JPS6370861A - Resin dispersion for electrophotographic developer - Google Patents
Resin dispersion for electrophotographic developerInfo
- Publication number
- JPS6370861A JPS6370861A JP61216119A JP21611986A JPS6370861A JP S6370861 A JPS6370861 A JP S6370861A JP 61216119 A JP61216119 A JP 61216119A JP 21611986 A JP21611986 A JP 21611986A JP S6370861 A JPS6370861 A JP S6370861A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- resin dispersion
- formula
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006185 dispersion Substances 0.000 title claims description 44
- 239000011347 resin Substances 0.000 title claims description 40
- 229920005989 resin Polymers 0.000 title claims description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 21
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 16
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 238000010992 reflux Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- -1 innonyl 7-acrylate Chemical compound 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 8
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 8
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- 230000000740 bleeding effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZZKYRALDQPIHDZ-UHFFFAOYSA-N 2-(2-sulfanylethoxymethoxy)ethanethiol Chemical compound SCCOCOCCS ZZKYRALDQPIHDZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MLFIYYDKLNZLAO-UHFFFAOYSA-N 2-aminoethane-1,1-diol Chemical compound NCC(O)O MLFIYYDKLNZLAO-UHFFFAOYSA-N 0.000 description 1
- ILZXXGLGJZQLTR-UHFFFAOYSA-N 2-phenylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=CC=C1 ILZXXGLGJZQLTR-UHFFFAOYSA-N 0.000 description 1
- YHCCCMIWRBJYHG-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane Chemical compound CCCCC(CC)COCC(CC)CCCC YHCCCMIWRBJYHG-UHFFFAOYSA-N 0.000 description 1
- PKBZUGSITIBLFK-UHFFFAOYSA-N 3-phenylpropyl prop-2-enoate Chemical compound C=CC(=O)OCCCC1=CC=CC=C1 PKBZUGSITIBLFK-UHFFFAOYSA-N 0.000 description 1
- HKJKONMZMPUGHJ-UHFFFAOYSA-N 4-amino-5-hydroxy-3-[(4-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=C(N=NC=3C=CC=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 HKJKONMZMPUGHJ-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- JHHASXMVMHKBLP-UHFFFAOYSA-N Bennol Natural products C1CC(C2)(CO)C=CC32C(O)CC2C(C)(C)CCCC2(C)C31 JHHASXMVMHKBLP-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- WLKAMFOFXYCYDK-UHFFFAOYSA-N [5-amino-4-[[3-[(2-amino-4-azaniumyl-5-methylphenyl)diazenyl]-4-methylphenyl]diazenyl]-2-methylphenyl]azanium;dichloride Chemical compound [Cl-].[Cl-].CC1=CC=C(N=NC=2C(=CC([NH3+])=C(C)C=2)N)C=C1N=NC1=CC(C)=C([NH3+])C=C1N WLKAMFOFXYCYDK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- LHASDYYYQWRSQC-UHFFFAOYSA-N but-1-ene-1-thiol Chemical compound CCC=CS LHASDYYYQWRSQC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRJIBMFDBVWHBJ-UHFFFAOYSA-N cycloheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCCC1 KRJIBMFDBVWHBJ-UHFFFAOYSA-N 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- VRFCNQCFVJBFMC-UHFFFAOYSA-N cyclooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCCCC1 VRFCNQCFVJBFMC-UHFFFAOYSA-N 0.000 description 1
- JXVKENWQKWGKOL-UHFFFAOYSA-N cyclooctyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCCCC1 JXVKENWQKWGKOL-UHFFFAOYSA-N 0.000 description 1
- WRAABIJFUKKEJQ-UHFFFAOYSA-N cyclopentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCC1 WRAABIJFUKKEJQ-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- BTQLDZMOTPTCGG-UHFFFAOYSA-N cyclopentyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCC1 BTQLDZMOTPTCGG-UHFFFAOYSA-N 0.000 description 1
- JVGAAIQCXGCLJH-UHFFFAOYSA-N cyclopropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CC1 JVGAAIQCXGCLJH-UHFFFAOYSA-N 0.000 description 1
- JUZDVEMPFDZWNY-UHFFFAOYSA-N cyclopropyl prop-2-enoate Chemical compound C=CC(=O)OC1CC1 JUZDVEMPFDZWNY-UHFFFAOYSA-N 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Liquid Developers In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
痩ａｈａすυ１盆！−二
本発明は電子写真液体現像剤に有用な新規な樹脂号ａ液
を提出するものであり、本発明の樹脂分散液を用い姓電
子写真液体現像剤は顔料の分散性がよいので画像のにじ
みが少なく且つ地汚れが少なくて製版枚数が多くなるの
で、オフセットマスター用やカラー電子複写用等に極め
て適している。[Detailed description of the invention] Lose weight ahasu υ1 Bon! -2 The present invention proposes a new resin No. A liquid useful for electrophotographic liquid developers. The electrophotographic liquid developer using the resin dispersion of the present invention has good pigment dispersibility, so that images can be improved. It is extremely suitable for use in offset mastering, color electronic copying, etc., since there is little bleeding and background smearing, and the number of platelets can be increased.
従遂！す支庸−：
従来、電子写真液体現像剤用の樹脂分散液としては、低
誘電率で＾電気絶縁性の有機溶媒（以下「媒体」という
）中の重合体に該媒体に不溶性の重合体を生成する単量
体をグラフト重合させることによって得られる樹脂分散
液が提案されていたが（例：ｕｆｆｉ昭５３−５４０２
９号）、コノヨうな樹脂分散液の製造法は煩雑であると
ともに現像剤としたときにしばしばゲルの生成を起こし
、安定な現像剤となる分散液を得難い等の問題点があっ
た。Obey! Traditionally, resin dispersions for electrophotographic liquid developers have been prepared using polymers in an organic solvent (hereinafter referred to as "medium") that has a low dielectric constant and electrical insulation properties, and are insoluble in the medium. A resin dispersion obtained by graft polymerization of a monomer that produces
No. 9), the method for producing a resin dispersion liquid is complicated, and when used as a developer, gels often form, making it difficult to obtain a dispersion liquid that can be used as a stable developer.
グラフト重合体の樹脂分散液の上記のような欠点を改良
する試みが近年行われるようになり、媒体に可溶性重合
体及び媒体と不溶性重合体とからなり、これ等重合体の
双方に−ＣＯＯＨ，−８ＯｓＨ又は−〇 〇 〇 ＣＨ
５等の極性官能基を含有させることによって、可溶性重
合体の極性官能基と不溶性重合体の極性官能基との間の
吸着能を利用し樹脂分散液の安定性を改善する技術が開
示されている（例：特開昭５９−８３１７４号）。Attempts have been made in recent years to improve the above-mentioned drawbacks of resin dispersions of graft polymers, which consist of a polymer soluble in the medium and a polymer insoluble in the medium, and both of these polymers contain -COOH, -8OsH or -〇 〇 〇 CH
A technique has been disclosed in which the stability of a resin dispersion is improved by incorporating a polar functional group such as No. (Example: Japanese Patent Application Laid-Open No. 59-83174).
発明が解決しようとする問題点：
しかしながら、本発明者等の研究の結果、上記のような
単に極性官能基を可溶性重合体及び不溶性重合体に持た
せた樹脂分散液では安定性は成る程度向上するものの、
画像のにじみ（輪郭のぼけ）や地汚れが屡々発生し、特
にオフセットマスター用電子写真液体現像剤に用いた場
合製版枚ｖ！Ｌ（以下現像液の製飄性という）が必ずし
も多くとれない等の問題があることが判ってきた。Problems to be Solved by the Invention: However, as a result of the research conducted by the present inventors, it has been found that the stability of a resin dispersion in which a soluble polymer and an insoluble polymer are simply provided with polar functional groups as described above can be improved to a certain extent. However,
Image bleeding (blurred outlines) and background smudges often occur, especially when used as an electrophotographic liquid developer for offset masters. It has been found that there are problems such as not necessarily being able to obtain a large amount of L (hereinafter referred to as developing ability).
本発明は従来技術の有する上記の問題点を解決し、安定
性が良好で、画像のにじみや地汚れも無く、しかも現像
液の製版性にすぐれた電子写真液体現像剤用の樹脂分子
！ｌＣ液を提供するものである。The present invention solves the above-mentioned problems of the prior art, and provides resin molecules for electrophotographic liquid developers that have good stability, no image bleeding or background smearing, and have excellent developer plate-making properties! It provides LC liquid.
ｌＩ ヴ するための− ：
本発明によれば、高絶縁性炭化水素媒体中に、（Ａ）
イ）式Ｉ
［こｔで、Ｘｌは水素又はメチルを表わし、Ｙは一〇
〇 ＯＲ＋ 、ＯＣＯＲｌ又は−ＯＲ，、好ましくは−
ＧＯＯＲ，又−０ＣＯＲ，、最ら好ましくは一〇〇ＯＲ
，を表わし、Ｒ，はＣ４〜Ｃ２゜、好ましくはＣ＠〜Ｃ
１２、最も好ましくはＣ１のアルキルを表わす１
の単量体８０〜５０重景部、好ましくは７５〜６０重量
部
口）式■
［こ）でｘ２は水素又はメチルを表わし、Ｒ２はＣコ〜
Ｃｓのシクロアルキル又はアルキル部分がＣｌ−０３で
あるアラルキルを表わす］の単量体２０〜５０重量部、
好ましくは２５〜４０重１１Ｒ（ただし、上記イ）及び
口）の合計が１００重量部となる）及び
ハ）少なくとも１つのチオール基をもつ有機メルカプタ
ンを硫黄含有量で０．０３〜２重量％、好ましくは０．
０３〜１重景％（ただし、イ）、口）及びハ）の合計当
りの硫黄含有量の重量％とする）
を含有してなる前記媒体に実質的に可溶性の共重合体及
び
（［１） 二）酢酸ビニール９７〜５０重量部、好ま
しくは９０〜６０重量部及び
ホ）弐■
［こ）で％ Ｘ ３は水素又はメチルを表わし、Ｒ１は
Ｃ４〜Ｃ２０ｑ好ましくはＣＩ ”” ＣＩ ！、最も
好ましくはＣ１のフルキル又はアルキル又はＣ３〜Ｃ，
のシクロアルキルを表わす１の単量体３〜５０重量部、
好ましくは１０〜４０重ｆｉｆ！ＩＳ（ただし、上記二
）及びホ）の合計が１００重量部となる）
を含有してなる前記媒体に実質的に不溶性の共重合体、
を含んでなることを特徴とするオフセットマスター用電
子写真現像剤に適した樹脂分散液が提供される。According to the present invention, in a highly insulating hydrocarbon medium, (A)
b) Formula I [In this, Xl represents hydrogen or methyl, and Y is 10
〇OR+, OCORl or -OR, preferably -
GOOR, also -0COR, most preferably 100OR
, R represents C4~C2°, preferably C@~C
12, most preferably C1 represents an alkyl monomer 80 to 50 parts by weight, preferably 75 to 60 parts by weight;
20 to 50 parts by weight of a monomer of cycloalkyl or aralkyl in which the alkyl moiety of Cs is Cl-03,
Preferably 25 to 40 parts by weight 11R (however, the total of the above a) and part) is 100 parts by weight) and c) an organic mercaptan having at least one thiol group with a sulfur content of 0.03 to 2% by weight, Preferably 0.
A copolymer substantially soluble in the medium containing a copolymer containing 03 to 1 weight percent (the weight percent of the sulfur content based on the sum of a), a), and a); ) 2) 97 to 50 parts by weight of vinyl acetate, preferably 90 to 60 parts by weight; and e) 2) % X 3 represents hydrogen or methyl, and R1 is C4 to C20q, preferably CI ``'' CI! , most preferably C1 furkyl or alkyl or C3-C,
3 to 50 parts by weight of monomer 1 representing cycloalkyl;
Preferably 10 to 40 times fif! IS (provided that the total of the above 2) and 5) is 100 parts by weight); a copolymer substantially insoluble in the medium; A resin dispersion suitable for a developer is provided.
本発明の電子写真現像剤用樹脂分散液は、好適には、該
可溶性の共重合体１重量部〜２ｏ重量部未満、好ましく
は１〜１５重量部、最も好ましくは５〜１０重量部に対
して、該不溶性の共重合体９９重量部〜８０重景部、好
ましくは９９〜８５重量部、最も好ましくは９５〜９０
ｆｉ量部（但し両者の合計が１００重量部となる）を含
有する。The resin dispersion for electrophotographic developers of the present invention is suitably based on 1 part to less than 20 parts by weight, preferably 1 to 15 parts by weight, most preferably 5 to 10 parts by weight of the soluble copolymer. 99 to 80 parts by weight of the insoluble copolymer, preferably 99 to 85 parts by weight, most preferably 95 to 90 parts by weight.
fi parts (however, the total of both is 100 parts by weight).
可溶性の共重合体が１重量部未満と少なすぎては分散液
の安定性が悪くなったり画像のにじみが生じるので好ま
しくなく、一方可溶性の共重合体が２０重量部以上と多
すぎてはオフセットマスター用現像液として用いた場合
印刷物の地汚れが生じたり現像液の製版性が悪くなるの
で好ましくない。If the amount of the soluble copolymer is too small (less than 1 part by weight), the stability of the dispersion will deteriorate and the image will smear, which is undesirable, while if the amount of the soluble copolymer is too large (20 parts by weight or more), offset will occur. When used as a master developer, it is not preferable because it causes background smearing on printed matter and impairs the plate-making properties of the developer.
本発の電子写真現像剤用樹脂分散液の更に好適な態様で
は、特許請求の範囲第２項における可溶性共重合体の重
電部数と特許請求の範囲第１項における弐ＩＩＩの単量
体の重合部数の合計重量部数が１０〜３５重量部、好ま
しくは１５〜３０重量部、最も好ましくは１８〜３０重
量部である。該合計重量部数が１０重量部未満と少なす
ぎては分散液の安定性が悪くなるので好ましくなく、一
方３５重量部を超えて多過ぎてはオフセットマスター用
現像液として用いた場合も現像液の製版性や製版物の耐
刷性、印刷物の地汚れ等が生じるので好ましくない。In a more preferred embodiment of the resin dispersion for electrophotographic developers of the present invention, the number of heavy electric moieties of the soluble copolymer in claim 2 and the monomer II III in claim 1 are as follows. The total number of polymerized parts is 10 to 35 parts by weight, preferably 15 to 30 parts by weight, and most preferably 18 to 30 parts by weight. If the total number of parts by weight is too small (less than 10 parts by weight), the stability of the dispersion liquid will deteriorate, which is undesirable, while if it is too large (more than 35 parts by weight), the developer will become unstable even when used as a developer for offset masters. This is not preferable because it causes plate-making properties, printing durability of the plate-made product, background stains, etc. of the printed matter.
可溶性の共重合体に含有される前記式（１）の単量体と
しては、ｎ−ブチルメタクリレート、インブチルメタク
リレ−）、ｎ−へキシルメタクリレート、ｎ−オクチル
メタクリレート、２−エチル八１シ：＋１１−ノ々ｓ＋
１＋−Ｌａａ＾ＩＩＮ−ＪｊｔＡｌｌｌ−−ト、ステア
リルメタクリレ−Ｆ１イソデシルメタクリレート、イソ
ノニルメタクリレート等のメタクリレート、ｎ−ブチル
７クリレート、インブチル７クリレート、ｎ−へキシル
アクリレート、ｎ −オクチルアクリレート、２−エチ
ルへキシルアクリレート、ラウリル７クリレート、ステ
７リルアクリレート、゛イソデシルアクリレート、イン
ノニル７クリレート等の７クリレート、酪酸ビニール、
バーサチック酸ビニール等の脂肪酸ビニル及びビニル及
１ビニールｎブチルエーテル、ビニールイソブチルエー
テル、ビニルｎヘキシルエーテル、ビニルｎオチルエー
テル、ビニルや２エチルヘキシルエーテル等のビニール
エーテル等を例示することができる。Examples of the monomer of formula (1) contained in the soluble copolymer include n-butyl methacrylate, inbutyl methacrylate), n-hexyl methacrylate, n-octyl methacrylate, and 2-ethyl methacrylate. :+11-nos+
1+-Laa^IIN-JjtAll--, stearyl methacrylate-F1 methacrylates such as isodecyl methacrylate, isononyl methacrylate, n-butyl 7-acrylate, inbutyl 7-acrylate, n-hexyl acrylate, n-octyl acrylate, 2- 7-acrylates such as ethylhexyl acrylate, lauryl 7-acrylate, stethyl 7-acrylate, isodecyl acrylate, innonyl 7-acrylate, vinyl butyrate,
Examples include fatty acid vinyl and vinyl such as vinyl versatate, and vinyl ethers such as 1-vinyl n-butyl ether, vinyl isobutyl ether, vinyl n-hexyl ether, vinyl n-otyl ether, and vinyl and 2-ethylhexyl ether.
式（１）の単量体としては、ｎ−オクチルメタクリレー
ト、２−エチルへキシルツタクリレート又はバーサチッ
ク酸ビニールが好適であり、殊にｎ−オクチルメタクリ
レート又は２−二チルヘキシルメタクリレートが好適で
ある。As the monomer of formula (1), n-octyl methacrylate, 2-ethylhexyltutacrylate or vinyl versatate is preferred, and n-octyl methacrylate or 2-nitylhexyl methacrylate is particularly preferred.
可溶性の共重合体に含有される靜記式（Ｈ）め棗量体と
しては、シクロプロピルメタクリレート、シクロヘプチ
ルメタクリレート、シクロヘキシルメタクリレート、シ
クロペンチルメタクリレート、シクロオクチルメタクリ
レート等のシクロアルキルメタクリレート、シクロプロ
ピルアクリレート、シクロペンチルアクリレート、シク
ロヘキシルアクリレート、シクロペンチルアクリレート
、シクロオクチルアクリレート等のシクロアルキルアク
リレート、γ−７二二ルブロピルメタ？ ＋７１ｚ −
）、β−フェニルエチルメタクリレート、ベンジルメタ
クリレート等の７フルキルメタクリレート並びにγ１−
フェニルプロピルアクリレート、β−７二二ルエチルア
クリレート及びベンノルアクリレート等の７ラルキル７
クリレート等を例示することができる。Examples of the Yoshiki formula (H) polymer contained in the soluble copolymer include cycloalkyl methacrylates such as cyclopropyl methacrylate, cycloheptyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, and cyclooctyl methacrylate, cyclopropyl acrylate, and cyclopentyl. Acrylate, cycloalkyl acrylate such as cyclohexyl acrylate, cyclopentyl acrylate, cyclooctyl acrylate, γ-722bropyl meth? +71z -
), 7-furkyl methacrylates such as β-phenylethyl methacrylate, benzyl methacrylate, and γ1-
7ralkyl 7 such as phenylpropyl acrylate, β-72ndylethyl acrylate and bennolacrylate
Examples include acrylate.
好適な式（１１）の単量体はＣ１〜・ジクロフルキルメ
タクリレート、Ｃ１〜、シクロアルキルアクリレート、
ベンノルメタクリレートまたはベンジルアクリレートで
あり、殊にシクロヘキシルメタクリレート、トクロヘキ
シルアクリレート、ベンノルメタクリレートまたはベン
シル７クリレートが好適に用いられる。Suitable monomers of formula (11) include C1~-dichlorofurkyl methacrylate, C1~, cycloalkyl acrylate,
Bennol methacrylate or benzyl acrylate, particularly cyclohexyl methacrylate, tochlohexyl acrylate, bennor methacrylate or benzyl 7-acrylate, is preferably used.
可溶性の共重合体に含有される、少なくとも一つのチオ
ール基をもつ有機メルカプタンは分子当り１から約４個
までのチオール基をもちまたチオール基当り１から約１
２個の炭素原子、好ましくは２からａｍの炭素原子を含
む、これらの有機メルカプタンは炭化水素基に加えて他
の置換基を含むことができ、そのような置換基にはカル
ホキフル基、ヒドロキシ基、エーテル基、エステル基、
スルフィド基、アミン基およびアミド基が含まれるが、
カルボキシル基を置換基として有する有機メルカプタン
が画像のにじみが殆んど無くなるので特に好適である。The organic mercaptan containing at least one thiol group contained in the soluble copolymer has from 1 to about 4 thiol groups per molecule and from 1 to about 1 thiol group per molecule.
Containing 2 carbon atoms, preferably 2 to am carbon atoms, these organic mercaptans can contain other substituents in addition to the hydrocarbon group, such substituents include carphokyfur, hydroxy groups, etc. , ether group, ester group,
Includes sulfide groups, amine groups and amide groups,
Organic mercaptans having a carboxyl group as a substituent are particularly preferred since they cause almost no bleeding in images.
少（とも一つのチオール基をもつ有機メルカプタンの例
にはメチルメルカプタン、エチルメルカプタン、ブチル
メルカプタン、オクチルメルカプタン、ラウリルメルカ
プタン、メルカプトエタ／−ル、メルカプトエタノール
、メルカプトブタノール、メルカプト酢酸、メルカプト
プロピオン酸、チオリンゴ酸、ベンジルメルカプタン、
フェニルメルカプタン、シクロヘキシルメルカプタン、
２アミノエタンチオール、１−チオグリセロール、２．
２′−ノメルカブトジエチルエーテル、２．２’−ジメ
ルカプトノブロピルエーテル、２．２’−ジメルカブト
ノイソプロビルエーテル、３．３’−ジメルカプトノブ
ロピルエーテル、２．２’−ジメルカプトノエチルスル
フイド、３．３’−シメルカプトジブロビルスルフイド
、１．１１−ジメルカプ）−３，９−ジオキサ−６−チ
アウンデカン、ビス（β−メルカプトエトキシ）メタン
、ビス（β−メルカプトエチルチオ
１、２、７’ロパンノチオール−１，２、ブタンノチオ
ール１，４、３．４−ノメルカプトブタノールー１、ト
リメチロールエタントリ（３−フルカプトプロピオナー
ト）、ペンタエリトリトールテトラ（３−フルカプトプ
ロピオナート）、トリノ千ロールプロパントリチオグリ
コフートおよびペンタエリトリトールテトラチオグリコ
ラートが含まれる。Examples of organic mercaptans with at least one thiol group include methyl mercaptan, ethyl mercaptan, butyl mercaptan, octyl mercaptan, lauryl mercaptan, mercaptoethanol, mercaptoethanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, and thiolingo. acid, benzyl mercaptan,
phenyl mercaptan, cyclohexyl mercaptan,
2-aminoethanethiol, 1-thioglycerol, 2.
2'-Nomercaptonopropyl ether, 2.2'-dimercaptonopropyl ether, 2.2'-dimercaptonoisopropyl ether, 3.3'-dimercaptonopropyl ether, 2.2' -dimercaptonoethyl sulfide, 3,3'-cymercaptodibrovir sulfide, 1,11-dimercap)-3,9-dioxa-6-thioundecane, bis(β-mercaptoethoxy)methane, Bis(β-mercaptoethylthio 1,2,7'ropannothiol-1,2, butanenothiol 1,4,3.4-nomercaptobutanol-1, trimethylolethane tri(3-flucaptopropionate) , pentaerythritol tetra(3-flucaptopropionate), trinothylolpropane trithioglycofoot, and pentaerythritol tetrathioglycolate.
好適な有機メルカプタンとしては、メルカプト酢酸、メ
ルカプトプロピオン酸、チオリンゴ酸、ラウリルメルカ
プタン、メルカプトエタノール、２アミノエタンジオー
ル等を挙げることができ、殊にメルカプト酢酸又はメル
カプトプロピオン酸が好適である。Suitable organic mercaptans include mercaptoacetic acid, mercaptopropionic acid, thiomalic acid, lauryl mercaptan, mercaptoethanol, 2-aminoethanediol, and the like, with mercaptoacetic acid or mercaptopropionic acid being particularly preferred.
可溶性の共重合体は、該共重合体当りの硫黄含有量で０
，Ｏ’３〜２重景％、好ましくは０．０３〜１重量％の
有機メルカプタンを含有するものであるが、０．０３重
量％未満と少な過ぎては現像剤とした場合沈降安定性が
悪くなり且つ印刷物の地汚れが発生しがちなので好まし
くなく、また１重量％を超えて多過ぎても樹脂分散液の
安定性が低下するので好ましくない。The soluble copolymer has a sulfur content of 0 per copolymer.
, O' 3 to 2% by weight, preferably 0.03 to 1% by weight of organic mercaptan, but if it is too small (less than 0.03% by weight), the sedimentation stability may deteriorate when used as a developer. This is not preferable because it tends to deteriorate and cause scumming on printed matter, and it is also not preferable if the amount exceeds 1% by weight because the stability of the resin dispersion decreases.
可溶性の共重合体の分子量は、好ましくは３。The molecular weight of the soluble copolymer is preferably 3.
０００〜５０，０００、最も好ましくは８，０００〜ｓ
ｏ，ｏｏｏである。000-50,000, most preferably 8,000-s
o, ooo.
不溶性の共重合体に含有される式（ＩＩＩ）の単量体と
しては、可溶性の共重合体に含有される式（１）の単量
体について例示したのと同じアルキルメタクリレート及
びアルキル７クリレート及び式（Ｕ）の単量体について
例示したのと同じシクロアルキルメタクリレート及びシ
クロアルキル７クリレートを例示することができる。As the monomer of formula (III) contained in the insoluble copolymer, the same alkyl methacrylate and alkyl 7-acrylate as exemplified for the monomer of formula (1) contained in the soluble copolymer, The same cycloalkyl methacrylates and cycloalkyl 7-acrylates as exemplified for the monomer of formula (U) can be exemplified.
式（１）の単量体としては、ｎ−オクチルメタクリレー
ト、２−エチルへキシルメタクリレート、シクロヘキシ
ルメタクリレートまたはシクロヘキシルアクリレートが
好適である。As the monomer of formula (1), n-octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate or cyclohexyl acrylate is suitable.
本発明で用いられる高絶縁性炭化水素媒体は低誘電率で
高電気絶縁性の有機溶媒であり、そのような有機溶媒と
しては、／ルマルパラフィン系炭化水素、イソパラフィ
ン系炭化水素、脂環族炭化水素、ハロゲン化脂肪族炭化
水素等を例示することができ、臭気や安全性及び乾燥性
の点から殊に沸点が１５０〜２００℃のパラフィン系又
は脂環族炭化水素が好ましく、例えば、アイソパーＧＨ
。The highly insulating hydrocarbon medium used in the present invention is an organic solvent with a low dielectric constant and high electrical insulating properties. Examples include hydrogen, halogenated aliphatic hydrocarbons, and paraffinic or alicyclic hydrocarbons having a boiling point of 150 to 200°C are particularly preferred from the viewpoint of odor, safety, and drying properties, such as Isopar GH.
.
Ｋ及びＬ（エクソン化学製）、アイピーフルベント（出
光石油製）、シェルゾール７１（シェル石油製）等が好
適に使用できる。K and L (manufactured by Exxon Chemical), IP Fluvent (manufactured by Idemitsu Petroleum), Shellsol 71 (manufactured by Shell Petroleum), etc. can be suitably used.
本発明の樹脂分散液としては、分散粒子の粒度分布が０
．５μ以下が７０％以上、好ましくは９０％以上のもの
が好適に用いられる。The resin dispersion of the present invention has a particle size distribution of 0.
．． A material having a ratio of 5μ or less to 70% or more, preferably 90% or more is suitably used.
本発明のａｆｔ！ｆｆｆｔ縁は、一般に、媒体中の可溶
性共重合体の溶液の中で不溶性重合体の重合を行うこと
によって、容易に製造することができるが、可溶性共重
合体及び不溶性重合体を別途に製造しておいて、両型合
体の共通溶媒に両型合体を溶解してから炭イε水素？、
媒体中に攪拌上滴下する等の方法によっても適宜製造す
ることができる。aft of the present invention! ffft edges can generally be easily produced by polymerizing an insoluble polymer in a solution of a soluble copolymer in a medium, but it is also possible to produce the soluble copolymer and insoluble polymer separately. After dissolving both types of coalescence in a common solvent for both types of coalescence, carbon and ε hydrogen? ,
It can also be produced as appropriate by a method such as dropping it into a medium with stirring.
樹脂分散液の粒度分布は、可溶性共重合体と不溶性重合
体の割合を変九ることにより調節することができ、また
不溶性重合体中の式（［Ｉ［）のメタアクリレ−）また
はアクリレートの配合割合を変えることによっても調節
することができる。The particle size distribution of the resin dispersion can be adjusted by varying the ratio of the soluble copolymer to the insoluble copolymer, and the incorporation of the formula (methacrylate of formula [I[)] or acrylate in the insoluble copolymer). It can also be adjusted by changing the ratio.
本発明の樹脂分散液から電子写真液体現像剤を製造する
には、分散粒子を着色し、荷電を与えればよい。In order to produce an electrophotographic liquid developer from the resin dispersion of the present invention, the dispersed particles may be colored and charged.
分散粒子の着色には、一般に電子５３８１体現像剤に用
いられている着色剤が用いられる。そのような例として
は、オイルブラック、オイルレッド、ビスマルクブラウ
ン等の塩基性アゾ染料、ウールブラック、アミドブラッ
クグリーン、プリーブラックＨＦ等の酸性７ゾ染料、グ
イレックトデーブラックＥ１コンゴ−ジッド等の直接染
料、スータンバイオレット、アシッドブルー等の７ント
ラキノン系染料、オーラミン、マラカイトグリーン、ク
リスタルバイオレット、ビクトリアブリー等のカルボニ
ウム染料、ローダミンＢのようなローダミン染料、す７
ニン、ニグロシン、メチレンブルー等のキノンイミン染
料等の染料や下記の顔料を挙げることができる。顔料と
してはカーボンブラック、７タロシ７ニンプルー、ベン
ジンイエロー、ウオツシングレッド等が例示でさ、更に
ニグロシンやローダミンＢで染色して表面処理した顔料
等も用いることができる。To color the dispersed particles, a coloring agent that is generally used in electronic 5381 body developers is used. Examples of such dyes include basic azo dyes such as oil black, oil red, and Bismarck brown; acidic 7zo dyes such as wool black, amido black green, and puri black HF; and gylectoday black E1 congo dyes. Direct dyes, 7-anthraquinone dyes such as sootane violet and acid blue, carbonium dyes such as auramine, malachite green, crystal violet, and Victoria Brie, rhodamine dyes such as Rhodamine B, etc.
Examples include dyes such as quinone imine dyes such as nigrosine, methylene blue, and the following pigments. Examples of pigments include carbon black, 7-taloshi 7-nin blue, benzine yellow, and washing red. Pigments that have been surface-treated by dyeing with nigrosine or rhodamine B can also be used.
樹脂分散液の着色法は、一般に染料溶液を調製して樹脂
分散液中に攪拌上滴下する方法を用いることができる。As a method for coloring the resin dispersion, a method can generally be used in which a dye solution is prepared and added dropwise into the resin dispersion while stirring.
染料に対する溶媒としては前記媒体と混和し、更に比較
的絶縁性を有し且つ高沸点の溶媒が好ましい。The solvent for the dye is preferably a solvent that is miscible with the medium, has relatively insulating properties, and has a high boiling point.
本発明の樹脂分散液の荷電には、荷電制御剤が用いられ
るが、その上うな電荷制御剤としては、ナフテン酸亜鉛
、ナフテン酸マンガン、オレイン酸銅、オクチル酸コバ
ルト、レシチン、ノオクチルスルホコハク酸ナトリウム
、ステペライトロノンのアルミニウム塩等を例示でさる
。A charge control agent is used to charge the resin dispersion of the present invention, and other charge control agents include zinc naphthenate, manganese naphthenate, copper oleate, cobalt octylate, lecithin, nooctylsulfosuccinic acid. Examples include sodium and aluminum salts of steperitronone.
２遭しし薄型−：
電子写真用液体現像剤は通常５％以下の希薄な液として
用いられるため、このような希釈状態での分散安定性が
必要であるが、本発明の樹脂分散液を用いた電子写真液
体現像剤はこのような分散安定性が良好であり、しかも
顔料の分散性がよいので画像のにじみが少なく且つ印刷
物の地汚れ（オフセット印刷において非画像部分に印刷
インキが付着して生じる汚れ）も少なく、しかも製版部
数を多くとれるので、オフセットマスター用がカラー電
子複写用に極めて好適である。2 Encountered Thin Type: Liquid developers for electrophotography are usually used as dilute solutions of 5% or less, so dispersion stability in such diluted states is required. The electrophotographic liquid developer used has such good dispersion stability, and also has good pigment dispersibility, so there is little bleeding of images and background stains on printed matter (printing ink adheres to non-image areas in offset printing). Offset masters are extremely suitable for color electronic copying because they cause less stains (stains caused by printing) and can produce a large number of plates.
Ｋ１九：
以下の実施例及び比較例で使用する数量及び収率は、特
にことわらない限り、重量に基づくものである。K19: Quantities and yields used in the following Examples and Comparative Examples are by weight unless otherwise specified.
実施例１
攪拌機、還流器、滴下装置を有する反応器中に２エチル
へキシルメタクリレート１３０部、シクロヘキシルメタ
クリレート７０部、メルカプトエタノール１ｆｆｌＳ１
アゾビスイソブチロニトリル０゜１部及びｎ−ヘキサン
４０部を加え、加熱して還流状態にて２時間反応させた
後トルエン４０部と７ゾビスイソブチロニトリル０．８
部の混合液を１時間で滴下し更に２時間反応させた。Example 1 130 parts of 2-ethylhexyl methacrylate, 70 parts of cyclohexyl methacrylate, and 1 fflS1 of mercaptoethanol were placed in a reactor equipped with a stirrer, a reflux device, and a dropping device.
Add 0.1 part of azobisisobutyronitrile and 40 parts of n-hexane, heat and react under reflux for 2 hours, then add 40 parts of toluene and 0.8 parts of 7zobisisobutyronitrile.
1 part of the mixture was added dropwise over 1 hour, and the mixture was allowed to react for an additional 2 hours.
得られた樹脂液７０部にｎ−へブタン１００部、酢酸ビ
ニル３５０部、２エチルへキシルアクリレート８０％、
シクロヘキシルメタクリレート４５部、過酸化ベンゾイ
ル４部を加え７０℃で５時間反応させた後れ−へブタン
１００部を加え加熱して還流状態下に酢酸ビニル３５０
部、２エチルへキシルメタクリレート８０部、シクロヘ
キシルメタクリレート４５部、ｎ−へブタン２００部、
パーロイルしく日本油脂製）４部を４時間で添加し、３
時間反応後ｎ−へブタン１５０部、パーロイル上２部の
混合物を１時間で滴下し、更に２時間反応させてからア
イソパー６２３０部を加えて冷却した。平均粒径０．１
μの半透明の樹脂分散液が得られた。To 70 parts of the obtained resin liquid, 100 parts of n-hebutane, 350 parts of vinyl acetate, 80% of 2-ethylhexyl acrylate,
45 parts of cyclohexyl methacrylate and 4 parts of benzoyl peroxide were added and reacted at 70°C for 5 hours. After that, 100 parts of hebutane was added and heated under reflux to produce 350 parts of vinyl acetate.
parts, 80 parts of 2-ethylhexyl methacrylate, 45 parts of cyclohexyl methacrylate, 200 parts of n-hebutane,
Add 4 parts of Nippon Oil Co., Ltd.) over 4 hours,
After reacting for an hour, a mixture of 150 parts of n-hebutane and 2 parts of perloyl was added dropwise over 1 hour, and after further reaction for 2 hours, 6230 parts of Isopar was added and cooled. Average particle size 0.1
A translucent resin dispersion of μ was obtained.
生成樹脂分散９６部にニグロシン染料０．５５部とアイ
ソパーＧ２４．５部を加えてボールミルにて１８時曲混
練し、さらにす７テン酸亜鉛０゜４部とアイソパー０３
３０部を加えて現像液とした。0.55 parts of nigrosine dye and 24.5 parts of Isopar G were added to 96 parts of the resulting resin dispersion and kneaded at 18:00 in a ball mill, and then 0.4 parts of zinc 7thenate and 24.5 parts of Isopar G were added.
30 parts were added to prepare a developer.
また生成樹脂分散液２２部に表面を水酸化アルミニウム
で処理したりオノーデンマゼンタＲ（東洋インキ製）１
．２部及びステアリン酸アルミニウム０．２５部を加え
、ボールミルにて１０時間練介した後アイソパー０９０
０部を加えて現像液とした。In addition, the surface of 22 parts of the resulting resin dispersion was treated with aluminum hydroxide, and 1 part of Onoden Magenta R (manufactured by Toyo Ink) was added.
．． After adding 2 parts and 0.25 parts of aluminum stearate and kneading in a ball mill for 10 hours, Isopar 090
0 parts was added to prepare a developer.
得られた現像液は室温にて７日放置しても殆ど沈降物が
生じず、現像後の画像濃度は極めて商く、また画像形成
した紙を積み重ねても全くブロッキングは生じなかった
。The resulting developer showed almost no sediment even after being left at room temperature for 7 days, the image density after development was extremely high, and no blocking occurred even when the image-formed papers were stacked up.
実施例２
実施例１の反応容器にｎ−オクチルメタクリレート４０
部、シクロヘキシルメタクリレート６０部、メルカプト
プロピオン酸１．５部を加え８０℃で表面に少量の空気
を導入しながら６時間反応させ更にｎ−へブタン２０部
とパーロイルしく日本油脂製）０．５部の混合液を３０
分毎に２回添加して反応させ不揮発分８０％分子量約１
５，０００の重合物からなる溶液を、得た。Example 2 40 n-octyl methacrylate was added to the reaction vessel of Example 1.
1 part, 60 parts of cyclohexyl methacrylate, and 1.5 parts of mercaptopropionic acid were reacted at 80°C for 6 hours while introducing a small amount of air to the surface. 30% of the mixture of
Add twice every minute to react.Non-volatile content: 80%Molecular weight: Approximately 1
A solution consisting of 5,000 polymers was obtained.
得られた樹脂液１００部に１−へブタン２０部を加え還
流状態を保ちながら酢酸ビニル２８５部とｎ−オクチル
７クリレート１５部及びパーロイリし３部、ｎ−へブタ
ン５０部の混合物を８時間で滴下４時間反応後ｎ−へブ
タン４０部とパーロイルし１．５部の混合物を１時間で
滴下して更に２時間熟成後アイソパー６１８０部部を加
えて冷却した。20 parts of 1-hebutane was added to 100 parts of the obtained resin liquid, and a mixture of 285 parts of vinyl acetate, 15 parts of n-octyl 7-acrylate, 3 parts of pearlylene, and 50 parts of n-hebutane was heated for 8 hours while maintaining the reflux state. After reacting for 4 hours, 40 parts of n-hebutane and 1.5 parts of the mixture were added dropwise over 1 hour, and after further aging for 2 hours, 6180 parts of Isopar was added and cooled.
得られた分散液２０？￥ＩｓにボントロンＮ−０４（オ
リエント化学工業（株）製）１．６部、アイソパー６１
８０部、ナフテン酸亜鉛１ｆｆｌＳを加え室温にてサン
ドミルで１２時間混練して濃縮現像液を得、これを１０
倍量にアイソパーＧで希釈したものを現像液とした。The resulting dispersion 20? 1.6 parts of Bontron N-04 (manufactured by Orient Chemical Industry Co., Ltd.), Isopar 61 for ¥Is
80 parts of zinc naphthenate and 1 fflS of zinc naphthenate were added and kneaded at room temperature in a sand mill for 12 hours to obtain a concentrated developer.
A developer solution was diluted with Isopar G to double the amount.
実施例３
実施例１の反応容器中に２エチルへキシルアクリレート
１１０ｇ、ベンノルメタクリレート９０部、ｎ−ヘキサ
ン４０部、メルカプト酢酸０．３部、７ソビスイジプチ
ロニトリル０．１部を入れ還流状！ａまで加熱して２時
間反応を継続し次にトルエン４０部と７ソビスイソブチ
ロニトリル０．８部の混合物を１時間で滴下還流状態で
４時間反応させた。これにｎ−へブタン５０部を加え還
流状態を保ちながら酢酸ビニル７０４部と２エチルへキ
シルアクリレート５３部、ベンジルメタクリレート４３
部、ｎ−へブタン１３５部及びパーブチルＯ（日本油脂
製）８部の混合物を８時間で滴下４時間反応後ｎ−へブ
タン１００部とパーブチル０４部の混合物を１時間で添
加し２時間反応を継続させた後アイソパー０６３５ＷＳ
を加えて冷却した。Example 3 110 g of 2-ethylhexyl acrylate, 90 parts of bennormethacrylate, 40 parts of n-hexane, 0.3 part of mercaptoacetic acid, and 0.1 part of 7-sobisidiptyronitrile were placed in the reaction vessel of Example 1 and refluxed. Status! The reaction was continued for 2 hours, and then a mixture of 40 parts of toluene and 0.8 parts of 7-sobisisobutyronitrile was added dropwise over 1 hour to react under reflux for 4 hours. To this was added 50 parts of n-hebutane, and while maintaining the reflux state, 704 parts of vinyl acetate, 53 parts of 2-ethylhexyl acrylate, and 43 parts of benzyl methacrylate were added.
A mixture of 135 parts of n-hebutane and 8 parts of Perbutyl O (Nippon Oil Co., Ltd.) was added dropwise over 8 hours, and after reaction for 4 hours, a mixture of 100 parts of n-hebutane and 4 parts of Perbutyl O was added over 1 hour, and the mixture was reacted for 2 hours. After continuing isopar 0635WS
was added and cooled.
得られた分散液は平均粒径が０．２μのやや透明性を有
する乳白色エマルジョンとなった。The resulting dispersion was a slightly transparent milky white emulsion with an average particle size of 0.2 μm.
生成樹脂分散液６５．に表面処理した７タロシアニンプ
ルー５．５ｇとフイソパーＧ３１４ｇ、ステアリン酸亜
鉛４ｇを加え、ボールミルにて２４時間練合し２１！厚
現像液を得た。この濃厚現像液をアイソパーＧにて１０
倍に希釈したものを現像液とした。Produced resin dispersion liquid 65. Add 5.5 g of surface-treated 7-thalocyanine blue, 314 g of Fisopar G, and 4 g of zinc stearate, and knead in a ball mill for 24 hours. A thick developer was obtained. Add this concentrated developer to Isopar G for 10
The diluted solution was used as a developer.
実施例４
実施例１の反応容器中にイソノニルメタクリレート７５
部、シクロヘキシルメタクリレート２５部、ｎ−ヘキサ
ン２０部、メルカプトエタノール１部、アソビスイソブ
チａニトリル０．２部を入れ還流状！！！まで加熱して
２時間反応を継続し、次にトルエン２０部と７ソビスイ
ソブチロニトリル０．４部の混合物を１時間で滴下して
還流状態で４時間反応させた。これにｎ−へブタン１６
０部を加え、還流状態を保ちながら酢酸ビニル８１０部
、ｎ−オクチルメタクリレート９０部、パーロイルし９
部を４時間で添加し２時間反応後、ｎ−へブタン１００
部、パーロイルＬ４８ｔＳの混合液を１時間で添加し更
に２時間反応させ、アイソパーＧを３００部加え冷却し
て乳白色の二マルクジンを得た。Example 4 Isononyl methacrylate 75 in the reaction vessel of Example 1
1 part, 25 parts of cyclohexyl methacrylate, 20 parts of n-hexane, 1 part of mercaptoethanol, and 0.2 part of asobisisobutyanitrile were added to reflux! ! ! The reaction was continued for 2 hours, and then a mixture of 20 parts of toluene and 0.4 parts of 7-sobisisobutyronitrile was added dropwise over 1 hour, and the mixture was reacted under reflux for 4 hours. To this, n-hebutane 16
Add 0 parts of vinyl acetate, 90 parts of n-octyl methacrylate, and 9 parts of perloyl while maintaining the reflux state.
After 2 hours of reaction, 100 parts of n-hebutane was added over 4 hours.
A mixture of 1 part and Perloil L48tS was added over 1 hour and reacted for an additional 2 hours, and 300 parts of Isopar G was added and cooled to obtain milky-white Dimarcuzin.
この生成樹脂分散液１０５ｇにアイソパー６１５０ｇを
加え、攪拌しながらオイルプラックＨＢＢ５．とキシレ
ン２０．の混合物を滴下し、ステアリン酸アルミニウム
１ｇを加えてからアイソパーＧを１０１７Ｊｉえて現像
液とした。Add 6150 g of Isopar to 105 g of the resulting resin dispersion, and add Oil Plaque HBB5. and xylene 20. The mixture was dropped, 1 g of aluminum stearate was added, and 1017 Ji of Isopar G was added to prepare a developer.
実施例５
実施例１の反応容器中に２エチルへキシルメタクリレー
ト１４０部、シクロヘキシルメタクリレート７０部、ｎ
−ヘキサン４０部、メルカプト酢ＮＩ０．５部、アゾビ
スイソブチロニトリル（）、１部を入れ還流状態まで加
熱して２時間反応をｍ続し次にトルエン４０部と７ゾビ
スイソブチロニトリル０．８部の混合物を１時間で滴下
還流状態で４時間反応させた。Example 5 In the reaction vessel of Example 1, 140 parts of 2-ethylhexyl methacrylate, 70 parts of cyclohexyl methacrylate, n
- Add 40 parts of hexane, 0.5 parts of mercapto vinegar NI, and 1 part of azobisisobutyronitrile, heat to reflux and continue reaction for 2 hours, then add 40 parts of toluene and 7zobisisobutyronitrile. A mixture of 0.8 parts of nitrile was added dropwise over 1 hour, and the mixture was reacted under reflux for 4 hours.
得られた樹脂液５６部にｎ−へブタン５０部を加えて加
熱し、還流状態下に、酢酸ビニル６０８部、２エチルへ
キシルメタクリレート１５２部、ｎ−へブタン２００部
、パーロイルＬ１５部を４時間で添加し、２時間反応後
ｎ−へブタン１５０部とパーロイルし７．５部の混合液
を１時間で添加し、更に２時間反応させアイソパーＧ５
０部を加えで冷却した。得られた分散液は平均粒径が０
゜３μの乳白色エマルションとなった。50 parts of n-hebutane was added to 56 parts of the obtained resin liquid and heated, and under reflux, 608 parts of vinyl acetate, 152 parts of 2-ethylhexyl methacrylate, 200 parts of n-hebutane, and 4 parts of Perloyl L were added. After reacting for 2 hours, a mixture of 7.5 parts of n-hebutane and 150 parts of n-hebutane was added over 1 hour, and the mixture was further reacted for 2 hours.
0 parts was added and cooled. The resulting dispersion has an average particle size of 0.
A milky white emulsion with a thickness of 3 μm was obtained.
得られた樹脂分散液２０部を用い実施例２と同様にして
現像液を得た。A developer was obtained in the same manner as in Example 2 using 20 parts of the obtained resin dispersion.
実施例６
実施例１の反応器中にｎ−オクチルメタクリレート１６
０ＷＳ、シクロヘキシルメタクリレート４ｏＷＳ、メル
カプト酢酸４部を加え８０℃で表面に少量の空気を導入
しながら６時間反応させ更にｎ−へブタン２０部とパー
ロイルしく日本油脂！り０゜５部の混合液を３０分毎に
２回添加して反応させ不揮発分８０％分子量約８，００
０の重合物からなる溶液を得た。Example 6 n-octyl methacrylate 16 in the reactor of Example 1
0WS, 4oWS of cyclohexyl methacrylate, and 4 parts of mercaptoacetic acid were added and reacted at 80°C for 6 hours while introducing a small amount of air to the surface, and then added with 20 parts of n-hebutane and Nippon Oil! Add 0.5 parts of the mixed solution twice every 30 minutes and react until the non-volatile content is 80% and the molecular weight is approximately 8,00.
A solution consisting of a polymer of 0 was obtained.
得られた樹脂［１２０ｗ６にｎ−ヘプタン２５部を加え
、加熱して還流状態下に酢酸ビニル８２８部、ｎ−オク
チルメタクリレート７２部、過酸化ベンゾイル９部、ｎ
−へブタン１５０部を８時間で滴下し、２時間反応後ｎ
−へブタン１２０部とパーロイルし４．５部の混合物を
１時間で滴下し更に２時間熟成後アイソパーＧ５０部部
を加え、冷却した。25 parts of n-heptane was added to the obtained resin [120w6, heated under reflux, and mixed with 828 parts of vinyl acetate, 72 parts of n-octyl methacrylate, 9 parts of benzoyl peroxide, and
- 150 parts of hebutane was added dropwise over 8 hours, and after 2 hours of reaction, n
- A mixture of 120 parts of hebutane and 4.5 parts of Perloyl was added dropwise over 1 hour, and after aging for 2 hours, 50 parts of Isopar G was added and cooled.
得られた樹脂分散液５０ｇを用い実施例３と同様にして
現像液を作製した。A developing solution was prepared in the same manner as in Example 3 using 50 g of the obtained resin dispersion.
比較例１
実施例１の反応容器中にステアリルメタクリレート１４
０ｆｆｌＳ、ｎ−ブチルメタクリレート６０部、ｎ−ヘ
キサン４０部、メルカプトエタノール０．５部、アゾビ
スイソブチロニトリル０．１ 部導入れ ”還流状態ま
で加熱して２時間反応を継続し次にトルエン４０部と７
ソビスイソプチロニトリル０゜８ＷＳの混合物を１時間
で滴下還流状態で４時間反応させた。これにｎ−へブタ
ン５０部を加え還流状態を保ちながら酢酸ビニル３００
部とパーブチル０２０ｆｆｌｓと１−へブタン４０部の
混合物を３時間で滴下し、１時間反応後火にｎ−へブタ
ン４０部、パーブチル０１０部の混合物を１時間で滴下
し２時間反応ｆ＆フィンパーＧ９０部を加えて冷却し乳
白色の安定な樹脂分散液を得た。Comparative Example 1 Stearyl methacrylate 14 was added to the reaction vessel of Example 1.
0fflS, 60 parts of n-butyl methacrylate, 40 parts of n-hexane, 0.5 parts of mercaptoethanol, and 0.1 part of azobisisobutyronitrile were introduced. ``Heat to reflux and continue the reaction for 2 hours, then add toluene. 40 parts and 7
A mixture of sobisisobutyronitrile 0°8WS was added dropwise over 1 hour, and the mixture was reacted under reflux for 4 hours. Add 50 parts of n-hebutane to this and add 300 parts of vinyl acetate while maintaining the reflux state.
After reacting for 1 hour, a mixture of 40 parts of n-hebutane and 0.1 parts of perbutyl was added dropwise over 1 hour and reacted for 2 hours. of the mixture was added and cooled to obtain a milky white stable resin dispersion.
生成樹脂分散８１２０部を用いて実施例２と同様にして
現像液を作製した。A developer was prepared in the same manner as in Example 2 using 8120 parts of the resulting resin dispersion.
比較例２
実施例３において用いたメルカプト酢酸０．３部の代り
にアクリル酸０．３部とし、それ以外は同様の方法で現
像液を作製した。Comparative Example 2 A developer was prepared in the same manner as in Example 3 except that 0.3 part of acrylic acid was used in place of 0.3 part of mercaptoacetic acid used in Example 3.
比較例３
実施例５の第２段重合で用いた酢酸ビニル６０８部と２
エチルへキシルメタクリレート１５２部の代りに酢酸ビ
ニル４５６部と２エチルへキシルメタクリレート３０４
部とした以外は、同様の方法により現像液を作製した。Comparative Example 3 608 parts of vinyl acetate used in the second stage polymerization of Example 5 and 2
456 parts of vinyl acetate and 304 parts of 2-ethylhexyl methacrylate instead of 152 parts of ethylhexyl methacrylate
A developing solution was prepared in the same manner except that
比較例４
実施例１の反応容器中にイソノニルメタクリレート１０
０部、メルカプトプロピオン酸ｏ、ｓＢ、ｎ−ヘキサン
２０部、アゾビスイソブチロニトリル０．０５５を入れ
、還流状態まで加熱して２時間反応を継続し、次にトル
エン２０部と７ゾビスイソブチロニトリル０．４部の混
合物を１時間で滴下し４時間反応させた１次にこれにｎ
−へブタン４０部を加え、還流状態下に酢酸ビニル３８
０部、２エチルへキシルメタクリレート２０部、ｎ−へ
ブタン１００部、パーロイルし４部を４時間で添加し、
３時間反応させた後ｎ−へブタン１００部、パーロイル
し２部の混合物を１時間で滴下し、更に２皓間反応させ
た後アイソパーＧを２６０部加え冷却して乳白色のエマ
ルシヨンを得た。Comparative Example 4 Isononyl methacrylate 10 was added to the reaction vessel of Example 1.
Add 0 parts of mercaptopropionic acid, o,sB, 20 parts of n-hexane, and 0.055 parts of azobisisobutyronitrile, heat to reflux and continue the reaction for 2 hours, then add 20 parts of toluene and 7zobis A mixture of 0.4 parts of isobutyronitrile was added dropwise over 1 hour and reacted for 4 hours.
- Add 40 parts of hebutane and 38 parts of vinyl acetate under reflux.
0 parts, 20 parts of 2-ethylhexyl methacrylate, 100 parts of n-hebutane, and 4 parts of perloyl were added over 4 hours.
After reacting for 3 hours, a mixture of 100 parts of n-hebutane and 2 parts of Perloyl was added dropwise over 1 hour. After further reaction for 2 hours, 260 parts of Isopar G was added and cooled to obtain a milky white emulsion.
生成樹脂分散［６部ｇを用いて、実施例３と同様の方法
で現像液を得た。A developer was obtained in the same manner as in Example 3 using 6 parts g of the resulting resin dispersion.
実施例２〜６及び比較例１〜４で得られたｕｘｍ分散液
の組成を第１表に示し、これらから得た現像液を用い、
酸化亜鉛を被覆したオフセットマスター静電記録紙上に
画像を形成させ、エツチング処理を行ってから市販オフ
セットインキを用いて印刷テストを行った成績を第２表
に示す。The compositions of the uxm dispersions obtained in Examples 2 to 6 and Comparative Examples 1 to 4 are shown in Table 1, and using the developing solutions obtained from these,
An image was formed on offset master electrostatic recording paper coated with zinc oxide, etched, and then a printing test was conducted using a commercially available offset ink. Table 2 shows the results.
第 ２ 表
１）室温にて７日放置後 ５；殆ど沈降物が生じない
４；僅かに沈降物が発生するも容易に分散 ３；若干沈
降物が発生するも軽く振ると容易に分散 ２；多量の沈
降物が発生するが強く振ると分散 １；発生沈降物中に
未分散物混入 ０；沈降物がデル化して分散せず
２）実施′ｇｑ２を標準（３）とし一定現保液量当りの
製版数が多くなる枚数を大軽くした
３） 実施例２を標準（３）として濃度が高くなる枚数
を大きくした
４）ｍ像のにじみは下記５点法により判定した
５：ｆ！像のにじみ全くなし
４： 〃 僅かに認められる
３： 〃 少しあり
２： 〃 あり
１：〃大
５） エツチング処理をした製版画像を原版として、上
質紙に市販オフセットインキで印刷を行い、細点部の画
像が消失するまでの印刷枚数によす評価した。Table 2 1) After being left at room temperature for 7 days 5: Almost no sediment is formed.
4; A small amount of sediment is generated, but it is easily dispersed. 3; A small amount of sediment is generated, but it is easily dispersed when shaken lightly. 2; A large amount of sediment is generated, but it is dispersed when shaken vigorously. 1; Contamination of dispersion 0; Sediment becomes del and does not disperse 2) Implementation'gq2 is set as standard (3) and the number of plate making increases per constant current retention liquid amount is greatly reduced 3) Example 2 is set as standard ( 3) The number of images with high density was increased. 4) The blurring of the m image was determined by the following 5-point method. 5:f! No image bleeding at all 4: Slightly observed 3: Slight 2: Yes 1: Large 5) Using the etched plate image as the original plate, print on high-quality paper with commercially available offset ink, and fine dots. The evaluation was based on the number of copies printed until the image disappeared.
ｓ：ｓ、ｏｏｏ枚以上
４：４，０００〜ｓ、ｏｏｏ枚
３ ：３．０００〜４，０００枚
２：２，０００〜３，０００枚
１：２，０００枚以下
６） 耐刷性試験をして得た印刷紙５枚を画像部を合わ
せて重ね、非画像部と同枚数の未印刷紙とを並べて比較
して、汚れ状況を判定した。s: s, ooo sheets or more 4: 4,000 to s, ooo sheets 3: 3,000 to 4,000 sheets 2: 2,000 to 3,000 sheets 1: 2,000 sheets or less 6) Printing durability test Five sheets of printed paper obtained in this manner were stacked with the image area aligned, and the non-image area and the same number of unprinted sheets were compared side by side to determine the stain status.
５：重ねても差が認められない
４：僅かに差が認められる
３：少し差が認められる
２：差が認められる
１：差が非常に大きく認められる
特許出願人 日本カーバイド工業株式会社代 理 人
弁理士 小田島 平 吉 、ニー１外２名′く〜・・
°□5: No difference is observed even after overlapping 4: A slight difference is observed 3: A slight difference is observed 2: A difference is observed 1: A very large difference is observed Patent applicant Representative of Nippon Carbide Industries Co., Ltd. Man
Patent attorney Heikichi Odajima, 1 and 2 others...
°□
Claims (1)
ＯＯＲ＿１、−ＯＣＯＲ＿１又は−ＯＲ＿１を表わし、
Ｒ＿１はＣ＿４〜Ｃ＿２＿０のアルキルを表わす］ の単量体８０〜５０重量部、 ロ）式II ▲数式、化学式、表等があります▼（II） ［こゝでＸ＿２は水素又はメチルを表わし、Ｒ＿２はＣ
＿３〜Ｃ＿８のシクロアルキル又はアルキル部分がＣ＿
１〜Ｃ＿３であるアラルキルを表わす］の単量体２０〜
５０重量部（ただし、上記イ）及びロ）の合計が１００
重量部となる）及び ハ）少なくとも１つのチオール基をもつ有機メルカプタ
ンを硫黄含有量で０．０３〜２重量％（ただし、イ）、
ロ）及びハ）の合計当りの硫黄含有量の重量％とする） を含有してなる前記媒体に実質的に可溶性の共重合体及
び （Ｂ）ニ）酢酸ビニール９７〜５０重量部及びホ）式I
II ▲数式、化学式、表等があります▼（III） ［こゝで、Ｘ＿３は水素又はメチルを表わし、Ｒ＿３は
Ｃ＿４〜Ｃ＿２＿０のアルキル又はアルキル又はＣ＿３
〜Ｃ＿８のシクロアルキルを表わす］の単量体３〜５０
重量部（ただし、上記ニ）及びホ）の合計が１００重量
部となる） を含有してなる前記媒体に実質的に不溶性の共重合体、 を含んでなることを特徴とする電子写真現像剤に適した
樹脂分散液。 ２、該可溶性の共重合体１重量部〜２０重量部未満に対
して該不溶性の共重合体９９重量部〜８０重量部（ただ
し、両者の合計が１００重量部となる）含有する特許請
求の範囲第１項に記載の樹脂分散液。 ３、該可溶性共重合体の重量部数と式IIIの単量体の重
量部数との合計重量部数が１０〜３５重量部である特許
請求の範囲第２項に記載の樹脂分散液。 ４、該有機メルカプタンがカルボキシル基を有する有機
メルカプタンである特許請求の範囲第１〜３項の何れか
に記載の樹脂分散液。 ５、式IIの単量体がシクロヘキシルメタアクリレート、
シクロヘキシルアクリレート、ベンジルメタクリレート
又はベンジルアクリレートである特許請求の範囲第１〜
４項の何れかに記載の樹脂分散液。 ６、該可溶性の共重合体の分子量が３，０００〜５０，
０００である特許請求の範囲第１〜５項の何れかに記載
の樹脂分散液。[Claims] 1. In the highly insulating hydrocarbon medium, (A) A) Formula I ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [Here, X_1 represents hydrogen or methyl, Y is -C
represents OOR_1, -OCOR_1 or -OR_1,
R_1 represents alkyl of C_4 to C_2_0] Monomer 80 to 50 parts by weight, b) Formula II ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) [Here, X_2 represents hydrogen or methyl, R_2 is C
The cycloalkyl or alkyl moiety of _3 to C_8 is C_
1 to C_3 representing aralkyl] monomer 20 to
50 parts by weight (however, the total of the above a) and b) is 100 parts by weight
(parts by weight) and c) an organic mercaptan having at least one thiol group with a sulfur content of 0.03 to 2% by weight (a),
(b) 97 to 50 parts by weight of vinyl acetate; and (B) d) 97 to 50 parts by weight of vinyl acetate, and e) Formula I
II ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [Here, X_3 represents hydrogen or methyl, and R_3 is alkyl or alkyl of C_4 to C_2_0 or C_3
-represents cycloalkyl of C_8] monomer 3-50
parts by weight (provided that the sum of d) and e) above is 100 parts by weight). An electrophotographic developer comprising: a copolymer substantially insoluble in the medium; Resin dispersion suitable for. 2. A patent claim containing 99 parts by weight to 80 parts by weight of the insoluble copolymer (however, the total of both is 100 parts by weight) for 1 part by weight to less than 20 parts by weight of the soluble copolymer. The resin dispersion according to scope 1. 3. The resin dispersion according to claim 2, wherein the total number of parts by weight of the soluble copolymer and the number of parts by weight of the monomer of formula III is 10 to 35 parts by weight. 4. The resin dispersion according to any one of claims 1 to 3, wherein the organic mercaptan is an organic mercaptan having a carboxyl group. 5. The monomer of formula II is cyclohexyl methacrylate,
Claims 1 to 3 are cyclohexyl acrylate, benzyl methacrylate, or benzyl acrylate.
The resin dispersion according to any one of Item 4. 6. The molecular weight of the soluble copolymer is 3,000 to 50,
000, the resin dispersion according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61216119A JP2514636B2 (en) | 1986-09-13 | 1986-09-13 | Resin dispersion for electrophotographic developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61216119A JP2514636B2 (en) | 1986-09-13 | 1986-09-13 | Resin dispersion for electrophotographic developer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6370861A true JPS6370861A (en) | 1988-03-31 |
| JP2514636B2 JP2514636B2 (en) | 1996-07-10 |
Family
ID=16683545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61216119A Expired - Fee Related JP2514636B2 (en) | 1986-09-13 | 1986-09-13 | Resin dispersion for electrophotographic developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2514636B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342722A (en) * | 1990-11-14 | 1994-08-30 | Mitsubishi Rayon Company Ltd. | Toner resin composition and process for preparing same |
| US5342724A (en) * | 1992-04-10 | 1994-08-30 | Eastman Kodak Company | Toner manufacture using chain transfer polyesters |
-
1986
- 1986-09-13 JP JP61216119A patent/JP2514636B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342722A (en) * | 1990-11-14 | 1994-08-30 | Mitsubishi Rayon Company Ltd. | Toner resin composition and process for preparing same |
| US5342724A (en) * | 1992-04-10 | 1994-08-30 | Eastman Kodak Company | Toner manufacture using chain transfer polyesters |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2514636B2 (en) | 1996-07-10 |
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