WO2024005185A1 - Additive composition for lubricating oils, and lubricating oil composition - Google Patents
Additive composition for lubricating oils, and lubricating oil composition Download PDFInfo
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- WO2024005185A1 WO2024005185A1 PCT/JP2023/024357 JP2023024357W WO2024005185A1 WO 2024005185 A1 WO2024005185 A1 WO 2024005185A1 JP 2023024357 W JP2023024357 W JP 2023024357W WO 2024005185 A1 WO2024005185 A1 WO 2024005185A1
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- WIPO (PCT)
- Prior art keywords
- group
- copolymer
- structural unit
- lubricating oil
- monomer
- Prior art date
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 166
- 239000000203 mixture Substances 0.000 title claims abstract description 164
- 239000000654 additive Substances 0.000 title claims abstract description 98
- 230000000996 additive effect Effects 0.000 title claims abstract description 93
- 229920001577 copolymer Polymers 0.000 claims abstract description 304
- 239000000178 monomer Substances 0.000 claims abstract description 200
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 96
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 86
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000011593 sulfur Substances 0.000 claims abstract description 80
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011574 phosphorus Substances 0.000 claims abstract description 64
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 41
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 23
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 78
- 238000004519 manufacturing process Methods 0.000 claims description 66
- 125000000217 alkyl group Chemical group 0.000 claims description 55
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 43
- 239000002199 base oil Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 37
- 125000000524 functional group Chemical group 0.000 claims description 34
- 125000002947 alkylene group Chemical group 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000000470 constituent Substances 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 76
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- 238000012360 testing method Methods 0.000 description 38
- 230000000694 effects Effects 0.000 description 31
- -1 methacryloyl group Chemical group 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 26
- 238000009826 distribution Methods 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 21
- 230000001050 lubricating effect Effects 0.000 description 19
- 239000002480 mineral oil Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 235000010446 mineral oil Nutrition 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 101100208720 Homo sapiens USP5 gene Proteins 0.000 description 15
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000004927 fusion Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 231100000241 scar Toxicity 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 101150018840 SPM1 gene Proteins 0.000 description 6
- 101100335888 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) GAL83 gene Proteins 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 101100009524 Anas platyrhynchos HSD17B12 gene Proteins 0.000 description 5
- 101100256975 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SIP2 gene Proteins 0.000 description 5
- 101100203850 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SPT2 gene Proteins 0.000 description 5
- 101100291461 Schizosaccharomyces pombe (strain 972 / ATCC 24843) spm2 gene Proteins 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000006078 metal deactivator Substances 0.000 description 5
- 229920000193 polymethacrylate Polymers 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002027 dichloromethane extract Substances 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010718 automatic transmission oil Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003879 lubricant additive Substances 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- HMNZROFMBSUMAB-UHFFFAOYSA-N 1-ethoxybutan-1-ol Chemical compound CCCC(O)OCC HMNZROFMBSUMAB-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- KXPXKNBDCUOENF-UHFFFAOYSA-N 2-(Octylthio)ethanol Chemical compound CCCCCCCCSCCO KXPXKNBDCUOENF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZPIRWAHWDCHWLM-UHFFFAOYSA-N 2-dodecylsulfanylethanol Chemical compound CCCCCCCCCCCCSCCO ZPIRWAHWDCHWLM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- FCQAFXHLHBGGSK-UHFFFAOYSA-N 4-nonyl-n-(4-nonylphenyl)aniline Chemical compound C1=CC(CCCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCCC)C=C1 FCQAFXHLHBGGSK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical group NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- DWLMIYNUGWGKQW-UHFFFAOYSA-N C(CCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCC)CCCC)CCCC Chemical compound C(CCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCC)CCCC)CCCC DWLMIYNUGWGKQW-UHFFFAOYSA-N 0.000 description 1
- WFHKDFKMMXNXBE-UHFFFAOYSA-N C(CCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCC)CCCCCC)CCCCCC Chemical compound C(CCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCC)CCCCCC)CCCCCC WFHKDFKMMXNXBE-UHFFFAOYSA-N 0.000 description 1
- QZHGURFFNXQTML-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCCCC)CCCCCCCC)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCCCC)CCCCCCCC)CCCCCCCC QZHGURFFNXQTML-UHFFFAOYSA-N 0.000 description 1
- YNLGQWRNZWQQMD-UHFFFAOYSA-N C(CCCCCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCCCCC)CCCCCCCCC)CCCCCCCCC Chemical compound C(CCCCCCCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCCCCCCC)CCCCCCCCC)CCCCCCCCC YNLGQWRNZWQQMD-UHFFFAOYSA-N 0.000 description 1
- KCGKYAORRXGWMN-UHFFFAOYSA-N CNS(=O)=O Chemical group CNS(=O)=O KCGKYAORRXGWMN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical group CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010725 compressor oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical group [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical group CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Chemical group SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- GWLOGZRVYXAHRE-UHFFFAOYSA-N n,4-dimethylbenzenesulfonamide Chemical group CNS(=O)(=O)C1=CC=C(C)C=C1 GWLOGZRVYXAHRE-UHFFFAOYSA-N 0.000 description 1
- XUMOVISJJBHALN-UHFFFAOYSA-N n-butyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCC)C1=CC=CC=C1 XUMOVISJJBHALN-UHFFFAOYSA-N 0.000 description 1
- VCQJSMBSGMLFKI-UHFFFAOYSA-N n-heptyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCC)C1=CC=CC=C1 VCQJSMBSGMLFKI-UHFFFAOYSA-N 0.000 description 1
- MKEUPRYKXJEVEJ-UHFFFAOYSA-N n-hexyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCC)C1=CC=CC=C1 MKEUPRYKXJEVEJ-UHFFFAOYSA-N 0.000 description 1
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 1
- UMKFCWWZAONEEQ-UHFFFAOYSA-N n-nonyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCCCC)C1=CC=CC=C1 UMKFCWWZAONEEQ-UHFFFAOYSA-N 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- ZLNMGXQGGUZIJL-UHFFFAOYSA-N n-octyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCCC)C1=CC=CC=C1 ZLNMGXQGGUZIJL-UHFFFAOYSA-N 0.000 description 1
- NCEGDHPVRKYIJN-UHFFFAOYSA-N n-pentyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCC)C1=CC=CC=C1 NCEGDHPVRKYIJN-UHFFFAOYSA-N 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 125000005029 naphthylthio group Chemical group C1(=CC=CC2=CC=CC=C12)S* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000007970 thio esters Chemical group 0.000 description 1
- 125000003441 thioacyl group Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003582 thiophosphoric acids Chemical group 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C10M145/10—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
- C10M145/12—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 monocarboxylic
- C10M145/14—Acrylate; Methacrylate
-
- 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
- C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
- C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
- C10M153/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a lubricating oil additive composition and a lubricating oil composition containing the lubricating oil additive composition.
- Various lubricating oil additives are blended into lubricating oils for the purpose of imparting properties and performance necessary for lubricating oils, or supplementing and enhancing them.
- One of the typical lubricating oil additives is a load-bearing additive that imparts wear resistance and extreme pressure properties to the lubricating oil.
- load-bearing additives low-molecular-weight compounds containing sulfur and phosphorus, such as dithiophosphoric acid esters, are widely used (for example, see Patent Document 1).
- low molecular weight compounds containing sulfur and phosphorus do not have sufficient wear resistance and extreme pressure properties, and there is room for further improvement. Furthermore, low molecular weight compounds containing sulfur and phosphorus have problems such as poor thermal stability and tend to generate sludge when used at high temperatures for long periods of time.
- the present invention provides an additive composition for lubricating oil that is suitable as a load-bearing additive and has excellent wear resistance, extreme pressure properties, and thermal stability, and a lubricating oil containing the additive composition for lubricating oil.
- An object of the present invention is to provide a composition.
- the present inventors conducted extensive studies to solve the above problems. As a result, it was discovered that a poly(meth)acrylate copolymer that includes structural units derived from a plurality of specific monomers and satisfies specific requirements can solve the above problems, leading to the completion of the present invention.
- the copolymer (X) has at least one of the following groups in the side chain.
- [2] A method of using the lubricating oil additive composition according to [1] above as a load-bearing additive.
- [3] A lubricating oil composition containing the lubricating oil additive composition according to [1] above and a lubricating oil base oil.
- [4] A method for producing a lubricating oil composition, comprising a step of mixing the lubricating oil additive composition described in [1] above and a lubricating oil base oil.
- an additive composition for lubricating oil that is suitable as a load-bearing additive and has excellent wear resistance, extreme pressure properties, and thermal stability, and a lubricating oil containing the additive composition for lubricating oil. It becomes possible to provide a composition.
- the lubricating oil additive composition of the present embodiment contains a copolymer (X) that includes the following structural units (a) and (b) and satisfies the following requirements (1) to (3).
- the copolymer (X) has at least one of the following groups in the side chain.
- the present inventors conducted extensive studies in order to solve the above problems. As a result, a copolymer (X) containing the structural unit (a) derived from the above monomer (A) and the structural unit (b) derived from the above monomer (B) and satisfying the above requirements (1) to (3) The present inventors have discovered that the copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability, and that the copolymer (X) can be suitably used as an additive for lubricating oils (particularly as a load-bearing additive). Ta.
- copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability is that oil solubility (solubility in base oil (especially mineral oil)) is ensured by containing the above structural unit (a). "phosphorus and sulfur” or “sulfur” is This is presumed to be due to the introduction of a predetermined amount into the side chain. More specifically, in the lubricating oil composition, "phosphorus and sulfur” or “sulfur” introduced into the side chain is protected by the steric hindrance of the copolymer (X), thereby improving thermal stability.
- the copolymer (X) is compressed and the "phosphorus and sulfur” or “sulfur” introduced into the side chain is exposed, so that the “phosphorus and sulfur” or “sulfur” is exposed. It is presumed that “sulfur” reacts with the metal, improving wear resistance and extreme pressure properties.
- the monomer (A) used in this embodiment has a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.
- the structural unit (a) derived from the monomer (A) mainly functions to exhibit oil solubility (solubility in mineral oil) in the copolymer (X).
- the monomers (A) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain only one type of structural unit (a) derived from the monomer (A), or may contain two or more types.
- the (meth)acryloyl group possessed by the monomer (A) functions as a polymerizable functional group, and may be either an acryloyl group or a methacryloyl group, but from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
- the (meth)acryloyl group that monomer (A) has is preferably an acryloyl group.
- the monomer (A) has an alkyl group having 8 to 20 carbon atoms.
- the number of carbon atoms in the alkyl group is less than 8, and when the number of carbon atoms in the alkyl group is more than 20, it becomes difficult to ensure the oil solubility of the copolymer (X).
- alkyl group having 8 to 20 carbon atoms examples include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and Examples include chain alkyl groups such as icosyl group. These may be linear or branched.
- the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
- the monomer (A) contains an alkyl (meth)acrylate (A1) described below.
- Alkyl (meth)acrylate (A1) is a monomer represented by the following general formula (a-1).
- the alkyl (meth)acrylates (A1) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (a1) derived from the alkyl (meth)acrylate (A1), or may contain two or more types.
- R a1 is a hydrogen atom or a methyl group. That is, the alkyl (meth)acrylate (A1) has an acryloyl group or a methacryloyl group as a polymerizable functional group. Monomers in which R a1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
- R a1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the alkyl (meth)acrylate (A1) has an acryloyl group as a polymerizable functional group.
- R a2 represents an alkyl group having 8 to 20 carbon atoms.
- the alkyl group having 8 to 20 carbon atoms that can be selected as R a2 include those mentioned above as the alkyl group constituting the monomer (A). These may be linear or branched.
- the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
- the content of the structural unit (a1) derived from the alkyl (meth)acrylate (A1) is preferably 50 mol% based on the total structural units of the structural unit (a) derived from the monomer (A). -100 mol%, more preferably 60 mol% - 100 mol%, even more preferably 70 mol% - 100 mol%, even more preferably 80 mol% - 100 mol%, even more preferably 90 mol% - 100 mol% It is.
- the monomer (B) used in this embodiment has a (meth)acryloyl group and a polar group.
- the structural unit (b) derived from the monomer (B) has a function of making the copolymer (X) a multi-point adsorption type copolymer, and is presumed to contribute to improving wear resistance.
- monomer (B) may be used individually by 1 type, and may be used in combination of 2 or more types. Therefore, the copolymer (X) may contain only one type of structural unit (b) derived from the monomer (B), or may contain two or more types.
- the (meth)acryloyl group possessed by the monomer (B) functions as a polymerizable functional group, and may be either an acryloyl group or a methacryloyl group, but from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
- the (meth)acryloyl group that monomer (B) has is preferably an acryloyl group.
- the monomer (B) has a polar group.
- the polar group does not include a group containing at least one selected from phosphorus and sulfur.
- the polar group preferably includes a nitrogen atom-containing group such as an amide group, a primary amino group, a secondary amino group, a tertiary amino group, a nitrile group, a urea group, and a urethane group; a hydroxyl group; a carboxyl group, etc. .
- the monomer (B) contains a polar group-containing (meth)acrylate (B1) described below.
- the polar group-containing (meth)acrylate (B1) includes a monomer having a (meth)acryloyl group and a nitrogen atom-containing group, a monomer having a (meth)acryloyl group and a hydroxyl group, and a monomer having a (meth)acryloyl group and a carboxyl group.
- One or more types selected from the group consisting of monomers having Therefore, the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1) may contain one type alone, or may contain two or more types.
- monomers having a (meth)acryloyl group and a nitrogen atom-containing group include amide group-containing acrylic monomers, primary amino group-containing acrylic monomers, Examples include secondary amino group-containing acrylic monomers, tertiary amino group-containing acrylic monomers, nitrile group-containing acrylic monomers, urea group-containing acrylic monomers, urethane group-containing acrylic monomers, and the like.
- amide group-containing acrylic monomers include (meth)acrylamide; N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, and monoalkylamino(meth)acrylamide such as N-isobutyl(meth)acrylamide; N-methylaminoethyl(meth)acrylamide, N-ethylaminoethyl(meth)acrylamide, N-isopropylamino-n-butyl(meth)acrylamide , N-butylamino-n-butyl (meth)acrylamide, and N-isobutylamino-n-butyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide; Dialkylamino(meth)acrylamides such as N,N-diethyl(meth)acrylamide, N,N-diisopropyl(
- acrylic monomer containing a primary amino group examples include aminoalkyl (meth)acrylate having an alkyl group having 2 to 6 carbon atoms, such as aminoethyl (meth)acrylate.
- acrylic monomer containing a secondary amino group examples include monoalkylaminoalkyl (meth)acrylates such as tert-butylaminoethyl (meth)acrylate and methylaminoethyl (meth)acrylate.
- acrylic monomer containing a tertiary amino group examples include dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
- Examples of the nitrile group-containing acrylic monomer include (meth)acrylonitrile.
- Examples of the urea group-containing acrylic monomer include 2-isocyanatoethyl (meth)acrylate.
- Examples of the urethane group-containing acrylic monomer include monofunctional urethane acrylate.
- - Monomer having a (meth)acryloyl group and a hydroxyl group examples include hydroxyl group-containing acrylic monomers.
- examples of hydroxyl group-containing acrylic monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2- or 3-hydroxypropyl (meth)acrylate; N,N-dihydroxymethyl (meth)acrylamide; , N,N-dihydroxypropyl (meth)acrylamide, N,N-di-2-hydroxybutyl (meth)acrylamide, and other mono- or dihydroxyalkyl-substituted (meth)acrylamides.
- Examples of the monomer having a (meth)acryloyl group and a carboxyl group include carboxyl group-containing acrylic monomers.
- Examples of the carboxyl group-containing acrylic monomer include (meth)acrylic acid; carboxyalkyl (meth)acrylates such as carboxyethyl (meth)acrylate.
- ⁇ Preferred acrylic monomer Among the above acrylic monomers, dialkylaminoalkyl (meth)acrylamide, hydroxyalkyl (meth)acrylate, and carboxyalkyl (meth)acrylate are selected from among the above-mentioned acrylic monomers, from the viewpoint of easily improving the effects of the present invention. One or more selected types are preferred.
- the number of carbon atoms in the alkyl groups of these monomers is preferably 1 to 6, more preferably 1 to 4, each independently.
- the content of the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1) is preferably 50% based on the total structural unit (b) derived from the monomer (B).
- mol% to 100 mol% more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%. It is mole%.
- the polar group-containing (meth)acrylate (B1) includes a hydroxyl group-containing (meth)acrylate (B11) from the viewpoint of making it easier to improve the effects of the present invention.
- the hydroxyl group-containing (meth)acrylate (B11) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11), or may contain two or more types.
- R b1 is a hydrogen atom or a methyl group. That is, the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group or a methacryloyl group as a polymerizable functional group.
- Monomers in which R b1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
- R b1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group as a polymerizable functional group.
- R b2 represents an alkylene group having 2 to 4 carbon atoms.
- the number of carbon atoms in the alkylene group is 1, the polarity becomes high and the oil solubility decreases.
- the number of carbon atoms in the alkylene group is 5 or more, the oil solubility increases too much and the adsorption to metals decreases.
- the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
- m1 represents an integer from 1 to 10.
- m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different.
- the bonding mode between the moieties represented by -(OR b2 ) m1 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
- the hydroxyl group-containing (meth)acrylate (B11) becomes a carboxylic acid, resulting in decreased oil solubility.
- m1 is an integer of 11 or more, the polarity becomes high due to the influence of the -(OR b2 )- moiety, and the oil solubility decreases.
- m1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2, and even more preferably 1.
- the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is based on all the structural units of the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1). and, preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably It is 90 mol% to 100 mol%.
- the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is preferably 50 mol based on the total structural unit (b) derived from the monomer (B). % to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%. %.
- requirement (1) is defined as follows.
- the copolymer (X) has at least one of the following groups in the side chain. Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
- the sulfur-containing group copolymer (X) does not have any of the above groups in the side chain, sufficient wear resistance and extreme pressure properties cannot be ensured.
- phosphorus and sulfur are elements that cause a decrease in thermal stability, they are elements that are generally not introduced from the viewpoint of ensuring thermal stability.
- the structural unit (a) derived from the monomer (A) and the monomer (B ) By introducing the above group into the side chain of the copolymer (X) in which the structural unit (b) derived from It has been found that the copolymer (X) as a whole has excellent thermal stability, as well as excellent abrasion resistance and extreme pressure properties.
- the above-mentioned group included in the side chain of the copolymer (X) includes at least one of the following groups. Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
- examples of the phosphorus- and sulfur-containing group include a thiophosphoric acid group, thiophosphoryl, and the like.
- examples of the phosphorus-containing group include a phosphonic acid group, a phosphorous acid group, a phosphinic acid group, a phosphorous acid group, and a phosphorous group.
- examples include acid groups, pyrophosphate groups, and ester groups thereof.
- the sulfur-containing group (a group having sulfur in one group and not having phosphorus) includes, for example, a mercapto group; an acetylthio group; a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
- thioester groups such as; dithioester groups; alkylthio groups such as methylthio and ethylthio groups; arylthio groups such as phenylthio, methylphenylthio, and naphthylthio groups; thioacyl groups; thioether groups; thiocyanate ester groups; isothiocyanate ester groups ; Sulfone ester groups such as methyl sulfonate group, ethyl sulfonate group, and phenyl sulfonate group; Sulfonamide groups such as phenylsulfonamide group, N-methylsulfonamide group, and N-methyl-p-toluenesulfonamide group ; thiocarboxyl group; dithiocarboxyl group; sulfo group; sulfonyl group; sulfinyl group; sulfenyl group.
- requirement (2) is defined as follows.
- the copolymer (X) contains a phosphorus atom the phosphorus atom content (P) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X). , it becomes easy to ensure sufficient wear resistance and extreme pressure properties.
- the phosphorus atom content (P) in the copolymer (X) is 2.0% by mass or less based on the total amount of the copolymer (X), the oil solubility of the copolymer (X) is It can be easily secured.
- the phosphorus atom content (P) in the copolymer (X) is preferably 0.02 The amount is preferably from 0.04% to 1.00% by weight, and even more preferably from 0.04% to 0.50% by weight.
- the phosphorus atom content (P) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricating oil base oil), and then calculating the amount of phosphorus in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
- an organic solvent for example, lubricating oil base oil
- requirement (3) is defined as follows.
- the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
- the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X)
- the sulfur atom content (S) in the copolymer (X) is preferably 0, based on the total amount of the copolymer (X).
- the content is .02% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.04% by mass.
- the sulfur atom content (S) in the copolymer (X) is Based on the total amount, it is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, even more preferably 1.00% by mass or less, even more preferably 0.50% by mass or less.
- the upper and lower limits of these numerical ranges can be arbitrarily combined.
- the sulfur atom content (S) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricant base oil), and then calculating the amount of sulfur in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
- an organic solvent for example, lubricant base oil
- the method for preparing the copolymer (X) that satisfies requirements (1) to (3) is not particularly limited, but preferably includes the following Preparation Examples 1 to 4, and more preferably the following Preparation Examples 1 to 2 are listed.
- a copolymer (X) that satisfies the above requirement (1) can be prepared by polymerizing a monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group together with monomers (A) and (B). . At that time, by adjusting the input amount of monomer (C), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
- a copolymer (X) satisfying the above requirement (1) can be prepared by polymerizing a monomer (D1) having a polymerizable functional group and a sulfur-containing group together with monomers (A) and (B). At that time, by adjusting the input amount of the monomer (D1), a copolymer (X) that also satisfies the above requirement (3) can be prepared. In addition, in Preparation Example 3, since the copolymer (X) does not contain a phosphorus atom, it is not necessary to satisfy the above requirement (2).
- a monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group, a monomer (D1) having a polymerizable functional group and a sulfur-containing group, and/or a monomer having a polymerizable functional group and a phosphorus-containing group By polymerizing (D2) together with monomers (A) and (B), a copolymer (X) that satisfies the above requirement (1) can be prepared. At that time, by adjusting the input amounts of monomer (C), monomer (D1), and monomer (D2), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
- the copolymer (X) further contains one or more structural units ( ⁇ ) containing the group specified in requirement (1).
- the monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group which can be suitably applied to Preparation Examples 1 to 5 (preferably Preparation Examples 1 to 2), a polymerizable functional group and a sulfur-containing group, A monomer (D1) having the following and a monomer (D2) having a polymerizable functional group and a phosphorus-containing group will be exemplified.
- the monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group includes a (meth)acryloyl group and a compound represented by the following general formula (1).
- Preferred examples include compounds having a monovalent group containing phosphorus and sulfur.
- the copolymer (X) contains the structural unit (c) derived from the monomer (C), phosphorus and sulfur-containing groups are introduced into the side chains of the copolymer (X), which improves wear resistance and polarity. It can improve pressure resistance.
- the monomer (C) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (c) derived from the monomer (C), or may contain two or more types.
- the monomer (C) has a (meth)acryloyl group as a polymerizable functional group.
- the polymerizable functional group that the monomer (C) has is preferably an acryloyl group.
- R 1 and R 2 are preferably each independently an alkyl group having 1 to 10 carbon atoms from the viewpoint of improving the effects of the present invention.
- Examples of the alkyl group having 1 to 10 carbon atoms that can be selected as R 1 and R 2 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.
- Examples include chain alkyl groups such as.
- the chain alkyl group may be linear or branched. From the viewpoint of improving the effects of the present invention, the alkyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and even more preferably 3 carbon atoms.
- the monomer (C) is preferably a compound represented by the following general formula (c-1).
- R c1 is preferably a hydrogen atom or a methyl group.
- R c1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
- R c2 is preferably an alkylene group having 2 to 4 carbon atoms.
- the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
- the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
- the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
- m2 is an integer from 0 to 10.
- m2 is an integer of 2 or more, a plurality of R c2 may be the same or different.
- the bonding mode between the moieties represented by -(OR c2 ) m2 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
- m2 is an integer of 10 or less, oil solubility can be easily ensured.
- m2 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
- L 1 represents a linker.
- Linkers that can be selected as L 1 include, for example, divalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, and butylene group; -O-; -OC(O) -;-O-C(O)-R C3 - (R C3 is an alkylene group having 2 to 4 carbon atoms), and the like.
- -OC(O)-R C3 - is preferred as the linker that can be selected as L 1 .
- L 1 may be a direct bond.
- R 1 and R 2 are as explained in the above general formula (1), and the preferred ranges are also as explained in the above general formula (1).
- ⁇ Monomer (D1) having a polymerizable functional group and a sulfur-containing group As the monomer (D1) having a polymerizable functional group and a sulfur-containing group (hereinafter also simply referred to as "monomer (D1)"), a compound represented by the following general formula (d1-1) is preferably mentioned.
- the copolymer (X) contains the structural unit (d1) derived from the monomer (D1), a sulfur-containing group is introduced into the side chain of the copolymer (X). Therefore, wear resistance and extreme pressure properties can be improved.
- the copolymer (X) further contains a structural unit (d2) derived from the monomer (D2). Thereby, the phosphorus-containing group is also introduced into the side chain of the copolymer (X), and the wear resistance and extreme pressure properties can be further improved.
- the monomer (D1) may be used alone or in combination of two or more types. Therefore, the copolymer (X) may contain only one type of structural unit (d1) derived from the monomer (D1), or may contain two or more types.
- R d11 is preferably a hydrogen atom or a methyl group.
- R d11 is preferably a hydrogen atom. That is, it is preferable that the monomer (D1) has an acryloyl group as a polymerizable functional group.
- R d12 represents an alkylene group having 2 to 4 carbon atoms.
- the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
- the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
- the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
- m3 is preferably an integer of 0 to 10, more preferably an integer of 1 to 10.
- a plurality of R d12 may be the same or different.
- the bonding mode between the moieties represented by -(OR d12 ) m3 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
- m3 is an integer of 10 or less, oil solubility can be easily ensured.
- m3 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
- R d13 is preferably an alkyl group having 4 to 20 carbon atoms.
- the number of carbon atoms in the alkyl group is 4 or more, and when the number of carbon atoms in the alkyl group is 20 or less, the effects of the present invention are more likely to be exhibited.
- alkyl group having 4 to 20 carbon atoms that can be selected as R d13 include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include chain alkyl groups such as a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group. These may be linear or branched.
- the number of carbon atoms in the alkyl group is preferably 6 to 18, more preferably 6 to 16, and even more preferably 6 to 14.
- ⁇ Monomer (D2) having a polymerizable functional group and a phosphorus-containing group As the monomer (D2) having a polymerizable functional group and a phosphorus-containing group (hereinafter also simply referred to as "monomer (D2)"), a compound represented by the following general formula (d2-1) is preferably mentioned.
- the copolymer (X) contains the structural unit (d2) derived from the monomer (D2), a phosphorus-containing group is introduced into the side chain of the copolymer (X). Therefore, when the copolymer (X) further contains the structural unit (d1) derived from the monomer (D1), a sulfur-containing group is also introduced into the side chain of the copolymer (X), which improves wear resistance and polarity. Pressure properties can be improved.
- the monomer (D2) may be used alone or in combination of two or more types. Therefore, the copolymer (X) may contain one type of structural unit (d2) derived from the monomer (D2), or may contain two or more types.
- R d21 is preferably a hydrogen atom or a methyl group.
- R d21 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the monomer (D2) has an acryloyl group as a polymerizable functional group.
- R d22 represents an ethylene group.
- m4 is an integer from 1 to 6.
- the plurality of R d2 may be the same or different.
- the bonding mode between the moieties represented by -(OR d22 ) m4 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
- m4 is 1 to 6, it is easy to ensure oil solubility.
- m4 is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.
- n represents an integer of 1 or 2.
- at least one of the plurality of R d23 represents a hydrogen atom.
- R d23 is a hydrogen atom.
- only one of the plurality of R d23 may be a hydrogen atom.
- the other of the plurality of R d23 is a hydrocarbon group.
- the hydrocarbon group is a methyl group or an ethyl group.
- the lubricating oil additive composition of the present embodiment further satisfies the following requirement (4) from the viewpoint of improving the effects of the present invention.
- - Requirement (4) When the copolymer (X) contains a phosphorus atom, the content ratio of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) [( S)/(P)] is 0.10 to 3.00 in mass ratio. From the viewpoint of making it easier to improve the effects of the present invention, the content ratio [(S)/(P)] is preferably 0.15 to 2.80, more preferably 0.15 to 2.60 in mass ratio. , more preferably 0.20 to 2.50.
- the content ratio [(S)/(P)] is a mass ratio, It is preferably 0.50 to 3.00, more preferably 1.00 to 3.00, even more preferably 1.50 to 2.50.
- the content ratio [(S)/(P)] is , in terms of mass ratio, is preferably 0.10 to 2.00, more preferably 0.10 to 1.00, even more preferably 0.20 to 0.80.
- the copolymer (X) contains the above structural units (a) and (b), furthermore, the structural unit (c) derived from the monomer (C), the structural unit (d1) derived from the monomer (D1), and the monomer (D2).
- structural units derived from other monomers may be contained within a range that does not impede the effects of the present invention.
- the other monomers include functional group-containing monomers other than monomers (A), (B), (C), (D1), and (D2).
- the copolymer (X) is derived from a functional group-containing monomer other than monomers (A), (B), (C), (D1), and (D2).
- the content of the structural units is preferably less than 50% by mass, more preferably less than 40% by mass, even more preferably less than 30% by mass, even more preferably less than 20% by mass, even more preferably 10% by mass, based on all the structural units. Less than % by mass.
- the copolymer (X) contains a total of monomers (A), monomers (B), and structural units derived from monomers (constituent units ( ⁇ )) used to satisfy requirements (1) to (3).
- the amount is based on all the constituent units of the copolymer (X), preferably 70% by mass to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more Preferably it is 95% by mass to 100% by mass.
- the content of the structural unit (a) in the copolymer (X) is preferably 50 mass based on the total amount of the copolymer (X) from the viewpoint of ensuring oil solubility and improving the effects of the present invention. % or more, more preferably 60% to 95% by weight, still more preferably 70% to 90% by weight.
- the content of the structural unit (b) in the copolymer (X) is preferably 1% by mass or more, more preferably 3% by mass, based on the total amount of the copolymer (X).
- the amount is preferably 6% to 25% by weight, preferably 6% to 25% by weight.
- the content of the structural unit (c) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
- the content of the structural unit (d1) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
- the content of the structural unit (d2) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. It is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, even more preferably 0.8% by mass to 3.0% by mass, based on the total amount of.
- the copolymer (X) of this embodiment has a content ratio of the structural unit (a) and the structural unit (b) [(a)/( b)] is preferably in a molar ratio of 50/50 to 90/10, more preferably 55/45 to 85/15.
- the mass average molecular weight (Mw) of the copolymer (X) of this embodiment is preferably 5,000 to 100,000, more preferably 5,000 to 100,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. ,000 to 70,000, more preferably 5,000 to 50,000.
- the mass average molecular weight (Mw) of the copolymer (X) is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 40,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. It is.
- the mass average molecular weight (Mw) of the copolymer (X) is preferably 5 from the viewpoint of ensuring oil solubility and improving the effect of the present invention. ,000 to 100,000, more preferably 5,000 to 70,000, even more preferably 5,000 to 50,000.
- the molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably is 3.4 or less.
- the molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment may be 1.01 or more, 1.3 or more, or 1.5 or more. good.
- the molecular weight distribution (Mw/Mn ) is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, from the viewpoint of making it easier to exhibit the effects of the present invention.
- the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
- the molecular weight distribution (Mw/Mn) of the copolymer (X) is preferably 4.0 or less in order to more easily improve the effects of the present invention. , more preferably 3.6 or less, still more preferably 3.4 or less.
- the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
- the mass average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) are values measured or calculated by the method described in the Examples described later.
- the polymerization mode of the copolymer (X) of this embodiment is not particularly limited, and may be any of block copolymerization, random copolymerization, and block/random copolymerization. Among these, random copolymerization is preferred from the viewpoint of ease of polymerization reaction.
- the method for producing an additive composition for lubricating oil includes a step (S) of producing a copolymer (X) by polymerizing monomers in one of the following combinations.
- Monomer (A), monomer (B), and monomer (C) (2) Monomer (A), monomer (B), monomer (D1), and monomer (D2) (3) Monomer (A), monomer (B), and monomer (D1) (4) Monomer (A), monomer (B), monomer (C), and monomer (D1) and/or monomer (D2)
- the method for producing the copolymer (X) is not particularly limited, and the copolymer (X) is produced by applying any known method. Examples of such methods include emulsion polymerization, suspension polymerization, and solution polymerization.
- the method for producing the copolymer (X) (polymerization method) is based on a lubricating oil base. It is preferable to employ a solution polymerization method in which a solvent soluble in oil is used as a solvent.
- the content ratio of each structural unit in the copolymer (X) usually corresponds to the ratio (feeding ratio) of each monomer constituting the copolymer (X). Therefore, the blending ratio of each of the above monomers is appropriately determined in consideration of the content ratio of each of the above structural units in the copolymer (X).
- solvents used in the solution polymerization method include alcohols such as methanol, ethanol, propanol, 2-propanol, and butanol; hydrocarbons such as benzene, toluene, xylene, and hexane; ethyl acetate, butyl acetate, and isobutyl acetate.
- Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ethers such as methoxybutanol, ethoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dioxane; Mineral oil; Poly- ⁇ - Examples include synthetic oils such as olefins, ethylene- ⁇ -olefin copolymers, alkylbenzenes, alkylnaphthalenes, polyphenyl ethers, alkyl-substituted diphenyl ethers, polyol esters, dibasic acid esters, hindered esters, monoesters, and GTL base oils. These may be used alone or in combination of two or more.
- initiators used in the solution polymerization method include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis- (N,N-dimethyleneisobutyramidine) dihydrochloride, azo initiators such as 1,1'-azobis(cyclohexyl-1-carbonitrile); hydrogen peroxide; benzoyl peroxide, t-butyl hydroperoxide, Organic peroxides such as cumene hydroperoxide, methyl ethyl ketone peroxide, and perbenzoic acid; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; hydrogen peroxide-Fe 2+ redox initiators; other existing radicals Examples include initiators.
- the molecular weight of the copolymer (X) is controlled by a known method.
- the molecular weight of the copolymer (X) can be controlled by the reaction temperature, reaction time, amount of initiator, amount of each monomer charged, type of solvent, use of chain transfer agent, etc.
- the additive composition for lubricating oil of the present embodiment has a content of copolymer (X) that can be added to Preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, based on the total amount of the agent composition. Preferably it is 95% by mass or more. Considering the purity of copolymer (X), the content of copolymer (X) is usually less than 99% by mass based on the total amount of the lubricating oil additive composition.
- the lubricating oil additive composition of this embodiment may be diluted with a diluting solvent from the viewpoint of solubility with the lubricating base oil and ease of handling.
- the content of the copolymer (X) in the additive composition for lubricating oil means the content based on the total amount of active ingredients in the additive composition for lubricating oil, excluding the dilution solvent.
- the lubricating oil additive composition of this embodiment has excellent wear resistance, extreme pressure properties, and thermal stability. Therefore, it is useful as a load-bearing additive. Therefore, in this embodiment, a method of using the lubricating oil additive composition as a load-bearing additive is provided.
- the lubricating oil composition of this embodiment contains a lubricating oil additive composition containing the copolymer (X) and a lubricating oil base oil.
- the content of the lubricating oil additive composition is determined such that the content of the resin component of the copolymer (X) is the same as the total amount of the lubricating oil composition, from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well. Based on the standard, it is preferably adjusted to 0.3% by mass to 10% by mass, more preferably 0.6% by mass to 8.0% by mass, and even more preferably 1.0% by mass to 6.0% by mass. Ru.
- the content of the lubricating oil additive composition is determined from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well, and the amount of sulfur derived from the copolymer (X) is determined by the total amount of the lubricating oil composition. Based on the standard, it is preferably 10 mass ppm to 300 mass ppm, more preferably 20 mass ppm to 200 mass ppm, and still more preferably 30 mass ppm to 150 mass ppm.
- the amount of phosphorus derived from the copolymer (X) is Based on the total amount of the composition, preferably 5 ppm to 150 ppm by weight, more preferably 10 ppm to 100 ppm by weight, and still more preferably 15 ppm to 75 ppm by weight.
- lubricating base oil any general base oil used in lubricating oil compositions can be used without particular limitation. Specifically, for example, one or more types selected from the group consisting of mineral oil and synthetic oil may be mentioned.
- the kinematic viscosity at 100° C. of the lubricating base oil is preferably in the range of 1 mm 2 /s to 50 mm 2 /s, more preferably in the range of 2 mm 2 /s to 30 mm 2 /s, and more preferably 3 mm 2 /s. More preferably, the speed is in the range of ⁇ 20 mm 2 /s.
- the viscosity index of the lubricating base oil is preferably 80 or more, more preferably 90 or more, and even more preferably 100 or more.
- the kinematic viscosity and viscosity index of the lubricating base oil are values measured or calculated according to JIS K2283:2000.
- lubricant base oils include, for example, distillate oil obtained by atmospheric distillation and/or vacuum distillation of paraffinic crude oil, intermediate crude oil, or naphthenic crude oil; refined oil obtained by refining the distillate oil according to a conventional method; oil; etc.
- Examples of the purification method for obtaining refined oil include solvent dewaxing treatment, hydroisomerization treatment, hydrofinishing treatment, clay treatment, and the like.
- Examples of synthetic oils include hydrocarbon oils, aromatic oils, ester oils, and ether oils.
- GTL Gas To Liquids obtained by isomerizing wax (GTL wax, Gas To Liquids WAX) produced from natural gas by the Fischer-Tropsch method or the like may be used.
- the lubricating oil composition of the present embodiment contains an antioxidant, an oily agent, a detergent dispersant, a viscosity index improver, a rust preventive agent, and a metal deactivator within a range that does not inhibit the effects of the above-mentioned lubricating oil additive composition.
- Other additives such as antifoaming agents and antifoaming agents may also be included. These may be used alone or in combination of two or more.
- a drug package is also provided.
- antioxidants As the antioxidant, amine antioxidants, phenolic antioxidants, etc. used in conventional lubricating oil compositions can be used. These antioxidants may be used alone or in combination of two or more.
- amine antioxidants include monoalkyldiphenylamine compounds such as monooctyldiphenylamine and monononyldiphenylamine; 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, , 4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; dialkyldiphenylamine compounds such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; Poly
- phenolic antioxidants include monophenolic compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; 4,4' -methylenebis(2,6-di-tert-butylphenol) and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) and other bisphenol compounds.
- the content of the antioxidant may be the minimum amount necessary to maintain the oxidative stability of the lubricating oil composition. Specifically, for example, it is preferably 0.01 to 1% by mass based on the total amount of the lubricating oil composition.
- oily agent examples include aliphatic alcohols; fatty acid compounds such as fatty acids and fatty acid metal salts; ester compounds such as polyol esters, sorbitan esters, and glycerides; and amine compounds such as aliphatic amines.
- the content of the oily agent is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
- Detergent-dispersing agents include metal sulfonates, metal salicylates, metal phenates, succinimides, and the like.
- the content of the detergent dispersant is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
- Viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, olefin copolymer (e.g., ethylene-propylene copolymer, etc.), dispersed olefin copolymer, styrene copolymer (e.g., styrene-diene hydrogenated copolymers, etc.).
- the content of the viscosity index improver is preferably 0.3 to 5% by mass, based on the total amount of the lubricating oil composition.
- rust preventive agent examples include metal sulfonates, succinic acid esters, and alkanolamines such as alkylamines and monoisopropanolamines.
- the content of the rust inhibitor is usually 0.01 to 5% by mass, preferably 0.03 to 3% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
- metal deactivator examples include benzotriazole and thiadiazole. From the viewpoint of the effect of addition, the preferred content of the metal deactivator is usually 0.01 to 5% by mass, preferably 0.01 to 1% by mass, based on the total amount of the lubricating oil composition.
- antifoaming agent examples include methyl silicone oil, fluorosilicone oil, and polyacrylate.
- the content of the antifoaming agent is usually 0.0005 to 0.01% by mass based on the total amount of the lubricating oil composition from the viewpoint of the effect of addition.
- the 100°C kinematic viscosity of the lubricating oil composition of the present embodiment is preferably 1.0 mm 2 /s to 50 mm 2 /s, more preferably 2.0 mm 2 / s to 30 mm 2 /s, even more preferably 3.0 mm. 2 /s to 20 mm 2 /s.
- the viscosity index of the lubricating oil composition of this embodiment is preferably 90 or more, more preferably 100 or more, and still more preferably 110 or more.
- the kinematic viscosity and viscosity index of the lubricating oil composition are values measured or calculated according to JIS K2283:2000.
- the lubricating oil composition (new oil) of the present embodiment has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.53 mm or less, and still more preferably 0. It is 52 mm or less.
- the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.53 mm or less, even more preferably 0.52 mm or less.
- the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less.
- the lubricating oil composition of this embodiment (the oil after the ISOT test) has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.50 mm or less, and even more preferably is 0.45 mm or less.
- the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.50 mm or less, even more preferably 0.45 mm or less.
- the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less.
- the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
- the lubricating oil composition (new oil) of the present embodiment has a maximum non-seizure load (LNL) of preferably 392N or more, more preferably 490N, as determined by the shell four-ball test load resistance (EP) test described in the Examples below. That's all. Further, the fusion load (WL) according to the same test is preferably 1236N or more.
- the maximum non-seizure load (LNL) is Preferably it is 392N or more, more preferably 490N or more.
- the fusion load (WL) is preferably 1236N or more.
- the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more.
- the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
- the lubricating oil composition (oil after ISOT test) of the present embodiment preferably has a maximum non-seizure load (LNL) of 490 N or more as determined by the shell four-ball test load resistance (EP) test described in the Examples below.
- the fusion load (WL) according to the same test is preferably 1236N or more, more preferably 1569N or more.
- the maximum non-seizure load (LNL) is Preferably it is 490N or more.
- the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more.
- the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2)
- the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more.
- the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
- the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
- the lubricating oil composition of the present embodiment preferably generates less than 10 mg/100 mL of sludge after the ISOT test described in Examples described below.
- the amount of sludge generated is preferably 10 mg/ It is less than 100 mL, more preferably less than 7.0 mg/100 mL, even more preferably less than 5.0 mg/100 mL.
- the amount of sludge generated is preferably less than 10 mg/100 mL.
- the method for producing the lubricating oil composition of this embodiment is not particularly limited.
- the method for producing a lubricating oil composition of the present embodiment includes a step of mixing the lubricating oil additive composition and a lubricating oil base oil.
- a method that includes a step of blending the lubricating oil additive composition with the lubricating oil base oil can be mentioned.
- the other additives mentioned above may also be added at the same time.
- each component may be blended in the form of a solution (dispersion) by adding diluting oil or the like. After blending each component, it is preferable to stir and disperse uniformly by a known method.
- the lubricating oil composition of this embodiment contains the copolymer (X), it has excellent wear resistance, extreme pressure properties, and thermal stability. Therefore, the lubricating oil composition of this embodiment is, for example, gear oil (manual transmission oil, differential oil, etc.), automatic transmission oil (automatic transmission oil, etc.), continuously variable transmission oil (belt CVT oil, toroidal CVT oil, etc.) Drive system oils such as power steering oils, shock absorber oils, and electric motor oils; Oils for internal combustion engines (engines) such as gasoline engines, diesel engines, and gas engines; Hydraulic oils; Turbine oils; Compressor oils ; Fluid bearing oil; Rolling bearing oil; Refrigerating machine oil, etc., as a lubricating oil composition that can be suitably used for various purposes, and is filled into equipment used in each of these applications to lubricate between the various parts of the equipment. It can be suitably used.
- gear oil manual transmission oil, differential oil, etc.
- automatic transmission oil automatic transmission oil, etc.
- continuously variable transmission oil belt CVT
- the lubricating method using the lubricating oil composition of the present embodiment is a method of filling the lubricating oil composition into equipment used in each of the above-mentioned applications and lubricating between each part of each of the equipment. can be mentioned.
- the lubricating oil additive composition of this embodiment can also be used by being mixed into a grease composition. That is, in this embodiment, it is also possible to provide a grease composition containing the above lubricating oil additive composition, a thickener, and a lubricating oil base oil.
- [1] to [15] are provided.
- the copolymer (X) has at least one of the following groups in the side chain. Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.) Said sulfur-containing group/requirement (2): When said copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in said copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
- the structural unit ( ⁇ ) is a structural unit (c) derived from the monomer (C) having a polymerizable functional group and the phosphorus- and sulfur-containing group. agent composition.
- the structural unit ( ⁇ ) is a structural unit (d1) derived from the monomer (D1) having a polymerizable functional group and the sulfur-containing group, and a monomer (D2) derived from the monomer (D2) having a polymerizable functional group and the phosphorus-containing group.
- the content ratio [(S)/(P)] of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) is 0 by mass ratio. .10 to 3.00.
- the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1).
- R a1 represents a hydrogen atom or a methyl group.
- R a2 represents an alkyl group having 8 to 20 carbon atoms.
- R b1 is a hydrogen atom or a methyl group.
- R b2 represents an alkylene group having 2 to 4 carbon atoms.
- m1 represents an integer from 1 to 10.
- R d11 is a hydrogen atom or a methyl group.
- R d12 represents an alkylene group having 2 to 4 carbon atoms.
- m3 represents an integer from 1 to 10.
- R d13 represents an alkyl group having 4 to 20 carbon atoms.
- the monomer (D1) is a compound represented by the following general formula (d1-1),
- R d11 is a hydrogen atom or a methyl group.
- R d12 represents an alkylene group having 2 to 4 carbon atoms.
- m3 represents an integer from 1 to 10.
- R d12 When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different.
- R d13 represents an alkyl group having 4 to 20 carbon atoms.
- R d21 is a hydrogen atom or a methyl group.
- R d22 represents an ethylene group.
- m4 represents an integer from 1 to 6. When m4 is an integer of 2 or more, a plurality of R d22 may be the same or different.
- n represents an integer of 1 or 2.
- the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1).
- the lubricating oil additive composition described in . [In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms.
- the structural unit (b) includes a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1).
- R b1 is a hydrogen atom or a methyl group.
- R b2 represents an alkylene group having 2 to 4 carbon atoms.
- m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different.
- [17] The lubricating oil additive composition according to any one of [1] to [16] above, which is used as a load-bearing additive. [18] A method of using the lubricating oil additive composition according to any one of [1] to [17] above as a load-bearing additive. [19] A lubricating oil composition containing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil. [20] A method for producing a lubricating oil composition, comprising the step of mixing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil.
- the sulfur content and phosphorus content of the copolymer (X) are determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (lubricating oil base oil). Calculated based on the results of measuring the sulfur and phosphorus amounts in accordance with JPI-5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
- Examples A1 to A6, Examples B1 to B7, Comparative Example 1 The lubricant base oil and lubricant additive composition shown below were thoroughly mixed in the amounts (mass%) shown in Tables 3 and 4, and Examples A1 to A6, Examples B1 to B7, and Comparative The lubricating oil compositions of Example 1 were each prepared. Details of the lubricant base oil and lubricant additive composition used in Examples A1 to A6, Examples B1 to B7, and Comparative Example 1 are as shown below.
- - Copolymer (X)-A1 Produced by the method described in Production Example A1.
- - Copolymer (X)-A2 Produced by the method described in Production Example A2.
- - Copolymer (X)-A3 Produced by the method described in Production Example A3.
- - Copolymer (X)-A4 Produced by the method described in Production Example A4.
- - Copolymer (X)-A5 Produced by the method described in Production Example A5.
- - Copolymer (X)-A6 Produced by the method described in Production Example A6.
- - Copolymer (X)-B1 Produced by the method described in Production Example B1.
- - Copolymer (X)-B2 Produced by the method described in Production Example B2.
- - Copolymer (X)-B3 Produced by the method described in Production Example B3.
- - Copolymer (X)-B4 Produced by the method described in Production Example B4.
- - Copolymer (X)-B5 Produced by the method described in Production Example B5.
- - Copolymer (X)-B6 Produced by the method described in Production Example B6.
- - Copolymer (X)-B7 Produced by the method described in Production Example B7.
- SPM1 A compound represented by the following structural formula was used.
- R c1 is a hydrogen atom
- R c2 is an ethylene group (an alkylene group having 2 carbon atoms)
- m2 1
- L 1 is -O-C(O)-R c3 -
- R c3 is a propylene group (alkylene group having 3 carbon atoms)
- R 1 and R 2 are isobutyl groups (alkyl group having 4 carbon atoms). It is a certain compound.
- the sulfur content is 15.0% by mass
- the phosphorus content is 7.3% by mass.
- SPM3 A compound represented by the following structural formula was used.
- R c1 is a hydrogen atom
- R c2 is an ethylene group (an alkylene group having 2 carbon atoms)
- m2 1
- L 1 is -O-C(O)-R c3 -
- R c3 is an ethylene group (alkylene group having 2 carbon atoms)
- R 1 and R 2 are ethylene groups (alkyl group having 2 carbon atoms); It is a certain compound.
- the sulfur content is 18.0% by mass, and the phosphorus content is 8.7% by mass. It was used as monomer (C).
- IRGALUBE353 is a compound represented by the following structural formula.
- copolymer (X)-A1 was diluted with mineral oil so that the content of copolymer (X)-A1 was 50% by mass, and mixed into lubricating base oil.
- Copolymer (X)-A2) was obtained by carrying out the same operation as in Production Example A1 except that 0.44 g (1.1 mmol) of SPM2 was charged instead of SPM1.
- the mass average molecular weight (Mw) of copolymer (X)-A2 was 19,700, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A2 was 760 mass ppm, and the sulfur content was 1700 mass ppm.
- Copolymer (X)-A2 was diluted with mineral oil so that the content of copolymer (X)-A2 was 50% by mass, and mixed into lubricating base oil.
- Copolymer (X)-A5 was obtained by carrying out the same operation as in Production Example A2 except that 22.0 g of 2-propanol was added as a solvent.
- the mass average molecular weight (Mw) of copolymer (X)-A5 was 34,200, and the molecular weight distribution (Mw/Mn) was 2.3. Further, the phosphorus content of copolymer (X)-A5 was 800 mass ppm, and the sulfur content was 1700 mass ppm.
- Copolymer (X)-A5 was diluted with mineral oil so that the content of copolymer (X)-A5 was 50% by mass, and mixed into lubricating base oil.
- Poly(meth)acrylate copolymer (X)-A6 is diluted with mineral oil so that the content of poly(meth)acrylate copolymer (X)-A6 is 50% by mass, and then mixed with lubricating oil. Mixed with base oil.
- composition of copolymer (X)-A1 to copolymer (X)-A6, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-A1 to copolymer (X)-A6 , and molecular weight distribution (Mw/Mn) are shown in Table 1.
- Mw/Mn molecular weight distribution
- copolymer (X)-B1 was diluted with mineral oil so that the content of copolymer (X)-B1 was 50% by mass, and mixed into lubricating base oil.
- Copolymer (X)-B2) was obtained by carrying out the same operation as in Production Example B1 except that 0.46 g (1.9 mmol) of OTA was charged instead of DTA.
- the mass average molecular weight (Mw) of copolymer (X)-B2 was 18,200, and the molecular weight distribution (Mw/Mn) was 1.9. Further, the phosphorus content of copolymer (X)-B2 was 3000 mass ppm, and the sulfur content was 1060 mass ppm.
- Copolymer (X)-B2 was diluted with mineral oil so that the content of copolymer (X)-B2 was 50% by mass, and mixed into lubricating base oil.
- Copolymer (X)-B3) was obtained by carrying out the same operation as in Production Example B1 except that 23.8 g of 2-propanol was charged as a solvent.
- the mass average molecular weight (Mw) of copolymer (X)-B3 was 46,400, and the molecular weight distribution (Mw/Mn) was 3.2. Further, the phosphorus content of copolymer (X)-B3 was 2,800 mass ppm, and the sulfur content was 1,040 mass ppm.
- Copolymer (X)-B3 was diluted with mineral oil so that the content of copolymer (X)-B3 was 50% by mass, and mixed into lubricating base oil.
- Copolymer (X)-B5) was obtained by carrying out the same operation as in Production Example B2 except that 23.8 g of 2-propanol was charged as a solvent.
- the mass average molecular weight (Mw) of copolymer (X)-B5 was 48,000, and the molecular weight distribution (Mw/Mn) was 3.3. Further, the phosphorus content of copolymer (X)-B5 was 2,800 mass ppm, and the sulfur content was 1,220 mass ppm.
- Copolymer (X)-B5 was diluted with mineral oil so that the content of copolymer (X)-B5 was 50% by mass, and mixed into lubricating base oil.
- copolymer (X)-B6 was diluted with mineral oil so that the content of copolymer (X)-B6 was 50% by mass, and mixed into lubricating base oil.
- composition of copolymer (X)-B1 to copolymer (X)-B7, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-B1 to copolymer (X)-B7 , and the molecular weight distribution (Mw/Mn) are shown in Table 2.
- Mw mass average molecular weight
- ⁇ Shell wear test> The wear resistance of the lubricating oil composition was determined using a shell abrasion tester in accordance with ASTM D 4172, setting the test conditions to be a load of 30 kg, a rotation speed of 1,200 rpm, a temperature of 80°C, and a test time of 30 minutes. was evaluated. The results were expressed as the wear scar diameter (mm) of the test hard ball. In this test, wear resistance was judged to be good if the wear scar diameter was 0.55 mm or less.
- ⁇ ISOT test> A copper piece and an iron piece were added as catalysts to the test oil (lubricating oil composition), and an ISOT test in accordance with JIS K 2514-1:2013 was conducted to forcefully degrade the test oil.
- the test temperature (oil temperature) was 150°C.
- the amount of sludge (mg/100 mL) was measured for the test oil 24 hours after the start of the ISOT test in accordance with JIS B 9931. And, if the amount of sludge was less than 10 mg/100 mL, it was determined that the thermal stability was good.
- the above-mentioned shell wear test and shell four-ball test load resistance (EP) test were conducted on the test oil 24 hours after the start of the ISOT test. As with the new oil, it was determined that the wear resistance was good if the wear scar diameter was 0.55 mm or less. Furthermore, if the maximum non-seizure load (LNL) was 392N or more and the fusion load (WL) was 1236N or more, it was determined that the extreme pressure property was good.
- LNL maximum non-seizure load
- WL fusion load
- the lubricating oil composition containing Copolymer (X)-B5, Copolymer (X)-B6, or Copolymer (X)-B7 has excellent wear resistance, extreme pressure properties, and thermal stability.
- the wear resistance and extreme pressure properties are excellent.
- the results shown in Comparative Example 1 show that a lubricating oil composition containing a low molecular weight sulfur- and phosphorus-containing compound has insufficient wear resistance and extreme pressure properties, and is clearly inferior in thermal stability.
Abstract
An additive composition for lubricating oils which includes a copolymer (X) that comprises the following constituent units (a) and (b) and satisfies the following requirements (1) to (3). Constituent unit (a): A constituent unit derived from a monomer (A) having a (meth)acryloyl group and a C8-C20 alkyl group
Constituent unit (b): A constituent unit derived from a monomer (B) having a (meth)acryloyl group and a polar group
Requirement (1): The copolymer (X) has one or more side chains having at least any of the following:
a phosphorus- and sulfur-containing group; a phosphorus-containing group and a sulfur-containing group (The phosphorus-containing group is a sulfur-free group and the sulfur-containing group is a phosphorus-free group.); and the sulfur-containing group.
Requirement (2): When the copolymer (X) contains phosphorus atoms, the phosphorus atom content (P) in the copolymer (X) is 0.01-2.00 mass% with respect to the whole copolymer (X).
Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01-2.00 mass% with respect to the whole copolymer (X).
Description
本発明は、潤滑油用添加剤組成物及び当該潤滑油用添加剤組成物を含有する潤滑油組成物に関する。
The present invention relates to a lubricating oil additive composition and a lubricating oil composition containing the lubricating oil additive composition.
潤滑油には、潤滑油として必要な性質及び性能を付与したり、補足増強したりする目的で、各種潤滑油用添加剤が配合される。
代表的な潤滑油用添加剤の一つとして、潤滑油に耐摩耗性及び極圧性を付与する耐荷重添加剤が挙げられる。耐荷重添加剤としては、例えば、ジチオリン酸エステル類等の、硫黄及びリンを含有する低分子量の化合物が汎用されている（例えば、特許文献１を参照）。 Various lubricating oil additives are blended into lubricating oils for the purpose of imparting properties and performance necessary for lubricating oils, or supplementing and enhancing them.
One of the typical lubricating oil additives is a load-bearing additive that imparts wear resistance and extreme pressure properties to the lubricating oil. As load-bearing additives, low-molecular-weight compounds containing sulfur and phosphorus, such as dithiophosphoric acid esters, are widely used (for example, see Patent Document 1).
代表的な潤滑油用添加剤の一つとして、潤滑油に耐摩耗性及び極圧性を付与する耐荷重添加剤が挙げられる。耐荷重添加剤としては、例えば、ジチオリン酸エステル類等の、硫黄及びリンを含有する低分子量の化合物が汎用されている（例えば、特許文献１を参照）。 Various lubricating oil additives are blended into lubricating oils for the purpose of imparting properties and performance necessary for lubricating oils, or supplementing and enhancing them.
One of the typical lubricating oil additives is a load-bearing additive that imparts wear resistance and extreme pressure properties to the lubricating oil. As load-bearing additives, low-molecular-weight compounds containing sulfur and phosphorus, such as dithiophosphoric acid esters, are widely used (for example, see Patent Document 1).
しかしながら、硫黄及びリンを含有する低分子量の化合物は、耐摩耗性及び極圧性が十分ではなく、さらなる改善の余地がある。また、硫黄及びリンを含有する低分子量の化合物は、熱安定性に乏しく、高温で長時間使用するとスラッジが発生しやすい等の問題がある。
However, low molecular weight compounds containing sulfur and phosphorus do not have sufficient wear resistance and extreme pressure properties, and there is room for further improvement. Furthermore, low molecular weight compounds containing sulfur and phosphorus have problems such as poor thermal stability and tend to generate sludge when used at high temperatures for long periods of time.
そこで、本発明は、耐荷重添加剤として好適であり、耐摩耗性、極圧性、及び熱安定性に優れる潤滑油用添加剤組成物、並びに当該潤滑油用添加剤組成物を含有する潤滑油組成物を提供することを課題とする。
Therefore, the present invention provides an additive composition for lubricating oil that is suitable as a load-bearing additive and has excellent wear resistance, extreme pressure properties, and thermal stability, and a lubricating oil containing the additive composition for lubricating oil. An object of the present invention is to provide a composition.
本発明者らは、上記課題を解決すべく、鋭意検討を行った。その結果、複数の特定のモノマー由来の構成単位を含み、かつ特定の要件を満たすポリ（メタ）アクリレート系共重合体が、上記課題を解決し得ることを見出し、本発明の完成に至った。
The present inventors conducted extensive studies to solve the above problems. As a result, it was discovered that a poly(meth)acrylate copolymer that includes structural units derived from a plurality of specific monomers and satisfies specific requirements can solve the above problems, leading to the completion of the present invention.
すなわち、本発明は、下記［１］～［４］に関する。
［１］ 下記構成単位（ａ）及び（ｂ）を含み、下記要件（１）～（３）を満たす共重合体（Ｘ）を含有する、潤滑油用添加剤組成物。
・構成単位（ａ）：（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有するモノマー（Ａ）由来の構成単位
・構成単位（ｂ）：（メタ）アクリロイル基と極性基とを有するモノマー（Ｂ）由来の構成単位
・要件（１）：前記共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
・要件（２）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中のリン原子含有量（Ｐ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
・要件（３）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％以上である。
［２］ 上記［１］に記載の潤滑油用添加剤組成物を、耐荷重添加剤として使用する、使用方法。
［３］ 上記［１］に記載の潤滑油用添加剤組成物と、潤滑油基油と、を含有する、潤滑油組成物。
［４］ 上記［１］に記載の潤滑油用添加剤組成物と、潤滑油基油と、を混合する工程を含む、潤滑油組成物の製造方法。 That is, the present invention relates to the following [1] to [4].
[1] An additive composition for lubricating oil containing a copolymer (X) containing the following structural units (a) and (b) and satisfying the following requirements (1) to (3).
・Structural unit (a): A structural unit derived from a monomer (A) having a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.・Structural unit (b): Having a (meth)acryloyl group and a polar group. Structural unit derived from monomer (B)/Requirement (1): The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
Said sulfur-containing group/requirement (2): When said copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in said copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
[2] A method of using the lubricating oil additive composition according to [1] above as a load-bearing additive.
[3] A lubricating oil composition containing the lubricating oil additive composition according to [1] above and a lubricating oil base oil.
[4] A method for producing a lubricating oil composition, comprising a step of mixing the lubricating oil additive composition described in [1] above and a lubricating oil base oil.
［１］ 下記構成単位（ａ）及び（ｂ）を含み、下記要件（１）～（３）を満たす共重合体（Ｘ）を含有する、潤滑油用添加剤組成物。
・構成単位（ａ）：（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有するモノマー（Ａ）由来の構成単位
・構成単位（ｂ）：（メタ）アクリロイル基と極性基とを有するモノマー（Ｂ）由来の構成単位
・要件（１）：前記共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
・要件（２）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中のリン原子含有量（Ｐ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
・要件（３）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％以上である。
［２］ 上記［１］に記載の潤滑油用添加剤組成物を、耐荷重添加剤として使用する、使用方法。
［３］ 上記［１］に記載の潤滑油用添加剤組成物と、潤滑油基油と、を含有する、潤滑油組成物。
［４］ 上記［１］に記載の潤滑油用添加剤組成物と、潤滑油基油と、を混合する工程を含む、潤滑油組成物の製造方法。 That is, the present invention relates to the following [1] to [4].
[1] An additive composition for lubricating oil containing a copolymer (X) containing the following structural units (a) and (b) and satisfying the following requirements (1) to (3).
・Structural unit (a): A structural unit derived from a monomer (A) having a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.・Structural unit (b): Having a (meth)acryloyl group and a polar group. Structural unit derived from monomer (B)/Requirement (1): The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
Said sulfur-containing group/requirement (2): When said copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in said copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
[2] A method of using the lubricating oil additive composition according to [1] above as a load-bearing additive.
[3] A lubricating oil composition containing the lubricating oil additive composition according to [1] above and a lubricating oil base oil.
[4] A method for producing a lubricating oil composition, comprising a step of mixing the lubricating oil additive composition described in [1] above and a lubricating oil base oil.
本発明によれば、耐荷重添加剤として好適であり、耐摩耗性、極圧性、及び熱安定性に優れる潤滑油用添加剤組成物、並びに当該潤滑油用添加剤組成物を含有する潤滑油組成物を提供することが可能となる。
According to the present invention, there is provided an additive composition for lubricating oil that is suitable as a load-bearing additive and has excellent wear resistance, extreme pressure properties, and thermal stability, and a lubricating oil containing the additive composition for lubricating oil. It becomes possible to provide a composition.
本明細書に記載された数値範囲の上限値および下限値は任意に組み合わせることができる。例えば、数値範囲として「Ａ～Ｂ」及び「Ｃ～Ｄ」が記載されている場合、「Ａ～Ｄ」及び「Ｃ～Ｂ」の数値範囲も、本発明の範囲に含まれる。
また、本明細書に記載された数値範囲「下限値～上限値」は、特に断りのない限り、下限値以上、上限値以下であることを意味する。
また、本明細書において、実施例の数値は、上限値又は下限値として用いられ得る数値である。
なお、本明細書において、「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味し、他の類似の用語についても同様の意味である。 The upper and lower limits of the numerical ranges described herein can be arbitrarily combined. For example, when "A to B" and "C to D" are described as numerical ranges, the numerical ranges of "A to D" and "C to B" are also included in the scope of the present invention.
Furthermore, the numerical range "lower limit to upper limit" described in this specification means that it is greater than or equal to the lower limit and less than or equal to the upper limit, unless otherwise specified.
Further, in this specification, the numerical values in Examples are numerical values that can be used as upper limit values or lower limit values.
In this specification, "(meth)acrylate" means acrylate or methacrylate, and other similar terms have the same meaning.
また、本明細書に記載された数値範囲「下限値～上限値」は、特に断りのない限り、下限値以上、上限値以下であることを意味する。
また、本明細書において、実施例の数値は、上限値又は下限値として用いられ得る数値である。
なお、本明細書において、「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味し、他の類似の用語についても同様の意味である。 The upper and lower limits of the numerical ranges described herein can be arbitrarily combined. For example, when "A to B" and "C to D" are described as numerical ranges, the numerical ranges of "A to D" and "C to B" are also included in the scope of the present invention.
Furthermore, the numerical range "lower limit to upper limit" described in this specification means that it is greater than or equal to the lower limit and less than or equal to the upper limit, unless otherwise specified.
Further, in this specification, the numerical values in Examples are numerical values that can be used as upper limit values or lower limit values.
In this specification, "(meth)acrylate" means acrylate or methacrylate, and other similar terms have the same meaning.
［潤滑油用添加剤組成物の態様］
本実施形態の潤滑油用添加剤組成物は、下記構成単位（ａ）及び（ｂ）を含み、下記要件（１）～（３）を満たす共重合体（Ｘ）を含有する。
・構成単位（ａ）：（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有するモノマー（Ａ）由来の構成単位
・構成単位（ｂ）：（メタ）アクリロイル基と極性基とを有するモノマー（Ｂ）由来の構成単位
・要件（１）：前記共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
・要件（２）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中のリン原子含有量（Ｐ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
・要件（３）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％以上である。 [Aspects of additive composition for lubricating oil]
The lubricating oil additive composition of the present embodiment contains a copolymer (X) that includes the following structural units (a) and (b) and satisfies the following requirements (1) to (3).
・Structural unit (a): A structural unit derived from a monomer (A) having a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.・Structural unit (b): Having a (meth)acryloyl group and a polar group. Structural unit derived from monomer (B)/requirement (1): The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
The sulfur-containing group/requirement (2): When the copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in the copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
本実施形態の潤滑油用添加剤組成物は、下記構成単位（ａ）及び（ｂ）を含み、下記要件（１）～（３）を満たす共重合体（Ｘ）を含有する。
・構成単位（ａ）：（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有するモノマー（Ａ）由来の構成単位
・構成単位（ｂ）：（メタ）アクリロイル基と極性基とを有するモノマー（Ｂ）由来の構成単位
・要件（１）：前記共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
・要件（２）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中のリン原子含有量（Ｐ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
・要件（３）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％以上である。 [Aspects of additive composition for lubricating oil]
The lubricating oil additive composition of the present embodiment contains a copolymer (X) that includes the following structural units (a) and (b) and satisfies the following requirements (1) to (3).
・Structural unit (a): A structural unit derived from a monomer (A) having a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.・Structural unit (b): Having a (meth)acryloyl group and a polar group. Structural unit derived from monomer (B)/requirement (1): The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
The sulfur-containing group/requirement (2): When the copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in the copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
本発明者らは、上記課題を解決すべく、鋭意検討を行った。その結果、上記モノマー（Ａ）に由来する構成単位（ａ）及び上記モノマー（Ｂ）に由来する構成単位（ｂ）を含み、上記要件（１）～（３）を満たす共重合体（Ｘ）が、耐摩耗性、極圧性、及び熱安定性に優れることを見出し、共重合体（Ｘ）を潤滑油用添加剤として（特に耐荷重添加剤として）好適に用いることができることを見出すに至った。
共重合体（Ｘ）が、耐摩耗性、極圧性、及び熱安定性に優れる理由は、上記構成単位（ａ）を含むことによって油溶性（基油（特に鉱油）への溶解性）が確保されること、上記構成単位（ｂ）を含むことによって多点吸着型のポリマーとなっていること、上記要件（１）～（３）を満たすことによって、「リン及び硫黄」又は「硫黄」が側鎖に所定量導入されていることによるものと推察される。より詳細には、潤滑油組成物中では、共重合体（Ｘ）の立体障害によって、側鎖に導入された「リン及び硫黄」又は「硫黄」が保護されて熱安定性が向上する。その一方で、摺動部では、共重合体（Ｘ）が圧縮されて、側鎖に導入された「リン及び硫黄」又は「硫黄」が剥き出しになることによって、当該「リン及び硫黄」又は「硫黄」が金属と反応し耐摩耗性及び極圧性が向上するものと推察される。 The present inventors conducted extensive studies in order to solve the above problems. As a result, a copolymer (X) containing the structural unit (a) derived from the above monomer (A) and the structural unit (b) derived from the above monomer (B) and satisfying the above requirements (1) to (3) The present inventors have discovered that the copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability, and that the copolymer (X) can be suitably used as an additive for lubricating oils (particularly as a load-bearing additive). Ta.
The reason why copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability is that oil solubility (solubility in base oil (especially mineral oil)) is ensured by containing the above structural unit (a). "phosphorus and sulfur" or "sulfur" is This is presumed to be due to the introduction of a predetermined amount into the side chain. More specifically, in the lubricating oil composition, "phosphorus and sulfur" or "sulfur" introduced into the side chain is protected by the steric hindrance of the copolymer (X), thereby improving thermal stability. On the other hand, in the sliding part, the copolymer (X) is compressed and the "phosphorus and sulfur" or "sulfur" introduced into the side chain is exposed, so that the "phosphorus and sulfur" or "sulfur" is exposed. It is presumed that "sulfur" reacts with the metal, improving wear resistance and extreme pressure properties.
共重合体（Ｘ）が、耐摩耗性、極圧性、及び熱安定性に優れる理由は、上記構成単位（ａ）を含むことによって油溶性（基油（特に鉱油）への溶解性）が確保されること、上記構成単位（ｂ）を含むことによって多点吸着型のポリマーとなっていること、上記要件（１）～（３）を満たすことによって、「リン及び硫黄」又は「硫黄」が側鎖に所定量導入されていることによるものと推察される。より詳細には、潤滑油組成物中では、共重合体（Ｘ）の立体障害によって、側鎖に導入された「リン及び硫黄」又は「硫黄」が保護されて熱安定性が向上する。その一方で、摺動部では、共重合体（Ｘ）が圧縮されて、側鎖に導入された「リン及び硫黄」又は「硫黄」が剥き出しになることによって、当該「リン及び硫黄」又は「硫黄」が金属と反応し耐摩耗性及び極圧性が向上するものと推察される。 The present inventors conducted extensive studies in order to solve the above problems. As a result, a copolymer (X) containing the structural unit (a) derived from the above monomer (A) and the structural unit (b) derived from the above monomer (B) and satisfying the above requirements (1) to (3) The present inventors have discovered that the copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability, and that the copolymer (X) can be suitably used as an additive for lubricating oils (particularly as a load-bearing additive). Ta.
The reason why copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability is that oil solubility (solubility in base oil (especially mineral oil)) is ensured by containing the above structural unit (a). "phosphorus and sulfur" or "sulfur" is This is presumed to be due to the introduction of a predetermined amount into the side chain. More specifically, in the lubricating oil composition, "phosphorus and sulfur" or "sulfur" introduced into the side chain is protected by the steric hindrance of the copolymer (X), thereby improving thermal stability. On the other hand, in the sliding part, the copolymer (X) is compressed and the "phosphorus and sulfur" or "sulfur" introduced into the side chain is exposed, so that the "phosphorus and sulfur" or "sulfur" is exposed. It is presumed that "sulfur" reacts with the metal, improving wear resistance and extreme pressure properties.
以下、モノマー（Ａ）、モノマー（Ｂ）、及び上記要件（１）～（３）について、詳細に説明する。
Hereinafter, the monomer (A), the monomer (B), and the above requirements (1) to (3) will be explained in detail.
＜モノマー（Ａ）＞
本実施形態において使用されるモノマー（Ａ）は、（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有する。モノマー（Ａ）に由来する構成単位（ａ）は、共重合体（Ｘ）において、主に油溶性（鉱油への溶解性）を発揮させる機能を担う。
モノマー（Ａ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、モノマー（Ａ）に由来する構成単位（ａ）を１種単独で含んでいてもよく、２種以上含んでいてもよい。 <Monomer (A)>
The monomer (A) used in this embodiment has a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms. The structural unit (a) derived from the monomer (A) mainly functions to exhibit oil solubility (solubility in mineral oil) in the copolymer (X).
The monomers (A) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain only one type of structural unit (a) derived from the monomer (A), or may contain two or more types.
本実施形態において使用されるモノマー（Ａ）は、（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有する。モノマー（Ａ）に由来する構成単位（ａ）は、共重合体（Ｘ）において、主に油溶性（鉱油への溶解性）を発揮させる機能を担う。
モノマー（Ａ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、モノマー（Ａ）に由来する構成単位（ａ）を１種単独で含んでいてもよく、２種以上含んでいてもよい。 <Monomer (A)>
The monomer (A) used in this embodiment has a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms. The structural unit (a) derived from the monomer (A) mainly functions to exhibit oil solubility (solubility in mineral oil) in the copolymer (X).
The monomers (A) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain only one type of structural unit (a) derived from the monomer (A), or may contain two or more types.
モノマー（Ａ）が有する（メタ）アクリロイル基は、重合性官能基として機能し、アクリロイル基及びメタクリロイル基のいずれであってもよいが、共重合体（Ｘ）の分子量を調整しやすくする観点から、モノマー（Ａ）が有する（メタ）アクリロイル基は、アクリロイル基であることが好ましい。
The (meth)acryloyl group possessed by the monomer (A) functions as a polymerizable functional group, and may be either an acryloyl group or a methacryloyl group, but from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). The (meth)acryloyl group that monomer (A) has is preferably an acryloyl group.
また、モノマー（Ａ）は、炭素数８～２０のアルキル基を有する。
当該アルキル基の炭素数が８未満である場合、当該アルキル基の炭素数が２０超である場合、いずれも共重合体（Ｘ）の油溶性を確保し難くなる。
炭素数８～２０のアルキル基としては、例えば、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、及びイコシル基等の鎖状アルキル基が挙げられる。これらは、直鎖状であっても分岐鎖状であってもよい。
ここで、共重合体（Ｘ）の油溶性をより確保しやすくする観点から、当該アルキル基の炭素数は、好ましくは１０～１８、より好ましくは１０～１６、更に好ましくは１０～１４である。 Furthermore, the monomer (A) has an alkyl group having 8 to 20 carbon atoms.
When the number of carbon atoms in the alkyl group is less than 8, and when the number of carbon atoms in the alkyl group is more than 20, it becomes difficult to ensure the oil solubility of the copolymer (X).
Examples of the alkyl group having 8 to 20 carbon atoms include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and Examples include chain alkyl groups such as icosyl group. These may be linear or branched.
Here, from the viewpoint of making it easier to ensure the oil solubility of the copolymer (X), the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
当該アルキル基の炭素数が８未満である場合、当該アルキル基の炭素数が２０超である場合、いずれも共重合体（Ｘ）の油溶性を確保し難くなる。
炭素数８～２０のアルキル基としては、例えば、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、及びイコシル基等の鎖状アルキル基が挙げられる。これらは、直鎖状であっても分岐鎖状であってもよい。
ここで、共重合体（Ｘ）の油溶性をより確保しやすくする観点から、当該アルキル基の炭素数は、好ましくは１０～１８、より好ましくは１０～１６、更に好ましくは１０～１４である。 Furthermore, the monomer (A) has an alkyl group having 8 to 20 carbon atoms.
When the number of carbon atoms in the alkyl group is less than 8, and when the number of carbon atoms in the alkyl group is more than 20, it becomes difficult to ensure the oil solubility of the copolymer (X).
Examples of the alkyl group having 8 to 20 carbon atoms include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and Examples include chain alkyl groups such as icosyl group. These may be linear or branched.
Here, from the viewpoint of making it easier to ensure the oil solubility of the copolymer (X), the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
ここで、本実施形態において、本発明の効果の向上の観点から、モノマー（Ａ）は、以下に説明するアルキル（メタ）アクリレート（Ａ１）を含むことが好ましい。
Here, in this embodiment, from the viewpoint of improving the effects of the present invention, it is preferable that the monomer (A) contains an alkyl (meth)acrylate (A1) described below.
（アルキル（メタ）アクリレート（Ａ１））
アルキル（メタ）アクリレート（Ａ１）は、下記一般式（ａ－１）で表されるモノマーである。
(Alkyl (meth)acrylate (A1))
Alkyl (meth)acrylate (A1) is a monomer represented by the following general formula (a-1).
アルキル（メタ）アクリレート（Ａ１）は、下記一般式（ａ－１）で表されるモノマーである。
Alkyl (meth)acrylate (A1) is a monomer represented by the following general formula (a-1).
アルキル（メタ）アクリレート（Ａ１）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、アルキル（メタ）アクリレート（Ａ１）に由来する構成単位（ａ１）を１種単独で含んでいてもよく、２種以上含んでいてもよい。
The alkyl (meth)acrylates (A1) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (a1) derived from the alkyl (meth)acrylate (A1), or may contain two or more types.
上記一般式（ａ－１）中、Ｒａ１は、水素原子又はメチル基である。すなわち、アルキル（メタ）アクリレート（Ａ１）は、重合性官能基として、アクリロイル基又はメタクリロイル基を有する。
Ｒａ１が水素原子及びメチル基以外の置換基であるモノマーは入手が困難であり、かつ当該モノマーは反応性が低いため、それらを重合することも困難である。
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒａ１は、水素原子であることが好ましい。すなわち、アルキル（メタ）アクリレート（Ａ１）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (a-1), R a1 is a hydrogen atom or a methyl group. That is, the alkyl (meth)acrylate (A1) has an acryloyl group or a methacryloyl group as a polymerizable functional group.
Monomers in which R a1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
Here, in this embodiment, R a1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the alkyl (meth)acrylate (A1) has an acryloyl group as a polymerizable functional group.
Ｒａ１が水素原子及びメチル基以外の置換基であるモノマーは入手が困難であり、かつ当該モノマーは反応性が低いため、それらを重合することも困難である。
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒａ１は、水素原子であることが好ましい。すなわち、アルキル（メタ）アクリレート（Ａ１）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (a-1), R a1 is a hydrogen atom or a methyl group. That is, the alkyl (meth)acrylate (A1) has an acryloyl group or a methacryloyl group as a polymerizable functional group.
Monomers in which R a1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
Here, in this embodiment, R a1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the alkyl (meth)acrylate (A1) has an acryloyl group as a polymerizable functional group.
上記一般式（ａ－１）中、Ｒａ２は、炭素数８～２０のアルキル基を示す。
当該アルキル基の炭素数が８未満である場合、当該アルキル基の炭素数が２０超である場合、いずれも共重合体（Ｘ）の油溶性を確保し難くなる。
Ｒａ２として選択し得る、炭素数８～２０のアルキル基としては、モノマー（Ａ）を構成するアルキル基として上述したものが挙げられる。これらは、直鎖状であっても分岐鎖状であってもよい。
ここで、共重合体（Ｘ）の油溶性をより確保しやすくする観点から、当該アルキル基の炭素数は、好ましくは１０～１８、より好ましくは１０～１６、更に好ましくは１０～１４である。 In the above general formula (a-1), R a2 represents an alkyl group having 8 to 20 carbon atoms.
When the number of carbon atoms in the alkyl group is less than 8, and when the number of carbon atoms in the alkyl group is more than 20, it becomes difficult to ensure the oil solubility of the copolymer (X).
Examples of the alkyl group having 8 to 20 carbon atoms that can be selected as R a2 include those mentioned above as the alkyl group constituting the monomer (A). These may be linear or branched.
Here, from the viewpoint of making it easier to ensure the oil solubility of the copolymer (X), the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
当該アルキル基の炭素数が８未満である場合、当該アルキル基の炭素数が２０超である場合、いずれも共重合体（Ｘ）の油溶性を確保し難くなる。
Ｒａ２として選択し得る、炭素数８～２０のアルキル基としては、モノマー（Ａ）を構成するアルキル基として上述したものが挙げられる。これらは、直鎖状であっても分岐鎖状であってもよい。
ここで、共重合体（Ｘ）の油溶性をより確保しやすくする観点から、当該アルキル基の炭素数は、好ましくは１０～１８、より好ましくは１０～１６、更に好ましくは１０～１４である。 In the above general formula (a-1), R a2 represents an alkyl group having 8 to 20 carbon atoms.
When the number of carbon atoms in the alkyl group is less than 8, and when the number of carbon atoms in the alkyl group is more than 20, it becomes difficult to ensure the oil solubility of the copolymer (X).
Examples of the alkyl group having 8 to 20 carbon atoms that can be selected as R a2 include those mentioned above as the alkyl group constituting the monomer (A). These may be linear or branched.
Here, from the viewpoint of making it easier to ensure the oil solubility of the copolymer (X), the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
なお、本実施形態において、アルキル（メタ）アクリレート（Ａ１）由来の構成単位（ａ１）の含有量は、モノマー（Ａ）由来の構成単位（ａ）の全構成単位基準で、好ましくは５０モル％～１００モル％、より好ましくは６０モル％～１００モル％、更に好ましくは７０モル％～１００モル％、より更に好ましくは８０モル％～１００モル％、更になお好ましくは９０モル％～１００モル％である。
In addition, in this embodiment, the content of the structural unit (a1) derived from the alkyl (meth)acrylate (A1) is preferably 50 mol% based on the total structural units of the structural unit (a) derived from the monomer (A). -100 mol%, more preferably 60 mol% - 100 mol%, even more preferably 70 mol% - 100 mol%, even more preferably 80 mol% - 100 mol%, even more preferably 90 mol% - 100 mol% It is.
＜モノマー（Ｂ）＞
本実施形態において使用されるモノマー（Ｂ）は、（メタ）アクリロイル基と極性基とを有する。モノマー（Ｂ）に由来する構成単位（ｂ）は、共重合体（Ｘ）を多点吸着型の共重合体にする機能を担っており、耐摩耗性の向上に資すると推察される。
なお、モノマー（Ｂ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、モノマー（Ｂ）に由来する構成単位（ｂ）を１種単独で含んでいてもよく、２種以上含んでいてもよい。 <Monomer (B)>
The monomer (B) used in this embodiment has a (meth)acryloyl group and a polar group. The structural unit (b) derived from the monomer (B) has a function of making the copolymer (X) a multi-point adsorption type copolymer, and is presumed to contribute to improving wear resistance.
In addition, monomer (B) may be used individually by 1 type, and may be used in combination of 2 or more types. Therefore, the copolymer (X) may contain only one type of structural unit (b) derived from the monomer (B), or may contain two or more types.
本実施形態において使用されるモノマー（Ｂ）は、（メタ）アクリロイル基と極性基とを有する。モノマー（Ｂ）に由来する構成単位（ｂ）は、共重合体（Ｘ）を多点吸着型の共重合体にする機能を担っており、耐摩耗性の向上に資すると推察される。
なお、モノマー（Ｂ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、モノマー（Ｂ）に由来する構成単位（ｂ）を１種単独で含んでいてもよく、２種以上含んでいてもよい。 <Monomer (B)>
The monomer (B) used in this embodiment has a (meth)acryloyl group and a polar group. The structural unit (b) derived from the monomer (B) has a function of making the copolymer (X) a multi-point adsorption type copolymer, and is presumed to contribute to improving wear resistance.
In addition, monomer (B) may be used individually by 1 type, and may be used in combination of 2 or more types. Therefore, the copolymer (X) may contain only one type of structural unit (b) derived from the monomer (B), or may contain two or more types.
モノマー（Ｂ）が有する（メタ）アクリロイル基は、重合性官能基として機能し、アクリロイル基及びメタクリロイル基のいずれであってもよいが、共重合体（Ｘ）の分子量を調整しやすくする観点から、モノマー（Ｂ）が有する（メタ）アクリロイル基は、アクリロイル基であることが好ましい。
The (meth)acryloyl group possessed by the monomer (B) functions as a polymerizable functional group, and may be either an acryloyl group or a methacryloyl group, but from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). The (meth)acryloyl group that monomer (B) has is preferably an acryloyl group.
また、モノマー（Ｂ）は、極性基を有する。
但し、当該極性基には、リン及び硫黄から選択される少なくとも１種を含む基は、包含されない。当該極性基としては、好ましくはアミド基、１級アミノ基、２級アミノ基、３級アミノ基、ニトリル基、ウレア基、及びウレタン基等の窒素原子含有基；水酸基；カルボキシル基等が挙げられる。 Moreover, the monomer (B) has a polar group.
However, the polar group does not include a group containing at least one selected from phosphorus and sulfur. The polar group preferably includes a nitrogen atom-containing group such as an amide group, a primary amino group, a secondary amino group, a tertiary amino group, a nitrile group, a urea group, and a urethane group; a hydroxyl group; a carboxyl group, etc. .
但し、当該極性基には、リン及び硫黄から選択される少なくとも１種を含む基は、包含されない。当該極性基としては、好ましくはアミド基、１級アミノ基、２級アミノ基、３級アミノ基、ニトリル基、ウレア基、及びウレタン基等の窒素原子含有基；水酸基；カルボキシル基等が挙げられる。 Moreover, the monomer (B) has a polar group.
However, the polar group does not include a group containing at least one selected from phosphorus and sulfur. The polar group preferably includes a nitrogen atom-containing group such as an amide group, a primary amino group, a secondary amino group, a tertiary amino group, a nitrile group, a urea group, and a urethane group; a hydroxyl group; a carboxyl group, etc. .
ここで、本実施形態において、本発明の効果の向上の観点から、モノマー（Ｂ）は、以下に説明する極性基含有（メタ）アクリレート（Ｂ１）を含むことが好ましい。
Here, in this embodiment, from the viewpoint of improving the effects of the present invention, it is preferable that the monomer (B) contains a polar group-containing (meth)acrylate (B1) described below.
（極性基含有（メタ）アクリレート（Ｂ１））
極性基含有（メタ）アクリレート（Ｂ１）としては、（メタ）アクリロイル基と窒素原子含有基とを有するモノマー、（メタ）アクリロイル基と水酸基とを有するモノマー、及び（メタ）アクリロイル基とカルボキシル基とを有するモノマーからなる群から選択される１種以上が挙げられる。したがって、極性基含有（メタ）アクリレート（Ｂ１）に由来する構成単位（ｂ１）は、１種を単独で含んでいてもよく、２種以上を含んでいてもよい。 (Polar group-containing (meth)acrylate (B1))
The polar group-containing (meth)acrylate (B1) includes a monomer having a (meth)acryloyl group and a nitrogen atom-containing group, a monomer having a (meth)acryloyl group and a hydroxyl group, and a monomer having a (meth)acryloyl group and a carboxyl group. One or more types selected from the group consisting of monomers having Therefore, the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1) may contain one type alone, or may contain two or more types.
極性基含有（メタ）アクリレート（Ｂ１）としては、（メタ）アクリロイル基と窒素原子含有基とを有するモノマー、（メタ）アクリロイル基と水酸基とを有するモノマー、及び（メタ）アクリロイル基とカルボキシル基とを有するモノマーからなる群から選択される１種以上が挙げられる。したがって、極性基含有（メタ）アクリレート（Ｂ１）に由来する構成単位（ｂ１）は、１種を単独で含んでいてもよく、２種以上を含んでいてもよい。 (Polar group-containing (meth)acrylate (B1))
The polar group-containing (meth)acrylate (B1) includes a monomer having a (meth)acryloyl group and a nitrogen atom-containing group, a monomer having a (meth)acryloyl group and a hydroxyl group, and a monomer having a (meth)acryloyl group and a carboxyl group. One or more types selected from the group consisting of monomers having Therefore, the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1) may contain one type alone, or may contain two or more types.
・（メタ）アクリロイル基と窒素原子含有基とを有するモノマー
（メタ）アクリロイル基と窒素原子含有基とを有するモノマーとしては、例えば、アミド基含有アクリル系モノマー、１級アミノ基含有アクリル系モノマー、２級アミノ基含有アクリル系モノマー、３級アミノ基含有アクリル系モノマー、ニトリル基含有アクリル系モノマー、ウレア基含有アクリル系モノマー、ウレタン基含有アクリル系モノマー等が挙げられる。 - Monomer having a (meth)acryloyl group and a nitrogen atom-containing group Examples of monomers having a (meth)acryloyl group and a nitrogen atom-containing group include amide group-containing acrylic monomers, primary amino group-containing acrylic monomers, Examples include secondary amino group-containing acrylic monomers, tertiary amino group-containing acrylic monomers, nitrile group-containing acrylic monomers, urea group-containing acrylic monomers, urethane group-containing acrylic monomers, and the like.
（メタ）アクリロイル基と窒素原子含有基とを有するモノマーとしては、例えば、アミド基含有アクリル系モノマー、１級アミノ基含有アクリル系モノマー、２級アミノ基含有アクリル系モノマー、３級アミノ基含有アクリル系モノマー、ニトリル基含有アクリル系モノマー、ウレア基含有アクリル系モノマー、ウレタン基含有アクリル系モノマー等が挙げられる。 - Monomer having a (meth)acryloyl group and a nitrogen atom-containing group Examples of monomers having a (meth)acryloyl group and a nitrogen atom-containing group include amide group-containing acrylic monomers, primary amino group-containing acrylic monomers, Examples include secondary amino group-containing acrylic monomers, tertiary amino group-containing acrylic monomers, nitrile group-containing acrylic monomers, urea group-containing acrylic monomers, urethane group-containing acrylic monomers, and the like.
アミド基含有アクリル系モノマーとしては、例えば、（メタ）アクリルアミド；Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ｎ－ブチル（メタ）アクリルアミド、及びＮ－イソブチル（メタ）アクリルアミド等のモノアルキルアミノ（メタ）アクリルアミド；Ｎ－メチルアミノエチル（メタ）アクリルアミド、Ｎ－エチルアミノエチル（メタ）アクリルアミド、Ｎ－イソプロピルアミノ－ｎ－ブチル（メタ）アクリルアミド、Ｎ－ｎ－ブチルアミノ－ｎ－ブチル（メタ）アクリルアミド、及びＮ－イソブチルアミノ－ｎ－ブチル（メタ）アクリルアミド等のモノアルキルアミノアルキル（メタ）アクリルアミド；Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジイソプロピル（メタ）アクリルアミド、及びＮ，Ｎ－ジ－ｎ－ブチル（メタ）アクリルアミド等のジアルキルアミノ（メタ）アクリルアミド；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、及びＮ，Ｎ－ジ－ｎ－ブチルアミノブチル（メタ）アクリルアミド等のジアルキルアミノアルキル（メタ）アクリルアミド；等が挙げられる。
Examples of amide group-containing acrylic monomers include (meth)acrylamide; N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, and monoalkylamino(meth)acrylamide such as N-isobutyl(meth)acrylamide; N-methylaminoethyl(meth)acrylamide, N-ethylaminoethyl(meth)acrylamide, N-isopropylamino-n-butyl(meth)acrylamide , N-butylamino-n-butyl (meth)acrylamide, and N-isobutylamino-n-butyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide; Dialkylamino(meth)acrylamides such as N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, and N,N-di-n-butyl(meth)acrylamide; N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and dialkylaminoalkyl (meth)acrylamide such as N,N-di-n-butylaminobutyl (meth)acrylamide. (meth)acrylamide; and the like.
１級アミノ基含有アクリル系モノマーとしては、アミノエチル（メタ）アクリレート等の炭素数２～６のアルキル基を有するアミノアルキル（メタ）アクリレート等が挙げられる。
Examples of the acrylic monomer containing a primary amino group include aminoalkyl (meth)acrylate having an alkyl group having 2 to 6 carbon atoms, such as aminoethyl (meth)acrylate.
２級アミノ基含有アクリル系モノマーとしては、例えば、ｔｅｒｔ－ブチルアミノエチル（メタ）アクリレート及びメチルアミノエチル（メタ）アクリレート等のモノアルキルアミノアルキル（メタ）アクリレート等が挙げられる。
Examples of the acrylic monomer containing a secondary amino group include monoalkylaminoalkyl (meth)acrylates such as tert-butylaminoethyl (meth)acrylate and methylaminoethyl (meth)acrylate.
３級アミノ基含有アクリル系モノマーとしては、例えば、ジメチルアミノエチル（メタ）アクリレート及びジエチルアミノエチル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレート等が挙げられる。
Examples of the acrylic monomer containing a tertiary amino group include dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
ニトリル基含有アクリル系モノマーしては、例えば、（メタ）アクリロニトリル等が挙げられる。
ウレア基含有アクリル系モノマーとしては、２－イソシアナトエチル（メタ）アクリレート等が挙げられる。
ウレタン基含有アクリル系モノマーとしては、単官能ウレタンアクリレート等が挙げられる。 Examples of the nitrile group-containing acrylic monomer include (meth)acrylonitrile.
Examples of the urea group-containing acrylic monomer include 2-isocyanatoethyl (meth)acrylate.
Examples of the urethane group-containing acrylic monomer include monofunctional urethane acrylate.
ウレア基含有アクリル系モノマーとしては、２－イソシアナトエチル（メタ）アクリレート等が挙げられる。
ウレタン基含有アクリル系モノマーとしては、単官能ウレタンアクリレート等が挙げられる。 Examples of the nitrile group-containing acrylic monomer include (meth)acrylonitrile.
Examples of the urea group-containing acrylic monomer include 2-isocyanatoethyl (meth)acrylate.
Examples of the urethane group-containing acrylic monomer include monofunctional urethane acrylate.
・（メタ）アクリロイル基と水酸基とを有するモノマー
（メタ）アクリロイル基と水酸基とを有するモノマーとしては、例えば、水酸基含有アクリル系モノマー等が挙げられる。
水酸基含有アクリル系モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、及び２－又は３－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；Ｎ，Ｎ－ジヒドロキシメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジヒドロキシプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジ－２－ヒドロキシブチル（メタ）アクリルアミド等のモノ－又はジ－ヒドロキシアルキル置換（メタ）アクリルアミド等が挙げられる。 - Monomer having a (meth)acryloyl group and a hydroxyl group Examples of the monomer having a (meth)acryloyl group and a hydroxyl group include hydroxyl group-containing acrylic monomers.
Examples of hydroxyl group-containing acrylic monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2- or 3-hydroxypropyl (meth)acrylate; N,N-dihydroxymethyl (meth)acrylamide; , N,N-dihydroxypropyl (meth)acrylamide, N,N-di-2-hydroxybutyl (meth)acrylamide, and other mono- or dihydroxyalkyl-substituted (meth)acrylamides.
（メタ）アクリロイル基と水酸基とを有するモノマーとしては、例えば、水酸基含有アクリル系モノマー等が挙げられる。
水酸基含有アクリル系モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、及び２－又は３－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；Ｎ，Ｎ－ジヒドロキシメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジヒドロキシプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジ－２－ヒドロキシブチル（メタ）アクリルアミド等のモノ－又はジ－ヒドロキシアルキル置換（メタ）アクリルアミド等が挙げられる。 - Monomer having a (meth)acryloyl group and a hydroxyl group Examples of the monomer having a (meth)acryloyl group and a hydroxyl group include hydroxyl group-containing acrylic monomers.
Examples of hydroxyl group-containing acrylic monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2- or 3-hydroxypropyl (meth)acrylate; N,N-dihydroxymethyl (meth)acrylamide; , N,N-dihydroxypropyl (meth)acrylamide, N,N-di-2-hydroxybutyl (meth)acrylamide, and other mono- or dihydroxyalkyl-substituted (meth)acrylamides.
・（メタ）アクリロイル基とカルボキシル基とを有するモノマー
（メタ）アクリロイル基とカルボキシル基とを有するモノマーとしては、例えば、カルボキシル基含有アクリル系モノマー等が挙げられる。
カルボキシル基含有アクリル系モノマーとしては、例えば、（メタ）アクリル酸；（メタ）アクリル酸カルボキシエチル等の（メタ）アクリル酸カルボキシアルキルが挙げられる。 - Monomer having a (meth)acryloyl group and a carboxyl group Examples of the monomer having a (meth)acryloyl group and a carboxyl group include carboxyl group-containing acrylic monomers.
Examples of the carboxyl group-containing acrylic monomer include (meth)acrylic acid; carboxyalkyl (meth)acrylates such as carboxyethyl (meth)acrylate.
（メタ）アクリロイル基とカルボキシル基とを有するモノマーとしては、例えば、カルボキシル基含有アクリル系モノマー等が挙げられる。
カルボキシル基含有アクリル系モノマーとしては、例えば、（メタ）アクリル酸；（メタ）アクリル酸カルボキシエチル等の（メタ）アクリル酸カルボキシアルキルが挙げられる。 - Monomer having a (meth)acryloyl group and a carboxyl group Examples of the monomer having a (meth)acryloyl group and a carboxyl group include carboxyl group-containing acrylic monomers.
Examples of the carboxyl group-containing acrylic monomer include (meth)acrylic acid; carboxyalkyl (meth)acrylates such as carboxyethyl (meth)acrylate.
・好ましいアクリル系モノマー
上記のアクリル系モノマーの中でも、本発明の効果をより向上させやすくする観点から、ジアルキルアミノアルキル（メタ）アクリルアミド、ヒドロキシアルキル（メタ）アクリレート、及び（メタ）アクリル酸カルボキシアルキルから選択される１種以上が好ましい。
なお、これらのモノマーが有するアルキル基の炭素数は、各々独立に、好ましくは１～６、より好ましくは１～４である。 ・Preferred acrylic monomer Among the above acrylic monomers, dialkylaminoalkyl (meth)acrylamide, hydroxyalkyl (meth)acrylate, and carboxyalkyl (meth)acrylate are selected from among the above-mentioned acrylic monomers, from the viewpoint of easily improving the effects of the present invention. One or more selected types are preferred.
The number of carbon atoms in the alkyl groups of these monomers is preferably 1 to 6, more preferably 1 to 4, each independently.
上記のアクリル系モノマーの中でも、本発明の効果をより向上させやすくする観点から、ジアルキルアミノアルキル（メタ）アクリルアミド、ヒドロキシアルキル（メタ）アクリレート、及び（メタ）アクリル酸カルボキシアルキルから選択される１種以上が好ましい。
なお、これらのモノマーが有するアルキル基の炭素数は、各々独立に、好ましくは１～６、より好ましくは１～４である。 ・Preferred acrylic monomer Among the above acrylic monomers, dialkylaminoalkyl (meth)acrylamide, hydroxyalkyl (meth)acrylate, and carboxyalkyl (meth)acrylate are selected from among the above-mentioned acrylic monomers, from the viewpoint of easily improving the effects of the present invention. One or more selected types are preferred.
The number of carbon atoms in the alkyl groups of these monomers is preferably 1 to 6, more preferably 1 to 4, each independently.
なお、本実施形態において、極性基含有（メタ）アクリレート（Ｂ１）由来の構成単位（ｂ１）の含有量は、モノマー（Ｂ）由来の構成単位（ｂ）の全構成単位基準で、好ましくは５０モル％～１００モル％、より好ましくは６０モル％～１００モル％、更に好ましくは７０モル％～１００モル％、より更に好ましくは８０モル％～１００モル％、更になお好ましくは９０モル％～１００モル％である。
In addition, in this embodiment, the content of the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1) is preferably 50% based on the total structural unit (b) derived from the monomer (B). mol% to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%. It is mole%.
ここで、本実施形態において、本発明の効果をより向上させやすくする観点から、極性基含有（メタ）アクリレート（Ｂ１）は、水酸基含有（メタ）アクリレート（Ｂ１１）を含むことが好ましい。
Here, in this embodiment, it is preferable that the polar group-containing (meth)acrylate (B1) includes a hydroxyl group-containing (meth)acrylate (B11) from the viewpoint of making it easier to improve the effects of the present invention.
（水酸基含有（メタ）アクリレート（Ｂ１１））
水酸基含有（メタ）アクリレート（Ｂ１１）は、下記一般式（ｂ－１）で表される。
(Hydroxy group-containing (meth)acrylate (B11))
The hydroxyl group-containing (meth)acrylate (B11) is represented by the following general formula (b-1).
水酸基含有（メタ）アクリレート（Ｂ１１）は、下記一般式（ｂ－１）で表される。
The hydroxyl group-containing (meth)acrylate (B11) is represented by the following general formula (b-1).
水酸基含有（メタ）アクリレート（Ｂ１１）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、水酸基含有（メタ）アクリレート（Ｂ１１）に由来する構成単位（ｂ１１）を１種単独で含んでいてもよく、２種以上含んでいてもよい。
The hydroxyl group-containing (meth)acrylate (B11) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11), or may contain two or more types.
上記一般式（ｂ－１）中、Ｒｂ１は、水素原子又はメチル基である。すなわち、水酸基含有（メタ）アクリレート（Ｂ１１）は、重合性官能基として、アクリロイル基又はメタクリロイル基を有する。
Ｒｂ１が水素原子及びメチル基以外の置換基であるモノマーは入手が困難であり、かつ当該モノマーは反応性が低いため、それらを重合することも困難である。
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｂ１は、水素原子であることが好ましい。すなわち、水酸基含有（メタ）アクリレート（Ｂ１１）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. That is, the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group or a methacryloyl group as a polymerizable functional group.
Monomers in which R b1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
Here, in this embodiment, R b1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group as a polymerizable functional group.
Ｒｂ１が水素原子及びメチル基以外の置換基であるモノマーは入手が困難であり、かつ当該モノマーは反応性が低いため、それらを重合することも困難である。
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｂ１は、水素原子であることが好ましい。すなわち、水酸基含有（メタ）アクリレート（Ｂ１１）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. That is, the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group or a methacryloyl group as a polymerizable functional group.
Monomers in which R b1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
Here, in this embodiment, R b1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group as a polymerizable functional group.
上記一般式（ｂ－１）中、Ｒｂ２は、炭素数２～４のアルキレン基を示す。
当該アルキレン基の炭素数が１である場合、極性が高くなり油溶性が低下する。
また、当該アルキレン基の炭素数が５以上である場合、油溶性が向上し過ぎて金属への吸着性が低下する。
ここで、適切な油溶性と金属への適切な吸着性を確保しやすくする観点から、当該アルキレン基の炭素数は、好ましくは２～３、より好ましくは２である。 In the above general formula (b-1), R b2 represents an alkylene group having 2 to 4 carbon atoms.
When the number of carbon atoms in the alkylene group is 1, the polarity becomes high and the oil solubility decreases.
Moreover, when the number of carbon atoms in the alkylene group is 5 or more, the oil solubility increases too much and the adsorption to metals decreases.
Here, the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
当該アルキレン基の炭素数が１である場合、極性が高くなり油溶性が低下する。
また、当該アルキレン基の炭素数が５以上である場合、油溶性が向上し過ぎて金属への吸着性が低下する。
ここで、適切な油溶性と金属への適切な吸着性を確保しやすくする観点から、当該アルキレン基の炭素数は、好ましくは２～３、より好ましくは２である。 In the above general formula (b-1), R b2 represents an alkylene group having 2 to 4 carbon atoms.
When the number of carbon atoms in the alkylene group is 1, the polarity becomes high and the oil solubility decreases.
Moreover, when the number of carbon atoms in the alkylene group is 5 or more, the oil solubility increases too much and the adsorption to metals decreases.
Here, the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
ｍ１は、１～１０の整数を示す。ｍ１が２以上の整数の場合の複数のＲｂ２は、同一であっても異なっていてもよい。また、－（ＯＲｂ２）ｍ１で表される部分同士の結合態様は、ランダム結合でもブロック結合であってもよいが、重合のしやすさの観点からは、ランダム結合であることが好ましい。
ｍ１が０である場合、水酸基含有（メタ）アクリレート（Ｂ１１）がカルボン酸となるため油溶性が低下する。
また、ｍ１が１１以上の整数である場合、－（ＯＲｂ２）－部分の影響で極性が高くなり、油溶性が低下する。
ここで、適切な油溶性を確保しやすくする観点から、ｍ１は、好ましくは１～６、より好ましくは１～４、更に好ましくは１～２、より更に好ましくは１である。 m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. Further, the bonding mode between the moieties represented by -(OR b2 ) m1 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m1 is 0, the hydroxyl group-containing (meth)acrylate (B11) becomes a carboxylic acid, resulting in decreased oil solubility.
Further, when m1 is an integer of 11 or more, the polarity becomes high due to the influence of the -(OR b2 )- moiety, and the oil solubility decreases.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2, and even more preferably 1.
ｍ１が０である場合、水酸基含有（メタ）アクリレート（Ｂ１１）がカルボン酸となるため油溶性が低下する。
また、ｍ１が１１以上の整数である場合、－（ＯＲｂ２）－部分の影響で極性が高くなり、油溶性が低下する。
ここで、適切な油溶性を確保しやすくする観点から、ｍ１は、好ましくは１～６、より好ましくは１～４、更に好ましくは１～２、より更に好ましくは１である。 m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. Further, the bonding mode between the moieties represented by -(OR b2 ) m1 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m1 is 0, the hydroxyl group-containing (meth)acrylate (B11) becomes a carboxylic acid, resulting in decreased oil solubility.
Further, when m1 is an integer of 11 or more, the polarity becomes high due to the influence of the -(OR b2 )- moiety, and the oil solubility decreases.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2, and even more preferably 1.
なお、本実施形態において、水酸基含有（メタ）アクリレート（Ｂ１１）由来の構成単位（ｂ１１）の含有量は、極性基含有（メタ）アクリレート（Ｂ１）由来の構成単位（ｂ１）の全構成単位基準で、好ましくは５０モル％～１００モル％、より好ましくは６０モル％～１００モル％、更に好ましくは７０モル％～１００モル％、より更に好ましくは８０モル％～１００モル％、更になお好ましくは９０モル％～１００モル％である。
また、本実施形態において、水酸基含有（メタ）アクリレート（Ｂ１１）由来の構成単位（ｂ１１）の含有量は、モノマー（Ｂ）由来の構成単位（ｂ）の全構成単位基準で、好ましくは５０モル％～１００モル％、より好ましくは６０モル％～１００モル％、更に好ましくは７０モル％～１００モル％、より更に好ましくは８０モル％～１００モル％、更になお好ましくは９０モル％～１００モル％である。 In addition, in this embodiment, the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is based on all the structural units of the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1). and, preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably It is 90 mol% to 100 mol%.
Further, in this embodiment, the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is preferably 50 mol based on the total structural unit (b) derived from the monomer (B). % to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%. %.
また、本実施形態において、水酸基含有（メタ）アクリレート（Ｂ１１）由来の構成単位（ｂ１１）の含有量は、モノマー（Ｂ）由来の構成単位（ｂ）の全構成単位基準で、好ましくは５０モル％～１００モル％、より好ましくは６０モル％～１００モル％、更に好ましくは７０モル％～１００モル％、より更に好ましくは８０モル％～１００モル％、更になお好ましくは９０モル％～１００モル％である。 In addition, in this embodiment, the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is based on all the structural units of the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1). and, preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably It is 90 mol% to 100 mol%.
Further, in this embodiment, the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is preferably 50 mol based on the total structural unit (b) derived from the monomer (B). % to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%. %.
＜要件（１）＞
本実施形態において、要件（１）は、次のように規定される。
共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
共重合体（Ｘ）が、側鎖に上記基のいずれも有しない場合、耐摩耗性及び極圧性を十分に確保することができない。
ここで、リン及び硫黄は熱安定性を低下させる要因となる元素であるため、熱安定性を確保する観点からは一般的には導入されない元素である。しかしながら、本発明者らは、耐摩耗性及び極圧性を向上させる観点から、リン及び／又は硫黄を導入することを検討する中で、モノマー（Ａ）由来の構成単位（ａ）とモノマー（Ｂ）由来の構成単位（ｂ）とが組み合わされた共重合体（Ｘ）の側鎖に、上記基を導入することで、リン及び／又は硫黄を導入することによる熱安定性の低下の問題が緩和され、共重合体（Ｘ）全体として熱安定性に優れ、しかも耐摩耗性及び極圧性にも優れるポリマーとなることを見出した。
なお、共重合体（Ｘ）が側鎖に有する上記基としては、耐摩耗性及び極圧性のさらなる向上の観点から、下記基の少なくともいずれかを有することが好ましい。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。） <Requirement (1)>
In this embodiment, requirement (1) is defined as follows.
The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
When the sulfur-containing group copolymer (X) does not have any of the above groups in the side chain, sufficient wear resistance and extreme pressure properties cannot be ensured.
Here, since phosphorus and sulfur are elements that cause a decrease in thermal stability, they are elements that are generally not introduced from the viewpoint of ensuring thermal stability. However, while considering the introduction of phosphorus and/or sulfur from the viewpoint of improving wear resistance and extreme pressure properties, the present inventors discovered that the structural unit (a) derived from the monomer (A) and the monomer (B ) By introducing the above group into the side chain of the copolymer (X) in which the structural unit (b) derived from It has been found that the copolymer (X) as a whole has excellent thermal stability, as well as excellent abrasion resistance and extreme pressure properties.
In addition, from the viewpoint of further improving wear resistance and extreme pressure properties, it is preferable that the above-mentioned group included in the side chain of the copolymer (X) includes at least one of the following groups.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
本実施形態において、要件（１）は、次のように規定される。
共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
共重合体（Ｘ）が、側鎖に上記基のいずれも有しない場合、耐摩耗性及び極圧性を十分に確保することができない。
ここで、リン及び硫黄は熱安定性を低下させる要因となる元素であるため、熱安定性を確保する観点からは一般的には導入されない元素である。しかしながら、本発明者らは、耐摩耗性及び極圧性を向上させる観点から、リン及び／又は硫黄を導入することを検討する中で、モノマー（Ａ）由来の構成単位（ａ）とモノマー（Ｂ）由来の構成単位（ｂ）とが組み合わされた共重合体（Ｘ）の側鎖に、上記基を導入することで、リン及び／又は硫黄を導入することによる熱安定性の低下の問題が緩和され、共重合体（Ｘ）全体として熱安定性に優れ、しかも耐摩耗性及び極圧性にも優れるポリマーとなることを見出した。
なお、共重合体（Ｘ）が側鎖に有する上記基としては、耐摩耗性及び極圧性のさらなる向上の観点から、下記基の少なくともいずれかを有することが好ましい。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。） <Requirement (1)>
In this embodiment, requirement (1) is defined as follows.
The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
When the sulfur-containing group copolymer (X) does not have any of the above groups in the side chain, sufficient wear resistance and extreme pressure properties cannot be ensured.
Here, since phosphorus and sulfur are elements that cause a decrease in thermal stability, they are elements that are generally not introduced from the viewpoint of ensuring thermal stability. However, while considering the introduction of phosphorus and/or sulfur from the viewpoint of improving wear resistance and extreme pressure properties, the present inventors discovered that the structural unit (a) derived from the monomer (A) and the monomer (B ) By introducing the above group into the side chain of the copolymer (X) in which the structural unit (b) derived from It has been found that the copolymer (X) as a whole has excellent thermal stability, as well as excellent abrasion resistance and extreme pressure properties.
In addition, from the viewpoint of further improving wear resistance and extreme pressure properties, it is preferable that the above-mentioned group included in the side chain of the copolymer (X) includes at least one of the following groups.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
本実施形態において、リン及び硫黄含有基（１つの基内にリン及び硫黄の双方を有する基）としては、例えば、チオリン酸基、チオホスホリル等が挙げられる。
In this embodiment, examples of the phosphorus- and sulfur-containing group (a group having both phosphorus and sulfur in one group) include a thiophosphoric acid group, thiophosphoryl, and the like.
本実施形態において、リン含有基（１つの基内にリンを有し、かつ硫黄を有しない基）としては、例えば、ホスホン酸基、亜ホスホン酸基、ホスフィン酸基、亜ホスフィン酸基、リン酸基、ピロホスファート基；これらのエステル基等が挙げられる。
In this embodiment, examples of the phosphorus-containing group (a group having phosphorus in one group and not having sulfur) include a phosphonic acid group, a phosphorous acid group, a phosphinic acid group, a phosphorous acid group, and a phosphorous group. Examples include acid groups, pyrophosphate groups, and ester groups thereof.
本実施形態において、硫黄含有基（１つの基内に硫黄を有し、かつリンを有しない基）としては、例えば、メルカプト基；アセチルチオ基；ベンゾイルチオ基、メチルチオカルボニル基、及びフェニルチオカルボニル基等のチオエステル基；ジチオエステル基；メチルチオ基及びエチルチオ基等のアルキルチオ基；フェニルチオ基、メチルフェニルチオ基、及びナフチルチオ基等のアリールチオ基；チオアシル基；チオエーテル基；チオシアン酸エステル基；イソチオシアン酸エステル基；スルホン酸メチル基、スルホン酸エチル基、及びスルホン酸フェニル基等のスルホンエステル基；フェニルスルホンアミド基、Ｎ－メチルスルホンアミド基、及びＮ－メチル－ｐ－トルエンスルホンアミド基等のスルホンアミド基；チオカルボキシル基；ジチオカルボキシル基；スルホ基；スルホニル基；スルフィニル基；スルフェニル基等が挙げられる。
In this embodiment, the sulfur-containing group (a group having sulfur in one group and not having phosphorus) includes, for example, a mercapto group; an acetylthio group; a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. thioester groups such as; dithioester groups; alkylthio groups such as methylthio and ethylthio groups; arylthio groups such as phenylthio, methylphenylthio, and naphthylthio groups; thioacyl groups; thioether groups; thiocyanate ester groups; isothiocyanate ester groups ; Sulfone ester groups such as methyl sulfonate group, ethyl sulfonate group, and phenyl sulfonate group; Sulfonamide groups such as phenylsulfonamide group, N-methylsulfonamide group, and N-methyl-p-toluenesulfonamide group ; thiocarboxyl group; dithiocarboxyl group; sulfo group; sulfonyl group; sulfinyl group; sulfenyl group.
＜要件（２）＞
本実施形態において、要件（２）は、次のように規定される。
・要件（２）：共重合体（Ｘ）がリン原子を含む場合、共重合体（Ｘ）中のリン原子含有量（Ｐ）が、共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
共重合体（Ｘ）がリン原子を含む場合、共重合体（Ｘ）中のリン原子含有量（Ｐ）が、共重合体（Ｘ）の全量基準で、０．０１質量％以上であると、耐摩耗性及び極圧性を十分に確保しやすくなる。
また、共重合体（Ｘ）中のリン原子含有量（Ｐ）が、共重合体（Ｘ）の全量基準で、２．０質量％以下である場合、共重合体（Ｘ）の油溶性を確保しやすくできる。
ここで、耐摩耗性及び極圧性を十分に確保しやすくする観点及び油溶性を確保しやすくする観点から、共重合体（Ｘ）中のリン原子含有量（Ｐ）は、好ましくは０．０２質量％～１．５０質量％、より好ましくは０．０４質量％～１．００質量％、更に好ましくは０．０４質量％～０．５０質量％である。
共重合体（Ｘ）のリン原子含有量（Ｐ）は、共重合体（Ｘ）を有機溶剤（例えば、潤滑油基油）に所定量溶解した後、当該有機溶剤中のリン量をＪＰＩ－５Ｓ－３８－０３に準拠して測定した結果と、有機溶剤への共重合体（Ｘ）の溶解量とに基づいて算出することができる。 <Requirement (2)>
In this embodiment, requirement (2) is defined as follows.
・Requirement (2): When the copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in the copolymer (X) is 0.01 based on the total amount of the copolymer (X). % by mass to 2.00% by mass.
When the copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X). , it becomes easy to ensure sufficient wear resistance and extreme pressure properties.
In addition, when the phosphorus atom content (P) in the copolymer (X) is 2.0% by mass or less based on the total amount of the copolymer (X), the oil solubility of the copolymer (X) is It can be easily secured.
Here, from the viewpoint of easily ensuring sufficient wear resistance and extreme pressure property and from the viewpoint of easily ensuring oil solubility, the phosphorus atom content (P) in the copolymer (X) is preferably 0.02 The amount is preferably from 0.04% to 1.00% by weight, and even more preferably from 0.04% to 0.50% by weight.
The phosphorus atom content (P) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricating oil base oil), and then calculating the amount of phosphorus in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
本実施形態において、要件（２）は、次のように規定される。
・要件（２）：共重合体（Ｘ）がリン原子を含む場合、共重合体（Ｘ）中のリン原子含有量（Ｐ）が、共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
共重合体（Ｘ）がリン原子を含む場合、共重合体（Ｘ）中のリン原子含有量（Ｐ）が、共重合体（Ｘ）の全量基準で、０．０１質量％以上であると、耐摩耗性及び極圧性を十分に確保しやすくなる。
また、共重合体（Ｘ）中のリン原子含有量（Ｐ）が、共重合体（Ｘ）の全量基準で、２．０質量％以下である場合、共重合体（Ｘ）の油溶性を確保しやすくできる。
ここで、耐摩耗性及び極圧性を十分に確保しやすくする観点及び油溶性を確保しやすくする観点から、共重合体（Ｘ）中のリン原子含有量（Ｐ）は、好ましくは０．０２質量％～１．５０質量％、より好ましくは０．０４質量％～１．００質量％、更に好ましくは０．０４質量％～０．５０質量％である。
共重合体（Ｘ）のリン原子含有量（Ｐ）は、共重合体（Ｘ）を有機溶剤（例えば、潤滑油基油）に所定量溶解した後、当該有機溶剤中のリン量をＪＰＩ－５Ｓ－３８－０３に準拠して測定した結果と、有機溶剤への共重合体（Ｘ）の溶解量とに基づいて算出することができる。 <Requirement (2)>
In this embodiment, requirement (2) is defined as follows.
・Requirement (2): When the copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in the copolymer (X) is 0.01 based on the total amount of the copolymer (X). % by mass to 2.00% by mass.
When the copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X). , it becomes easy to ensure sufficient wear resistance and extreme pressure properties.
In addition, when the phosphorus atom content (P) in the copolymer (X) is 2.0% by mass or less based on the total amount of the copolymer (X), the oil solubility of the copolymer (X) is It can be easily secured.
Here, from the viewpoint of easily ensuring sufficient wear resistance and extreme pressure property and from the viewpoint of easily ensuring oil solubility, the phosphorus atom content (P) in the copolymer (X) is preferably 0.02 The amount is preferably from 0.04% to 1.00% by weight, and even more preferably from 0.04% to 0.50% by weight.
The phosphorus atom content (P) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricating oil base oil), and then calculating the amount of phosphorus in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
＜要件（３）＞
本実施形態において、要件（３）は、次のように規定される。
・要件（３）：共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、共重合体（Ｘ）の全量基準で、０．０１質量％以上である。
共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、共重合体（Ｘ）の全量基準で、０．０１質量％以上である場合、耐摩耗性及び極圧性を十分に確保しやすくなる。
ここで、耐摩耗性及び極圧性を十分に確保しやすくする観点から、共重合体（Ｘ）中の硫黄原子含有量（Ｓ）は、共重合体（Ｘ）の全量基準で、好ましくは０．０２質量％以上、より好ましくは０．０３質量％以上、更に好ましくは０．０４質量％である。
また、共重合体（Ｘ）中の硫黄原子含有量と本発明の効果とのバランスを考慮すると、共重合体（Ｘ）中の硫黄原子含有量（Ｓ）は、共重合体（Ｘ）の全量基準で、好ましくは２．００質量％以下、より好ましくは１．５０質量％以下、更に好ましくは１．００質量％以下、より更に好ましくは０．５０質量％以下である。
これらの数値範囲の上限値及び下限値は任意に組み合わせることができる。具体的には、好ましくは０．０２質量％～２．００質量％、より好ましくは０．０３質量％～１．５０質量％、更に好ましくは０．０４質量％～１．００質量％、より更に好ましくは０．０４質量％～０．５０質量％である。
共重合体（Ｘ）の硫黄原子含有量（Ｓ）は、共重合体（Ｘ）を有機溶剤（例えば、潤滑油基油）に所定量溶解した後、当該有機溶剤中の硫黄量をＪＰＩ－５Ｓ－３８－０３に準拠して測定した結果と、有機溶剤への共重合体（Ｘ）の溶解量とに基づいて算出することができる。 <Requirement (3)>
In this embodiment, requirement (3) is defined as follows.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
When the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X), it is easy to ensure sufficient wear resistance and extreme pressure properties. Become.
Here, from the viewpoint of easily ensuring sufficient wear resistance and extreme pressure properties, the sulfur atom content (S) in the copolymer (X) is preferably 0, based on the total amount of the copolymer (X). The content is .02% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.04% by mass.
Furthermore, considering the balance between the sulfur atom content in the copolymer (X) and the effects of the present invention, the sulfur atom content (S) in the copolymer (X) is Based on the total amount, it is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, even more preferably 1.00% by mass or less, even more preferably 0.50% by mass or less.
The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, preferably 0.02% by mass to 2.00% by mass, more preferably 0.03% by mass to 1.50% by mass, even more preferably 0.04% by mass to 1.00% by mass, or more. More preferably, it is 0.04% by mass to 0.50% by mass.
The sulfur atom content (S) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricant base oil), and then calculating the amount of sulfur in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
本実施形態において、要件（３）は、次のように規定される。
・要件（３）：共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、共重合体（Ｘ）の全量基準で、０．０１質量％以上である。
共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、共重合体（Ｘ）の全量基準で、０．０１質量％以上である場合、耐摩耗性及び極圧性を十分に確保しやすくなる。
ここで、耐摩耗性及び極圧性を十分に確保しやすくする観点から、共重合体（Ｘ）中の硫黄原子含有量（Ｓ）は、共重合体（Ｘ）の全量基準で、好ましくは０．０２質量％以上、より好ましくは０．０３質量％以上、更に好ましくは０．０４質量％である。
また、共重合体（Ｘ）中の硫黄原子含有量と本発明の効果とのバランスを考慮すると、共重合体（Ｘ）中の硫黄原子含有量（Ｓ）は、共重合体（Ｘ）の全量基準で、好ましくは２．００質量％以下、より好ましくは１．５０質量％以下、更に好ましくは１．００質量％以下、より更に好ましくは０．５０質量％以下である。
これらの数値範囲の上限値及び下限値は任意に組み合わせることができる。具体的には、好ましくは０．０２質量％～２．００質量％、より好ましくは０．０３質量％～１．５０質量％、更に好ましくは０．０４質量％～１．００質量％、より更に好ましくは０．０４質量％～０．５０質量％である。
共重合体（Ｘ）の硫黄原子含有量（Ｓ）は、共重合体（Ｘ）を有機溶剤（例えば、潤滑油基油）に所定量溶解した後、当該有機溶剤中の硫黄量をＪＰＩ－５Ｓ－３８－０３に準拠して測定した結果と、有機溶剤への共重合体（Ｘ）の溶解量とに基づいて算出することができる。 <Requirement (3)>
In this embodiment, requirement (3) is defined as follows.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
When the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X), it is easy to ensure sufficient wear resistance and extreme pressure properties. Become.
Here, from the viewpoint of easily ensuring sufficient wear resistance and extreme pressure properties, the sulfur atom content (S) in the copolymer (X) is preferably 0, based on the total amount of the copolymer (X). The content is .02% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.04% by mass.
Furthermore, considering the balance between the sulfur atom content in the copolymer (X) and the effects of the present invention, the sulfur atom content (S) in the copolymer (X) is Based on the total amount, it is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, even more preferably 1.00% by mass or less, even more preferably 0.50% by mass or less.
The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, preferably 0.02% by mass to 2.00% by mass, more preferably 0.03% by mass to 1.50% by mass, even more preferably 0.04% by mass to 1.00% by mass, or more. More preferably, it is 0.04% by mass to 0.50% by mass.
The sulfur atom content (S) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricant base oil), and then calculating the amount of sulfur in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
＜要件（１）～（３）を満たす共重合体（Ｘ）の調製方法＞
要件（１）～（３）を満たす共重合体（Ｘ）の調製方法は、特に限定されるものではないが、例えば、好ましくは下記調製例１～４が挙げられ、より好ましくは下記調製例１～２が挙げられる。 <Method for preparing copolymer (X) satisfying requirements (1) to (3)>
The method for preparing the copolymer (X) that satisfies requirements (1) to (3) is not particularly limited, but preferably includes the following Preparation Examples 1 to 4, and more preferably the following Preparation Examples 1 to 2 are listed.
要件（１）～（３）を満たす共重合体（Ｘ）の調製方法は、特に限定されるものではないが、例えば、好ましくは下記調製例１～４が挙げられ、より好ましくは下記調製例１～２が挙げられる。 <Method for preparing copolymer (X) satisfying requirements (1) to (3)>
The method for preparing the copolymer (X) that satisfies requirements (1) to (3) is not particularly limited, but preferably includes the following Preparation Examples 1 to 4, and more preferably the following Preparation Examples 1 to 2 are listed.
（調製例１）
重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｃ）の投入量を調整することで、上記要件（２）及び（３）も満たす共重合体（Ｘ）を調製し得る。 (Preparation example 1)
A copolymer (X) that satisfies the above requirement (1) can be prepared by polymerizing a monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group together with monomers (A) and (B). . At that time, by adjusting the input amount of monomer (C), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｃ）の投入量を調整することで、上記要件（２）及び（３）も満たす共重合体（Ｘ）を調製し得る。 (Preparation example 1)
A copolymer (X) that satisfies the above requirement (1) can be prepared by polymerizing a monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group together with monomers (A) and (B). . At that time, by adjusting the input amount of monomer (C), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
（調製例２）
重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）及び重合性官能基とリン含有基とを有するモノマー（Ｄ２）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｄ１）及びモノマー（Ｄ２）の投入量を各々調整することで、上記要件（２）及び（３）も満たす共重合体（Ｘ）を調製し得る。 (Preparation example 2)
The above requirements ( A copolymer (X) satisfying 1) can be prepared. At that time, by adjusting the input amounts of monomer (D1) and monomer (D2), it is possible to prepare a copolymer (X) that also satisfies the above requirements (2) and (3).
重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）及び重合性官能基とリン含有基とを有するモノマー（Ｄ２）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｄ１）及びモノマー（Ｄ２）の投入量を各々調整することで、上記要件（２）及び（３）も満たす共重合体（Ｘ）を調製し得る。 (Preparation example 2)
The above requirements ( A copolymer (X) satisfying 1) can be prepared. At that time, by adjusting the input amounts of monomer (D1) and monomer (D2), it is possible to prepare a copolymer (X) that also satisfies the above requirements (2) and (3).
（調製例３）
重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｄ１）の投入量を各々調整することで、上記要件（３）も満たす共重合体（Ｘ）を調製し得る。なお、調製例３では、共重合体（Ｘ）がリン原子を含有しないため、上記要件（２）を満たす必要はない。 (Preparation example 3)
A copolymer (X) satisfying the above requirement (1) can be prepared by polymerizing a monomer (D1) having a polymerizable functional group and a sulfur-containing group together with monomers (A) and (B). At that time, by adjusting the input amount of the monomer (D1), a copolymer (X) that also satisfies the above requirement (3) can be prepared. In addition, in Preparation Example 3, since the copolymer (X) does not contain a phosphorus atom, it is not necessary to satisfy the above requirement (2).
重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｄ１）の投入量を各々調整することで、上記要件（３）も満たす共重合体（Ｘ）を調製し得る。なお、調製例３では、共重合体（Ｘ）がリン原子を含有しないため、上記要件（２）を満たす必要はない。 (Preparation example 3)
A copolymer (X) satisfying the above requirement (1) can be prepared by polymerizing a monomer (D1) having a polymerizable functional group and a sulfur-containing group together with monomers (A) and (B). At that time, by adjusting the input amount of the monomer (D1), a copolymer (X) that also satisfies the above requirement (3) can be prepared. In addition, in Preparation Example 3, since the copolymer (X) does not contain a phosphorus atom, it is not necessary to satisfy the above requirement (2).
（調製例４）
重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）、並びに、重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）及び／又は重合性官能基とリン含有基とを有するモノマー（Ｄ２）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｃ）、モノマー（Ｄ１）、及びモノマー（Ｄ２）の投入量を各々調整することで、上記要件（２）及び（３）も満たす共重合体（Ｘ）を調製し得る。 (Preparation example 4)
A monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group, a monomer (D1) having a polymerizable functional group and a sulfur-containing group, and/or a monomer having a polymerizable functional group and a phosphorus-containing group By polymerizing (D2) together with monomers (A) and (B), a copolymer (X) that satisfies the above requirement (1) can be prepared. At that time, by adjusting the input amounts of monomer (C), monomer (D1), and monomer (D2), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）、並びに、重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）及び／又は重合性官能基とリン含有基とを有するモノマー（Ｄ２）を、モノマー（Ａ）及び（Ｂ）とともに重合することにより、上記要件（１）を満たす共重合体（Ｘ）を調製し得る。その際、モノマー（Ｃ）、モノマー（Ｄ１）、及びモノマー（Ｄ２）の投入量を各々調整することで、上記要件（２）及び（３）も満たす共重合体（Ｘ）を調製し得る。 (Preparation example 4)
A monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group, a monomer (D1) having a polymerizable functional group and a sulfur-containing group, and/or a monomer having a polymerizable functional group and a phosphorus-containing group By polymerizing (D2) together with monomers (A) and (B), a copolymer (X) that satisfies the above requirement (1) can be prepared. At that time, by adjusting the input amounts of monomer (C), monomer (D1), and monomer (D2), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
調製例１～４により、共重合体（Ｘ）は、要件（１）に規定する基を含む１以上の構成単位（α）をさらに含むものとなる。
以下に、調製例１～５（好ましくは調製例１～２）に好適に適用し得る、重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）、重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）、及び重合性官能基とリン含有基とを有するモノマー（Ｄ２）について例示する。 According to Preparation Examples 1 to 4, the copolymer (X) further contains one or more structural units (α) containing the group specified in requirement (1).
Below, the monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group, which can be suitably applied to Preparation Examples 1 to 5 (preferably Preparation Examples 1 to 2), a polymerizable functional group and a sulfur-containing group, A monomer (D1) having the following and a monomer (D2) having a polymerizable functional group and a phosphorus-containing group will be exemplified.
以下に、調製例１～５（好ましくは調製例１～２）に好適に適用し得る、重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）、重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）、及び重合性官能基とリン含有基とを有するモノマー（Ｄ２）について例示する。 According to Preparation Examples 1 to 4, the copolymer (X) further contains one or more structural units (α) containing the group specified in requirement (1).
Below, the monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group, which can be suitably applied to Preparation Examples 1 to 5 (preferably Preparation Examples 1 to 2), a polymerizable functional group and a sulfur-containing group, A monomer (D1) having the following and a monomer (D2) having a polymerizable functional group and a phosphorus-containing group will be exemplified.
＜重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）＞
重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）（以下、単に「モノマー（Ｃ）」ともいう）としては、（メタ）アクリロイル基と、下記一般式（１）で表されるリン及び硫黄を含む１価基とを有する化合物が好ましく挙げられる。
<Monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group>
The monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group (hereinafter also simply referred to as "monomer (C)") includes a (meth)acryloyl group and a compound represented by the following general formula (1). Preferred examples include compounds having a monovalent group containing phosphorus and sulfur.
重合性官能基とリン及び硫黄含有基とを有するモノマー（Ｃ）（以下、単に「モノマー（Ｃ）」ともいう）としては、（メタ）アクリロイル基と、下記一般式（１）で表されるリン及び硫黄を含む１価基とを有する化合物が好ましく挙げられる。
The monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group (hereinafter also simply referred to as "monomer (C)") includes a (meth)acryloyl group and a compound represented by the following general formula (1). Preferred examples include compounds having a monovalent group containing phosphorus and sulfur.
共重合体（Ｘ）が、モノマー（Ｃ）に由来する構成単位（ｃ）を含有することで、リン及び硫黄含有基が共重合体（Ｘ）の側鎖に導入され、耐摩耗性及び極圧性を向上させ得る。
Since the copolymer (X) contains the structural unit (c) derived from the monomer (C), phosphorus and sulfur-containing groups are introduced into the side chains of the copolymer (X), which improves wear resistance and polarity. It can improve pressure resistance.
なお、モノマー（Ｃ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、モノマー（Ｃ）に由来する構成単位（ｃ）を１種単独で含んでいてもよく、２種以上含んでいてもよい。
Incidentally, the monomer (C) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (c) derived from the monomer (C), or may contain two or more types.
モノマー（Ｃ）は、重合性官能基として、（メタ）アクリロイル基を有する。本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、モノマー（Ｃ）が有する重合性官能基は、アクリロイル基であることが好ましい。
The monomer (C) has a (meth)acryloyl group as a polymerizable functional group. In this embodiment, from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X), the polymerizable functional group that the monomer (C) has is preferably an acryloyl group.
上記一般式（１）中、Ｒ１及びＲ２は、本発明の効果の向上の観点から、各々独立に、炭素数１～１０のアルキル基であることが好ましい。
In the above general formula (1), R 1 and R 2 are preferably each independently an alkyl group having 1 to 10 carbon atoms from the viewpoint of improving the effects of the present invention.
Ｒ１及びＲ２として選択し得る、炭素数１～１０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の鎖状アルキル基が挙げられる。当該鎖状アルキル基は、直鎖状であっても分岐鎖状であってもよい。なお、本発明の効果の向上の観点から、当該アルキル基の炭素数は、好ましくは２～８、より好ましくは２～６、更に好ましくは２～４、より更に好ましくは３である。
Examples of the alkyl group having 1 to 10 carbon atoms that can be selected as R 1 and R 2 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. Examples include chain alkyl groups such as. The chain alkyl group may be linear or branched. From the viewpoint of improving the effects of the present invention, the alkyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and even more preferably 3 carbon atoms.
ここで、モノマー（Ｃ）は、具体的には、下記一般式（ｃ－１）で表される化合物であることが好ましい。
Specifically, the monomer (C) is preferably a compound represented by the following general formula (c-1).
上記一般式（ｃ－１）中、Ｒｃ１は、水素原子又はメチル基であることが好ましい。
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｃ１は、水素原子であることが好ましい。 In the above general formula (c-1), R c1 is preferably a hydrogen atom or a methyl group.
Here, in this embodiment, R c1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｃ１は、水素原子であることが好ましい。 In the above general formula (c-1), R c1 is preferably a hydrogen atom or a methyl group.
Here, in this embodiment, R c1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
上記一般式（ｃ－１）中、Ｒｃ２は、炭素数２～４のアルキレン基であることが好ましい。
当該アルキレン基の炭素数が２以上であると、油溶性を確保しやすい。
また、当該アルキレン基の炭素数が４以下であると、金属への吸着性を良好なものとしやすい。
ここで、適切な油溶性と金属への適切な吸着性を確保しやすくする観点から、当該アルキレン基の炭素数は、好ましくは２～３、より好ましくは２である。 In the above general formula (c-1), R c2 is preferably an alkylene group having 2 to 4 carbon atoms.
When the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
Moreover, when the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
Here, the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
当該アルキレン基の炭素数が２以上であると、油溶性を確保しやすい。
また、当該アルキレン基の炭素数が４以下であると、金属への吸着性を良好なものとしやすい。
ここで、適切な油溶性と金属への適切な吸着性を確保しやすくする観点から、当該アルキレン基の炭素数は、好ましくは２～３、より好ましくは２である。 In the above general formula (c-1), R c2 is preferably an alkylene group having 2 to 4 carbon atoms.
When the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
Moreover, when the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
Here, the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
ｍ２は、０～１０の整数であることが好ましい。ｍ２が２以上の整数の場合の複数のＲｃ２は、同一であっても異なっていてもよい。また、－（ＯＲｃ２）ｍ２で表される部分同士の結合態様は、ランダム結合でもブロック結合であってもよいが、重合のしやすさの観点からは、ランダム結合であることが好ましい。
ｍ２が１０以下の整数であると、油溶性を確保しやすい。
ここで、適切な油溶性を確保しやすくする観点から、ｍ２は、好ましくは１～４、より好ましくは１～２、更に好ましくは１である。 Preferably, m2 is an integer from 0 to 10. When m2 is an integer of 2 or more, a plurality of R c2 may be the same or different. Further, the bonding mode between the moieties represented by -(OR c2 ) m2 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m2 is an integer of 10 or less, oil solubility can be easily ensured.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m2 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
ｍ２が１０以下の整数であると、油溶性を確保しやすい。
ここで、適切な油溶性を確保しやすくする観点から、ｍ２は、好ましくは１～４、より好ましくは１～２、更に好ましくは１である。 Preferably, m2 is an integer from 0 to 10. When m2 is an integer of 2 or more, a plurality of R c2 may be the same or different. Further, the bonding mode between the moieties represented by -(OR c2 ) m2 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m2 is an integer of 10 or less, oil solubility can be easily ensured.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m2 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
上記一般式（ｃ－１）中、Ｌ１は、リンカーを示す。
Ｌ１として選択され得るリンカーとしては、例えば、メチレン基、エチレン基、プロピレン基、及びブチレン基等の炭素数１～４の二価の脂肪族炭化水素基；－Ｏ－；－ＯＣ（Ｏ）－；－Ｏ－Ｃ（Ｏ）－ＲＣ３－（ＲＣ３は炭素数２～４のアルキレン基である。）等が挙げられる。これらの中でも、Ｌ１として選択され得るリンカーとしては、－Ｏ－Ｃ（Ｏ）－ＲＣ３－が好ましい。
また、Ｌ１は、直接結合であってもよい。すなわち、ｍ２＝０である場合、（メタ）アクリロイル基を構成するカルボニル基の炭素原子と上記一般式（１）で表される１価基の硫黄原子とが直接結合していてもよい。ｍ２が１以上である場合、－（ＯＲｃ２）ｍ２－と上記一般式（１）で表される１価基の硫黄原子とが直接結合していてもよい。 In the above general formula (c-1), L 1 represents a linker.
Linkers that can be selected as L 1 include, for example, divalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, and butylene group; -O-; -OC(O) -;-O-C(O)-R C3 - (R C3 is an alkylene group having 2 to 4 carbon atoms), and the like. Among these, -OC(O)-R C3 - is preferred as the linker that can be selected as L 1 .
Further, L 1 may be a direct bond. That is, when m2=0, the carbon atom of the carbonyl group constituting the (meth)acryloyl group and the sulfur atom of the monovalent group represented by the above general formula (1) may be directly bonded. When m2 is 1 or more, -(OR c2 ) m2 - and the sulfur atom of the monovalent group represented by the above general formula (1) may be directly bonded.
Ｌ１として選択され得るリンカーとしては、例えば、メチレン基、エチレン基、プロピレン基、及びブチレン基等の炭素数１～４の二価の脂肪族炭化水素基；－Ｏ－；－ＯＣ（Ｏ）－；－Ｏ－Ｃ（Ｏ）－ＲＣ３－（ＲＣ３は炭素数２～４のアルキレン基である。）等が挙げられる。これらの中でも、Ｌ１として選択され得るリンカーとしては、－Ｏ－Ｃ（Ｏ）－ＲＣ３－が好ましい。
また、Ｌ１は、直接結合であってもよい。すなわち、ｍ２＝０である場合、（メタ）アクリロイル基を構成するカルボニル基の炭素原子と上記一般式（１）で表される１価基の硫黄原子とが直接結合していてもよい。ｍ２が１以上である場合、－（ＯＲｃ２）ｍ２－と上記一般式（１）で表される１価基の硫黄原子とが直接結合していてもよい。 In the above general formula (c-1), L 1 represents a linker.
Linkers that can be selected as L 1 include, for example, divalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, and butylene group; -O-; -OC(O) -;-O-C(O)-R C3 - (R C3 is an alkylene group having 2 to 4 carbon atoms), and the like. Among these, -OC(O)-R C3 - is preferred as the linker that can be selected as L 1 .
Further, L 1 may be a direct bond. That is, when m2=0, the carbon atom of the carbonyl group constituting the (meth)acryloyl group and the sulfur atom of the monovalent group represented by the above general formula (1) may be directly bonded. When m2 is 1 or more, -(OR c2 ) m2 - and the sulfur atom of the monovalent group represented by the above general formula (1) may be directly bonded.
上記一般式（ｃ－１）中、Ｒ１及びＲ２は、上記一般式（１）において説明したとおりであり、好ましい範囲も上記一般式（１）において説明したとおりである。
In the above general formula (c-1), R 1 and R 2 are as explained in the above general formula (1), and the preferred ranges are also as explained in the above general formula (1).
＜重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）＞
重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）（以下、単に「モノマー（Ｄ１）」ともいう）としては、下記一般式（ｄ１－１）で表される化合物が好ましく挙げられる。
<Monomer (D1) having a polymerizable functional group and a sulfur-containing group>
As the monomer (D1) having a polymerizable functional group and a sulfur-containing group (hereinafter also simply referred to as "monomer (D1)"), a compound represented by the following general formula (d1-1) is preferably mentioned.
重合性官能基と硫黄含有基とを有するモノマー（Ｄ１）（以下、単に「モノマー（Ｄ１）」ともいう）としては、下記一般式（ｄ１－１）で表される化合物が好ましく挙げられる。
As the monomer (D1) having a polymerizable functional group and a sulfur-containing group (hereinafter also simply referred to as "monomer (D1)"), a compound represented by the following general formula (d1-1) is preferably mentioned.
共重合体（Ｘ）が、モノマー（Ｄ１）に由来する構成単位（ｄ１）を含有することで、硫黄含有基が共重合体（Ｘ）の側鎖に導入される。したがって、耐摩耗性及び極圧性が向上し得る。また、好ましくは、共重合体（Ｘ）がモノマー（Ｄ２）に由来する構成単位（ｄ２）をさらに含有することである。これにより、リン含有基も共重合体（Ｘ）の側鎖に導入され、耐摩耗性及び極圧性がより向上し得る。
When the copolymer (X) contains the structural unit (d1) derived from the monomer (D1), a sulfur-containing group is introduced into the side chain of the copolymer (X). Therefore, wear resistance and extreme pressure properties can be improved. Preferably, the copolymer (X) further contains a structural unit (d2) derived from the monomer (D2). Thereby, the phosphorus-containing group is also introduced into the side chain of the copolymer (X), and the wear resistance and extreme pressure properties can be further improved.
なお、モノマー（Ｄ１）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、モノマー（Ｄ１）に由来する構成単位（ｄ１）を１種単独で含んでいてもよく、２種以上含んでいてもよい。
In addition, the monomer (D1) may be used alone or in combination of two or more types. Therefore, the copolymer (X) may contain only one type of structural unit (d1) derived from the monomer (D1), or may contain two or more types.
上記一般式（ｄ１－１）中、Ｒｄ１１は、水素原子又はメチル基であることが好ましい。
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｄ１１は、水素原子であることが好ましい。すなわち、モノマー（Ｄ１）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (d1-1), R d11 is preferably a hydrogen atom or a methyl group.
Here, in this embodiment, from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X), R d11 is preferably a hydrogen atom. That is, it is preferable that the monomer (D1) has an acryloyl group as a polymerizable functional group.
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｄ１１は、水素原子であることが好ましい。すなわち、モノマー（Ｄ１）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (d1-1), R d11 is preferably a hydrogen atom or a methyl group.
Here, in this embodiment, from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X), R d11 is preferably a hydrogen atom. That is, it is preferable that the monomer (D1) has an acryloyl group as a polymerizable functional group.
上記一般式（ｄ１－１）中、Ｒｄ１２は、炭素数２～４のアルキレン基を示す。
当該アルキレン基の炭素数が２以上であると、油溶性を確保しやすい。
また、当該アルキレン基の炭素数が４以下であると、金属への吸着性を良好なものとしやすい。
ここで、適切な油溶性と金属への適切な吸着性を確保しやすくする観点から、当該アルキレン基の炭素数は、好ましくは２～３、より好ましくは２である。 In the above general formula (d1-1), R d12 represents an alkylene group having 2 to 4 carbon atoms.
When the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
Moreover, when the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
Here, the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
当該アルキレン基の炭素数が２以上であると、油溶性を確保しやすい。
また、当該アルキレン基の炭素数が４以下であると、金属への吸着性を良好なものとしやすい。
ここで、適切な油溶性と金属への適切な吸着性を確保しやすくする観点から、当該アルキレン基の炭素数は、好ましくは２～３、より好ましくは２である。 In the above general formula (d1-1), R d12 represents an alkylene group having 2 to 4 carbon atoms.
When the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
Moreover, when the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
Here, the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
ｍ３は、０～１０の整数であることが好ましく、１～１０の整数であることがより好ましい。ｍ３が２以上の整数の場合の複数のＲｄ１２は、同一であっても異なっていてもよい。また、－（ＯＲｄ１２）ｍ３で表される部分同士の結合態様は、ランダム結合でもブロック結合であってもよいが、重合のしやすさの観点からは、ランダム結合であることが好ましい。
ｍ３が１０以下の整数であると、油溶性を確保しやすい。
ここで、適切な油溶性を確保しやすくする観点から、ｍ３は、好ましくは１～４、より好ましくは１～２、更に好ましくは１である。 m3 is preferably an integer of 0 to 10, more preferably an integer of 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. Further, the bonding mode between the moieties represented by -(OR d12 ) m3 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m3 is an integer of 10 or less, oil solubility can be easily ensured.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m3 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
ｍ３が１０以下の整数であると、油溶性を確保しやすい。
ここで、適切な油溶性を確保しやすくする観点から、ｍ３は、好ましくは１～４、より好ましくは１～２、更に好ましくは１である。 m3 is preferably an integer of 0 to 10, more preferably an integer of 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. Further, the bonding mode between the moieties represented by -(OR d12 ) m3 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m3 is an integer of 10 or less, oil solubility can be easily ensured.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m3 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
上記一般式（ｄ１－１）中、Ｒｄ１３は、炭素数４～２０のアルキル基であることが好ましい。
当該アルキル基の炭素数が４以上である場合、当該アルキル基の炭素数が２０以下である場合、本発明の効果が発揮されやすくなる。 In the above general formula (d1-1), R d13 is preferably an alkyl group having 4 to 20 carbon atoms.
When the number of carbon atoms in the alkyl group is 4 or more, and when the number of carbon atoms in the alkyl group is 20 or less, the effects of the present invention are more likely to be exhibited.
当該アルキル基の炭素数が４以上である場合、当該アルキル基の炭素数が２０以下である場合、本発明の効果が発揮されやすくなる。 In the above general formula (d1-1), R d13 is preferably an alkyl group having 4 to 20 carbon atoms.
When the number of carbon atoms in the alkyl group is 4 or more, and when the number of carbon atoms in the alkyl group is 20 or less, the effects of the present invention are more likely to be exhibited.
Ｒｄ１３として選択し得る、炭素数４～２０のアルキル基としては、例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、及びイコシル基等の鎖状アルキル基が挙げられる。これらは、直鎖状であっても分岐鎖状であってもよい。
Examples of the alkyl group having 4 to 20 carbon atoms that can be selected as R d13 include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include chain alkyl groups such as a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group. These may be linear or branched.
なお、共重合体（Ｘ）の油溶性をより確保しやすくする観点から、当該アルキル基の炭素数は、好ましくは６～１８、より好ましくは６～１６、更に好ましくは６～１４である。
In addition, from the viewpoint of making it easier to ensure the oil solubility of the copolymer (X), the number of carbon atoms in the alkyl group is preferably 6 to 18, more preferably 6 to 16, and even more preferably 6 to 14.
＜重合性官能基とリン含有基とを有するモノマー（Ｄ２）＞
重合性官能基とリン含有基とを有するモノマー（Ｄ２）（以下、単に「モノマー（Ｄ２）」ともいう）としては、下記一般式（ｄ２－１）で表される化合物が好ましく挙げられる。
<Monomer (D2) having a polymerizable functional group and a phosphorus-containing group>
As the monomer (D2) having a polymerizable functional group and a phosphorus-containing group (hereinafter also simply referred to as "monomer (D2)"), a compound represented by the following general formula (d2-1) is preferably mentioned.
重合性官能基とリン含有基とを有するモノマー（Ｄ２）（以下、単に「モノマー（Ｄ２）」ともいう）としては、下記一般式（ｄ２－１）で表される化合物が好ましく挙げられる。
As the monomer (D2) having a polymerizable functional group and a phosphorus-containing group (hereinafter also simply referred to as "monomer (D2)"), a compound represented by the following general formula (d2-1) is preferably mentioned.
共重合体（Ｘ）が、モノマー（Ｄ２）に由来する構成単位（ｄ２）を含有することで、リン含有基が共重合体（Ｘ）の側鎖に導入される。したがって、共重合体（Ｘ）がモノマー（Ｄ１）に由来する構成単位（ｄ１）をさらに含有することで、硫黄含有基も共重合体（Ｘ）の側鎖に導入され、耐摩耗性及び極圧性が向上し得る。
When the copolymer (X) contains the structural unit (d2) derived from the monomer (D2), a phosphorus-containing group is introduced into the side chain of the copolymer (X). Therefore, when the copolymer (X) further contains the structural unit (d1) derived from the monomer (D1), a sulfur-containing group is also introduced into the side chain of the copolymer (X), which improves wear resistance and polarity. Pressure properties can be improved.
なお、モノマー（Ｄ２）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。したがって、共重合体（Ｘ）は、モノマー（Ｄ２）に由来する構成単位（ｄ２）を１種単独で含んでいてもよく、２種以上含んでいてもよい。
In addition, the monomer (D2) may be used alone or in combination of two or more types. Therefore, the copolymer (X) may contain one type of structural unit (d2) derived from the monomer (D2), or may contain two or more types.
上記一般式（ｄ２－１）中、Ｒｄ２１は、水素原子又はメチル基であることが好ましい。
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｄ２１は、水素原子であることが好ましい。すなわち、モノマー（Ｄ２）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (d2-1), R d21 is preferably a hydrogen atom or a methyl group.
Here, in this embodiment, R d21 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the monomer (D2) has an acryloyl group as a polymerizable functional group.
ここで、本実施形態では、共重合体（Ｘ）の分子量を調整しやすくする観点から、Ｒｄ２１は、水素原子であることが好ましい。すなわち、モノマー（Ｄ２）は、重合性官能基として、アクリロイル基を有することが好ましい。 In the above general formula (d2-1), R d21 is preferably a hydrogen atom or a methyl group.
Here, in this embodiment, R d21 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the monomer (D2) has an acryloyl group as a polymerizable functional group.
上記一般式（ｄ２－１）中、Ｒｄ２２は、エチレン基を示す。
In the above general formula (d2-1), R d22 represents an ethylene group.
ｍ４は、１～６の整数であることが好ましい。ｍ４が２以上の整数の場合の複数のＲｄ２は、同一であっても異なっていてもよい。また、－（ＯＲｄ２２）ｍ４で表される部分同士の結合態様は、ランダム結合でもブロック結合であってもよいが、重合のしやすさの観点からは、ランダム結合であることが好ましい。
ｍ４が１～６である場合、油溶性を確保しやすい。
ここで、適切な油溶性を確保しやすくする観点から、ｍ４は、好ましくは１～４、より好ましくは１～２、更に好ましくは１である。 Preferably, m4 is an integer from 1 to 6. When m4 is an integer of 2 or more, the plurality of R d2 may be the same or different. Further, the bonding mode between the moieties represented by -(OR d22 ) m4 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m4 is 1 to 6, it is easy to ensure oil solubility.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m4 is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.
ｍ４が１～６である場合、油溶性を確保しやすい。
ここで、適切な油溶性を確保しやすくする観点から、ｍ４は、好ましくは１～４、より好ましくは１～２、更に好ましくは１である。 Preferably, m4 is an integer from 1 to 6. When m4 is an integer of 2 or more, the plurality of R d2 may be the same or different. Further, the bonding mode between the moieties represented by -(OR d22 ) m4 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
When m4 is 1 to 6, it is easy to ensure oil solubility.
Here, from the viewpoint of easily ensuring appropriate oil solubility, m4 is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.
ｎは、１又は２の整数を示す。ｎ＝１である場合、複数のＲｄ２３のうちの少なくとも１つは水素原子を示す。ｎ＝２である場合、Ｒｄ２３は水素原子である。なお、ｎ＝１である場合、複数のＲｄ２３のうちの一方のみが水素原子であってもよい。この場合、複数のＲｄ２３のうちの他方は炭化水素基である。
ここで、ｎ＝１である場合、複数のＲｄ２３のうちの他方が炭化水素基であるならば、本発明の効果を向上させやすくする観点から、当該炭化水素基は、メチル基又はエチル基であることが好ましい。
また、ｎ＝１である場合、本発明の効果をより向上させやすくする観点から、複数のＲｄ２３はいずれも水素原子であることが好ましい。
ここで、本発明の効果を向上させやすくする観点から、モノマー（Ｄ２）は、ｎ＝１であるモノマー（Ｄ２１）を主成分として含むことが好ましい。
本明細書において、「主成分」とは、その含有量が５０質量％を超える成分をいう。すなわち、ｎ＝１であるモノマー（Ｄ２１）の含有量は、モノマー（Ｄ２）の全量基準で、好ましくは５０質量％超～１００質量％、より好ましくは６０質量％～１００質量％、更に好ましくは７０質量％～１００質量％、より更に好ましくは８０質量％～１００質量％、更になお好ましくは９０質量％～１００質量％である。
また、ｎ＝１であるモノマー（Ｄ２１）に由来する構成単位（ｄ２１）の含有量は、モノマー（Ｄ２）に由来する構成単位（ｄ２）の全量基準で、好ましくは５０質量％超～１００質量％、より好ましくは６０質量％～１００質量％、更に好ましくは７０質量％～１００質量％、より更に好ましくは８０質量％～１００質量％、更になお好ましくは９０質量％～１００質量％である。 n represents an integer of 1 or 2. When n=1, at least one of the plurality of R d23 represents a hydrogen atom. When n=2, R d23 is a hydrogen atom. Note that when n=1, only one of the plurality of R d23 may be a hydrogen atom. In this case, the other of the plurality of R d23 is a hydrocarbon group.
Here, when n=1, if the other of the plurality of R d23 is a hydrocarbon group, from the viewpoint of easily improving the effects of the present invention, the hydrocarbon group is a methyl group or an ethyl group. It is preferable that
Furthermore, when n=1, all of the plurality of R d23 are preferably hydrogen atoms from the viewpoint of further improving the effects of the present invention.
Here, from the viewpoint of easily improving the effects of the present invention, it is preferable that the monomer (D2) contains a monomer (D21) in which n=1 as a main component.
As used herein, the term "main component" refers to a component whose content exceeds 50% by mass. That is, the content of the monomer (D21) where n=1 is preferably more than 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably It is 70% by weight to 100% by weight, even more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight.
Further, the content of the structural unit (d21) derived from the monomer (D21) where n=1 is preferably more than 50% by mass to 100% by mass based on the total amount of the structural unit (d2) derived from the monomer (D2). %, more preferably 60% to 100% by weight, even more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight.
ここで、ｎ＝１である場合、複数のＲｄ２３のうちの他方が炭化水素基であるならば、本発明の効果を向上させやすくする観点から、当該炭化水素基は、メチル基又はエチル基であることが好ましい。
また、ｎ＝１である場合、本発明の効果をより向上させやすくする観点から、複数のＲｄ２３はいずれも水素原子であることが好ましい。
ここで、本発明の効果を向上させやすくする観点から、モノマー（Ｄ２）は、ｎ＝１であるモノマー（Ｄ２１）を主成分として含むことが好ましい。
本明細書において、「主成分」とは、その含有量が５０質量％を超える成分をいう。すなわち、ｎ＝１であるモノマー（Ｄ２１）の含有量は、モノマー（Ｄ２）の全量基準で、好ましくは５０質量％超～１００質量％、より好ましくは６０質量％～１００質量％、更に好ましくは７０質量％～１００質量％、より更に好ましくは８０質量％～１００質量％、更になお好ましくは９０質量％～１００質量％である。
また、ｎ＝１であるモノマー（Ｄ２１）に由来する構成単位（ｄ２１）の含有量は、モノマー（Ｄ２）に由来する構成単位（ｄ２）の全量基準で、好ましくは５０質量％超～１００質量％、より好ましくは６０質量％～１００質量％、更に好ましくは７０質量％～１００質量％、より更に好ましくは８０質量％～１００質量％、更になお好ましくは９０質量％～１００質量％である。 n represents an integer of 1 or 2. When n=1, at least one of the plurality of R d23 represents a hydrogen atom. When n=2, R d23 is a hydrogen atom. Note that when n=1, only one of the plurality of R d23 may be a hydrogen atom. In this case, the other of the plurality of R d23 is a hydrocarbon group.
Here, when n=1, if the other of the plurality of R d23 is a hydrocarbon group, from the viewpoint of easily improving the effects of the present invention, the hydrocarbon group is a methyl group or an ethyl group. It is preferable that
Furthermore, when n=1, all of the plurality of R d23 are preferably hydrogen atoms from the viewpoint of further improving the effects of the present invention.
Here, from the viewpoint of easily improving the effects of the present invention, it is preferable that the monomer (D2) contains a monomer (D21) in which n=1 as a main component.
As used herein, the term "main component" refers to a component whose content exceeds 50% by mass. That is, the content of the monomer (D21) where n=1 is preferably more than 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably It is 70% by weight to 100% by weight, even more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight.
Further, the content of the structural unit (d21) derived from the monomer (D21) where n=1 is preferably more than 50% by mass to 100% by mass based on the total amount of the structural unit (d2) derived from the monomer (D2). %, more preferably 60% to 100% by weight, even more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight.
＜要件（４）＞
本実施形態の潤滑油用添加剤組成物は、本発明の効果の向上の観点から、さらに次の要件（４）を満たすことが好ましい。
・要件（４）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）とリン原子含有量（Ｐ）との含有比率［（Ｓ）／（Ｐ）］が、質量比で、０．１０～３．００である。
本発明の効果をより向上させやすくする観点から、含有比率［（Ｓ）／（Ｐ）］は、質量比で、好ましくは０．１５～２．８０、より好ましくは０．１５～２．６０、更に好ましくは０．２０～２．５０である。
ここで、共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、含有比率［（Ｓ）／（Ｐ）］は、質量比で、好ましくは０．５０～３．００、より好ましくは１．００～３．００、更に好ましくは１．５０～２．５０である。
また、共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、含有比率［（Ｓ）／（Ｐ）］は、質量比で、好ましくは０．１０～２．００、より好ましくは０．１０～１．００、更に好ましくは０．２０～０．８０である。 <Requirement (4)>
It is preferable that the lubricating oil additive composition of the present embodiment further satisfies the following requirement (4) from the viewpoint of improving the effects of the present invention.
- Requirement (4): When the copolymer (X) contains a phosphorus atom, the content ratio of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) [( S)/(P)] is 0.10 to 3.00 in mass ratio.
From the viewpoint of making it easier to improve the effects of the present invention, the content ratio [(S)/(P)] is preferably 0.15 to 2.80, more preferably 0.15 to 2.60 in mass ratio. , more preferably 0.20 to 2.50.
Here, when the copolymer (X) contains a structural unit (a), a structural unit (b), and a structural unit (c), the content ratio [(S)/(P)] is a mass ratio, It is preferably 0.50 to 3.00, more preferably 1.00 to 3.00, even more preferably 1.50 to 2.50.
In addition, when the copolymer (X) contains a structural unit (a), a structural unit (b), a structural unit (d1), and a structural unit (d2), the content ratio [(S)/(P)] is , in terms of mass ratio, is preferably 0.10 to 2.00, more preferably 0.10 to 1.00, even more preferably 0.20 to 0.80.
本実施形態の潤滑油用添加剤組成物は、本発明の効果の向上の観点から、さらに次の要件（４）を満たすことが好ましい。
・要件（４）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）とリン原子含有量（Ｐ）との含有比率［（Ｓ）／（Ｐ）］が、質量比で、０．１０～３．００である。
本発明の効果をより向上させやすくする観点から、含有比率［（Ｓ）／（Ｐ）］は、質量比で、好ましくは０．１５～２．８０、より好ましくは０．１５～２．６０、更に好ましくは０．２０～２．５０である。
ここで、共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、含有比率［（Ｓ）／（Ｐ）］は、質量比で、好ましくは０．５０～３．００、より好ましくは１．００～３．００、更に好ましくは１．５０～２．５０である。
また、共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、含有比率［（Ｓ）／（Ｐ）］は、質量比で、好ましくは０．１０～２．００、より好ましくは０．１０～１．００、更に好ましくは０．２０～０．８０である。 <Requirement (4)>
It is preferable that the lubricating oil additive composition of the present embodiment further satisfies the following requirement (4) from the viewpoint of improving the effects of the present invention.
- Requirement (4): When the copolymer (X) contains a phosphorus atom, the content ratio of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) [( S)/(P)] is 0.10 to 3.00 in mass ratio.
From the viewpoint of making it easier to improve the effects of the present invention, the content ratio [(S)/(P)] is preferably 0.15 to 2.80, more preferably 0.15 to 2.60 in mass ratio. , more preferably 0.20 to 2.50.
Here, when the copolymer (X) contains a structural unit (a), a structural unit (b), and a structural unit (c), the content ratio [(S)/(P)] is a mass ratio, It is preferably 0.50 to 3.00, more preferably 1.00 to 3.00, even more preferably 1.50 to 2.50.
In addition, when the copolymer (X) contains a structural unit (a), a structural unit (b), a structural unit (d1), and a structural unit (d2), the content ratio [(S)/(P)] is , in terms of mass ratio, is preferably 0.10 to 2.00, more preferably 0.10 to 1.00, even more preferably 0.20 to 0.80.
＜他のモノマー＞
共重合体（Ｘ）は、上記構成単位（ａ）及び（ｂ）、さらにはモノマー（Ｃ）由来の構成単位（ｃ）、モノマー（Ｄ１）由来の構成単位（ｄ１）、及びモノマー（Ｄ２）由来の構成単位（ｄ２）以外に、本発明の効果を阻害することのない範囲で、他のモノマー由来の構成単位を含有していてもよい。当該他のモノマーとしては、モノマー（Ａ）、（Ｂ）、（Ｃ）、（Ｄ１）、及び（Ｄ２）以外の官能基含有モノマーが挙げられる。
但し、本発明の効果の向上の観点から、共重合体（Ｘ）は、モノマー（Ａ）、（Ｂ）、（Ｃ）、（Ｄ１）、及び（Ｄ２）以外の官能基含有モノマーに由来する構成単位の含有量が、全構成単位基準で、好ましくは５０質量％未満、より好ましくは４０質量％未満、更に好ましくは３０質量％未満、より更に好ましくは２０質量％未満、更になお好ましくは１０質量％未満である。
また、共重合体（Ｘ）は、モノマー（Ａ）、モノマー（Ｂ）、及び要件（１）～（３）を満たすために用いられるモノマー由来の構成単位（構成単位（α））の合計含有量が、共重合体（Ｘ）の全構成単位基準で、好ましくは７０質量％～１００質量％、より好ましくは８０質量％～１００質量％、更に好ましくは９０質量％～１００質量％、より更に好ましくは９５質量％～１００質量％である。 <Other monomers>
The copolymer (X) contains the above structural units (a) and (b), furthermore, the structural unit (c) derived from the monomer (C), the structural unit (d1) derived from the monomer (D1), and the monomer (D2). In addition to the derived structural unit (d2), structural units derived from other monomers may be contained within a range that does not impede the effects of the present invention. Examples of the other monomers include functional group-containing monomers other than monomers (A), (B), (C), (D1), and (D2).
However, from the viewpoint of improving the effects of the present invention, the copolymer (X) is derived from a functional group-containing monomer other than monomers (A), (B), (C), (D1), and (D2). The content of the structural units is preferably less than 50% by mass, more preferably less than 40% by mass, even more preferably less than 30% by mass, even more preferably less than 20% by mass, even more preferably 10% by mass, based on all the structural units. Less than % by mass.
In addition, the copolymer (X) contains a total of monomers (A), monomers (B), and structural units derived from monomers (constituent units (α)) used to satisfy requirements (1) to (3). The amount is based on all the constituent units of the copolymer (X), preferably 70% by mass to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more Preferably it is 95% by mass to 100% by mass.
共重合体（Ｘ）は、上記構成単位（ａ）及び（ｂ）、さらにはモノマー（Ｃ）由来の構成単位（ｃ）、モノマー（Ｄ１）由来の構成単位（ｄ１）、及びモノマー（Ｄ２）由来の構成単位（ｄ２）以外に、本発明の効果を阻害することのない範囲で、他のモノマー由来の構成単位を含有していてもよい。当該他のモノマーとしては、モノマー（Ａ）、（Ｂ）、（Ｃ）、（Ｄ１）、及び（Ｄ２）以外の官能基含有モノマーが挙げられる。
但し、本発明の効果の向上の観点から、共重合体（Ｘ）は、モノマー（Ａ）、（Ｂ）、（Ｃ）、（Ｄ１）、及び（Ｄ２）以外の官能基含有モノマーに由来する構成単位の含有量が、全構成単位基準で、好ましくは５０質量％未満、より好ましくは４０質量％未満、更に好ましくは３０質量％未満、より更に好ましくは２０質量％未満、更になお好ましくは１０質量％未満である。
また、共重合体（Ｘ）は、モノマー（Ａ）、モノマー（Ｂ）、及び要件（１）～（３）を満たすために用いられるモノマー由来の構成単位（構成単位（α））の合計含有量が、共重合体（Ｘ）の全構成単位基準で、好ましくは７０質量％～１００質量％、より好ましくは８０質量％～１００質量％、更に好ましくは９０質量％～１００質量％、より更に好ましくは９５質量％～１００質量％である。 <Other monomers>
The copolymer (X) contains the above structural units (a) and (b), furthermore, the structural unit (c) derived from the monomer (C), the structural unit (d1) derived from the monomer (D1), and the monomer (D2). In addition to the derived structural unit (d2), structural units derived from other monomers may be contained within a range that does not impede the effects of the present invention. Examples of the other monomers include functional group-containing monomers other than monomers (A), (B), (C), (D1), and (D2).
However, from the viewpoint of improving the effects of the present invention, the copolymer (X) is derived from a functional group-containing monomer other than monomers (A), (B), (C), (D1), and (D2). The content of the structural units is preferably less than 50% by mass, more preferably less than 40% by mass, even more preferably less than 30% by mass, even more preferably less than 20% by mass, even more preferably 10% by mass, based on all the structural units. Less than % by mass.
In addition, the copolymer (X) contains a total of monomers (A), monomers (B), and structural units derived from monomers (constituent units (α)) used to satisfy requirements (1) to (3). The amount is based on all the constituent units of the copolymer (X), preferably 70% by mass to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more Preferably it is 95% by mass to 100% by mass.
＜構成単位（ａ）の含有量＞
共重合体（Ｘ）中における構成単位（ａ）の含有量は、油溶性の確保の観点及び本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは５０質量％以上、より好ましくは６０質量％～９５質量％、更に好ましくは７０質量％～９０質量％である。 <Content of structural unit (a)>
The content of the structural unit (a) in the copolymer (X) is preferably 50 mass based on the total amount of the copolymer (X) from the viewpoint of ensuring oil solubility and improving the effects of the present invention. % or more, more preferably 60% to 95% by weight, still more preferably 70% to 90% by weight.
共重合体（Ｘ）中における構成単位（ａ）の含有量は、油溶性の確保の観点及び本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは５０質量％以上、より好ましくは６０質量％～９５質量％、更に好ましくは７０質量％～９０質量％である。 <Content of structural unit (a)>
The content of the structural unit (a) in the copolymer (X) is preferably 50 mass based on the total amount of the copolymer (X) from the viewpoint of ensuring oil solubility and improving the effects of the present invention. % or more, more preferably 60% to 95% by weight, still more preferably 70% to 90% by weight.
＜構成単位（ｂ）の含有量＞
共重合体（Ｘ）中における構成単位（ｂ）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは１質量％以上、より好ましくは３質量％～３０質量％、更に好ましくは６質量％～２５質量％である。 <Content of structural unit (b)>
From the viewpoint of improving the effects of the present invention, the content of the structural unit (b) in the copolymer (X) is preferably 1% by mass or more, more preferably 3% by mass, based on the total amount of the copolymer (X). The amount is preferably 6% to 25% by weight, preferably 6% to 25% by weight.
共重合体（Ｘ）中における構成単位（ｂ）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは１質量％以上、より好ましくは３質量％～３０質量％、更に好ましくは６質量％～２５質量％である。 <Content of structural unit (b)>
From the viewpoint of improving the effects of the present invention, the content of the structural unit (b) in the copolymer (X) is preferably 1% by mass or more, more preferably 3% by mass, based on the total amount of the copolymer (X). The amount is preferably 6% to 25% by weight, preferably 6% to 25% by weight.
＜構成単位（ｃ）の含有量＞
共重合体（Ｘ）が構成単位（ｃ）を含む場合、共重合体（Ｘ）中における構成単位（ｃ）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは０．１質量％～１０質量％、より好ましくは０．５質量％～５質量％、更に好ましくは０．８質量％～３．０質量％である。 <Content of structural unit (c)>
When the copolymer (X) contains the structural unit (c), the content of the structural unit (c) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
共重合体（Ｘ）が構成単位（ｃ）を含む場合、共重合体（Ｘ）中における構成単位（ｃ）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは０．１質量％～１０質量％、より好ましくは０．５質量％～５質量％、更に好ましくは０．８質量％～３．０質量％である。 <Content of structural unit (c)>
When the copolymer (X) contains the structural unit (c), the content of the structural unit (c) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
＜構成単位（ｄ１）の含有量＞
共重合体（Ｘ）が構成単位（ｄ１）を含む場合、共重合体（Ｘ）中における構成単位（ｄ１）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは０．１質量％～１０質量％、より好ましくは０．５質量％～５質量％、更に好ましくは０．８質量％～３．０質量％である。 <Content of structural unit (d1)>
When the copolymer (X) contains the structural unit (d1), the content of the structural unit (d1) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
共重合体（Ｘ）が構成単位（ｄ１）を含む場合、共重合体（Ｘ）中における構成単位（ｄ１）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で、好ましくは０．１質量％～１０質量％、より好ましくは０．５質量％～５質量％、更に好ましくは０．８質量％～３．０質量％である。 <Content of structural unit (d1)>
When the copolymer (X) contains the structural unit (d1), the content of the structural unit (d1) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
＜構成単位（ｄ２）の含有量＞
共重合体（Ｘ）が構成単位（ｄ２）を含む場合、共重合体（Ｘ）中における構成単位（ｄ２）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で好ましくは０．１質量％～１０質量％、より好ましくは０．５質量％～５質量％、更に好ましくは０．８質量％～３．０質量％である。 <Content of structural unit (d2)>
When the copolymer (X) contains the structural unit (d2), the content of the structural unit (d2) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. It is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, even more preferably 0.8% by mass to 3.0% by mass, based on the total amount of.
共重合体（Ｘ）が構成単位（ｄ２）を含む場合、共重合体（Ｘ）中における構成単位（ｄ２）の含有量は、本発明の効果の向上の観点から、共重合体（Ｘ）の全量基準で好ましくは０．１質量％～１０質量％、より好ましくは０．５質量％～５質量％、更に好ましくは０．８質量％～３．０質量％である。 <Content of structural unit (d2)>
When the copolymer (X) contains the structural unit (d2), the content of the structural unit (d2) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. It is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, even more preferably 0.8% by mass to 3.0% by mass, based on the total amount of.
＜含有比率［（ａ）／（ｂ）］＞
本実施形態の共重合体（Ｘ）は、本発明の効果の向上の観点及び油溶性の観点から、上記構成単位（ａ）と上記構成単位（ｂ）との含有比率［（ａ）／（ｂ）］が、モル比で、好ましくは５０／５０～９０／１０、より好ましくは５５／４５～８５／１５である。 <Content ratio [(a)/(b)]>
The copolymer (X) of this embodiment has a content ratio of the structural unit (a) and the structural unit (b) [(a)/( b)] is preferably in a molar ratio of 50/50 to 90/10, more preferably 55/45 to 85/15.
本実施形態の共重合体（Ｘ）は、本発明の効果の向上の観点及び油溶性の観点から、上記構成単位（ａ）と上記構成単位（ｂ）との含有比率［（ａ）／（ｂ）］が、モル比で、好ましくは５０／５０～９０／１０、より好ましくは５５／４５～８５／１５である。 <Content ratio [(a)/(b)]>
The copolymer (X) of this embodiment has a content ratio of the structural unit (a) and the structural unit (b) [(a)/( b)] is preferably in a molar ratio of 50/50 to 90/10, more preferably 55/45 to 85/15.
＜共重合体（Ｘ）の物性等＞
（質量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ））
本実施形態の共重合体（Ｘ）の質量平均分子量（Ｍｗ）は、油溶性の確保の観点及び本発明の効果の向上の観点から、好ましくは５，０００～１００，０００、より好ましくは５，０００～７０，０００、更に好ましくは５，０００～５０，０００である。
ここで、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、共重合体（Ｘ）の質量平均分子量（Ｍｗ）は、油溶性の確保の観点及び本発明の効果の向上の観点から、好ましくは５，０００～１００，０００、より好ましくは５，０００～５０，０００、更に好ましくは５，０００～４０，０００である。
また、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、共重合体（Ｘ）の質量平均分子量（Ｍｗ）は、油溶性の確保の観点及び本発明の効果の向上の観点から、好ましくは５，０００～１００，０００、より好ましくは５，０００～７０，０００、更に好ましくは５，０００～５０，０００である。
本実施形態の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、本発明の効果をより発揮させやすくする観点から、好ましくは４．０以下、より好ましくは３．６以下、更に好ましくは３．４以下である。なお、本実施形態の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、１．０１以上であってもよく、１．３以上であってもよく、１．５以上であってもよい。
ここで、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、本発明の効果をより発揮させやすくする観点から、好ましくは３．５以下、より好ましくは３．０以下、更に好ましくは２．５以下である。なお、この場合の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、１．０１以上であってもよく、１．３以上であってもよく、１．５以上であってもよい。
また、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、本発明の効果をより向上させやすくする観点から、好ましくは４．０以下、より好ましくは３．６以下、更に好ましくは３．４以下である。なお、この場合の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、１．０１以上であってもよく、１．３以上であってもよく、１．５以上であってもよい。
質量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）は、後述する実施例に記載の方法にて測定又は算出される値である。 <Physical properties of copolymer (X), etc.>
(Mass average molecular weight (Mw), molecular weight distribution (Mw/Mn))
The mass average molecular weight (Mw) of the copolymer (X) of this embodiment is preferably 5,000 to 100,000, more preferably 5,000 to 100,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. ,000 to 70,000, more preferably 5,000 to 50,000.
Here, when the copolymer (X) of this embodiment includes the structural unit (a), the structural unit (b), and the structural unit (c), the mass average molecular weight (Mw) of the copolymer (X) is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 40,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. It is.
In addition, when the copolymer (X) of the present embodiment contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b), the structural unit When containing the unit (d1) and the structural unit (d2), the mass average molecular weight (Mw) of the copolymer (X) is preferably 5 from the viewpoint of ensuring oil solubility and improving the effect of the present invention. ,000 to 100,000, more preferably 5,000 to 70,000, even more preferably 5,000 to 50,000.
The molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably is 3.4 or less. The molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment may be 1.01 or more, 1.3 or more, or 1.5 or more. good.
Here, when the copolymer (X) of this embodiment contains the structural unit (a), the structural unit (b), and the structural unit (c), the molecular weight distribution (Mw/Mn ) is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, from the viewpoint of making it easier to exhibit the effects of the present invention. In addition, the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
In addition, when the copolymer (X) of this embodiment contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b), the structural unit When containing the unit (d1) and the structural unit (d2), the molecular weight distribution (Mw/Mn) of the copolymer (X) is preferably 4.0 or less in order to more easily improve the effects of the present invention. , more preferably 3.6 or less, still more preferably 3.4 or less. In addition, the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
The mass average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) are values measured or calculated by the method described in the Examples described later.
（質量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ））
本実施形態の共重合体（Ｘ）の質量平均分子量（Ｍｗ）は、油溶性の確保の観点及び本発明の効果の向上の観点から、好ましくは５，０００～１００，０００、より好ましくは５，０００～７０，０００、更に好ましくは５，０００～５０，０００である。
ここで、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、共重合体（Ｘ）の質量平均分子量（Ｍｗ）は、油溶性の確保の観点及び本発明の効果の向上の観点から、好ましくは５，０００～１００，０００、より好ましくは５，０００～５０，０００、更に好ましくは５，０００～４０，０００である。
また、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、共重合体（Ｘ）の質量平均分子量（Ｍｗ）は、油溶性の確保の観点及び本発明の効果の向上の観点から、好ましくは５，０００～１００，０００、より好ましくは５，０００～７０，０００、更に好ましくは５，０００～５０，０００である。
本実施形態の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、本発明の効果をより発揮させやすくする観点から、好ましくは４．０以下、より好ましくは３．６以下、更に好ましくは３．４以下である。なお、本実施形態の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、１．０１以上であってもよく、１．３以上であってもよく、１．５以上であってもよい。
ここで、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、本発明の効果をより発揮させやすくする観点から、好ましくは３．５以下、より好ましくは３．０以下、更に好ましくは２．５以下である。なお、この場合の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、１．０１以上であってもよく、１．３以上であってもよく、１．５以上であってもよい。
また、本実施形態の共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、本発明の効果をより向上させやすくする観点から、好ましくは４．０以下、より好ましくは３．６以下、更に好ましくは３．４以下である。なお、この場合の共重合体（Ｘ）の分子量分布（Ｍｗ／Ｍｎ）は、１．０１以上であってもよく、１．３以上であってもよく、１．５以上であってもよい。
質量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）は、後述する実施例に記載の方法にて測定又は算出される値である。 <Physical properties of copolymer (X), etc.>
(Mass average molecular weight (Mw), molecular weight distribution (Mw/Mn))
The mass average molecular weight (Mw) of the copolymer (X) of this embodiment is preferably 5,000 to 100,000, more preferably 5,000 to 100,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. ,000 to 70,000, more preferably 5,000 to 50,000.
Here, when the copolymer (X) of this embodiment includes the structural unit (a), the structural unit (b), and the structural unit (c), the mass average molecular weight (Mw) of the copolymer (X) is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 40,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. It is.
In addition, when the copolymer (X) of the present embodiment contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b), the structural unit When containing the unit (d1) and the structural unit (d2), the mass average molecular weight (Mw) of the copolymer (X) is preferably 5 from the viewpoint of ensuring oil solubility and improving the effect of the present invention. ,000 to 100,000, more preferably 5,000 to 70,000, even more preferably 5,000 to 50,000.
The molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably is 3.4 or less. The molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment may be 1.01 or more, 1.3 or more, or 1.5 or more. good.
Here, when the copolymer (X) of this embodiment contains the structural unit (a), the structural unit (b), and the structural unit (c), the molecular weight distribution (Mw/Mn ) is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, from the viewpoint of making it easier to exhibit the effects of the present invention. In addition, the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
In addition, when the copolymer (X) of this embodiment contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b), the structural unit When containing the unit (d1) and the structural unit (d2), the molecular weight distribution (Mw/Mn) of the copolymer (X) is preferably 4.0 or less in order to more easily improve the effects of the present invention. , more preferably 3.6 or less, still more preferably 3.4 or less. In addition, the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
The mass average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) are values measured or calculated by the method described in the Examples described later.
（重合態様）
本実施形態の共重合体（Ｘ）の重合態様は特に限定されず、ブロック共重合、ランダム共重合、ブロック／ランダム共重合のいずれであってもよい。これらの中でも、重合反応の容易さの観点から、ランダム共重合であることが好ましい。 (Polymerization mode)
The polymerization mode of the copolymer (X) of this embodiment is not particularly limited, and may be any of block copolymerization, random copolymerization, and block/random copolymerization. Among these, random copolymerization is preferred from the viewpoint of ease of polymerization reaction.
本実施形態の共重合体（Ｘ）の重合態様は特に限定されず、ブロック共重合、ランダム共重合、ブロック／ランダム共重合のいずれであってもよい。これらの中でも、重合反応の容易さの観点から、ランダム共重合であることが好ましい。 (Polymerization mode)
The polymerization mode of the copolymer (X) of this embodiment is not particularly limited, and may be any of block copolymerization, random copolymerization, and block/random copolymerization. Among these, random copolymerization is preferred from the viewpoint of ease of polymerization reaction.
［潤滑油用添加剤組成物の製造方法］
本実施形態の潤滑油用添加剤組成物の製造方法は、以下にいずれかの組み合わせでモノマーを重合させて、共重合体（Ｘ）を製造する工程（Ｓ）を含む。
（１）モノマー（Ａ）、モノマー（Ｂ）、及びモノマー（Ｃ）
（２）モノマー（Ａ）、モノマー（Ｂ）、モノマー（Ｄ１）、及びモノマー（Ｄ２）
（３）モノマー（Ａ）、モノマー（Ｂ）、及びモノマー（Ｄ１）
（４）モノマー（Ａ）、モノマー（Ｂ）、モノマー（Ｃ）、並びに、モノマー（Ｄ１）及び／又はモノマー（Ｄ２） [Method for producing additive composition for lubricating oil]
The method for producing an additive composition for lubricating oil according to the present embodiment includes a step (S) of producing a copolymer (X) by polymerizing monomers in one of the following combinations.
(1) Monomer (A), monomer (B), and monomer (C)
(2) Monomer (A), monomer (B), monomer (D1), and monomer (D2)
(3) Monomer (A), monomer (B), and monomer (D1)
(4) Monomer (A), monomer (B), monomer (C), and monomer (D1) and/or monomer (D2)
本実施形態の潤滑油用添加剤組成物の製造方法は、以下にいずれかの組み合わせでモノマーを重合させて、共重合体（Ｘ）を製造する工程（Ｓ）を含む。
（１）モノマー（Ａ）、モノマー（Ｂ）、及びモノマー（Ｃ）
（２）モノマー（Ａ）、モノマー（Ｂ）、モノマー（Ｄ１）、及びモノマー（Ｄ２）
（３）モノマー（Ａ）、モノマー（Ｂ）、及びモノマー（Ｄ１）
（４）モノマー（Ａ）、モノマー（Ｂ）、モノマー（Ｃ）、並びに、モノマー（Ｄ１）及び／又はモノマー（Ｄ２） [Method for producing additive composition for lubricating oil]
The method for producing an additive composition for lubricating oil according to the present embodiment includes a step (S) of producing a copolymer (X) by polymerizing monomers in one of the following combinations.
(1) Monomer (A), monomer (B), and monomer (C)
(2) Monomer (A), monomer (B), monomer (D1), and monomer (D2)
(3) Monomer (A), monomer (B), and monomer (D1)
(4) Monomer (A), monomer (B), monomer (C), and monomer (D1) and/or monomer (D2)
以下、共重合体（Ｘ）を製造する工程（Ｓ）について、詳細に説明する。
Hereinafter, the step (S) of producing the copolymer (X) will be explained in detail.
＜共重合体（Ｘ）を製造する工程（Ｓ）＞
共重合体（Ｘ）の製造方法（重合方法）は、特に限定されず、公知の方法のいずれかを適用して製造される。このような方法としては、例えば、乳化重合法、懸濁重合法、溶液重合法等が挙げられる。
ここで、本発明における共重合体（Ｘ）の用途、すなわち、潤滑油用添加剤組成物としての用途の観点から、共重合体（Ｘ）の製造方法（重合方法）としては、潤滑油基油に溶解する溶剤を溶媒として使用する溶液重合法を採用することが好ましい。 <Step (S) of producing copolymer (X)>
The method for producing the copolymer (X) (polymerization method) is not particularly limited, and the copolymer (X) is produced by applying any known method. Examples of such methods include emulsion polymerization, suspension polymerization, and solution polymerization.
Here, from the viewpoint of the use of the copolymer (X) in the present invention, that is, the use as an additive composition for lubricating oil, the method for producing the copolymer (X) (polymerization method) is based on a lubricating oil base. It is preferable to employ a solution polymerization method in which a solvent soluble in oil is used as a solvent.
共重合体（Ｘ）の製造方法（重合方法）は、特に限定されず、公知の方法のいずれかを適用して製造される。このような方法としては、例えば、乳化重合法、懸濁重合法、溶液重合法等が挙げられる。
ここで、本発明における共重合体（Ｘ）の用途、すなわち、潤滑油用添加剤組成物としての用途の観点から、共重合体（Ｘ）の製造方法（重合方法）としては、潤滑油基油に溶解する溶剤を溶媒として使用する溶液重合法を採用することが好ましい。 <Step (S) of producing copolymer (X)>
The method for producing the copolymer (X) (polymerization method) is not particularly limited, and the copolymer (X) is produced by applying any known method. Examples of such methods include emulsion polymerization, suspension polymerization, and solution polymerization.
Here, from the viewpoint of the use of the copolymer (X) in the present invention, that is, the use as an additive composition for lubricating oil, the method for producing the copolymer (X) (polymerization method) is based on a lubricating oil base. It is preferable to employ a solution polymerization method in which a solvent soluble in oil is used as a solvent.
（溶液重合法）
溶液重合法は、例えば、上記各モノマー、並びに溶媒及び開始剤を反応器に仕込み、反応器内を窒素置換した後、６０℃～１００℃で、２時間～１０時間、撹拌して反応させることにより行われる。反応器には、上記各モノマー以外の他のモノマーも任意に仕込まれる。 (Solution polymerization method)
In the solution polymerization method, for example, each of the above monomers, a solvent and an initiator are charged into a reactor, the inside of the reactor is replaced with nitrogen, and then the mixture is stirred and reacted at 60° C. to 100° C. for 2 hours to 10 hours. This is done by Monomers other than the above-mentioned monomers are also optionally charged into the reactor.
溶液重合法は、例えば、上記各モノマー、並びに溶媒及び開始剤を反応器に仕込み、反応器内を窒素置換した後、６０℃～１００℃で、２時間～１０時間、撹拌して反応させることにより行われる。反応器には、上記各モノマー以外の他のモノマーも任意に仕込まれる。 (Solution polymerization method)
In the solution polymerization method, for example, each of the above monomers, a solvent and an initiator are charged into a reactor, the inside of the reactor is replaced with nitrogen, and then the mixture is stirred and reacted at 60° C. to 100° C. for 2 hours to 10 hours. This is done by Monomers other than the above-mentioned monomers are also optionally charged into the reactor.
なお、共重合体（Ｘ）における各構成単位の含有割合は、通常、共重合体（Ｘ）を構成する各モノマーの比率（仕込み比）に一致する。したがって、上記各モノマーの配合割合は、共重合体（Ｘ）における上記各構成単位の含有割合を考慮して適宜決定される。
Note that the content ratio of each structural unit in the copolymer (X) usually corresponds to the ratio (feeding ratio) of each monomer constituting the copolymer (X). Therefore, the blending ratio of each of the above monomers is appropriately determined in consideration of the content ratio of each of the above structural units in the copolymer (X).
溶液重合法において使用される溶媒としては、例えば、メタノール、エタノール、プロパノール、２－プロパノール、ブタノール等のアルコール類；ベンゼン、トルエン、キシレン、ヘキサン等の炭化水素類；酢酸エチル、酢酸ブチル、酢酸イソブチル等のエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；メトキシブタノール、エトキシブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、ジオキサン等のエーテル類；鉱油；ポリ－α－オレフィン、エチレン－α－オレフィン共重合体、アルキルベンゼン、アルキルナフタレン、ポリフェニルエーテル、アルキル置換ジフェニルエーテル、ポリオールエステル、二塩基酸エステル、ヒンダードエステル、モノエステル、ＧＴＬ基油等の合成油が挙げられる。
これらは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of solvents used in the solution polymerization method include alcohols such as methanol, ethanol, propanol, 2-propanol, and butanol; hydrocarbons such as benzene, toluene, xylene, and hexane; ethyl acetate, butyl acetate, and isobutyl acetate. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ethers such as methoxybutanol, ethoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dioxane; Mineral oil; Poly-α- Examples include synthetic oils such as olefins, ethylene-α-olefin copolymers, alkylbenzenes, alkylnaphthalenes, polyphenyl ethers, alkyl-substituted diphenyl ethers, polyol esters, dibasic acid esters, hindered esters, monoesters, and GTL base oils.
These may be used alone or in combination of two or more.
これらは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of solvents used in the solution polymerization method include alcohols such as methanol, ethanol, propanol, 2-propanol, and butanol; hydrocarbons such as benzene, toluene, xylene, and hexane; ethyl acetate, butyl acetate, and isobutyl acetate. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ethers such as methoxybutanol, ethoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dioxane; Mineral oil; Poly-α- Examples include synthetic oils such as olefins, ethylene-α-olefin copolymers, alkylbenzenes, alkylnaphthalenes, polyphenyl ethers, alkyl-substituted diphenyl ethers, polyol esters, dibasic acid esters, hindered esters, monoesters, and GTL base oils.
These may be used alone or in combination of two or more.
溶液重合法において使用される開始剤としては、例えば、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２－アミジノプロパン）二塩酸塩、２，２’－アゾビス－（Ｎ，Ｎ－ジメチレンイソブチルアミジン）二塩酸塩、１，１’－アゾビス（シクロヘキシル－１－カルボニトリル）等のアゾ系開始剤；過酸化水素；過酸化ベンゾイル、ｔ－ブチルヒドロパーオキシド、クメンヒドロパーオキシド、メチルエチルケトンパーオキシド、過安息香酸等の有機過酸化物；過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩；過酸化水素－Ｆｅ２＋のレドックス開始剤；その他既存のラジカル開始剤が挙げられる。
Examples of initiators used in the solution polymerization method include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis- (N,N-dimethyleneisobutyramidine) dihydrochloride, azo initiators such as 1,1'-azobis(cyclohexyl-1-carbonitrile); hydrogen peroxide; benzoyl peroxide, t-butyl hydroperoxide, Organic peroxides such as cumene hydroperoxide, methyl ethyl ketone peroxide, and perbenzoic acid; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; hydrogen peroxide-Fe 2+ redox initiators; other existing radicals Examples include initiators.
なお、共重合体（Ｘ）の分子量は、公知の方法で制御される。例えば、反応温度、反応時間、開始剤の量、各モノマーの仕込み量、溶媒の種類、連鎖移動剤の使用等により、共重合体（Ｘ）の分子量を制御することができる。
Note that the molecular weight of the copolymer (X) is controlled by a known method. For example, the molecular weight of the copolymer (X) can be controlled by the reaction temperature, reaction time, amount of initiator, amount of each monomer charged, type of solvent, use of chain transfer agent, etc.
＜潤滑油用添加剤組成物中の共重合体（Ｘ）の含有量＞
本実施形態の潤滑油用添加剤組成物は、潤滑油基油に添加した際に本発明の効果をより発揮させやすくする観点から、共重合体（Ｘ）の含有量が、潤滑油用添加剤組成物の全量基準で、好ましくは５０質量％以上、より好ましくは６０質量％以上、更に好ましくは７０質量％以上、より更に好ましくは８０質量％以上、更になお好ましくは９０質量％以上、一層好ましくは９５質量％以上である。共重合体（Ｘ）の純度を考慮すると、共重合体（Ｘ）の含有量は、潤滑油用添加剤組成物の全量基準で、通常９９質量％未満である。
本実施形態の潤滑油用添加剤組成物は、潤滑油基油との溶解性や取扱性の観点から、希釈溶剤により希釈されていてもよい。なお、潤滑油用添加剤組成物中の共重合体（Ｘ）の含有量は、希釈溶剤を除いた、潤滑油用添加剤組成物中の有効成分の全量基準に対する含有量を意味する。 <Content of copolymer (X) in lubricating oil additive composition>
The additive composition for lubricating oil of the present embodiment has a content of copolymer (X) that can be added to Preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, based on the total amount of the agent composition. Preferably it is 95% by mass or more. Considering the purity of copolymer (X), the content of copolymer (X) is usually less than 99% by mass based on the total amount of the lubricating oil additive composition.
The lubricating oil additive composition of this embodiment may be diluted with a diluting solvent from the viewpoint of solubility with the lubricating base oil and ease of handling. The content of the copolymer (X) in the additive composition for lubricating oil means the content based on the total amount of active ingredients in the additive composition for lubricating oil, excluding the dilution solvent.
本実施形態の潤滑油用添加剤組成物は、潤滑油基油に添加した際に本発明の効果をより発揮させやすくする観点から、共重合体（Ｘ）の含有量が、潤滑油用添加剤組成物の全量基準で、好ましくは５０質量％以上、より好ましくは６０質量％以上、更に好ましくは７０質量％以上、より更に好ましくは８０質量％以上、更になお好ましくは９０質量％以上、一層好ましくは９５質量％以上である。共重合体（Ｘ）の純度を考慮すると、共重合体（Ｘ）の含有量は、潤滑油用添加剤組成物の全量基準で、通常９９質量％未満である。
本実施形態の潤滑油用添加剤組成物は、潤滑油基油との溶解性や取扱性の観点から、希釈溶剤により希釈されていてもよい。なお、潤滑油用添加剤組成物中の共重合体（Ｘ）の含有量は、希釈溶剤を除いた、潤滑油用添加剤組成物中の有効成分の全量基準に対する含有量を意味する。 <Content of copolymer (X) in lubricating oil additive composition>
The additive composition for lubricating oil of the present embodiment has a content of copolymer (X) that can be added to Preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, based on the total amount of the agent composition. Preferably it is 95% by mass or more. Considering the purity of copolymer (X), the content of copolymer (X) is usually less than 99% by mass based on the total amount of the lubricating oil additive composition.
The lubricating oil additive composition of this embodiment may be diluted with a diluting solvent from the viewpoint of solubility with the lubricating base oil and ease of handling. The content of the copolymer (X) in the additive composition for lubricating oil means the content based on the total amount of active ingredients in the additive composition for lubricating oil, excluding the dilution solvent.
＜潤滑油用添加剤組成物の用途＞
本実施形態の潤滑油用添加剤組成物は、耐摩耗性、極圧性、及び熱安定性に優れる。したがって、耐荷重添加剤として有用である。
したがって、本実施形態では、当該潤滑油用添加剤組成物を、耐荷重添加剤として使用する使用方法が提供される。 <Applications of additive composition for lubricating oil>
The lubricating oil additive composition of this embodiment has excellent wear resistance, extreme pressure properties, and thermal stability. Therefore, it is useful as a load-bearing additive.
Therefore, in this embodiment, a method of using the lubricating oil additive composition as a load-bearing additive is provided.
本実施形態の潤滑油用添加剤組成物は、耐摩耗性、極圧性、及び熱安定性に優れる。したがって、耐荷重添加剤として有用である。
したがって、本実施形態では、当該潤滑油用添加剤組成物を、耐荷重添加剤として使用する使用方法が提供される。 <Applications of additive composition for lubricating oil>
The lubricating oil additive composition of this embodiment has excellent wear resistance, extreme pressure properties, and thermal stability. Therefore, it is useful as a load-bearing additive.
Therefore, in this embodiment, a method of using the lubricating oil additive composition as a load-bearing additive is provided.
［潤滑油組成物］
本実施形態の潤滑油組成物は、共重合体（Ｘ）を含有する潤滑油用添加剤組成物と、潤滑油基油とを含有する。
潤滑油用添加剤組成物の含有量は、潤滑油用添加剤組成物の添加効果を良好に発揮させる観点から、共重合体（Ｘ）の樹脂分の含有量が、潤滑油組成物の全量基準で、好ましくは０．３質量％～１０質量％、より好ましくは０．６質量％～８．０質量％、更に好ましくは１．０質量％～６．０質量％となるように調整される。
また、潤滑油用添加剤組成物の含有量は、潤滑油用添加剤組成物の添加効果を良好に発揮させる観点から、共重合体（Ｘ）由来の硫黄量は、潤滑油組成物の全量基準で、好ましくは１０質量ｐｐｍ～３００質量ｐｐｍ、より好ましくは２０質量ｐｐｍ～２００質量ｐｐｍ、更に好ましくは３０質量ｐｐｍ～１５０質量ｐｐｍである。
また、共重合体（Ｘ）が、リン含有（メタ）アクリレート（Ｄ）由来の構成単位（ｄ）を含有する場合、同様の観点から、共重合体（Ｘ）由来のリン量は、潤滑油組成物の全量基準で、好ましくは５質量ｐｐｍ～１５０質量ｐｐｍ、より好ましくは１０質量ｐｐｍ～１００質量ｐｐｍ、更に好ましくは１５質量ｐｐｍ～７５質量ｐｐｍである。 [Lubricating oil composition]
The lubricating oil composition of this embodiment contains a lubricating oil additive composition containing the copolymer (X) and a lubricating oil base oil.
The content of the lubricating oil additive composition is determined such that the content of the resin component of the copolymer (X) is the same as the total amount of the lubricating oil composition, from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well. Based on the standard, it is preferably adjusted to 0.3% by mass to 10% by mass, more preferably 0.6% by mass to 8.0% by mass, and even more preferably 1.0% by mass to 6.0% by mass. Ru.
In addition, the content of the lubricating oil additive composition is determined from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well, and the amount of sulfur derived from the copolymer (X) is determined by the total amount of the lubricating oil composition. Based on the standard, it is preferably 10 mass ppm to 300 mass ppm, more preferably 20 mass ppm to 200 mass ppm, and still more preferably 30 mass ppm to 150 mass ppm.
In addition, when the copolymer (X) contains the structural unit (d) derived from the phosphorus-containing (meth)acrylate (D), from the same viewpoint, the amount of phosphorus derived from the copolymer (X) is Based on the total amount of the composition, preferably 5 ppm to 150 ppm by weight, more preferably 10 ppm to 100 ppm by weight, and still more preferably 15 ppm to 75 ppm by weight.
本実施形態の潤滑油組成物は、共重合体（Ｘ）を含有する潤滑油用添加剤組成物と、潤滑油基油とを含有する。
潤滑油用添加剤組成物の含有量は、潤滑油用添加剤組成物の添加効果を良好に発揮させる観点から、共重合体（Ｘ）の樹脂分の含有量が、潤滑油組成物の全量基準で、好ましくは０．３質量％～１０質量％、より好ましくは０．６質量％～８．０質量％、更に好ましくは１．０質量％～６．０質量％となるように調整される。
また、潤滑油用添加剤組成物の含有量は、潤滑油用添加剤組成物の添加効果を良好に発揮させる観点から、共重合体（Ｘ）由来の硫黄量は、潤滑油組成物の全量基準で、好ましくは１０質量ｐｐｍ～３００質量ｐｐｍ、より好ましくは２０質量ｐｐｍ～２００質量ｐｐｍ、更に好ましくは３０質量ｐｐｍ～１５０質量ｐｐｍである。
また、共重合体（Ｘ）が、リン含有（メタ）アクリレート（Ｄ）由来の構成単位（ｄ）を含有する場合、同様の観点から、共重合体（Ｘ）由来のリン量は、潤滑油組成物の全量基準で、好ましくは５質量ｐｐｍ～１５０質量ｐｐｍ、より好ましくは１０質量ｐｐｍ～１００質量ｐｐｍ、更に好ましくは１５質量ｐｐｍ～７５質量ｐｐｍである。 [Lubricating oil composition]
The lubricating oil composition of this embodiment contains a lubricating oil additive composition containing the copolymer (X) and a lubricating oil base oil.
The content of the lubricating oil additive composition is determined such that the content of the resin component of the copolymer (X) is the same as the total amount of the lubricating oil composition, from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well. Based on the standard, it is preferably adjusted to 0.3% by mass to 10% by mass, more preferably 0.6% by mass to 8.0% by mass, and even more preferably 1.0% by mass to 6.0% by mass. Ru.
In addition, the content of the lubricating oil additive composition is determined from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well, and the amount of sulfur derived from the copolymer (X) is determined by the total amount of the lubricating oil composition. Based on the standard, it is preferably 10 mass ppm to 300 mass ppm, more preferably 20 mass ppm to 200 mass ppm, and still more preferably 30 mass ppm to 150 mass ppm.
In addition, when the copolymer (X) contains the structural unit (d) derived from the phosphorus-containing (meth)acrylate (D), from the same viewpoint, the amount of phosphorus derived from the copolymer (X) is Based on the total amount of the composition, preferably 5 ppm to 150 ppm by weight, more preferably 10 ppm to 100 ppm by weight, and still more preferably 15 ppm to 75 ppm by weight.
＜潤滑油基油＞
潤滑油基油は、潤滑油組成物に用いられる一般的な基油を、特に制限なく用いることができる。具体的には、例えば、鉱油及び合成油からなる群から選択される１種以上が挙げられる。
潤滑油基油の１００℃における動粘度は１ｍｍ２／ｓ～５０ｍｍ２／ｓの範囲にあることが好ましく、２ｍｍ２／ｓ～３０ｍｍ２／ｓの範囲にあることがより好ましく、３ｍｍ２／ｓ～２０ｍｍ２／ｓの範囲にあることが更に好ましい。また、潤滑油基油の粘度指数は８０以上であることが好ましく、９０以上であることがより好ましく、１００以上であることがより更に好ましい。
潤滑油基油の動粘度及び粘度指数はＪＩＳ Ｋ２２８３：２０００に準じて測定又は算出される値である。 <Lubricant base oil>
As the lubricating base oil, any general base oil used in lubricating oil compositions can be used without particular limitation. Specifically, for example, one or more types selected from the group consisting of mineral oil and synthetic oil may be mentioned.
The kinematic viscosity at 100° C. of the lubricating base oil is preferably in the range of 1 mm 2 /s to 50 mm 2 /s, more preferably in the range of 2 mm 2 /s to 30 mm 2 /s, and more preferably 3 mm 2 /s. More preferably, the speed is in the range of ~20 mm 2 /s. Further, the viscosity index of the lubricating base oil is preferably 80 or more, more preferably 90 or more, and even more preferably 100 or more.
The kinematic viscosity and viscosity index of the lubricating base oil are values measured or calculated according to JIS K2283:2000.
潤滑油基油は、潤滑油組成物に用いられる一般的な基油を、特に制限なく用いることができる。具体的には、例えば、鉱油及び合成油からなる群から選択される１種以上が挙げられる。
潤滑油基油の１００℃における動粘度は１ｍｍ２／ｓ～５０ｍｍ２／ｓの範囲にあることが好ましく、２ｍｍ２／ｓ～３０ｍｍ２／ｓの範囲にあることがより好ましく、３ｍｍ２／ｓ～２０ｍｍ２／ｓの範囲にあることが更に好ましい。また、潤滑油基油の粘度指数は８０以上であることが好ましく、９０以上であることがより好ましく、１００以上であることがより更に好ましい。
潤滑油基油の動粘度及び粘度指数はＪＩＳ Ｋ２２８３：２０００に準じて測定又は算出される値である。 <Lubricant base oil>
As the lubricating base oil, any general base oil used in lubricating oil compositions can be used without particular limitation. Specifically, for example, one or more types selected from the group consisting of mineral oil and synthetic oil may be mentioned.
The kinematic viscosity at 100° C. of the lubricating base oil is preferably in the range of 1 mm 2 /s to 50 mm 2 /s, more preferably in the range of 2 mm 2 /s to 30 mm 2 /s, and more preferably 3 mm 2 /s. More preferably, the speed is in the range of ~20 mm 2 /s. Further, the viscosity index of the lubricating base oil is preferably 80 or more, more preferably 90 or more, and even more preferably 100 or more.
The kinematic viscosity and viscosity index of the lubricating base oil are values measured or calculated according to JIS K2283:2000.
潤滑油基油の具体例を以下に挙げる。
鉱油としては、例えば、パラフィン基原油、中間基原油、又はナフテン基原油を常圧蒸留及び／又は減圧蒸留して得られる留出油；当該留出油を常法に従って精製することによって得られる精製油；等が挙げられる。精製油を得るための精製方法としては、例えば、溶剤脱ろう処理、水素化異性化処理、水素化仕上げ処理、白土処理等が挙げられる。
合成油としては、例えば、炭化水素系油、芳香族系油、エステル系油、エーテル系油等が挙げられる。また、合成油としては、天然ガスからフィッシャー・トロプシュ法等により製造されるワックス（ＧＴＬワックス，Ｇａｓ Ｔｏ Ｌｉｑｕｉｄｓ ＷＡＸ）を異性化することで得られるＧＴＬ（Ｇａｓ Ｔｏ Ｌｉｑｕｉｄｓ）を用いてもよい。 Specific examples of lubricant base oils are listed below.
Mineral oils include, for example, distillate oil obtained by atmospheric distillation and/or vacuum distillation of paraffinic crude oil, intermediate crude oil, or naphthenic crude oil; refined oil obtained by refining the distillate oil according to a conventional method; oil; etc. Examples of the purification method for obtaining refined oil include solvent dewaxing treatment, hydroisomerization treatment, hydrofinishing treatment, clay treatment, and the like.
Examples of synthetic oils include hydrocarbon oils, aromatic oils, ester oils, and ether oils. Further, as the synthetic oil, GTL (Gas To Liquids) obtained by isomerizing wax (GTL wax, Gas To Liquids WAX) produced from natural gas by the Fischer-Tropsch method or the like may be used.
鉱油としては、例えば、パラフィン基原油、中間基原油、又はナフテン基原油を常圧蒸留及び／又は減圧蒸留して得られる留出油；当該留出油を常法に従って精製することによって得られる精製油；等が挙げられる。精製油を得るための精製方法としては、例えば、溶剤脱ろう処理、水素化異性化処理、水素化仕上げ処理、白土処理等が挙げられる。
合成油としては、例えば、炭化水素系油、芳香族系油、エステル系油、エーテル系油等が挙げられる。また、合成油としては、天然ガスからフィッシャー・トロプシュ法等により製造されるワックス（ＧＴＬワックス，Ｇａｓ Ｔｏ Ｌｉｑｕｉｄｓ ＷＡＸ）を異性化することで得られるＧＴＬ（Ｇａｓ Ｔｏ Ｌｉｑｕｉｄｓ）を用いてもよい。 Specific examples of lubricant base oils are listed below.
Mineral oils include, for example, distillate oil obtained by atmospheric distillation and/or vacuum distillation of paraffinic crude oil, intermediate crude oil, or naphthenic crude oil; refined oil obtained by refining the distillate oil according to a conventional method; oil; etc. Examples of the purification method for obtaining refined oil include solvent dewaxing treatment, hydroisomerization treatment, hydrofinishing treatment, clay treatment, and the like.
Examples of synthetic oils include hydrocarbon oils, aromatic oils, ester oils, and ether oils. Further, as the synthetic oil, GTL (Gas To Liquids) obtained by isomerizing wax (GTL wax, Gas To Liquids WAX) produced from natural gas by the Fischer-Tropsch method or the like may be used.
＜他の添加剤＞
本実施形態の潤滑油組成物は、上記潤滑油用添加剤組成物の効果を阻害しない範囲で、酸化防止剤、油性剤、清浄分散剤、粘度指数向上剤、防錆剤、金属不活性化剤、及び消泡剤等の他の添加剤を含有してもよい。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
また、本実施形態では、共重合体（Ｘ）を含有する潤滑油用添加剤組成物とともに、共重合体（Ｘ）を含有する潤滑油用添加剤組成物以外の他の添加剤として、酸化防止剤、油性剤、清浄分散剤、粘度指数向上剤、防錆剤、金属不活性化剤、及び消泡剤等から選択される１種以上の添加剤を含有する潤滑油組成物用の添加剤パッケージも提供される。 <Other additives>
The lubricating oil composition of the present embodiment contains an antioxidant, an oily agent, a detergent dispersant, a viscosity index improver, a rust preventive agent, and a metal deactivator within a range that does not inhibit the effects of the above-mentioned lubricating oil additive composition. Other additives such as antifoaming agents and antifoaming agents may also be included. These may be used alone or in combination of two or more.
In addition, in this embodiment, in addition to the lubricating oil additive composition containing the copolymer (X), oxidized Addition for lubricating oil compositions containing one or more additives selected from inhibitors, oiliness agents, detergent dispersants, viscosity index improvers, rust inhibitors, metal deactivators, antifoaming agents, etc. A drug package is also provided.
本実施形態の潤滑油組成物は、上記潤滑油用添加剤組成物の効果を阻害しない範囲で、酸化防止剤、油性剤、清浄分散剤、粘度指数向上剤、防錆剤、金属不活性化剤、及び消泡剤等の他の添加剤を含有してもよい。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
また、本実施形態では、共重合体（Ｘ）を含有する潤滑油用添加剤組成物とともに、共重合体（Ｘ）を含有する潤滑油用添加剤組成物以外の他の添加剤として、酸化防止剤、油性剤、清浄分散剤、粘度指数向上剤、防錆剤、金属不活性化剤、及び消泡剤等から選択される１種以上の添加剤を含有する潤滑油組成物用の添加剤パッケージも提供される。 <Other additives>
The lubricating oil composition of the present embodiment contains an antioxidant, an oily agent, a detergent dispersant, a viscosity index improver, a rust preventive agent, and a metal deactivator within a range that does not inhibit the effects of the above-mentioned lubricating oil additive composition. Other additives such as antifoaming agents and antifoaming agents may also be included. These may be used alone or in combination of two or more.
In addition, in this embodiment, in addition to the lubricating oil additive composition containing the copolymer (X), oxidized Addition for lubricating oil compositions containing one or more additives selected from inhibitors, oiliness agents, detergent dispersants, viscosity index improvers, rust inhibitors, metal deactivators, antifoaming agents, etc. A drug package is also provided.
（酸化防止剤）
酸化防止剤としては、従来の潤滑油組成物に使用されているアミン系酸化防止剤、フェノール系酸化防止剤等を使用することができる。これらの酸化防止剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
アミン系酸化防止剤としては、例えば、モノオクチルジフェニルアミン及びモノノニルジフェニルアミン等のモノアルキルジフェニルアミン系化合物；４，４’－ジブチルジフェニルアミン、４，４’－ジペンチルジフェニルアミン、４，４’－ジヘキシルジフェニルアミン、４，４’－ジヘプチルジフェニルアミン、４，４’－ジオクチルジフェニルアミン、及び４，４’－ジノニルジフェニルアミン等のジアルキルジフェニルアミン系化合物；テトラブチルジフェニルアミン、テトラヘキシルジフェニルアミン、テトラオクチルジフェニルアミン、及びテトラノニルジフェニルアミン等のポリアルキルジフェニルアミン系化合物；α－ナフチルアミン、フェニル－α－ナフチルアミン、ブチルフェニル－α－ナフチルアミン、ペンチルフェニル－α－ナフチルアミン、ヘキシルフェニル－α－ナフチルアミン、ヘプチルフェニル－α－ナフチルアミン、オクチルフェニル－α－ナフチルアミン、及びノニルフェニル－α－ナフチルアミン等のナフチルアミン系化合物が挙げられる。
フェノール系酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール及び２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール等のモノフェノール系化合物；４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）及び２，２’－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）等のビスフェノール系化合物が挙げられる。
酸化防止剤の含有量は、潤滑油組成物の酸化安定性を保つのに必要な最低量を加えれば良い。具体的には、例えば、潤滑油組成物の全量基準で、０．０１～１質量％が好ましい。 (Antioxidant)
As the antioxidant, amine antioxidants, phenolic antioxidants, etc. used in conventional lubricating oil compositions can be used. These antioxidants may be used alone or in combination of two or more.
Examples of amine antioxidants include monoalkyldiphenylamine compounds such as monooctyldiphenylamine and monononyldiphenylamine; 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, , 4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; dialkyldiphenylamine compounds such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; Polyalkyldiphenylamine compounds; α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine , and naphthylamine compounds such as nonylphenyl-α-naphthylamine.
Examples of phenolic antioxidants include monophenolic compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; 4,4' -methylenebis(2,6-di-tert-butylphenol) and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) and other bisphenol compounds.
The content of the antioxidant may be the minimum amount necessary to maintain the oxidative stability of the lubricating oil composition. Specifically, for example, it is preferably 0.01 to 1% by mass based on the total amount of the lubricating oil composition.
酸化防止剤としては、従来の潤滑油組成物に使用されているアミン系酸化防止剤、フェノール系酸化防止剤等を使用することができる。これらの酸化防止剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
アミン系酸化防止剤としては、例えば、モノオクチルジフェニルアミン及びモノノニルジフェニルアミン等のモノアルキルジフェニルアミン系化合物；４，４’－ジブチルジフェニルアミン、４，４’－ジペンチルジフェニルアミン、４，４’－ジヘキシルジフェニルアミン、４，４’－ジヘプチルジフェニルアミン、４，４’－ジオクチルジフェニルアミン、及び４，４’－ジノニルジフェニルアミン等のジアルキルジフェニルアミン系化合物；テトラブチルジフェニルアミン、テトラヘキシルジフェニルアミン、テトラオクチルジフェニルアミン、及びテトラノニルジフェニルアミン等のポリアルキルジフェニルアミン系化合物；α－ナフチルアミン、フェニル－α－ナフチルアミン、ブチルフェニル－α－ナフチルアミン、ペンチルフェニル－α－ナフチルアミン、ヘキシルフェニル－α－ナフチルアミン、ヘプチルフェニル－α－ナフチルアミン、オクチルフェニル－α－ナフチルアミン、及びノニルフェニル－α－ナフチルアミン等のナフチルアミン系化合物が挙げられる。
フェノール系酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール及び２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール等のモノフェノール系化合物；４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）及び２，２’－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）等のビスフェノール系化合物が挙げられる。
酸化防止剤の含有量は、潤滑油組成物の酸化安定性を保つのに必要な最低量を加えれば良い。具体的には、例えば、潤滑油組成物の全量基準で、０．０１～１質量％が好ましい。 (Antioxidant)
As the antioxidant, amine antioxidants, phenolic antioxidants, etc. used in conventional lubricating oil compositions can be used. These antioxidants may be used alone or in combination of two or more.
Examples of amine antioxidants include monoalkyldiphenylamine compounds such as monooctyldiphenylamine and monononyldiphenylamine; 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, , 4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; dialkyldiphenylamine compounds such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; Polyalkyldiphenylamine compounds; α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine , and naphthylamine compounds such as nonylphenyl-α-naphthylamine.
Examples of phenolic antioxidants include monophenolic compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; 4,4' -methylenebis(2,6-di-tert-butylphenol) and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) and other bisphenol compounds.
The content of the antioxidant may be the minimum amount necessary to maintain the oxidative stability of the lubricating oil composition. Specifically, for example, it is preferably 0.01 to 1% by mass based on the total amount of the lubricating oil composition.
（油性剤）
油性剤としては、脂肪族アルコール；脂肪酸及び脂肪酸金属塩等の脂肪酸化合物；ポリオールエステル、ソルビタンエステル、及びグリセライド等のエステル化合物；脂肪族アミン等のアミン化合物等を挙げることができる。
油性剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．１～２０質量％であり、好ましくは０．５～１０質量％である。 (Oil-based agent)
Examples of the oily agent include aliphatic alcohols; fatty acid compounds such as fatty acids and fatty acid metal salts; ester compounds such as polyol esters, sorbitan esters, and glycerides; and amine compounds such as aliphatic amines.
The content of the oily agent is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
油性剤としては、脂肪族アルコール；脂肪酸及び脂肪酸金属塩等の脂肪酸化合物；ポリオールエステル、ソルビタンエステル、及びグリセライド等のエステル化合物；脂肪族アミン等のアミン化合物等を挙げることができる。
油性剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．１～２０質量％であり、好ましくは０．５～１０質量％である。 (Oil-based agent)
Examples of the oily agent include aliphatic alcohols; fatty acid compounds such as fatty acids and fatty acid metal salts; ester compounds such as polyol esters, sorbitan esters, and glycerides; and amine compounds such as aliphatic amines.
The content of the oily agent is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
（清浄分散剤）
清浄分散剤としては、金属スルホネート、金属サリチレート、金属フェネート、及びコハク酸イミド等が挙げられる。
清浄分散剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０１～１０質量％であり、好ましくは０．１～５質量％である。 (Cleaning dispersant)
Detergent-dispersing agents include metal sulfonates, metal salicylates, metal phenates, succinimides, and the like.
The content of the detergent dispersant is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
清浄分散剤としては、金属スルホネート、金属サリチレート、金属フェネート、及びコハク酸イミド等が挙げられる。
清浄分散剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０１～１０質量％であり、好ましくは０．１～５質量％である。 (Cleaning dispersant)
Detergent-dispersing agents include metal sulfonates, metal salicylates, metal phenates, succinimides, and the like.
The content of the detergent dispersant is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
（粘度指数向上剤）
粘度指数向上剤としては、例えば、ポリメタクリレート、分散型ポリメタクリレート、オレフィン系共重合体（例えば、エチレン－プロピレン共重合体等）、分散型オレフィン系共重合体、スチレン系共重合体（例えば、スチレン－ジエン水素化共重合体等）等が挙げられる。
粘度指数向上剤の含有量は、好ましくは、潤滑油組成物の全量基準で、０．３～５質量％である。 (Viscosity index improver)
Examples of the viscosity index improver include polymethacrylate, dispersed polymethacrylate, olefin copolymer (e.g., ethylene-propylene copolymer, etc.), dispersed olefin copolymer, styrene copolymer (e.g., styrene-diene hydrogenated copolymers, etc.).
The content of the viscosity index improver is preferably 0.3 to 5% by mass, based on the total amount of the lubricating oil composition.
粘度指数向上剤としては、例えば、ポリメタクリレート、分散型ポリメタクリレート、オレフィン系共重合体（例えば、エチレン－プロピレン共重合体等）、分散型オレフィン系共重合体、スチレン系共重合体（例えば、スチレン－ジエン水素化共重合体等）等が挙げられる。
粘度指数向上剤の含有量は、好ましくは、潤滑油組成物の全量基準で、０．３～５質量％である。 (Viscosity index improver)
Examples of the viscosity index improver include polymethacrylate, dispersed polymethacrylate, olefin copolymer (e.g., ethylene-propylene copolymer, etc.), dispersed olefin copolymer, styrene copolymer (e.g., styrene-diene hydrogenated copolymers, etc.).
The content of the viscosity index improver is preferably 0.3 to 5% by mass, based on the total amount of the lubricating oil composition.
（防錆剤）
防錆剤としては、金属系スルホネート、コハク酸エステル、並びにアルキルアミン及びモノイソプロパノールアミンなどのアルカノールアミン等を挙げることができる。
防錆剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０１～５質量％であり、好ましくは０．０３～３質量％である。 (anti-rust)
Examples of the rust preventive agent include metal sulfonates, succinic acid esters, and alkanolamines such as alkylamines and monoisopropanolamines.
The content of the rust inhibitor is usually 0.01 to 5% by mass, preferably 0.03 to 3% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
防錆剤としては、金属系スルホネート、コハク酸エステル、並びにアルキルアミン及びモノイソプロパノールアミンなどのアルカノールアミン等を挙げることができる。
防錆剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０１～５質量％であり、好ましくは０．０３～３質量％である。 (anti-rust)
Examples of the rust preventive agent include metal sulfonates, succinic acid esters, and alkanolamines such as alkylamines and monoisopropanolamines.
The content of the rust inhibitor is usually 0.01 to 5% by mass, preferably 0.03 to 3% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
（金属不活性剤）
金属不活性剤としては、ベンゾトリアゾール及びチアジアゾール等を挙げることができる。
金属不活性剤の好ましい含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０１～５質量％であり、好ましくは０．０１～１質量％である。 (metal deactivator)
Examples of metal deactivators include benzotriazole and thiadiazole.
From the viewpoint of the effect of addition, the preferred content of the metal deactivator is usually 0.01 to 5% by mass, preferably 0.01 to 1% by mass, based on the total amount of the lubricating oil composition.
金属不活性剤としては、ベンゾトリアゾール及びチアジアゾール等を挙げることができる。
金属不活性剤の好ましい含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０１～５質量％であり、好ましくは０．０１～１質量％である。 (metal deactivator)
Examples of metal deactivators include benzotriazole and thiadiazole.
From the viewpoint of the effect of addition, the preferred content of the metal deactivator is usually 0.01 to 5% by mass, preferably 0.01 to 1% by mass, based on the total amount of the lubricating oil composition.
（消泡剤）
消泡剤としては、メチルシリコーン油、フルオロシリコーン油、及びポリアクリレート等を挙げることができる。
消泡剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０００５～０．０１質量％である。 (antifoaming agent)
Examples of antifoaming agents include methyl silicone oil, fluorosilicone oil, and polyacrylate.
The content of the antifoaming agent is usually 0.0005 to 0.01% by mass based on the total amount of the lubricating oil composition from the viewpoint of the effect of addition.
消泡剤としては、メチルシリコーン油、フルオロシリコーン油、及びポリアクリレート等を挙げることができる。
消泡剤の含有量は、添加効果の点から、潤滑油組成物の全量基準で、通常０．０００５～０．０１質量％である。 (antifoaming agent)
Examples of antifoaming agents include methyl silicone oil, fluorosilicone oil, and polyacrylate.
The content of the antifoaming agent is usually 0.0005 to 0.01% by mass based on the total amount of the lubricating oil composition from the viewpoint of the effect of addition.
＜潤滑油組成物の物性等＞
（動粘度、粘度指数）
本実施形態の潤滑油組成物の１００℃動粘度は、好ましくは１．０ｍｍ２／ｓ～５０ｍｍ２／ｓ、より好ましくは２．０ｍｍ２／ｓ～３０ｍｍ２／ｓ、更に好ましくは３．０ｍｍ２／ｓ～２０ｍｍ２／ｓである。
本実施形態の潤滑油組成物の粘度指数は、好ましくは９０以上、より好ましくは１００以上、更に好ましくは１１０以上である。
潤滑油組成物の動粘度及び粘度指数は、ＪＩＳ Ｋ２２８３：２０００に準じて測定又は算出される値である。 <Physical properties, etc. of lubricating oil composition>
(Kinematic viscosity, viscosity index)
The 100°C kinematic viscosity of the lubricating oil composition of the present embodiment is preferably 1.0 mm 2 /s to 50 mm 2 /s, more preferably 2.0 mm 2 / s to 30 mm 2 /s, even more preferably 3.0 mm. 2 /s to 20 mm 2 /s.
The viscosity index of the lubricating oil composition of this embodiment is preferably 90 or more, more preferably 100 or more, and still more preferably 110 or more.
The kinematic viscosity and viscosity index of the lubricating oil composition are values measured or calculated according to JIS K2283:2000.
（動粘度、粘度指数）
本実施形態の潤滑油組成物の１００℃動粘度は、好ましくは１．０ｍｍ２／ｓ～５０ｍｍ２／ｓ、より好ましくは２．０ｍｍ２／ｓ～３０ｍｍ２／ｓ、更に好ましくは３．０ｍｍ２／ｓ～２０ｍｍ２／ｓである。
本実施形態の潤滑油組成物の粘度指数は、好ましくは９０以上、より好ましくは１００以上、更に好ましくは１１０以上である。
潤滑油組成物の動粘度及び粘度指数は、ＪＩＳ Ｋ２２８３：２０００に準じて測定又は算出される値である。 <Physical properties, etc. of lubricating oil composition>
(Kinematic viscosity, viscosity index)
The 100°C kinematic viscosity of the lubricating oil composition of the present embodiment is preferably 1.0 mm 2 /s to 50 mm 2 /s, more preferably 2.0 mm 2 / s to 30 mm 2 /s, even more preferably 3.0 mm. 2 /s to 20 mm 2 /s.
The viscosity index of the lubricating oil composition of this embodiment is preferably 90 or more, more preferably 100 or more, and still more preferably 110 or more.
The kinematic viscosity and viscosity index of the lubricating oil composition are values measured or calculated according to JIS K2283:2000.
（耐摩耗性（新油））
本実施形態の潤滑油組成物（新油）は、後述する実施例に記載のシェル摩耗試験による摩耗痕径が、好ましくは０．５５ｍｍ以下、より好ましくは０．５３ｍｍ以下、更に好ましくは０．５２ｍｍ以下である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５３ｍｍ以下、更に好ましくは０．５２ｍｍ以下である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下、より更に好ましくは０．４３ｍｍ以下である。 (Abrasion resistance (new oil))
The lubricating oil composition (new oil) of the present embodiment has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.53 mm or less, and still more preferably 0. It is 52 mm or less.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.53 mm or less, even more preferably 0.52 mm or less.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less.
本実施形態の潤滑油組成物（新油）は、後述する実施例に記載のシェル摩耗試験による摩耗痕径が、好ましくは０．５５ｍｍ以下、より好ましくは０．５３ｍｍ以下、更に好ましくは０．５２ｍｍ以下である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５３ｍｍ以下、更に好ましくは０．５２ｍｍ以下である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下、より更に好ましくは０．４３ｍｍ以下である。 (Abrasion resistance (new oil))
The lubricating oil composition (new oil) of the present embodiment has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.53 mm or less, and still more preferably 0. It is 52 mm or less.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.53 mm or less, even more preferably 0.52 mm or less.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less.
（耐摩耗性（ＩＳＯＴ試験後の油））
本実施形態の潤滑油組成物（ＩＳＯＴ試験後の油）は、後述する実施例に記載のシェル摩耗試験による摩耗痕径が、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下、より更に好ましくは０．４３ｍｍ以下である。 なお、ＩＳＯＴ試験後の油とは、実施例に記載の方法で行われるＩＳＯＴ試験による強制劣化後の油を意味する。 (Abrasion resistance (oil after ISOT test))
The lubricating oil composition of this embodiment (the oil after the ISOT test) has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.50 mm or less, and even more preferably is 0.45 mm or less.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.50 mm or less, even more preferably 0.45 mm or less.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less. Note that the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
本実施形態の潤滑油組成物（ＩＳＯＴ試験後の油）は、後述する実施例に記載のシェル摩耗試験による摩耗痕径が、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該摩耗痕径は、好ましくは０．５５ｍｍ以下、より好ましくは０．５０ｍｍ以下、更に好ましくは０．４５ｍｍ以下、より更に好ましくは０．４３ｍｍ以下である。 なお、ＩＳＯＴ試験後の油とは、実施例に記載の方法で行われるＩＳＯＴ試験による強制劣化後の油を意味する。 (Abrasion resistance (oil after ISOT test))
The lubricating oil composition of this embodiment (the oil after the ISOT test) has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.50 mm or less, and even more preferably is 0.45 mm or less.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.50 mm or less, even more preferably 0.45 mm or less.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less. Note that the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
（極圧性（新油））
本実施形態の潤滑油組成物（新油）は、後述する実施例に記載のシェル四球試験耐荷重性（ＥＰ）試験による最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上である。
また、同試験による融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上、更に好ましくは６１８Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上、更に好ましくは１９６１Ｎ以上である。 (Extreme pressure (new oil))
The lubricating oil composition (new oil) of the present embodiment has a maximum non-seizure load (LNL) of preferably 392N or more, more preferably 490N, as determined by the shell four-ball test load resistance (EP) test described in the Examples below. That's all.
Further, the fusion load (WL) according to the same test is preferably 1236N or more.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the maximum non-seizure load (LNL) is Preferably it is 392N or more, more preferably 490N or more. Further, the fusion load (WL) is preferably 1236N or more.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more. Further, the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
本実施形態の潤滑油組成物（新油）は、後述する実施例に記載のシェル四球試験耐荷重性（ＥＰ）試験による最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上である。
また、同試験による融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上、更に好ましくは６１８Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上、更に好ましくは１９６１Ｎ以上である。 (Extreme pressure (new oil))
The lubricating oil composition (new oil) of the present embodiment has a maximum non-seizure load (LNL) of preferably 392N or more, more preferably 490N, as determined by the shell four-ball test load resistance (EP) test described in the Examples below. That's all.
Further, the fusion load (WL) according to the same test is preferably 1236N or more.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the maximum non-seizure load (LNL) is Preferably it is 392N or more, more preferably 490N or more. Further, the fusion load (WL) is preferably 1236N or more.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more. Further, the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
（極圧性（ＩＳＯＴ試験後の油））
本実施形態の潤滑油組成物（ＩＳＯＴ試験後の油）は、後述する実施例に記載のシェル四球試験耐荷重性（ＥＰ）試験による最大非焼付荷重（ＬＮＬ）が、好ましくは４９０Ｎ以上である。
また、同試験による融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは４９０Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上、更に好ましくは６１８Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上、更に好ましくは１９６１Ｎ以上である。
なお、ＩＳＯＴ試験後の油とは、実施例に記載の方法で行われるＩＳＯＴ試験による強制劣化後の油を意味する。 (Extreme pressure property (oil after ISOT test))
The lubricating oil composition (oil after ISOT test) of the present embodiment preferably has a maximum non-seizure load (LNL) of 490 N or more as determined by the shell four-ball test load resistance (EP) test described in the Examples below. .
Further, the fusion load (WL) according to the same test is preferably 1236N or more, more preferably 1569N or more.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the maximum non-seizure load (LNL) is Preferably it is 490N or more. Further, the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more. Further, the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
Note that the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
本実施形態の潤滑油組成物（ＩＳＯＴ試験後の油）は、後述する実施例に記載のシェル四球試験耐荷重性（ＥＰ）試験による最大非焼付荷重（ＬＮＬ）が、好ましくは４９０Ｎ以上である。
また、同試験による融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは４９０Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、当該最大非焼付荷重（ＬＮＬ）が、好ましくは３９２Ｎ以上、より好ましくは４９０Ｎ以上、更に好ましくは６１８Ｎ以上である。また、当該融着荷重（ＷＬ）が、好ましくは１２３６Ｎ以上、より好ましくは１５６９Ｎ以上、更に好ましくは１９６１Ｎ以上である。
なお、ＩＳＯＴ試験後の油とは、実施例に記載の方法で行われるＩＳＯＴ試験による強制劣化後の油を意味する。 (Extreme pressure property (oil after ISOT test))
The lubricating oil composition (oil after ISOT test) of the present embodiment preferably has a maximum non-seizure load (LNL) of 490 N or more as determined by the shell four-ball test load resistance (EP) test described in the Examples below. .
Further, the fusion load (WL) according to the same test is preferably 1236N or more, more preferably 1569N or more.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the maximum non-seizure load (LNL) is Preferably it is 490N or more. Further, the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more. Further, the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
Note that the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
（熱安定性）
本実施形態の潤滑油組成物は、後述する実施例に記載のＩＳＯＴ試験後において、スラッジの発生量が、好ましくは１０ｍｇ／１００ｍＬ未満である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、スラッジの発生量が、好ましくは１０ｍｇ／１００ｍＬ未満、より好ましくは７．０ｍｇ／１００ｍＬ未満、更に好ましくは５．０ｍｇ／１００ｍＬ未満である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、スラッジの発生量が、好ましくは１０ｍｇ／１００ｍＬ未満である。 (thermal stability)
The lubricating oil composition of the present embodiment preferably generates less than 10 mg/100 mL of sludge after the ISOT test described in Examples described below.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the amount of sludge generated is preferably 10 mg/ It is less than 100 mL, more preferably less than 7.0 mg/100 mL, even more preferably less than 5.0 mg/100 mL.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the amount of sludge generated is preferably less than 10 mg/100 mL.
本実施形態の潤滑油組成物は、後述する実施例に記載のＩＳＯＴ試験後において、スラッジの発生量が、好ましくは１０ｍｇ／１００ｍＬ未満である。
ここで、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｃ）を含む場合、スラッジの発生量が、好ましくは１０ｍｇ／１００ｍＬ未満、より好ましくは７．０ｍｇ／１００ｍＬ未満、更に好ましくは５．０ｍｇ／１００ｍＬ未満である。
また、潤滑油組成物に含まれる共重合体（Ｘ）が、構成単位（ａ）、構成単位（ｂ）、及び構成単位（ｄ１）を含む場合、又は構成単位（ａ）、構成単位（ｂ）、構成単位（ｄ１）、及び構成単位（ｄ２）を含む場合、スラッジの発生量が、好ましくは１０ｍｇ／１００ｍＬ未満である。 (thermal stability)
The lubricating oil composition of the present embodiment preferably generates less than 10 mg/100 mL of sludge after the ISOT test described in Examples described below.
Here, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (c), the amount of sludge generated is preferably 10 mg/ It is less than 100 mL, more preferably less than 7.0 mg/100 mL, even more preferably less than 5.0 mg/100 mL.
In addition, when the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2), the amount of sludge generated is preferably less than 10 mg/100 mL.
［潤滑油組成物の製造方法］
本実施形態の潤滑油組成物の製造方法は、特に制限されない。
例えば、本実施形態の潤滑油組成物の製造方法は、上記潤滑油用添加剤組成物と、潤滑油基油と、を混合する工程を含む。
上記潤滑油用添加剤組成物と潤滑油基油とを混合する方法としては、特に制限はないが、例えば、潤滑油基油に、上記潤滑油用添加剤組成物を配合する工程を有する方法が挙げられる。その際、上記その他の添加剤も同時に配合してもよい。また、各成分は、希釈油等を加えて溶液（分散体）の形態とした上で配合してもよい。各成分を配合した後、公知の方法により、撹拌して均一に分散させることが好ましい。 [Method for producing lubricating oil composition]
The method for producing the lubricating oil composition of this embodiment is not particularly limited.
For example, the method for producing a lubricating oil composition of the present embodiment includes a step of mixing the lubricating oil additive composition and a lubricating oil base oil.
There are no particular restrictions on the method for mixing the lubricating oil additive composition and the lubricating oil base oil, but for example, a method that includes a step of blending the lubricating oil additive composition with the lubricating oil base oil can be mentioned. At that time, the other additives mentioned above may also be added at the same time. Further, each component may be blended in the form of a solution (dispersion) by adding diluting oil or the like. After blending each component, it is preferable to stir and disperse uniformly by a known method.
本実施形態の潤滑油組成物の製造方法は、特に制限されない。
例えば、本実施形態の潤滑油組成物の製造方法は、上記潤滑油用添加剤組成物と、潤滑油基油と、を混合する工程を含む。
上記潤滑油用添加剤組成物と潤滑油基油とを混合する方法としては、特に制限はないが、例えば、潤滑油基油に、上記潤滑油用添加剤組成物を配合する工程を有する方法が挙げられる。その際、上記その他の添加剤も同時に配合してもよい。また、各成分は、希釈油等を加えて溶液（分散体）の形態とした上で配合してもよい。各成分を配合した後、公知の方法により、撹拌して均一に分散させることが好ましい。 [Method for producing lubricating oil composition]
The method for producing the lubricating oil composition of this embodiment is not particularly limited.
For example, the method for producing a lubricating oil composition of the present embodiment includes a step of mixing the lubricating oil additive composition and a lubricating oil base oil.
There are no particular restrictions on the method for mixing the lubricating oil additive composition and the lubricating oil base oil, but for example, a method that includes a step of blending the lubricating oil additive composition with the lubricating oil base oil can be mentioned. At that time, the other additives mentioned above may also be added at the same time. Further, each component may be blended in the form of a solution (dispersion) by adding diluting oil or the like. After blending each component, it is preferable to stir and disperse uniformly by a known method.
［潤滑油組成物の用途］
本実施形態の潤滑油組成物は、共重合体（Ｘ）を含有するため、耐摩耗性、極圧性、及び熱安定性に優れる。
そのため、本実施形態の潤滑油組成物は、例えば、ギア油（マニュアルトランスミッション油、デファレンシャル油等）、自動変速機油（オートマチックトランスミッション油等）、無段変速機油（ベルトＣＶＴ油、トロイダルＣＶＴ油等）、パワーステアリング油、ショックアブソーバー油、及び電動モーター油等の駆動系油；ガソリンエンジン用、ディーゼルエンジン用、及びガスエンジン用等の内燃機関（エンジン）用油；油圧作動油；タービン油；圧縮機油；流体軸受け油；転がり軸受油；冷凍機油等をはじめ各種の用途に好適に使用でき、これら各用途で使用される装置に充填し、当該装置に係る各部品間を潤滑する潤滑油組成物として好適に使用することができる。 [Applications of lubricating oil composition]
Since the lubricating oil composition of this embodiment contains the copolymer (X), it has excellent wear resistance, extreme pressure properties, and thermal stability.
Therefore, the lubricating oil composition of this embodiment is, for example, gear oil (manual transmission oil, differential oil, etc.), automatic transmission oil (automatic transmission oil, etc.), continuously variable transmission oil (belt CVT oil, toroidal CVT oil, etc.) Drive system oils such as power steering oils, shock absorber oils, and electric motor oils; Oils for internal combustion engines (engines) such as gasoline engines, diesel engines, and gas engines; Hydraulic oils; Turbine oils; Compressor oils ; Fluid bearing oil; Rolling bearing oil; Refrigerating machine oil, etc., as a lubricating oil composition that can be suitably used for various purposes, and is filled into equipment used in each of these applications to lubricate between the various parts of the equipment. It can be suitably used.
本実施形態の潤滑油組成物は、共重合体（Ｘ）を含有するため、耐摩耗性、極圧性、及び熱安定性に優れる。
そのため、本実施形態の潤滑油組成物は、例えば、ギア油（マニュアルトランスミッション油、デファレンシャル油等）、自動変速機油（オートマチックトランスミッション油等）、無段変速機油（ベルトＣＶＴ油、トロイダルＣＶＴ油等）、パワーステアリング油、ショックアブソーバー油、及び電動モーター油等の駆動系油；ガソリンエンジン用、ディーゼルエンジン用、及びガスエンジン用等の内燃機関（エンジン）用油；油圧作動油；タービン油；圧縮機油；流体軸受け油；転がり軸受油；冷凍機油等をはじめ各種の用途に好適に使用でき、これら各用途で使用される装置に充填し、当該装置に係る各部品間を潤滑する潤滑油組成物として好適に使用することができる。 [Applications of lubricating oil composition]
Since the lubricating oil composition of this embodiment contains the copolymer (X), it has excellent wear resistance, extreme pressure properties, and thermal stability.
Therefore, the lubricating oil composition of this embodiment is, for example, gear oil (manual transmission oil, differential oil, etc.), automatic transmission oil (automatic transmission oil, etc.), continuously variable transmission oil (belt CVT oil, toroidal CVT oil, etc.) Drive system oils such as power steering oils, shock absorber oils, and electric motor oils; Oils for internal combustion engines (engines) such as gasoline engines, diesel engines, and gas engines; Hydraulic oils; Turbine oils; Compressor oils ; Fluid bearing oil; Rolling bearing oil; Refrigerating machine oil, etc., as a lubricating oil composition that can be suitably used for various purposes, and is filled into equipment used in each of these applications to lubricate between the various parts of the equipment. It can be suitably used.
［潤滑油組成物を用いる潤滑方法］
本実施形態の潤滑油組成物を用いる潤滑方法としては、好ましくは、前記潤滑油組成物を、前述した各用途で使用される装置に充填し、当該各装置に係る各部品間を潤滑する方法が挙げられる。 [Lubrication method using lubricating oil composition]
Preferably, the lubricating method using the lubricating oil composition of the present embodiment is a method of filling the lubricating oil composition into equipment used in each of the above-mentioned applications and lubricating between each part of each of the equipment. can be mentioned.
本実施形態の潤滑油組成物を用いる潤滑方法としては、好ましくは、前記潤滑油組成物を、前述した各用途で使用される装置に充填し、当該各装置に係る各部品間を潤滑する方法が挙げられる。 [Lubrication method using lubricating oil composition]
Preferably, the lubricating method using the lubricating oil composition of the present embodiment is a method of filling the lubricating oil composition into equipment used in each of the above-mentioned applications and lubricating between each part of each of the equipment. can be mentioned.
［グリース組成物］
本実施形態の潤滑油用添加剤組成物は、グリース組成物に配合して用いることもできる。
すなわち、本実施形態では、上記潤滑油用添加剤組成物と、増ちょう剤と、潤滑油基油とを含有するグリース組成物を提供することもできる。 [Grease composition]
The lubricating oil additive composition of this embodiment can also be used by being mixed into a grease composition.
That is, in this embodiment, it is also possible to provide a grease composition containing the above lubricating oil additive composition, a thickener, and a lubricating oil base oil.
本実施形態の潤滑油用添加剤組成物は、グリース組成物に配合して用いることもできる。
すなわち、本実施形態では、上記潤滑油用添加剤組成物と、増ちょう剤と、潤滑油基油とを含有するグリース組成物を提供することもできる。 [Grease composition]
The lubricating oil additive composition of this embodiment can also be used by being mixed into a grease composition.
That is, in this embodiment, it is also possible to provide a grease composition containing the above lubricating oil additive composition, a thickener, and a lubricating oil base oil.
［提供される本発明の一態様］
本発明の一態様によれば、下記［１］～［１５］が提供される。
［１］ 下記構成単位（ａ）及び（ｂ）を含み、下記要件（１）～（３）を満たす共重合体（Ｘ）を含有する、潤滑油用添加剤組成物。
・構成単位（ａ）：（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有するモノマー（Ａ）由来の構成単位
・構成単位（ｂ）：（メタ）アクリロイル基と極性基とを有するモノマー（Ｂ）由来の構成単位
・要件（１）：前記共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
・要件（２）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中のリン原子含有量（Ｐ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
・要件（３）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％以上である。
［２］ 前記要件（１）に規定する基を含む１以上の構成単位（α）をさらに含む、上記［１］に記載の潤滑油用添加剤組成物。
［３］ 前記構成単位（α）は、重合性官能基と前記リン及び硫黄含有基とを有するモノマー（Ｃ）由来の構成単位（ｃ）である、上記［２］に記載の潤滑油用添加剤組成物。
［４］ 前記構成単位（α）は、重合性官能基と前記硫黄含有基とを有するモノマー（Ｄ１）由来の構成単位（ｄ１）である、上記［２］に記載の潤滑油用添加剤組成物。
［５］ 前記構成単位（α）は、重合性官能基と前記硫黄含有基とを有するモノマー（Ｄ１）由来の構成単位（ｄ１）及び重合性官能基と前記リン含有基とを有するモノマー（Ｄ２）由来の構成単位（ｄ２）である、上記［２］に記載の潤滑油用添加剤組成物。
［６］ さらに、下記要件（４）を満たす、上記［１］～［５］のいずれか１つに記載の潤滑油用添加剤組成物。
・要件（４）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）とリン原子含有量（Ｐ）との含有比率［（Ｓ）／（Ｐ）］が、質量比で、０．１０～３．００である。
［７］ 前記構成単位（ａ）が、下記一般式（ａ－１）で表されるモノマー（Ａ１）に由来する構成単位（ａ１）を含む、上記［１］～［６］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ａ－１）中、Ｒａ１は、水素原子又はメチル基を示す。Ｒａ２は、炭素数８～２０のアルキル基を示す。］
［８］ 前記構成単位（ｂ）が、下記一般式（ｂ－１）で表されるモノマー（Ｂ１１）に由来する構成単位（ｂ１１）を含む、上記［１］～［７］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ｂ－１）中、Ｒｂ１は、水素原子又はメチル基である。Ｒｂ２は、炭素数２～４のアルキレン基を示す。ｍ１は、１～１０の整数を示す。ｍ１が２以上の整数の場合の複数のＲｂ２は、同一であっても異なっていてもよい。］
［９］ 前記モノマー（Ｃ）が、（メタ）アクリロイル基と、下記一般式（１）で表されるリン及び硫黄を含む１価基とを有する、上記［３］に記載の潤滑油用添加剤組成物。
［上記一般式（１）中、Ｒ１及びＲ２は、各々独立に、炭素数１～１０のアルキル基である。］
［１０］ 前記モノマー（Ｄ１）が、下記一般式（ｄ１－１）で表される化合物である、上記［４］に記載の潤滑油用添加剤組成物。
［上記一般式（ｄ１－１）中、Ｒｄ１１は、水素原子又はメチル基である。Ｒｄ１２は、炭素数２～４のアルキレン基を示す。ｍ３は、１～１０の整数を示す。ｍ３が２以上の整数の場合の複数のＲｄ１２は、同一であっても異なっていてもよい。Ｒｄ１３は、炭素数４～２０のアルキル基を示す。］
［１１］ 前記モノマー（Ｄ１）が、下記一般式（ｄ１－１）で表される化合物であり、
［上記一般式（ｄ１－１）中、Ｒｄ１１は、水素原子又はメチル基である。Ｒｄ１２は、炭素数２～４のアルキレン基を示す。ｍ３は、１～１０の整数を示す。ｍ３が２以上の整数の場合の複数のＲｄ１２は、同一であっても異なっていてもよい。Ｒｄ１３は、炭素数４～２０のアルキル基を示す。］
前記モノマー（Ｄ２）が、下記一般式（ｄ２－１）で表される化合物である、上記［５］に記載の潤滑油用添加剤組成物。
［上記一般式（ｄ２－１）中、Ｒｄ２１は、水素原子又はメチル基である。Ｒｄ２２は、エチレン基を示す。ｍ４は、１～６の整数を示す。ｍ４が２以上の整数の場合の複数のＲｄ２２は、同一であっても異なっていてもよい。ｎは、１又は２の整数を示す。ｎ＝１である場合、複数のＲｄ２３のうちの少なくとも１つは水素原子を示し、他方はメチル基又はエチル基である。ｎ＝２である場合、Ｒｄ２３は水素原子である。］
［１２］ 前記構成単位（ａ）が、下記一般式（ａ－１）で表されるモノマー（Ａ１）に由来する構成単位（ａ１）を含む、上記［９］～［１１］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ａ－１）中、Ｒａ１は、水素原子又はメチル基を示す。Ｒａ２は、炭素数８～２０のアルキル基を示す。］
［１３］ 前記構成単位（ｂ）が、下記一般式（ｂ－１）で表されるモノマー（Ｂ１１）に由来する構成単位（ｂ１１）を含む、上記［９］～［１２］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ｂ－１）中、Ｒｂ１は、水素原子又はメチル基である。Ｒｂ２は、炭素数２～４のアルキレン基を示す。ｍ１は、１～１０の整数を示す。ｍ１が２以上の整数の場合の複数のＲｂ２は、同一であっても異なっていてもよい。］
［１４］ 前記共重合体（Ｘ）の質量平均分子量が、５，０００～１００，０００である、上記［１］～［１３］のいずれか１つに記載の潤滑油用添加剤組成物。
［１５］ 前記構成単位（ａ）の含有量が、前記共重合体（Ｘ）の全構成単位基準で、５０質量％以上である、上記［１］～［１４］のいずれか１つに記載の潤滑油用添加剤組成物。
［１６］ 前記構成単位（ｂ）の含有量が、前記共重合体（Ｘ）の全構成単位基準で、１質量％以上である、上記［１］～［１５］のいずれか１つに記載の潤滑油用添加剤組成物。
［１７］ 耐荷重添加剤として用いられる、上記［１］～［１６］のいずれか１つに記載の潤滑油用添加剤組成物。
［１８］ 上記［１］～［１７］のいずれか１つに記載の潤滑油用添加剤組成物を、耐荷重添加剤として使用する、使用方法。
［１９］ 上記［１］～［１７］のいずれか１つに記載の潤滑油用添加剤組成物と、潤滑油基油と、を含有する、潤滑油組成物。
［２０］ 上記［１］～［１７］のいずれか１つに記載の潤滑油用添加剤組成物と、潤滑油基油と、を混合する工程を含む、潤滑油組成物の製造方法。 [One aspect of the provided invention]
According to one aspect of the present invention, the following [1] to [15] are provided.
[1] An additive composition for lubricating oil containing a copolymer (X) containing the following structural units (a) and (b) and satisfying the following requirements (1) to (3).
・Structural unit (a): A structural unit derived from a monomer (A) having a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.・Structural unit (b): Having a (meth)acryloyl group and a polar group. Structural unit derived from monomer (B)/Requirement (1): The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
Said sulfur-containing group/requirement (2): When said copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in said copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
[2] The lubricating oil additive composition according to [1] above, further comprising one or more structural units (α) containing the group defined in requirement (1) above.
[3] The addition for lubricating oil according to [2] above, wherein the structural unit (α) is a structural unit (c) derived from the monomer (C) having a polymerizable functional group and the phosphorus- and sulfur-containing group. agent composition.
[4] The lubricating oil additive composition according to [2] above, wherein the structural unit (α) is a structural unit (d1) derived from a monomer (D1) having a polymerizable functional group and the sulfur-containing group. thing.
[5] The structural unit (α) is a structural unit (d1) derived from the monomer (D1) having a polymerizable functional group and the sulfur-containing group, and a monomer (D2) derived from the monomer (D2) having a polymerizable functional group and the phosphorus-containing group. ), the lubricating oil additive composition according to [2] above, wherein the structural unit (d2) is derived from
[6] The lubricating oil additive composition according to any one of [1] to [5] above, which further satisfies the following requirement (4).
- Requirement (4): The content ratio [(S)/(P)] of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) is 0 by mass ratio. .10 to 3.00.
[7] Any one of [1] to [6] above, wherein the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1). The lubricating oil additive composition described in .
[In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms. ]
[8] Any one of [1] to [7] above, wherein the structural unit (b) includes a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1). The lubricating oil additive composition described in .
[In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. R b2 represents an alkylene group having 2 to 4 carbon atoms. m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. ]
[9] The addition for lubricating oil according to [3] above, wherein the monomer (C) has a (meth)acryloyl group and a monovalent group containing phosphorus and sulfur represented by the following general formula (1) agent composition.
[In the above general formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms. ]
[10] The lubricating oil additive composition according to [4] above, wherein the monomer (D1) is a compound represented by the following general formula (d1-1).
[In the above general formula (d1-1), R d11 is a hydrogen atom or a methyl group. R d12 represents an alkylene group having 2 to 4 carbon atoms. m3 represents an integer from 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. R d13 represents an alkyl group having 4 to 20 carbon atoms. ]
[11] The monomer (D1) is a compound represented by the following general formula (d1-1),
[In the above general formula (d1-1), R d11 is a hydrogen atom or a methyl group. R d12 represents an alkylene group having 2 to 4 carbon atoms. m3 represents an integer from 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. R d13 represents an alkyl group having 4 to 20 carbon atoms. ]
The lubricating oil additive composition according to [5] above, wherein the monomer (D2) is a compound represented by the following general formula (d2-1).
[In the above general formula (d2-1), R d21 is a hydrogen atom or a methyl group. R d22 represents an ethylene group. m4 represents an integer from 1 to 6. When m4 is an integer of 2 or more, a plurality of R d22 may be the same or different. n represents an integer of 1 or 2. When n=1, at least one of the plurality of R d23 represents a hydrogen atom, and the other is a methyl group or an ethyl group. When n=2, R d23 is a hydrogen atom. ]
[12] Any one of [9] to [11] above, wherein the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1). The lubricating oil additive composition described in .
[In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms. ]
[13] Any one of [9] to [12] above, wherein the structural unit (b) includes a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1). The lubricating oil additive composition described in .
[In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. R b2 represents an alkylene group having 2 to 4 carbon atoms. m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. ]
[14] The lubricating oil additive composition according to any one of [1] to [13] above, wherein the copolymer (X) has a mass average molecular weight of 5,000 to 100,000.
[15] The content of the structural unit (a) is 50% by mass or more based on all the structural units of the copolymer (X), according to any one of [1] to [14] above. Additive composition for lubricating oil.
[16] According to any one of [1] to [15] above, wherein the content of the structural unit (b) is 1% by mass or more based on all structural units of the copolymer (X). Additive composition for lubricating oil.
[17] The lubricating oil additive composition according to any one of [1] to [16] above, which is used as a load-bearing additive.
[18] A method of using the lubricating oil additive composition according to any one of [1] to [17] above as a load-bearing additive.
[19] A lubricating oil composition containing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil.
[20] A method for producing a lubricating oil composition, comprising the step of mixing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil.
本発明の一態様によれば、下記［１］～［１５］が提供される。
［１］ 下記構成単位（ａ）及び（ｂ）を含み、下記要件（１）～（３）を満たす共重合体（Ｘ）を含有する、潤滑油用添加剤組成物。
・構成単位（ａ）：（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有するモノマー（Ａ）由来の構成単位
・構成単位（ｂ）：（メタ）アクリロイル基と極性基とを有するモノマー（Ｂ）由来の構成単位
・要件（１）：前記共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
・要件（２）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中のリン原子含有量（Ｐ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
・要件（３）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％以上である。
［２］ 前記要件（１）に規定する基を含む１以上の構成単位（α）をさらに含む、上記［１］に記載の潤滑油用添加剤組成物。
［３］ 前記構成単位（α）は、重合性官能基と前記リン及び硫黄含有基とを有するモノマー（Ｃ）由来の構成単位（ｃ）である、上記［２］に記載の潤滑油用添加剤組成物。
［４］ 前記構成単位（α）は、重合性官能基と前記硫黄含有基とを有するモノマー（Ｄ１）由来の構成単位（ｄ１）である、上記［２］に記載の潤滑油用添加剤組成物。
［５］ 前記構成単位（α）は、重合性官能基と前記硫黄含有基とを有するモノマー（Ｄ１）由来の構成単位（ｄ１）及び重合性官能基と前記リン含有基とを有するモノマー（Ｄ２）由来の構成単位（ｄ２）である、上記［２］に記載の潤滑油用添加剤組成物。
［６］ さらに、下記要件（４）を満たす、上記［１］～［５］のいずれか１つに記載の潤滑油用添加剤組成物。
・要件（４）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）とリン原子含有量（Ｐ）との含有比率［（Ｓ）／（Ｐ）］が、質量比で、０．１０～３．００である。
［７］ 前記構成単位（ａ）が、下記一般式（ａ－１）で表されるモノマー（Ａ１）に由来する構成単位（ａ１）を含む、上記［１］～［６］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ａ－１）中、Ｒａ１は、水素原子又はメチル基を示す。Ｒａ２は、炭素数８～２０のアルキル基を示す。］
［８］ 前記構成単位（ｂ）が、下記一般式（ｂ－１）で表されるモノマー（Ｂ１１）に由来する構成単位（ｂ１１）を含む、上記［１］～［７］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ｂ－１）中、Ｒｂ１は、水素原子又はメチル基である。Ｒｂ２は、炭素数２～４のアルキレン基を示す。ｍ１は、１～１０の整数を示す。ｍ１が２以上の整数の場合の複数のＲｂ２は、同一であっても異なっていてもよい。］
［９］ 前記モノマー（Ｃ）が、（メタ）アクリロイル基と、下記一般式（１）で表されるリン及び硫黄を含む１価基とを有する、上記［３］に記載の潤滑油用添加剤組成物。
［上記一般式（１）中、Ｒ１及びＲ２は、各々独立に、炭素数１～１０のアルキル基である。］
［１０］ 前記モノマー（Ｄ１）が、下記一般式（ｄ１－１）で表される化合物である、上記［４］に記載の潤滑油用添加剤組成物。
［上記一般式（ｄ１－１）中、Ｒｄ１１は、水素原子又はメチル基である。Ｒｄ１２は、炭素数２～４のアルキレン基を示す。ｍ３は、１～１０の整数を示す。ｍ３が２以上の整数の場合の複数のＲｄ１２は、同一であっても異なっていてもよい。Ｒｄ１３は、炭素数４～２０のアルキル基を示す。］
［１１］ 前記モノマー（Ｄ１）が、下記一般式（ｄ１－１）で表される化合物であり、
［上記一般式（ｄ１－１）中、Ｒｄ１１は、水素原子又はメチル基である。Ｒｄ１２は、炭素数２～４のアルキレン基を示す。ｍ３は、１～１０の整数を示す。ｍ３が２以上の整数の場合の複数のＲｄ１２は、同一であっても異なっていてもよい。Ｒｄ１３は、炭素数４～２０のアルキル基を示す。］
前記モノマー（Ｄ２）が、下記一般式（ｄ２－１）で表される化合物である、上記［５］に記載の潤滑油用添加剤組成物。
［上記一般式（ｄ２－１）中、Ｒｄ２１は、水素原子又はメチル基である。Ｒｄ２２は、エチレン基を示す。ｍ４は、１～６の整数を示す。ｍ４が２以上の整数の場合の複数のＲｄ２２は、同一であっても異なっていてもよい。ｎは、１又は２の整数を示す。ｎ＝１である場合、複数のＲｄ２３のうちの少なくとも１つは水素原子を示し、他方はメチル基又はエチル基である。ｎ＝２である場合、Ｒｄ２３は水素原子である。］
［１２］ 前記構成単位（ａ）が、下記一般式（ａ－１）で表されるモノマー（Ａ１）に由来する構成単位（ａ１）を含む、上記［９］～［１１］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ａ－１）中、Ｒａ１は、水素原子又はメチル基を示す。Ｒａ２は、炭素数８～２０のアルキル基を示す。］
［１３］ 前記構成単位（ｂ）が、下記一般式（ｂ－１）で表されるモノマー（Ｂ１１）に由来する構成単位（ｂ１１）を含む、上記［９］～［１２］のいずれか１つに記載の潤滑油用添加剤組成物。
［上記一般式（ｂ－１）中、Ｒｂ１は、水素原子又はメチル基である。Ｒｂ２は、炭素数２～４のアルキレン基を示す。ｍ１は、１～１０の整数を示す。ｍ１が２以上の整数の場合の複数のＲｂ２は、同一であっても異なっていてもよい。］
［１４］ 前記共重合体（Ｘ）の質量平均分子量が、５，０００～１００，０００である、上記［１］～［１３］のいずれか１つに記載の潤滑油用添加剤組成物。
［１５］ 前記構成単位（ａ）の含有量が、前記共重合体（Ｘ）の全構成単位基準で、５０質量％以上である、上記［１］～［１４］のいずれか１つに記載の潤滑油用添加剤組成物。
［１６］ 前記構成単位（ｂ）の含有量が、前記共重合体（Ｘ）の全構成単位基準で、１質量％以上である、上記［１］～［１５］のいずれか１つに記載の潤滑油用添加剤組成物。
［１７］ 耐荷重添加剤として用いられる、上記［１］～［１６］のいずれか１つに記載の潤滑油用添加剤組成物。
［１８］ 上記［１］～［１７］のいずれか１つに記載の潤滑油用添加剤組成物を、耐荷重添加剤として使用する、使用方法。
［１９］ 上記［１］～［１７］のいずれか１つに記載の潤滑油用添加剤組成物と、潤滑油基油と、を含有する、潤滑油組成物。
［２０］ 上記［１］～［１７］のいずれか１つに記載の潤滑油用添加剤組成物と、潤滑油基油と、を混合する工程を含む、潤滑油組成物の製造方法。 [One aspect of the provided invention]
According to one aspect of the present invention, the following [1] to [15] are provided.
[1] An additive composition for lubricating oil containing a copolymer (X) containing the following structural units (a) and (b) and satisfying the following requirements (1) to (3).
・Structural unit (a): A structural unit derived from a monomer (A) having a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.・Structural unit (b): Having a (meth)acryloyl group and a polar group. Structural unit derived from monomer (B)/Requirement (1): The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
Said sulfur-containing group/requirement (2): When said copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in said copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
[2] The lubricating oil additive composition according to [1] above, further comprising one or more structural units (α) containing the group defined in requirement (1) above.
[3] The addition for lubricating oil according to [2] above, wherein the structural unit (α) is a structural unit (c) derived from the monomer (C) having a polymerizable functional group and the phosphorus- and sulfur-containing group. agent composition.
[4] The lubricating oil additive composition according to [2] above, wherein the structural unit (α) is a structural unit (d1) derived from a monomer (D1) having a polymerizable functional group and the sulfur-containing group. thing.
[5] The structural unit (α) is a structural unit (d1) derived from the monomer (D1) having a polymerizable functional group and the sulfur-containing group, and a monomer (D2) derived from the monomer (D2) having a polymerizable functional group and the phosphorus-containing group. ), the lubricating oil additive composition according to [2] above, wherein the structural unit (d2) is derived from
[6] The lubricating oil additive composition according to any one of [1] to [5] above, which further satisfies the following requirement (4).
- Requirement (4): The content ratio [(S)/(P)] of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) is 0 by mass ratio. .10 to 3.00.
[7] Any one of [1] to [6] above, wherein the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1). The lubricating oil additive composition described in .
[In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms. ]
[8] Any one of [1] to [7] above, wherein the structural unit (b) includes a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1). The lubricating oil additive composition described in .
[In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. R b2 represents an alkylene group having 2 to 4 carbon atoms. m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. ]
[9] The addition for lubricating oil according to [3] above, wherein the monomer (C) has a (meth)acryloyl group and a monovalent group containing phosphorus and sulfur represented by the following general formula (1) agent composition.
[In the above general formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms. ]
[10] The lubricating oil additive composition according to [4] above, wherein the monomer (D1) is a compound represented by the following general formula (d1-1).
[In the above general formula (d1-1), R d11 is a hydrogen atom or a methyl group. R d12 represents an alkylene group having 2 to 4 carbon atoms. m3 represents an integer from 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. R d13 represents an alkyl group having 4 to 20 carbon atoms. ]
[11] The monomer (D1) is a compound represented by the following general formula (d1-1),
[In the above general formula (d1-1), R d11 is a hydrogen atom or a methyl group. R d12 represents an alkylene group having 2 to 4 carbon atoms. m3 represents an integer from 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. R d13 represents an alkyl group having 4 to 20 carbon atoms. ]
The lubricating oil additive composition according to [5] above, wherein the monomer (D2) is a compound represented by the following general formula (d2-1).
[In the above general formula (d2-1), R d21 is a hydrogen atom or a methyl group. R d22 represents an ethylene group. m4 represents an integer from 1 to 6. When m4 is an integer of 2 or more, a plurality of R d22 may be the same or different. n represents an integer of 1 or 2. When n=1, at least one of the plurality of R d23 represents a hydrogen atom, and the other is a methyl group or an ethyl group. When n=2, R d23 is a hydrogen atom. ]
[12] Any one of [9] to [11] above, wherein the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1). The lubricating oil additive composition described in .
[In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms. ]
[13] Any one of [9] to [12] above, wherein the structural unit (b) includes a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1). The lubricating oil additive composition described in .
[In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. R b2 represents an alkylene group having 2 to 4 carbon atoms. m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. ]
[14] The lubricating oil additive composition according to any one of [1] to [13] above, wherein the copolymer (X) has a mass average molecular weight of 5,000 to 100,000.
[15] The content of the structural unit (a) is 50% by mass or more based on all the structural units of the copolymer (X), according to any one of [1] to [14] above. Additive composition for lubricating oil.
[16] According to any one of [1] to [15] above, wherein the content of the structural unit (b) is 1% by mass or more based on all structural units of the copolymer (X). Additive composition for lubricating oil.
[17] The lubricating oil additive composition according to any one of [1] to [16] above, which is used as a load-bearing additive.
[18] A method of using the lubricating oil additive composition according to any one of [1] to [17] above as a load-bearing additive.
[19] A lubricating oil composition containing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil.
[20] A method for producing a lubricating oil composition, comprising the step of mixing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil.
本発明について、以下の実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。
The present invention will be specifically explained with reference to the following examples, but the present invention is not limited to the following examples.
［各種物性値の測定方法］
各実施例及び各比較例で用いた各原料並びに各実施例及び各比較例の潤滑油組成物の各性状の測定は、以下に示す要領に従って行ったものである。 [Methods for measuring various physical property values]
The properties of each raw material used in each Example and each Comparative Example and the lubricating oil composition of each Example and each Comparative Example were measured according to the procedures shown below.
各実施例及び各比較例で用いた各原料並びに各実施例及び各比較例の潤滑油組成物の各性状の測定は、以下に示す要領に従って行ったものである。 [Methods for measuring various physical property values]
The properties of each raw material used in each Example and each Comparative Example and the lubricating oil composition of each Example and each Comparative Example were measured according to the procedures shown below.
（１）動粘度、粘度指数
潤滑油組成物の４０℃動粘度、１００℃動粘度、及び粘度指数は、ＪＩＳ Ｋ２２８３：２０００に準拠して測定又は算出した。 (1) Kinematic viscosity, viscosity index The 40°C kinematic viscosity, 100°C kinematic viscosity, and viscosity index of the lubricating oil composition were measured or calculated in accordance with JIS K2283:2000.
潤滑油組成物の４０℃動粘度、１００℃動粘度、及び粘度指数は、ＪＩＳ Ｋ２２８３：２０００に準拠して測定又は算出した。 (1) Kinematic viscosity, viscosity index The 40°C kinematic viscosity, 100°C kinematic viscosity, and viscosity index of the lubricating oil composition were measured or calculated in accordance with JIS K2283:2000.
（２）質量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）
Ｗａｔｅｒｓ社製の「１５１５アイソクラティックＨＰＬＣポンプ」、「２４１４示差屈折率（ＲＩ）検出器」に、東ソー社製のカラム「ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨＺ－Ｌ」を１本、及び「ＴＳＫＳｕｐｅｒＭｕｌｔｉｐｏｒｅ ＨＺ－Ｍ」を２本、上流側からこの順で取り付け、測定温度：４０℃、移動相：テトラヒドロフラン、流速：０．３５ｍｌ／分、試料濃度１．０ｍｇ／ｍｌの条件で測定し、標準ポリスチレン換算にて求めた。 (2) Mass average molecular weight (Mw), molecular weight distribution (Mw/Mn)
Waters'"1515 isocratic HPLC pump", "2414 differential refractive index (RI) detector", one Tosoh column "TSKguardcolumn SuperHZ-L", and two "TSKSSuperMultipore HZ-M" The sample was attached in this order from the upstream side, and the measurement temperature was 40°C, the mobile phase was tetrahydrofuran, the flow rate was 0.35 ml/min, and the sample concentration was 1.0 mg/ml, and the measurements were made in terms of standard polystyrene.
Ｗａｔｅｒｓ社製の「１５１５アイソクラティックＨＰＬＣポンプ」、「２４１４示差屈折率（ＲＩ）検出器」に、東ソー社製のカラム「ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨＺ－Ｌ」を１本、及び「ＴＳＫＳｕｐｅｒＭｕｌｔｉｐｏｒｅ ＨＺ－Ｍ」を２本、上流側からこの順で取り付け、測定温度：４０℃、移動相：テトラヒドロフラン、流速：０．３５ｍｌ／分、試料濃度１．０ｍｇ／ｍｌの条件で測定し、標準ポリスチレン換算にて求めた。 (2) Mass average molecular weight (Mw), molecular weight distribution (Mw/Mn)
Waters'"1515 isocratic HPLC pump", "2414 differential refractive index (RI) detector", one Tosoh column "TSKguardcolumn SuperHZ-L", and two "TSKSSuperMultipore HZ-M" The sample was attached in this order from the upstream side, and the measurement temperature was 40°C, the mobile phase was tetrahydrofuran, the flow rate was 0.35 ml/min, and the sample concentration was 1.0 mg/ml, and the measurements were made in terms of standard polystyrene.
（３）硫黄量及びリン量
共重合体（Ｘ）の硫黄含有量及びリン含有量は、共重合体（Ｘ）を有機溶剤（潤滑油基油）に所定量溶解した後、当該有機溶剤中の硫黄量及びリン量をＪＰＩ－５Ｓ－３８－０３に準拠して測定した結果と、有機溶剤への共重合体（Ｘ）の溶解量とに基づいて算出した。 (3) Amount of Sulfur and Amount of Phosphorus The sulfur content and phosphorus content of the copolymer (X) are determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (lubricating oil base oil). Calculated based on the results of measuring the sulfur and phosphorus amounts in accordance with JPI-5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
共重合体（Ｘ）の硫黄含有量及びリン含有量は、共重合体（Ｘ）を有機溶剤（潤滑油基油）に所定量溶解した後、当該有機溶剤中の硫黄量及びリン量をＪＰＩ－５Ｓ－３８－０３に準拠して測定した結果と、有機溶剤への共重合体（Ｘ）の溶解量とに基づいて算出した。 (3) Amount of Sulfur and Amount of Phosphorus The sulfur content and phosphorus content of the copolymer (X) are determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (lubricating oil base oil). Calculated based on the results of measuring the sulfur and phosphorus amounts in accordance with JPI-5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
［実施例Ａ１～Ａ６、実施例Ｂ１～Ｂ７、比較例１］
以下に示す潤滑油基油及び潤滑油用添加剤組成物を、表３及び表４に示す配合量（質量％）で十分に混合し、実施例Ａ１～Ａ６、実施例Ｂ１～Ｂ７、及び比較例１の潤滑油組成物をそれぞれ調製した。
実施例Ａ１～Ａ６、実施例Ｂ１～Ｂ７、及び比較例１で用いた潤滑油基油及び潤滑油用添加剤組成物の詳細は、以下に示すとおりである。 [Examples A1 to A6, Examples B1 to B7, Comparative Example 1]
The lubricant base oil and lubricant additive composition shown below were thoroughly mixed in the amounts (mass%) shown in Tables 3 and 4, and Examples A1 to A6, Examples B1 to B7, and Comparative The lubricating oil compositions of Example 1 were each prepared.
Details of the lubricant base oil and lubricant additive composition used in Examples A1 to A6, Examples B1 to B7, and Comparative Example 1 are as shown below.
以下に示す潤滑油基油及び潤滑油用添加剤組成物を、表３及び表４に示す配合量（質量％）で十分に混合し、実施例Ａ１～Ａ６、実施例Ｂ１～Ｂ７、及び比較例１の潤滑油組成物をそれぞれ調製した。
実施例Ａ１～Ａ６、実施例Ｂ１～Ｂ７、及び比較例１で用いた潤滑油基油及び潤滑油用添加剤組成物の詳細は、以下に示すとおりである。 [Examples A1 to A6, Examples B1 to B7, Comparative Example 1]
The lubricant base oil and lubricant additive composition shown below were thoroughly mixed in the amounts (mass%) shown in Tables 3 and 4, and Examples A1 to A6, Examples B1 to B7, and Comparative The lubricating oil compositions of Example 1 were each prepared.
Details of the lubricant base oil and lubricant additive composition used in Examples A1 to A6, Examples B1 to B7, and Comparative Example 1 are as shown below.
＜潤滑油基油＞
ＡＰＩ分類でグループＩＩに分類される鉱油（１５０Ｎ） <Lubricant base oil>
Mineral oil (150N) classified as Group II by API classification
ＡＰＩ分類でグループＩＩに分類される鉱油（１５０Ｎ） <Lubricant base oil>
Mineral oil (150N) classified as Group II by API classification
＜潤滑油用添加剤組成物＞
・共重合体（Ｘ）－Ａ１：製造例Ａ１に説明する方法で製造した。
・共重合体（Ｘ）－Ａ２：製造例Ａ２に説明する方法で製造した。
・共重合体（Ｘ）－Ａ３：製造例Ａ３に説明する方法で製造した。
・共重合体（Ｘ）－Ａ４：製造例Ａ４に説明する方法で製造した。
・共重合体（Ｘ）－Ａ５：製造例Ａ５に説明する方法で製造した。
・共重合体（Ｘ）－Ａ６：製造例Ａ６に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ１：製造例Ｂ１に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ２：製造例Ｂ２に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ３：製造例Ｂ３に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ４：製造例Ｂ４に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ５：製造例Ｂ５に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ６：製造例Ｂ６に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ７：製造例Ｂ７に説明する方法で製造した。
・ＩＲＧＡＬＵＢＥ ６２（ＢＡＳＦジャパン株式会社製）：下記構造式で表されるジチオリン酸エステル系誘導体である。表２中では、「硫黄リン含有低分子化合物」と表記する。
<Additive composition for lubricating oil>
- Copolymer (X)-A1: Produced by the method described in Production Example A1.
- Copolymer (X)-A2: Produced by the method described in Production Example A2.
- Copolymer (X)-A3: Produced by the method described in Production Example A3.
- Copolymer (X)-A4: Produced by the method described in Production Example A4.
- Copolymer (X)-A5: Produced by the method described in Production Example A5.
- Copolymer (X)-A6: Produced by the method described in Production Example A6.
- Copolymer (X)-B1: Produced by the method described in Production Example B1.
- Copolymer (X)-B2: Produced by the method described in Production Example B2.
- Copolymer (X)-B3: Produced by the method described in Production Example B3.
- Copolymer (X)-B4: Produced by the method described in Production Example B4.
- Copolymer (X)-B5: Produced by the method described in Production Example B5.
- Copolymer (X)-B6: Produced by the method described in Production Example B6.
- Copolymer (X)-B7: Produced by the method described in Production Example B7.
-IRGALUBE 62 (manufactured by BASF Japan Co., Ltd.): A dithiophosphoric acid ester derivative represented by the following structural formula. In Table 2, it is written as "sulfur phosphorus-containing low molecular compound".
・共重合体（Ｘ）－Ａ１：製造例Ａ１に説明する方法で製造した。
・共重合体（Ｘ）－Ａ２：製造例Ａ２に説明する方法で製造した。
・共重合体（Ｘ）－Ａ３：製造例Ａ３に説明する方法で製造した。
・共重合体（Ｘ）－Ａ４：製造例Ａ４に説明する方法で製造した。
・共重合体（Ｘ）－Ａ５：製造例Ａ５に説明する方法で製造した。
・共重合体（Ｘ）－Ａ６：製造例Ａ６に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ１：製造例Ｂ１に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ２：製造例Ｂ２に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ３：製造例Ｂ３に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ４：製造例Ｂ４に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ５：製造例Ｂ５に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ６：製造例Ｂ６に説明する方法で製造した。
・共重合体（Ｘ）－Ｂ７：製造例Ｂ７に説明する方法で製造した。
・ＩＲＧＡＬＵＢＥ ６２（ＢＡＳＦジャパン株式会社製）：下記構造式で表されるジチオリン酸エステル系誘導体である。表２中では、「硫黄リン含有低分子化合物」と表記する。
- Copolymer (X)-A1: Produced by the method described in Production Example A1.
- Copolymer (X)-A2: Produced by the method described in Production Example A2.
- Copolymer (X)-A3: Produced by the method described in Production Example A3.
- Copolymer (X)-A4: Produced by the method described in Production Example A4.
- Copolymer (X)-A5: Produced by the method described in Production Example A5.
- Copolymer (X)-A6: Produced by the method described in Production Example A6.
- Copolymer (X)-B1: Produced by the method described in Production Example B1.
- Copolymer (X)-B2: Produced by the method described in Production Example B2.
- Copolymer (X)-B3: Produced by the method described in Production Example B3.
- Copolymer (X)-B4: Produced by the method described in Production Example B4.
- Copolymer (X)-B5: Produced by the method described in Production Example B5.
- Copolymer (X)-B6: Produced by the method described in Production Example B6.
- Copolymer (X)-B7: Produced by the method described in Production Example B7.
-IRGALUBE 62 (manufactured by BASF Japan Co., Ltd.): A dithiophosphoric acid ester derivative represented by the following structural formula. In Table 2, it is written as "sulfur phosphorus-containing low molecular compound".
＜製造例Ａ１～Ａ６＞
（製造例Ａ１～Ａ６で用いたモノマー）
・「ドデシルアクリレート（ＤＯＡ）」：上記一般式（ａ－１）中、Ｒａ１が水素原子であり、Ｒａ２がｎ－ドデシル基（炭素数１２のアルキル基）である化合物である。モノマー（Ａ）（モノマー（Ａ１））として使用した。
・「２－ヒドロキシエチルアクリレート（ＨＥＡ）」：上記一般式（ｂ－１）中、Ｒｂ１が水素原子であり、Ｒｂ２がエチレン基（炭素数２のアルキレン基）であり、ｍ１＝１である化合物である。モノマー（Ｂ）（モノマー（Ｂ１１））として使用した。
・「ＳＰＭ１」：下記構造式で表される化合物を用いた。下記構造式で表される化合物は、上記一般式（ｃ－１）中、Ｒｃ１が水素原子であり、Ｒｃ２がエチレン基（炭素数２のアルキレン基）であり、ｍ２＝１であり、Ｌ１が－Ｏ－Ｃ（Ｏ）－Ｒｃ３－であり、Ｒｃ３がプロピレン基（炭素数３のアルキレン基）であり、Ｒ１及びＲ２がイソブチル基（炭素数４のアルキル基）である化合物である。硫黄含有量は１５．０質量％、リン含有量は７．３質量％である。モノマー（Ｃ）として使用した。
・「ＳＰＭ２」：下記構造式で表される化合物を用いた。下記構造式で表される化合物は、上記一般式（ｃ－１）中、Ｒｃ１が水素原子であり、Ｒｃ２がエチレン基（炭素数２のアルキレン基）であり、ｍ２＝１であり、Ｌ１が－Ｏ－Ｃ（Ｏ）－Ｒｃ３－であり、Ｒｃ３がエチレン基（炭素数２のアルキレン基）であり、Ｒ１及びＲ２がイソプロピル基（炭素数３のアルキル基）である化合物である。硫黄含有量は１６．７質量％、リン含有量は８．１質量％である。モノマー（Ｃ）として使用した。
・「ＳＰＭ３」：下記構造式で表される化合物を用いた。下記構造式で表される化合物は、上記一般式（ｃ－１）中、Ｒｃ１が水素原子であり、Ｒｃ２がエチレン基（炭素数２のアルキレン基）であり、ｍ２＝１であり、Ｌ１が－Ｏ－Ｃ（Ｏ）－Ｒｃ３－であり、Ｒｃ３がエチレン基（炭素数２のアルキレン基）であり、Ｒ１及びＲ２がエチレン基（炭素数２のアルキル基）である化合物である。硫黄含有量は１８．０質量％、リン含有量は８．７質量％である。モノマー（Ｃ）として使用した。
<Production examples A1 to A6>
(Monomer used in Production Examples A1 to A6)
- "Dodecyl acrylate (DOA)": A compound in the above general formula (a-1) in which R a1 is a hydrogen atom and R a2 is an n-dodecyl group (an alkyl group having 12 carbon atoms). It was used as monomer (A) (monomer (A1)).
・"2-Hydroxyethyl acrylate (HEA)": In the above general formula (b-1), R b1 is a hydrogen atom, R b2 is an ethylene group (alkylene group having 2 carbon atoms), m1 = 1, It is a certain compound. It was used as monomer (B) (monomer (B11)).
- "SPM1": A compound represented by the following structural formula was used. In the compound represented by the following structural formula, in the above general formula (c-1), R c1 is a hydrogen atom, R c2 is an ethylene group (an alkylene group having 2 carbon atoms), and m2 = 1, L 1 is -O-C(O)-R c3 -, R c3 is a propylene group (alkylene group having 3 carbon atoms), and R 1 and R 2 are isobutyl groups (alkyl group having 4 carbon atoms). It is a certain compound. The sulfur content is 15.0% by mass, and the phosphorus content is 7.3% by mass. It was used as monomer (C).
- "SPM2": A compound represented by the following structural formula was used. In the compound represented by the following structural formula, in the above general formula (c-1), R c1 is a hydrogen atom, R c2 is an ethylene group (an alkylene group having 2 carbon atoms), and m2 = 1, L 1 is -O-C(O)-R c3 -, R c3 is an ethylene group (alkylene group having 2 carbon atoms), and R 1 and R 2 are isopropyl groups (alkyl group having 3 carbon atoms); It is a certain compound. The sulfur content is 16.7% by mass, and the phosphorus content is 8.1% by mass. It was used as monomer (C).
- "SPM3": A compound represented by the following structural formula was used. In the compound represented by the following structural formula, in the above general formula (c-1), R c1 is a hydrogen atom, R c2 is an ethylene group (an alkylene group having 2 carbon atoms), and m2 = 1, L 1 is -O-C(O)-R c3 -, R c3 is an ethylene group (alkylene group having 2 carbon atoms), and R 1 and R 2 are ethylene groups (alkyl group having 2 carbon atoms); It is a certain compound. The sulfur content is 18.0% by mass, and the phosphorus content is 8.7% by mass. It was used as monomer (C).
（製造例Ａ１～Ａ６で用いたモノマー）
・「ドデシルアクリレート（ＤＯＡ）」：上記一般式（ａ－１）中、Ｒａ１が水素原子であり、Ｒａ２がｎ－ドデシル基（炭素数１２のアルキル基）である化合物である。モノマー（Ａ）（モノマー（Ａ１））として使用した。
・「２－ヒドロキシエチルアクリレート（ＨＥＡ）」：上記一般式（ｂ－１）中、Ｒｂ１が水素原子であり、Ｒｂ２がエチレン基（炭素数２のアルキレン基）であり、ｍ１＝１である化合物である。モノマー（Ｂ）（モノマー（Ｂ１１））として使用した。
・「ＳＰＭ１」：下記構造式で表される化合物を用いた。下記構造式で表される化合物は、上記一般式（ｃ－１）中、Ｒｃ１が水素原子であり、Ｒｃ２がエチレン基（炭素数２のアルキレン基）であり、ｍ２＝１であり、Ｌ１が－Ｏ－Ｃ（Ｏ）－Ｒｃ３－であり、Ｒｃ３がプロピレン基（炭素数３のアルキレン基）であり、Ｒ１及びＲ２がイソブチル基（炭素数４のアルキル基）である化合物である。硫黄含有量は１５．０質量％、リン含有量は７．３質量％である。モノマー（Ｃ）として使用した。
・「ＳＰＭ２」：下記構造式で表される化合物を用いた。下記構造式で表される化合物は、上記一般式（ｃ－１）中、Ｒｃ１が水素原子であり、Ｒｃ２がエチレン基（炭素数２のアルキレン基）であり、ｍ２＝１であり、Ｌ１が－Ｏ－Ｃ（Ｏ）－Ｒｃ３－であり、Ｒｃ３がエチレン基（炭素数２のアルキレン基）であり、Ｒ１及びＲ２がイソプロピル基（炭素数３のアルキル基）である化合物である。硫黄含有量は１６．７質量％、リン含有量は８．１質量％である。モノマー（Ｃ）として使用した。
・「ＳＰＭ３」：下記構造式で表される化合物を用いた。下記構造式で表される化合物は、上記一般式（ｃ－１）中、Ｒｃ１が水素原子であり、Ｒｃ２がエチレン基（炭素数２のアルキレン基）であり、ｍ２＝１であり、Ｌ１が－Ｏ－Ｃ（Ｏ）－Ｒｃ３－であり、Ｒｃ３がエチレン基（炭素数２のアルキレン基）であり、Ｒ１及びＲ２がエチレン基（炭素数２のアルキル基）である化合物である。硫黄含有量は１８．０質量％、リン含有量は８．７質量％である。モノマー（Ｃ）として使用した。
(Monomer used in Production Examples A1 to A6)
- "Dodecyl acrylate (DOA)": A compound in the above general formula (a-1) in which R a1 is a hydrogen atom and R a2 is an n-dodecyl group (an alkyl group having 12 carbon atoms). It was used as monomer (A) (monomer (A1)).
・"2-Hydroxyethyl acrylate (HEA)": In the above general formula (b-1), R b1 is a hydrogen atom, R b2 is an ethylene group (alkylene group having 2 carbon atoms), m1 = 1, It is a certain compound. It was used as monomer (B) (monomer (B11)).
- "SPM1": A compound represented by the following structural formula was used. In the compound represented by the following structural formula, in the above general formula (c-1), R c1 is a hydrogen atom, R c2 is an ethylene group (an alkylene group having 2 carbon atoms), and m2 = 1, L 1 is -O-C(O)-R c3 -, R c3 is a propylene group (alkylene group having 3 carbon atoms), and R 1 and R 2 are isobutyl groups (alkyl group having 4 carbon atoms). It is a certain compound. The sulfur content is 15.0% by mass, and the phosphorus content is 7.3% by mass. It was used as monomer (C).
- "SPM2": A compound represented by the following structural formula was used. In the compound represented by the following structural formula, in the above general formula (c-1), R c1 is a hydrogen atom, R c2 is an ethylene group (an alkylene group having 2 carbon atoms), and m2 = 1, L 1 is -O-C(O)-R c3 -, R c3 is an ethylene group (alkylene group having 2 carbon atoms), and R 1 and R 2 are isopropyl groups (alkyl group having 3 carbon atoms); It is a certain compound. The sulfur content is 16.7% by mass, and the phosphorus content is 8.1% by mass. It was used as monomer (C).
- "SPM3": A compound represented by the following structural formula was used. In the compound represented by the following structural formula, in the above general formula (c-1), R c1 is a hydrogen atom, R c2 is an ethylene group (an alkylene group having 2 carbon atoms), and m2 = 1, L 1 is -O-C(O)-R c3 -, R c3 is an ethylene group (alkylene group having 2 carbon atoms), and R 1 and R 2 are ethylene groups (alkyl group having 2 carbon atoms); It is a certain compound. The sulfur content is 18.0% by mass, and the phosphorus content is 8.7% by mass. It was used as monomer (C).
（ＳＰＭ１の合成方法）
２００ｍＬナスフラスコにＩＲＧＡＬＵＢＥ３５３（ＢＡＳＦジャパン株式会社製、１３．２ｇ，４０．２ｍｍｏｌ）、トルエン（２５ｍＬ）を加え室温で攪拌している中へ、塩化チオニル（８．７５ｇ，７４．１ｍｍｏｌ）を滴下した。オイルバスで６０℃に昇温し、４時間反応させた後、減圧下加熱濃縮した。得られた濃縮物にジクロロメタン（９０ｍＬ）を加え、氷浴下、ヒドロキシエチルアクリレート（７．００ｇ，６０．３ｍｍｏｌ）を滴下し、室温で３時間攪拌した。反応終了後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＳＰＭ１（６．５２ｇ，１５．３ｍｍｏｌ）を得た。
なお、ＩＲＧＡＬＵＢＥ３５３は、下記構造式で表される化合物である。
(Synthesis method of SPM1)
IRGALUBE353 (manufactured by BASF Japan Co., Ltd., 13.2 g, 40.2 mmol) and toluene (25 mL) were added to a 200 mL eggplant flask, and while stirring at room temperature, thionyl chloride (8.75 g, 74.1 mmol) was added dropwise. . The temperature was raised to 60° C. in an oil bath, and the mixture was reacted for 4 hours, followed by heating and concentration under reduced pressure. Dichloromethane (90 mL) was added to the obtained concentrate, hydroxyethyl acrylate (7.00 g, 60.3 mmol) was added dropwise under an ice bath, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, water was added, and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain SPM1 (6.52 g, 15.3 mmol).
Note that IRGALUBE353 is a compound represented by the following structural formula.
２００ｍＬナスフラスコにＩＲＧＡＬＵＢＥ３５３（ＢＡＳＦジャパン株式会社製、１３．２ｇ，４０．２ｍｍｏｌ）、トルエン（２５ｍＬ）を加え室温で攪拌している中へ、塩化チオニル（８．７５ｇ，７４．１ｍｍｏｌ）を滴下した。オイルバスで６０℃に昇温し、４時間反応させた後、減圧下加熱濃縮した。得られた濃縮物にジクロロメタン（９０ｍＬ）を加え、氷浴下、ヒドロキシエチルアクリレート（７．００ｇ，６０．３ｍｍｏｌ）を滴下し、室温で３時間攪拌した。反応終了後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＳＰＭ１（６．５２ｇ，１５．３ｍｍｏｌ）を得た。
なお、ＩＲＧＡＬＵＢＥ３５３は、下記構造式で表される化合物である。
IRGALUBE353 (manufactured by BASF Japan Co., Ltd., 13.2 g, 40.2 mmol) and toluene (25 mL) were added to a 200 mL eggplant flask, and while stirring at room temperature, thionyl chloride (8.75 g, 74.1 mmol) was added dropwise. . The temperature was raised to 60° C. in an oil bath, and the mixture was reacted for 4 hours, followed by heating and concentration under reduced pressure. Dichloromethane (90 mL) was added to the obtained concentrate, hydroxyethyl acrylate (7.00 g, 60.3 mmol) was added dropwise under an ice bath, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, water was added, and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain SPM1 (6.52 g, 15.3 mmol).
Note that IRGALUBE353 is a compound represented by the following structural formula.
（ＳＰＭ２の合成方法）
１ＬナスフラスコにＩＲＧＡＬＵＢＥ６２（３１．４ｇ，１００ｍｍｏｌ）、メタノール（１５０ｍＬ）を加え０℃で攪拌している中へ、５％水酸化ナトリウム水溶液（２００ｍＬ）を滴下した。反応終了後、２Ｍ塩酸水溶液（１５０ｍＬ）を加え、酢酸エチルで抽出し、無水硫酸マグネシウムで乾燥させた後、得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりカルボン酸誘導体（２４．８ｇ，８６．７ｍｍｏｌ）を得た。
５００ｍＬナスフラスコに上記カルボン酸誘導体、トルエン（５４ｍＬ）を加え室温で攪拌している中へ、塩化チオニル（１８．９ｇ，１５９．８ｍｍｏｌ）を滴下した。オイルバスで６０℃に昇温し、４時間反応させた後、減圧下加熱濃縮した。得られた濃縮物にジクロロメタン（２００ｍＬ）を加え、氷浴下、ヒドロキシエチルアクリレート（１５．１ｇ，１３０ｍｍｏｌ）を滴下し、室温で３時間攪拌した。反応終了後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＳＰＭ２（３６．４ｇ，９４．９ｍｍｏｌ）を得た。 (Synthesis method of SPM2)
IRGALUBE62 (31.4 g, 100 mmol) and methanol (150 mL) were added to a 1 L eggplant flask, and while stirring at 0° C., 5% aqueous sodium hydroxide solution (200 mL) was added dropwise. After the reaction was completed, 2M aqueous hydrochloric acid solution (150 mL) was added, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the resulting concentrate was purified by silica gel column chromatography to obtain the carboxylic acid derivative (24. 8 g, 86.7 mmol) was obtained.
The above carboxylic acid derivative and toluene (54 mL) were added to a 500 mL eggplant flask, and while stirring at room temperature, thionyl chloride (18.9 g, 159.8 mmol) was added dropwise. The temperature was raised to 60° C. in an oil bath, and the mixture was reacted for 4 hours, followed by heating and concentration under reduced pressure. Dichloromethane (200 mL) was added to the obtained concentrate, hydroxyethyl acrylate (15.1 g, 130 mmol) was added dropwise under an ice bath, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, water was added, and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain SPM2 (36.4 g, 94.9 mmol).
１ＬナスフラスコにＩＲＧＡＬＵＢＥ６２（３１．４ｇ，１００ｍｍｏｌ）、メタノール（１５０ｍＬ）を加え０℃で攪拌している中へ、５％水酸化ナトリウム水溶液（２００ｍＬ）を滴下した。反応終了後、２Ｍ塩酸水溶液（１５０ｍＬ）を加え、酢酸エチルで抽出し、無水硫酸マグネシウムで乾燥させた後、得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりカルボン酸誘導体（２４．８ｇ，８６．７ｍｍｏｌ）を得た。
５００ｍＬナスフラスコに上記カルボン酸誘導体、トルエン（５４ｍＬ）を加え室温で攪拌している中へ、塩化チオニル（１８．９ｇ，１５９．８ｍｍｏｌ）を滴下した。オイルバスで６０℃に昇温し、４時間反応させた後、減圧下加熱濃縮した。得られた濃縮物にジクロロメタン（２００ｍＬ）を加え、氷浴下、ヒドロキシエチルアクリレート（１５．１ｇ，１３０ｍｍｏｌ）を滴下し、室温で３時間攪拌した。反応終了後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＳＰＭ２（３６．４ｇ，９４．９ｍｍｏｌ）を得た。 (Synthesis method of SPM2)
IRGALUBE62 (31.4 g, 100 mmol) and methanol (150 mL) were added to a 1 L eggplant flask, and while stirring at 0° C., 5% aqueous sodium hydroxide solution (200 mL) was added dropwise. After the reaction was completed, 2M aqueous hydrochloric acid solution (150 mL) was added, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the resulting concentrate was purified by silica gel column chromatography to obtain the carboxylic acid derivative (24. 8 g, 86.7 mmol) was obtained.
The above carboxylic acid derivative and toluene (54 mL) were added to a 500 mL eggplant flask, and while stirring at room temperature, thionyl chloride (18.9 g, 159.8 mmol) was added dropwise. The temperature was raised to 60° C. in an oil bath, and the mixture was reacted for 4 hours, followed by heating and concentration under reduced pressure. Dichloromethane (200 mL) was added to the obtained concentrate, hydroxyethyl acrylate (15.1 g, 130 mmol) was added dropwise under an ice bath, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, water was added, and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain SPM2 (36.4 g, 94.9 mmol).
（ＳＰＭ３の合成方法）
５００ｍＬナスフラスコに水酸化カリウム（１１．２ｇ，１９９ｍｍｏｌ）、水（４０ｍＬ）クロロホルム（１４０ｍＬ）、ジチオリン酸 Ｏ，Ｏ’－ジエチル（３２．７ｇ，１７５ｍｍｏｌ）、３－クロロプロピオン酸（２０．０ｇ，１７６ｍｍｏｌ）を加えオイルバスで６０℃に昇温し、７時間反応させた。有機層を水で洗浄後、無水硫酸マグネシウムで乾燥・濃縮することにより、カルボン酸誘導体（２１．６ｇ，８３．６ｍｍｏｌ）を得た。
１００ｍＬナスフラスコに上記カルボン酸誘導体（１０ｇ，３８．７ｍｍｏｌ）、ジクロロメタン（５０ｍＬ）を加え０℃で攪拌している中へ、塩化オキサリル（１６．０ｇ，１２５．９ｍｍｏｌ）を滴下した。室温で２時間反応させた後、減圧下加熱濃縮し得られた濃縮物にジクロロメタン（８６ｍＬ）を加え、氷浴下、ヒドロキシエチルアクリレート（６．７ｇ，５８．１ｍｍｏｌ）を滴下し、室温で４時間攪拌した。反応終了後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＳＰＭ３（４．８８ｇ，１３．７ｍｍｏｌ）を得た。 (Synthesis method of SPM3)
Potassium hydroxide (11.2 g, 199 mmol), water (40 mL), chloroform (140 mL), O,O'-diethyl dithiophosphate (32.7 g, 175 mmol), 3-chloropropionic acid (20.0 g, 176 mmol) was added thereto, the temperature was raised to 60°C in an oil bath, and the mixture was reacted for 7 hours. After washing the organic layer with water, the organic layer was dried and concentrated over anhydrous magnesium sulfate to obtain a carboxylic acid derivative (21.6 g, 83.6 mmol).
The above carboxylic acid derivative (10 g, 38.7 mmol) and dichloromethane (50 mL) were added to a 100 mL eggplant flask, and while stirring at 0° C., oxalyl chloride (16.0 g, 125.9 mmol) was added dropwise. After reacting at room temperature for 2 hours, dichloromethane (86 mL) was added to the concentrate obtained by heating and concentrating under reduced pressure, and hydroxyethyl acrylate (6.7 g, 58.1 mmol) was added dropwise in an ice bath. Stir for hours. After the reaction was completed, water was added and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain SPM3 (4.88 g, 13.7 mmol).
５００ｍＬナスフラスコに水酸化カリウム（１１．２ｇ，１９９ｍｍｏｌ）、水（４０ｍＬ）クロロホルム（１４０ｍＬ）、ジチオリン酸 Ｏ，Ｏ’－ジエチル（３２．７ｇ，１７５ｍｍｏｌ）、３－クロロプロピオン酸（２０．０ｇ，１７６ｍｍｏｌ）を加えオイルバスで６０℃に昇温し、７時間反応させた。有機層を水で洗浄後、無水硫酸マグネシウムで乾燥・濃縮することにより、カルボン酸誘導体（２１．６ｇ，８３．６ｍｍｏｌ）を得た。
１００ｍＬナスフラスコに上記カルボン酸誘導体（１０ｇ，３８．７ｍｍｏｌ）、ジクロロメタン（５０ｍＬ）を加え０℃で攪拌している中へ、塩化オキサリル（１６．０ｇ，１２５．９ｍｍｏｌ）を滴下した。室温で２時間反応させた後、減圧下加熱濃縮し得られた濃縮物にジクロロメタン（８６ｍＬ）を加え、氷浴下、ヒドロキシエチルアクリレート（６．７ｇ，５８．１ｍｍｏｌ）を滴下し、室温で４時間攪拌した。反応終了後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＳＰＭ３（４．８８ｇ，１３．７ｍｍｏｌ）を得た。 (Synthesis method of SPM3)
Potassium hydroxide (11.2 g, 199 mmol), water (40 mL), chloroform (140 mL), O,O'-diethyl dithiophosphate (32.7 g, 175 mmol), 3-chloropropionic acid (20.0 g, 176 mmol) was added thereto, the temperature was raised to 60°C in an oil bath, and the mixture was reacted for 7 hours. After washing the organic layer with water, the organic layer was dried and concentrated over anhydrous magnesium sulfate to obtain a carboxylic acid derivative (21.6 g, 83.6 mmol).
The above carboxylic acid derivative (10 g, 38.7 mmol) and dichloromethane (50 mL) were added to a 100 mL eggplant flask, and while stirring at 0° C., oxalyl chloride (16.0 g, 125.9 mmol) was added dropwise. After reacting at room temperature for 2 hours, dichloromethane (86 mL) was added to the concentrate obtained by heating and concentrating under reduced pressure, and hydroxyethyl acrylate (6.7 g, 58.1 mmol) was added dropwise in an ice bath. Stir for hours. After the reaction was completed, water was added and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain SPM3 (4.88 g, 13.7 mmol).
（製造例Ａ１：共重合体（Ｘ）－Ａ１の製造）
温度計、窒素導入管、及び撹拌機を取り付けた２００ｍＬ容の４つ口フラスコに、ドデシルアクリレートを３３．９ｇ（１３７ｍｍоｌ）、２－ヒドロキシエチルアクリレートを１０．５ｇ（９０．６ｍｍоｌ）、ＳＰＭ１を０．４３ｇ（１．０ｍｍоｌ）、溶媒として２－プロパノールを４３．９ｇ仕込んだ。
次いで、フラスコ内を窒素置換し、開始剤として２，２’－アゾビス（イソブチロニトリル）を０．１８ｇ添加した後、撹拌しながらゆっくり昇温し、７５～８５℃の温度で還流させながら４時間反応させて、反応終了後に溶媒を減圧留去することにより、共重合体（Ｘ）－Ａ１を得た。
共重合体（Ｘ）－Ａ１の質量平均分子量（Ｍｗ）は１９，８００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ａ１のリン含有量は７２０質量ｐｐｍ、硫黄含有量は１５６０質量ｐｐｍであった。
共重合体（Ｘ）－Ａ１は、共重合体（Ｘ）－Ａ１の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A1: Production of copolymer (X)-A1)
In a 200 mL four-necked flask equipped with a thermometer, nitrogen inlet tube, and stirrer, add 33.9 g (137 mmol) of dodecyl acrylate, 10.5 g (90.6 mmol) of 2-hydroxyethyl acrylate, and 0 of SPM1. .43 g (1.0 mmol) and 43.9 g of 2-propanol as a solvent were charged.
Next, the inside of the flask was purged with nitrogen, and after adding 0.18 g of 2,2'-azobis(isobutyronitrile) as an initiator, the temperature was slowly raised while stirring, and the mixture was refluxed at a temperature of 75 to 85°C. After reacting for 4 hours, the solvent was distilled off under reduced pressure to obtain copolymer (X)-A1.
The mass average molecular weight (Mw) of copolymer (X)-A1 was 19,800, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A1 was 720 mass ppm, and the sulfur content was 1560 mass ppm.
Copolymer (X)-A1 was diluted with mineral oil so that the content of copolymer (X)-A1 was 50% by mass, and mixed into lubricating base oil.
温度計、窒素導入管、及び撹拌機を取り付けた２００ｍＬ容の４つ口フラスコに、ドデシルアクリレートを３３．９ｇ（１３７ｍｍоｌ）、２－ヒドロキシエチルアクリレートを１０．５ｇ（９０．６ｍｍоｌ）、ＳＰＭ１を０．４３ｇ（１．０ｍｍоｌ）、溶媒として２－プロパノールを４３．９ｇ仕込んだ。
次いで、フラスコ内を窒素置換し、開始剤として２，２’－アゾビス（イソブチロニトリル）を０．１８ｇ添加した後、撹拌しながらゆっくり昇温し、７５～８５℃の温度で還流させながら４時間反応させて、反応終了後に溶媒を減圧留去することにより、共重合体（Ｘ）－Ａ１を得た。
共重合体（Ｘ）－Ａ１の質量平均分子量（Ｍｗ）は１９，８００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ａ１のリン含有量は７２０質量ｐｐｍ、硫黄含有量は１５６０質量ｐｐｍであった。
共重合体（Ｘ）－Ａ１は、共重合体（Ｘ）－Ａ１の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A1: Production of copolymer (X)-A1)
In a 200 mL four-necked flask equipped with a thermometer, nitrogen inlet tube, and stirrer, add 33.9 g (137 mmol) of dodecyl acrylate, 10.5 g (90.6 mmol) of 2-hydroxyethyl acrylate, and 0 of SPM1. .43 g (1.0 mmol) and 43.9 g of 2-propanol as a solvent were charged.
Next, the inside of the flask was purged with nitrogen, and after adding 0.18 g of 2,2'-azobis(isobutyronitrile) as an initiator, the temperature was slowly raised while stirring, and the mixture was refluxed at a temperature of 75 to 85°C. After reacting for 4 hours, the solvent was distilled off under reduced pressure to obtain copolymer (X)-A1.
The mass average molecular weight (Mw) of copolymer (X)-A1 was 19,800, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A1 was 720 mass ppm, and the sulfur content was 1560 mass ppm.
Copolymer (X)-A1 was diluted with mineral oil so that the content of copolymer (X)-A1 was 50% by mass, and mixed into lubricating base oil.
（製造例Ａ２：共重合体（Ｘ）－Ａ２の製造）
製造例Ａ１においてＳＰＭ１の代わりにＳＰＭ２を０．４４ｇ（１．１ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ２を得た。
共重合体（Ｘ）－Ａ２の質量平均分子量（Ｍｗ）は１９，７００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ａ２のリン含有量は７６０質量ｐｐｍ、硫黄含有量は１７００質量ｐｐｍであった。
共重合体（Ｘ）－Ａ２は、共重合体（Ｘ）－Ａ２の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A2: Production of copolymer (X)-A2)
Copolymer (X)-A2 was obtained by carrying out the same operation as in Production Example A1 except that 0.44 g (1.1 mmol) of SPM2 was charged instead of SPM1.
The mass average molecular weight (Mw) of copolymer (X)-A2 was 19,700, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A2 was 760 mass ppm, and the sulfur content was 1700 mass ppm.
Copolymer (X)-A2 was diluted with mineral oil so that the content of copolymer (X)-A2 was 50% by mass, and mixed into lubricating base oil.
製造例Ａ１においてＳＰＭ１の代わりにＳＰＭ２を０．４４ｇ（１．１ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ２を得た。
共重合体（Ｘ）－Ａ２の質量平均分子量（Ｍｗ）は１９，７００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ａ２のリン含有量は７６０質量ｐｐｍ、硫黄含有量は１７００質量ｐｐｍであった。
共重合体（Ｘ）－Ａ２は、共重合体（Ｘ）－Ａ２の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A2: Production of copolymer (X)-A2)
Copolymer (X)-A2 was obtained by carrying out the same operation as in Production Example A1 except that 0.44 g (1.1 mmol) of SPM2 was charged instead of SPM1.
The mass average molecular weight (Mw) of copolymer (X)-A2 was 19,700, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A2 was 760 mass ppm, and the sulfur content was 1700 mass ppm.
Copolymer (X)-A2 was diluted with mineral oil so that the content of copolymer (X)-A2 was 50% by mass, and mixed into lubricating base oil.
（製造例Ａ３：共重合体（Ｘ）－Ａ３の製造）
製造例Ａ１においてＳＰＭ１の代わりにＳＰＭ３を０．４４ｇ（１．２ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ３を得た。
共重合体（Ｘ）－Ａ３の質量平均分子量（Ｍｗ）は１９，１００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ａ３のリン含有量は８４０質量ｐｐｍ、硫黄含有量は１７６０質量ｐｐｍであった。
共重合体（Ｘ）－Ａ３は、共重合体（Ｘ）－Ａ３の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A3: Production of copolymer (X)-A3)
Copolymer (X)-A3 was obtained by carrying out the same operation as in Production Example A1 except that 0.44 g (1.2 mmol) of SPM3 was charged instead of SPM1.
The mass average molecular weight (Mw) of copolymer (X)-A3 was 19,100, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A3 was 840 mass ppm, and the sulfur content was 1760 mass ppm.
Copolymer (X)-A3 was diluted with mineral oil so that the content of copolymer (X)-A3 was 50% by mass, and mixed into lubricating base oil.
製造例Ａ１においてＳＰＭ１の代わりにＳＰＭ３を０．４４ｇ（１．２ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ３を得た。
共重合体（Ｘ）－Ａ３の質量平均分子量（Ｍｗ）は１９，１００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ａ３のリン含有量は８４０質量ｐｐｍ、硫黄含有量は１７６０質量ｐｐｍであった。
共重合体（Ｘ）－Ａ３は、共重合体（Ｘ）－Ａ３の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A3: Production of copolymer (X)-A3)
Copolymer (X)-A3 was obtained by carrying out the same operation as in Production Example A1 except that 0.44 g (1.2 mmol) of SPM3 was charged instead of SPM1.
The mass average molecular weight (Mw) of copolymer (X)-A3 was 19,100, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A3 was 840 mass ppm, and the sulfur content was 1760 mass ppm.
Copolymer (X)-A3 was diluted with mineral oil so that the content of copolymer (X)-A3 was 50% by mass, and mixed into lubricating base oil.
（製造例Ａ４：共重合体（Ｘ）－Ａ４の製造）
製造例２においてドデシルアクリレートを４７．９ｇ（１９９ｍｍоｌ）、２－ヒドロキシエチルアクリレートを５．８ｇ（４９．８ｍｍоｌ）、ＳＰＭ２を０．５２ｇ（１．０ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ４を得た。
共重合体（Ｘ）－Ａ４の質量平均分子量（Ｍｗ）は１９，７００であり、分子量分布（Ｍｗ／Ｍｎ）は２．２であった。また、共重合体（Ｘ）－Ａ４のリン含有量は７６０質量ｐｐｍ、硫黄含有量は１６６０質量ｐｐｍであった。
共重合体（Ｘ）－Ａ４は、共重合体（Ｘ）－Ａ４の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A4: Production of copolymer (X)-A4)
The same operation as in Production Example 2 was carried out except that 47.9 g (199 mmol) of dodecyl acrylate, 5.8 g (49.8 mmol) of 2-hydroxyethyl acrylate, and 0.52 g (1.0 mmol) of SPM2 were charged. , Copolymer (X)-A4 was obtained.
The mass average molecular weight (Mw) of copolymer (X)-A4 was 19,700, and the molecular weight distribution (Mw/Mn) was 2.2. Further, the phosphorus content of copolymer (X)-A4 was 760 mass ppm, and the sulfur content was 1660 mass ppm.
Copolymer (X)-A4 was diluted with mineral oil so that the content of copolymer (X)-A4 was 50% by mass, and mixed into lubricating base oil.
製造例２においてドデシルアクリレートを４７．９ｇ（１９９ｍｍоｌ）、２－ヒドロキシエチルアクリレートを５．８ｇ（４９．８ｍｍоｌ）、ＳＰＭ２を０．５２ｇ（１．０ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ４を得た。
共重合体（Ｘ）－Ａ４の質量平均分子量（Ｍｗ）は１９，７００であり、分子量分布（Ｍｗ／Ｍｎ）は２．２であった。また、共重合体（Ｘ）－Ａ４のリン含有量は７６０質量ｐｐｍ、硫黄含有量は１６６０質量ｐｐｍであった。
共重合体（Ｘ）－Ａ４は、共重合体（Ｘ）－Ａ４の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A4: Production of copolymer (X)-A4)
The same operation as in Production Example 2 was carried out except that 47.9 g (199 mmol) of dodecyl acrylate, 5.8 g (49.8 mmol) of 2-hydroxyethyl acrylate, and 0.52 g (1.0 mmol) of SPM2 were charged. , Copolymer (X)-A4 was obtained.
The mass average molecular weight (Mw) of copolymer (X)-A4 was 19,700, and the molecular weight distribution (Mw/Mn) was 2.2. Further, the phosphorus content of copolymer (X)-A4 was 760 mass ppm, and the sulfur content was 1660 mass ppm.
Copolymer (X)-A4 was diluted with mineral oil so that the content of copolymer (X)-A4 was 50% by mass, and mixed into lubricating base oil.
（製造例Ａ５：共重合体（Ｘ）－Ａ５の製造）
製造例Ａ２において溶媒として２－プロパノールを２２．０ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ５を得た。
共重合体（Ｘ）－Ａ５の質量平均分子量（Ｍｗ）は３４，２００であり、分子量分布（Ｍｗ／Ｍｎ）は２．３であった。また、共重合体（Ｘ）－Ａ５のリン含有量は８００質量ｐｐｍ、硫黄含有量は１７００質量ｐｐｍであった。
共重合体（Ｘ）－Ａ５は、共重合体（Ｘ）－Ａ５の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A5: Production of copolymer (X)-A5)
Copolymer (X)-A5 was obtained by carrying out the same operation as in Production Example A2 except that 22.0 g of 2-propanol was added as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-A5 was 34,200, and the molecular weight distribution (Mw/Mn) was 2.3. Further, the phosphorus content of copolymer (X)-A5 was 800 mass ppm, and the sulfur content was 1700 mass ppm.
Copolymer (X)-A5 was diluted with mineral oil so that the content of copolymer (X)-A5 was 50% by mass, and mixed into lubricating base oil.
製造例Ａ２において溶媒として２－プロパノールを２２．０ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ５を得た。
共重合体（Ｘ）－Ａ５の質量平均分子量（Ｍｗ）は３４，２００であり、分子量分布（Ｍｗ／Ｍｎ）は２．３であった。また、共重合体（Ｘ）－Ａ５のリン含有量は８００質量ｐｐｍ、硫黄含有量は１７００質量ｐｐｍであった。
共重合体（Ｘ）－Ａ５は、共重合体（Ｘ）－Ａ５の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A5: Production of copolymer (X)-A5)
Copolymer (X)-A5 was obtained by carrying out the same operation as in Production Example A2 except that 22.0 g of 2-propanol was added as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-A5 was 34,200, and the molecular weight distribution (Mw/Mn) was 2.3. Further, the phosphorus content of copolymer (X)-A5 was 800 mass ppm, and the sulfur content was 1700 mass ppm.
Copolymer (X)-A5 was diluted with mineral oil so that the content of copolymer (X)-A5 was 50% by mass, and mixed into lubricating base oil.
（製造例Ａ６：共重合体（Ｘ）－Ａ６の製造）
製造例Ａ２において溶媒として２－プロパノールを１４４．０ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ６を得た。
共重合体（Ｘ）－Ａ６の質量平均分子量（Ｍｗ）は８，７００であり、分子量分布（Ｍｗ／Ｍｎ）は１．６であった。また、共重合体（Ｘ）－Ａ６のリン含有量は７６０質量ｐｐｍ、硫黄含有量は１６２０質量ｐｐｍであった。
ポリ（メタ）アクリレート系共重合体（Ｘ）－Ａ６は、ポリ（メタ）アクリレート系共重合体（Ｘ）－Ａ６の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A6: Production of copolymer (X)-A6)
Copolymer (X)-A6 was obtained by carrying out the same operation as in Production Example A2 except that 144.0 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-A6 was 8,700, and the molecular weight distribution (Mw/Mn) was 1.6. Further, the phosphorus content of copolymer (X)-A6 was 760 mass ppm, and the sulfur content was 1620 mass ppm.
Poly(meth)acrylate copolymer (X)-A6 is diluted with mineral oil so that the content of poly(meth)acrylate copolymer (X)-A6 is 50% by mass, and then mixed with lubricating oil. Mixed with base oil.
製造例Ａ２において溶媒として２－プロパノールを１４４．０ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ａ６を得た。
共重合体（Ｘ）－Ａ６の質量平均分子量（Ｍｗ）は８，７００であり、分子量分布（Ｍｗ／Ｍｎ）は１．６であった。また、共重合体（Ｘ）－Ａ６のリン含有量は７６０質量ｐｐｍ、硫黄含有量は１６２０質量ｐｐｍであった。
ポリ（メタ）アクリレート系共重合体（Ｘ）－Ａ６は、ポリ（メタ）アクリレート系共重合体（Ｘ）－Ａ６の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example A6: Production of copolymer (X)-A6)
Copolymer (X)-A6 was obtained by carrying out the same operation as in Production Example A2 except that 144.0 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-A6 was 8,700, and the molecular weight distribution (Mw/Mn) was 1.6. Further, the phosphorus content of copolymer (X)-A6 was 760 mass ppm, and the sulfur content was 1620 mass ppm.
Poly(meth)acrylate copolymer (X)-A6 is diluted with mineral oil so that the content of poly(meth)acrylate copolymer (X)-A6 is 50% by mass, and then mixed with lubricating oil. Mixed with base oil.
共重合体（Ｘ）－Ａ１～共重合体（Ｘ）－Ａ６の組成、共重合体（Ｘ）－Ａ１～共重合体（Ｘ）－Ａ６の硫黄量及びリン量、質量平均分子量（Ｍｗ）、及び分子量分布（Ｍｗ／Ｍｎ）を表１に示す。
なお、質量平均分子量（Ｍｗ）は、有効数字２桁で示した。 Composition of copolymer (X)-A1 to copolymer (X)-A6, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-A1 to copolymer (X)-A6 , and molecular weight distribution (Mw/Mn) are shown in Table 1.
In addition, the mass average molecular weight (Mw) is shown in two significant digits.
なお、質量平均分子量（Ｍｗ）は、有効数字２桁で示した。 Composition of copolymer (X)-A1 to copolymer (X)-A6, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-A1 to copolymer (X)-A6 , and molecular weight distribution (Mw/Mn) are shown in Table 1.
In addition, the mass average molecular weight (Mw) is shown in two significant digits.
＜製造例Ｂ１～Ｂ７＞
（製造例Ｂ１～Ｂ７で用いたモノマー）
・「ドデシルアクリレート（ＤＯＡ）」：上記一般式（ａ－１）中、Ｒａ１が水素原子であり、Ｒａ２がドデシル基（炭素数１２のアルキル基）である化合物である。モノマー（Ａ）（モノマー（Ａ１））として使用した。
・「２－ヒドロキシエチルアクリレート（ＨＥＡ）」：上記一般式（ｂ－１）中、Ｒｂ１が水素原子であり、Ｒｂ２がエチレン基（炭素数２のアルキレン基）であり、ｍ１＝１である化合物である。モノマー（Ｂ）（モノマー（Ｂ１１））として使用した。
・「ドデシルチオエチルアクリレート（ＤＴＡ）」：硫黄含有量＝１０．７質量％
上記一般式（ｄ１－１）中、Ｒｄ１１が水素原子であり、Ｒｄ１２がエチレン基（炭素数２のアルキレン基）であり、ｍ３＝１であり、Ｒｄ１３がドデシル基（炭素数１２のアルキル基）である化合物である。モノマー（Ｄ１）として使用した。製造法は以下の通りである。
５００ｍＬナスフラスコに２－（ドデシルチオ）エタノール（１５．３ｇ，６１．９ｍｍｏｌ）、ジクロロメタン（１２４ｍｌ）を加え０℃で攪拌している中へ、塩化アクリロイル（５．６ｇ，６１．９ｍｍｏｌ）、ピリジン（４．８９ｇ，６１．９ｍｍｏｌ）を滴下した。室温で１時間反応させた後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＤＴＡ（５．１９ｇ，１７．３ｍｍｏｌ）を得た。
・「オクチルチオエチルアクリレート（ＯＴＡ）」：硫黄含有量＝１３．１質量％
上記一般式（ｄ１－１）中、Ｒｄ１１が水素原子であり、Ｒｄ１２がエチレン基（炭素数２のアルキレン基）であり、ｍ３＝１であり、Ｒｄ１３がオクチル基（炭素数８のアルキル基）である化合物である。モノマー（Ｄ１）として使用した。製造法は以下の通りである。
ＤＴＡ製造法において、２－（ドデシルチオ）エタノールの代わりに２－（オクチルチオ）エタノールを（１１．７ｇ，６１．９ｍｍｏｌ）仕込んだこと以外は同様の操作を行って、ＯＴＡ（３．８８ｇ，１５．９ｍｍｏｌ）を得た。
・「リン酸エチルアクリレート（ＰＥＡ）」：共栄社化学株式会社製、Ｐ－１Ａ（Ｎ）、リン含有量＝１４．３質量％
上記一般式（ｄ２－１）中、ｎ＝１である化合物を主成分とし、ｎ＝２である化合物も含む混合物である。なお、両化合物とも、Ｒｄ２１が水素原子であり、ｍ４＝１である。また、両化合物とも、Ｒｄ２３は水素原子である。モノマー（Ｄ２）として使用した。 <Production examples B1 to B7>
(Monomer used in Production Examples B1 to B7)
- "Dodecyl acrylate (DOA)": A compound in the above general formula (a-1) in which R a1 is a hydrogen atom and R a2 is a dodecyl group (alkyl group having 12 carbon atoms). It was used as monomer (A) (monomer (A1)).
・"2-Hydroxyethyl acrylate (HEA)": In the above general formula (b-1), R b1 is a hydrogen atom, R b2 is an ethylene group (alkylene group having 2 carbon atoms), m1 = 1, It is a certain compound. It was used as monomer (B) (monomer (B11)).
・"Dodecylthioethyl acrylate (DTA)": Sulfur content = 10.7% by mass
In the above general formula (d1-1), R d11 is a hydrogen atom, R d12 is an ethylene group (an alkylene group with 2 carbon atoms), m3=1, and R d13 is a dodecyl group (an alkylene group with 12 carbon atoms). It is a compound that is an alkyl group). It was used as monomer (D1). The manufacturing method is as follows.
Acryloyl chloride (5.6 g, 61.9 mmol), pyridine ( 4.89 g, 61.9 mmol) was added dropwise. After reacting at room temperature for 1 hour, water was added and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain DTA (5.19 g, 17.3 mmol).
・"Octylthioethyl acrylate (OTA)": Sulfur content = 13.1% by mass
In the above general formula (d1-1), R d11 is a hydrogen atom, R d12 is an ethylene group (an alkylene group with 2 carbon atoms), m3=1, and R d13 is an octyl group (an alkylene group with 8 carbon atoms). It is a compound that is an alkyl group). It was used as monomer (D1). The manufacturing method is as follows.
In the DTA production method, OTA (3.88 g, 15.9 mmol) was prepared by performing the same procedure except that 2-(octylthio)ethanol (11.7 g, 61.9 mmol) was added instead of 2-(dodecylthio)ethanol. 9 mmol) was obtained.
・“Ethyl acrylate phosphate (PEA)”: manufactured by Kyoeisha Chemical Co., Ltd., P-1A (N), phosphorus content = 14.3% by mass
In the above general formula (d2-1), it is a mixture containing a compound where n=1 as a main component and also a compound where n=2. In addition, in both compounds, R d21 is a hydrogen atom, and m4=1. Further, in both compounds, R d23 is a hydrogen atom. It was used as monomer (D2).
（製造例Ｂ１～Ｂ７で用いたモノマー）
・「ドデシルアクリレート（ＤＯＡ）」：上記一般式（ａ－１）中、Ｒａ１が水素原子であり、Ｒａ２がドデシル基（炭素数１２のアルキル基）である化合物である。モノマー（Ａ）（モノマー（Ａ１））として使用した。
・「２－ヒドロキシエチルアクリレート（ＨＥＡ）」：上記一般式（ｂ－１）中、Ｒｂ１が水素原子であり、Ｒｂ２がエチレン基（炭素数２のアルキレン基）であり、ｍ１＝１である化合物である。モノマー（Ｂ）（モノマー（Ｂ１１））として使用した。
・「ドデシルチオエチルアクリレート（ＤＴＡ）」：硫黄含有量＝１０．７質量％
上記一般式（ｄ１－１）中、Ｒｄ１１が水素原子であり、Ｒｄ１２がエチレン基（炭素数２のアルキレン基）であり、ｍ３＝１であり、Ｒｄ１３がドデシル基（炭素数１２のアルキル基）である化合物である。モノマー（Ｄ１）として使用した。製造法は以下の通りである。
５００ｍＬナスフラスコに２－（ドデシルチオ）エタノール（１５．３ｇ，６１．９ｍｍｏｌ）、ジクロロメタン（１２４ｍｌ）を加え０℃で攪拌している中へ、塩化アクリロイル（５．６ｇ，６１．９ｍｍｏｌ）、ピリジン（４．８９ｇ，６１．９ｍｍｏｌ）を滴下した。室温で１時間反応させた後、水を加えてジクロロメタン抽出液を、無水硫酸マグネシウムで乾燥し、減圧下加熱濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーにて精製する事によりＤＴＡ（５．１９ｇ，１７．３ｍｍｏｌ）を得た。
・「オクチルチオエチルアクリレート（ＯＴＡ）」：硫黄含有量＝１３．１質量％
上記一般式（ｄ１－１）中、Ｒｄ１１が水素原子であり、Ｒｄ１２がエチレン基（炭素数２のアルキレン基）であり、ｍ３＝１であり、Ｒｄ１３がオクチル基（炭素数８のアルキル基）である化合物である。モノマー（Ｄ１）として使用した。製造法は以下の通りである。
ＤＴＡ製造法において、２－（ドデシルチオ）エタノールの代わりに２－（オクチルチオ）エタノールを（１１．７ｇ，６１．９ｍｍｏｌ）仕込んだこと以外は同様の操作を行って、ＯＴＡ（３．８８ｇ，１５．９ｍｍｏｌ）を得た。
・「リン酸エチルアクリレート（ＰＥＡ）」：共栄社化学株式会社製、Ｐ－１Ａ（Ｎ）、リン含有量＝１４．３質量％
上記一般式（ｄ２－１）中、ｎ＝１である化合物を主成分とし、ｎ＝２である化合物も含む混合物である。なお、両化合物とも、Ｒｄ２１が水素原子であり、ｍ４＝１である。また、両化合物とも、Ｒｄ２３は水素原子である。モノマー（Ｄ２）として使用した。 <Production examples B1 to B7>
(Monomer used in Production Examples B1 to B7)
- "Dodecyl acrylate (DOA)": A compound in the above general formula (a-1) in which R a1 is a hydrogen atom and R a2 is a dodecyl group (alkyl group having 12 carbon atoms). It was used as monomer (A) (monomer (A1)).
・"2-Hydroxyethyl acrylate (HEA)": In the above general formula (b-1), R b1 is a hydrogen atom, R b2 is an ethylene group (alkylene group having 2 carbon atoms), m1 = 1, It is a certain compound. It was used as monomer (B) (monomer (B11)).
・"Dodecylthioethyl acrylate (DTA)": Sulfur content = 10.7% by mass
In the above general formula (d1-1), R d11 is a hydrogen atom, R d12 is an ethylene group (an alkylene group with 2 carbon atoms), m3=1, and R d13 is a dodecyl group (an alkylene group with 12 carbon atoms). It is a compound that is an alkyl group). It was used as monomer (D1). The manufacturing method is as follows.
Acryloyl chloride (5.6 g, 61.9 mmol), pyridine ( 4.89 g, 61.9 mmol) was added dropwise. After reacting at room temperature for 1 hour, water was added and the dichloromethane extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure by heating. The obtained concentrate was purified by silica gel column chromatography to obtain DTA (5.19 g, 17.3 mmol).
・"Octylthioethyl acrylate (OTA)": Sulfur content = 13.1% by mass
In the above general formula (d1-1), R d11 is a hydrogen atom, R d12 is an ethylene group (an alkylene group with 2 carbon atoms), m3=1, and R d13 is an octyl group (an alkylene group with 8 carbon atoms). It is a compound that is an alkyl group). It was used as monomer (D1). The manufacturing method is as follows.
In the DTA production method, OTA (3.88 g, 15.9 mmol) was prepared by performing the same procedure except that 2-(octylthio)ethanol (11.7 g, 61.9 mmol) was added instead of 2-(dodecylthio)ethanol. 9 mmol) was obtained.
・“Ethyl acrylate phosphate (PEA)”: manufactured by Kyoeisha Chemical Co., Ltd., P-1A (N), phosphorus content = 14.3% by mass
In the above general formula (d2-1), it is a mixture containing a compound where n=1 as a main component and also a compound where n=2. In addition, in both compounds, R d21 is a hydrogen atom, and m4=1. Further, in both compounds, R d23 is a hydrogen atom. It was used as monomer (D2).
（製造例Ｂ１：共重合体（Ｘ）－Ｂ１の製造）
温度計、窒素導入管、及び撹拌機を取り付けた２００ｍＬ容の４つ口フラスコに、ドデシルアクリレートを３５．７ｇ（１４８ｍｍоｌ）、２－ヒドロキシエチルアクリレートを１１．４ｇ（９８．１ｍｍоｌ）、ＤＴＡを０．４６ｇ（１．５ｍｍоｌ）、ＰＥＡを０．９５ｇ（４．８ｍｍоｌ）、溶媒として２－プロパノールを４７．５ｇ仕込んだ。
次いで、フラスコ内を窒素置換し、開始剤として２，２’－アゾビス（イソブチロニトリル）を０．２ｇ添加した後、撹拌しながらゆっくり昇温し、７５～８５℃の温度で還流させながら４時間反応させて、反応終了後に溶媒を減圧留去することにより、共重合体（Ｘ）－Ｂ１を得た。
共重合体（Ｘ）－Ｂ１の質量平均分子量（Ｍｗ）は１８，２００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ｂ１のリン含有量は２８００質量ｐｐｍ、硫黄含有量は８８０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ１は、共重合体（Ｘ）－Ｂ１の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B1: Production of copolymer (X)-B1)
In a 200 mL four-necked flask equipped with a thermometer, nitrogen inlet tube, and stirrer, add 35.7 g (148 mmol) of dodecyl acrylate, 11.4 g (98.1 mmol) of 2-hydroxyethyl acrylate, and 0.0 g of DTA. 0.95 g (4.8 mmol) of PEA, and 47.5 g of 2-propanol as a solvent were charged.
Next, the inside of the flask was purged with nitrogen, and after adding 0.2 g of 2,2'-azobis(isobutyronitrile) as an initiator, the temperature was slowly raised while stirring, and the mixture was refluxed at a temperature of 75 to 85°C. After reacting for 4 hours, the solvent was distilled off under reduced pressure to obtain copolymer (X)-B1.
The mass average molecular weight (Mw) of copolymer (X)-B1 was 18,200, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-B1 was 2,800 mass ppm, and the sulfur content was 880 mass ppm.
Copolymer (X)-B1 was diluted with mineral oil so that the content of copolymer (X)-B1 was 50% by mass, and mixed into lubricating base oil.
温度計、窒素導入管、及び撹拌機を取り付けた２００ｍＬ容の４つ口フラスコに、ドデシルアクリレートを３５．７ｇ（１４８ｍｍоｌ）、２－ヒドロキシエチルアクリレートを１１．４ｇ（９８．１ｍｍоｌ）、ＤＴＡを０．４６ｇ（１．５ｍｍоｌ）、ＰＥＡを０．９５ｇ（４．８ｍｍоｌ）、溶媒として２－プロパノールを４７．５ｇ仕込んだ。
次いで、フラスコ内を窒素置換し、開始剤として２，２’－アゾビス（イソブチロニトリル）を０．２ｇ添加した後、撹拌しながらゆっくり昇温し、７５～８５℃の温度で還流させながら４時間反応させて、反応終了後に溶媒を減圧留去することにより、共重合体（Ｘ）－Ｂ１を得た。
共重合体（Ｘ）－Ｂ１の質量平均分子量（Ｍｗ）は１８，２００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ｂ１のリン含有量は２８００質量ｐｐｍ、硫黄含有量は８８０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ１は、共重合体（Ｘ）－Ｂ１の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B1: Production of copolymer (X)-B1)
In a 200 mL four-necked flask equipped with a thermometer, nitrogen inlet tube, and stirrer, add 35.7 g (148 mmol) of dodecyl acrylate, 11.4 g (98.1 mmol) of 2-hydroxyethyl acrylate, and 0.0 g of DTA. 0.95 g (4.8 mmol) of PEA, and 47.5 g of 2-propanol as a solvent were charged.
Next, the inside of the flask was purged with nitrogen, and after adding 0.2 g of 2,2'-azobis(isobutyronitrile) as an initiator, the temperature was slowly raised while stirring, and the mixture was refluxed at a temperature of 75 to 85°C. After reacting for 4 hours, the solvent was distilled off under reduced pressure to obtain copolymer (X)-B1.
The mass average molecular weight (Mw) of copolymer (X)-B1 was 18,200, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-B1 was 2,800 mass ppm, and the sulfur content was 880 mass ppm.
Copolymer (X)-B1 was diluted with mineral oil so that the content of copolymer (X)-B1 was 50% by mass, and mixed into lubricating base oil.
（製造例Ｂ２：共重合体（Ｘ）－Ｂ２の製造）
製造例Ｂ１においてＤＴＡの代わりにＯＴＡを０．４６ｇ（１．９ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ２を得た。
共重合体（Ｘ）－Ｂ２の質量平均分子量（Ｍｗ）は１８，２００であり、分子量分布（Ｍｗ／Ｍｎ）は１．９であった。また、共重合体（Ｘ）－Ｂ２のリン含有量は３０００質量ｐｐｍ、硫黄含有量は１０６０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ２は、共重合体（Ｘ）－Ｂ２の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B2: Production of copolymer (X)-B2)
Copolymer (X)-B2 was obtained by carrying out the same operation as in Production Example B1 except that 0.46 g (1.9 mmol) of OTA was charged instead of DTA.
The mass average molecular weight (Mw) of copolymer (X)-B2 was 18,200, and the molecular weight distribution (Mw/Mn) was 1.9. Further, the phosphorus content of copolymer (X)-B2 was 3000 mass ppm, and the sulfur content was 1060 mass ppm.
Copolymer (X)-B2 was diluted with mineral oil so that the content of copolymer (X)-B2 was 50% by mass, and mixed into lubricating base oil.
製造例Ｂ１においてＤＴＡの代わりにＯＴＡを０．４６ｇ（１．９ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ２を得た。
共重合体（Ｘ）－Ｂ２の質量平均分子量（Ｍｗ）は１８，２００であり、分子量分布（Ｍｗ／Ｍｎ）は１．９であった。また、共重合体（Ｘ）－Ｂ２のリン含有量は３０００質量ｐｐｍ、硫黄含有量は１０６０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ２は、共重合体（Ｘ）－Ｂ２の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B2: Production of copolymer (X)-B2)
Copolymer (X)-B2 was obtained by carrying out the same operation as in Production Example B1 except that 0.46 g (1.9 mmol) of OTA was charged instead of DTA.
The mass average molecular weight (Mw) of copolymer (X)-B2 was 18,200, and the molecular weight distribution (Mw/Mn) was 1.9. Further, the phosphorus content of copolymer (X)-B2 was 3000 mass ppm, and the sulfur content was 1060 mass ppm.
Copolymer (X)-B2 was diluted with mineral oil so that the content of copolymer (X)-B2 was 50% by mass, and mixed into lubricating base oil.
（製造例Ｂ３：共重合体（Ｘ）－Ｂ３の製造）
製造例Ｂ１において溶媒として２－プロパノールを２３．８ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ３を得た。
共重合体（Ｘ）－Ｂ３の質量平均分子量（Ｍｗ）は４６，４００であり、分子量分布（Ｍｗ／Ｍｎ）は３．２であった。また、共重合体（Ｘ）－Ｂ３のリン含有量は２８００質量ｐｐｍ、硫黄含有量は１０４０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ３は、共重合体（Ｘ）－Ｂ３の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B3: Production of copolymer (X)-B3)
Copolymer (X)-B3 was obtained by carrying out the same operation as in Production Example B1 except that 23.8 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-B3 was 46,400, and the molecular weight distribution (Mw/Mn) was 3.2. Further, the phosphorus content of copolymer (X)-B3 was 2,800 mass ppm, and the sulfur content was 1,040 mass ppm.
Copolymer (X)-B3 was diluted with mineral oil so that the content of copolymer (X)-B3 was 50% by mass, and mixed into lubricating base oil.
製造例Ｂ１において溶媒として２－プロパノールを２３．８ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ３を得た。
共重合体（Ｘ）－Ｂ３の質量平均分子量（Ｍｗ）は４６，４００であり、分子量分布（Ｍｗ／Ｍｎ）は３．２であった。また、共重合体（Ｘ）－Ｂ３のリン含有量は２８００質量ｐｐｍ、硫黄含有量は１０４０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ３は、共重合体（Ｘ）－Ｂ３の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B3: Production of copolymer (X)-B3)
Copolymer (X)-B3 was obtained by carrying out the same operation as in Production Example B1 except that 23.8 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-B3 was 46,400, and the molecular weight distribution (Mw/Mn) was 3.2. Further, the phosphorus content of copolymer (X)-B3 was 2,800 mass ppm, and the sulfur content was 1,040 mass ppm.
Copolymer (X)-B3 was diluted with mineral oil so that the content of copolymer (X)-B3 was 50% by mass, and mixed into lubricating base oil.
（製造例Ｂ４：共重合体（Ｘ）－Ｂ４の製造）
製造例Ｂ１において溶媒として２－プロパノールを１４３ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ４を得た。
共重合体（Ｘ）－Ｂ４の質量平均分子量（Ｍｗ）は１０，１００であり、分子量分布（Ｍｗ／Ｍｎ）は１．７であった。また、共重合体（Ｘ）－Ｂ４のリン含有量は２８００質量ｐｐｍ、硫黄含有量は１１００質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ４は、共重合体（Ｘ）－Ｂ４の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B4: Production of copolymer (X)-B4)
Copolymer (X)-B4 was obtained by carrying out the same operation as in Production Example B1 except that 143 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-B4 was 10,100, and the molecular weight distribution (Mw/Mn) was 1.7. Further, the phosphorus content of copolymer (X)-B4 was 2,800 mass ppm, and the sulfur content was 1,100 mass ppm.
Copolymer (X)-B4 was diluted with mineral oil so that the content of copolymer (X)-B4 was 50% by mass, and mixed into lubricating base oil.
製造例Ｂ１において溶媒として２－プロパノールを１４３ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ４を得た。
共重合体（Ｘ）－Ｂ４の質量平均分子量（Ｍｗ）は１０，１００であり、分子量分布（Ｍｗ／Ｍｎ）は１．７であった。また、共重合体（Ｘ）－Ｂ４のリン含有量は２８００質量ｐｐｍ、硫黄含有量は１１００質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ４は、共重合体（Ｘ）－Ｂ４の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B4: Production of copolymer (X)-B4)
Copolymer (X)-B4 was obtained by carrying out the same operation as in Production Example B1 except that 143 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-B4 was 10,100, and the molecular weight distribution (Mw/Mn) was 1.7. Further, the phosphorus content of copolymer (X)-B4 was 2,800 mass ppm, and the sulfur content was 1,100 mass ppm.
Copolymer (X)-B4 was diluted with mineral oil so that the content of copolymer (X)-B4 was 50% by mass, and mixed into lubricating base oil.
（製造例Ｂ５：共重合体（Ｘ）－Ｂ５の製造）
製造例Ｂ２において溶媒として２－プロパノールを２３．８ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ５を得た。
共重合体（Ｘ）－Ｂ５の質量平均分子量（Ｍｗ）は４８，０００であり、分子量分布（Ｍｗ／Ｍｎ）は３．３であった。また、共重合体（Ｘ）－Ｂ５のリン含有量は２８００質量ｐｐｍ、硫黄含有量は１２２０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ５は、共重合体（Ｘ）－Ｂ５の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B5: Production of copolymer (X)-B5)
Copolymer (X)-B5 was obtained by carrying out the same operation as in Production Example B2 except that 23.8 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-B5 was 48,000, and the molecular weight distribution (Mw/Mn) was 3.3. Further, the phosphorus content of copolymer (X)-B5 was 2,800 mass ppm, and the sulfur content was 1,220 mass ppm.
Copolymer (X)-B5 was diluted with mineral oil so that the content of copolymer (X)-B5 was 50% by mass, and mixed into lubricating base oil.
製造例Ｂ２において溶媒として２－プロパノールを２３．８ｇ仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ５を得た。
共重合体（Ｘ）－Ｂ５の質量平均分子量（Ｍｗ）は４８，０００であり、分子量分布（Ｍｗ／Ｍｎ）は３．３であった。また、共重合体（Ｘ）－Ｂ５のリン含有量は２８００質量ｐｐｍ、硫黄含有量は１２２０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ５は、共重合体（Ｘ）－Ｂ５の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B5: Production of copolymer (X)-B5)
Copolymer (X)-B5 was obtained by carrying out the same operation as in Production Example B2 except that 23.8 g of 2-propanol was charged as a solvent.
The mass average molecular weight (Mw) of copolymer (X)-B5 was 48,000, and the molecular weight distribution (Mw/Mn) was 3.3. Further, the phosphorus content of copolymer (X)-B5 was 2,800 mass ppm, and the sulfur content was 1,220 mass ppm.
Copolymer (X)-B5 was diluted with mineral oil so that the content of copolymer (X)-B5 was 50% by mass, and mixed into lubricating base oil.
（製造例Ｂ６：共重合体（Ｘ）－Ｂ６の製造）
温度計、窒素導入管、及び撹拌機を取り付けた２００ｍＬ容の４つ口フラスコに、ドデシルアクリレートを３６．３ｇ（１５１ｍｍоｌ）、２－ヒドロキシエチルアクリレートを１１．６ｇ（１００ｍｍоｌ）、ＤＴＡを０．４６ｇ（１．５ｍｍоｌ）、溶媒として２－プロパノールを４７．５ｇ仕込んだ。
次いで、フラスコ内を窒素置換し、開始剤として２，２’－アゾビス（イソブチロニトリル）を０．２ｇ添加した後、撹拌しながらゆっくり昇温し、７５～８５℃の温度で還流させながら４時間反応させて、反応終了後に溶媒を減圧留去することにより、共重合体（Ｘ）－Ｂ６を得た。
共重合体（Ｘ）－Ｂ６の質量平均分子量（Ｍｗ）は２０，６００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ｂ６の硫黄含有量は１０４０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ６は、共重合体（Ｘ）－Ｂ６の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B6: Production of copolymer (X)-B6)
In a 200 mL four-necked flask equipped with a thermometer, nitrogen inlet tube, and stirrer, add 36.3 g (151 mmol) of dodecyl acrylate, 11.6 g (100 mmol) of 2-hydroxyethyl acrylate, and 0.46 g of DTA. (1.5 mmol) and 47.5 g of 2-propanol as a solvent were charged.
Next, the inside of the flask was purged with nitrogen, and after adding 0.2 g of 2,2'-azobis(isobutyronitrile) as an initiator, the temperature was slowly raised while stirring, and the mixture was refluxed at a temperature of 75 to 85°C. The reaction was allowed to proceed for 4 hours, and after the reaction was completed, the solvent was distilled off under reduced pressure to obtain copolymer (X)-B6.
The mass average molecular weight (Mw) of copolymer (X)-B6 was 20,600, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the sulfur content of copolymer (X)-B6 was 1040 ppm by mass.
Copolymer (X)-B6 was diluted with mineral oil so that the content of copolymer (X)-B6 was 50% by mass, and mixed into lubricating base oil.
温度計、窒素導入管、及び撹拌機を取り付けた２００ｍＬ容の４つ口フラスコに、ドデシルアクリレートを３６．３ｇ（１５１ｍｍоｌ）、２－ヒドロキシエチルアクリレートを１１．６ｇ（１００ｍｍоｌ）、ＤＴＡを０．４６ｇ（１．５ｍｍоｌ）、溶媒として２－プロパノールを４７．５ｇ仕込んだ。
次いで、フラスコ内を窒素置換し、開始剤として２，２’－アゾビス（イソブチロニトリル）を０．２ｇ添加した後、撹拌しながらゆっくり昇温し、７５～８５℃の温度で還流させながら４時間反応させて、反応終了後に溶媒を減圧留去することにより、共重合体（Ｘ）－Ｂ６を得た。
共重合体（Ｘ）－Ｂ６の質量平均分子量（Ｍｗ）は２０，６００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ｂ６の硫黄含有量は１０４０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ６は、共重合体（Ｘ）－Ｂ６の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B6: Production of copolymer (X)-B6)
In a 200 mL four-necked flask equipped with a thermometer, nitrogen inlet tube, and stirrer, add 36.3 g (151 mmol) of dodecyl acrylate, 11.6 g (100 mmol) of 2-hydroxyethyl acrylate, and 0.46 g of DTA. (1.5 mmol) and 47.5 g of 2-propanol as a solvent were charged.
Next, the inside of the flask was purged with nitrogen, and after adding 0.2 g of 2,2'-azobis(isobutyronitrile) as an initiator, the temperature was slowly raised while stirring, and the mixture was refluxed at a temperature of 75 to 85°C. The reaction was allowed to proceed for 4 hours, and after the reaction was completed, the solvent was distilled off under reduced pressure to obtain copolymer (X)-B6.
The mass average molecular weight (Mw) of copolymer (X)-B6 was 20,600, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the sulfur content of copolymer (X)-B6 was 1040 ppm by mass.
Copolymer (X)-B6 was diluted with mineral oil so that the content of copolymer (X)-B6 was 50% by mass, and mixed into lubricating base oil.
（製造例Ｂ７：共重合体（Ｘ）－Ｂ７の製造）
製造例Ｂ６においてＤＴＡの代わりにＯＴＡを０．４６ｇ（１．９ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ７を得た。
共重合体（Ｘ）－Ｂ７の質量平均分子量（Ｍｗ）は２０，２００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ｂ７の硫黄含有量は１２６０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ７は、共重合体（Ｘ）－Ｂ７の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B7: Production of copolymer (X)-B7)
Copolymer (X)-B7 was obtained by carrying out the same operation as in Production Example B6 except that 0.46 g (1.9 mmol) of OTA was charged instead of DTA.
The mass average molecular weight (Mw) of copolymer (X)-B7 was 20,200, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the sulfur content of copolymer (X)-B7 was 1260 ppm by mass.
Copolymer (X)-B7 was diluted with mineral oil so that the content of copolymer (X)-B7 was 50% by mass, and mixed into lubricating base oil.
製造例Ｂ６においてＤＴＡの代わりにＯＴＡを０．４６ｇ（１．９ｍｍоｌ）仕込んだこと以外は同様の操作を行って、共重合体（Ｘ）－Ｂ７を得た。
共重合体（Ｘ）－Ｂ７の質量平均分子量（Ｍｗ）は２０，２００であり、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、共重合体（Ｘ）－Ｂ７の硫黄含有量は１２６０質量ｐｐｍであった。
共重合体（Ｘ）－Ｂ７は、共重合体（Ｘ）－Ｂ７の含有量が５０質量％となるように鉱物油で希釈して、潤滑油基油に混合した。 (Production Example B7: Production of copolymer (X)-B7)
Copolymer (X)-B7 was obtained by carrying out the same operation as in Production Example B6 except that 0.46 g (1.9 mmol) of OTA was charged instead of DTA.
The mass average molecular weight (Mw) of copolymer (X)-B7 was 20,200, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the sulfur content of copolymer (X)-B7 was 1260 ppm by mass.
Copolymer (X)-B7 was diluted with mineral oil so that the content of copolymer (X)-B7 was 50% by mass, and mixed into lubricating base oil.
共重合体（Ｘ）－Ｂ１～共重合体（Ｘ）－Ｂ７の組成、共重合体（Ｘ）－Ｂ１～共重合体（Ｘ）－Ｂ７の硫黄量及びリン量、質量平均分子量（Ｍｗ）、及び分子量分布（Ｍｗ／Ｍｎ）を表２に示す。
なお、質量平均分子量（Ｍｗ）は、有効数字２桁で示した。 Composition of copolymer (X)-B1 to copolymer (X)-B7, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-B1 to copolymer (X)-B7 , and the molecular weight distribution (Mw/Mn) are shown in Table 2.
In addition, the mass average molecular weight (Mw) is shown in two significant digits.
なお、質量平均分子量（Ｍｗ）は、有効数字２桁で示した。 Composition of copolymer (X)-B1 to copolymer (X)-B7, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-B1 to copolymer (X)-B7 , and the molecular weight distribution (Mw/Mn) are shown in Table 2.
In addition, the mass average molecular weight (Mw) is shown in two significant digits.
［評価方法］
以下に説明する試験を実施し、耐摩耗性、極圧性、及び熱安定性について評価を行った。 [Evaluation method]
The tests described below were conducted to evaluate wear resistance, extreme pressure properties, and thermal stability.
以下に説明する試験を実施し、耐摩耗性、極圧性、及び熱安定性について評価を行った。 [Evaluation method]
The tests described below were conducted to evaluate wear resistance, extreme pressure properties, and thermal stability.
＜シェル摩耗試験＞
シェル摩耗試験機を用いて、ＡＳＴＭ Ｄ ４１７２に準拠して、試験条件を、荷重３０ｋｇ、回転数１，２００ｒｐｍ、温度８０℃、試験時間３０分に設定して、潤滑油組成物の耐摩耗性を評価した。結果は、試験剛球の摩耗痕径（ｍｍ）で表した。
本試験においては摩耗痕径が０．５５ｍｍ以下であれば、耐摩耗性が良好であると判断した。 <Shell wear test>
The wear resistance of the lubricating oil composition was determined using a shell abrasion tester in accordance with ASTM D 4172, setting the test conditions to be a load of 30 kg, a rotation speed of 1,200 rpm, a temperature of 80°C, and a test time of 30 minutes. was evaluated. The results were expressed as the wear scar diameter (mm) of the test hard ball.
In this test, wear resistance was judged to be good if the wear scar diameter was 0.55 mm or less.
シェル摩耗試験機を用いて、ＡＳＴＭ Ｄ ４１７２に準拠して、試験条件を、荷重３０ｋｇ、回転数１，２００ｒｐｍ、温度８０℃、試験時間３０分に設定して、潤滑油組成物の耐摩耗性を評価した。結果は、試験剛球の摩耗痕径（ｍｍ）で表した。
本試験においては摩耗痕径が０．５５ｍｍ以下であれば、耐摩耗性が良好であると判断した。 <Shell wear test>
The wear resistance of the lubricating oil composition was determined using a shell abrasion tester in accordance with ASTM D 4172, setting the test conditions to be a load of 30 kg, a rotation speed of 1,200 rpm, a temperature of 80°C, and a test time of 30 minutes. was evaluated. The results were expressed as the wear scar diameter (mm) of the test hard ball.
In this test, wear resistance was judged to be good if the wear scar diameter was 0.55 mm or less.
＜シェル四球試験耐荷重性（ＥＰ）試験＞
ＡＳＴＭ Ｄ ２７８３に準拠して、四球試験機により回転数１，８００回転／分、油温（室温：２５±５℃）の条件で行い、最大非焼付荷重（ＬＮＬ）と、融着荷重（ＷＬ）とを測定した。これらの値が大きいほど極圧性が良好である。
本試験においては、最大非焼付荷重（ＬＮＬ）が３９２Ｎ以上であり、かつ融着荷重（ＷＬ）が１２３６Ｎ以上であれば、極圧性が良好であると判断した。 <Shell four-ball test load-bearing (EP) test>
In accordance with ASTM D 2783, the maximum non-seizure load (LNL) and fusion load (WL) were measured using a four-ball tester at a rotation speed of 1,800 rpm and an oil temperature (room temperature: 25 ± 5°C). ) was measured. The larger these values are, the better the extreme pressure properties are.
In this test, if the maximum non-seizing load (LNL) was 392N or more and the fusion load (WL) was 1236N or more, it was determined that the extreme pressure property was good.
ＡＳＴＭ Ｄ ２７８３に準拠して、四球試験機により回転数１，８００回転／分、油温（室温：２５±５℃）の条件で行い、最大非焼付荷重（ＬＮＬ）と、融着荷重（ＷＬ）とを測定した。これらの値が大きいほど極圧性が良好である。
本試験においては、最大非焼付荷重（ＬＮＬ）が３９２Ｎ以上であり、かつ融着荷重（ＷＬ）が１２３６Ｎ以上であれば、極圧性が良好であると判断した。 <Shell four-ball test load-bearing (EP) test>
In accordance with ASTM D 2783, the maximum non-seizure load (LNL) and fusion load (WL) were measured using a four-ball tester at a rotation speed of 1,800 rpm and an oil temperature (room temperature: 25 ± 5°C). ) was measured. The larger these values are, the better the extreme pressure properties are.
In this test, if the maximum non-seizing load (LNL) was 392N or more and the fusion load (WL) was 1236N or more, it was determined that the extreme pressure property was good.
＜ＩＳＯＴ試験＞
試験油（潤滑油組成物）に触媒として銅片と鉄片を入れ、ＪＩＳ Ｋ ２５１４－１：２０１３に準拠するＩＳＯＴ試験を実施して、試験油を強制劣化させた。試験温度（油温）は１５０℃とした。そして、ＩＳＯＴ試験開始から２４時間後の試験油について、ＪＩＳ Ｂ ９９３１に準拠して、スラッジ量（ｍｇ／１００ｍＬ）を測定した。
そして、スラッジ量が１０ｍｇ／１００ｍＬ未満であれば、熱安定性が良好であると判断した。 <ISOT test>
A copper piece and an iron piece were added as catalysts to the test oil (lubricating oil composition), and an ISOT test in accordance with JIS K 2514-1:2013 was conducted to forcefully degrade the test oil. The test temperature (oil temperature) was 150°C. Then, the amount of sludge (mg/100 mL) was measured for the test oil 24 hours after the start of the ISOT test in accordance with JIS B 9931.
And, if the amount of sludge was less than 10 mg/100 mL, it was determined that the thermal stability was good.
試験油（潤滑油組成物）に触媒として銅片と鉄片を入れ、ＪＩＳ Ｋ ２５１４－１：２０１３に準拠するＩＳＯＴ試験を実施して、試験油を強制劣化させた。試験温度（油温）は１５０℃とした。そして、ＩＳＯＴ試験開始から２４時間後の試験油について、ＪＩＳ Ｂ ９９３１に準拠して、スラッジ量（ｍｇ／１００ｍＬ）を測定した。
そして、スラッジ量が１０ｍｇ／１００ｍＬ未満であれば、熱安定性が良好であると判断した。 <ISOT test>
A copper piece and an iron piece were added as catalysts to the test oil (lubricating oil composition), and an ISOT test in accordance with JIS K 2514-1:2013 was conducted to forcefully degrade the test oil. The test temperature (oil temperature) was 150°C. Then, the amount of sludge (mg/100 mL) was measured for the test oil 24 hours after the start of the ISOT test in accordance with JIS B 9931.
And, if the amount of sludge was less than 10 mg/100 mL, it was determined that the thermal stability was good.
また、ＩＳＯＴ試験開始から２４時間後の試験油について、既述のシェル摩耗試験及びシェル四球試験耐荷重性（ＥＰ）試験を実施した。そして、新油の場合と同様、摩耗痕径が０．５５ｍｍ以下であれば、耐摩耗性が良好であると判断した。また、最大非焼付荷重（ＬＮＬ）が３９２Ｎ以上であり、かつ融着荷重（ＷＬ）が１２３６Ｎ以上であれば、極圧性が良好であると判断した。
In addition, the above-mentioned shell wear test and shell four-ball test load resistance (EP) test were conducted on the test oil 24 hours after the start of the ISOT test. As with the new oil, it was determined that the wear resistance was good if the wear scar diameter was 0.55 mm or less. Furthermore, if the maximum non-seizure load (LNL) was 392N or more and the fusion load (WL) was 1236N or more, it was determined that the extreme pressure property was good.
結果を表３及び表４に示す。表３及び表４中、潤滑油用添加剤組成物の含有量の括弧内の数値は、樹脂分換算の含有量を意味する。
The results are shown in Tables 3 and 4. In Tables 3 and 4, the numerical value in parentheses for the content of the lubricating oil additive composition means the content in terms of resin content.
表３及び表４より、以下のことがわかる。
実施例Ａ１～Ａ６に示す結果から、共重合体（Ｘ）－Ａ１、共重合体（Ｘ）－Ａ２、共重合体（Ｘ）－Ａ３、共重合体（Ｘ）－Ａ４、共重合体（Ｘ）－Ａ５、又は共重合体（Ｘ）－Ａ６を配合した潤滑油組成物は、耐摩耗性、極圧性、及び熱安定性に優れることがわかる。また、ＩＳＯＴ試験後においても耐摩耗性及び極圧性に優れることがわかる。
また、実施例Ｂ１～Ｂ７に示す結果から、共重合体（Ｘ）－Ｂ１、共重合体（Ｘ）－Ｂ２、共重合体（Ｘ）－Ｂ３、共重合体（Ｘ）－Ｂ４、共重合体（Ｘ）－Ｂ５、共重合体（Ｘ）－Ｂ６、又は共重合体（Ｘ）－Ｂ７を配合した潤滑油組成物は、耐摩耗性、極圧性、及び熱安定性に優れることがわかる。また、ＩＳＯＴ試験後においても耐摩耗性及び極圧性に優れることがわかる。
一方、比較例１に示す結果から、低分子量の硫黄及びリン含有化合物を配合した潤滑油組成物は、耐摩耗性及び極圧性が不十分であり、熱安定性も明らかに劣ることがわかる。 The following can be seen from Tables 3 and 4.
From the results shown in Examples A1 to A6, copolymer (X)-A1, copolymer (X)-A2, copolymer (X)-A3, copolymer (X)-A4, copolymer ( It can be seen that the lubricating oil compositions containing X)-A5 or copolymer (X)-A6 have excellent wear resistance, extreme pressure properties, and thermal stability. Furthermore, it can be seen that even after the ISOT test, the wear resistance and extreme pressure properties are excellent.
Furthermore, from the results shown in Examples B1 to B7, copolymer (X)-B1, copolymer (X)-B2, copolymer (X)-B3, copolymer (X)-B4, copolymer It can be seen that the lubricating oil composition containing Copolymer (X)-B5, Copolymer (X)-B6, or Copolymer (X)-B7 has excellent wear resistance, extreme pressure properties, and thermal stability. . Furthermore, it can be seen that even after the ISOT test, the wear resistance and extreme pressure properties are excellent.
On the other hand, the results shown in Comparative Example 1 show that a lubricating oil composition containing a low molecular weight sulfur- and phosphorus-containing compound has insufficient wear resistance and extreme pressure properties, and is clearly inferior in thermal stability.
実施例Ａ１～Ａ６に示す結果から、共重合体（Ｘ）－Ａ１、共重合体（Ｘ）－Ａ２、共重合体（Ｘ）－Ａ３、共重合体（Ｘ）－Ａ４、共重合体（Ｘ）－Ａ５、又は共重合体（Ｘ）－Ａ６を配合した潤滑油組成物は、耐摩耗性、極圧性、及び熱安定性に優れることがわかる。また、ＩＳＯＴ試験後においても耐摩耗性及び極圧性に優れることがわかる。
また、実施例Ｂ１～Ｂ７に示す結果から、共重合体（Ｘ）－Ｂ１、共重合体（Ｘ）－Ｂ２、共重合体（Ｘ）－Ｂ３、共重合体（Ｘ）－Ｂ４、共重合体（Ｘ）－Ｂ５、共重合体（Ｘ）－Ｂ６、又は共重合体（Ｘ）－Ｂ７を配合した潤滑油組成物は、耐摩耗性、極圧性、及び熱安定性に優れることがわかる。また、ＩＳＯＴ試験後においても耐摩耗性及び極圧性に優れることがわかる。
一方、比較例１に示す結果から、低分子量の硫黄及びリン含有化合物を配合した潤滑油組成物は、耐摩耗性及び極圧性が不十分であり、熱安定性も明らかに劣ることがわかる。 The following can be seen from Tables 3 and 4.
From the results shown in Examples A1 to A6, copolymer (X)-A1, copolymer (X)-A2, copolymer (X)-A3, copolymer (X)-A4, copolymer ( It can be seen that the lubricating oil compositions containing X)-A5 or copolymer (X)-A6 have excellent wear resistance, extreme pressure properties, and thermal stability. Furthermore, it can be seen that even after the ISOT test, the wear resistance and extreme pressure properties are excellent.
Furthermore, from the results shown in Examples B1 to B7, copolymer (X)-B1, copolymer (X)-B2, copolymer (X)-B3, copolymer (X)-B4, copolymer It can be seen that the lubricating oil composition containing Copolymer (X)-B5, Copolymer (X)-B6, or Copolymer (X)-B7 has excellent wear resistance, extreme pressure properties, and thermal stability. . Furthermore, it can be seen that even after the ISOT test, the wear resistance and extreme pressure properties are excellent.
On the other hand, the results shown in Comparative Example 1 show that a lubricating oil composition containing a low molecular weight sulfur- and phosphorus-containing compound has insufficient wear resistance and extreme pressure properties, and is clearly inferior in thermal stability.
Claims (20)
- 下記構成単位（ａ）及び（ｂ）を含み、下記要件（１）～（３）を満たす共重合体（Ｘ）を含有する、潤滑油用添加剤組成物。
・構成単位（ａ）：（メタ）アクリロイル基と炭素数８～２０のアルキル基とを有するモノマー（Ａ）由来の構成単位
・構成単位（ｂ）：（メタ）アクリロイル基と極性基とを有するモノマー（Ｂ）由来の構成単位
・要件（１）：前記共重合体（Ｘ）は、側鎖に下記基の少なくともいずれかを有する。
リン及び硫黄含有基
リン含有基及び硫黄含有基（但し、前記リン含有基は硫黄非含有基であり、前記硫黄含有基はリン非含有基である。）
前記硫黄含有基
・要件（２）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中のリン原子含有量（Ｐ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％～２．００質量％である。
・要件（３）：前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）が、前記共重合体（Ｘ）の全量基準で、０．０１質量％以上である。 An additive composition for lubricating oil containing a copolymer (X) containing the following structural units (a) and (b) and satisfying the following requirements (1) to (3).
・Structural unit (a): A structural unit derived from a monomer (A) having a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.・Structural unit (b): Having a (meth)acryloyl group and a polar group. Structural unit derived from monomer (B)/Requirement (1): The copolymer (X) has at least one of the following groups in the side chain.
Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
Said sulfur-containing group/requirement (2): When said copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in said copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
- Requirement (3): The sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X). - 前記要件（１）に規定する基を含む１以上の構成単位（α）をさらに含む、請求項１に記載の潤滑油用添加剤組成物。 The lubricating oil additive composition according to claim 1, further comprising one or more structural units (α) containing the group defined in requirement (1).
- 前記構成単位（α）は、重合性官能基と前記リン及び硫黄含有基とを有するモノマー（Ｃ）由来の構成単位（ｃ）である、請求項２に記載の潤滑油用添加剤組成物。 The lubricating oil additive composition according to claim 2, wherein the structural unit (α) is a structural unit (c) derived from a monomer (C) having a polymerizable functional group and the phosphorus- and sulfur-containing group.
- 前記構成単位（α）は、重合性官能基と前記硫黄含有基とを有するモノマー（Ｄ１）由来の構成単位（ｄ１）である、請求項２に記載の潤滑油用添加剤組成物。 The lubricating oil additive composition according to claim 2, wherein the structural unit (α) is a structural unit (d1) derived from a monomer (D1) having a polymerizable functional group and the sulfur-containing group.
- 前記構成単位（α）は、重合性官能基と前記硫黄含有基とを有するモノマー（Ｄ１）由来の構成単位（ｄ１）及び重合性官能基と前記リン含有基とを有するモノマー（Ｄ２）由来の構成単位（ｄ２）である、請求項２に記載の潤滑油用添加剤組成物。 The structural unit (α) is a structural unit (d1) derived from a monomer (D1) having a polymerizable functional group and the sulfur-containing group, and a structural unit (d1) derived from a monomer (D2) having a polymerizable functional group and the phosphorus-containing group. The lubricating oil additive composition according to claim 2, which is the structural unit (d2).
- さらに、下記要件（４）を満たす、請求項１～５のいずれか１項に記載の潤滑油用添加剤組成物。
・要件（４）：前記共重合体（Ｘ）がリン原子を含む場合、前記共重合体（Ｘ）中の硫黄原子含有量（Ｓ）とリン原子含有量（Ｐ）との含有比率［（Ｓ）／（Ｐ）］が、質量比で、０．１０～３．００である。 The lubricating oil additive composition according to any one of claims 1 to 5, which further satisfies the following requirement (4).
- Requirement (4): When the copolymer (X) contains a phosphorus atom, the content ratio of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) [( S)/(P)] is 0.10 to 3.00 in mass ratio. - 前記構成単位（ａ）が、下記一般式（ａ－１）で表されるモノマー（Ａ１）に由来する構成単位（ａ１）を含む、請求項１～６のいずれか１項に記載の潤滑油用添加剤組成物。
［上記一般式（ａ－１）中、Ｒａ１は、水素原子又はメチル基を示す。Ｒａ２は、炭素数８～２０のアルキル基を示す。］ The lubricating oil according to any one of claims 1 to 6, wherein the structural unit (a) contains a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1). additive composition for use.
[In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms. ] - 前記構成単位（ｂ）が、下記一般式（ｂ－１）で表されるモノマー（Ｂ１１）に由来する構成単位（ｂ１１）を含む、請求項１～７のいずれか１項に記載の潤滑油用添加剤組成物。
［上記一般式（ｂ－１）中、Ｒｂ１は、水素原子又はメチル基である。Ｒｂ２は、炭素数２～４のアルキレン基を示す。ｍ１は、１～１０の整数を示す。ｍ１が２以上の整数の場合の複数のＲｂ２は、同一であっても異なっていてもよい。］ The lubricating oil according to any one of claims 1 to 7, wherein the structural unit (b) contains a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1). additive composition for use.
[In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. R b2 represents an alkylene group having 2 to 4 carbon atoms. m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. ] - 前記モノマー（Ｃ）が、（メタ）アクリロイル基と、下記一般式（１）で表されるリン及び硫黄を含む１価基とを有する、請求項３に記載の潤滑油用添加剤組成物。
［上記一般式（１）中、Ｒ１及びＲ２は、各々独立に、炭素数１～１０のアルキル基である。］ The lubricating oil additive composition according to claim 3, wherein the monomer (C) has a (meth)acryloyl group and a monovalent group containing phosphorus and sulfur represented by the following general formula (1).
[In the above general formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms. ] - 前記モノマー（Ｄ１）が、下記一般式（ｄ１－１）で表される化合物である、請求項４に記載の潤滑油用添加剤組成物。
［上記一般式（ｄ１－１）中、Ｒｄ１１は、水素原子又はメチル基である。Ｒｄ１２は、炭素数２～４のアルキレン基を示す。ｍ３は、１～１０の整数を示す。ｍ３が２以上の整数の場合の複数のＲｄ１２は、同一であっても異なっていてもよい。Ｒｄ１３は、炭素数４～２０のアルキル基を示す。］ The lubricating oil additive composition according to claim 4, wherein the monomer (D1) is a compound represented by the following general formula (d1-1).
[In the above general formula (d1-1), R d11 is a hydrogen atom or a methyl group. R d12 represents an alkylene group having 2 to 4 carbon atoms. m3 represents an integer from 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. R d13 represents an alkyl group having 4 to 20 carbon atoms. ] - 前記モノマー（Ｄ１）が、下記一般式（ｄ１－１）で表される化合物であり、
［上記一般式（ｄ１－１）中、Ｒｄ１１は、水素原子又はメチル基である。Ｒｄ１２は、炭素数２～４のアルキレン基を示す。ｍ３は、１～１０の整数を示す。ｍ３が２以上の整数の場合の複数のＲｄ１２は、同一であっても異なっていてもよい。Ｒｄ１３は、炭素数４～２０のアルキル基を示す。］
前記モノマー（Ｄ２）が、下記一般式（ｄ２－１）で表される化合物である、請求項５に記載の潤滑油用添加剤組成物。
［上記一般式（ｄ２－１）中、Ｒｄ２１は、水素原子又はメチル基である。Ｒｄ２２は、エチレン基を示す。ｍ４は、１～６の整数を示す。ｍ４が２以上の整数の場合の複数のＲｄ２２は、同一であっても異なっていてもよい。ｎは、１又は２の整数を示す。ｎ＝１である場合、複数のＲｄ２３のうちの少なくとも１つは水素原子を示し、他方はメチル基又はエチル基である。ｎ＝２である場合、Ｒｄ２３は水素原子である。］ The monomer (D1) is a compound represented by the following general formula (d1-1),
[In the above general formula (d1-1), R d11 is a hydrogen atom or a methyl group. R d12 represents an alkylene group having 2 to 4 carbon atoms. m3 represents an integer from 1 to 10. When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different. R d13 represents an alkyl group having 4 to 20 carbon atoms. ]
The lubricating oil additive composition according to claim 5, wherein the monomer (D2) is a compound represented by the following general formula (d2-1).
[In the above general formula (d2-1), R d21 is a hydrogen atom or a methyl group. R d22 represents an ethylene group. m4 represents an integer from 1 to 6. When m4 is an integer of 2 or more, a plurality of R d22 may be the same or different. n represents an integer of 1 or 2. When n=1, at least one of the plurality of R d23 represents a hydrogen atom, and the other is a methyl group or an ethyl group. When n=2, R d23 is a hydrogen atom. ] - 前記構成単位（ａ）が、下記一般式（ａ－１）で表されるモノマー（Ａ１）に由来する構成単位（ａ１）を含む、請求項９～１１のいずれか１項に記載の潤滑油用添加剤組成物。
［上記一般式（ａ－１）中、Ｒａ１は、水素原子又はメチル基を示す。Ｒａ２は、炭素数８～２０のアルキル基を示す。］ The lubricating oil according to any one of claims 9 to 11, wherein the structural unit (a) contains a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1). additive composition for use.
[In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms. ] - 前記構成単位（ｂ）が、下記一般式（ｂ－１）で表されるモノマー（Ｂ１１）に由来する構成単位（ｂ１１）を含む、請求項９～１２のいずれか１項に記載の潤滑油用添加剤組成物。
［上記一般式（ｂ－１）中、Ｒｂ１は、水素原子又はメチル基である。Ｒｂ２は、炭素数２～４のアルキレン基を示す。ｍ１は、１～１０の整数を示す。ｍ１が２以上の整数の場合の複数のＲｂ２は、同一であっても異なっていてもよい。］ The lubricating oil according to any one of claims 9 to 12, wherein the structural unit (b) contains a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1). additive composition for use.
[In the above general formula (b-1), R b1 is a hydrogen atom or a methyl group. R b2 represents an alkylene group having 2 to 4 carbon atoms. m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different. ] - 前記共重合体（Ｘ）の質量平均分子量が、５，０００～１００，０００である、請求項１～１３のいずれか１項に記載の潤滑油用添加剤組成物。 The additive composition for lubricating oil according to any one of claims 1 to 13, wherein the copolymer (X) has a mass average molecular weight of 5,000 to 100,000.
- 前記構成単位（ａ）の含有量が、前記共重合体（Ｘ）の全構成単位基準で、５０質量％以上である、請求項１～１４のいずれか１項に記載の潤滑油用添加剤組成物。 The lubricating oil additive according to any one of claims 1 to 14, wherein the content of the structural unit (a) is 50% by mass or more based on all structural units of the copolymer (X). Composition.
- 前記構成単位（ｂ）の含有量が、前記共重合体（Ｘ）の全構成単位基準で、１質量％以上である、請求項１～１５のいずれか１項に記載の潤滑油用添加剤組成物。 The lubricating oil additive according to any one of claims 1 to 15, wherein the content of the structural unit (b) is 1% by mass or more based on all the structural units of the copolymer (X). Composition.
- 耐荷重添加剤として用いられる、請求項１～１６のいずれか１項に記載の潤滑油用添加剤組成物。 The lubricating oil additive composition according to any one of claims 1 to 16, which is used as a load-bearing additive.
- 請求項１～１７のいずれか１項に記載の潤滑油用添加剤組成物を、耐荷重添加剤として使用する、使用方法。 A method of using the lubricating oil additive composition according to any one of claims 1 to 17 as a load-bearing additive.
- 請求項１～１７のいずれか１項に記載の潤滑油用添加剤組成物と、潤滑油基油と、を含有する、潤滑油組成物。 A lubricating oil composition comprising the lubricating oil additive composition according to any one of claims 1 to 17 and a lubricating oil base oil.
- 請求項１～１７のいずれか１項に記載の潤滑油用添加剤組成物と、潤滑油基油と、を混合する工程を含む、潤滑油組成物の製造方法。 A method for producing a lubricating oil composition, comprising the step of mixing the lubricating oil additive composition according to any one of claims 1 to 17 and a lubricating oil base oil.
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| JP2022106709A JP2024006117A (en) | 2022-06-30 | 2022-06-30 | Additive composition for lubricating oils, and lubricating oil composition |
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