JPS62231267A - Liquid developer for electrostatic photography - Google Patents
Liquid developer for electrostatic photographyInfo
- Publication number
- JPS62231267A JPS62231267A JP61074507A JP7450786A JPS62231267A JP S62231267 A JPS62231267 A JP S62231267A JP 61074507 A JP61074507 A JP 61074507A JP 7450786 A JP7450786 A JP 7450786A JP S62231267 A JPS62231267 A JP S62231267A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- polymer
- medium
- soluble
- liquid developer
- 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
- 239000007788 liquid Substances 0.000 title claims description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 abstract description 42
- 230000001112 coagulating effect Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 16
- 238000007639 printing Methods 0.000 description 11
- -1 alkyd-JJY Polymers 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 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 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 2
- NYNZQNWKBKUAII-KBXCAEBGSA-N (3s)-n-[5-[(2r)-2-(2,5-difluorophenyl)pyrrolidin-1-yl]pyrazolo[1,5-a]pyrimidin-3-yl]-3-hydroxypyrrolidine-1-carboxamide Chemical compound C1[C@@H](O)CCN1C(=O)NC1=C2N=C(N3[C@H](CCC3)C=3C(=CC=C(F)C=3)F)C=CN2N=C1 NYNZQNWKBKUAII-KBXCAEBGSA-N 0.000 description 2
- XUQOHDOVMVGYSM-UHFFFAOYSA-N 2-methylprop-2-enoic acid;octadecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(O)=O.CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C XUQOHDOVMVGYSM-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000013040 bath agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QKEIHNZGXPRKJV-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(=O)OC1CCCCC1 QKEIHNZGXPRKJV-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DWDNMCTZTCXXDP-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCCCOC(=O)C(C)=C DWDNMCTZTCXXDP-UHFFFAOYSA-N 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001117 oleyl 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])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003505 polymerization initiator 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
- 239000002002 slurry Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-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
- DILISPNYIVRDBP-UHFFFAOYSA-N 2-[3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]-2-naphthalen-2-ylimidazol-4-yl]acetonitrile Chemical compound OC(CNC1=NC=CC(=N1)N1C(=NC=C1CC#N)C1=CC2=CC=CC=C2C=C1)C DILISPNYIVRDBP-UHFFFAOYSA-N 0.000 description 1
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XHULUQRDNLRXPF-UHFFFAOYSA-N 3-ethenyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OCC1=O XHULUQRDNLRXPF-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MCTQNEBFZMBRSQ-GEEYTBSJSA-N Chrysoidine Chemical compound Cl.NC1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 MCTQNEBFZMBRSQ-GEEYTBSJSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 101100274389 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) chz-1 gene Proteins 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 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
- 230000005856 abnormality Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000003849 aromatic solvent 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
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 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
- 239000012792 core layer Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GYMAGYJEGVPXNW-UHFFFAOYSA-N dodecyl prop-2-enoate;ethenyl acetate;furan-2,5-dione Chemical compound CC(=O)OC=C.O=C1OC(=O)C=C1.CCCCCCCCCCCCOC(=O)C=C GYMAGYJEGVPXNW-UHFFFAOYSA-N 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 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 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000787 lecithin Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 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 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009875 water degumming Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
Abstract
Description
【発明の詳細な説明】
（雄業用の利用分野）
本発明は電子写真やＹ＃電記録等のｉ＃電潜像現像用の
液体現像剤に関するものでめシ、保存性、安定性、定着
性Ｅｆｄすれ特に高−質を達成し得る液体現像剤に関す
るものである。Detailed Description of the Invention (Field of Application) The present invention relates to a liquid developer for developing i# latent images in electrophotography, Y# electrographic recording, etc. This invention relates to a liquid developer that can achieve especially high quality fixing properties.
（従来技術）
静電潜像液体現像剤としては既に故多くのものが知られ
ている。例えばカーボンブラックやシアニンブルー、ニ
グロシン、オイル染料等の着色剤顔料又は染料を高絶縁
性媒体中にロジン、アルキッド−Ｊｊｙ、アクリル樹脂
、合成ゴム等の樹脂と共に、ボールミル、アトライター
、ホモジナイザー等で機械的に分散し、更に金属セッケ
ンやアミン、高級脂肪酸等を加えて該分散物の分散粒子
に′颯荷を安定に付与させる方法が歳も一般的であった
。(Prior Art) Many types of electrostatic latent image liquid developers are already known. For example, colorant pigments or dyes such as carbon black, cyanine blue, nigrosine, and oil dyes are mixed with resins such as rosin, alkyd-JJY, acrylic resin, and synthetic rubber in a highly insulating medium using a ball mill, attritor, homogenizer, etc. For many years, it has been common practice to disperse particles of the dispersion and then add metal soaps, amines, higher fatty acids, etc. to stably impart a charge to the dispersed particles of the dispersion.
しかしながら、該方法で得られた液体現像剤は現像剤と
しての分散粒子の粒径分布が大きい為に、沈殿物が多く
発生したり、荷電安定性や製造安定性に劣シ、安定した
画像を得にくいという欠点を有していた。However, since the liquid developer obtained by this method has a large particle size distribution of dispersed particles as a developer, it generates a lot of precipitates, has poor charge stability and manufacturing stability, and cannot produce stable images. It had the disadvantage of being difficult to obtain.
特公昭５３−５４０２９号、同５７−１２９８５号など
に述べられている様に前駆体ポリマーに高分子反応によ
り重合可能なビニル基をあらかじめ導入しておき、これ
の存在下にモノマーを菫合せしめグラフト共重合体を生
成させ、これを染料で着色する事によシ液体現像剤を得
る方法がある。As described in Japanese Patent Publication Nos. 53-54029 and 57-12985, a vinyl group that can be polymerized by a polymer reaction is introduced into a precursor polymer in advance, and monomers are combined in the presence of this vinyl group. There is a method of obtaining a liquid developer by producing a graft copolymer and coloring it with a dye.
該方法は優れた方法といえるが、ビニル基の等大のコン
トロール及び再現性に問題があり、しばしばゲルの生成
を伴なったり、分散粒子が女定に形成し麹い場合があり
、１μ以上の粗大粒子や０．１μ以下の微小な粒子が生
成する事があり実用上好ましくない。Although this method can be said to be an excellent method, there are problems in controlling and reproducibility of the equal size of vinyl groups, often accompanied by gel formation, and dispersed particles forming irregularly and becoming koji. Coarse particles and fine particles of 0.1 μm or less may be generated, which is not desirable in practical terms.
更に特開昭５９−８３１７４号、同５９−１７７５７２
号、同５９−２１２８５０号、同５９−２１２８５１号
、同６０−１６４７５７号、同６０−１７９７５１号、
同６０−１８５９６２号、同６０−１８５９６３号等に
は、高絶縁性媒体に可溶な重合体存在下で該溶媒に可溶
であるが重合体を形成すると不溶となるモノマーを重合
し、得られた樹脂分散物を液体現像剤として用いる￥が
述べられている。該方法は工東的製造安定性、分散安定
性等優れたものである。しかしながら該方法で得られる
樹脂を用いた液体現像剤を静電記録材上にクーロン力で
画像形成させた場合、分散粒子自身の持つクーロン力に
よる１ｍ ’ＭＥ的相互反撥や分散安定化ポリマーの一
度が上昇して反砿し合う体積排除効果などが生ずる。こ
の為に一゛蹴記縁材の有効な表面電位が低下してくると
画像周辺ににじみ状のゴーストが発生し易いという欠点
を有していた。また該方法で得られた樹脂を用いた液体
現像剤を実−に補充しなから連続・匣用すると溶媒可溶
性の−）ｊａが蓄積し、用いた可−往樹脂の種類にもよ
るが、分散粒子の荷・框量に影響を与えるという欠点も
有していた。Furthermore, JP-A-59-83174 and JP-A-59-177572
No. 59-212850, No. 59-212851, No. 60-164757, No. 60-179751,
No. 60-185962, No. 60-185963, etc. disclose that monomers which are soluble in a highly insulating medium but become insoluble when formed into a polymer are polymerized in the presence of a polymer soluble in the highly insulating medium. This article describes the use of a resin dispersion as a liquid developer. This method has excellent manufacturing stability and dispersion stability. However, when a liquid developer using a resin obtained by this method is used to form an image on an electrostatic recording material using Coulomb force, 1 m' ME-like mutual repulsion due to the Coulomb force of the dispersed particles themselves, and once the dispersion stabilizing polymer increases, and a volume exclusion effect occurs in which the metals repel each other. For this reason, once the effective surface potential of the edge material decreases, a bleed-like ghost tends to occur around the image, which is a drawback. Furthermore, if a liquid developer using the resin obtained by this method is used continuously without being actually replenished, solvent-soluble -JA will accumulate, depending on the type of liquid developer used. It also had the disadvantage of affecting the load and frame amount of dispersed particles.
（発明の目的）
本発明の目的は前記ＫＭけた従来の欠点を改良した液体
現像剤を提供するものであり、特に画像周辺部ににじみ
状のゴーストがない鮮明な画像を与え、かつ長期に亘る
連続使用にも画像劣化の少ない液体現像剤を提供する事
である。(Object of the Invention) The object of the present invention is to provide a liquid developer which improves the conventional drawbacks by KM, which provides a clear image with no smudge-like ghost especially in the peripheral area of the image, and which lasts for a long time. To provide a liquid developer that causes little image deterioration even when used continuously.
本発明の他の目的は感光体として酸化亜鉛や有機千尋体
を用いたオフセット平版印刷版の現像剤として優れた印
刷品質を与える液体現像剤を提供する事である。Another object of the present invention is to provide a liquid developer that provides excellent printing quality as a developer for offset lithographic printing plates using zinc oxide or organic chirode as a photoreceptor.
（発明の構成）
本発明は、高絶縁性員化水素媒体中に、少なくとも分散
した樹脂粒子を含む靜電写冥用液体現像剤において、該
樹脂が、下記の重合体（Ｓ）の存在下で、下記モノマー
囚及びモノマー（Ｂ）を重合して得られる樹脂であるこ
とを特徴とする靜′屯写真用液体３ｊ！−剤。(Structure of the Invention) The present invention provides a liquid developer for Seidenshamei containing at least resin particles dispersed in a highly insulating membered hydrogen medium, in which the resin is in the presence of the following polymer (S). , a photographic liquid 3j characterized by being a resin obtained by polymerizing the following monomers and monomer (B)! -Agent.
本発明に用いる高絶縁性炭化木葉媒体とはノルマルパラ
フィン系炭化水素、インパラフィン系炭化水素、脂環族
炭化水系、ノーロゲン化脂肪族炭化水素等が挙げられる
が、安全性、陣抛性等の面から実用上好ましくはイソパ
ラフィン系炭化水素溶媒であるシェルシルア１（シェル
石７１ｉ１Ｍ）、アイソパー０、アイソパーＨ１アイン
パーに１アインパーＬ、アイソパーＧ（アイソパーはエ
クソン社の商品名）やアイビーソルベント（出光石油化
学展）等が使用出来る。The highly insulating carbonized wood leaf medium used in the present invention includes normal paraffinic hydrocarbons, imparaffinic hydrocarbons, alicyclic hydrocarbons, norogenated aliphatic hydrocarbons, etc. Practically preferred isoparaffinic hydrocarbon solvents such as Shell Silua 1 (Shell Stone 71i 1M), Isopar 0, Isopar H1 Ainpar, 1 Ainpar L, Isopar G (Isopar is a trade name of Exxon), and Ivy Solvent (Idemitsu Petrochemical). Exhibition) etc. can be used.
本発明の液体現像剤に用いる樹脂の構成及び樹脂分散物
（以下エマルジ冒ンとよぶ）の形成機構について説明す
る。本発明に用いる前記溶媒に不溶でカルボキシル基を
有する重合体但）をシェルポリマーとよぶ事にする。又
該溶媒に不溶で重合すると不溶化するそツマー囚の重合
体をＰ１ポリマーとし、該溶媒に可溶で重合体を形成し
ても可溶なモノマー（Ｂ）の重合体をＰ２ポリマーとす
る。本発明に用いるエマルジ璽ンの重合曲始前の最も一
般的な態様は、前記溶媒、シェルポリマー、モノマー囚
及びモノマー但）である。（得られたエマルジ冒ン粒子
のＴｍ％Ｔｇ等の物性をコントロールをする為にいづれ
の材料も場合によって２種以上用いても良い）また重合
時の発熱をコントロールする為に用いるモノマーを分割
して後添加しても良い。The structure of the resin used in the liquid developer of the present invention and the formation mechanism of the resin dispersion (hereinafter referred to as emulsion) will be explained. The polymer used in the present invention that is insoluble in the solvent and has a carboxyl group (provided) is referred to as a shell polymer. Further, the polymer of the monomer (B) which is insoluble in the solvent and becomes insolubilized when polymerized is referred to as the P1 polymer, and the polymer of the monomer (B) which is soluble in the solvent and is soluble even if a polymer is formed is referred to as the P2 polymer. The most common aspects of the emulsion used in the present invention before polymerization start are the above-mentioned solvent, shell polymer, monomer particles, and monomers. (In order to control the physical properties such as Tm%Tg of the obtained emulsion particles, two or more of the materials may be used depending on the case.) In addition, the monomers used may be divided to control the heat generation during polymerization. It may be added after.
エマルジ目ン粒子の形成機構は大別して２通シある。そ
の第１は前記重合開始前の状態が均−系のケースである
。この揚台本来シェルポリマーは該溶媒に不溶であるに
もかかわらず均−系となる事実は、モノマー囚又はモノ
マー（Ｂ）に溶解してしまう為である。The formation mechanism of emulsion particles can be broadly classified into two types. The first case is that the state before the start of the polymerization is homogeneous. The fact that the shell polymer becomes homogeneous even though it is originally insoluble in the solvent is because it dissolves in monomer particles or monomer (B).
水系を加熱し、重合開始剤を添加する憂によってラジカ
ルが発生し重合がスタートする。モノマー囚から生成す
るＰ１ポリマー成分は該溶媒に不溶であるので、該溶媒
に可溶なＰ２ポリマー成分を保Ｕコロイドとして粒子を
形成し白面化しエマルジョンを生成する。By heating the water system and adding a polymerization initiator, radicals are generated and polymerization starts. Since the P1 polymer component produced from the monomer particles is insoluble in the solvent, the P2 polymer component soluble in the solvent is used as a holding U colloid to form particles and whiten to produce an emulsion.
粒子径はＰ２ポリマー成分蓋すなわち仕込みモノマー（
Ｂ）ｉによって比較的自由に賀える事ができる。The particle size is determined by the P2 polymer component lid, that is, the charged monomer (
B) i allows you to celebrate relatively freely.
仕込みモノマー（Ａ）／モノマー但）比は勿論生成する
ポリマーの該溶媒に対する溶解性や凝集性に依存するが
、重量比で９８／２〜２０／８０の範囲で地板的安定な
エマルジョンが得られるが９５１５〜５０１５０程度が
好適である。The ratio of charged monomer (A)/monomer (however) naturally depends on the solubility and cohesiveness of the polymer to be produced in the solvent, but a stable emulsion can be obtained within the range of 98/2 to 20/80 in terms of weight ratio. is preferably about 9,515 to 50,150.
重合が進行するとシェルポリマーは可溶化されるべきモ
ノマーがポリマーとして消費されてしまう為に系内に均
一に溶解できなくなる。従って不溶化してくることにな
るが、実際にはＰ１ポリマーが形成するエマルジョン粒
子表面に沈着してくる。As the polymerization progresses, the shell polymer cannot be uniformly dissolved in the system because the monomer to be solubilized is consumed as a polymer. Therefore, it becomes insolubilized, but actually it is deposited on the surface of the emulsion particles formed by the P1 polymer.
この現象は後述の実施例から明らかにされる。エマルジ
ョンの沈降安定性や粒径はシェルポリマーの種類、量に
も依存し、シェルポリマーが多過ぎる場合沈殿が生じ易
い。但しこの場合モノマー但）の量を増量させておけば
分散安定性は改良される。This phenomenon will be made clear from the examples described below. The sedimentation stability and particle size of the emulsion also depend on the type and amount of shell polymer, and if there is too much shell polymer, precipitation is likely to occur. However, in this case, dispersion stability can be improved by increasing the amount of the monomer.
シェルポリマーの量は前述の通り、モノマーＮ１モノマ
ーの）のｆｆｆｌｆｉ、ｉ及びシェルポリマーのｔｉ類
にもよるが、モノマー囚の１−〜５０％（！ｍ比）、好
ましくは３〜２５％が好適である。As mentioned above, the amount of the shell polymer depends on the ffflfi, i of the monomer N1 monomer) and the ti of the shell polymer, but it accounts for 1-50% (!m ratio) of the monomers, preferably 3-25%. suitable.
従って形成されたエマルジ目ン粒子は内部に主にＰ１ポ
リマーからなるコア層、その外側に沈積したシェルポリ
マーからなるシェル層、更に最外部に粒子を該溶媒中に
安定化させている主にＰ２ポリマーからなる分散層の３
７ｍ格造金形成していると考えられる。勿論、粒子形成
機構から判る様に各層間に明確な界面などは存在せず、
各成分が３鳩化状態に、よシ局在化していると推測され
る。特にシェル層の存在は後述の例からも推測される。Therefore, the formed emulsion particles have a core layer mainly composed of P1 polymer inside, a shell layer composed of shell polymer deposited on the outside, and a shell layer mainly composed of P2 polymer which stabilizes the particles in the solvent on the outermost layer. 3 of the dispersed layer made of polymer
It is thought to have been formed into a 7m-high gold mine. Of course, as can be seen from the particle formation mechanism, there are no clear interfaces between each layer,
It is presumed that each component is highly localized in three clusters. In particular, the existence of a shell layer can be inferred from the examples described below.
エマルジ璽ン粒子の第２の形成機構は、前記重合開始前
の状態が不均一系のケースである。この場合このまｔ重
合を開始させても良いが、好ましくは比較的低沸点の補
助溶剤を添加して系内を均−系にした方が良い。稟１の
形成機構と同様に重合を開始させるとＰ２ポリマー成分
を保賎コロイドとしてＰ１ポリマー成分主体の白？Ｍｊ
化したエマルジョンを生成する。重合終了後に補助浴剤
を′ｄ去すればシェルポリマーはエマルジ四ン粒子の表
面に沈着する。補助浴剤を余シに多く必要とする場合に
は均一なエマルジョンが生成されない事がある。The second formation mechanism of emulsion particles is a case where the state before the start of polymerization is heterogeneous. In this case, the polymerization may be started immediately, but it is preferable to add an auxiliary solvent having a relatively low boiling point to make the system homogeneous. If polymerization is started in the same way as the formation mechanism of 熟1, the P2 polymer component will be used as a holding colloid to form a white material mainly composed of the P1 polymer component. Mj
to produce a solidified emulsion. When the auxiliary bath agent is removed after the polymerization is completed, the shell polymer is deposited on the surface of the emulsion particles. If a large amount of auxiliary bath agent is required, a uniform emulsion may not be produced.
補助溶媒としては、例えばテトラヒドロフラン、エチル
アルコール、イソプロピルアルコール、メチルエチルケ
トン、酢酸エチル等が挙げられる。Examples of the auxiliary solvent include tetrahydrofuran, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, and ethyl acetate.
本発明に用いるシェルポリマーはカルボキシル基を有し
、隔絶縁性炭化水紮媒体には不溶で、重合すると該溶媒
に不溶化するモノマーには可溶な性質を有さねばならな
いので、使用する七ツマ−によって当然変ってくる。又
、最も虚ましい最終的なエマルジョンの態様はシェルポ
リマーを得られたエマルジ四ン粒子の表面に局在化させ
る事である。見方を変えれば粒子表面をカルボキシル基
を有するポリマーで改質する事である。The shell polymer used in the present invention has a carboxyl group, is insoluble in the insulating hydrocarbon medium, and must have the property of being soluble in the monomer that becomes insolubilized in the solvent when polymerized. -Of course it changes depending on. Moreover, the most desirable final emulsion embodiment is to localize the shell polymer on the surface of the resulting emulsion particles. Another way to look at it is to modify the particle surface with a polymer having carboxyl groups.
この様な性質を発揮させるポリマーは例えば一般式〔■
〕及び例えば一般式［１１］で示されるモノマーの共重
合体から得る事ができる。For example, polymers that exhibit such properties have the general formula [■
] and, for example, from a copolymer of monomers represented by the general formula [11].
一般式ＣＤ
ＣＨｚ１＝ＣＺ２−Ｇｏｏｎ
（Ｚｌ、Ｚ２ＵＨ，メチルｇ、−ＣＨ２ＣＯＯ）ｌ、
−Ｃ０ＯＨ基を表わす。〕
一般式〔■〕
（Ｒ１とＲ２はＨ，アルキル基、−ＣＯＯＲ４、−ＣＨ
２ＣＯＯＲｓを説わし、几Ｓ ｓ Ｒ４、”５は置換基
を有しても良い月ａ肪族基を表わす。）
一般式（１１で示されるモノマーはアクリル酸、メタア
クリル酸、クロトン酸、イタコン酸、マレイン酸、７マ
ール酸等の不飽和カルボン酸等が挙げられる。更にカル
ボキシル基を有するモノマーは「合成高分子」（朝倉書
店刊）、「高分子データハンドブック」（培風館刊）Ｑ
！に皐げられている。シェルポリマーとしてはカルボキ
シル基を有している事が重髪であるので使用できるモノ
マーが一般式〔Ｉ〕に限られるものではない。General formula CD CHz1=CZ2-Goon (Zl, Z2UH, methyl g, -CH2COO)l,
-C0OH group. ] General formula [■] (R1 and R2 are H, alkyl group, -COOR4, -CH
2COORs, 几S s R4, "5 represents an aliphatic group which may have a substituent.) The monomer represented by the general formula (11) is acrylic acid, methacrylic acid, crotonic acid, itacon Examples include unsaturated carboxylic acids such as acid, maleic acid, and 7-maric acid.In addition, monomers with carboxyl groups are listed in "Synthetic Polymers" (published by Asakura Shoten) and "Komunshi Data Handbook" (published by Baifukan)Q.
! It's hard to believe. Since it is important for the shell polymer to have a carboxyl group, the monomers that can be used are not limited to the general formula [I].
一般式ＣＩＩ）で表わされるモノマーはアクリル酸、メ
タアクリル酸、クロトン酸、マレイン酸、イタコン酸等
の不飽和カルボン酸のエステル化物であシ、脂肪族基の
エステルであれば例えばメチル、エチル、プロピル、ブ
チル、アミル、ヘキシル、エチルヘキシル、ドデシル、
トリデシル、ヘキサデシル、ドコサニル、ヘキサデセニ
ル、オレイル、等が挙げられる。これらはハロゲン原子
、アミ７基、アルコキシｉｖで置侠されていても良く、
又窒業、酸素、イオウ等の原子で結合が結ばれていても
良い。The monomer represented by the general formula CII) is an esterified product of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc. If it is an ester of an aliphatic group, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, ethylhexyl, dodecyl,
Examples include tridecyl, hexadecyl, docosanyl, hexadecenyl, oleyl, and the like. These may be substituted with a halogen atom, an amino group, or an alkoxy group,
Bonds may also be formed by atoms of nitrogen, oxygen, sulfur, etc.
またシェルポリマーの物性をａ１４整する為に第３成分
として共重合可能なモノマーを共重合しても良い。更に
シェルポリマーとしてｄａのポリマーを用いてもかまわ
ない。Further, in order to adjust the physical properties of the shell polymer to a14, a copolymerizable monomer may be copolymerized as a third component. Furthermore, a da polymer may be used as the shell polymer.
シェルポリマーの重合は公知の菖合方法で得る事ができ
るが、シェルポリマーを原材料としてエマルジ奮ンを合
成する為に、エマルジ習ン合成時に用いる溶媒と同一か
又は良く混合する溶媒中で溶液重合によって得る事が最
も好ましい。更にシェルポリマーの物性として該溶媒に
高温で溶解してしまう性質を有するものは余！ＯＷまし
くない。Polymerization of shell polymers can be obtained by the well-known polymerization method, but in order to synthesize emulsion using shell polymer as raw material, solution polymerization is performed in a solvent that is the same as or mixed well with the solvent used for emulsion synthesis. It is most preferable to obtain it by Furthermore, there are no shell polymers that have the property of being dissolved in the solvent at high temperatures! Not OW.
なぜならば液体現像剤の特性が温度に依存してしまい籍
に温度が上昇した時にシェルポリマーが粒子から脱着し
てトナー粒子の物性を変えてしまう恐れがあるからであ
る。This is because the properties of the liquid developer depend on temperature, and when the temperature rises, the shell polymer may be detached from the particles and change the physical properties of the toner particles.
本発明に用いるシェルポリマー〇共重合体例を挙げるが
勿論これに限られるわけではない。（）内は鵞世比であ
る。Examples of the shell polymer 〇 copolymer used in the present invention will be given below, but of course the invention is not limited thereto. The numbers in parentheses are Goosebi.
（イ）ｎ−へキシルメタアクリレート−メタアクリル酸
（ロ）ラウリルアクリレート−アクリルｌ１ｉ２ （
９３／７）（ハ）ステアリルメタクリレート−メタアク
リル酸（Ｓ８／１２）に）ステアリルメタアクリレート
−酢酸とニル−クロトン酸 （９０／８／２ ）
（ホ）シクロヘキシルメタアクリレート−メタアクリル
酸（へ）ラウリルアクリレート−酢酸ビニル−無水マレ
イン酸 （９２／６／２ ）
（ト）ラウリルアクリレート−ブチルメタアクリレート
−メタアクリル酸 （４５１５０１５）
不発明に用いる、該溶媒に可溶で重合すると不滴化する
ポリマーを与えるモノマー（Ａ）としては例エバ面ば、
プロピオン酸、酪酸等のビニルエステル類やアリルエス
テル類。イタコン酸、マレイン酸、クロトン酸等のアル
キルニスデル−（但し長鎖アルキルのポリマーは可俗化
してしまうので炭素＠４まで）等、更にはアクリル酸や
メタアクリル酸の置換基を有しても良い低級アルキルエ
ステルやアミド類。スチレン、メチルスチレン、ビニル
トルエン等スチレン訪Ｗ体、Ｎ−ビニルピロリドン、Ｎ
−ビニルオキサゾリドン等の′４ｉ素城を有するもの等
が挙げられる。得られたエマルジ冒ン粒子の物性を？Ａ
整する為に塩基性のモノマーやエーテル結合を有するモ
ノマー等共重合可能な第２成分を共重合してもかまわな
い。(a) n-hexyl methacrylate-methacrylic acid (b) lauryl acrylate-acrylic l1i2 (
93/7) (c) Stearyl methacrylate-methacrylic acid (S8/12)) Stearyl methacrylate-acetic acid and nyl-crotonic acid (90/8/2) (e) Cyclohexyl methacrylate-methacrylic acid (f) Lauryl acrylate-vinyl acetate-maleic anhydride (92/6/2) (t)Lauryl acrylate-butyl methacrylate-methacrylic acid (4515015) A polymer used in the invention that is soluble in the solvent and becomes non-droplet when polymerized. Examples of monomers (A) that give
Vinyl esters and allyl esters such as propionic acid and butyric acid. Itaconic acid, maleic acid, crotonic acid, etc., have substituents such as alkylnisdale (however, long-chain alkyl polymers are viscosifiable, so up to 4 carbon atoms), as well as acrylic acid and methacrylic acid substituents. Also good for lower alkyl esters and amides. Styrene, methylstyrene, vinyltoluene, etc., styrene derivatives, N-vinylpyrrolidone, N
-Vinyl oxazolidone and the like having a '4i elemental structure can be mentioned. What are the physical properties of the obtained emulsion particles? A
A copolymerizable second component such as a basic monomer or a monomer having an ether bond may be copolymerized in order to achieve the desired alignment.
本発明に用いる、該溶媒に可溶で重合しても可溶なポリ
マーを与えるモノマー（Ｂ）は例えば下記一般式〔■〕
で示される。The monomer (B) used in the present invention that gives a polymer that is soluble in the solvent and soluble even when polymerized is, for example, the following general formula [■]
It is indicated by.
一般式〔■〕
一般式Ｃｕ１ｌ）中孔は炭素数８以上の脂肪族基を表わ
し、Ｂはエステル基又はアミド’ｌｈｓ Ｑｌｓ Ｑ２
は水素原子、アルキル基、−ＣＯＯＲ／、−ＣＨ２ＣＯ
ＯＲ”を表わす。ｎ’、ａ’は脂肪族ｉを表わす。General formula [■] General formula Cu1l) The middle hole represents an aliphatic group having 8 or more carbon atoms, and B is an ester group or an amide group Qls Q2
is a hydrogen atom, an alkyl group, -COOR/, -CH2CO
OR". n' and a' represent aliphatic i.
モノマー（Ｂ）の例としてはアクリル酸、メタアクリル
酸、クロトン酸、マレイン酸、イタコン酸のエステル化
物及びアミド化物であシ、例えば脂肪族基の場合デシル
、ドデシル、トリデシル、ヘキサデシル、ドコサニル、
ヘキサデセニル、オレイル等が挙げられる。Examples of the monomer (B) include esters and amides of acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; for example, in the case of aliphatic groups, decyl, dodecyl, tridecyl, hexadecyl, docosanyl,
Examples include hexadecenyl and oleyl.
これらはハロゲン原子、アミ７基、アルコキシ基、ヒド
ロキシ基等で置換されていても良く、又窒素、酸素、イ
オウ等の原子で結合が結ばれていても良い。These may be substituted with a halogen atom, an amide group, an alkoxy group, a hydroxyl group, etc., or may be bonded with atoms such as nitrogen, oxygen, sulfur, etc.
モノマー囚及び（Ｂ）の必要特性は、前記シェルポリマ
ーを溶解させる事が好ましいが必ずしも各々のモノマー
がシェルポリマーを溶解する必要はなく 、ＦＪ、 溶
媒ｓシェルポリマー、モノマー（至）及ヒβ）が混合さ
れた時に実質的に均−系であれば問題ない。また溶解性
が恣く不均一系となる場合には比較的低沸点の補助溶媒
を用いて重合が完了した後に留去すれば良い。The necessary properties of the monomer and (B) are that, although it is preferable that the shell polymer be dissolved, it is not necessary that each monomer dissolve the shell polymer. There is no problem if the mixture is substantially homogeneous. If the solubility is arbitrary and the system becomes heterogeneous, a co-solvent with a relatively low boiling point may be used and distilled off after the polymerization is completed.
本発明で得られたエマルジ璽ンを静電写真用液体現像剤
とするには、分散樹脂粒子を着色し荷・−を与えれば良
い。分散粒子の着色剤としては一般に液体現像剤用層色
剤として知られているものが任意に使用できる。例えば
オイルブラック、オイルレッド等の油溶性染料、ビスマ
ルクブラウン、クリソイジン等の塩抽性アゾ染料、ウー
ルブラック、アミドブラックグリーン、ブルーブラック
ＨＦ等の酸性アゾ染料、コンゴーレッド等のｒｉｓ、後
染料、スーダンバイオレット、アシッドブルー等のアン
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、ビクトリアブルー等のカルボ
ニウム染料、ローダミンＢの如くロータミン染料、す７
ラニン、ニグロシン、メチレンブルー等のキノンイミン
染料等の栄科が挙げられる。顔料としては、カーボンブ
ラック、フタロシアニンブルー、フタロシアニングリー
ン、ウオツシングレッド、ベンジジンイエロー等が挙げ
られる。又表面処理を施した顔料、例えばニグロシンで
染色したカーボンブラック、グラフトカーボン、ローダ
ミンＨで染色した酸化硅素微粉末、マイクロリスブルー
等を用いる事ができる。In order to use the emulsion bottle obtained in the present invention as a liquid developer for electrostatic photography, the dispersed resin particles may be colored and charged. As the coloring agent for the dispersed particles, any one generally known as a layer coloring agent for liquid developers can be used. For example, oil-soluble dyes such as oil black and oil red, salt-extractable azo dyes such as Bismarck brown and chrysoidine, acidic azo dyes such as wool black, amide black green, and blue black HF, RIS such as Congo red, post dyes, and Sudan. Anthraquinone dyes such as violet and acid blue, auramine, malachite green,
Carbonium dyes such as crystal violet and Victoria blue, rotamine dyes such as Rhodamine B, Su7
Examples include quinoneimine dyes such as lanin, nigrosine, and methylene blue. Examples of the pigment include carbon black, phthalocyanine blue, phthalocyanine green, washing red, and benzidine yellow. Also, surface-treated pigments such as carbon black dyed with nigrosine, grafted carbon, silicon oxide fine powder dyed with rhodamine H, microlith blue, etc. can be used.
分散粒子への着色方法は、使用する着色剤を溶解する溶
剤にあらかじめ溶解しておき、この着色剤溶液をエマル
ジ冒ン中に滴下攪拌する方法が最も簡便である。特にオ
イル染料をトルエン、キシレン等の芳香族溶媒に溶解し
滴下攪拌すると、うまく着色できる。使用した溶媒はト
ナー溶媒と混合するので品質上悪影響がない限シ除去す
る必要はない。また特開昭５７−４８７３８にみられる
様な溶媒系を用いて、後で溶媒除去をしても良い。The simplest method for coloring the dispersed particles is to dissolve the colorant to be used in advance in a solvent, and then dropwise add and stir this colorant solution into the emulsion. In particular, coloring can be achieved well by dissolving the oil dye in an aromatic solvent such as toluene or xylene and adding it dropwise with stirring. Since the used solvent is mixed with the toner solvent, there is no need to remove it unless there is an adverse effect on quality. Alternatively, the solvent may be removed later by using a solvent system as disclosed in JP-A-57-48738.
更に他の着色方法として、得られたエマルジ冒ンと着色
剤をコロイドミル、ボールミル、振動ミル等の分散機に
加え穢緘的−一を与える事によって着色しても良い。As another method of coloring, the obtained emulsion and coloring agent may be added to a dispersing machine such as a colloid mill, a ball mill, or a vibrating mill, and then colored by adding a pollutant.
本発明の液体現像剤は電荷制御剤、着色剤等を選択すれ
ば正′≦荷を有するトナー又は負′−荷を有するトナー
を自由に製造する事が可能である。In the liquid developer of the present invention, by selecting a charge control agent, a coloring agent, etc., it is possible to freely produce a toner having a positive load or a toner having a negative charge.
本発明の液体現像剤に用いられる電荷制御剤としては、
例えばオレイン酸銅、ナンテン献コバルト、ナフテン酸
亜鉛、ナフテン酸マンガン、オクチル酸コバルト、レシ
チン、ジオクチルスルホコハク敵ナトリウム、ステベラ
イトレジンのアルミニウム塩等が皐げられる。The charge control agent used in the liquid developer of the present invention includes:
Examples include copper oleate, cobalt nandhenate, zinc naphthenate, manganese naphthenate, cobalt octylate, lecithin, sodium dioctyl sulfosuccinate, and aluminum salt of steverite resin.
また特公昭４９−２６５９４号、同４９−２６５９５号
、特開昭６０−１７３５５８号、向６０−１７５０６０
号、同６０−１７９７５０号、同６０−１８２４４７号
、同６０−２１８６６２号、特ム昭６０−７８０６２号
等に挙げられた電荷制御剤も用いる事ができる。Also, JP-B No. 49-26594, JP-A No. 49-26595, JP-A No. 60-173558, Mukai 60-175060
It is also possible to use the charge control agents listed in No. 60-179750, No. 60-182447, No. 60-218662, Tokumu No. 60-78062, and the like.
本発明で得られた液体現像剤は特公昭３７−１７１６２
号、同３８−６９６１号、同４１−２４２６号、同４６
−３９４０５号、特開昭５０−１９５０９号、同５０−
１９５１０号、同５４−１４５５３８号、同５４−８９
８０１号、同５４−１３４６３２号、同５４−１９８０
３号、同５５−１０５２４４号、同５７−１６１８６３
号、向５８−７６８．４３号、同５８−７６８４４号、
同５８−１２２８９７号等に記載される様な平版印刷版
に対しても用いる事ができる。これらの平版印刷版用に
用いた場合には、アルカリ溶出液に対してレジスト性を
有さねばならない。本発明によって得られた液体現像剤
の場合は、ベンジルアルコール等の浸透剤を用いない無
機アルカリ溶出液で溶出する場合に特に艮好な印刷版を
与える。The liquid developer obtained by the present invention is disclosed in Japanese Patent Publication No. 37-17162.
No. 38-6961, No. 41-2426, No. 46
-39405, JP-A-50-19509, JP-A No. 50-
No. 19510, No. 54-145538, No. 54-89
No. 801, No. 54-134632, No. 54-1980
No. 3, No. 55-105244, No. 57-161863
No. 58-768.43, No. 58-76844,
It can also be used for lithographic printing plates such as those described in No. 58-122897. When used for these lithographic printing plates, it must have resistivity to alkaline eluents. The liquid developer obtained according to the present invention provides printing plates that are particularly good when eluted with an inorganic alkaline eluent without a penetrant such as benzyl alcohol.
実施例１（本発明のエマルジ曹ンの合成）既知の溶液重
合法でｎ−へキシルメタアクリレート−メタアクリル酸
共重合体（本発明の例示シェルポリマーヒ））の４０％
キシレン溶液を得た。Example 1 (Synthesis of emulsion carbonate of the present invention) 40% of n-hexyl methacrylate-methacrylic acid copolymer (exemplary shell polymer of the present invention) by known solution polymerization method
A xylene solution was obtained.
この溶液３５９を１ｔのヘキサン中に加えると、共重合
体の沈殿物がスラリー状として得られた。When this solution 359 was added to 1 t of hexane, a copolymer precipitate was obtained in the form of a slurry.
ヘキサンで数回洗浄デカンテーシ冒ンしたスラリーを、
Ｎ２ガス導入管、ＴｒｉＬｋ計、攪拌機、冷却管を偏見
た１ｔの４ツロフラスコ中に加え、４５０１のＩＰソル
ベント（出光石油化学社Ｎ）を加えた。Wash the decanted slurry several times with hexane,
A N2 gas inlet tube, a TriLk meter, a stirrer, and a cooling tube were placed in a 1 ton 4-ton flask, and 4501 IP solvent (Idemitsu Petrochemical Co., Ltd. N) was added.
この段１＞７では、良く攪拌しても該共重合体はＩＰソ
ルベントに全く溶解せずに沈殿したままである。In this stage 1>7, the copolymer remains precipitated without being dissolved at all in the IP solvent even after thorough stirring.
次に１３６ｆの酢酸ビニル（モノマー囚に相当）、３０
ｆのラウリルメタアクリレート（モノマーの）に相当）
を加えて良く攪拌すると均一な透明溶液となった。８０
℃でＮ２ガス置換した後に、重合開始剤としてアゾビス
イソブチロニトリル（ＡＩＢＮ）を１１加えると重合が
開始し、約５０分後に白濁し始め内温は１１５℃まで上
昇した。内温が８０℃に低下してからも更に２時間加熱
を加えた。残存している酢酸ビニルモノマーを除去する
為に内部を減圧にし留去させ、約２２の留出物を得た。Next, 136f vinyl acetate (equivalent to monomer prisoner), 30
equivalent to lauryl methacrylate (monomer) of f)
When added and stirred well, a homogeneous transparent solution was obtained. 80
After purging with N2 gas at ℃, 11 times of azobisisobutyronitrile (AIBN) was added as a polymerization initiator to start polymerization, and after about 50 minutes, it started to become cloudy and the internal temperature rose to 115 ℃. Heating was continued for an additional 2 hours even after the internal temperature had dropped to 80°C. In order to remove the remaining vinyl acetate monomer, the internal pressure was reduced and distillation was performed to obtain about 22 distillates.
得られた白色のエマルジ四ンには全く沈殿物はなく、又
モノマー臭もほとんど感じられなかった。電子顕ｇｌ鏡
で粒径を測定したところ０．２８μの粒径で粒度分布は
ほとんどなかった。The obtained white emulsion had no precipitates at all, and almost no monomer odor was detected. When the particle size was measured using an electron microscope, the particle size was 0.28μ and there was almost no particle size distribution.
実施例２〜９
冥２Ｉ−例１と同様な方法によって、以下の表に示され
る組成でエマルシヨンを合成した。シェルポリマーは略
称Ｓで表わし、量は固城分で示した。Examples 2-9 Mei 2I - Emulsions were synthesized by a method similar to Example 1 with the compositions shown in the table below. The shell polymer is abbreviated as S, and the amount is expressed in hardness.
モノマー囚、そツマー但）は、各々Ａ％Ｂ１と略して示
した。なお実施例３及び４については補助溶媒としてメ
チルエチルケトン２０９を使用した。The monomers and monomers are abbreviated as A%B1, respectively. Note that in Examples 3 and 4, methyl ethyl ketone 209 was used as an auxiliary solvent.
本実施例で得られたエマルシヨンは沈殿物がほとんどな
くかつ数カ月自然保存しても沈殿物は増加せず安定なも
のであった。エマルシヨンの粒径は電子顕＠鏡撮影から
測定した結果エマルシヨンの種類によって正はあるが０
．１５〜０．３μ程度であった。しかし各々のエマルジ
四ンはほとんど単分散の粒度分布を示し、かつ粗大粒子
や微小粒子がみられず、極めて良く粒径が揃っていた。The emulsion obtained in this example contained almost no precipitate and was stable without increasing the amount of precipitate even after being stored naturally for several months. The particle size of the emulsion is determined by electron microscopy and may be positive depending on the type of emulsion, but it may be 0.
．． It was about 15 to 0.3μ. However, each emulsion had an almost monodisperse particle size distribution, and no coarse particles or fine particles were observed, and the particle sizes were extremely uniform.
なお室温で粒子が融着して観察できないものはレプリカ
法で測定した。In addition, particles that could not be observed due to fusion at room temperature were measured using the replica method.
比較例１（比較エマルシヨンの合成）
既知の溶液麓合法でステアリルメタアクリレート−メタ
アクリル酸共重合体（重量比９８／２ ）の４０％ヘキ
サン溶液を得た。このポリマー浴液７０ｔを４５０ｔの
ＩＰソルベントとともに実施例１と同様に４ツロフラス
コに加えると均一な透明溶液となった。（本ポリマーは
シェルポリマーではなく、従来技術に用いられていた可
溶性ポリマーに相当する）
以下実施例１と全く同様にモノマーを加えて重合を行な
りたところ内温は１０５℃まで上昇した。Comparative Example 1 (Synthesis of Comparative Emulsion) A 40% hexane solution of stearyl methacrylate-methacrylic acid copolymer (weight ratio 98/2) was obtained by a known solution method. When 70 t of this polymer bath solution was added to a 4-tube flask together with 450 t of IP solvent in the same manner as in Example 1, a uniform transparent solution was obtained. (This polymer is not a shell polymer, but corresponds to a soluble polymer used in the prior art.) Monomers were added and polymerization was carried out in exactly the same manner as in Example 1, and the internal temperature rose to 105°C.
残存モノマーを留去後の白色エマルシヨンには全く沈殿
物もなく、モノマー臭もほとんどなかった。The white emulsion after distilling off the remaining monomers had no precipitates at all and almost no monomer odor.
粒径は０．２μで粒度分布はなかった。The particle size was 0.2μ and there was no particle size distribution.
実施例−１０（正帯電性液体現像剤の製造例）実施例−
１で得られた２５０ｔのエマルジ璽ン中に、４０２のキ
シレンに溶解した５ｆのオイルブラックＨＢＢ（オリエ
ント化学社製）を超音波をかけながら滴下しエマルジ冒
ン粒子を着色した。Example-10 (Production example of positively chargeable liquid developer) Example-
5F oil black HBB (manufactured by Orient Chemical Co., Ltd.) dissolved in 402 xylene was dropped into the 250 t emulsion bottle obtained in step 1 while applying ultrasonic waves to color the emulsion particles.
次いで電荷制御剤として１チのステペライトレジンのア
ルミニウム塩のキシレン溶液１０ｆを加えコンク（−一
）トナーを得た。Next, 10 f of a xylene solution of aluminum salt of stepelite resin was added as a charge control agent to obtain a conc (-1) toner.
このコンクトナーをアイソパーＧでトータルを１０ｔに
希釈し正帯′４性の７反体現像剤（Ｐ−１トナー）を得
た。This condenser was diluted with Isopar G to a total of 10 tons to obtain a 7-antibody developer (P-1 toner) with regular band '4 properties.
′Ａ′ＪＪｉ例−１１（負帯電性液体現像剤の一造例）
エマルジ璽ン粒子の着色までは実施例−１０と全く同様
に行ない、負帯電性の′４荷制御剤としてジオクチルス
ルホサクシネートのナトリウム塩を０．３５Ｆ加えコン
クトナーを得た。'A'JJi Example-11 (An example of creating a negatively charged liquid developer)
The coloring of the emulsion particles was carried out in exactly the same manner as in Example 10, and a condenser was obtained by adding 0.35 F of sodium salt of dioctyl sulfosuccinate as a negative charge control agent.
得られた；ンクトナーをアイソパーＧでトータルをＩＯ
ｔに希釈し、負帯電性の液体現像剤（Ｎ−１トナー）を
得た。Obtained; total IO of Ncttoner with Isopar G
A negatively charged liquid developer (N-1 toner) was obtained.
実施例−１２
実施例２〜９で得られたエマルシヨンを正帯電性現像剤
とする為に実施例−１０と同様な方法で製造したところ
、粒子帯電能は各々多少異なるものの良好な正帯電性液
体現像剤が得られた。（Ｐ−２〜Ｐ−９トナー）
実施例−１３
実施例２〜９で得られたエマルジョンを負葡電性現像剤
とする為に実施例−１１と同様な方法で製造したところ
、粒子帯゛４能は各々多少異なるものの良好な負帯電性
液体現像剤が得られた。〔Ｎ−２〜Ｎ−９トナー〕
実施例−１４（比較用液体現像剤の製造）比較例−１で
合成したエマルジョンを用いて、正帯電性用として実施
例−１０と全く同様な方法で、負ｖ電住用として実施例
−１１と全く同様な方法で液体現像剤を得た。（比ＭＰ
−１）ナー、比較Ｎ−１トナー）
実施例−１５（可溶性樹脂成分の測定）囚 実施例−１
Ｏで得られたコンクトナー３０２をアイビーソルベント
で３００１７！に希釈しセミコンクトナーを得た。電極
板として２枚のアルミニウム板をこのセミコンクトナー
中に入れ直流３０００Ｖの電圧を印加した。＄蛍’にし
ているエマル９１７粒子はｅ電極に付着し液の濁度が徐
々に低下した。新しいアルミニウム板で３〜５回繰返す
とエマルジ冒ン粒子は見金に′−極上へ除去され濁りの
ない淡赤色の残液が得られた。本残液にエバボレートし
正確に固型分を測定するとわずかに０．０３Ｆであった
。Example 12 The emulsions obtained in Examples 2 to 9 were produced in the same manner as in Example 10 in order to make positively chargeable developers, and although the particle chargeability was slightly different, good positive chargeability was obtained. A liquid developer was obtained. (P-2 to P-9 toners) Example 13 The emulsions obtained in Examples 2 to 9 were produced in the same manner as in Example 11 to make negative electrostatic developers. Although the performance of each developer was slightly different, a good negatively chargeable liquid developer was obtained. [N-2 to N-9 toners] Example 14 (Manufacture of liquid developer for comparison) Using the emulsion synthesized in Comparative Example 1, toners with positive chargeability were prepared in exactly the same manner as in Example 10. A liquid developer for use in negative V-electronics was obtained in exactly the same manner as in Example 11. (ratio MP
-1) toner, comparative N-1 toner) Example-15 (Measurement of soluble resin component) Example-1
30017 with Ivy Solvent using conctator 302 obtained with O! The mixture was diluted to obtain a semi-condensed toner. Two aluminum plates were placed as electrode plates in this semiconductor, and a DC voltage of 3000 V was applied. The Emul 917 particles that made the $fireflies adhered to the e-electrode, and the turbidity of the liquid gradually decreased. When the process was repeated 3 to 5 times using a new aluminum plate, the emulsion particles were removed to a fine layer, leaving a pale red residual liquid with no turbidity. When this residual liquid was evaporated and the solid content was accurately measured, it was only 0.03F.
但）一方比較例−１で合成したエマルジョンを用いた場
合に全く同様な深作を行なうと、渇シのない淡赤色残液
が得られた。しかしこの残液をエバボレートして固型分
を測定すると０．８９ｒであった。However, when the emulsion synthesized in Comparative Example 1 was used and the same deep cultivation was carried out, a pale red residual liquid without dryness was obtained. However, when this residual liquid was evaporated and the solid content was measured, it was 0.89r.
従って可溶性樹脂存在下に蔗合を行なって得たエマルジ
ョンは、可溶性ｔａｈぼ成分が該溶脈中に溶解して存在
している確率が問いといえる。Therefore, in the case of emulsions obtained by merging in the presence of soluble resins, the question is the probability that soluble tether components exist dissolved in the weld veins.
しかしながら本発明のエマルジョンは可陽性部がほとん
どみられず、シェルポリマーは粒子に成層しているとみ
るのが妥当であろう。However, in the emulsion of the present invention, almost no positive parts were observed, and it is reasonable to assume that the shell polymer is layered in the particles.
（Ｑ 実施例−１２で得られたコンクトナーについても
同様の央訣を行なったが固型分は０．０２〜０．８２の
範囲で０３）の場合と比較して明らかに少なかった。(A similar process was carried out for the compactor obtained in Q Example-12, but the solid content was clearly lower in the range of 0.02 to 0.82 than in the case of 03).
実施例−１６
実施例−１０で得られたＰ−１トナー、実施例１２で得
られたＰ−２〜Ｐ−９トナーを液体現像剤とし、ＢＰ−
１２（三菱製紙伝）製ダイレクト製版機）を用いて、電
子写真ダイレクト印刷版ＬＯＭ−ｎＢｌＪ版したところ
いづれもエッヂのしっかりした画像が得られ、本刷版を
用いた印Ｍ物も美しい仕上シでめった。比較として実施
例−１４で得られた比較トナーＰ−１の場合画像部の周
囲に、にじみ状のゴーストが発生した。また１ｉｌｉ像
も崩れ気味であった。本刷版を使用した印刷物は虫じた
画像故障のパターンが印刷物に現われてしまい不可であ
った。Example-16 The P-1 toner obtained in Example-10 and the P-2 to P-9 toners obtained in Example 12 were used as liquid developers to develop BP-1.
12 (Direct Plate Making Machine manufactured by Mitsubishi Seishiden)), the electrophotographic direct printing plate LOM-nBlJ plate was printed, and images with firm edges were obtained in all cases, and the printed M items using this printing plate also had a beautiful finished image. I failed. For comparison, in the case of comparative toner P-1 obtained in Example-14, a smudge-like ghost occurred around the image area. The statue of 1ili also seemed to be crumbling. Prints using this printing plate were not acceptable because a pattern of image defects appeared on the prints.
実施例−１７
貌水化処理が施されたアルミニウム板に、酸価の高いア
クリル樹脂中に分散した乙−型銅フタロシアニン顔料を
塗布乾燥し印刷用原版とした。（バインター／顔料比＝
７５／２５） 該原版を暗所でコロナ帯電にて正帯電
させた後に画像露光を行なった。実施例−１３で得られ
たＮ−２トナーで現像した後に熱定着した。冷却後にＤ
Ｐ−４（富士写真フィルム（ロ））ＰＳ版用現像液）を
水で１０倍に希釈した液の中に１０秒間浸漬した後に水
洗した。Example 17 An O-type copper phthalocyanine pigment dispersed in an acrylic resin with a high acid value was coated on an aluminum plate that had been subjected to a water-refining treatment and dried to obtain a printing original plate. (binter/pigment ratio =
75/25) After the original plate was positively charged by corona charging in a dark place, image exposure was performed. After developing with the N-2 toner obtained in Example 13, heat fixing was performed. D after cooling
It was immersed for 10 seconds in a solution prepared by diluting P-4 (Fuji Photo Film (b) PS plate developer) 10 times with water, and then washed with water.
トナー画像部だけが美しい画像として残り、非画像部は
元金に溶出された印刷版が出来た。Only the toner image area remained as a beautiful image, and the non-image area was eluted into the original metal to create a printing plate.
一方実施例−１４で得られた比較Ｎ−１トナーで現像し
た場合には画像部の周囲に、にじみ状のゴーストが発生
し、ＤＰ−４で非画１家部を浴出した後もそのパターン
は残ってしまった。また、Ｎ−３〜Ｎ−９トナーで実施
した場合も良好な印刷版が得られ、印刷物もシャープな
画像であつ九が、比較Ｎ−１トナーだけは画像部ノ面辺
のゴーストの為に美しい仕上りとはならなかった。On the other hand, when developing with Comparative N-1 toner obtained in Example-14, a smudge-like ghost was generated around the image area, and even after the non-image area was washed away with DP-4, The pattern remained. Also, when using N-3 to N-9 toners, good printing plates were obtained, and the printed images were sharp. It was not a beautiful finish.
更にＮ−２トナー及び比較Ｎ−１）ナーの各１ｔを用い
てＢ−４版の原版で連続処理を行なうと２０版０で比較
ｌＮ−１）ナーの場合ゴーストの発生が截しく使用不可
となってしまったが、Ｎ−２トナーは７０版処理しても
全く異常はなかった。Furthermore, when continuous processing is performed on the original B-4 plate using 1 t each of N-2 toner and comparative N-1) toner, comparison is made with 20 plate 0. In the case of N-1) toner, ghosting occurs and it cannot be used However, there was no abnormality at all with the N-2 toner even after 70 plate processing.
以上の実施例より本発明のエマルジ菅ンを用いた液体現
像剤を用いた場合、良好な刷版及び美しい仕上りの印刷
物が得られる事が判る。From the above examples, it can be seen that when a liquid developer using the emulsion tube of the present invention is used, a good printing plate and a printed matter with a beautiful finish can be obtained.
Claims (1)
子を含む静電写真用液体現像剤において、該樹脂が、下
記の重合体（Ｓ）の存在下で、下記のモノマー（Ａ）及
びモノマー（Ｂ）を重合して得られる樹脂であることを
特徴とする静電写真用液体現像剤。 重合体（Ｓ）：該媒体に不溶であり、かつカルボキシル
基を有する重合体。 モノマー（Ａ）：該媒体には可溶で重合により不溶化す
るモノマー。 モノマー（Ｂ）：該媒体に可溶で重合しても可溶な重合
体を形成するモノマー。[Scope of Claims] An electrostatographic liquid developer comprising at least resin particles dispersed in a highly insulating hydrocarbon medium, wherein the resin contains the following monomer in the presence of the following polymer (S). A liquid developer for electrostatic photography, characterized in that it is a resin obtained by polymerizing (A) and a monomer (B). Polymer (S): A polymer that is insoluble in the medium and has a carboxyl group. Monomer (A): A monomer that is soluble in the medium and becomes insolubilized by polymerization. Monomer (B): A monomer that is soluble in the medium and forms a soluble polymer upon polymerization.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61074507A JPS62231267A (en) | 1986-03-31 | 1986-03-31 | Liquid developer for electrostatic photography |
| US07/033,002 US4873166A (en) | 1986-03-31 | 1987-03-31 | Liquid developer for electrophotography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61074507A JPS62231267A (en) | 1986-03-31 | 1986-03-31 | Liquid developer for electrostatic photography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62231267A true JPS62231267A (en) | 1987-10-09 |
| JPH0431587B2 JPH0431587B2 (en) | 1992-05-26 |
Family
ID=13549304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61074507A Granted JPS62231267A (en) | 1986-03-31 | 1986-03-31 | Liquid developer for electrostatic photography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62231267A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389575A (en) * | 1986-09-24 | 1988-04-20 | アクゾ・ナームローゼ・フェンノートシャップ | Aqueous coating composition |
| US5398105A (en) * | 1990-06-06 | 1995-03-14 | Mitsubishi Paper Mills Limited | Method of electrophotographic wet reversal development |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60164757A (en) * | 1984-02-07 | 1985-08-27 | Fuji Photo Film Co Ltd | Liquid developer for electrophotography |
| JPS60179751A (en) * | 1984-02-28 | 1985-09-13 | Fuji Photo Film Co Ltd | Liquid developer for electrostatic photography |
| JPS60225858A (en) * | 1984-04-24 | 1985-11-11 | Mitsubishi Paper Mills Ltd | Electrophotographic liquid developer |
-
1986
- 1986-03-31 JP JP61074507A patent/JPS62231267A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60164757A (en) * | 1984-02-07 | 1985-08-27 | Fuji Photo Film Co Ltd | Liquid developer for electrophotography |
| JPS60179751A (en) * | 1984-02-28 | 1985-09-13 | Fuji Photo Film Co Ltd | Liquid developer for electrostatic photography |
| JPS60225858A (en) * | 1984-04-24 | 1985-11-11 | Mitsubishi Paper Mills Ltd | Electrophotographic liquid developer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389575A (en) * | 1986-09-24 | 1988-04-20 | アクゾ・ナームローゼ・フェンノートシャップ | Aqueous coating composition |
| US5398105A (en) * | 1990-06-06 | 1995-03-14 | Mitsubishi Paper Mills Limited | Method of electrophotographic wet reversal development |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0431587B2 (en) | 1992-05-26 |
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