JP5513252B2 - Method for producing aqueous dispersion of polyester resin for toner - Google Patents
Method for producing aqueous dispersion of polyester resin for toner Download PDFInfo
- Publication number
- JP5513252B2 JP5513252B2 JP2010109895A JP2010109895A JP5513252B2 JP 5513252 B2 JP5513252 B2 JP 5513252B2 JP 2010109895 A JP2010109895 A JP 2010109895A JP 2010109895 A JP2010109895 A JP 2010109895A JP 5513252 B2 JP5513252 B2 JP 5513252B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- resin
- toner
- aqueous dispersion
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001225 polyester resin Polymers 0.000 title claims description 135
- 239000004645 polyester resin Substances 0.000 title claims description 122
- 239000006185 dispersion Substances 0.000 title claims description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 42
- 239000002245 particle Substances 0.000 claims description 109
- -1 alkyl urea Chemical compound 0.000 claims description 105
- 229920005989 resin Polymers 0.000 claims description 100
- 239000011347 resin Substances 0.000 claims description 100
- 238000000034 method Methods 0.000 claims description 64
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 56
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 47
- 239000004202 carbamide Substances 0.000 claims description 43
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 37
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000002776 aggregation Effects 0.000 claims description 27
- 238000004220 aggregation Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 230000003472 neutralizing effect Effects 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000012736 aqueous medium Substances 0.000 claims description 12
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 11
- 150000002357 guanidines Chemical class 0.000 claims description 11
- 238000012643 polycondensation polymerization Methods 0.000 claims description 10
- 150000003672 ureas Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 description 41
- 238000012546 transfer Methods 0.000 description 39
- 235000013877 carbamide Nutrition 0.000 description 38
- 229960004198 guanidine Drugs 0.000 description 30
- 239000010936 titanium Substances 0.000 description 28
- 239000002736 nonionic surfactant Substances 0.000 description 25
- 239000000654 additive Substances 0.000 description 19
- 239000003086 colorant Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- 239000010419 fine particle Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000011258 core-shell material Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- WQGWDDDVZFFDIG-UHFFFAOYSA-N trihydroxybenzene Natural products OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 229940079877 pyrogallol Drugs 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000004931 aggregating effect Effects 0.000 description 4
- 229920006127 amorphous resin Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229940074391 gallic acid Drugs 0.000 description 4
- 235000004515 gallic acid Nutrition 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 235000019809 paraffin wax Nutrition 0.000 description 4
- 235000019271 petrolatum Nutrition 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 229910020923 Sn-O Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 229910020813 Sn-C Inorganic materials 0.000 description 2
- 229910018732 Sn—C Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 2
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 2
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、トナー用ポリエステル系樹脂の水系分散液の製造方法に関する。 The present invention relates to a method for producing an aqueous dispersion of a polyester resin for toner.
電子写真用トナーの製造方法の一つとして、乳化凝集法が提案されている。これは、構造制御（コア・シェル）によるトナー高機能化や、高いトナー表面形状制御による画質の改善等の優位性を有しているためである。
例えば、特許文献１には、耐熱保管性や画像かぶりを課題として、少なくとも樹脂と着色剤を含有するコアの表面にシェルを有するコア・シェル構造の静電荷像現像用トナーと樹脂被覆キャリアからなる静電荷像現像用現像剤であって、（１）当該静電荷像現像用トナーのシェルの８点平均膜厚が１００〜３００ｎｍであり、（２）当該シェルの最大膜厚をＨｍａｘ、最小膜厚をＨｍｉｎとしたときに、両者の比：Ｈｍａｘ／Ｈｍｉｎが１．００〜１．５０であり、（３）当該コアのガラス転移温度をＴｇ１、当該シェルのガラス転移温度をＴｇ２としたとき、３０℃≦Ｔｇ１≦４０℃、４５℃≦Ｔｇ２≦５５℃であり、かつ（４）当該樹脂被覆キャリアの体積平均粒径が２０〜４０μｍである、静電荷像現像用現像剤が開示されている。
特許文献２には、スズ系触媒不使用のポリエステル樹脂を用い帯電特性、発色性、低温定着を課題として、１種類以上の非結晶性樹脂を含有する樹脂微粒子分散液と、着色剤を分散した着色剤分散液とを混合し、該樹脂微粒子及び着色剤を水系媒体中でトナー粒子径に凝集させて凝集体を形成し、これを加熱し融合させる、静電荷像現像用トナーの製造方法が開示されている。
As one of the methods for producing an electrophotographic toner, an emulsion aggregation method has been proposed. This is because the toner has advantages such as enhancement of toner functions by structure control (core shell) and improvement of image quality by high toner surface shape control.
For example, Patent Document 1 includes a core-shell structure electrostatic image developing toner having a shell on the surface of a core containing at least a resin and a colorant, and a resin-coated carrier, with heat storage stability and image fog as problems. A developer for developing an electrostatic image, wherein (1) the eight-point average film thickness of the electrostatic image developing toner shell is 100 to 300 nm, (2) the maximum film thickness of the shell is Hmax, and the minimum film When the thickness is Hmin, the ratio of both: Hmax / Hmin is 1.00 to 1.50, (3) When the glass transition temperature of the core is Tg1, and the glass transition temperature of the shell is Tg2, There is disclosed a developer for developing an electrostatic charge image, wherein 30 ° C. ≦ Tg1 ≦ 40 ° C., 45 ° C. ≦ Tg2 ≦ 55 ° C., and (4) the volume average particle diameter of the resin-coated carrier is 20 to 40 μm. .
In Patent Document 2, a resin resin fine particle dispersion containing at least one amorphous resin and a colorant are dispersed using a polyester resin that does not use a tin-based catalyst for the purpose of charging characteristics, color developability, and low-temperature fixing. A method for producing a toner for developing an electrostatic image, comprising mixing a colorant dispersion, aggregating the resin fine particles and the colorant to a toner particle diameter in an aqueous medium to form an aggregate, and heating and fusing the aggregate. It is disclosed.
従来の乳化凝集法では、樹脂分散液と着色剤粒子分散液を作製し、これらを混合し、混合溶液中の粒子を凝集させ凝集粒子を得、その後、凝集粒子を熱融合させることで電子写真用トナーを得る。しかし、熱融合の際、加熱時間、加熱温度を調整しても、分散粒子の形状をコントロールすることは困難であり、転写効率の高いトナーを得ることは困難であった。
本発明の課題は、転写効率の高い電子写真用トナーを得ることにあり、該トナー用のポリエステル系樹脂の水系分散液の製造方法を提供することにある。
In the conventional emulsion aggregation method, a resin dispersion and a colorant particle dispersion are prepared, mixed, and the particles in the mixed solution are aggregated to obtain aggregated particles. Get toner for use. However, even when the heating time and the heating temperature are adjusted during heat fusion, it is difficult to control the shape of the dispersed particles, and it is difficult to obtain a toner with high transfer efficiency.
An object of the present invention is to obtain a toner for electrophotography with high transfer efficiency, and to provide a method for producing an aqueous dispersion of a polyester resin for the toner.
本発明は、下記［１］〜［４］に関する。
［１］尿素及びアルキル尿素から選ばれる１種以上の尿素系化合物及び／又はグアニジン、アルキルグアニジン及びそれらの酸付加塩から選ばれる１種以上のグアニジン系化合物、並びに中和剤の存在下、ポリエステル系樹脂を水系媒体中に分散させる工程を含む、トナー用ポリエステル系樹脂の水系分散液の製造方法。
［２］前記［１］に記載の製造方法により得られるトナー用ポリエステル系樹脂の水系分散液。
［３］前記［２］に記載のトナー用ポリエステル系樹脂の水系分散液を凝集工程に付す工程を含む、電子写真用トナーの製造方法。
［４］前記［３］に記載の製造方法により得られる電子写真用トナー。
The present invention relates to the following [1] to [4].
[1] One or more urea compounds selected from urea and alkylurea and / or one or more guanidine compounds selected from guanidine, alkylguanidine and acid addition salts thereof, and a polyester in the presence of a neutralizing agent A method for producing an aqueous dispersion of a polyester resin for toner, comprising a step of dispersing a resin in an aqueous medium.
[2] An aqueous dispersion of a polyester resin for toner obtained by the production method according to [1].
[3] A method for producing an electrophotographic toner, comprising a step of subjecting the aqueous dispersion of the polyester resin for toner according to [2] to an aggregation step.
[4] An electrophotographic toner obtained by the production method according to [3].
本発明の製造方法により得られるトナー用ポリエステル系樹脂の水系分散液は、分散径が均一であり、該水系分散液を用いて得られる電子写真用トナーは、転写効率に優れる。 The aqueous dispersion of the polyester resin for toner obtained by the production method of the present invention has a uniform dispersion diameter, and the electrophotographic toner obtained using the aqueous dispersion is excellent in transfer efficiency.
本発明者等は、尿素やグアニジンをポリエステル系分散液の製造時に用いることにより、該分散液を凝集・合一して得られるトナーの転写効率が高くなることを見出した。これは、尿素やグアニジンをポリエステルの分散時に存在させることで、ポリエステルのエステル基に由来する水素結合を分断し、ポリエステル間の結合力が低下することで分散粒子径が均一化され、該分散粒子が凝集、熱融合した後のトナー粒子が、より球形化したためと推定される。
以下、各構成について詳細に記載する。
The present inventors have found that the use of urea or guanidine in the production of a polyester dispersion increases the transfer efficiency of the toner obtained by aggregating and coalescing the dispersion. This is because the presence of urea or guanidine at the time of dispersion of the polyester breaks the hydrogen bonds derived from the ester groups of the polyester, and the bond strength between the polyesters decreases, thereby making the dispersed particle diameter uniform. It is presumed that the toner particles after flocculation and thermal fusion were more spherical.
Each configuration will be described in detail below.
［トナー用ポリエステル系樹脂の水系分散液及びその製造方法］
本発明のトナー用ポリエステル系樹脂の水系分散液は、尿素及びアルキル尿素から選ばれる１種以上の尿素系化合物及び／又はグアニジン、アルキルグアニジン及びそれらの酸付加塩から選ばれる１種以上のグアニジン系化合物、並びに中和剤の存在下、ポリエステル系樹脂を水系媒体中に分散させる工程を含む方法により製造される水系分散液である。
[Aqueous dispersion of polyester resin for toner and method for producing the same]
The aqueous dispersion of the polyester resin for toner of the present invention comprises one or more urea compounds selected from urea and alkyl urea and / or one or more guanidines selected from guanidine, alkyl guanidine and acid addition salts thereof. An aqueous dispersion produced by a method comprising a step of dispersing a polyester resin in an aqueous medium in the presence of a compound and a neutralizing agent.
（尿素系化合物）
尿素系化合物としては、尿素及びアルキル尿素からなる群から選ばれる１種以上の尿素系化合物が用いられる。分散粒子径を均一にし、トナーの転写効率を高める観点から、尿素が好ましい。
アルキル尿素の具体例としては、メチル尿素、ジメチル尿素、トリメチル尿素、テトラメチル尿素、エチル尿素、ジエチル尿素等のＮ−アルキル置換された尿素が挙げられる。アルキル基としては、炭素数１〜６が好ましく、炭素数１〜３がより好ましく、ヒドロキシル基を有するアルキル基であってもよい。尿素系化合物におけるアルキル基の置換基数は、好ましくは１又は２である。
(Urea compound)
As the urea compound, one or more urea compounds selected from the group consisting of urea and alkylurea are used. Urea is preferable from the viewpoint of making the dispersed particle size uniform and increasing the toner transfer efficiency.
Specific examples of the alkyl urea include N-alkyl substituted ureas such as methyl urea, dimethyl urea, trimethyl urea, tetramethyl urea, ethyl urea, diethyl urea and the like. As an alkyl group, C1-C6 is preferable, C1-C3 is more preferable, and the alkyl group which has a hydroxyl group may be sufficient. The number of substituents of the alkyl group in the urea compound is preferably 1 or 2.
（グアニジン系化合物）
グアニジン系化合物としては、グアニジン、アルキルグアニジン及びそれらの酸付加塩からなる群から選ばれる１種以上のグアニジン系化合物が用いられ、酸付加塩であることが好ましい。また、分散粒子径を均一にし、トナーの転写効率を高める観点から、グアニジンが好ましい。
アルキルグアニジンの具体例としては、メチルグアニジン、エチルグアニジン、ｎ−プロピルグアニジン、イソプロピルグアニジン、ｎ−ブチルグアニジン、２−メチルプロピルグアニジン、ｔ−ブチルグアニジン、ｎ−ペンチルグアニジン、ｎ−ヘキシルグアニジン等のＮ−アルキル置換されたグアニジンが挙げられる。アルキル基としては、炭素数１〜６が好ましく、炭素数１〜３がより好ましく、ヒドロキシル基を有するアルキル基であってもよい。グアニジン系化合物におけるアルキル基の置換基数は、好ましくは１又は２である。
酸付加塩としては、塩酸塩、硝酸塩、炭酸塩等の無機酸塩、コハク酸塩、酢酸塩、グルタミン酸塩、乳酸塩、クエン酸塩、シュウ酸塩等の有機酸塩が挙げられる。
(Guanidine compounds)
As the guanidine compound, one or more guanidine compounds selected from the group consisting of guanidine, alkylguanidine and acid addition salts thereof are used, and acid addition salts are preferable. Further, guanidine is preferable from the viewpoint of making the dispersed particle diameter uniform and improving the transfer efficiency of the toner.
Specific examples of the alkylguanidine include N such as methylguanidine, ethylguanidine, n-propylguanidine, isopropylguanidine, n-butylguanidine, 2-methylpropylguanidine, t-butylguanidine, n-pentylguanidine, n-hexylguanidine and the like. -Alkyl substituted guanidines. As an alkyl group, C1-C6 is preferable, C1-C3 is more preferable, and the alkyl group which has a hydroxyl group may be sufficient. The number of substituents of the alkyl group in the guanidine compound is preferably 1 or 2.
Examples of the acid addition salt include inorganic acid salts such as hydrochloride, nitrate, and carbonate, and organic acid salts such as succinate, acetate, glutamate, lactate, citrate, and oxalate.
（ポリエステル系樹脂）
本発明に用いられるポリエステル系樹脂は、転写効率の効果を発揮する観点から、非晶質樹脂であることが好ましい。「非晶質樹脂」とは、結晶性指数が１．４を超えるか、０．６未満の樹脂をいい、結晶性指数は、軟化点と示差走査熱量計（ＤＳＣ）による吸熱の最大ピーク温度との比、即ち「軟化点／吸熱の最大ピーク温度」で定義される。
(Polyester resin)
The polyester resin used in the present invention is preferably an amorphous resin from the viewpoint of exhibiting the effect of transfer efficiency. “Amorphous resin” refers to a resin having a crystallinity index of more than 1.4 or less than 0.6, and the crystallinity index is the softening point and the maximum endothermic peak temperature by a differential scanning calorimeter (DSC). Ratio, that is, “softening point / maximum endothermic peak temperature”.
また、転写効率の効果を発揮する観点から、炭素数２〜５の脂肪族ジオール又は後述する式（Ｉ）で表されるビスフェノールＡのアルキレンオキサイド付加物を含有するアルコール成分とカルボン酸成分とを縮重合して得られるポリエステル系樹脂であることが好ましい。通常、炭素数２〜５の脂肪族ジオールを用いて得られるポリエステル系樹脂は、均一な樹脂粒子を得にくく、転写効率を高めることが困難である。これは、炭素数２〜５の脂肪族ジオールを用いて得られるポリエステル系樹脂のエステル価が高く、水素結合に基づく樹脂粒子間の相互影響が大きいためと推定される。これに対し、本発明のトナー用ポリエステル系樹脂の水系分散液は、炭素数２〜５の脂肪族ジオールを用いて得られるポリエステル系樹脂を用いても、転写効率に優れたトナーを提供することができる。 Further, from the viewpoint of exhibiting the effect of transfer efficiency, an alcohol component and a carboxylic acid component containing an aliphatic diol having 2 to 5 carbon atoms or an alkylene oxide adduct of bisphenol A represented by the formula (I) described later. A polyester resin obtained by condensation polymerization is preferable. Usually, polyester resins obtained using aliphatic diols having 2 to 5 carbon atoms are difficult to obtain uniform resin particles, and it is difficult to increase transfer efficiency. This is presumably because the polyester resin obtained using an aliphatic diol having 2 to 5 carbon atoms has a high ester value, and the mutual influence between resin particles based on hydrogen bonds is large. On the other hand, the aqueous dispersion of the polyester resin for toner of the present invention provides a toner having excellent transfer efficiency even when a polyester resin obtained using an aliphatic diol having 2 to 5 carbon atoms is used. Can do.
＜アルコール成分＞
ポリエステル系樹脂の原料モノマーであるアルコール成分は、トナーの低温定着性を高める観点及び転写効率の効果を発揮する観点から、炭素数２〜５、好ましくは炭素数３〜４の脂肪族ジオール又は下記式（Ｉ）で表されるビスフェノールＡのアルキレンオキサイド付加物を含有することが好ましい。
The alcohol component, which is a raw material monomer of the polyester-based resin, is an aliphatic diol having 2 to 5 carbon atoms, preferably 3 to 4 carbon atoms, from the viewpoint of enhancing the low-temperature fixability of the toner and exhibiting the effect of transfer efficiency. It is preferable to contain an alkylene oxide adduct of bisphenol A represented by the formula (I).
炭素数２〜５の脂肪族ジオールとしては、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、１，２−ペンタンジオール、１，３−ペンタンジオール、１，４−ペンタンジオール、１，５−ペンタンジオール、ネオペンチルグリコール、２，３−ペンタンジオール、２，４−ペンタンジオール等が挙げられる。上述した観点から、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、２，３−ブタンジオール、ネオペンチルグリコールからなる群から選ばれる少なくとも１種が好ましく、１，２−プロパンジオール、２，３−ブタンジオールがより好ましい。
炭素数２〜５の脂肪族ジオールは、トナーの転写効率の観点から、アルコール成分中、好ましくは７０〜１００モル％、より好ましくは８０〜１００モル％、更に好ましくは９０〜１００モル％含有される。
Examples of the aliphatic diol having 2 to 5 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 2,3-pentanediol, 2,4- A pentanediol etc. are mentioned. In view of the above, at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,3-butanediol, and neopentyl glycol is preferable, and 1,2-propanediol 2,3-butanediol is more preferred.
From the viewpoint of transfer efficiency of the toner, the aliphatic diol having 2 to 5 carbon atoms is preferably contained in the alcohol component in an amount of 70 to 100 mol%, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%. The
前記式（Ｉ）で表されるビスフェノールＡのアルキレンオキサイド付加物として、具体的には、２，２−ビス（４−ヒドロキシフェニル）プロパンのポリオキシプロピレン付加物、２，２−ビス（４−ヒドロキシフェニル）プロパンのポリオキシエチレン付加物等が挙げられる。
前記式（Ｉ）で表されるビスフェノールＡのアルキレンオキサイド付加物は、トナーの保存安定性及び転写効率を高める観点から、アルコール成分中、好ましくは７０〜１００モル％、より好ましくは８０〜１００モル％、更に好ましくは９０〜１００モル％含有される。
As the alkylene oxide adduct of bisphenol A represented by the above formula (I), specifically, a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxyphenyl) propane polyoxyethylene adduct and the like.
The alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 70 to 100 mol%, more preferably 80 to 100 mol in the alcohol component from the viewpoint of enhancing the storage stability and transfer efficiency of the toner. %, More preferably 90 to 100 mol%.
炭素数２〜５の脂肪族ジオール及び芳香族ジオール以外の多価アルコール成分としては、例えば、炭素数６〜１０の脂肪族ジオール、３価以上のアルコールが挙げられる。
炭素数６〜１０の脂肪族ジオールとして、具体的には、１，６−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール等が挙げられる。
３価以上のアルコールとして、具体的には、グリセリン、ペンタエリスリトール、トリメチロールプロパン等が挙げられる。
Examples of polyhydric alcohol components other than aliphatic diols having 2 to 5 carbon atoms and aromatic diols include aliphatic diols having 6 to 10 carbon atoms and trihydric or higher alcohols.
Specific examples of the aliphatic diol having 6 to 10 carbon atoms include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and the like.
Specific examples of the trivalent or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.
＜カルボン酸成分＞
カルボン酸成分は、帯電率の観点から、フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸化合物を含有することが好ましい。カルボン酸成分中、芳香族ジカルボン酸化合物の含有量は、トナーの低温定着性及び保存性の観点から、好ましくは３０〜９５モル％、より好ましくは４０〜９０モル％、更に好ましくは５０〜８５モル％である。
<Carboxylic acid component>
The carboxylic acid component preferably contains an aromatic dicarboxylic acid compound such as phthalic acid, isophthalic acid, and terephthalic acid from the viewpoint of the charge rate. In the carboxylic acid component, the content of the aromatic dicarboxylic acid compound is preferably 30 to 95 mol%, more preferably 40 to 90 mol%, still more preferably 50 to 85, from the viewpoint of low-temperature fixability and storage stability of the toner. Mol%.
芳香族ジカルボン酸化合物以外のジカルボン酸化合物としては、シュウ酸、マロン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸、コハク酸、アジピン酸、セバシン酸、アゼライン酸等の炭素数２〜１０（好ましくは炭素数４〜１０、より好ましくは炭素数４〜８）の脂肪族ジカルボン酸；シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；及びこれらの酸の無水物、アルキル（炭素数１〜３）エステル等が挙げられる。本発明においては、カルボン酸並びにその酸無水物及びそのアルキル（炭素数１〜３）エステル等の誘導体等を、カルボン酸化合物と総称する。 Examples of dicarboxylic acid compounds other than aromatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, and azelaic acid. 10 to 10 (preferably 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms); alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and anhydrides of these acids, alkyl (1 carbon atoms) -3) An ester etc. are mentioned. In the present invention, the carboxylic acid, its acid anhydride, its alkyl (carbon number 1 to 3) ester derivative and the like are collectively referred to as a carboxylic acid compound.
カルボン酸成分は、３価以上の多価カルボン酸化合物を含有してもよい。３価以上の多価カルボン酸化合物としては、１，２，４−ベンゼントリカルボン酸（トリメリット酸）、２，５，７−ナフタレントリカルボン酸、ピロメリット酸等の芳香族カルボン酸、及びこれらの酸無水物、アルキル（炭素数１〜３）エステル等の誘導体が挙げられる。また、カルボン酸成分は、その他のカルボン酸化合物として、ロジン；フマル酸、マレイン酸、アクリル酸等で変性されたロジン等を含有してもよい。 The carboxylic acid component may contain a trivalent or higher polyvalent carboxylic acid compound. Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and aromatic carboxylic acids such as pyromellitic acid, and these Derivatives such as acid anhydrides and alkyl (1 to 3 carbon atoms) esters may be mentioned. The carboxylic acid component may contain rosin; rosin modified with fumaric acid, maleic acid, acrylic acid, or the like as other carboxylic acid compounds.
本発明において、カルボン酸成分は、樹脂の分子量を上げ、トナーの耐キャリア汚染性及び保存性を高める観点から、３価以上の多価カルボン酸化合物、好ましくはトリメリット酸化合物、より好ましくは無水トリメリット酸を含有していることが好ましい。３価以上の多価カルボン酸化合物の含有量は、カルボン酸成分中、０．１〜３０モル％が好ましく、１〜２５モル％がより好ましく、５〜２５モル％が更に好ましい。 In the present invention, the carboxylic acid component is a trivalent or higher polyvalent carboxylic acid compound, preferably a trimellitic acid compound, more preferably anhydrous, from the viewpoint of increasing the molecular weight of the resin and improving the carrier contamination resistance and storage stability of the toner. It is preferable to contain trimellitic acid. The content of the trivalent or higher polyvalent carboxylic acid compound is preferably 0.1 to 30 mol%, more preferably 1 to 25 mol%, and still more preferably 5 to 25 mol% in the carboxylic acid component.
＜変性樹脂＞
本発明において、上記のアルコール成分とカルボン酸成分とを縮重合して得られるポリエステル系樹脂には、ポリエステル樹脂のみならず、その変性樹脂も含まれる。
変性樹脂としては、例えば、ポリエステルがウレタン結合で変性されたウレタン変性ポリエステル、ポリエステルがエポキシ結合で変性されたエポキシ変性ポリエステル、及びポリエステル成分を含む２種以上の樹脂成分を有するハイブリッド樹脂等が挙げられる。
ポリエステル系樹脂として、前記ポリエステル成分を有する樹脂及びその変性樹脂は、いずれか一方であっても、両者が併用されてもよく、具体的にはポリエステル成分及び／又はポリエステル成分とビニル系樹脂成分とを有するハイブリッド樹脂であってもよい。
<Modified resin>
In the present invention, the polyester resin obtained by condensation polymerization of the alcohol component and the carboxylic acid component includes not only the polyester resin but also a modified resin thereof.
Examples of the modified resin include urethane-modified polyester in which polyester is modified with a urethane bond, epoxy-modified polyester in which polyester is modified with an epoxy bond, and a hybrid resin having two or more kinds of resin components including a polyester component. .
As the polyester-based resin, the resin having the polyester component and the modified resin thereof may be either one or both may be used together. Specifically, the polyester component and / or the polyester component and the vinyl-based resin component It may be a hybrid resin having
ポリエステル成分とビニル系樹脂成分とを有するハイブリッド樹脂は、それぞれの樹脂を必要に応じて開始剤等の存在下に溶融混練する方法、それぞれの樹脂を溶剤に溶解させ混合する方法、それぞれの樹脂の原料モノマー混合物を重合させる方法等の、いずれの方法により製造されたものでもよい。好ましくは、前記ポリエステル成分の原料モノマー及びビニル系樹脂成分の原料モノマーを用いて、縮重合反応と付加重合反応とを行う方法により得られる樹脂（特開平７−９８５１８号公報）である。 A hybrid resin having a polyester component and a vinyl resin component is prepared by a method of melt-kneading each resin in the presence of an initiator or the like, a method of dissolving and mixing each resin in a solvent, It may be produced by any method such as a method of polymerizing the raw material monomer mixture. Preferably, it is a resin obtained by the method of performing a polycondensation reaction and an addition polymerization reaction using the raw material monomer of the said polyester component, and the raw material monomer of a vinyl resin component (Unexamined-Japanese-Patent No. 7-98518).
ビニル系樹脂成分の原料モノマーとしては、スチレン、α−メチルスチレン等のスチレン化合物；エチレン、プロピレン等のエチレン性不飽和モノオレフィン類；ブタジエン等のジオレフィン類；塩化ビニル等のハロビニル類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；（メタ）アクリル酸のアルキル（炭素数１〜１８）エステル、（メタ）アクリル酸ジメチルアミノエチル等のエチレン性モノカルボン酸のエステル；ビニルメチルエーテル等のビニルエーテル類；ビニリデンクロリド等のビニリデンハロゲン化物；Ｎ−ビニルピロリドン等のＮ−ビニル化合物類等が挙げられる。反応性、粉砕性及び帯電安定性の観点から、スチレン、アクリル酸ブチル、アクリル酸２−エチルヘキシル、及びメタクリル酸メチルが好ましく、スチレン及び／又は（メタ）アクリル酸のアルキルエステルが、ビニル系樹脂成分中、５０重量％以上含有されていることが好ましく、より好ましくは８０〜１００重量％である。
なお、ビニル系樹脂成分の原料モノマーを重合させる際には、重合開始剤、架橋剤等を必要に応じて使用してもよい。
Raw material monomers for vinyl resin components include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate Vinyl esters such as vinyl propionate; alkyl (carbon number 1 to 18) esters of (meth) acrylic acid; esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether And vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone and the like. Styrene, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate are preferred from the viewpoints of reactivity, grindability, and charge stability, and alkyl ester of styrene and / or (meth) acrylic acid is a vinyl resin component. The content is preferably 50% by weight or more, more preferably 80 to 100% by weight.
In addition, when polymerizing the raw material monomer of a vinyl-type resin component, you may use a polymerization initiator, a crosslinking agent, etc. as needed.
ビニル系樹脂成分の原料モノマーに対するポリエステル成分の原料モノマーの重量比（ポリエステル成分の原料モノマー／ビニル系樹脂成分の原料モノマー）は、ポリエステル成分により連続相を形成する観点から、好ましくは５５／４５〜９５／５、より好ましくは６０／４０〜９５／５、７０／３０〜９０／１０が更に好ましい。 The weight ratio of the raw material monomer of the polyester component to the raw material monomer of the vinyl resin component (the raw material monomer of the polyester component / the raw material monomer of the vinyl resin component) is preferably 55/45 from the viewpoint of forming a continuous phase with the polyester component. 95/5, more preferably 60/40 to 95/5, and 70/30 to 90/10 are even more preferable.
＜ポリエステル系樹脂の物性＞
本発明に用いられるポリエステル系樹脂の軟化点は、定着性の観点から、好ましくは７０〜１８０℃、より好ましくは１００〜１６０℃であり、ガラス転移温度は、定着性の観点から、好ましくは４５〜８０℃、より好ましくは５５〜７５℃である。なお、ガラス転移温度は非晶質樹脂に特有の物性であり、融解熱の最大ピーク温度とは区別される。
数平均分子量は、定着性の観点から、１，０００〜６，０００が好ましく、２，０００〜５，０００がより好ましい。また、重量平均分子量の下限値は、好ましくは１０，０００以上、より好ましくは３０，０００以上、更に好ましくは１００，０００以上であり、その上限値は、好ましくは１，０００，０００以下、より好ましくは５００，０００以下である。なお、数平均分子量及び重量平均分子量は、いずれもテトラヒドロフラン可溶分を測定した値をいう。
ポリエステル系樹脂の酸価は、分散した樹脂粒子を安定にし、かつ小粒径のトナーをシャープな粒度分布にし、トナーの転写効率を高める観点から、１〜４０ｍｇＫＯＨ／ｇが好ましく、２〜３５ｍｇＫＯＨ／ｇがより好ましく、３〜３０ｍｇＫＯＨ／ｇが更に好ましい。
ポリエステル系樹脂の水酸基価は、上記と同様の観点から、１〜４０ｍｇＫＯＨ／ｇが好ましく、２〜３５ｍｇＫＯＨ／ｇがより好ましく、３〜３０ｍｇＫＯＨ／ｇが更に好ましい。
<Physical properties of polyester resin>
The softening point of the polyester-based resin used in the present invention is preferably 70 to 180 ° C., more preferably 100 to 160 ° C. from the viewpoint of fixability, and the glass transition temperature is preferably 45 from the viewpoint of fixability. It is -80 degreeC, More preferably, it is 55-75 degreeC. The glass transition temperature is a physical property peculiar to an amorphous resin, and is distinguished from the maximum peak temperature of heat of fusion.
The number average molecular weight is preferably 1,000 to 6,000, and more preferably 2,000 to 5,000, from the viewpoint of fixability. Further, the lower limit of the weight average molecular weight is preferably 10,000 or more, more preferably 30,000 or more, still more preferably 100,000 or more, and the upper limit thereof is preferably 1,000,000 or less. Preferably it is 500,000 or less. The number average molecular weight and the weight average molecular weight are both values obtained by measuring the tetrahydrofuran-soluble content.
The acid value of the polyester resin is preferably 1 to 40 mgKOH / g, and preferably 2 to 35 mgKOH / g from the viewpoint of stabilizing the dispersed resin particles, making the toner having a small particle diameter a sharp particle size distribution, and increasing the transfer efficiency of the toner. g is more preferable, and 3 to 30 mgKOH / g is still more preferable.
The hydroxyl value of the polyester resin is preferably 1 to 40 mgKOH / g, more preferably 2 to 35 mgKOH / g, and still more preferably 3 to 30 mgKOH / g from the same viewpoint as described above.
＜縮重合＞
アルコール成分とカルボン酸成分との縮重合は、エステル化触媒の存在下で行うことが好ましく、貯蔵弾性率の高いポリエステルを得る観点から、エステル化触媒とピロガロール化合物の共存在下で行うことがより好ましい。
<Condensation polymerization>
The polycondensation of the alcohol component and the carboxylic acid component is preferably performed in the presence of an esterification catalyst. From the viewpoint of obtaining a polyester having a high storage elastic modulus, it is more preferably performed in the presence of an esterification catalyst and a pyrogallol compound. preferable.
＜エステル化触媒＞
上記縮重合に好適に用いられるエステル化触媒としては、チタン化合物及びＳｎ−Ｃ結合を有していない錫（II）化合物が挙げられ、これらは１種又は２種以上を併せて使用することができる。
<Esterification catalyst>
Examples of the esterification catalyst suitably used for the condensation polymerization include a titanium compound and a tin (II) compound having no Sn—C bond, and these may be used alone or in combination of two or more. it can.
チタン化合物としては、Ｔｉ−Ｏ結合を有するチタン化合物が好ましく、総炭素数１〜２８のアルコキシ基、アルケニルオキシ基又はアシルオキシ基を有する化合物がより好ましい。
チタン化合物の具体例としては、チタンジイソプロピレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ3Ｈ7Ｏ)2〕、チタンジイソプロピレートビスジエタノールアミネート〔Ｔｉ(Ｃ4Ｈ10Ｏ2Ｎ)2(Ｃ3Ｈ7Ｏ)2〕、チタンジペンチレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ5Ｈ11Ｏ)2〕、チタンジエチレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ2Ｈ5Ｏ)2〕、チタンジヒドロキシオクチレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(ＯＨＣ8Ｈ16Ｏ)2〕、チタンジステアレートビストリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)2(Ｃ18Ｈ37Ｏ)2〕、チタントリイソプロピレートトリエタノールアミネート〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)1(Ｃ3Ｈ7Ｏ)3〕、及びチタンモノプロピレートトリス(トリエタノールアミネート)〔Ｔｉ(Ｃ6Ｈ14Ｏ3Ｎ)3(Ｃ3Ｈ7Ｏ)1〕等が挙げられる。これらの中ではチタンジイソプロピレートビストリエタノールアミネート、チタンジイソプロピレートビスジエタノールアミネート、及びチタンジペンチレートビストリエタノールアミネートが好ましく、これらは、例えば（株）マツモト交商の市販品としても入手可能である。
As a titanium compound, the titanium compound which has a Ti-O bond is preferable, and the compound which has a C1-28 total carbon number alkoxy group, an alkenyloxy group, or an acyloxy group is more preferable.
Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C 6 H 14 O 3 N) 2 (C 3 H 7 O) 2 ], titanium diisopropylate bisdiethanolamate [Ti (C 4 H 10 O 2 N) 2 (C 3 H 7 O) 2 ], titanium dipentylate bistriethanolamate [Ti (C 6 H 14 O 3 N) 2 (C 5 H 11 O) 2 ], titanium diety rate bis triethanolaminate [Ti (C 6 H 14 O 3 N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate [Ti (C 6 H 14 O 3 N) 2 (OHC 8 H 16 O) 2 ], titanium distearate bistriethanolamate [Ti (C 6 H 14 O 3 N) 2 (C 18 H 37 O) 2 ], titanium triisopropylate triethanolamate [Ti (C 6 H 14 O 3 N) 1 ( C 3 7 O) 3], and titanium monopropylate tris (triethanolaminate) [Ti (C 6 H 14 O 3 N) 3 (C 3 H 7 O) 1 ], and the like. Of these, titanium diisopropylate bistriethanolaminate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolamate are preferred, and these are also available as commercial products of Matsumoto Trading Co., Ltd. It is.
他の好ましいチタン化合物の具体例としては、テトラ−ｎ−ブチルチタネート〔Ｔｉ(Ｃ4Ｈ9Ｏ)4〕、テトラプロピルチタネート〔Ｔｉ(Ｃ3Ｈ7Ｏ)4〕、テトラステアリルチタネート〔Ｔｉ(Ｃ18Ｈ37Ｏ)4〕、テトラミリスチルチタネート〔Ｔｉ(Ｃ14Ｈ29Ｏ)4〕、テトラオクチルチタネート〔Ｔｉ(Ｃ8Ｈ17Ｏ)4〕、ジオクチルジヒドロキシオクチルチタネート〔Ｔｉ(Ｃ8Ｈ17Ｏ)2(ＯＨＣ8Ｈ16Ｏ)2〕、及びジミリスチルジオクチルチタネート〔Ｔｉ(Ｃ14Ｈ29Ｏ)2(Ｃ8Ｈ17Ｏ)2〕等が挙げられる。これらの中ではテトラステアリルチタネート、テトラミリスチルチタネート、テトラオクチルチタネート、及びジオクチルジヒドロキシオクチルチタネートが好ましく、これらは、例えばハロゲン化チタンを対応するアルコールと反応させることにより得ることもできるが、ニッソー（株）等の市販品としても入手可能である。 Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C 4 H 9 O) 4 ], tetrapropyl titanate [Ti (C 3 H 7 O) 4 ], tetrastearyl titanate [Ti ( C 18 H 37 O) 4 ], tetramyristyl titanate [Ti (C 14 H 29 O) 4 ], tetraoctyl titanate [Ti (C 8 H 17 O) 4 ], dioctyl dihydroxyoctyl titanate [Ti (C 8 H 17 O) 2 (OHC 8 H 16 O) 2 ], dimyristyl dioctyl titanate [Ti (C 14 H 29 O) 2 (C 8 H 17 O) 2 ] and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate, and dioctyl dihydroxy octyl titanate are preferable. These can be obtained by reacting, for example, titanium halide with a corresponding alcohol. It is also available as a commercial product such as
Ｓｎ−Ｃ結合を有していない錫（II）化合物としては、Ｓｎ−Ｏ結合を有する錫（II）化合物、Ｓｎ−Ｘ（Ｘはハロゲン原子を示す）結合を有する錫（II）化合物等が好ましく挙げられ、Ｓｎ−Ｏ結合を有する錫（II）化合物がより好ましい。
Ｓｎ−Ｏ結合を有する錫（II）化合物としては、シュウ酸錫（II）、ジ酢酸錫（II）、ジオクタン酸錫（II）、ジラウリル酸錫（II）、ジステアリン酸錫（II）、及びジオレイン酸錫（II）等の炭素数２〜２８のカルボン酸基を有するカルボン酸錫（II）；ジオクチロキシ錫（II）、ジラウロキシ錫（II）、ジステアロキシ錫（II）、及びジオレイロキシ錫（II）等の炭素数２〜２８のアルコキシ基を有するジアルコキシ錫（II）；酸化錫（II）；硫酸錫（II）等が挙げられる。
Ｓｎ−Ｘ（Ｘはハロゲン原子を示す）結合を有する化合物としては、塩化錫（II）、臭化錫（II）等のハロゲン化錫（II）等が挙げられる。これらの中では、帯電立ち上がり効果及び触媒能の点から、(Ｒ1ＣＯＯ)2Ｓｎ（ここでＲ1は炭素数５〜１９のアルキル基又はアルケニル基を示す）で表される脂肪酸錫（II）、(Ｒ2Ｏ)2Ｓｎ（ここでＲ2は炭素数６〜２０のアルキル基又はアルケニル基を示す）で表されるジアルコキシ錫（II）、及びＳｎＯで表される酸化錫（II）が好ましく、(Ｒ1ＣＯＯ)2Ｓｎで表される脂肪酸錫（II）及び酸化錫（II）がより好ましく、ジオクタン酸錫（II）、ジステアリン酸錫（II）、及び酸化錫（II）が更に好ましく用いられる。
Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred examples include tin (II) compounds having a Sn-O bond.
Examples of tin (II) compounds having a Sn-O bond include tin (II) oxalate, tin (II) diacetate, tin (II) dioctanoate, tin (II) dilaurate, tin (II) distearate, and Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) dioleate; dioctyloxytin (II), dilauroxytin (II), distearoxytin (II), and dioleoxytin (II) Dialkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms, such as tin oxide (II) and tin sulfate (II).
Examples of the compound having a Sn-X (X represents a halogen atom) bond include tin (II) halides such as tin (II) chloride and tin (II) bromide. Among these, fatty acid tin (II) represented by (R 1 COO) 2 Sn (wherein R 1 represents an alkyl group or alkenyl group having 5 to 19 carbon atoms) from the viewpoint of the charge rising effect and catalytic ability. ), (R 2 O) 2 Sn (wherein R 2 represents an alkyl group or alkenyl group having 6 to 20 carbon atoms), and tin oxide (II) represented by SnO Fatty acid tin (II) and tin (II) oxide represented by (R 1 COO) 2 Sn are more preferred, tin (II) dioctanoate, tin (II) distearate, and tin (II) oxide Is more preferably used.
上記エステル化触媒の存在量は、アルコール成分とカルボン酸成分との総量１００重量部に対して、０．０１〜１重量部が好ましく、０．１〜０．６重量部がより好ましい。 The amount of the esterification catalyst present is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.6 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.
＜ピロガロール化合物＞
ピロガロール化合物は、互いに隣接する３個の水素原子が水酸基で置換されたベンゼン環を有するものであり、ピロガロール、没食子酸、没食子酸エステル、２，３，４−トリヒドロキシベンゾフェノン、２，２’，３，４−テトラヒドロキシベンゾフェノン等のベンゾフェノン誘導体、エピガロカテキン、エピガロカテキンガレート等のカテキン誘導体等が挙げられる。
縮重合反応におけるピロガロール化合物の存在量は、縮重合反応に供されるアルコール成分とカルボン酸成分との総量１００重量部に対して、０．００１〜１重量部が好ましく、０．００５〜０．４重量部がより好ましく、０．０１〜０．２重量部が更に好ましい。ここで、ピロガロール化合物の存在量とは、縮重合反応に供したピロガロール化合物の全配合量を意味する。
ピロガロール化合物とエステル化触媒との重量比（ピロガロール化合物／エステル化触媒）は、樹脂の耐久性の観点から、０．０１〜０．５が好ましく、０．０３〜０．３がより好ましく、０．０５〜０．２が更に好ましい。
<Pyrogallol compound>
A pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with a hydroxyl group, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ′, Examples include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone, and catechin derivatives such as epigallocatechin and epigallocatechin gallate.
The abundance of the pyrogallol compound in the condensation polymerization reaction is preferably 0.001 to 1 part by weight, and preferably 0.005 to 0.005 parts per 100 parts by weight of the total amount of the alcohol component and carboxylic acid component subjected to the condensation polymerization reaction. 4 parts by weight is more preferable, and 0.01 to 0.2 parts by weight is still more preferable. Here, the abundance of the pyrogallol compound means the total amount of the pyrogallol compound subjected to the condensation polymerization reaction.
The weight ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably 0.01 to 0.5, more preferably 0.03 to 0.3, from the viewpoint of the durability of the resin. 0.05 to 0.2 is more preferable.
アルコール成分とカルボン酸成分との縮重合は、例えば、前記エステル化触媒の存在下、不活性ガス雰囲気中にて、１２０〜２５０℃の温度で行うことができる。
また、例えば樹脂の強度を上げるために全モノマーを一括仕込みしたり、低分子量成分を少なくするために２価のモノマーを先ず反応させた後、３価以上のモノマーを添加して反応させる等の方法を用いてもよい。また、重合の後半に反応系を減圧することにより、反応を促進させてもよい。
The polycondensation of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 120 to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst.
In addition, for example, all monomers are charged together to increase the strength of the resin, or divalent monomers are first reacted to reduce low molecular weight components, and then trivalent or higher monomers are added and reacted. A method may be used. Further, the reaction may be accelerated by reducing the pressure of the reaction system in the latter half of the polymerization.
（水系媒体）
水系媒体は、水を含有している媒体で、有機溶剤等の溶剤を含有していてもよいが、媒体中、水を好ましくは７０重量％以上、好ましくは８０重量％以上、より好ましくは９０重量％以上、さらに好ましくは９９重量％以上含有するものである。なお、溶剤を使用する場合には樹脂の溶解性を考慮し、後述する水に溶解する有機溶剤が好ましい。また、「ポリエステル系樹脂の水系分散液」とは、ポリエステル系樹脂を水系媒体に分散した液のことをいう。
(Aqueous medium)
The aqueous medium is a medium containing water, and may contain a solvent such as an organic solvent. In the medium, water is preferably 70% by weight or more, preferably 80% by weight or more, more preferably 90%. It contains at least 99% by weight, more preferably at least 99% by weight. In addition, when using a solvent, the solubility of resin is considered and the organic solvent which melt | dissolves in the water mentioned later is preferable. The “aqueous dispersion of polyester resin” refers to a liquid in which a polyester resin is dispersed in an aqueous medium.
（中和剤）
中和剤としては、水酸化リチウム、水酸化ナトリウム、及び水酸化カリウム等のアルカリ金属の水酸化物；アンモニア、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、トリエタノールアミン、及びトリブチルアミン等の有機塩基が挙げられる。
ポリエステル系樹脂の中和度は、分散粒子径を均一に、且つ小粒径化させ、転写効率を高める観点から、４０〜１２０モル％が好ましく、４０〜１００モル％が好ましく、５０〜８０モル％が更に好ましい。
(Neutralizer)
Examples of neutralizing agents include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; organic bases such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. It is done.
The degree of neutralization of the polyester-based resin is preferably 40 to 120 mol%, preferably 40 to 100 mol%, and preferably 50 to 80 mol, from the viewpoint of making the dispersed particle size uniform and small, and improving transfer efficiency. % Is more preferable.
（トナー用ポリエステル系樹脂の水系分散液の製造方法）
本発明の方法は、尿素及びアルキル尿素から選ばれる１種以上の尿素系化合物及び／又はグアニジン、アルキルグアニジン及びそれらの酸付加塩から選ばれる１種以上のグアニジン系化合物、並びに中和剤の存在下、ポリエステル系樹脂を水系媒体中に分散させる工程を含む。
本発明の方法における尿素系化合物の使用量は、分散粒子径を均一に且つ小粒径化させ、トナーの転写効率を高める観点から、ポリエステル系樹脂１００重量部に対して、好ましくは０．５〜１５重量部、より好ましくは０．５〜１０重量部、更に好ましくは１〜８重量部、より更に好ましくは２〜８重量部である。
本発明の方法におけるグアニジン系化合物の合計の使用量は、分散粒子径を均一に且つ小粒径化させ、トナーの転写効率を高める観点から、ポリエステル系樹脂１００重量部に対して、好ましくは０．５〜１５重量部、より好ましくは０．５〜１０重量部、更に好ましくは１〜８重量部、より更に好ましくは２〜８重量部である。
本発明の方法における尿素系化合物及びグアニジン系化合物の合計の使用量は、分散粒子径を均一に且つ小粒径化させ、トナーの転写効率を高める観点から、ポリエステル系樹脂１００重量部に対して、好ましくは０．５〜１５重量部、より好ましくは０．５〜１０重量部、更に好ましくは１〜８重量部、より更に好ましくは２〜８重量部である。
(Method for producing aqueous dispersion of polyester resin for toner)
The method of the present invention comprises one or more urea compounds selected from urea and alkyl urea and / or one or more guanidine compounds selected from guanidine, alkyl guanidine and acid addition salts thereof, and the presence of a neutralizing agent. The process includes a step of dispersing the polyester resin in an aqueous medium.
The amount of the urea compound used in the method of the present invention is preferably 0.5 with respect to 100 parts by weight of the polyester resin from the viewpoint of making the dispersed particle diameter uniform and small and increasing the transfer efficiency of the toner. -15 parts by weight, more preferably 0.5-10 parts by weight, still more preferably 1-8 parts by weight, still more preferably 2-8 parts by weight.
The total amount of the guanidine compound used in the method of the present invention is preferably 0 with respect to 100 parts by weight of the polyester resin from the viewpoint of making the dispersed particle diameter uniform and small, and improving the transfer efficiency of the toner. 0.5 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 1 to 8 parts by weight, and still more preferably 2 to 8 parts by weight.
The total use amount of the urea compound and the guanidine compound in the method of the present invention is based on 100 parts by weight of the polyester resin from the viewpoint of making the dispersed particle diameter uniform and small and increasing the toner transfer efficiency. The amount is preferably 0.5 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 1 to 8 parts by weight, and still more preferably 2 to 8 parts by weight.
本発明の方法における尿素系化合物とグアニジン系化合物との合計モル数とポリエステル系樹脂の未中和のカルボキシ基及び水酸基の合計モル数とのモル比（尿素系化合物とグアニジン系化合物との合計モル数／ポリエステル系樹脂の未中和のカルボキシ基及び水酸基の合計モル数）は、分散粒子径を均一に且つ小粒径化させ、トナーの転写効率を高める観点から、好ましくは０．１〜１０、より好ましくは０．３〜５、更に好ましくは０．５〜３である。
ポリエステル系樹脂の未中和のカルボキシ基と水酸基との合計モル数は下記の式から、求めることができる。
ポリエステル系樹脂の未中和カルボキシ基及び水酸基の合計モル数＝〔ポリエステル系樹脂の酸価（ＫＯＨｍｇ／ｇ）×［（１００−中和度）／１００］＋ポリエステル系樹脂の水酸基価（ＫＯＨｍｇ／ｇ）〕／５６０００×［樹脂の重量（ｇ）］
（但し、中和度が１００を超える場合は、ポリエステルの未中和カルボキシ基のモル数は０とする。中和度は、後述する計算式により求めることができる。）
In the method of the present invention, the molar ratio between the total number of moles of the urea compound and the guanidine compound and the total number of unneutralized carboxy groups and hydroxyl groups of the polyester resin (the total mole of the urea compound and the guanidine compound) Number / the total number of moles of unneutralized carboxy groups and hydroxyl groups of the polyester-based resin) is preferably 0.1 to 10 from the viewpoint of making the dispersed particle diameter uniform and small and increasing the transfer efficiency of the toner. More preferably, it is 0.3-5, More preferably, it is 0.5-3.
The total number of moles of unneutralized carboxy groups and hydroxyl groups of the polyester resin can be determined from the following formula.
Total number of moles of unneutralized carboxy group and hydroxyl group of polyester resin = [acid value of polyester resin (KOHmg / g) × [(100−degree of neutralization) / 100] + hydroxyl value of polyester resin (KOHmg / g)] / 56000 × [weight of resin (g)]
(However, when the degree of neutralization exceeds 100, the number of moles of unneutralized carboxy groups in the polyester is 0. The degree of neutralization can be determined by the calculation formula described below.)
本発明の方法としては、好ましくは下記方法（Ａ）又は（Ｂ）が挙げられる。
＜方法（Ａ）＞
下記工程Ａ１及びＡ２を含む、トナー用ポリエステル系樹脂の水系分散液の製造方法である。
工程Ａ１：ポリエステル系樹脂、尿素系化合物及び／又はグアニジン系化合物、中和剤、有機溶剤並びに水、更に必要に応じて界面活性剤、を混合し、ポリエステル系樹脂の分散液を得る工程。
工程Ａ２：前記工程Ａ１で得られた分散液から、有機溶剤を除去することにより、ポリエステル系樹脂の水系分散液を得る工程。
The method of the present invention is preferably the following method (A) or (B).
<Method (A)>
A method for producing an aqueous dispersion of a polyester resin for toner, comprising the following steps A1 and A2.
Step A1: A step of mixing a polyester resin, a urea compound and / or a guanidine compound, a neutralizing agent, an organic solvent and water, and further, if necessary, a surfactant to obtain a polyester resin dispersion.
Step A2: A step of obtaining an aqueous dispersion of a polyester resin by removing an organic solvent from the dispersion obtained in Step A1.
工程Ａ１において、尿素系化合物及び／又はグアニジン系化合物の添加順序に限定はなく、ポリエステル系樹脂、尿素系化合物及び／又はグアニジン系化合物、有機溶剤を混合した後、水、中和剤、更に必要に応じて界面活性剤を混合してポリエステル系樹脂の分散液を得てもよく、ポリエステル系樹脂、中和剤、有機溶剤、水、更に必要に応じて界面活性剤を混合し、ポリエステル系樹脂の分散液を得た後、尿素化合物及び／又はグアニジン化合物を分散液に添加してもよい。
より好ましくは、トナーの転写効率の観点から、ポリエステル系樹脂を有機溶剤に溶解した後、得られた溶液に、尿素系化合物及び／又はグアニジン系化合物を添加し、更に中和剤及び水を添加して、分散液を得ることが好ましい。
工程Ａ１は、ポリエステル系樹脂の分散性の観点から、好ましくは３０〜９０℃、より好ましくは４０〜８０℃で分散液を得ることが好ましい。
工程Ａ２では、当該分散液から蒸留等によって有機溶剤を除去することによりポリエステル系樹脂の水系分散液を得る方法がより好ましい。
In step A1, the order of addition of the urea compound and / or the guanidine compound is not limited, and after mixing the polyester resin, the urea compound and / or the guanidine compound and the organic solvent, water, a neutralizing agent, and further necessary If necessary, a surfactant may be mixed to obtain a dispersion of a polyester resin. A polyester resin, a neutralizing agent, an organic solvent, water and, if necessary, a surfactant may be mixed to obtain a polyester resin. After obtaining the dispersion liquid, a urea compound and / or a guanidine compound may be added to the dispersion liquid.
More preferably, from the viewpoint of toner transfer efficiency, after dissolving the polyester resin in an organic solvent, a urea compound and / or a guanidine compound are added to the resulting solution, and a neutralizer and water are further added. Thus, it is preferable to obtain a dispersion.
In the step A1, it is preferable to obtain a dispersion at 30 to 90 ° C., more preferably 40 to 80 ° C. from the viewpoint of dispersibility of the polyester resin.
In Step A2, a method of obtaining an aqueous dispersion of a polyester resin by removing an organic solvent from the dispersion by distillation or the like is more preferable.
有機溶剤としては、ポリエステル系樹脂の分散性並びに尿素系及びグアニジン系化合物によるトナーの転写効率を高める観点から、溶解性パラメータ（ＳＰ値：ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ ＴＨＩＲＤ ＥＤＩＴＩＯＮ １９８９ ｂｙ Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ）で表したとき、１５．０〜２６．０ＭＰａ1/2であるものが好ましく、１６．０〜２４．０ＭＰａ1/2であるものがより好ましく、１７．０〜２２．０ＭＰａ1/2であるものが更に好ましい。
具体例としては、エタノール（２６．０）、イソプロパノール（２３．５）、及びイソブタノール（２１．５）等のアルコール系溶媒；アセトン（２０．３）、メチルエチルケトン（１９．０）、メチルイソブチルケトン（１７．２）、及びジエチルケトン（１８．０）等のケトン系溶媒；ジブチルエーテル、テトラヒドロフラン（１８．６）、及びジオキサン（２０．５）等のエーテル系溶媒；酢酸エチル（１８．６）が挙げられる。カッコ内は、ＳＰ値を示す。これらの中では、ポリエステル系樹脂の分散性の観点から、メチルエチルケトン、酢酸エチルが好ましい。
界面活性剤としては、例えば、硫酸エステル系、スルホン酸塩系、リン酸エステル系、せっけん系（例えばアルキルエーテルカルボン酸塩等）等のアニオン性界面活性剤；アミン塩型、第４級アンモニウム塩型等のカチオン性界面活性剤；後述の非イオン性界面活性剤等が挙げられる。
混合の際は、アンカー翼等の一般的に用いられている混合撹拌装置で撹拌することが好ましい。また、前記工程Ａ２で有機溶剤を除去する方法は蒸留に限定されず、任意の方法で行うことができる。
The organic solvent is represented by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc.) from the viewpoint of enhancing the dispersibility of the polyester resin and the transfer efficiency of the toner by the urea and guanidine compounds. when, preferably has a 15.0～26.0MPa 1/2, more preferably those which are 16.0～24.0MPa 1/2, those which are 17.0～22.0MPa 1/2 Further preferred.
Specific examples include alcohol solvents such as ethanol (26.0), isopropanol (23.5), and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl isobutyl ketone. Ketone solvents such as (17.2) and diethyl ketone (18.0); ether solvents such as dibutyl ether, tetrahydrofuran (18.6), and dioxane (20.5); ethyl acetate (18.6) Is mentioned. The value in parentheses indicates the SP value. Among these, methyl ethyl ketone and ethyl acetate are preferable from the viewpoint of dispersibility of the polyester resin.
Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate ester, and soap (such as alkyl ether carboxylate); amine salt type, quaternary ammonium salt Examples include cationic surfactants such as molds; nonionic surfactants described later.
In mixing, it is preferable to stir with a commonly used mixing stirrer such as an anchor blade. Moreover, the method of removing the organic solvent in the step A2 is not limited to distillation, and can be performed by any method.
前記方法（Ａ）において、尿素系化合物及びグアニジン系化合物の合計使用量及びモル数は、前述のとおりである。
前記方法（Ａ）において、中和剤及び中和度は、前述のとおりである。
有機溶剤の使用量は、ポリエステル系樹脂の分散性並びに尿素系及びグアニジン系化合物によるトナーの転写効率を高める観点から、ポリエステル系樹脂１００重量部に対して、好ましくは１００〜１０００重量部、より好ましくは１５０〜６００重量部、更に好ましくは２００〜４００重量部である。
ポリエステル系樹脂と混合する際に用いる水の使用量は、ポリエステル系樹脂の分散性の観点から、有機溶剤１００重量部に対して、好ましくは１００〜１０００重量部、より好ましくは１２０〜５００重量部、更に好ましくは１３０〜３００重量部である。
界面活性剤を使用する場合、その使用量は、ポリエステル系樹脂の分散性の観点から、ポリエステル系樹脂１００重量部に対して、好ましくは０．１〜２０重量部、より好ましくは０．５〜１０重量部である。
In the said method (A), the total usage-amount and mole number of a urea type compound and a guanidine type compound are as above-mentioned.
In the method (A), the neutralizing agent and the degree of neutralization are as described above.
The amount of the organic solvent used is preferably 100 to 1000 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the polyester resin, from the viewpoint of increasing the dispersibility of the polyester resin and the transfer efficiency of the toner with the urea and guanidine compounds. Is 150 to 600 parts by weight, more preferably 200 to 400 parts by weight.
The amount of water used for mixing with the polyester resin is preferably 100 to 1000 parts by weight, more preferably 120 to 500 parts by weight, with respect to 100 parts by weight of the organic solvent, from the viewpoint of dispersibility of the polyester resin. More preferably, it is 130 to 300 parts by weight.
When using a surfactant, the amount used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the polyester resin from the viewpoint of dispersibility of the polyester resin. 10 parts by weight.
＜方法（Ｂ）＞
下記工程Ｂ１及びＢ２を含む、トナー用ポリエステル系樹脂の水系分散液の製造方法である。
工程Ｂ１：ポリエステル系樹脂、尿素系化合物及び／又はグアニジン系化合物、非イオン性界面活性剤、並びに中和剤、更に必要に応じて界面活性剤と混合する工程。
工程Ｂ２：前記工程Ｂ１で得られた混合液に、水を添加することにより、ポリエステル系樹脂の水系分散液を得る工程。
<Method (B)>
A method for producing an aqueous dispersion of a polyester resin for toner, comprising the following steps B1 and B2.
Step B1: A step of mixing with a polyester-based resin, a urea-based compound and / or a guanidine-based compound, a nonionic surfactant, a neutralizing agent, and, if necessary, a surfactant.
Step B2: A step of obtaining an aqueous dispersion of a polyester resin by adding water to the mixed liquid obtained in the step B1.
工程Ｂ１において、尿素系化合物及び／又はグアニジン系化合物の添加順序に限定はなく、ポリエステル系樹脂、尿素系化合物及び／又はグアニジン系化合物、非イオン性界面活性剤及び中和剤、更に必要に応じて他の界面活性剤と混合し、撹拌してもよく、ポリエステル系樹脂、非イオン性界面活性剤及び中和剤、更に必要に応じて他の界面活性剤と混合した後、尿素系化合物及び／又はグアニジン系化合物と混合し、撹拌してもよい。
より好ましくは、ポリエステル系樹脂、尿素系化合物及び／又はグアニジン系化合物、非イオン性界面活性剤を混合した後、中和剤及び更に必要に応じて、他の界面活性剤を混合する方法である。
中和剤及び中和度は、前述の通りである。工程Ｂ１の温度は、ポリエステル系樹脂を非イオン性界面活性剤と混合する観点から、３０〜２００℃が好ましく、４０〜１５０℃が更に好ましい。
尚、工程Ｂ１及びＢ２では実質的に有機溶剤を用いない。
In step B1, there is no limitation on the order of addition of the urea compound and / or guanidine compound, polyester resin, urea compound and / or guanidine compound, nonionic surfactant and neutralizing agent, and further if necessary. It may be mixed with other surfactants and stirred, and after mixing with polyester-based resin, nonionic surfactant and neutralizing agent, and further with other surfactant if necessary, urea-based compound and It may be mixed with a guanidine compound and / or stirred.
More preferably, after mixing a polyester-based resin, a urea-based compound and / or a guanidine-based compound and a nonionic surfactant, a neutralizing agent and, if necessary, another surfactant are mixed. .
The neutralizing agent and the degree of neutralization are as described above. The temperature of the step B1 is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, from the viewpoint of mixing the polyester resin with the nonionic surfactant.
In Steps B1 and B2, substantially no organic solvent is used.
ポリエステルを非イオン性界面活性剤と混合すると、非イオン性界面活性剤がポリエステルに相溶して、得られる混合物の粘度が低下し、ポリエステルの軟化点が見掛け上、低下する。方法（Ｂ）では、この現象を利用して、非イオン性界面活性剤が相溶したポリエステルの見かけ上の軟化点を水の沸点以下に下げることができ、樹脂単独では１００℃以上の融点又は軟化点を有するポリエステルでも、Ｂ２工程で、水を添加することにより、ポリエステルが水中に分散した分散液を得ることができる。
また、方法（Ｂ）は、少なくとも水及び非イオン性界面活性剤があればよいため、有機溶剤に不溶な樹脂にも適用できる他、有機溶剤の回収や作業環境維持のための設備負担が不要であり、また機械的手段を利用する場合に必要とされる特別な装置も不要であるため、経済的に樹脂粒子分散液を製造できるという利点も有する。
When the polyester is mixed with the nonionic surfactant, the nonionic surfactant is compatible with the polyester, the viscosity of the resulting mixture is lowered, and the softening point of the polyester is apparently lowered. In the method (B), using this phenomenon, the apparent softening point of the polyester compatible with the nonionic surfactant can be lowered below the boiling point of water. Even with a polyester having a softening point, a dispersion in which the polyester is dispersed in water can be obtained by adding water in step B2.
In addition, since the method (B) only needs to have at least water and a nonionic surfactant, it can be applied to a resin insoluble in an organic solvent, and there is no need for an equipment burden for recovering the organic solvent and maintaining the working environment. In addition, since a special device required when using mechanical means is unnecessary, there is an advantage that the resin particle dispersion can be produced economically.
非イオン性界面活性剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類；ポリオキシエチレンオレイルエーテル、及びポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンソルビタンモノラウレート、及びポリオキシエチレンソルビタンモノステアレート等のポリオキシエチレンソルビタンエステル類；ポリエチレングルコールモノラウレート、ポリエチレングルコールモノステアレート、及びポリエチレングルコールモノオレエート等のポリオキシエチレン脂肪酸エステル類；オキシエチレン／オキシプロピレンブロックコポリマー等が挙げられる。また、非イオン性界面活性剤にアニオン性界面活性剤やカチオン性界面活性剤を併用してもよい。 Examples of the nonionic surfactant include polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; polyoxy Polyoxyethylene sorbitan esters such as ethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate; polyoxyethylene fatty acids such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate Examples of esters include oxyethylene / oxypropylene block copolymers. In addition, an anionic surfactant or a cationic surfactant may be used in combination with the nonionic surfactant.
非イオン性界面活性剤としては、ポリエステル系樹脂との相溶性のよいものを選択することが好ましい。安定なポリエステルの分散液を得るためには、非イオン性界面活性剤のＨＬＢは１２〜１８であることが好ましく、ポリエステル系樹脂の種類によっては２種以上の異なるＨＬＢの非イオン性界面活性剤を用いることがより好ましい。たとえば、親水性が高い樹脂の場合は、ＨＬＢが１２〜１８の非イオン性界面活性剤を少なくとも１種用いればよいが、疎水性の高い樹脂の場合は、ＨＬＢの低いもの、例えば７〜１０程度のものと、ＨＬＢの高いもの、例えば１４〜２０ものを併用して、両者のＨＬＢの加重平均を１２〜１８に調整することが好ましい。この場合、主としてＨＬＢが７〜１０程度のものはポリエステル系樹脂を相溶化させることができ、ＨＬＢの高いものは水中での樹脂の分散を安定化させることができると推定される。
非イオン性界面活性剤の曇点は、常圧、水中でポリエステルを微粒化させる場合には、７０〜１０５℃が好ましく、８０〜１０５℃がより好ましい。
As the nonionic surfactant, it is preferable to select a nonionic surfactant having good compatibility with the polyester resin. In order to obtain a stable polyester dispersion, the HLB of the nonionic surfactant is preferably 12 to 18, and depending on the type of the polyester resin, two or more different HLB nonionic surfactants are used. It is more preferable to use For example, in the case of a highly hydrophilic resin, at least one nonionic surfactant having an HLB of 12 to 18 may be used. In the case of a highly hydrophobic resin, a low HLB, for example, 7 to 10 is used. It is preferable to adjust the weighted average of both HLBs to 12 to 18 by using those having the same level and those having a high HLB, for example, 14 to 20 in combination. In this case, it is presumed that those having an HLB of about 7 to 10 can compatibilize the polyester resin, and those having a high HLB can stabilize the dispersion of the resin in water.
The clouding point of the nonionic surfactant is preferably 70 to 105 ° C, more preferably 80 to 105 ° C when the polyester is atomized under normal pressure and water.
方法（Ｂ）において、尿素系化合物及びグアニジン系化合物の合計使用量及び使用モル数は、前述のとおりである。
非イオン性界面活性剤の使用量は、ポリエステル系樹脂１００重量部に対して、ポリエステル系樹脂の融点を下げる観点並びに尿素系及びグアニジン系化合物によるトナーの転写効率を高める観点からは５重量部以上が好ましく、トナーに残存する非イオン性界面活性剤を制御する観点からは８０重量部以下が好ましい。したがって、これらを両立させる観点から、非イオン性界面活性剤の使用量は、ポリエステル系樹脂１００重量部に対して、５〜８０重量部が好ましく、１０〜７０重量部がより好ましく、２０〜６０重量部が更に好ましい。尚、工程Ｂ１において、本発明を損なわない限り、水が一部含有されていてもよい。工程Ｂ１で得られた混合液は、溶液又は分散液であることが好ましい。
工程Ｂ２では、工程１で得られた混合液に水を添加することで、水系分散液を得る。
添加する水の量は、ポリエステル系樹脂１００重量部に対して、１００〜５０００重量部が好ましく、２００〜３０００重量部がより好ましく、３００〜２０００重量部が更に好ましい。
In the method (B), the total amount used and the number of moles used of the urea compound and the guanidine compound are as described above.
The amount of the nonionic surfactant used is 5 parts by weight or more with respect to 100 parts by weight of the polyester resin from the viewpoint of lowering the melting point of the polyester resin and increasing the transfer efficiency of the toner with the urea and guanidine compounds. From the viewpoint of controlling the nonionic surfactant remaining in the toner, the amount is preferably 80 parts by weight or less. Therefore, from the viewpoint of achieving both of these, the amount of the nonionic surfactant used is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, with respect to 100 parts by weight of the polyester resin. Part by weight is more preferred. In addition, in process B1, unless the present invention is impaired, a part of water may be contained. The mixed solution obtained in step B1 is preferably a solution or a dispersion.
In step B2, an aqueous dispersion is obtained by adding water to the mixed solution obtained in step 1.
The amount of water added is preferably 100 to 5000 parts by weight, more preferably 200 to 3000 parts by weight, and still more preferably 300 to 2000 parts by weight with respect to 100 parts by weight of the polyester resin.
（トナー用ポリエステル系樹脂の水系分散液）
ポリエステル系樹脂の水系分散液の固形分濃度は、適宜水を加えることにより、好ましくは３〜５０重量％、より好ましくは５〜３０重量％、更に好ましくは７〜１５重量％に調整される。
得られるポリエステル系樹脂の分散粒子の平均粒径は、トナーの転写効率を向上させる観点から、体積中位粒径で０．０５〜０．８μｍが好ましく、０．０５〜０．５μｍがより好ましく、０．０５〜０．２５μｍが更に好ましい。
ポリエステル系樹脂の分散粒子のＣＶ値（％）は、粒子の均一性によるトナーの転写効率を向上させる観点から、３０以下が好ましく、２５以下がより好ましく、生産効率の観点から５以上が好ましく、１５以上がより好ましく、これらの観点から、５〜３０が好ましく、１５〜３０がより好ましく、１５〜２５がより更に好ましい。
本発明の製造方法により得られた水系分散液中に分散するポリエステル系樹脂粒子は、体積中位粒径が小さく、かつ粒度分布の変動係数（ＣＶ値）が小さいという特徴を有する。そのため、該ポリエステル系樹脂の水系分散液を用いて得られる本発明の電子写真用トナーは、トナーの転写効率に優れる。
(Aqueous dispersion of polyester resin for toner)
The solid content concentration of the aqueous dispersion of the polyester resin is preferably adjusted to 3 to 50% by weight, more preferably 5 to 30% by weight, and even more preferably 7 to 15% by weight by appropriately adding water.
From the viewpoint of improving the transfer efficiency of the toner, the average particle size of the resulting polyester resin dispersed particles is preferably 0.05 to 0.8 μm, more preferably 0.05 to 0.5 μm in terms of volume-median particle size. 0.05 to 0.25 μm is more preferable.
The CV value (%) of the dispersed particles of the polyester resin is preferably 30 or less, more preferably 25 or less, and more preferably 5 or more from the viewpoint of production efficiency, from the viewpoint of improving toner transfer efficiency due to particle uniformity. 15 or more are more preferable, 5-30 are preferable from these viewpoints, 15-30 are more preferable, and 15-25 are still more preferable.
The polyester resin particles dispersed in the aqueous dispersion obtained by the production method of the present invention are characterized by a small volume median particle size and a small variation coefficient (CV value) of particle size distribution. Therefore, the electrophotographic toner of the present invention obtained using the aqueous dispersion of the polyester resin is excellent in toner transfer efficiency.
［電子写真用トナーの製造方法］
本発明のトナーの製造方法は、前記方法により得られるポリエステル系樹脂の水系分散液（好ましくはポリエステル系樹脂の水系分散液及び着色剤の分散液）を凝集工程に付す工程を含み、更に合一工程に付す工程を含むことが好ましい。
コアシェル粒子からなるトナーを製造する場合、下記工程１及び２を含む製造方法が好ましく、更に下記工程３を含む製造方法がより好ましい。
工程１：ポリエステル系樹脂（ａ）の水系分散液を凝集工程に付し、樹脂粒子（Ａ）の水系分散液を得る工程。
工程２：工程１で得られた樹脂粒子（Ａ）の水系分散液と、ポリエステル系樹脂（ｂ）の水系分散液とを、凝集工程に付し、樹脂粒子（Ｂ）の水系分散液を得る工程。
工程３：工程２で得られた樹脂粒子（Ｂ）を合一工程に付し、合一粒子を得る工程。
ここで、ポリエステル系樹脂（ａ）（コア形成用樹脂）及び／又はポリエステル系樹脂（ｂ）（シェル形成用樹脂）の水系分散液は、前記方法により得られるポリエステル系樹脂の水系分散液である。ポリエステル系樹脂（ｂ）は、コアシェル粒子のシェルの形状に直接起因する分散粒子であるため、得られるトナーの形状を均一化し、トナーの転写効率を高める観点から、ポリエステル系樹脂（ｂ）の水系分散液が、前記方法により得られるポリエステル系樹脂の水系分散液であることが好ましい。また、ポリエステル系樹脂（ａ）及び（ｂ）の水系分散液の両方が、前記方法により得られるポリエステル系樹脂の水系分散液が更に好ましい。
以下、工程１〜工程３について順に説明する。
[Method for producing toner for electrophotography]
The method for producing a toner of the present invention includes a step of subjecting an aqueous dispersion of a polyester resin obtained by the above method (preferably an aqueous dispersion of a polyester resin and a dispersion of a colorant) to an agglomeration step. It is preferable to include the process attached | subjected to a process.
In the case of producing toner composed of core-shell particles, a production method including the following steps 1 and 2 is preferable, and a production method further including the following step 3 is more preferable.
Step 1: A step of subjecting an aqueous dispersion of polyester resin (a) to an aggregation step to obtain an aqueous dispersion of resin particles (A).
Step 2: The aqueous dispersion of resin particles (A) obtained in Step 1 and the aqueous dispersion of polyester resin (b) are subjected to an aggregation step to obtain an aqueous dispersion of resin particles (B). Process.
Process 3: The process of attaching | subjecting the resin particle (B) obtained at the process 2 to a coalescing process, and obtaining coalesced particles.
Here, the aqueous dispersion of the polyester resin (a) (core forming resin) and / or the polyester resin (b) (shell forming resin) is an aqueous dispersion of the polyester resin obtained by the above method. . Since the polyester-based resin (b) is a dispersed particle directly resulting from the shape of the shell of the core-shell particles, the aqueous system of the polyester-based resin (b) is used from the viewpoint of uniformizing the shape of the obtained toner and increasing the toner transfer efficiency. It is preferable that the dispersion is an aqueous dispersion of a polyester resin obtained by the above method. Moreover, both the aqueous dispersions of polyester resins (a) and (b) are more preferably aqueous dispersions of polyester resins obtained by the above method.
Hereinafter, step 1 to step 3 will be described in order.
＜工程１＞
工程１は、ポリエステル系樹脂（ａ）の水系分散液及び着色剤の分散液を凝集工程に付して、樹脂粒子（Ａ）の水系分散液を得る工程である。
凝集工程では、着色剤、荷電制御剤、離型剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、及び老化防止剤等の添加剤を添加してから凝集させてもよい。該添加剤は、水系分散液としてから使用することもできる。
<Step 1>
Step 1 is a step of obtaining an aqueous dispersion of resin particles (A) by subjecting an aqueous dispersion of a polyester resin (a) and a dispersion of a colorant to an aggregation step.
In the agglomeration process, additives such as colorants, charge control agents, release agents, conductivity modifiers, extender pigments, reinforcing fillers such as fibrous substances, antioxidants, and anti-aging agents are added before agglomeration. You may let them. The additive can also be used as an aqueous dispersion.
着色剤としては、特に制限はなく公知の着色剤が挙げられ、目的に応じて適宜選択することができる。具体的には、カーボンブラック、無機系複合酸化物、クロムイエロー、ハンザイエロー、ベンジジンイエロー、スレンイエロー、キノリンイエロー、パーマネントオレンジＧＴＲ、ピラゾロンオレンジ、バルカンオレンジ、ウオッチヤングレッド、パーマネントレッド、ブリリアンカーミン３Ｂ、ブリリアンカーミン６Ｂ、デュポンオイルレッド、ピラゾロンレッド、リソールレッド、ローダミンＢレーキ、レーキレッドＣ、ベンガル、アニリンブルー、ウルトラマリンブルー、カルコオイルブルー、メチレンブルークロライド、フタロシアニンブルー、フタロシアニングリーン、及びマラカイトグリーンオクサレート等の種々の顔料；アクリジン系、キサンテン系、アゾ系、ベンゾキノン系、アジン系、アントラキノン系、インジコ系、チオインジコ系、フタロシアニン系、アニリンブラック系、ポリメチン系、トリフェニルメタン系、ジフェニルメタン系、チアジン系、及びチアゾール系等の各種染料が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて使用することができる。着色剤を添加する場合、その添加量は、ポリエステル系樹脂（ａ）１００重量部に対して、０．１〜２０重量部が好ましく、１〜１０重量部がより好ましい。 There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, Indigo dyes, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more. When adding a coloring agent, 0.1-20 weight part is preferable with respect to 100 weight part of polyester-type resin (a), and 1-10 weight part is more preferable.
荷電制御剤としては、クロム系アゾ染料、鉄系アゾ染料、アルミニウムアゾ染料、及びサリチル酸金属錯体等が挙げられる。各種荷電制御剤は１種を単独で又は２種以上を組み合わせて使用してもよい。荷電制御剤を添加する場合、その添加量は、ポリエステル系樹脂（ａ）１００重量部に対して、０．１〜８重量部が好ましく、０．３〜７重量部がより好ましい。 Examples of charge control agents include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. Various charge control agents may be used alone or in combination of two or more. When adding a charge control agent, the addition amount is preferably 0.1 to 8 parts by weight, and more preferably 0.3 to 7 parts by weight with respect to 100 parts by weight of the polyester resin (a).
離型剤としては、オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、及びステアリン酸アミド等の脂肪酸アミド類；カルナバロウワックス、ライスワックス、キャンデリラワックス、木ロウ、及びホホバ油等の植物系ワックス；ミツロウ等の動物系ワックス；モンタンワックス、オゾケライト、セレシン、マイクロクリスタリンワックス、及びフィッシャートロプシュワックス等の鉱物・石油系ワックス等のワックス；ポリオレフィンワックス、パラフィンワックス及びシリコーン類等が挙げられる。離型剤は、１種を単独で又は２種以上を組み合わせて使用してもよい。離型剤の融点は、低温定着性、耐キャリア汚染性及び帯電率の観点から、６０〜１４０℃が好ましく、６０〜１００℃がより好ましい。
離型剤を添加する場合、その添加量は、ポリエステル系樹脂（ａ）１００重量部に対して、樹脂中への分散性の観点から、０．５〜１０重量部が好ましく、１〜８重量部がより好ましく、１〜７重量部が更に好ましい。
凝集工程において、系内の固形分濃度は、均一な凝集を起こさせるために、５〜５０重量％が好ましく、５〜３０重量％がより好ましく、５〜２０重量％が更に好ましい。
Release agents include fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide; plant waxes such as carnauba wax, rice wax, candelilla wax, wood wax, and jojoba oil; Animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax; polyolefin waxes, paraffin waxes and silicones. You may use a mold release agent individually by 1 type or in combination of 2 or more types. The melting point of the release agent is preferably 60 to 140 ° C., more preferably 60 to 100 ° C., from the viewpoints of low-temperature fixability, carrier contamination resistance and charge rate.
When adding a mold release agent, the addition amount is preferably 0.5 to 10 parts by weight, and 1 to 8 parts by weight, from the viewpoint of dispersibility in the resin with respect to 100 parts by weight of the polyester resin (a). Part is more preferable, and 1 to 7 parts by weight is still more preferable.
In the aggregation process, the solid content concentration in the system is preferably 5 to 50% by weight, more preferably 5 to 30% by weight, and still more preferably 5 to 20% by weight in order to cause uniform aggregation.
凝集工程における系内のｐＨは、混合液の分散安定性と、樹脂粒子の凝集性とを両立させる観点から、２〜１０が好ましく、２〜９がより好ましく、３〜８が更に好ましい。
同様の観点から、凝集工程における系内の温度は、「ポリエステル系樹脂（ａ）の軟化点−６０℃」（ポリエステル系樹脂（ａ）の軟化点より６０℃低い温度を意味する、以下同様）以上、且つポリエステル系樹脂（ａ）の軟化点以下であることが好ましい。マスターバッチを使用する場合は、それに用いた樹脂をも含めて加重平均した温度を、混合樹脂の軟化点とする。
The pH in the system in the aggregation step is preferably 2 to 10, more preferably 2 to 9, and still more preferably 3 to 8, from the viewpoint of achieving both the dispersion stability of the mixed solution and the aggregation property of the resin particles.
From the same viewpoint, the temperature in the system in the aggregation process is “the softening point of the polyester resin (a) −60 ° C.” (meaning a temperature lower by 60 ° C. than the softening point of the polyester resin (a), the same applies hereinafter). Above and below the softening point of the polyester resin (a) is preferred. When using a master batch, the weighted average temperature including the resin used in the master batch is taken as the softening point of the mixed resin.
また、着色剤、荷電制御剤等の添加剤は、樹脂粒子を調製する際にポリエステル系樹脂（ａ）に予め混合してもよく、別途各添加剤を水等の分散媒中に分散させた分散液を調製して、ポリエステル系樹脂（ａ）の水系分散液と混合し、凝集工程に供してもよい。
樹脂粒子を調製する際にポリエステル系樹脂（ａ）に添加剤を予め混合する場合には、予めポリエステル系樹脂（ａ）と添加剤とを溶融混練することが好ましい。
溶融混練には、オープンロール型二軸混練機を使用することが好ましい。オープンロール型二軸混練機は、２本のロールが平行に近接して配設された混練機であり、各ロールに熱媒体を通すことにより、加熱機能又は冷却機能を付与することができる。したがって、オープンロール型二軸混練機は、溶融混練する部分がオープン型であり、また加熱ロールと冷却ロールを備えていることから、通常の二軸押出機と異なり、溶融混練の際に発生する混練熱を容易に放熱することができる。
別途各添加剤を水等の分散媒中に分散させた分散液を調製する場合は、工程１は、ポリエステル系樹脂（ａ）の水系分散液及び着色剤の分散液を凝集工程に付し、樹脂粒子（Ａ）の水系分散液を得る工程であることが好ましい。
In addition, additives such as a colorant and a charge control agent may be mixed in advance with the polyester resin (a) when preparing the resin particles, and each additive is separately dispersed in a dispersion medium such as water. A dispersion may be prepared, mixed with an aqueous dispersion of the polyester resin (a), and subjected to an aggregation step.
When the additive is previously mixed with the polyester resin (a) when preparing the resin particles, it is preferable to melt and knead the polyester resin (a) and the additive in advance.
For melt kneading, it is preferable to use an open roll type biaxial kneader. An open roll type biaxial kneader is a kneader in which two rolls are arranged close to each other in parallel, and a heating function or a cooling function can be imparted by passing a heat medium through each roll. Therefore, the open-roll type twin-screw kneader is an open-type part to be melt-kneaded, and is provided with a heating roll and a cooling roll, so that it occurs during melt-kneading unlike a normal twin-screw extruder. The kneading heat can be easily dissipated.
In the case of preparing a dispersion in which each additive is separately dispersed in a dispersion medium such as water, Step 1 includes subjecting the aqueous dispersion of the polyester resin (a) and the dispersion of the colorant to an aggregation step, A step of obtaining an aqueous dispersion of the resin particles (A) is preferred.
凝集工程においては、凝集を効果的に行うために凝集剤を添加することができる。凝集剤としては、有機系では、４級塩のカチオン性界面活性剤、及びポリエチレンイミン等が用いられ、無機系では、無機金属塩、無機アンモニウム塩及び２価以上の金属錯体等が用いられる。
無機金属塩としては、例えば、硫酸ナトリウム、塩化ナトリウム、塩化カルシウム、硝酸カルシウム、塩化バリウム、塩化マグネシウム、塩化亜鉛、塩化アルミニウム、及び硫酸アルミニウム等の金属塩；ポリ塩化アルミニウム、ポリ水酸化アルミニウム、及び多硫化カルシウム等の無機金属塩重合体が挙げられる。無機アンモニウム塩としては、例えば硫酸アンモニウム、塩化アンモニウム、硝酸アンモニウム等が挙げられる。
凝集剤を添加する場合、その添加量は、トナーの耐環境特性の観点から、ポリエステル系樹脂（ａ）１００重量部に対して、６０重量部以下が好ましく、５５重量部以下がより好ましく、５０重量部以下が更に好ましい。
凝集剤は、水系媒体に溶解させて添加することが好ましく、凝集剤の添加時及び添加終了後は十分撹拌することが好ましい。
In the aggregation process, an aggregating agent can be added in order to effectively perform aggregation. As the flocculant, a quaternary salt cationic surfactant, polyethyleneimine, and the like are used in the organic system, and an inorganic metal salt, an inorganic ammonium salt, a divalent or higher metal complex, and the like are used in the inorganic system.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; polyaluminum chloride, polyaluminum hydroxide, and Examples thereof include inorganic metal salt polymers such as calcium polysulfide. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, and ammonium nitrate.
When the flocculant is added, the addition amount is preferably 60 parts by weight or less, more preferably 55 parts by weight or less, with respect to 100 parts by weight of the polyester-based resin (a), from the viewpoint of environmental resistance characteristics of the toner. More preferred are parts by weight or less.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.
ポリエステル系樹脂（ａ）を含む水系分散液と、必要に応じて用いられる各種添加剤との混合物を、均一に分散させる観点から、好ましくはポリエステル系樹脂（ａ）の軟化点未満の温度、より好ましくは「該軟化点−３０℃」以下の温度で分散処理を行う。具体的には、好ましくは６５℃以下、より好ましくは５５℃以下であり、また、媒体の流動性及び樹脂の水系分散液の製造エネルギーの観点から、分散処理は０℃より高い温度で行なうことが好ましく、１０℃以上で行うことがより好ましい。
これらの観点から、好ましくは０〜６５℃、より好ましくは１０〜５５℃程度の温度で撹拌して分散処理する等の通常の方法により、均一な樹脂分散液を調製することができる。
From the viewpoint of uniformly dispersing the mixture of the aqueous dispersion containing the polyester resin (a) and various additives used as necessary, the temperature is preferably less than the softening point of the polyester resin (a). Preferably, the dispersion treatment is performed at a temperature of “the softening point −30 ° C.” or lower. Specifically, the temperature is preferably 65 ° C. or less, more preferably 55 ° C. or less, and the dispersion treatment should be performed at a temperature higher than 0 ° C. from the viewpoint of fluidity of the medium and production energy of the aqueous dispersion of the resin. It is more preferable to carry out at 10 ° C. or higher.
From these viewpoints, a uniform resin dispersion can be prepared by a usual method such as stirring at a temperature of preferably about 0 to 65 ° C., more preferably about 10 to 55 ° C. for dispersion treatment.
分散処理の方法としては、ウルトラディスパー（商品名、浅田鉄工株式会社製）、エバラマイルダー（商品名、株式会社荏原製作所製）、及びＴＫホモミクサー（商品名、プライミクス株式会社製）等の高速撹拌混合装置；高圧ホモゲナイザー（商品名、株式会社イズミフードマシナリ製）、ミニラボ８．３Ｈ型（商品名、Rannie社製）に代表されるホモバルブ式の高圧ホモジナイザー；マイクロフルイダイザー（商品名、Microfluidics社製）、及びナノマイザー（商品名、ナノマイザー株式会社製）等のチャンバー式の高圧ホモジナイザー等が挙げられる。 As a method of dispersion treatment, high-speed stirring such as Ultra Disper (trade name, manufactured by Asada Tekko Co., Ltd.), Ebara Milder (trade name, manufactured by Ebara Manufacturing Co., Ltd.), and TK Homomixer (trade name, manufactured by Primix Co., Ltd.) High pressure homogenizer (trade name, manufactured by Izumi Food Machinery Co., Ltd.), homovalve type high pressure homogenizer represented by Minilab 8.3H type (trade name, manufactured by Rannie); Microfluidizer (trade name, manufactured by Microfluidics) ) And Nanomizer (trade name, manufactured by Nanomizer Co., Ltd.).
工程１で得られる樹脂粒子（Ａ）の体積中位粒径は、続く工程３で均一に合一させ、コアシェル構造のトナー粒子を製造する観点から、１〜１０μｍが好ましく、２〜８μｍがより好ましく、３〜７μｍが更に好ましい。 The volume median particle size of the resin particles (A) obtained in step 1 is preferably 1 to 10 μm, more preferably 2 to 8 μm from the viewpoint of uniformly coalescing in the subsequent step 3 to produce core-shell toner particles. Preferably, 3-7 micrometers is still more preferable.
＜工程２＞
工程２は、工程１で得られた樹脂粒子（Ａ）の水系分散液とポリエステル系樹脂（ｂ）の水系分散液とを混合し、凝集させて樹脂粒子（Ｂ）の水系分散液を得る工程である。ポリエステル系樹脂（ｂ）は、コアシェル構造におけるシェル部を形成する観点から非晶質ポリエステルであることが好ましい。
工程２においては、混合するポリエステル系樹脂（ｂ）の体積中位粒径は、均一なコアシェル粒子を製造する観点から、０．０５〜０．８μｍが好ましく、０．０５〜０．５μｍがより好ましく、０．０５〜０．２５μｍが更に好ましい。
工程１で得られた樹脂粒子（Ａ）１００重量部に対して、混合するポリエステル系樹脂（ｂ）は、好ましくは５〜２００重量部が好ましく、より好ましくは１０〜１００重量部、更に好ましくは１０〜５０重量部である。
工程２で得られる樹脂粒子（Ｂ）の平均粒径は、続く工程３で均一に合一させ、トナー粒子を製造する観点から、体積中位粒径で１〜１０μｍが好ましく、２〜８μｍがより好ましく、３〜７μｍが更に好ましい。凝集条件は、前述の工程１と同じである。
<Process 2>
Step 2 is a step of mixing the aqueous dispersion of the resin particles (A) obtained in Step 1 and the aqueous dispersion of the polyester resin (b) and aggregating them to obtain an aqueous dispersion of the resin particles (B). It is. The polyester resin (b) is preferably an amorphous polyester from the viewpoint of forming a shell portion in the core-shell structure.
In step 2, the volume median particle size of the polyester resin (b) to be mixed is preferably 0.05 to 0.8 μm, more preferably 0.05 to 0.5 μm, from the viewpoint of producing uniform core-shell particles. 0.05 to 0.25 μm is more preferable.
The polyester resin (b) to be mixed is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, still more preferably 100 parts by weight of the resin particles (A) obtained in the step 1. 10 to 50 parts by weight.
The average particle size of the resin particles (B) obtained in step 2 is preferably 1 to 10 μm in terms of volume-median particle size, preferably 2 to 8 μm, from the viewpoint of uniformly uniting in the subsequent step 3 to produce toner particles. More preferably, 3-7 micrometers is still more preferable. Aggregation conditions are the same as in Step 1 described above.
＜工程３＞
工程３は、工程２で得られた樹脂粒子（Ｂ）を合一工程に付し、合一粒子を得る工程である。
工程３では、工程２で得られた樹脂粒子（Ｂ）の水系分散液に必要に応じて凝集停止剤を加えた後、合一工程に付すことができ、また、工程２で得られた凝集粒子を、加熱することにより合一させることができる。
工程３における系内の温度は、目的とするトナーの粒径、粒度分布、形状制御及び粒子の融着性の観点から、「結着樹脂の軟化点−３０℃」以上、「該軟化点＋１０℃」以下が好ましく、「該軟化点−２５℃」以上、「該軟化点＋１０℃」以下がより好ましく、「該軟化点−２０℃」以上、「該軟化点＋１０℃」以下が更に好ましい。具体的には、好ましくは４０〜９０℃、より好ましくは５０〜８０℃に維持することが好ましい。また、撹拌速度は、凝集粒子が沈降しない速度が好ましい。本明細書において「結着樹脂の軟化点」とは、ポリエステル系樹脂（ａ）の軟化点及びポリエステル系樹脂（ｂ）の軟化点を加重平均した温度をいう。
なお、凝集停止剤を用いる場合、凝集停止剤として界面活性剤を用いることが好ましく、アニオン性界面活性剤を用いることがより好ましい。アニオン性界面活性剤のうち、アルキルエーテル硫酸塩、アルキル硫酸塩、及び直鎖アルキルベンゼンスルホン酸塩からなる群から選ばれる少なくとも１種を用いることが更に好ましい。
<Step 3>
Step 3 is a step in which the resin particles (B) obtained in Step 2 are subjected to a coalescence step to obtain coalesced particles.
In step 3, after adding an aggregation terminator to the aqueous dispersion of the resin particles (B) obtained in step 2 as necessary, it can be subjected to a coalescence step, and the agglomeration obtained in step 2 The particles can be coalesced by heating.
The temperature in the system in step 3 is not less than “softening point of binder resin—30 ° C.” or more and “the softening point + 10” from the viewpoints of the target toner particle size, particle size distribution, shape control and particle fusing property. "Softening point-25 ° C" or higher, "softening point + 10 ° C" or lower, more preferably "softening point-20 ° C" or higher, and "softening point + 10 ° C" or lower. Specifically, it is preferably maintained at 40 to 90 ° C, more preferably 50 to 80 ° C. The stirring speed is preferably a speed at which the aggregated particles do not settle. In this specification, the “softening point of the binder resin” refers to a temperature obtained by weighted averaging of the softening point of the polyester resin (a) and the softening point of the polyester resin (b).
In addition, when using an aggregation terminator, it is preferable to use a surfactant as the aggregation terminator, and it is more preferable to use an anionic surfactant. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates.
［電子写真用トナー］
凝集工程及び／又は合一工程で得られた樹脂粒子を、適宜、ろ過等の固液分離工程、洗浄工程、乾燥工程に供することにより、本発明の電子写真用トナー（単にトナーと称することがある）を得ることができる。
洗浄工程では、トナーとして十分な帯電特性及び信頼性を確保する目的から、トナー表面の金属イオンを除去するため、酸を用いることが好ましい。また、添加した非イオン性界面活性剤も洗浄により完全に除去することが好ましく、非イオン性界面活性剤の曇点以下での水系溶液での洗浄が好ましい。洗浄は複数回行うことが好ましい。
また、乾燥工程では、振動型流動乾燥法、スプレードライ法、冷凍乾燥法、フラッシュジェット法等、任意の方法を採用することができる。トナーの乾燥後の水分含量は、帯電性の観点から、好ましくは１．５重量％以下、更には１．０重量％以下に調整することが好ましい。
[Electrophotographic toner]
The resin particles obtained in the aggregation step and / or the coalescence step are appropriately subjected to a solid-liquid separation step such as filtration, a washing step, and a drying step, whereby the toner for electrophotography of the present invention (simply referred to as toner). There is).
In the washing step, it is preferable to use an acid in order to remove metal ions on the surface of the toner in order to ensure sufficient charging characteristics and reliability as the toner. Further, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably adjusted to 1.5% by weight or less, more preferably 1.0% by weight or less, from the viewpoint of chargeability.
本発明の電子写真用トナーは、ポリエステル系樹脂と、前記尿素系化合物及び／又は前記グアニジン系化合物とを含有する。
トナー中、尿素系化合物及びグアニジン系化合物の合計の含有量は、分散粒子径を均一化及び小粒径化させ、トナーの転写効率を高める観点から、好ましくは１〜１０００ｐｐｍ、より好ましくは１０〜５００ｐｐｍ、更により好ましくは２０〜１００ｐｐｍである。
The electrophotographic toner of the present invention contains a polyester resin and the urea compound and / or the guanidine compound.
The total content of the urea compound and the guanidine compound in the toner is preferably from 1 to 1000 ppm, more preferably from 10 to 1000 ppm, from the viewpoint of uniformizing the dispersed particle size and reducing the particle size and increasing the transfer efficiency of the toner. 500 ppm, still more preferably 20-100 ppm.
（外添剤）
以上のようにして得られたトナーは、外添処理時の融着性が低いため、流動化剤等の助剤を外添剤としてトナー粒子表面に容易に添加することができる。外添剤としては、表面を疎水化処理したシリカ微粒子、酸化チタン微粒子、アルミナ微粒子、酸化セリウム微粒子、及びカーボンブラック等の無機微粒子；ポリカーボネート、ポリメチルメタクリレート、及びシリコーン樹脂等のポリマー微粒子等、任意の微粒子が使用できる。
外添剤の個数平均粒子径は、好ましくは４〜２００ｎｍ、より好ましくは８〜３０ｎｍである。外添剤の個数平均粒子径は、走査型電子顕微鏡又は透過型電子顕微鏡を用いて求められる。
(External additive)
Since the toner obtained as described above has low fusing property at the time of external addition treatment, an auxiliary agent such as a fluidizing agent can be easily added to the toner particle surface as an external additive. Examples of external additives include silica fine particles whose surfaces are hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and inorganic fine particles such as carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Fine particles can be used.
The number average particle diameter of the external additive is preferably 4 to 200 nm, more preferably 8 to 30 nm. The number average particle diameter of the external additive is determined using a scanning electron microscope or a transmission electron microscope.
外添剤を添加する場合、その添加量は、帯電度の環境安定性及び加重保存安定性の観点から、外添剤による処理前のトナー１００重量部に対して、０．８〜５重量部が好ましく、１〜５重量部がより好ましく、１．５〜３．５重量部が更に好ましい。ただし、外添剤として疎水性シリカを用いる場合は、外添剤による処理前のトナー１００重量部に対して、疎水性シリカを０．８〜３．５重量部、好ましくは１〜３重量部用いることで、前記所望の効果が得られる。 When the external additive is added, the addition amount is 0.8 to 5 parts by weight with respect to 100 parts by weight of the toner before the processing with the external additive, from the viewpoint of environmental stability of charge degree and weighted storage stability. 1 to 5 parts by weight is more preferable, and 1.5 to 3.5 parts by weight is still more preferable. However, when hydrophobic silica is used as the external additive, 0.8 to 3.5 parts by weight, preferably 1 to 3 parts by weight of hydrophobic silica is used with respect to 100 parts by weight of the toner before processing with the external additive. By using this, the desired effect can be obtained.
（電子写真用トナーの物性）
本発明の電子写真用トナーの体積中位粒径は、トナーの高画質化及び生産性の観点から、１〜１０μｍが好ましく、２〜８μｍがより好ましく、３〜７μｍが更に好ましい。
本発明のトナーがコアシェル粒子からなる場合、コア部のポリエステル系樹脂（ａ）及びシェル部のポリエステル系樹脂（ｂ）の重量比［ポリエステル系樹脂（ｂ）／ポリエステル系樹脂（ａ）］は、トナーの転写効率の観点から、５／９５〜４０／６０が好ましく、６／９４〜３０／７０がより好ましく、７／９３〜２５／７５が更に好ましい。
トナーに用いられる結着樹脂の酸価は、トナーの帯電性及び転写効率の観点より、１〜４０ｍｇＫＯＨ／ｇが好ましく、２〜３５ｍｇＫＯＨ／ｇがより好ましく、３〜３０ｍｇＫＯＨ／ｇが更に好ましい。
トナーに用いられる結着樹脂の軟化点は、トナーの低温定着性及び転写効率の観点から、８０〜１６０℃が好ましく、８０〜１５０℃がより好ましく、９０〜１４０℃が更に好ましい。また、結着樹脂のガラス転移温度は、上記同様の観点から、４５〜８０℃が好ましく、５０〜７０℃がより好ましい。
(Physical properties of electrophotographic toner)
The volume median particle size of the electrophotographic toner of the present invention is preferably from 1 to 10 μm, more preferably from 2 to 8 μm, and even more preferably from 3 to 7 μm, from the viewpoints of high image quality and productivity of the toner.
When the toner of the present invention comprises core-shell particles, the weight ratio [polyester resin (b) / polyester resin (a)] of the polyester resin (a) in the core and the polyester resin (b) in the shell is: From the viewpoint of toner transfer efficiency, 5/95 to 40/60 is preferable, 6/94 to 30/70 is more preferable, and 7/93 to 25/75 is still more preferable.
The acid value of the binder resin used for the toner is preferably from 1 to 40 mgKOH / g, more preferably from 2 to 35 mgKOH / g, and even more preferably from 3 to 30 mgKOH / g, from the viewpoints of chargeability and transfer efficiency of the toner.
The softening point of the binder resin used for the toner is preferably from 80 to 160 ° C, more preferably from 80 to 150 ° C, and even more preferably from 90 to 140 ° C, from the viewpoint of low-temperature fixability and transfer efficiency of the toner. Moreover, 45-80 degreeC is preferable and 50-70 degreeC is more preferable from the same viewpoint as the glass transition temperature of the binder resin.
本発明の電子写真用トナーは、本発明の効果を損なわない範囲で、前記結着樹脂とは異なる公知のトナー用結着樹脂、例えば、ポリエステル、スチレン−アクリル樹脂等のスチレン系樹脂、エポキシ樹脂、ポリカーボネート、ポリウレタン等の樹脂を含有していてもよい。
本発明の電子写真用トナーにおいて、本発明のトナー用結着樹脂の含有量は、全結着樹脂中、５０重量％以上が好ましく、７０重量％以上がより好ましく、８０重量％以上がより好ましく、９０重量％以上が更に好ましく、実質的に１００重量％であることがより更に好ましい。
本発明の電子写真用トナーは、一成分系現像剤として、又はキャリアと混合して二成分系現像剤として使用することができる。
The electrophotographic toner of the present invention is a known toner binder resin different from the binder resin, for example, a styrene resin such as polyester or styrene-acrylic resin, or an epoxy resin, as long as the effects of the present invention are not impaired. Further, it may contain a resin such as polycarbonate or polyurethane.
In the electrophotographic toner of the present invention, the content of the binder resin for toner of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more, and more preferably 80% by weight or more in the total binder resin. 90% by weight or more is still more preferable, and it is still more preferable that it is substantially 100% by weight.
The electrophotographic toner of the present invention can be used as a one-component developer or a two-component developer mixed with a carrier.
［樹脂物性の測定］
実施例及び比較例で得られた樹脂の物性、並びに各粒子の体積中位粒径（Ｄ50）の測定及びＣＶ値の算出は次の通りに行った。
[Measurement of resin properties]
The physical properties of the resins obtained in Examples and Comparative Examples, the volume median particle size (D 50 ) of each particle, and the calculation of the CV value were performed as follows.
＜樹脂の軟化点＞
フローテスター（（株）島津製作所製、商品名：「ＣＦＴ−５００Ｄ」）を用い、１ｇの試料を昇温速度６℃／ｍｉｎで加熱しながら、プランジャーにより１．９６ＭＰａの荷重を与え、直径１ｍｍ、長さ１ｍｍのノズルから押し出した。温度に対し、フローテスターのプランジャー降下量をプロットし、試料の半量が流出した温度を軟化点とした。
<Softening point of resin>
Using a flow tester (manufactured by Shimadzu Corporation, trade name: “CFT-500D”), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
＜樹脂の吸熱の最大ピーク温度＞
示差走査熱量計（ＤＳＣ；ティー・エイ・インスツルメント・ジャパン社製、商品名：「Ｑ−１００」）を用いて、室温（２０℃）から降温速度１０℃／分で０℃まで冷却した試料をそのまま１分間静止させ、その後、昇温速度１０℃／分で１８０℃まで昇温しながら測定した。観測される吸熱ピークのうち、最も高温側にあるピークの温度を吸熱の最大ピーク温度（１ｓｔ ＲＵＮの吸熱の最大ピーク温度）とした。
<Maximum peak temperature of resin endotherm>
Using a differential scanning calorimeter (DSC; manufactured by TA Instruments Japan Co., Ltd., trade name: “Q-100”), it was cooled from room temperature (20 ° C.) to 0 ° C. at a cooling rate of 10 ° C./min. The sample was allowed to stand for 1 minute, and then measured while the temperature was raised to 180 ° C. at a temperature raising rate of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side was defined as the maximum endothermic peak temperature (the maximum peak temperature of the 1st RUN endotherm).
＜ガラス転移温度＞
示差走査熱量計（ＤＳＣ；ティー・エイ・インスツルメント・ジャパン社製、商品名：「Ｑ−１００」）を用いて、試料を０．０１〜０．０２ｇをアルミパンに計量し、２００℃まで昇温し、その温度から降温速度１０℃／ｍｉｎで０℃まで冷却したサンプルを昇温速度１０℃／ｍｉｎで昇温し、吸熱の最大ピーク温度以下のベースラインの延長線とピークの立ち上がり部分からピークの頂点までの最大傾斜を示す接線との交点の温度をガラス転移温度とした。
<Glass transition temperature>
Using a differential scanning calorimeter (DSC; manufactured by TA Instruments Japan, trade name: “Q-100”), 0.01 to 0.02 g of a sample was weighed into an aluminum pan, and 200 ° C. The sample was cooled to 0 ° C at a rate of temperature decrease of 10 ° C / min from that temperature, and the sample was heated at a rate of temperature increase of 10 ° C / min. The temperature at the intersection with the tangent indicating the maximum slope from the portion to the peak apex was defined as the glass transition temperature.
＜樹脂の酸価、水酸基価＞
ＪＩＳ Ｋ ００７０の方法に基づき測定した。ただし、測定溶媒のみＪＩＳ Ｋ ００７０の規定のエタノールとエーテルの混合溶媒から、アセトンとトルエンの混合溶媒（アセトン：トルエン＝１：１（容量比））に変更した。
また、樹脂の水酸基価は、ＪＩＳ Ｋ １５５７に基づき下記条件で測定した。
試料量：２ｇ
アセチル化試薬：無水酢酸６５ｍＬとピリジン９３５ｍＬとを混合した溶液１０ｍＬ
触媒：なし
反応温度：９９℃
反応時間：２時間
溶媒：アセトンとトルエンの混合溶媒（アセトン：トルエン＝１：１（容量比））
滴定液：０．５ｍｏｌ／Ｌ ＫＯＨエタノール溶液
<Resin acid value, hydroxyl value>
It measured based on the method of JISK0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
Moreover, the hydroxyl value of resin was measured on condition of the following based on JISK1557.
Sample amount: 2g
Acetylating reagent: 10 mL of a mixed solution of 65 mL of acetic anhydride and 935 mL of pyridine
Catalyst: None Reaction temperature: 99 ° C
Reaction time: 2 hours Solvent: Mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio))
Titration solution: 0.5 mol / L KOH ethanol solution
＜数平均分子量＞
以下の方法により、ゲル浸透クロマトグラフィー（ＧＰＣ）法により分子量分布を測定し、樹脂の数平均分子量を求めた。
（１）試料溶液の調製
濃度が０．０４ｇ／１０ｍｌになるように、ポリエステルをテトラヒドロフランに溶解させた。ついで、この溶液をメッシュ０．４５μｍのフッ素樹脂フィルター（アドバンテック（株）製、商品名：「ＤＩＳＭＩＣ−２５ＪＰ」）を用いて濾過して不溶成分を除き、試料溶液とした。
（２）分子量測定
下記装置を用いて、溶離液としてテトラヒドロフランを毎分１ｍｌの流速で流し、４０℃の恒温槽中でカラムを安定させた。そこに試料溶液１００μｌを注入して測定を行った。試料の分子量は、あらかじめ作製した検量線に基づき算出した。このときの検量線には、数種類の単分散ポリスチレン（東ソー（株）製の単分散ポリスチレン；２．６３×１０3、２．０６×１０4、１．０２×１０5、ジーエルサイエンス（株）製の単分散ポリスチレン；２．１０×１０3、７．００×１０3、５．０４×１０4（数平均分子量））を標準試料として作成したものを用いた。
測定装置：ＨＬＣ−８２２０ ＧＰＣ（商品名、東ソー（株）製）
分析カラム：ＧＭＨXL＋Ｇ３０００ＨXL（いずれも商品名、東ソー（株）製）
<Number average molecular weight>
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method according to the following method to determine the number average molecular weight of the resin.
(1) Preparation of sample solution Polyester was dissolved in tetrahydrofuran so that the concentration was 0.04 g / 10 ml. Subsequently, this solution was filtered using a fluororesin filter (manufactured by Advantech Co., Ltd., trade name: “DISMIC-25JP”) having a mesh of 0.45 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following apparatus, tetrahydrofuran was flowed as an eluent at a flow rate of 1 ml per minute, and the column was stabilized in a constant temperature bath at 40 ° C. Measurement was performed by injecting 100 μl of the sample solution. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodisperse polystyrene (monodisperse polystyrene manufactured by Tosoh Corporation; 2.63 × 10 3 , 2.06 × 10 4 , 1.02 × 10 5 , GL Sciences Inc.) Monodispersed polystyrenes made from 2.10 × 10 3 , 7.00 × 10 3 , 5.04 × 10 4 (number average molecular weight)) were used as standard samples.
Measuring device: HLC-8220 GPC (trade name, manufactured by Tosoh Corporation)
Analytical column: GMH XL + G3000H XL (both trade names, manufactured by Tosoh Corporation)
＜樹脂の中和度＞
樹脂の中和度（％）は、下記式によって求めた。
中和度＝｛［中和剤の重量（ｇ）／中和剤の当量］／〔［樹脂の酸価（ＫＯＨｍｇ／ｇ）×樹脂の重量（ｇ）］／（５６×１０００）〕｝×１００
<Degree of neutralization of resin>
The degree of neutralization (%) of the resin was determined by the following formula.
Degree of neutralization = {[weight of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (KOH mg / g) × resin weight (g)] / (56 × 1000)]} × 100
＜樹脂粒子、着色剤微粒子、離型剤微粒子及び荷電制御剤微粒子の体積中位粒径（Ｄ50）及びＣＶ値＞
レーザー回折型粒径測定機（（株）堀場製作所製、商品名：「ＬＡ−９２０」）を用いて、測定用セルに蒸留水を加え、吸光度が適正範囲になる濃度で体積中位粒径（Ｄ50）を測定した。
また、ＣＶ値は下記の式に従って算出した。水系分散液中の樹脂粒子のＣＶ値が低い方が、粒径が揃っていることを示す。
ＣＶ値（％）＝（粒径分布の標準偏差／体積中位粒径（Ｄ50））×１００
<Volume Median Particle Size (D 50 ) and CV Value of Resin Particles, Colorant Fine Particles, Release Agent Fine Particles, and Charge Control Agent Fine Particles>
Using a laser diffraction particle size analyzer (Horiba, Ltd., trade name: “LA-920”), distilled water is added to the measurement cell, and the volume-median particle size is adjusted so that the absorbance is in the proper range. (D 50 ) was measured.
The CV value was calculated according to the following formula. A lower CV value of the resin particles in the aqueous dispersion indicates that the particle diameters are uniform.
CV value (%) = (standard deviation of particle size distribution / volume median particle size (D 50 )) × 100
製造例１〜３
（非晶質ポリエステルＡ〜Ｃの製造）
表１に示す無水トリメリット酸以外の原料、並びにチタンジイソプロピレートビストリエタノールアミネート４０ｇ及び没食子酸２ｇを、窒素導入管、９８℃の熱水を通した分留管を装備した脱水管、撹拌器及び熱電対を装備した１０リットル容の四つ口フラスコに入れ、窒素雰囲気下、１８０℃から２３０℃まで１０℃／ｈｒで昇温し、その後２３０℃で反応率が９０％に到達するまで縮重合反応させた。その後、無水トリメリット酸を添加して、２１０℃で１時間常圧にて反応させた後、２０ｋＰａにて所望の軟化点に達するまで反応を行って、非晶質ポリエステルＡ〜Ｃを得た。ここで反応率とは、アルコール成分及びカルボン酸成分のカルボキシ基と水酸基とから計算される理論反応水の排出完了時を１００％として換算された値である。
Production Examples 1-3
(Production of amorphous polyesters A to C)
Raw materials other than trimellitic anhydride shown in Table 1, and 40 g of titanium diisopropylate bistriethanolamate and 2 g of gallic acid, a dehydrating tube equipped with a nitrogen introducing tube, a fractionating tube through which hot water of 98 ° C. was passed, stirring In a 10-liter four-necked flask equipped with a vessel and thermocouple, heated from 180 ° C. to 230 ° C. at 10 ° C./hr under a nitrogen atmosphere, and then at 230 ° C. until the reaction rate reaches 90% A condensation polymerization reaction was performed. Thereafter, trimellitic anhydride was added and reacted at 210 ° C. for 1 hour at normal pressure, and then reacted at 20 kPa until the desired softening point was reached, whereby amorphous polyesters A to C were obtained. . Here, the reaction rate is a value converted with 100% as the completion of the theoretical reaction water discharge calculated from the carboxy group and hydroxyl group of the alcohol component and carboxylic acid component.
製造例４
（非晶質ポリエステルＤの製造）
表１に示す無水トリメリット酸以外の原料、並びにチタンジイソプロピレートビストリエタノールアミネート４０ｇ及び没食子酸２ｇを、脱水管、撹拌器及び熱電対を装備した１０リットル容の四つ口フラスコに入れ、窒素雰囲気下、２３０℃で反応率が９０％に到達するまで縮重合反応させた。その後、無水トリメリット酸を添加して、２１０℃で１時間常圧にて反応させた後、２０ｋＰａにて所望の軟化点に達するまで反応を行って、非晶質ポリエステルＤを得た。
Production Example 4
(Production of amorphous polyester D)
Raw materials other than trimellitic anhydride shown in Table 1, and 40 g of titanium diisopropylate bistriethanolamate and 2 g of gallic acid were placed in a 10-liter four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, Under a nitrogen atmosphere, the condensation polymerization reaction was performed at 230 ° C. until the reaction rate reached 90%. Thereafter, trimellitic anhydride was added and reacted at 210 ° C. for 1 hour at normal pressure, and then reacted at 20 kPa until the desired softening point was reached, whereby amorphous polyester D was obtained.
製造例５
（着色剤分散液の調製）
銅フタロシアニン（大日精化工業（株）製、型番：「ＥＣＢ−３０１」）５０ｇノニオン性界面活性剤（花王（株）製、商品名：「エマルゲン１５０」）５ｇ及びイオン交換水２００ｇを混合し、銅フタロシアニンを分散させ、ホモジナイザーを用いて１０分間分散させて、分散した着色剤分散液を得た。体積中位粒径（Ｄ50）は１２０ｎｍであった。
Production Example 5
(Preparation of colorant dispersion)
Copper phthalocyanine (manufactured by Dainichi Seika Kogyo Co., Ltd., model number: “ECB-301”) 50 g Nonionic surfactant (Kao Co., Ltd., trade name: “Emulgen 150”) 5 g and ion-exchanged water 200 g are mixed. Copper phthalocyanine was dispersed and dispersed for 10 minutes using a homogenizer to obtain a dispersed colorant dispersion. The volume median particle size (D 50 ) was 120 nm.
製造例６
（ワックス分散液の調製）
パラフィンワックス（日本精蝋（株）製、商品名：「ＨＮＰ０１９０」、融点：８５℃）５０ｇ、カチオン性界面活性剤（花王（株）製、商品名：「サニゾールＢ５０」）５ｇ及びイオン交換水２００ｇを９５℃に加熱して、ホモジナイザーを用いて、パラフィンワックスを分散させた後、圧力吐出型ホモジナイザーで分散処理し、ワックス分散液を得た。パラフィンワックスの体積中位粒径（Ｄ50）は５５０ｎｍであった。
Production Example 6
(Preparation of wax dispersion)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name: “HNP0190”, melting point: 85 ° C.) 50 g, cationic surfactant (trade name: “Sanisol B50” manufactured by Kao Corporation) and ion-exchanged water 200 g was heated to 95 ° C., and the paraffin wax was dispersed using a homogenizer, followed by dispersion treatment using a pressure discharge homogenizer to obtain a wax dispersion. The volume median particle size (D 50 ) of the paraffin wax was 550 nm.
製造例７
（荷電制御剤分散液の調製）
荷電制御剤（オリエント化学工業（株）製、商品名：「ボントロンＥ−８４」）５０ｇ、ノニオン性界面活性剤（花王（株）製、商品名：「エマルゲン１５０」）５ｇ及びイオン交換水２００ｇを混合し、ガラスビーズを使用し、サンドグラインダーを用いて１０分間分散させて、荷電制御剤分散液を得た。荷電制御剤の体積中位粒径（Ｄ50）は５００ｎｍであった。
Production Example 7
(Preparation of charge control agent dispersion)
50 g of charge control agent (Orient Chemical Industries, trade name: “Bontron E-84”), 5 g of nonionic surfactant (trade name: “Emulgen 150”, manufactured by Kao Corporation) and 200 g of ion-exchanged water Were mixed using glass beads and dispersed for 10 minutes using a sand grinder to obtain a charge control agent dispersion. The volume median particle size (D 50 ) of the charge control agent was 500 nm.
実施例１〜７及び比較例１〜５
（ポリエステル系樹脂の水系分散液の製造）
撹拌機、還流冷却器、滴下ロート、温度計及び窒素導入管を備えた５Ｌ容の容器にメチルエチルケトン６００ｇを投入し、製造例１〜４で製造した非晶質ポリエステル２００ｇをそれぞれ６０℃で添加し、溶解させた。更に、表２に記載の量の尿素５０％水溶液、グアニジン塩酸塩５０％水溶液又はフェニル尿素５０％水溶液を加えて、５分間、６０℃で撹拌した。得られた溶液に５％水酸化ナトリウムを添加して中和度７０％相当となるように中和し、続いてイオン交換水１０００ｇを添加した後、２５０ｒ／ｍｉｎの撹拌速度で、減圧下、５０℃以下の温度でメチルエチルケトンを留去し、自己分散型の樹脂粒子の水系分散液を得た（樹脂含有量：１９．４重量％（固形分換算））。
Examples 1-7 and Comparative Examples 1-5
(Production of aqueous dispersion of polyester resin)
Into a 5 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 600 g of methyl ethyl ketone was added, and 200 g of amorphous polyester produced in Production Examples 1 to 4 was added at 60 ° C. , Dissolved. Furthermore, urea 50% aqueous solution, guanidine hydrochloride 50% aqueous solution or phenylurea 50% aqueous solution in the amount shown in Table 2 was added and stirred at 60 ° C. for 5 minutes. 5% sodium hydroxide was added to the resulting solution to neutralize it to a degree of neutralization of 70%, and then 1000 g of ion-exchanged water was added, followed by stirring at a rate of 250 r / min under reduced pressure. Methyl ethyl ketone was distilled off at a temperature of 50 ° C. or less to obtain an aqueous dispersion of self-dispersing resin particles (resin content: 19.4% by weight (in terms of solid content)).
表２から明らかなように、ポリエステルを水系媒体中に分散するときに尿素を添加しなかった比較例１〜４及びフェニル尿素を添加した比較例５の水系分散液は、ＣＶ値が３４〜３８％の範囲内で、体積中位粒径が２８５〜３０５ｎｍの範囲内であった。これに対し、ポリエステルを水系媒体中に分散するときに尿素又はグアニジンを添加した実施例１〜７の水系分散液は、ＣＶ値が１９〜２９％の範囲内で、体積中位粒径が１７０〜２５５ｎｍの範囲内であった。
このことから、実施例１〜７の水系分散液は、比較例１〜５の水系分散液に比べて、粒子径が均一でかつ小さいことがわかる。特に、実施例１〜３の対比から、尿素の添加量がポリエステル１００重量部に対して８重量部程度である場合にその効果が顕著であることがわかる。また、実施例２及び４〜６の対比から、ポリエステルのアルコール成分が炭素数２〜５の脂肪族ジオールを含む場合にその効果が顕著であることがわかる。
As is clear from Table 2, the aqueous dispersions of Comparative Examples 1 to 4 in which urea was not added when the polyester was dispersed in the aqueous medium and Comparative Example 5 in which phenyl urea was added had a CV value of 34 to 38. %, The volume median particle size was in the range of 285-305 nm. In contrast, the aqueous dispersions of Examples 1 to 7 to which urea or guanidine was added when the polyester was dispersed in the aqueous medium had a CV value in the range of 19 to 29% and a volume median particle size of 170. It was in the range of ˜255 nm.
From this, it can be seen that the aqueous dispersions of Examples 1 to 7 have a uniform and small particle size as compared with the aqueous dispersions of Comparative Examples 1 to 5. In particular, the comparison between Examples 1 to 3 shows that the effect is remarkable when the amount of urea added is about 8 parts by weight with respect to 100 parts by weight of the polyester. Moreover, it turns out that the effect is remarkable when the alcohol component of polyester contains C2-C5 aliphatic diol from contrast of Example 2 and 4-6.
実施例８〜１８及び比較例６〜９
（コアシェル樹脂粒子の分散液及びトナーの製造）
表３に示すコア形成用非晶質ポリエステル水系分散液２５０ｇ、着色剤分散液２０ｇ、ワックス分散液５ｇ、荷電制御剤分散液４ｇ、及びカチオン性界面活性剤（花王（株）製、商品名：「サニゾールＢ５０」）１．５ｇを、丸型のステンレス製フラスコ中でホモジナイザーを用いて混合し、分散させた後、加熱用オイルバス中でフラスコ内を撹拌しながら４８℃まで加熱した。更に４８℃で１時間保持して、凝集粒子を形成した。このときの凝集粒子の体積中位平均粒径は５．１μｍであった。その後、表３に示すシェル形成用非晶質ポリエステル水系分散液５０ｇを加え、撹拌して分散させることにより、カプセル化したコアシェル粒子である凝集粒子を得た。
コアシェル凝集粒子が形成された凝集粒子分散液に、アニオン性界面活性剤（花王（株）製、商品名：「ペレックスＳＳ−Ｌ」）３ｇを添加した後、前記ステンレス製フラスコに還流管を装着し、撹拌を継続しながら、０．１℃／ｍｉｎの速度で８０℃まで加熱し、２時間保持して、凝集粒子を合一し、融合させた。その後、冷却し、融合粒子をろ過し、イオン交換水で十分に洗浄した後、乾燥させることにより着色樹脂微粒子粉末を得た。得られた着色樹脂微粒子粉末の体積中位粒径（Ｄ50）はいずれも約５．０μｍであった。
トナー母粒子１００重量部に対し、外添剤「アエロジル Ｒ−９７２」（疎水性シリカ、商品名、日本アエロジル（株）製）１．０重量部を添加し、ヘンシェルミキサーで３６００ｒ／ｍｉｎ、５分間混合することにより、外添剤処理を行い、トナー粒子（体積中位粒径Ｄ50＝５．０μｍ）からなるトナーを得た。
Examples 8-18 and Comparative Examples 6-9
(Manufacture of dispersion of core-shell resin particles and toner)
Amorphous polyester aqueous dispersion 250 g for core formation shown in Table 3, 20 g of colorant dispersion, 5 g of wax dispersion, 4 g of charge control agent dispersion, and cationic surfactant (manufactured by Kao Corporation, trade name: 1.5 g of “Sanisol B50”) was mixed and dispersed in a round stainless steel flask using a homogenizer, and then heated to 48 ° C. while stirring the inside of the flask in a heating oil bath. Furthermore, it hold | maintained at 48 degreeC for 1 hour, and the aggregated particle was formed. The volume median average particle size of the aggregated particles at this time was 5.1 μm. Then, 50 g of an amorphous polyester aqueous dispersion for shell formation shown in Table 3 was added and dispersed by stirring to obtain aggregated particles that were encapsulated core-shell particles.
After adding 3 g of an anionic surfactant (trade name: “Perex SS-L”, manufactured by Kao Corporation) to the aggregated particle dispersion in which the core-shell aggregated particles are formed, a reflux tube is attached to the stainless steel flask. Then, while continuing stirring, the mixture was heated to 80 ° C. at a rate of 0.1 ° C./min and held for 2 hours to coalesce and fuse the aggregated particles. Thereafter, the mixture was cooled, the fused particles were filtered, sufficiently washed with ion exchange water, and then dried to obtain colored resin fine particle powder. All of the obtained colored resin fine particle powders had a volume-median particle size (D 50 ) of about 5.0 μm.
To 100 parts by weight of toner base particles, 1.0 part by weight of an external additive “Aerosil R-972” (hydrophobic silica, trade name, manufactured by Nippon Aerosil Co., Ltd.) is added, and 3600 r / min, 5 by a Henschel mixer. By mixing for a minute, an external additive treatment was performed to obtain a toner composed of toner particles (volume median particle size D 50 = 5.0 μm).
［評価］
＜転写効率（転写残）＞
カラープリンター「ＭＩＣＲＯＬＩＮＥ ５４００」（商品名、（株）沖データ製）にトナーを実装して、ベタ画像を印刷した。この際、ベタ画像の感光体上のトナー量を０．４０〜０．５０ｍｇ／ｃｍ2に調整し、ベタ画像の印字途中でマシンを停止させ、転写部を通過した後の感光体にメンディングテープを貼付して、転写されず感光体上に残存したトナーをメンディングテープに移し取り、感光体からメンディングテープを剥離した。剥離したメンディングテープと未使用のメンディングテープの色相色差を色差計「Ｘ−Ｒｉｔｅ」（商品名、Ｘ−Ｒｉｔｅ社製）で測定し、色差濃度ΔＥをもとに、転写効率を評価した。なお、ΔＥが５．０未満であれば、転写効率が良好であることを示す。結果を表３に示す。
[Evaluation]
<Transfer efficiency (transfer residue)>
A toner was mounted on a color printer “MICROLINE 5400” (trade name, manufactured by Oki Data Co., Ltd.), and a solid image was printed. At this time, the toner amount of the solid image on the photoconductor is adjusted to 0.40 to 0.50 mg / cm 2 , the machine is stopped during the printing of the solid image, and the mending is performed on the photoconductor after passing through the transfer portion. A tape was affixed, the toner that was not transferred and remained on the photoconductor was transferred to a mending tape, and the mending tape was peeled off from the photoconductor. The hue difference between the peeled and unused mending tape was measured with a color difference meter “X-Rite” (trade name, manufactured by X-Rite), and the transfer efficiency was evaluated based on the color difference density ΔE. . If ΔE is less than 5.0, the transfer efficiency is good. The results are shown in Table 3.
表３から明らかなように、比較例６〜９のトナーは色差濃度ΔＥが高いのに対し、実施例８〜１８のトナーでは抑制することができた。このことから、本発明の方法により得られるポリエステル系樹脂の水系分散液を用いて得られるトナーは、比較例のトナーに比べて転写効率が高いことがわかる。
なお、実施例１１、１２及び１８のトナーは、シェル樹脂粒子分散液のみが本発明の方法により得られたものである。また、実施例１６及び１７のトナーは、コア樹脂粒子分散液のみが本発明の方法により得られたものである。表３から、これらのトナーも転写効率が高いことがわかる。
As is apparent from Table 3, the toners of Comparative Examples 6 to 9 have a high color difference density ΔE, whereas the toners of Examples 8 to 18 could be suppressed. From this, it can be seen that the toner obtained using the aqueous dispersion of the polyester resin obtained by the method of the present invention has higher transfer efficiency than the toner of the comparative example.
In the toners of Examples 11, 12 and 18, only the shell resin particle dispersion was obtained by the method of the present invention. In the toners of Examples 16 and 17, only the core resin particle dispersion was obtained by the method of the present invention. From Table 3, it can be seen that these toners also have high transfer efficiency.
本発明により得られるトナー用ポリエステル系樹脂の水系分散液は、分散粒子径が小さくかつ均一である。この水系分散液を用いて得られるトナーは、転写効率が高いという特性を有するため、電子写真法、静電記録法、静電印刷法等に用いられる電子写真用トナーとして好適に使用できる。 The aqueous dispersion of polyester resin for toner obtained by the present invention has a small dispersed particle size and is uniform. Since the toner obtained using this aqueous dispersion has the property of high transfer efficiency, it can be suitably used as an electrophotographic toner used in electrophotography, electrostatic recording method, electrostatic printing method and the like.
Claims (7)
工程１：ポリエステル系樹脂（ａ）の水系分散液を凝集工程に付し、樹脂粒子（Ａ）の水系分散液を得る工程。
工程２：工程１で得られた樹脂粒子（Ａ）の水系分散液と、ポリエステル系樹脂（ｂ）の水系分散液とを、凝集工程に付し、樹脂粒子（Ｂ）の水系分散液を得る工程。 Including the following steps 1 and 2, wherein the aqueous dispersion of the polyester resin (a) and / or (b) is one or more urea compounds selected from urea and alkyl urea and / or guanidine, alkylguanidine, and their An aqueous dispersion of a polyester resin for toner obtained by a production method comprising a step of dispersing a polyester resin in an aqueous medium in the presence of one or more guanidine compounds selected from acid addition salts and a neutralizing agent. The method for producing an electrophotographic toner according to claim 1 .
Step 1: A step of subjecting an aqueous dispersion of polyester resin (a) to an aggregation step to obtain an aqueous dispersion of resin particles (A).
Step 2: The aqueous dispersion of resin particles (A) obtained in Step 1 and the aqueous dispersion of polyester resin (b) are subjected to an aggregation step to obtain an aqueous dispersion of resin particles (B). Process.
工程３：工程２で得られた樹脂粒子（Ｂ）を合一工程に付し、合一粒子を得る工程。 The method for producing an electrophotographic toner according to claim 2 , further comprising the following step 3.
Process 3: The process of attaching | subjecting the resin particle (B) obtained at the process 2 to a coalescing process, and obtaining coalesced particles.
工程Ａ１：ポリエステル系樹脂、前記の尿素系化合物及び／又はグアニジン系化合物、有機溶剤、中和剤並びに水を混合し、ポリエステル系樹脂の分散液を得る工程。Step A1: A step of mixing a polyester resin, the above urea compound and / or guanidine compound, an organic solvent, a neutralizing agent and water to obtain a polyester resin dispersion.
工程Ａ２：前記工程Ａ１で得られた分散液から、有機溶剤を除去することにより、ポリエステル系樹脂の水系分散液を得る工程。Step A2: A step of obtaining an aqueous dispersion of a polyester resin by removing an organic solvent from the dispersion obtained in Step A1.
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