。 The lubricating film agent for metal plastic working is used to form a coating type lubricating film. The lubricating film agent for metal plastic working can be used by a known method. Usually, a metal film that is pretreated by a conventional method such as degreasing, pickling, shot blasting, or wet blasting is brought into contact with a lubricant film for metal plastic working by coating or the like. Thereafter, it is dried to form a lubricating film on the surface of the metal material.
好ましくは、上記のような前処理を行った後、温水に金属材料を浸漬させる等あらかじめ金属材料自体の加熱を行い、その後、金属塑性加工用潤滑皮膜剤を接触させ、乾燥させて金属材料表面に潤滑皮膜を形成させる。金属塑性加工用潤滑皮膜剤に含まれる水分の蒸発を早くすることで、生産効率を向上可能となる。 Preferably, after the pretreatment as described above, the metal material itself is heated in advance, such as by immersing the metal material in warm water, and then the metal film surface is contacted with a lubricant film for metal plastic working and dried. To form a lubricating film. Production efficiency can be improved by speeding up the evaporation of moisture contained in the lubricant film for metal plastic working.
また、金属塑性加工用潤滑皮膜剤自体をあらかじめ３０〜８０℃程度に適宜加温し、その後金属材料に接触させることで、水分の蒸発を早くすることもできる。 Moreover, the evaporation of moisture can be accelerated by appropriately heating the lubricating film agent for metal plastic working to about 30 to 80 ° C. in advance and then bringing it into contact with the metal material.
また、状況に応じて、複数工程による金属塑性加工を行う場合には、例えば一度鍛造等を行った金属材料に対し、さらに金属塑性加工用潤滑皮膜剤を重ね塗りして使用してもよい。また、本願が開示する金属塑性加工用潤滑皮膜剤以外の潤滑剤が付着した金属材料に対して、本願が開示する金属塑性加工用潤滑皮膜剤を重ね塗りして使用してもよい。 Moreover, when performing metal plastic working by a plurality of processes depending on the situation, for example, a metal film that has been once forged may be further coated with a lubricant film for metal plastic working. In addition, the metal film lubricating lubricant film disclosed in the present application may be applied over a metal material to which a lubricant other than the metal plastic processing lubricant film disclosed in the present application is attached.
金属材料は金属塑性加工分野で使用可能のものであれば特に限定されない。鉄、ステンレス、チタン、マグネシウム、アルミニウム、銅及び／又は黄銅を基材とする金属材料が好ましい。 The metal material is not particularly limited as long as it can be used in the metal plastic working field. Metal materials based on iron, stainless steel, titanium, magnesium, aluminum, copper and / or brass are preferred.
金属材料に金属塑性加工用潤滑皮膜剤を接触させる方法は特に限定されず、周知の方法を適宜採用可能である。あえて例を挙げると、浸漬、流しかけ、スプレー塗布、刷毛による塗布等がある。 There is no particular limitation on the method of bringing the metal material into contact with the lubricating film agent for metal plastic working, and a known method can be appropriately employed. For example, there are immersion, pouring, spray coating, brush coating, and the like.
金属材料に金属塑性加工用潤滑皮膜剤を接触させた後は、乾燥工程が必要である。当該乾燥工程は、水を除去する目的で行う。良好な効果を発揮する潤滑皮膜（乾燥皮膜）が得られるように水が除去されれば十分である。 After the metal film is brought into contact with the lubricant film for metal plastic working, a drying step is necessary. The drying step is performed for the purpose of removing water. It is sufficient if water is removed so that a lubricating film (dry film) that exhibits a good effect is obtained.
上記乾燥の方法は適宜選択可能である。常温下での放置により乾燥させてもよく、温風を当てることや、乾燥炉に投入する等して乾燥させてもよい。なお、金属材料を予め３０〜１００℃に加温しておき、その後金属塑性加工用潤滑皮膜剤を接触させると、乾燥効率がよい。形成された潤滑皮膜の膜厚や重量は、金属塑性加工の条件等を考慮して適宜決定可能である。 The drying method can be appropriately selected. It may be dried by being left at room temperature, or may be dried by applying warm air or putting it in a drying furnace. If the metal material is preheated to 30 to 100 ° C. and then brought into contact with a lubricant film for metal plastic working, the drying efficiency is good. The film thickness and weight of the formed lubricating film can be appropriately determined in consideration of the conditions of metal plastic working.
以上のとおり、本願は、金属塑性加工用潤滑皮膜剤を金属材料の表面に接触させ、次いで乾燥して当該金属材料の表面に潤滑皮膜をコーティングさせた金属塑性加工用金属材料を開示する。 As described above, the present application discloses a metal material for metal plastic working in which a lubricant film for metal plastic working is brought into contact with the surface of the metal material and then dried to coat the surface of the metal material with the lubricant film.
なお、本願において「コーティング」は、金属材料の表面に潤滑皮膜が形成されれば足りる。潤滑皮膜は、金属材料の表面全体に形成されてもよい。また、潤滑皮膜は、金属材料の表面の一部に形成されてもよい。 In the present application, the “coating” is sufficient if a lubricating film is formed on the surface of the metal material. The lubricating film may be formed on the entire surface of the metal material. Moreover, the lubricating film may be formed on a part of the surface of the metal material.
本願は、また、上記金属塑性加工用潤滑皮膜剤を金属材料の表面に接触させる工程、及び、乾燥して当該金属材料の表面に潤滑皮膜をコーティングさせる工程を含む金属塑性加工用金属材料の製造方法を開示する。当該金属塑性加工用金属材料の製造方法では、上記実施形態の記載を参照できる。 The present application also includes the step of bringing the lubricant film for metal plastic working into contact with the surface of the metal material and the step of drying and coating the surface of the metal material with the lubricant film to produce a metal material for metal plastic working A method is disclosed. In the method for producing the metal material for metal plastic working, the description of the above embodiment can be referred to.
金属塑性加工用金属材料は、冷間鍛造又は温間鍛造で使用される。但し、被加工材である金属材料の加工直前の温度は４００℃以下とし、好ましくは３００℃以下である。金型の温度は０〜３００℃とすることが好ましい。 The metal material for metal plastic working is used in cold forging or warm forging. However, the temperature immediately before the processing of the metal material as the workpiece is 400 ° C. or less, preferably 300 ° C. or less. The temperature of the mold is preferably 0 to 300 ° C.
上記金属塑性加工用潤滑皮膜剤を使用して得た塗布型潤滑皮膜は潤滑性に優れ、高皮膜追随性を有する。よって、金属塑性加工用金属材料は、精密鍛造加工、引抜加工、伸線加工、プレス加工にも好適である。 A coating-type lubricating film obtained by using the above-mentioned lubricating film agent for metal plastic working has excellent lubricity and high film followability. Therefore, the metal material for metal plastic working is also suitable for precision forging, drawing, wire drawing, and pressing.
以下、本願が開示する発明の実施例を記載する。本願が開示する発明の技術的範囲は以下の実施例に限定されない。 Examples of the invention disclosed in the present application will be described below. The technical scope of the invention disclosed in the present application is not limited to the following examples.
まず、後掲の表の説明をする。各成分の含有量を示す数値の単位は質量％である。（Ａ）成分、（Ｂ１）成分、（Ｂ２）成分、（Ｄ）成分及び（Ｅ）成分に該当する成分については、符号してその種別を示した。「（Ａ）／（Ｂ）」欄には、（Ａ）成分と、（Ｂ１）成分及び（Ｂ２）成分の合計との質量基準の含有比を記載した。 First, the table below will be explained. The unit of the numerical value indicating the content of each component is mass%. Components corresponding to (A) component, (B1) component, (B2) component, (D) component, and (E) component are labeled and their types are indicated. In the “(A) / (B)” column, the mass-based content ratio of the component (A) and the sum of the components (B1) and (B2) is described.
なお、比較例で使用した「四ホウ酸Ｋ」は（Ｂ１）成分に対する比較成分である。また、「硫酸Ｎａ」及び「硫酸Ｋ」は（Ｂ２）成分に対する比較成分である。 “Tetraborate K” used in the comparative example is a comparative component for the component (B1). Further, “sulfuric acid Na” and “sulfuric acid K” are comparative components for the component (B2).
〔金属塑性加工用潤滑皮膜剤の調製〕
実施例１〜３３及び比較例１〜７に係る１剤式の金属塑性加工用潤滑皮膜剤を常法により調製した。各例に係る金属塑性加工用潤滑皮膜剤は、塗布型潤滑皮膜を形成するために使用され、２５℃で液状である。[Preparation of lubricant coating for metal plastic working]
One-component type lubricant coatings for metal plastic working according to Examples 1 to 33 and Comparative Examples 1 to 7 were prepared by a conventional method. The lubricant film for metal plastic working according to each example is used to form a coating-type lubricant film and is liquid at 25 ° C.
〔塗布型潤滑皮膜の形成〕
テストピース（塑性加工される金属材料）は、材質がＳ４５Ｃ（サイズ：φ２５×２０ｍｍ）である。テストピースはあらかじめアルカリ脱脂を行い、その後湯洗を行った。そのテストピースを適宜水で希釈した実施例１〜３３及び比較例１〜７に係る各金属塑性加工用潤滑皮膜剤に浸漬させ、すばやく引き上げ、温風乾燥することによりテストピース表面に潤滑皮膜を形成させた。なお、塗布型潤滑皮膜の重量は４（ｇ／ｍ２）とした。[Formation of coating type lubricant film]
The test piece (metal material to be plastically processed) is S45C (size: φ25 × 20 mm). The test piece was alkali degreased in advance and then washed with hot water. The test piece was appropriately diluted with water and immersed in each metal plastic working lubricant film according to Examples 1 to 33 and Comparative Examples 1 to 7, quickly pulled up, and dried with hot air to form a lubricant film on the surface of the test piece. Formed. The weight of the coating type lubricating film was 4 (g / m 2 ).
〔反応型潤滑皮膜を使用した比較例〕
比較例８は、塗布型潤滑皮膜ではなく、反応型潤滑皮膜を使用した。実施例と潤滑皮膜の型が異なるので、比較例８は参考例としての意義を有している。[Comparative example using reactive lubricant film]
In Comparative Example 8, a reactive lubricating film was used instead of a coating type lubricating film. Since the example and the type of the lubricant film are different, Comparative Example 8 has significance as a reference example.
テストピース（材質はＳ４５Ｃ、サイズはφ２５×２０ｍｍ）を湯洗し、アルカリ脱脂を行い、リン酸亜鉛化成処理（パルーブ１８１Ｘ、日本パーカライジング社製、９０ｇ／Ｌ、液温８０℃、浸漬１０分）を行い、反応石鹸処理（パルーブ２３５、日本パーカライジング社製、７０ｇ／ｍ２、液温８５℃、浸漬３分）を行い、テストピース表面に潤滑皮膜を形成させた。The test piece (material is S45C, size is φ25 × 20mm) is washed with hot water, alkaline degreasing is performed, and zinc phosphate chemical conversion treatment (Palube 181X, Nihon Parkerizing Co., Ltd., 90 g / L, liquid temperature 80 ° C., immersion 10 minutes) And a reactive soap treatment (Palube 235, manufactured by Nihon Parkerizing Co., Ltd., 70 g / m 2 , liquid temperature 85 ° C., immersion 3 minutes) was performed to form a lubricating film on the surface of the test piece.
〔スパイク試験、潤滑性評価〕
−使用機器等−
プレス機は、２００ｔクランクプレス機（コマツ産機製）を使用した。ストローク長は２５０ｍｍ、ストローク数は２５ｓｐｍ、ダイギャップは２．５ｍｍとした。
金型は、材質がＳＫＤ６１であり、スパイク試験前に♯１０００のサンドペーパーで研磨した。
なお、上記テストピース及び金型の材質は「ＪＩＳハンドブック２００５」に記載された組成に従っている。[Spike test, lubricity evaluation]
-Equipment used-
The press machine used was a 200t crank press machine (manufactured by Komatsu Industries). The stroke length was 250 mm, the number of strokes was 25 spm, and the die gap was 2.5 mm.
The mold was made of SKD61 and polished with # 1000 sandpaper before the spike test.
The material of the test piece and the mold follows the composition described in “JIS Handbook 2005”.
−試験及び評価基準−
テストピースを３０℃、金型温度を１５０℃に加温してスパイク試験を行った。
押込荷重測定用のロードセルで、テストピース加工時の最大押込荷重（ｔｏｎｆ）を測定した。また、加工後のテストピースのスパイク高さ（ｍｍ）も測定した。上記非特許文献１Ｆｉｇ．９（ａ）右側に、「Ｓｐｉｋｅ ｈｅｉｇｈｔ Ｈ」としてスパイク高さが図示されている。各実施例及び各比較例について、試験は５連行った。-Test and evaluation criteria-
The spike test was performed by heating the test piece to 30 ° C. and the mold temperature to 150 ° C.
The maximum indentation load (tonf) at the time of test piece processing was measured with a load cell for indentation load measurement. Moreover, the spike height (mm) of the test piece after processing was also measured. Non-Patent Document 1 FIG. 9 (a) On the right side, the spike height is shown as “Spike height H”. About each Example and each comparative example, the test was done 5 times.
各実施例及び各比較例について、「スパイク高さ（ｍｍ）」の平均値及び「最大押込荷重（ｔｏｎｆ）」の平均値から、「スパイク高さ／最大押込荷重（ｍｍ／ｔｏｎｆ）」を求めた。当該比率の数値は表中の「スパイク試験」欄に記載した。 For each example and each comparative example, “spike height / maximum indentation load (mm / tonf)” is obtained from the average value of “spike height (mm)” and the average value of “maximum indentation load (tonf)”. It was. The numerical value of the ratio is described in the “spike test” column in the table.
表中の「潤滑性評価」欄には、当該比率が０．０９５０未満の場合を「×」０．０９５０〜０．０９８０の場合を「○」、０．０９８０を超える場合を「◎」として評価を記載した。比較例８はリン酸亜鉛を使用した反応型潤滑皮膜を使用している。反応型潤滑皮膜と同等程度又はそれを超える潤滑性を示す場合は「○」又は「◎」と評価される。 In the “Lubricity Evaluation” column of the table, “x” indicates that the ratio is less than 0.0950, “◯” indicates that the ratio is 0.0950 to 0.0980, and “◎” indicates that the ratio exceeds 0.0980. The evaluation is described. Comparative Example 8 uses a reactive lubricant film using zinc phosphate. When it shows a lubricity comparable to or exceeding that of a reactive lubricant film, it is evaluated as “◯” or “「 ”.
〔皮膜の追随性評価〕
上記スパイク試験による加工後のテストピースのスパイク部（新生面）を目視で観察し、最大の皮膜追随を示した箇所を確認して、皮膜の追随性を評価した。各実施例及び比較例について、最も多かった評価結果を各例の評価結果として採用した。最も多い評価結果が複数となった場合は、低い方の評価を採用することとした。各例の評価結果は表中に記載した。[Film followability evaluation]
The spike part (new surface) of the test piece after processing by the spike test was visually observed, and the portion showing the maximum film follow-up was confirmed to evaluate the film followability. About each Example and the comparative example, the most frequent evaluation result was employ | adopted as an evaluation result of each example. When the most frequent evaluation results were multiple, the lower evaluation was adopted. The evaluation results for each example are listed in the table.
−評価基準−
スパイク高さ方向に沿って、スパイク部（新生面）の基底部〜スパイク部の先端までにおいて、
スパイク部先端まで皮膜が伸びている場合を「◎」、
１／２を超えスパイク部先端未満の位置まで皮膜が伸びている場合を「○」、
１／４を超え１／２以下の位置まで皮膜が伸びている場合を「△」、
皮膜の伸びがない、又は１／４以下の位置まで皮膜が伸びている場合を「×」、と評価した。-Evaluation criteria-
Along the spike height direction, from the base of the spike part (new surface) to the tip of the spike part,
When the film extends to the tip of the spike part,
When the film extends to a position exceeding 1/2 and below the tip of the spike part,
The case where the film extends to a position exceeding 1/4 and 1/2 or less is indicated by “△”.
The case where the film was not stretched or the film was stretched to a position of 1/4 or less was evaluated as “x”.
〔表１〕
[Table 1]
〔表２〕
[Table 2]
〔表３〕
[Table 3]
〔表４〕
[Table 4]
上記各実施例は、いずれも潤滑性に優れ、高皮膜追随性を有する塗布型潤滑皮膜を得た。よって、各実施例に係る金属塑性加工用潤滑皮膜剤は金属材料の表面に形成させる潤滑皮膜を合理的に薄くでき、これにより加工後の金型内の皮膜残渣を低減できる。なお、反応型潤滑皮膜を使用した比較例８に対して、塗布型潤滑皮膜の形成工程は簡便であり、環境負荷の抑制もできた。各実施例に係る金属塑性加工用潤滑皮膜剤は、リン酸塩を使用する反応型潤滑皮膜と同等程度又はそれを超える加工性を有する潤滑皮膜を形成可能と考えられる。よって、各実施例に係る金属塑性加工用潤滑皮膜剤を使用して製造した金属塑性加工用金属材料は、精密鍛造加工、引抜加工、伸線加工、プレス加工にも好適であると考えられた。 In each of the above examples, a coating-type lubricating film having excellent lubricity and high film followability was obtained. Therefore, the lubricating film agent for metal plastic working according to each embodiment can reasonably thin the lubricating film formed on the surface of the metal material, thereby reducing the film residue in the mold after processing. In addition, compared with the comparative example 8 using a reactive lubricant film, the formation process of a coating type lubricant film was simple and the environmental load could be suppressed. It is considered that the lubricating film agent for metal plastic working according to each example can form a lubricating film having workability equivalent to or exceeding that of a reactive lubricating film using phosphate. Therefore, it was considered that the metal material for metal plastic working produced using the lubricant film for metal plastic working according to each example is suitable for precision forging, drawing, wire drawing, and press working. .
一方、（Ａ）成分、（Ｂ１）成分、及び（Ｂ２）成分のいずれかを含まない比較例１〜７は、不十分な評価結果となった。特に、いずれの比較例も皮膜の追随性評価が不十分であった。（Ｂ２）成分にかえて「硫酸Ｎａ」又は「硫酸Ｋ」を含む比較例５〜６並びに、（Ｂ１）成分にかえて「四ホウ酸Ｋ」を含む比較例７は、従来知られていた塗布型潤滑皮膜を使用した例であり、潤滑性評価は優れていたものの皮膜の追随性評価が不十分であった。 On the other hand, Comparative Examples 1-7 that did not contain any of the component (A), the component (B1), and the component (B2) resulted in insufficient evaluation results. In particular, in any of the comparative examples, the followability evaluation of the film was insufficient. (B2) Comparative Examples 5 to 6 including “sulfuric acid Na” or “sulfuric acid K” instead of the component and Comparative Example 7 including “tetraboric acid K” instead of the (B1) component have been conventionally known. In this example, a coating-type lubricating film was used, and although the evaluation of lubricity was excellent, the following evaluation of the film was insufficient.
実施例１〜９より、（Ａ）成分として様々な滑剤が使用可能と考えられた。更に、潤滑性の観点から、好ましい特定の滑剤があると考えられた。 From Examples 1 to 9, it was considered that various lubricants could be used as the component (A). Furthermore, from the viewpoint of lubricity, it was considered that there was a preferable specific lubricant.
実施例１、１３〜１９及び３２より、（Ｂ１）成分としてリン酸アルカリ金属塩（但し、リン酸リチウム塩を除く。）が使用可能と考えられた。皮膜追随性の観点及び潤滑性の観点から、好ましい特定のリン酸アルカリ金属塩があると考えられた。 From Examples 1, 13 to 19, and 32, it was considered that an alkali metal phosphate (excluding lithium phosphate) can be used as the component (B1). From the viewpoint of film followability and lubricity, it was considered that there was a preferable specific alkali metal phosphate.
実施例１、２０〜２２及び３３より、（Ｂ２）成分として無機化合物リチウム塩が使用可能と考えられた。潤滑性及び皮膜追随性をバランスよく向上する観点から、好ましい特定の無機化合物リチウム塩があると考えられた。 From Examples 1, 20, 22 and 33, it was considered that an inorganic compound lithium salt can be used as the component (B2). From the viewpoint of improving the lubricity and film followability in a well-balanced manner, it was considered that there was a preferable specific inorganic compound lithium salt.
実施例１０〜１２及び２３より、（Ａ）成分〜（Ｃ）成分に加え、更に（Ｄ）成分及び／又は（Ｅ）成分を含有することで、金属塑性加工用潤滑皮膜剤の効果がより向上すると考えられた。 From Examples 10-12 and 23, in addition to the (A) component to the (C) component, the effect of the lubricating coating agent for metal plastic working is further increased by further containing the (D) component and / or the (E) component. It was thought to improve.
実施例２４〜３１より、（Ａ）成分と、（Ｂ１）成分及び（Ｂ２）成分の合計との含有比について、好ましい範囲があると考えられた。 From Examples 24-31, it was thought that there exists a preferable range about content ratio with (A) component and the sum total of (B1) component and (B2) component.
〔潤滑皮膜の吸湿性の検討〕
実施例１、比較例１、比較例３、比較例４、比較例５、及び比較例７に係る各金属塑性加工用潤滑皮膜剤を使用して潤滑皮膜を形成させたテストピースについて、形成した潤滑皮膜の吸湿性を検討した。[Examination of hygroscopicity of lubricating film]
It formed about the test piece which formed the lubricating film using the lubricating film agent for metal plastic working which concerns on Example 1, Comparative Example 1, Comparative Example 3, Comparative Example 4, Comparative Example 5, and Comparative Example 7. The hygroscopicity of the lubricating film was examined.
−試験−
材質がＳＰＣＣ、サイズが１５０×７０ｍｍ（厚さ０．８ｍｍ）の板状のテストピースを使用した。テストピースはあらかじめアルカリ脱脂を行い、その後湯洗を行った。そのテストピースを適宜水で希釈した各例に係る金属塑性加工用潤滑皮膜剤に浸漬させ、すばやく引き上げ、温風乾燥することによりテストピース表面に潤滑皮膜を形成させた。なお、潤滑皮膜の重量は４（ｇ／ｍ２）とした。-Test-
A plate-like test piece having a material of SPCC and a size of 150 × 70 mm (thickness 0.8 mm) was used. The test piece was alkali degreased in advance and then washed with hot water. The test piece was immersed in a lubricating coating agent for metal plastic working according to each example diluted with water as appropriate, quickly pulled up, and dried with warm air to form a lubricating coating on the surface of the test piece. The weight of the lubricating film was 4 (g / m 2 ).
潤滑皮膜を形成後、テストピースを２５℃、７５％ＲＨの恒温恒湿槽内に６０分間入れて強制的に吸湿させた。各例について、試験は５連行った。なお、上記テストピースの材質は「ＪＩＳハンドブック２００５」に記載された組成に従っている。 After forming the lubricating film, the test piece was forced to absorb moisture by placing it in a constant temperature and humidity chamber at 25 ° C. and 75% RH for 60 minutes. For each example, the test was conducted 5 times. Note that the material of the test piece follows the composition described in “JIS Handbook 2005”.
−評価基準−
吸湿前後のテストピースの重量差と、テストピースに形成された潤滑皮膜の重量から、下記式により吸湿率を算出した。-Evaluation criteria-
From the weight difference between the test pieces before and after moisture absorption and the weight of the lubricant film formed on the test pieces, the moisture absorption rate was calculated by the following formula.
吸湿率（％）＝
〔（吸湿後の潤滑皮膜が形成されたテストピース重量（ｇ）−吸湿前の潤滑皮膜が形成されたテストピース重量（ｇ））／潤滑皮膜の重量〕×１００Moisture absorption rate (%) =
[(Weight of test piece on which lubricating film after moisture absorption is formed (g) −weight of test piece on which lubricating film before moisture absorption is formed (g)) / weight of lubricating film] × 100
各例について吸湿率の平均値を求め、当該平均値が１５％未満の場合を「○」、１５％以上の場合を「×」と評価し、評価結果を表５に記載した。なお、表５には、各例の吸湿率（％）の平均値も併記した。 The average value of the moisture absorption rate was obtained for each example, the case where the average value was less than 15% was evaluated as “◯”, the case where the average value was 15% or more was evaluated as “x”, and the evaluation results are shown in Table 5. In Table 5, the average value of the moisture absorption rate (%) of each example is also shown.
〔表５〕
[Table 5]
金属塑性加工用潤滑皮膜剤が（Ｂ２）成分を含むと、形成された潤滑皮膜の吸湿を抑制できると考えられた。 It was considered that when the lubricating film agent for metal plastic working contains the component (B2), moisture absorption of the formed lubricating film can be suppressed.
吸湿を抑制することで、潤滑皮膜の吸湿による潤滑性及び皮膜追随性の低下を抑制でき、実際の塑性加工現場における生産ラインの一時停止等が起こった場合にも安定した生産が可能となる。また、金属塑性加工用潤滑皮膜剤の塗布から鍛造までを連続的に行うインライン形式で使用する以外にも、一定数量の材料を一度にまとめて単位操作ごとに区切り処理を行うバッチ処理が可能となる。また、加工後の防錆性にも優れる。 By suppressing moisture absorption, it is possible to suppress a decrease in lubricity and film followability due to moisture absorption of the lubricant film, and stable production is possible even when the production line is temporarily stopped at the actual plastic working site. In addition to using the in-line method that continuously applies from the application of the lubricant coating for metal plastic working to forging, it is possible to perform batch processing that separates a certain number of materials at once and separates them for each unit operation. Become. Moreover, it is excellent also in the rust prevention property after a process.
本願により、潤滑性に優れ、高皮膜追随性を有する潤滑皮膜を形成でき、環境への負荷を低減した金属塑性加工用潤滑皮膜剤が提供される。また、本願により、当該金属塑性加工用潤滑皮膜剤を使用して潤滑皮膜をコーティングさせた金属塑性加工用金属材料が提供される。 According to the present application, there is provided a lubricating coating agent for metal plastic working that can form a lubricating coating that has excellent lubricity and has high coating followability and that reduces the load on the environment. In addition, according to the present application, a metal material for metal plastic working is provided in which the lubricant film is coated using the lubricant film for metal plastic working.
Claims (7)
（Ａ）滑剤から選ばれる１種又２種以上。
（Ｂ１）リン酸アルカリ金属塩（但し、リン酸リチウム塩を除く）から選ばれる１種又２種以上。
（Ｂ２）塩化リチウム、硝酸リチウム、亜硝酸リチウム、硫酸リチウム、臭化リチウム、モリブデン酸リチウム、フッ化リチウム、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、チタン酸リチウムから選ばれる１種又２種以上の無機化合物リチウム塩。
（Ｃ）水。 A lubricating coating agent for metal plastic working containing the following component (A), component (B1), component (B2), and component (C).
(A) One or more selected from lubricants.
(B1) One type or two or more types selected from alkali metal phosphates (excluding lithium phosphates).
(B2) One or two selected from lithium chloride, lithium nitrate, lithium nitrite, lithium sulfate, lithium bromide, lithium molybdate, lithium fluoride, lithium cobaltate, lithium nickelate, lithium manganate, and lithium titanate More than one kind of inorganic compound lithium salt.
(C) Water.
（Ａ）滑剤から選ばれる１種又２種以上。
（Ｂ１）リン酸アルカリ金属塩（但し、リン酸リチウム塩を除く）から選ばれる１種又２種以上。
（Ｂ２）塩化リチウム、硝酸リチウム、亜硝酸リチウム、硫酸リチウム、水酸化リチウム、臭化リチウム、モリブデン酸リチウム、フッ化リチウム、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、チタン酸リチウムから選ばれる１種又２種以上の無機化合物リチウム塩。
（Ｃ）水。
（Ｅ）シランカップリング剤から選ばれる１種又２種以上。 A lubricating coating agent for metal plastic working containing the following component (A), component (B1), component (B2), component (C), and component (E) .
(A) One or more selected from lubricants.
(B1) One type or two or more types selected from alkali metal phosphates (excluding lithium phosphates).
(B2) selected from lithium chloride, lithium nitrate, lithium nitrite, lithium sulfate, lithium hydroxide, lithium bromide, lithium molybdate, lithium fluoride, lithium cobaltate, lithium nickelate, lithium manganate, lithium titanate One or more inorganic compound lithium salts.
(C) Water.
(E) One type or two or more types selected from silane coupling agents.
（Ｄ）水溶性樹脂及び水分散性樹脂から選ばれる１種又は２種以上。 The lubricating coating agent for metal plastic working according to claim 1 or 2 , wherein the lubricating coating agent for metal plastic working further contains the following component (D).
(D) One or more selected from water-soluble resins and water-dispersible resins.
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| ZA963198B (en) * | 1995-05-16 | 1996-10-25 | Timcal Ltd | Lubricant composition for use on workpieces in the hot forming of metals |
| JP3511815B2 (en) * | 1996-10-15 | 2004-03-29 | 住友金属工業株式会社 | Surface lubricated metal material with excellent scratch resistance and film removal properties |
| JP2002226885A (en) * | 2001-02-07 | 2002-08-14 | Yuukou Shoji Kk | Aqueous lubricating agent for plastic working of metal |
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| WO2015005142A1 (en) * | 2013-07-10 | 2015-01-15 | 日本パーカライジング株式会社 | Aqueous lubricant for plastic working of metal material and having superior gas clogging resistance and post-moisture absorption workability |
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