JP4880539B2 - Resin dispersion for toner - Google Patents
Resin dispersion for toner Download PDFInfo
- Publication number
- JP4880539B2 JP4880539B2 JP2007197989A JP2007197989A JP4880539B2 JP 4880539 B2 JP4880539 B2 JP 4880539B2 JP 2007197989 A JP2007197989 A JP 2007197989A JP 2007197989 A JP2007197989 A JP 2007197989A JP 4880539 B2 JP4880539 B2 JP 4880539B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- toner
- compound
- tin
- condensation polymerization
- 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.)
- Active
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- 239000011347 resin Substances 0.000 title claims description 195
- 229920005989 resin Polymers 0.000 title claims description 195
- 239000006185 dispersion Substances 0.000 title claims description 69
- 239000002245 particle Substances 0.000 claims description 109
- -1 tin (II) compound Chemical class 0.000 claims description 75
- 238000012643 polycondensation polymerization Methods 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 41
- WQGWDDDVZFFDIG-UHFFFAOYSA-N trihydroxybenzene Natural products OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 27
- 229940079877 pyrogallol Drugs 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 19
- 229910020813 Sn-C Inorganic materials 0.000 claims description 17
- 229910018732 Sn—C Inorganic materials 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 230000004931 aggregating effect Effects 0.000 claims description 5
- 229910020923 Sn-O Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000002736 nonionic surfactant Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000003960 organic solvent Substances 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 19
- 238000006068 polycondensation reaction Methods 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 14
- 239000012736 aqueous medium Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 11
- 238000004220 aggregation Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229940074391 gallic acid Drugs 0.000 description 4
- 235000004515 gallic acid Nutrition 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 2
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 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
- 239000012153 distilled water 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
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 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
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 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
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-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
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-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
- 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
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920005792 styrene-acrylic resin Polymers 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- 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 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 description 1
- APVNRHLATFVPPS-UHFFFAOYSA-N (2-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1O APVNRHLATFVPPS-UHFFFAOYSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- PXRFIHSUMBQIOK-CVBJKYQLSA-L (z)-octadec-9-enoate;tin(2+) Chemical compound [Sn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O PXRFIHSUMBQIOK-CVBJKYQLSA-L 0.000 description 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZNLXEDDUXFMEML-UHFFFAOYSA-N 2-[5-(2-chloroacetyl)thiophen-2-yl]acetic acid Chemical compound OC(=O)CC1=CC=C(C(=O)CCl)S1 ZNLXEDDUXFMEML-UHFFFAOYSA-N 0.000 description 1
- TXRCHGMTTXKTPE-UHFFFAOYSA-N 2-aminohexan-3-ol Chemical compound CCCC(O)C(C)N TXRCHGMTTXKTPE-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-UHFFFAOYSA-N 2-dodec-1-enylbutanedioic acid Chemical compound CCCCCCCCCCC=CC(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
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- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 235000010386 dodecyl gallate Nutrition 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- DZYNKLUGCOSVKS-UHFFFAOYSA-N epigallocatechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3cc(O)c(O)c(O)c3 DZYNKLUGCOSVKS-UHFFFAOYSA-N 0.000 description 1
- 229940030275 epigallocatechin gallate Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019277 ethyl gallate Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- YTCQFLFGFXZUSN-BAQGIRSFSA-N microline Chemical compound OC12OC3(C)COC2(O)C(C(/Cl)=C/C)=CC(=O)C21C3C2 YTCQFLFGFXZUSN-BAQGIRSFSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 229920000747 poly(lactic acid) Polymers 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
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- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Developing Agents For Electrophotography (AREA)
Description
本発明は、トナー用樹脂分散液及びこれを用いて得られる電子写真用トナーに関する。 The present invention relates to a resin dispersion for toner and an electrophotographic toner obtained using the same.
従来、トナーの結着樹脂としては、スチレンアクリル樹脂やポリエステルが知られているが、耐久性及び定着性に優れることからポリエステルを含有したトナーが汎用されている。このようなトナーとして、特に定着性の観点から、ポリエステルを結着樹脂として用いる溶融混練粉砕法によるトナーが開示されている(特許文献1、2参照)。 Conventionally, styrene acrylic resins and polyesters are known as toner binder resins, but toners containing polyester are widely used because of their excellent durability and fixability. As such a toner, in particular, from the viewpoint of fixability, a toner by a melt kneading and pulverizing method using polyester as a binder resin is disclosed (see Patent Documents 1 and 2).
一方、近年、高画質化の追求から、定着性に優れた小粒径トナーの開発が望まれている。しかし、ポリエステルを主体とした結着樹脂を含有した小粒径トナーを溶融混練粉砕法で製造する場合は、粉砕制御が困難である。そこで、例えば、特許文献3には、カルボキシル基を有するバインダー樹脂を有機溶剤に分散させる、湿式製法である乳化凝集法によってトナーを製造する方法が開示されている。 On the other hand, in recent years, from the pursuit of high image quality, development of a small particle size toner excellent in fixing property has been desired. However, when a small particle toner containing a binder resin mainly composed of polyester is produced by a melt kneading pulverization method, pulverization control is difficult. Therefore, for example, Patent Document 3 discloses a method for producing a toner by an emulsion aggregation method, which is a wet production method, in which a binder resin having a carboxyl group is dispersed in an organic solvent.
さらに、安全性等の観点から、酸化ジブチル錫等のSn−C結合を有する錫化合物よりも、Sn−C結合を有していない錫(II)化合物が触媒として使用される傾向がある(特許文献4参照)。
しかしながら、近年のマシンの高画質化にともない、さらなるトナーの小粒径化と、粒度分布のシャープ化が求められているが、Sn-C結合を有していない錫(II)化合物の存在下で縮重合して得られる結着樹脂を用いて湿式法でトナーを製造する場合、樹脂分散液中の樹脂粒子の粒径及び粒度分布の制御が困難であり(即ち乳化性が悪く)、該樹脂粒子を用いて得られるトナーの画像特性、特に転写性が劣る結果となる。 However, with the recent increase in image quality of machines, there is a demand for further reduction in toner particle size and sharpening of the particle size distribution, but in the presence of a tin (II) compound having no Sn—C bond. When a toner is produced by a wet method using a binder resin obtained by condensation polymerization in step (b), it is difficult to control the particle size and particle size distribution of the resin particles in the resin dispersion (that is, the emulsifying properties are poor), This results in inferior image characteristics, particularly transferability, of the toner obtained using the resin particles.
本発明の課題は、Sn-C結合を有していない錫(II)化合物の存在下で原料モノマーを縮重合させて得られる縮重合系樹脂を用いた場合でも乳化性能が良好であり、また、転写性に優れるトナーが得られるトナー用樹脂分散液、及び該樹脂分散液を用いて得られる電子写真用トナーを提供することにある。 The problem of the present invention is that the emulsification performance is good even when a condensation polymerization resin obtained by condensation polymerization of a raw material monomer in the presence of a tin (II) compound having no Sn-C bond is used. Another object of the present invention is to provide a resin dispersion for toners that provides a toner with excellent transferability, and an electrophotographic toner obtained using the resin dispersion.
本発明は、
〔1〕 縮重合系樹脂を含有してなる樹脂粒子を含むトナー用樹脂分散液であって、前記縮重合系樹脂がSn-C結合を有していない錫(II)化合物と互いに隣接する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ピロガロール化合物との存在下、原料モノマーを縮重合させて得られる縮重合系樹脂である、トナー用樹脂分散液、並びに
〔2〕 前記〔1〕記載のトナー用樹脂分散液中の樹脂粒子を凝集、合一させる工程を含む方法により得られる電子写真用トナー
に関する。
The present invention
[1] A resin dispersion for toner containing resin particles containing a condensation polymerization resin, wherein the condensation polymerization resin is adjacent to a tin (II) compound having no Sn—C bond. A resin dispersion for toner, which is a condensation polymerization resin obtained by condensation polymerization of a raw material monomer in the presence of a pyrogallol compound having a benzene ring in which a number of hydrogen atoms are substituted with hydroxyl groups, and [2] [1] The present invention relates to an electrophotographic toner obtained by a method comprising a step of aggregating and coalescing resin particles in the toner resin dispersion described above.
本発明によれば、Sn-C結合を有していない錫(II)化合物の存在下で原料モノマーを縮重合させて得られる縮重合系樹脂を用いた場合でも乳化性能が良好であり、また、転写性に優れるトナーが得られるトナー用樹脂分散液、及び該樹脂分散液を用いて得られる電子写真用トナーを提供することができる。 According to the present invention, even when a condensation polymerization resin obtained by condensation polymerization of a raw material monomer in the presence of a tin (II) compound having no Sn—C bond is used, the emulsification performance is good. In addition, it is possible to provide a resin dispersion for toners that provides a toner with excellent transferability, and an electrophotographic toner obtained using the resin dispersion.
本発明のトナー用樹脂分散液は、Sn-C結合を有していない錫(II)化合物と互いに隣接する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ピロガロール化合物との存在下、原料モノマーを縮重合させて得られる縮重合系樹脂を含む樹脂粒子を含有している点に大きな特徴を有しており、かかる樹脂粒子は、小粒径でシャープな粒度分布を有する。 The resin dispersion for toner of the present invention comprises a tin (II) compound having no Sn-C bond and a pyrogallol compound having a benzene ring in which three adjacent hydrogen atoms are substituted with a hydroxyl group, The resin particles have a great feature in that they contain resin particles containing a condensation polymerization resin obtained by condensation polymerization of raw material monomers. Such resin particles have a small particle size and a sharp particle size distribution.
Sn-C結合を有していない錫(II)化合物を触媒として用いて得られる縮重合系樹脂を有機溶剤中で分散させると、樹脂粒子は小粒径化されずブロードな粒度分布となるが、この原因の1つとして触媒の構造変化が原因と考えられる。即ち、上記縮重合系樹脂を有機溶剤中に溶解させると白い沈殿物が析出し溶液が白濁してくることから、Sn-C結合を有していない錫(II)化合物の存在下での重合中に、触媒の一部に構造変化が起こり、得られる樹脂中に残存した残留物が樹脂粒子の粒径及び粒度分布の制御を妨げているのではないかと考えられる。しかしながら、本発明の樹脂分散液に含まれる縮重合系樹脂は、原料モノマーの縮重合において、Sn-C結合を有していない錫(II)に化合物にピロガロール化合物を助触媒として共存させて得られたものであり、有機溶剤に溶解させても沈殿物も存在せず、小粒径で粒度分布がシャープな、縮重合系樹脂を含む樹脂粒子が形成される。これは、助触媒として用いたピロガロール化合物がSn-C結合を有していない錫(II)の構造変化を抑制できるためと推察される。そして、この樹脂分散液中の樹脂粒子を凝集、合一させて得られるトナーは転写性に優れるため、画像特性に優れるという効果を奏する。 When a condensation polymerization resin obtained by using a tin (II) compound having no Sn-C bond as a catalyst is dispersed in an organic solvent, the resin particles have a broad particle size distribution without being reduced in size. One of the causes is considered to be a change in the structure of the catalyst. That is, when the above polycondensation resin is dissolved in an organic solvent, a white precipitate is formed and the solution becomes cloudy. Thus, polymerization in the presence of a tin (II) compound having no Sn—C bond is performed. It is considered that a structural change occurs in a part of the catalyst, and the residue remaining in the obtained resin hinders control of the particle size and particle size distribution of the resin particles. However, the condensation polymerization resin contained in the resin dispersion of the present invention is obtained by co-existing a pyrogallol compound as a co-catalyst with tin (II) having no Sn—C bond in the condensation polymerization of the raw material monomer. As a result, resin particles containing a condensation polymerization resin having a small particle size and a sharp particle size distribution are formed even when dissolved in an organic solvent. This is presumably because the pyrogallol compound used as a cocatalyst can suppress the structural change of tin (II) having no Sn—C bond. The toner obtained by agglomerating and coalescing the resin particles in the resin dispersion is excellent in transferability, and thus has an effect of excellent image characteristics.
さらに、Sn-C結合を有していない錫(II)化合物と前記ピロガロール化合物との存在下、原料モノマーを縮重合させて得られる縮重合系樹脂を水系媒体中で分散させた場合であっても、小粒径で粒度分布がシャープな樹脂粒子を得ることができ、樹脂粒子を凝集・合一して得られるトナーも転写性に優れるため、画像特性に優れることを見出した。 Furthermore, when a polycondensation resin obtained by polycondensing a raw material monomer in the presence of a tin (II) compound having no Sn—C bond and the pyrogallol compound is dispersed in an aqueous medium, However, the present inventors have found that resin particles having a small particle size and a sharp particle size distribution can be obtained, and toner obtained by agglomerating and coalescing resin particles is also excellent in transferability, and thus has excellent image characteristics.
前記ピロガロール化合物としては、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、これらの中では、得られる樹脂の透明性の観点から、式(I): Examples of the pyrogallol compound include pyrogallol, gallic acid, gallic ester, benzophenone derivatives such as 2,3,4-trihydroxybenzophenone, 2,2 ', 3,4-tetrahydroxybenzophenone, epigallocatechin, and epigallocatechin gallate. Among these, from the viewpoint of the transparency of the obtained resin, among them, the formula (I):
(式中、R1〜R3はそれぞれ独立して、水素原子又は−COOR4(R4は水素原子又は炭素数1〜12の炭化水素基、好ましくはアルキル基又はアルケニル基を示す)を示す)
で表される化合物が好ましい。式中、R4の炭化水素基の炭素数は、1〜8が好ましく、反応活性の観点から、炭素数1〜4がより好ましい。式(I)で表される化合物のなかでは、R1及びR3が水素原子、R2が水素原子又は−COOR4である化合物がより好ましい。具体例としては、ピロガロール(R1〜R3:水素原子)、没食子酸(R1及びR3:水素原子、R2:−COOH)、没食子酸エチル(R1及びR3:水素原子、R2:−COOC2H5)、没食子酸プロピル(R1及びR3:水素原子、R2:−COOC3H7)、没食子酸ブチル(R1及びR3:水素原子、R2:−COOC4H9)、没食子酸オクチル(R1及びR3:水素原子、R2:−COOC8H17)、没食子酸ラウリル(R1及びR3:水素原子、R2:−COOC12H25)等の没食子酸エステル等が挙げられる。樹脂の透明性の観点からは、没食子酸及び没食子酸エステルが好ましい。
Wherein R 1 to R 3 each independently represent a hydrogen atom or —COOR 4 (R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group or an alkenyl group). )
The compound represented by these is preferable. In the formula, the hydrocarbon group of R 4 preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms from the viewpoint of reaction activity. Among the compounds represented by the formula (I), a compound in which R 1 and R 3 are hydrogen atoms and R 2 is a hydrogen atom or —COOR 4 is more preferable. Specific examples include pyrogallol (R 1 to R 3 : hydrogen atom), gallic acid (R 1 and R 3 : hydrogen atom, R 2 : —COOH), ethyl gallate (R 1 and R 3 : hydrogen atom, R 2 : —COOC 2 H 5 ), propyl gallate (R 1 and R 3 : hydrogen atom, R 2 : —COOC 3 H 7 ), butyl gallate (R 1 and R 3 : hydrogen atom, R 2 : —COOC) 4 H 9 ), octyl gallate (R 1 and R 3 : hydrogen atom, R 2 : —COOC 8 H 17 ), lauryl gallate (R 1 and R 3 : hydrogen atom, R 2 : —COOC 12 H 25 ) And gallic acid esters. From the viewpoint of the transparency of the resin, gallic acid and gallic acid ester are preferable.
前記ピロガロール化合物とともに、縮重合反応用触媒として用いられる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、Sn-O結合を有する錫(II)化合物がより好ましい。 A tin (II) compound having no Sn—C bond used as a catalyst for polycondensation reaction together with the pyrogallol compound includes a tin (II) compound having a Sn—O bond, Sn—X (X is a halogen atom) And a tin (II) compound having a Sn—O bond is more preferable.
Sn-O結合を有する錫(II)化合物としては、シュウ酸錫(II)、酢酸錫(II)、オクタン酸錫(II)、2-エチルヘキサン酸錫(II)、ラウリル酸錫(II)、ステアリン酸錫(II)、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);オクチロキシ錫(II)、ラウロキシ錫(II)、ステアロキシ錫(II)、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アルコキシ錫(II);酸化錫(II);硫酸錫(II)等が、Sn-X(Xはハロゲン原子を示す)結合を有する錫(II)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、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、オクタン酸錫(II)、2-エチルヘキサン酸錫(II)、ステアリン酸錫(II)及び酸化錫(II)がさらに好ましい。 Examples of tin (II) compounds having Sn-O bonds include tin (II) oxalate, tin (II) acetate, tin (II) octoate, tin (II) 2-ethylhexanoate, and tin (II) laurate. , Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), stearoxy tin (II) ), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as oleyloxytin (II); tin (II) oxide; tin (II) sulfate, Sn—X (X represents a halogen atom) Examples of the tin (II) compound having a bond include tin (II) halides such as tin (II) chloride and tin (II) bromide, and among these, from the standpoint of charge rising effect and catalytic ability , (R 1 COO) 2 Sn (wherein R 1 represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R 2 O) 2 Sn (where R 2 Is C 6-20 alk An alkoxytin (II) represented by SnO or a tin (II) oxide represented by SnO, and a fatty acid tin (II) and tin oxide represented by (R 1 COO) 2 Sn (II) is more preferred, and tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferred.
縮重合反応として、代表的な例としては、カルボキシル基と水酸基の脱水縮合によりエステル結合(-COO-)を有するポリエステルユニット、カルボキシル基とアミノ基の脱水縮合によりアミド結合(-CONH-)を有するポリアミドユニット、エステル結合とアミド結合の両方を有するポリエステルポリアミドユニット等の縮重合系樹脂ユニットを形成する反応等が挙げられ、エステル結合を有する縮重合系樹脂ユニットの形成において、本発明の効果がより顕著に発揮される。なお、本発明においては、異なる原料モノマー間の反応に限らず、異種官能基を1分子内にもつモノマー、例えば、水酸基とカルボキシル基を有する乳酸から、脱水縮合によりポリ乳酸を生成させる反応も縮重合反応に含まれる。 Typical examples of the condensation polymerization reaction include a polyester unit having an ester bond (-COO-) by dehydration condensation of a carboxyl group and a hydroxyl group, and an amide bond (-CONH-) by dehydration condensation of a carboxyl group and an amino group. The reaction of forming a polycondensation resin unit such as a polyamide unit and a polyester polyamide unit having both an ester bond and an amide bond can be mentioned, and in the formation of a polycondensation resin unit having an ester bond, the effect of the present invention is more effective. Prominently demonstrated. In the present invention, not only the reaction between different raw material monomers, but also the reaction of producing polylactic acid by dehydration condensation from a monomer having different functional groups in one molecule, for example, lactic acid having a hydroxyl group and a carboxyl group. Included in the polymerization reaction.
ポリエステルユニットの原料モノマーとしては、通常、アルコール成分とカルボン酸成分とが用いられる。 As the raw material monomer for the polyester unit, an alcohol component and a carboxylic acid component are usually used.
アルコール成分としては、ポリオキシプロピレン-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシエチレン-2,2-ビス(4-ヒドロキシフェニル)プロパン等の、式(II): Examples of the alcohol component include polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane, which are represented by the formula (II):
(式中、R5Oはアルキレンオキシ基であり、R5は炭素数2又は3のアルキレン基、x及びyはアルキレンオキサイドの平均付加モル数を示す正の数であり、xとyの和は1〜16、好ましくは1.5〜5である)
で表されるビスフェノールのアルキレンオキサイド付加物等の芳香族ジオール、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、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,4-ブテンジオール、1,3-ブタンジオール、ネオペンチルグリコール等の脂肪族ジオール、グリセリン等の3価以上の多価アルコール等が挙げられる。
Wherein R 5 O is an alkyleneoxy group, R 5 is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average number of moles of alkylene oxide added, and the sum of x and y Is 1 to 16, preferably 1.5 to 5)
Aromatic diols such as alkylene oxide adducts of bisphenol represented by: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Aliphatic diols such as hexanediol, 1,4-butenediol, 1,3-butanediol and neopentyl glycol, and trihydric or higher polyhydric alcohols such as glycerin.
カルボン酸成分としては、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、n-ドデシルコハク酸、n-ドデセニルコハク酸等の脂肪族ジカルボン酸;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;シクロヘキサンジカルボン酸等の脂環式ジカルボン酸;トリメリット酸、ピロメリット酸等の3価以上の多価カルボン酸;及びこれらの酸の無水物、アルキル(炭素数1〜3)エステル;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が挙げられる。上記のような酸、これらの酸の無水物、及び酸のアルキルエステルを、本明細書では総称してカルボン酸化合物と呼ぶ。本発明においては、帯電性の観点から、芳香族ジカルボン酸化合物が好ましい。芳香族ジカルボン酸化合物の含有量は、カルボン酸成分中、70モル%以上が好ましく、90モル%以上がより好ましい。 Examples of carboxylic acid components include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, etc. Aliphatic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; And anhydrides of these acids, alkyl (1 to 3 carbon atoms) esters; rosins; rosins modified with fumaric acid, maleic acid, acrylic acid, and the like. Such acids, anhydrides of these acids, and alkyl esters of these acids are collectively referred to herein as carboxylic acid compounds. In the present invention, an aromatic dicarboxylic acid compound is preferred from the viewpoint of chargeability. 70 mol% or more is preferable in a carboxylic acid component, and, as for content of an aromatic dicarboxylic acid compound, 90 mol% or more is more preferable.
なお、アルコール成分には1価のアルコールが、カルボン酸成分には1価のカルボン酸化合物が、分子量調整や耐オフセット性向上の観点から、適宜含有されていてもよい。 The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoints of molecular weight adjustment and offset resistance improvement.
さらに、ポリエステルポリアミドユニットやポリアミドユニットにおけるアミド結合を形成するための原料モノマーとしては、公知の各種ポリアミン、アミノカルボン酸類、アミノアルコール等が挙げられ、好ましくはヘキサメチレンジアミン及びε-カプロラクタムである。 Furthermore, examples of the raw material monomer for forming an amide bond in the polyester polyamide unit and the polyamide unit include various known polyamines, aminocarboxylic acids, aminoalcohols, etc., preferably hexamethylenediamine and ε-caprolactam.
なお、以上の原料モノマーには、通常開環重合モノマーに分類されるものも含まれているが、これらは、他のモノマーの縮重合反応で生成する水等の存在により加水分解して縮重合に供されるため、広義には縮重合系樹脂の原料モノマーに含まれると考えられる。 The above raw material monomers also include those normally classified as ring-opening polymerization monomers, but these are hydrolyzed by condensation due to the presence of water or the like produced by the condensation polymerization reaction of other monomers. Therefore, it is considered to be included in the raw material monomer of the condensation polymerization resin in a broad sense.
縮重合反応における前記ピロガロール化合物の存在量は、縮重合反応に供される原料モノマー100重量部に対して、0.001〜1.0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重量部がさらに好ましい。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。 The abundance of the pyrogallol compound in the condensation polymerization reaction is preferably 0.001 to 1.0 part by weight, more preferably 0.005 to 0.4 part by weight, and more preferably 0.01 to 0.2 part by weight with respect to 100 parts by weight of the raw material monomer subjected to the condensation polymerization reaction. Is more preferable. Here, the abundance of the pyrogallol compound means the total amount of the pyrogallol compound subjected to the condensation polymerization reaction.
一方、前記錫(II)化合物の存在量は、縮重合反応に供される原料モノマー100重量部に対して、0.01〜2.0重量部が好ましく、0.1〜1.5重量部がより好ましく、0.2〜1.0重量部がさらに好ましい。ここで、錫(II)化合物の存在量とは、縮重合反応に供した錫(II)化合物の全配合量を意味する。 On the other hand, the abundance of the tin (II) compound is preferably 0.01 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight, and more preferably 0.2 to 1.0 parts by weight with respect to 100 parts by weight of the raw material monomer subjected to the condensation polymerization reaction. Part is more preferred. Here, the abundance of the tin (II) compound means the total amount of the tin (II) compound subjected to the condensation polymerization reaction.
ピロガロール化合物と前記錫(II)化合物の重量比(ピロガロール化合物/錫(II)化合物)は、0.01〜0.5が好ましく、0.03〜0.3がより好ましく、0.05〜0.2がさらに好ましい。 The weight ratio of the pyrogallol compound to the tin (II) compound (pyrogallol compound / tin (II) compound) is preferably 0.01 to 0.5, more preferably 0.03 to 0.3, and even more preferably 0.05 to 0.2.
縮重合反応は、前記錫(II)化合物及びピロガロール化合物の存在下、不活性ガス雰囲気中にて、180〜250℃の温度で行うことが好ましい。前記錫(II)化合物とピロガロール化合物は、両者を混合して反応系に添加してもよく、別々に添加してもよい。また、カルボン酸成分やアルコール成分と混合して添加してもよい。前記錫(II)化合物及びピロガロール化合物を反応系に添加する時期は、反応開始前及び反応途中のいずれであってもよいが、縮重合反応の促進に対してより高い効果が得られる観点から、反応温度に達するより前の時点であることが好ましく、反応開始前であることがより好ましい。なお、本発明において、反応開始前とは、縮重合反応に伴う水が生成されていない状態を意味する。 The polycondensation reaction is preferably performed at a temperature of 180 to 250 ° C. in an inert gas atmosphere in the presence of the tin (II) compound and the pyrogallol compound. The tin (II) compound and pyrogallol compound may be mixed and added to the reaction system, or may be added separately. Moreover, you may mix and add with a carboxylic acid component and an alcohol component. The timing of adding the tin (II) compound and pyrogallol compound to the reaction system may be any before the start of the reaction and during the reaction, from the viewpoint of obtaining a higher effect for the promotion of the polycondensation reaction, A time point before reaching the reaction temperature is preferable, and a time point before starting the reaction is more preferable. In the present invention, “before starting the reaction” means a state in which water accompanying the condensation polymerization reaction is not generated.
本発明における縮重合系樹脂とは、縮重合系樹脂ユニットを含む樹脂をいい、前記縮重合反応により得られるポリエステル、ポリエステルポリアミド、ポリアミド等の縮重合系樹脂ユニットからなる樹脂だけでなく、前記縮重合系樹脂ユニットを含む、2種以上の樹脂成分を有するハイブリッド樹脂、例えば、縮重合系樹脂ユニットと付加重合系樹脂ユニットとが部分的に化学結合したハイブリッド樹脂も含まれる。 The polycondensation resin in the present invention refers to a resin containing a polycondensation resin unit, and includes not only a resin comprising a polycondensation resin unit such as polyester, polyester polyamide, and polyamide obtained by the above polycondensation reaction, but also the above polycondensation resin unit. A hybrid resin including two or more kinds of resin components including a polymerization resin unit, for example, a hybrid resin in which a condensation polymerization resin unit and an addition polymerization resin unit are partially chemically bonded is also included.
また、縮重合系樹脂は、実質的にその特性を損なわない程度に変性されていてもよい。例えば、変性されたポリエステルとしては、特開平11−133668号公報、特開平10−239903号公報、特開平8−20636号公報等に記載の方法によりフェノール、ウレタン、エポキシ等によりグラフト化やブロック化したポリエステルをいう。 Further, the condensation polymerization resin may be modified to such an extent that the properties are not substantially impaired. For example, the modified polyester may be grafted or blocked with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, etc. Polyester.
トナー用結着樹脂としての用途を考慮すると、縮重合系樹脂の軟化点は、定着性、保存性及び耐久性の観点から、90〜160℃が好ましく、95〜155℃がより好ましく、98〜150℃がさらに好ましい。ガラス転移点は、定着性、保存性及び耐久性の観点から、45〜85℃が好ましく、50〜80℃がより好ましい。帯電性と環境安定性の観点から、酸価は、1〜90mgKOH/gが好ましく、5〜90mgKOH/gがより好ましく、5〜88mgKOH/gがさらに好ましく、水酸基価は、1〜80mgKOH/gが好ましく、8〜60mgKOH/gがより好ましく、8〜55mgKOH/gがさらに好ましい。 Considering the use as a binder resin for toner, the softening point of the condensation polymerization resin is preferably 90 to 160 ° C, more preferably 95 to 155 ° C, from the viewpoint of fixability, storage stability and durability, 98 to 150 ° C. is more preferable. The glass transition point is preferably 45 to 85 ° C, more preferably 50 to 80 ° C, from the viewpoints of fixability, storage stability and durability. From the viewpoint of chargeability and environmental stability, the acid value is preferably 1 to 90 mgKOH / g, more preferably 5 to 90 mgKOH / g, further preferably 5 to 88 mgKOH / g, and the hydroxyl value is 1 to 80 mgKOH / g. Preferably, 8 to 60 mgKOH / g is more preferable, and 8 to 55 mgKOH / g is more preferable.
本発明の樹脂分散液は、縮重合系樹脂を含有した樹脂粒子を水系媒体中に分散させる工程を含む方法により得られるものが好ましいが、その製造方法は特に限定されない。樹脂分散液の製造方法としては、例えば、縮重合系樹脂を含む樹脂粒子を、非イオン性界面活性剤の存在下、水系媒体中で生成させる方法(方法a)、縮重合系樹脂を有機溶剤中に溶解又は分散させて調製された混合溶液に、水系媒体中を導入した後、有機溶剤を除去し、自己分散型の水系樹脂粒子を分散させる方法(方法b)、縮重合系樹脂を溶解したラジカル重合性単量体溶液を乳化重合して樹脂粒子を得、この樹脂粒子を水系媒体中で乳化させる方法(方法c)、縮重合系樹脂の加熱溶融体を、樹脂の溶融状態を維持しながら、有機溶剤を含まない水系媒体中に分散する方法(方法d)等が挙げられ、方法a及び方法bがより好ましい。 The resin dispersion of the present invention is preferably obtained by a method including a step of dispersing resin particles containing a condensation polymerization resin in an aqueous medium, but the production method is not particularly limited. As a method for producing a resin dispersion, for example, a method in which resin particles containing a condensation polymerization resin are produced in an aqueous medium in the presence of a nonionic surfactant (method a), the condensation polymerization resin is converted into an organic solvent. After introducing the aqueous medium into the mixed solution prepared by dissolving or dispersing in, a method of removing the organic solvent and dispersing the self-dispersing aqueous resin particles (Method b), dissolving the condensation polymerization resin A method of emulsifying the radically polymerizable monomer solution obtained to obtain resin particles, and emulsifying the resin particles in an aqueous medium (Method c), maintaining a molten state of the resin by heating the melt of the condensation polymerization resin However, a method of dispersing in an aqueous medium not containing an organic solvent (method d) and the like are mentioned, and method a and method b are more preferable.
なお、本発明において、水系媒体は、有機溶剤等の溶剤を含有していてもよいが、水を好ましくは50重量%以上、好ましくは70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。本発明における縮重合系樹脂は、有機溶剤中に溶解しても沈殿物が析出しないため、方法aのように有機溶剤を使用することなく樹脂分散液が得られる方法のみならず、方法b、c、dのように、製造過程で有機溶剤の使用が必須とされる製造方法においても好適に使用することができる。 In the present invention, the aqueous medium may contain a solvent such as an organic solvent, but water is preferably 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably. Contains 99% by weight or more. Since the condensation polymerization resin in the present invention does not precipitate even when dissolved in an organic solvent, not only the method of obtaining a resin dispersion without using an organic solvent as in method a, but also method b, Like c and d, it can be suitably used in a production method in which the use of an organic solvent is essential in the production process.
以下、方法a及び方法bについてさらに説明する。 Hereinafter, the method a and the method b will be further described.
〔方法a〕
方法aでは、縮重合系樹脂と非イオン性界面活性剤とを混合することにより、混合物の粘度が低下し、縮重合系樹脂を微粒化させることができるが、これは、混合物の粘度の低下が、非イオン性界面活性剤が樹脂に相溶し、樹脂の軟化点が見掛け上、低下することによるものである。この現象を利用して、非イオン性界面活性剤が相溶した縮重合系樹脂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縮重合系樹脂でも、常圧で水を滴下することにより、縮重合系樹脂を含有する樹脂の乳化粒子が水中に分散した樹脂分散液を得ることができる。この方法では、少なくとも水と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、経済的に樹脂分散液を製造できるという利点も有する。
[Method a]
In the method a, by mixing the condensation polymerization resin and the nonionic surfactant, the viscosity of the mixture can be reduced, and the condensation polymerization resin can be atomized. This is a decrease in the viscosity of the mixture. However, the nonionic surfactant is compatible with the resin, and the softening point of the resin apparently decreases. Utilizing this phenomenon, the apparent softening point of the condensation polymerization resin in which the nonionic surfactant is compatible can be lowered below the boiling point of water. Even with the condensation polymerization resin having, a resin dispersion in which emulsified particles of the resin containing the condensation polymerization resin are dispersed in water can be obtained by dropping water at normal pressure. This method requires at least water and a nonionic surfactant, so that it can be applied to resins that are insoluble in organic solvents, and does not require the burden of equipment for recovering organic solvents and maintaining the work environment. There is also an advantage that a resin dispersion can be produced economically because a special device required when using mechanical means is not required.
水系媒体は、前記のように、有機溶剤等の溶剤を含有していてもよいが、水を好ましくは50重量%以上、好ましくは70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り、上記方法によれば、実質的に有機溶剤を用いることなく水のみを用いても縮重合系樹脂を微粒化させることができる。なお、溶剤を使用する場合には樹脂の溶解性を考慮し、メチルエチルケトン、テトラヒドロフラン、トルエン、酢酸エチル等が好ましい。 As described above, the aqueous medium may contain a solvent such as an organic solvent, but water is preferably 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably. According to the above method, the condensation polymerization resin can be atomized by using only water without using an organic solvent. In the case of using a solvent, methyl ethyl ketone, tetrahydrofuran, toluene, ethyl acetate, etc. are preferable in consideration of the solubility of the resin.
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、ポリオキシエチレンオレイルエーテル、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アリルエーテルあるいは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、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、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。 Nonionic surfactants include, for example, polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl ethers, polyoxyethylene sorbitan mono Polyoxyethylene sorbitan esters such as laurate, polyoxyethylene sorbitan monostearate, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, oxyethylene / Oxypropylene block copolymer and the like. 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、樹脂との相溶性のよいものを選択することが好ましい。安定な縮重合系樹脂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、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。 As the nonionic surfactant, it is preferable to select a nonionic surfactant having good compatibility with the resin. In order to obtain a stable polycondensation resin dispersion, the HLB of the nonionic surfactant is preferably 12 to 18, and depending on the type of resin, two or more different HLB nonionic surfactants may be used. It is more preferable to use an agent.
非イオン性界面活性剤の使用量は、縮重合系樹脂の融点を下げる観点から、縮重合系樹脂100重量部に対して、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。従って、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、縮重合系樹脂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重量部がさらに好ましい。 The amount of the nonionic surfactant used is preferably 5 parts by weight or more with respect to 100 parts by weight of the condensation polymerization resin from the viewpoint of lowering the melting point of the condensation polymerization resin, and the nonionic surfactant remaining in the toner. From the viewpoint of controlling the amount, 80 parts by weight or less is preferable. Therefore, from the viewpoint of making these compatible, the amount of the nonionic surfactant used is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, and more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the condensation polymerization resin. More preferred is 60 parts by weight.
縮重合系樹脂を含む樹脂粒子を、非イオン性界面活性剤の存在下、水系媒体中で生成させる際、系内の温度は、非イオン性界面活性剤の分散能及び分散効率の低下を防止する観点から、非イオン性界面活性剤の曇点から上下にそれぞれ10℃、好ましくは8℃、より好ましくは5℃の温度範囲内に保つことが望ましい。 When resin particles containing a polycondensation resin are produced in an aqueous medium in the presence of a nonionic surfactant, the temperature in the system prevents a decrease in the dispersibility and dispersion efficiency of the nonionic surfactant. From this viewpoint, it is desirable to keep the nonionic surfactant within the temperature range of 10 ° C., preferably 8 ° C., more preferably 5 ° C. above and below the cloud point.
例えば、縮重合系樹脂及び非イオン性界面活性剤の混合物を攪拌し、系内に均一に混合した状態で、水系媒体(好ましくは、脱イオン水又は蒸留水)を滴下することが好ましい。なお、着色剤を使用する場合には、非イオン性界面活性剤と相溶した着色剤を含む縮重合系樹脂が水と分離しないようにすることが好ましい。 For example, it is preferable to drop an aqueous medium (preferably deionized water or distilled water) in a state where the mixture of the condensation polymerization resin and the nonionic surfactant is stirred and uniformly mixed in the system. In addition, when using a coloring agent, it is preferable not to isolate | separate the polycondensation-type resin containing the coloring agent compatible with the nonionic surfactant from water.
水系媒体の使用量は、続く工程で均一な凝集粒子を得る観点から、縮重合系樹脂100重量部に対して100〜3000重量部が好ましく、400〜3000重量部がより好ましく、800〜3000重量部がさらに好ましい。 The amount of the aqueous medium used is preferably 100 to 3000 parts by weight, more preferably 400 to 3000 parts by weight, and more preferably 800 to 3000 parts by weight with respect to 100 parts by weight of the condensation polymerization resin from the viewpoint of obtaining uniform aggregated particles in the subsequent steps. Part is more preferred.
なお、縮重合系樹脂がカルボキシル基、スルホン基等の酸性基を有する場合は、縮重合系の全部もしくは一部を中和した後、又は中和しながら水を添加してもよい。縮重合系樹脂に酸性基を有するものを用いる場合は、非イオン性界面活性剤の因子に加え、樹脂の自己乳化性が樹脂粒子の粒径の制御因子となる。 In the case where the condensation polymerization resin has an acidic group such as a carboxyl group or a sulfone group, water may be added after neutralizing all or part of the condensation polymerization system or while neutralizing. When a resin having an acidic group is used as the condensation polymerization resin, the self-emulsifying property of the resin becomes a control factor of the particle size of the resin particles in addition to the factor of the nonionic surfactant.
縮重合系樹脂の溶融粘度及び融点の低下、並びに生成する樹脂粒子の分散性の向上を目的として、分散剤を用いることができる。分散剤としては、例えば、ポリビニルアルコール、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース等の水溶性高分子;ドデシルベンゼンスルホン酸ナトリウム、オクタデシル硫酸ナトリウム等のアニオン界面活性剤;ラウリルアミンアセテート、ステアリルアミンアセテート、ラウリルトリメチルアンモニウムクロライド等のカチオン界面活性剤;ラウリルジメチルアミンオキサイド等の両性界面活性剤;リン酸三カルシウム、水酸化アルミニウム、硫酸カルシウム、炭酸カルシウム等の無機塩が挙げられる。分散剤の使用量は、乳化安定性及び洗浄性の観点から、縮重合系樹脂100重量部に対して、20重量部以下が好ましく、15重量部以下がより好ましく、10重量部以下がさらに好ましい。 A dispersant can be used for the purpose of lowering the melt viscosity and melting point of the condensation polymerization resin and improving the dispersibility of the resin particles produced. Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose; anionic surfactants such as sodium dodecylbenzenesulfonate and sodium octadecylsulfate; laurylamine acetate, stearylamine acetate, Cationic surfactants such as lauryltrimethylammonium chloride; amphoteric surfactants such as lauryldimethylamine oxide; inorganic salts such as tricalcium phosphate, aluminum hydroxide, calcium sulfate, and calcium carbonate. The amount of the dispersant used is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, even more preferably 10 parts by weight or less, with respect to 100 parts by weight of the condensation polymerization resin, from the viewpoint of emulsion stability and detergency. .
樹脂分散液を調製する系内の固形分濃度は、分散液の安定性と凝集工程での分散液の取扱い性の観点から、7〜50重量%が好ましく、より好ましくは7〜40重量%、さらに好ましくは10〜30重量%である。なお、固形分には、樹脂、非イオン性界面活性剤等の不揮発性成分が含まれる。 The solid concentration in the system for preparing the resin dispersion is preferably 7 to 50% by weight, more preferably 7 to 40% by weight, from the viewpoint of the stability of the dispersion and the handling of the dispersion in the aggregation step. More preferably, it is 10 to 30% by weight. The solid content includes non-volatile components such as a resin and a nonionic surfactant.
〔方法b〕
方法bでは、例えば、縮重合系樹脂を有機溶剤に溶解させ、中和剤を加えて該縮重合系樹脂の酸基をイオン化し、次いで水を加えた後、有機溶剤を留去して水系に転相することにより、自己分散型の水系樹脂粒子を含有した樹脂分散液が得られる。より具体的には、例えば、攪拌機、還流冷却管、温度計、滴下ロート及び窒素ガス導入管を装備した反応器を準備し、有機溶剤に溶解した縮重合系樹脂に、中和剤等を加え、酸基をイオン化し(すでにイオン化されている場合は不要)、次いで水を加えた後、有機溶剤を留去して水系に転相することにより得られる。有機溶剤への溶解、中和剤の添加は、通常溶剤、特に、有機溶剤の沸点以下の温度で行い、また、ここで用いられる水としては、例えばイオン交換水等が挙げられる。
[Method b]
In the method b, for example, a polycondensation resin is dissolved in an organic solvent, a neutralizing agent is added to ionize the acid groups of the polycondensation resin, and then water is added. By phase inversion, a resin dispersion containing self-dispersing water-based resin particles can be obtained. More specifically, for example, a reactor equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction pipe is prepared, and a neutralizing agent is added to the condensation polymerization resin dissolved in the organic solvent. It is obtained by ionizing an acid group (not required if already ionized), adding water, and then distilling off the organic solvent to invert to an aqueous system. The dissolution in the organic solvent and the addition of the neutralizing agent are usually performed at a temperature not higher than the boiling point of the solvent, particularly the organic solvent, and examples of the water used here include ion-exchanged water.
有機溶剤としては、乳化性の観点からケトン系溶剤が好ましく、ケトン系溶剤としては、例えば、アセトン、メチルエチルケトン、ジエチルケトン、ジプロピルケトン、メチルイソブチルケトン、メチルイソプロピルケトン等が挙げられ、好ましくは、メチルエチルケトンである。 As the organic solvent, a ketone solvent is preferable from the viewpoint of emulsification, and examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, and the like. Methyl ethyl ketone.
また、中和剤としては、例えばアンモニア水、水酸化ナトリウム等のアルカリ水溶液、アリルアミン、イソプロピルアミン、ジイソプロピルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、2-エチルヘキシルアミン、3-エトキシプロピルアミン、ジイソブチルアミン、3-ジエチルアミノプロピルアミン、トリ-n-オクチルアミン、t-ブチルアミン、sec-ブチルアミン、プロピルアミン、メチルアミノプロピルアミン、ジメチルアミノプロピルアミン、n-プロパノールアミン、ブタノールアミン、2-アミノ-4-ペンタノール、2-アミノ-3-ヘキサノール、5-アミノ-4-オクタノール、3-アミノ-3-メチル-2-ブタノール、モノエタノールアミン、イソプロパノールアミン、ネオペンタノールアミン、ジグリコールアミン、エチレンジアミン、1,3-ジアミノプロパン、1,2-ジアミノプロパン、1,6-ジアミノヘキサン、1,9-ジアミノノナン、1,12-ジアミノドデカン、二量体脂肪酸ジアミン、2,2,4-トリメチルヘキサメチレンジアミン、2,4,4-トリメチルヘキサメチレンジアミン、ヘキサメチレンジアミン、N-アミノエチルピペラジン、N-アミノプロピルピペラジン、N-アミノプロピルジピペリジプロパン、ピペラジン等のアミン類等が挙げられる。これらの中和剤の使用量は、少なくとも縮重合系樹脂の酸価を中和できる量であれば良い。 Examples of the neutralizing agent include aqueous alkaline solutions such as aqueous ammonia and sodium hydroxide, allylamine, isopropylamine, diisopropylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3- Diethylaminopropylamine, tri-n-octylamine, t-butylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, n-propanolamine, butanolamine, 2-amino-4-pentanol, 2 -Amino-3-hexanol, 5-amino-4-octanol, 3-amino-3-methyl-2-butanol, monoethanolamine, isopropanolamine, neopentanolamine, diglycolamine, ethylenediamine, 1,3-diamin Propane, 1,2-diaminopropane, 1,6-diaminohexane, 1,9-diaminononane, 1,12-diaminododecane, dimer fatty acid diamine, 2,2,4-trimethylhexamethylenediamine, 2,4, Examples include amines such as 4-trimethylhexamethylenediamine, hexamethylenediamine, N-aminoethylpiperazine, N-aminopropylpiperazine, N-aminopropyldipiperidipropane, and piperazine. These neutralizing agents may be used in an amount that can neutralize at least the acid value of the condensation polymerization resin.
このようにして得られる樹脂分散液中の水系樹脂粒子の数平均分子量は、2,500〜70,000が好ましい。 The number average molecular weight of the aqueous resin particles in the resin dispersion thus obtained is preferably 2,500 to 70,000.
樹脂粒子の体積平均粒径(D4)は、本発明の樹脂分散液を用いてトナーを製造する場合は、均一に凝集させる観点から、0.05〜3μmが好ましく、0.05〜1μmがより好ましく、0.05〜0.8μmがさらに好ましい。本発明において樹脂粒子の体積平均粒径(D4)とは、本発明において体積平均粒径(D4)とは、体積分率(全粒子の体積に対する、ある粒径をもった粒子が占める体積の割合)で計算した平均粒径を意味し、レーザー回折型粒径測定機等により測定できる。 The volume average particle diameter (D 4 ) of the resin particles is preferably 0.05 to 3 μm, more preferably 0.05 to 1 μm, more preferably 0.05 to 1 μm from the viewpoint of uniformly agglomerating when the resin dispersion of the present invention is used to produce a toner. More preferably, it is ˜0.8 μm. The volume average particle diameter of the resin particles in the present invention (D 4) is provided with a volume average particle diameter in the present invention (D 4), to the volume of the volume fraction (all particles occupy particles having a certain particle size Mean particle diameter calculated by volume ratio), which can be measured by a laser diffraction particle size measuring machine or the like.
本発明のトナー用樹脂分散液を用い、樹脂分散液中で樹脂粒子を凝集、合一させる工程を含む方法により本発明の電子写真用トナーが得られる。 The toner for electrophotography of the present invention can be obtained by a method including the step of agglomerating and coalescing resin particles in the resin dispersion using the resin dispersion for toner of the present invention.
なお、トナーには、本発明の効果を損なわない範囲で、公知の結着樹脂、例えば、スチレン-アクリル樹脂等のビニル系樹脂、エポキシ樹脂、ポリカーボネート、ポリウレタン等の他の樹脂が併用されていてもよいが、本発明の縮重合系樹脂の含有量は、結着樹脂中、70重量%以上が好ましく、80重量%以上がより好ましく、90重量%以上がさらに好ましく、実質的に100重量%であることがさらに好ましい。 In the toner, a known binder resin, for example, a vinyl resin such as a styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like is used in combination as long as the effects of the present invention are not impaired. However, the content of the condensation polymerization resin of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and substantially 100% by weight in the binder resin. More preferably.
トナーには、さらに、着色剤、離型剤、荷電制御剤、磁性粉、流動性向上剤、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、老化防止剤、クリーニング性向上剤等の添加剤が適宜含有されていてもよい。 The toner further includes a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, an extender, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, Additives such as a cleaning property improving agent may be appropriately contained.
着色剤としては、トナー用着色剤として用いられている染料、顔料等のすべてを使用することができ、カーボンブラック、フタロシアニンブルー、パーマネントブラウンFG、ブリリアントファーストスカーレット、ピグメントグリーンB、ローダミン−Bベース、ソルベントレッド49、ソルベントレッド146、ソルベントブルー35、キナクリドン、カーミン6B、ジスアゾエロー等が用いることができ、本発明のトナーは、黒トナー、カラートナーのいずれであってもよい。着色剤の含有量は、結着樹脂100重量部に対して、1〜40重量部が好ましく、2〜10重量部がより好ましい。 As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
着色剤、荷電制御剤等の添加剤等、本発明の樹脂分散液以外のトナー原料は、樹脂分散液を調製する際に縮重合系樹脂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、樹脂粒子と混合し、凝集工程に供してもよい。樹脂粒子を調製する際に縮重合系樹脂に添加剤を予め混合する場合には、予め縮重合系樹脂と添加剤とを溶融混錬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本のロールが並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。従って、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、従来用いられている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。 Toner raw materials other than the resin dispersion of the present invention, such as additives such as a colorant and a charge control agent, may be premixed in the condensation polymerization resin when preparing the resin dispersion, and each additive is added separately with water. A dispersion liquid dispersed in a dispersion medium such as the like may be prepared, mixed with resin particles, and subjected to an aggregation step. When the additive is previously mixed with the condensation polymerization resin when preparing the resin particles, it is preferable to melt and knead the condensation polymerization resin and the additive in advance. For melt kneading, it is preferable to use an open roll type biaxial kneader. The open roll type twin-screw 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. The heat of kneading generated can be easily dissipated.
樹脂粒子を凝集させる凝集工程における系内の固形分濃度は、縮重合系樹脂の分散液に水を添加して調整することができ、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%がさらに好ましい。 The solid content concentration in the system in the aggregation process for aggregating the resin particles can be adjusted by adding water to the dispersion of the condensation polymerization resin, and 5 to 50% by weight is required to cause uniform aggregation. Preferably, 5 to 30% by weight is more preferable, and 5 to 20% by weight is more preferable.
凝集工程における系内のpHは、混合液の分散安定性と、縮重合系樹脂等の微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がさらに好ましい。 The pH in the system in the aggregation step is preferably 2 to 10, more preferably 2 to 9, more preferably 3 to 8 from the viewpoint of achieving both the dispersion stability of the mixed solution and the aggregation property of fine particles such as a condensation polymerization resin. Is more preferable.
同様の観点から、凝集工程における系内の温度は、縮重合系樹脂の軟化点−60℃以上、軟化点以下が好ましい。 From the same viewpoint, the temperature in the system in the aggregation process is preferably a softening point of the condensation polymerization resin of −60 ° C. or more and a softening point or less.
なお、樹脂粒子を凝集させる際には、樹脂粒子のみを凝集させるだけでなく(ホモ凝集)、別途、本発明の樹脂分散液と同様にして得られた他の樹脂微粒子の分散液等を樹脂粒子の分散液と混合し、樹脂粒子と他の樹脂微粒子とを凝集させてもよい(ヘテロ凝集)。 When the resin particles are aggregated, not only the resin particles are aggregated (homo-aggregation), but also a dispersion of other resin fine particles obtained in the same manner as the resin dispersion of the present invention is used as the resin. The resin particles and other resin fine particles may be aggregated by mixing with a particle dispersion (heteroaggregation).
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、ポリエチレンイミン等、無機系では、無機金属塩、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、硫酸アルミニウム等の金属塩、及びポリ塩化アルミニウム、ポリ水酸化アルミニウム、多硫化カルシウム等の無機金属塩重合体が挙げられる。 In the aggregation process, an aggregating agent can be added in order to effectively perform aggregation. As an aggregating agent, a quaternary salt cationic surfactant, polyethyleneimine, or the like is used in an organic system, and an inorganic metal salt, a divalent or higher metal complex, or the like is used in an inorganic system. Examples of inorganic metal salts include metal salts such as sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, polyaluminum chloride, polyaluminum hydroxide, Examples thereof include inorganic metal salt polymers such as calcium sulfide.
凝集剤の使用量は、トナーの耐環境特性の観点から、縮重合系樹脂100重量部に対して、30重量部以下が好ましく、20重量部以下がより好ましく、10重量部以下がさらに好ましい。 The amount of the flocculant used is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less with respect to 100 parts by weight of the condensation polymerization resin from the viewpoint of environmental resistance characteristics of the toner.
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攪拌することが好ましい。 The flocculant is preferably added after being dissolved in an aqueous medium, and is preferably sufficiently stirred at the time of addition of the flocculant and after completion of the addition.
続いて、前記凝集工程で得られた少なくとも縮重合系樹脂を含有した凝集粒子を加熱して、合一させる(合一工程)。 Subsequently, the agglomerated particles containing at least the condensation polymerization resin obtained in the agglomeration step are heated and coalesced (a coalescence step).
合一工程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、縮重合系樹脂の軟化点−30℃以上、軟化点+10℃以下が好ましく、軟化点−25℃以上、軟化点+10℃以下がより好ましく、軟化点−20℃以上、軟化点+10℃以下がさらに好ましい。また、攪拌速度は凝集粒子が沈降しない速度が好ましい。 The temperature in the system in the coalescence process is such that the softening point of the condensation polymerization resin is −30 ° C. or higher, and the softening point is + 10 ° C. The softening point is preferably −25 ° C. or higher, the softening point + 10 ° C. or lower is more preferable, and the softening point −20 ° C. or higher and the softening point + 10 ° C. or lower is more preferable. The stirring speed is preferably a speed at which the aggregated particles do not settle.
得られた合一粒子を、適宜、ろ過などの固液分離工程、洗浄工程、乾燥工程に供することにより、トナーを得ることができる。 The toner can be obtained by subjecting the obtained coalesced particles to a solid-liquid separation step such as filtration, a washing step, and a drying step as appropriate.
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。 In the washing step, it is preferable to use an acid in order to remove metal ions on the toner surface 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.
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、さらには1.0重量%以下に調整することが好ましい。 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.
本発明のトナーの体積中位粒径(D50)は、3〜15μmが好ましく、3〜10μmがより好ましい。なお、本明細書において、体積中位粒径(D50)とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して50%になる粒径を意味する。トナーの表面には、疎水性シリカ等の外添剤が添加されていてもよい。 The volume median particle size (D 50 ) of the toner of the present invention is preferably 3 to 15 μm, more preferably 3 to 10 μm. In the present specification, the volume-median particle size (D 50 ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. An external additive such as hydrophobic silica may be added to the surface of the toner.
本発明のトナーは、一成分現像用トナーとして、又はキャリアと混合して二成分現像剤として用いることができる。 The toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.
〔樹脂の軟化点〕
フローテスター(島津製作所、CFT-500D)を用い、1gの試料を昇温速度6℃/分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルから押出する。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する。
[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min, and a 1.96 MPa load is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.
〔樹脂のガラス転移点〕
示差走査熱量計(セイコー電子工業社製、DSC210)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℃/分で0℃まで冷却したサンプルを昇温速度10℃/分で昇温し、吸熱の最高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とする。
[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and from that temperature to 0 ° C at a rate of 10 ° C / min. The temperature of the cooled sample is raised at a heating rate of 10 ° C / min, and the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent that indicates the maximum slope from the peak rise to the peak apex To do.
〔樹脂粒子の粒径〕
レーザー回折型粒径測定機「LA-920」(HORIBA製)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平均粒径(D4)を測定する。粒度分布は、CV値(粒度分布の標準偏差/体積平均粒径(D4)×100)で示す。
[Particle size of resin particles]
Using a laser diffraction particle size analyzer “LA-920” (manufactured by HORIBA), distilled water is added to the measurement cell, and the volume average particle size (D 4 ) is measured at a concentration at which the absorbance falls within an appropriate range. The particle size distribution is indicated by a CV value (standard deviation of particle size distribution / volume average particle size (D 4 ) × 100).
〔トナーの体積中位粒径(D50)〕
測定機:コールターマルチサイザーII(ベックマンコールター社製)
アパチャー径:50μm
解析ソフト:コールターマルチサイザーアキュコンプ バージョン 1.19(ベックマンコールター社製)
電解液:アイソトンII(ベックマンコールター社製)
分散液:エマルゲン109P(花王社製、ポリオキシエチレンラウリルエーテル、HLB:13.6)5%電解液
分散条件:分散液5mlに測定試料10mgを添加し、超音波分散機にて1分間分散させ、その後、電解液25mlを添加し、さらに、超音波分散機にて1分間分散させる。
測定条件:ビーカーに電解液100mlと分散液を加え、3万個の粒子の粒径を20秒で測定できる濃度で、3万個の粒子を測定し、その粒度分布から体積中位粒径(D50)を求める。
[Volume-median particle diameter of toner (D 50 )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D 50).
樹脂製造例1〜8
ポリオキシプロピレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン5145g、ポリオキシエチレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン2048g、テレフタル酸2092g、表1に示す触媒及びピロガロール化合物を、窒素導入管、脱水管、攪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、235℃で酸価が10mgKOH/gに達するまで縮重合反応させた後、180℃まで温度を下げ、フマル酸901g及びハイドロキノン5gを添加し、180℃から210℃まで3時間かけて昇温しながら反応させ、210℃に到達した後、さらに8kPaにて反応し、樹脂A〜Hを得た。なお、いずれの樹脂も、軟化点が105℃、ガラス転移点が61℃であった。
Resin production examples 1-8
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 5145 g, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2048 g, terephthalic acid 2092 g, as shown in Table 1 Put the catalyst and pyrogallol compound into a 10-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, and perform condensation polymerization in a nitrogen atmosphere at 235 ° C until the acid value reaches 10 mgKOH / g. After the reaction, the temperature was lowered to 180 ° C., 901 g of fumaric acid and 5 g of hydroquinone were added, and the reaction was carried out while raising the temperature from 180 ° C. to 210 ° C. over 3 hours. After reaching 210 ° C., further at 8 kPa Reaction was carried out to obtain resins A to H. All the resins had a softening point of 105 ° C. and a glass transition point of 61 ° C.
実施例A1〜A7及び比較例A1
攪拌機、還流冷却器、滴下ロート、温度計及び窒素導入管を備えた5リットル容の容器にメチルエチルケトン600gを投入し、表2に示す樹脂 200gを室温にて添加し、溶解させた。得られた溶液に、トリエチルアミン10gを添加して中和し、続いてイオン交換水2000gを添加した後、250r/minの攪拌速度で、減圧下、50℃以下の温度でメチルエチルケトンを留去し、自己分散型の水系樹脂粒子が分散した樹脂分散液(樹脂含有量:9.6重量%(固形分換算))を得た。得られた樹脂分散液中に分散する樹脂粒子の体積平均粒径(D4)は0.096μmであった。
Examples A1 to A7 and Comparative Example A1
600 g of methyl ethyl ketone was put into a 5 liter container equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube, and 200 g of the resin shown in Table 2 was added and dissolved at room temperature. The resulting solution was neutralized by adding 10 g of triethylamine, and then 2000 g of ion exchange water was added, and then methyl ethyl ketone was distilled off at a temperature of 50 ° C. or lower under reduced pressure at a stirring speed of 250 r / min. A resin dispersion (resin content: 9.6% by weight (in terms of solid content)) in which self-dispersing water-based resin particles are dispersed was obtained. The volume average particle diameter (D 4 ) of the resin particles dispersed in the obtained resin dispersion was 0.096 μm.
銅フタロシアニン(大日精化社製)50g、ノニオン性界面活性剤(エマルゲン150、花王(株)製)5g及びイオン交換水200gを混合し、銅フタロシアニンを溶解させ、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。 Copper phthalocyanine (manufactured by Dainichi Seika Co., Ltd.) 50 g, nonionic surfactant (Emulgen 150, manufactured by Kao Corporation) 5 g and ion-exchanged water 200 g are mixed, copper phthalocyanine is dissolved, and dispersed using a homogenizer for 10 minutes. Thus, a dispersed colorant dispersion was obtained.
パラフィンワックス(HNP0190、日本精蝋(株)製、融点:85℃)50g、カチオン性界面活性剤(サニゾールB50、花王(株)製)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、パラフィンワックスが平均粒径550nmで分散した離型剤分散液を得た。 Paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point: 85 ° C) 50g, cationic surfactant (Sanisol B50, manufactured by Kao Corp.) 5g and ion-exchanged water 200g are heated to 95 ° C and homogenizer. Was used to disperse the paraffin wax, followed by dispersion with a pressure discharge type homogenizer to obtain a release agent dispersion in which the paraffin wax was dispersed with an average particle size of 550 nm.
荷電制御剤(ボントロンE-84、オリエント化学工業社製)50g、ノニオン性界面活性剤(エマルゲン150、花王(株)製)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、荷電制御剤が平均粒径500nmで分散した荷電制御剤分散液を調製したが、分散液中には粗大粒子の残留が観測された。 Mix the charge control agent (Bontron E-84, manufactured by Orient Chemical Co., Ltd.) 50 g, nonionic surfactant (Emulgen 150, manufactured by Kao Corporation) and 200 g of ion-exchanged water, use glass beads, sand grinder Was used for dispersion for 10 minutes to prepare a charge control agent dispersion in which the charge control agent was dispersed with an average particle size of 500 nm, and coarse particles remained in the dispersion.
得られた樹脂粒子分散液490g、着色剤分散液20g、離型剤分散液15g、荷電制御剤分散液g及びカチオン性界面活性剤(サニゾールB50、花王(株)製)2g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攪拌しながら48℃まで加熱した。さらに、48℃で1時間保持した後、体積中位粒径(D50)が7.0μmの凝集粒子が形成されていることが確認された。 490 g of the obtained resin particle dispersion, 20 g of the colorant dispersion, 15 g of the release agent dispersion, 15 g of the charge control agent dispersion, and 2 g of the cationic surfactant (Sanisol B50, manufactured by Kao Corporation) After mixing and dispersing in a stainless steel flask using a homogenizer, the flask was heated to 48 ° C. while stirring in the oil bath for heating. Furthermore, after maintaining at 48 ° C. for 1 hour, it was confirmed that aggregated particles having a volume median particle size (D 50 ) of 7.0 μm were formed.
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(ペレックスSS-L、花王(株)製)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、攪拌を継続しながら、5℃/minの速度で80℃まで加熱し、5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、得られた着色樹脂微粒子粉末の体積中位粒径(D50)は7.1μmであった。 After adding 3 g of an anionic surfactant (Perex SS-L, manufactured by Kao Corporation) to the aggregated particle dispersion in which the aggregated particles are formed, a reflux tube is attached to the stainless steel flask and stirring is continued. While heating to 80 ° C. at a rate of 5 ° C./min and holding for 5 hours, the aggregated particles were coalesced and fused. Thereafter, the mixture was cooled, the fused particles were filtered, washed thoroughly with ion-exchanged water, and then dried, whereby the volume median particle size (D 50 ) of the obtained colored resin fine particle powder was 7.1 μm.
得られた着色樹脂微粒子粉末100重量部に対して1.0重量部の疎水性シリカ(TS530、ワッカーケミー社製、個数平均粒子径:8nm)を添加し、ヘンシェルミキサーを用いて混合して外添し、シアントナーとした。得られたシアントナーの体積中位粒径(D50)は7.1μmであった。 1.0 part by weight of hydrophobic silica (TS530, manufactured by Wacker Chemie, number average particle size: 8 nm) is added to 100 parts by weight of the obtained colored resin fine particle powder, and the mixture is externally added using a Henschel mixer. Cyan toner was used. The resulting cyan toner had a volume-median particle size (D 50 ) of 7.1 μm.
なお、比較例A1では、樹脂分散液中に白色の沈殿物の析出が認められた。 In Comparative Example A1, white precipitates were observed in the resin dispersion.
実施例B1及び比較例B1
表2に示す樹脂 200g及び非イオン性界面活性剤(ポリオキシエチレンラウリルエーテル(EO=9モル付加)、曇点:98℃、HLB:15.3)100gを、5リットル容のステンレス容器中でカイ型の攪拌機で200r/minの攪拌下、170℃で溶融させた。内容物を非イオン性界面活性剤の曇点より3℃低い95℃で安定させ、カイ型の攪拌機で200r/minの攪拌下、中和剤として水酸化ナトリウム水溶液(濃度:5重量%)75.5gを滴下した。続いて、カイ型の攪拌機で300r/minの攪拌下、脱イオン水を6g/minで滴下し、計1624.5gを添加した。この間、系の温度は95℃に保持し、200メッシュ(目開き:105μm)の金網を通して、樹脂の乳化粒子が分散した樹脂分散液(樹脂乳化液)を得た。得られた樹脂分散液中の乳化粒子(樹脂粒子)の体積平均粒径(D4)は0.135μm、固形濃度は12.0重量%、金網上には樹脂成分は何も残らなかった。
Example B1 and Comparative Example B1
200 g of resin shown in Table 2 and 100 g of nonionic surfactant (polyoxyethylene lauryl ether (EO = 9 mol addition), cloud point: 98 ° C., HLB: 15.3) in a 5 liter stainless steel container The mixture was melted at 170 ° C. with stirring at 200 r / min. The contents were stabilized at 95 ° C, 3 ° C lower than the cloud point of the nonionic surfactant, and sodium hydroxide aqueous solution (concentration: 5% by weight) 75.5 as a neutralizer under stirring at 200r / min with a chi-type stirrer g was added dropwise. Subsequently, deionized water was added dropwise at 6 g / min with stirring at 300 r / min with a Kai-type stirrer, and a total of 1624.5 g was added. During this time, the temperature of the system was maintained at 95 ° C., and a resin dispersion (resin emulsion) in which resin emulsified particles were dispersed was obtained through a 200 mesh (mesh: 105 μm) wire mesh. The volume average particle diameter (D 4 ) of the emulsified particles (resin particles) in the obtained resin dispersion was 0.135 μm, the solid concentration was 12.0% by weight, and no resin component remained on the wire mesh.
得られた樹脂分散液400g(濃度:12.3重量%)、シアン顔料の水分散液40g(濃度:5重量%)及びパラフィンワックス(HNP-9、日本精蝋(株)製、融点:78℃)の水分散液7g(濃度:35重量%、非イオン性界面活性剤:エマルゲン108(花王(株)社製)5重量%、ワックスの分散径(体積中位粒径):0.30μm)を1リットル容の容器で室温下混合した。 400 g of the obtained resin dispersion (concentration: 12.3 wt%), 40 g of cyan pigment aqueous dispersion (concentration: 5 wt%) and paraffin wax (HNP-9, manufactured by Nippon Seiwa Co., Ltd., melting point: 78 ° C.) 7 g (concentration: 35 wt%, nonionic surfactant: Emulgen 108 (manufactured by Kao Corporation) 5 wt%, wax dispersion diameter (volume median particle size): 0.30 μm) The mixture was mixed at room temperature in a liter container.
次に、この混合物に凝集剤として塩化カルシウム1g分の水溶液を加え、炭酸ナトリウム水溶液(濃度:10重量%)でpH=7に調整した後、ホモミキサーを用いて、5000r/minの回転数で室温下1時間攪拌した。その結果、得られた混合分散液を1リットル容のオートクレーブに移し、90℃に加熱して500r/minで6時間攪拌し、凝集粒子を形成させた。 Next, an aqueous solution corresponding to 1 g of calcium chloride is added to this mixture as a flocculant, adjusted to pH = 7 with an aqueous sodium carbonate solution (concentration: 10% by weight), and then at a rotational speed of 5000 r / min using a homomixer. Stir at room temperature for 1 hour. As a result, the obtained mixed dispersion was transferred to a 1 liter autoclave, heated to 90 ° C. and stirred at 500 r / min for 6 hours to form aggregated particles.
その後、100℃に昇温し、さらに1時間攪拌して、凝集粒子を合一させた後、吸引ろ過工程、洗浄工程及び乾燥工程を経て着色樹脂微粒子粉末を得た。着色樹脂微粒子粉末の体積中位粒径(D50)は6.9μm、水分含量は0.3重量%であった。 Thereafter, the temperature was raised to 100 ° C., and the mixture was further stirred for 1 hour to coalesce the aggregated particles, and then colored resin fine particle powder was obtained through a suction filtration step, a washing step and a drying step. The volume median particle size (D 50 ) of the colored fine resin particle powder was 6.9 μm, and the water content was 0.3% by weight.
得られた着色樹脂微粒子粉末100重量部に対して1.0重量部の疎水性シリカ(TS530、ワッカーケミー社製、個数平均粒子径:8nm)を添加し、ヘンシェルミキサーを用いて混合して外添し、シアントナーとした。得られたシアントナーの体積中位粒径(D50)は6.9μmであった。 1.0 part by weight of hydrophobic silica (TS530, manufactured by Wacker Chemie, number average particle size: 8 nm) is added to 100 parts by weight of the obtained colored resin fine particle powder, and the mixture is externally added using a Henschel mixer. Cyan toner was used. The resulting cyan toner had a volume-median particle size (D 50 ) of 6.9 μm.
試験例1〔転写効率〕
カラープリンター「MICROLINE 5400」(沖データ社製)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を白紙に貼り付け、白紙に貼り付けたメンディングテープの色相を色差計「X-Rite」(X-Rite社製)で測定し、色差(ΔE)をもとに、転写効率を評価した。転写効率は、ΔEが4.0以下を良好とする。結果を表2に示す。
Test Example 1 [Transfer efficiency]
A solid image was printed by mounting toner on a color printer "MICROLINE 5400" (Oki Data). At this time, the amount of toner on the photoconductor for the solid image 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 tape is applied to the photoconductor after passing through the transfer portion. Then, 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 peeled and unused mending tapes are pasted on a blank sheet, and the hue of the mending tape stuck on the blank sheet is measured with a color difference meter “X-Rite” (manufactured by X-Rite). ) To evaluate the transfer efficiency. The transfer efficiency is good when ΔE is 4.0 or less. The results are shown in Table 2.
以上の結果より、ピロガロール化合物を助触媒として用いて得られたポリエステルを使用した実施例のトナーは、比較例のトナーと対比して樹脂粒子の粒径が小さく、粒度分布もシャープであり、転写効率に優れていることが分かる。また、ピロガロール化合物を助触媒として用いて得られたポリエステルを使用することにより、有機溶剤を使用した実施例B1の方法でも、沈殿物の析出もなく良好な樹脂分散液が得られる。 From the above results, the toner of the example using the polyester obtained by using the pyrogallol compound as a co-catalyst has a small particle size of the resin particles and a sharp particle size distribution as compared with the toner of the comparative example, and the transfer It turns out that it is excellent in efficiency. In addition, by using a polyester obtained using a pyrogallol compound as a cocatalyst, even in the method of Example B1 using an organic solvent, a good resin dispersion can be obtained without precipitation.
本発明のトナー用樹脂分散液を用いて得られた電子写真用トナーは、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像等に用いられる。 The electrophotographic toner obtained by using the resin dispersion for toner of the present invention is used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.
Claims (6)
で表される、請求項1記載のトナー用樹脂分散液。 The pyrogallol compound has the formula (I):
The resin dispersion for toner according to claim 1, represented by:
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