JPS63210852A - Manufacture of toner for electrostatic charge image - Google Patents
Manufacture of toner for electrostatic charge imageInfo
- Publication number
- JPS63210852A JPS63210852A JP62043070A JP4307087A JPS63210852A JP S63210852 A JPS63210852 A JP S63210852A JP 62043070 A JP62043070 A JP 62043070A JP 4307087 A JP4307087 A JP 4307087A JP S63210852 A JPS63210852 A JP S63210852A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- toner
- coupling agent
- black
- aluminum coupling
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 39
- 239000007822 coupling agent Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000012798 spherical particle Substances 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 28
- 241000872198 Serjania polyphylla Species 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- 239000002609 medium Substances 0.000 abstract description 7
- 238000004040 coloring Methods 0.000 abstract description 5
- 239000010419 fine particle Substances 0.000 abstract description 2
- 239000007870 radical polymerization initiator Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 isogren Chemical compound 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFYOYKPJLRMJI-UHFFFAOYSA-N Lercanidipine hydrochloride Chemical compound Cl.COC(=O)C1=C(C)NC(C)=C(C(=O)OC(C)(C)CN(C)CCC(C=2C=CC=CC=2)C=2C=CC=CC=2)C1C1=CC=CC([N+]([O-])=O)=C1 WMFYOYKPJLRMJI-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OTKLRHWBZHQJOP-UHFFFAOYSA-N 3-aminopropyl prop-2-enoate Chemical compound NCCCOC(=O)C=C OTKLRHWBZHQJOP-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- MCOQHIWZJUDQIC-UHFFFAOYSA-N barban Chemical class ClCC#CCOC(=O)NC1=CC=CC(Cl)=C1 MCOQHIWZJUDQIC-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KFKPWTFHOVSSSI-UHFFFAOYSA-N butyl 2-hydroxyprop-2-enoate Chemical compound CCCCOC(=O)C(O)=C KFKPWTFHOVSSSI-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- VGIYPVFBQRUBDD-UHFFFAOYSA-N ethenoxycyclohexane Chemical compound C=COC1CCCCC1 VGIYPVFBQRUBDD-UHFFFAOYSA-N 0.000 description 1
- PSYUBHDPOIZRST-UHFFFAOYSA-N ethyl pyruvate Chemical compound CCOC(=O)C(O)=C PSYUBHDPOIZRST-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005484 gravity Effects 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- OGOBWYZAVILZEC-UHFFFAOYSA-N propyl 2-hydroxyprop-2-enoate Chemical compound CCCOC(=O)C(O)=C OGOBWYZAVILZEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- LXMSZDCAJNLERA-ZHYRCANASA-N spironolactone Chemical compound C([C@@H]1[C@]2(C)CC[C@@H]3[C@@]4(C)CCC(=O)C=C4C[C@H]([C@@H]13)SC(=O)C)C[C@@]21CCC(=O)O1 LXMSZDCAJNLERA-ZHYRCANASA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene 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
- G03G9/09—Colouring agents for toner particles
- G03G9/0906—Organic dyes
- G03G9/0908—Anthracene dyes
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明者は静電荷像現像用トナーの製造方法に関するも
ので、より詳細には、流動性、黒色度。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present inventor relates to a method for producing a toner for developing electrostatic images, and more specifically, the field of the present invention relates to fluidity and blackness.
着色 力に優れたトナーを定着用樹脂の重合工程中で収
率よく製造する方法に関する。The present invention relates to a method for producing a toner with excellent coloring power in a high yield during the polymerization process of a fixing resin.
（従来の技術）
電子写真法等で静電荷像を可視像化（現像）するための
トナーとしては、スチレン系樹脂等の定着用樹脂媒質と
、この樹脂媒質中に分散させたカーボンブラック等の着
色剤との組成物を粒状化したものが広く使用されている
。(Prior art) A toner for visualizing (developing) an electrostatic charge image using electrophotography or the like uses a fixing resin medium such as styrene resin, and carbon black etc. dispersed in this resin medium. A granulated composition containing a coloring agent is widely used.
このトナーの最も代表的な製法は、前述した樹脂媒質と
着色剤とを溶融混練し、この墨線組成物を冷却粉砕し、
粉砕物を分級して一定の粒度範囲に揃える工程から成る
。しかしながら、カーボンブラックは樹脂中でもチェン
構造をとりやすく、樹脂中に一様に微粒化分散すること
が困難である。The most typical manufacturing method for this toner is to melt and knead the above-mentioned resin medium and colorant, cool and pulverize this ink line composition, and
It consists of the process of classifying the pulverized material and aligning it within a certain particle size range. However, carbon black tends to form a chain structure even in the resin, making it difficult to uniformly atomize and disperse it in the resin.
この欠点を解消するものとして、特開昭６０−９３４５
２号公報には、アルミニウム系力ツノリング剤によって
処理されたカービンブラックを、溶融混線によってバイ
ンダー樹脂中に均一に分散させ、次いで粉砕・分級によ
ってトナーを製造することが記載されている。As a solution to this drawback, Japanese Patent Application Laid-Open No. 60-9345
Publication No. 2 describes that carbine black treated with an aluminum-based force-toning agent is uniformly dispersed in a binder resin by melt mixing, and then pulverized and classified to produce a toner.
（発明が解決しようとする問題点）
しかしながら、この粉砕・分級によシ得られるトナーの
収率は低く、またこれらの操作のために多大な設備を必
要とし、そのためにトナーの製造コストを極めて高いも
のとしている。また、得られる粒子の形状が不規則であ
るため、トナーの流動性が概して低く、ブロッキングを
発生し易いという欠点も認められる。(Problems to be Solved by the Invention) However, the yield of toner obtained by this pulverization and classification is low, and a large amount of equipment is required for these operations, resulting in extremely high toner production costs. It is considered expensive. Further, since the shape of the obtained particles is irregular, the fluidity of the toner is generally low, and there is also a drawback that blocking is likely to occur.
更に、定着用樹脂との溶融混線によっては、カーメンブ
ラックの表面処理を行っても、完全な微粒化分散は未だ
困難である。Further, even if surface treatment with carmen black is performed, complete atomization and dispersion is still difficult due to melt cross-contamination with the fixing resin.
定着用樹脂媒質中でのカービンブラックの分散が不均一
であると、黒色度、着色力が劣シ、画像濃度の低下をも
たらす。また、カップリング剤によるカーボンブラック
の処理の効果は、単にカップリング剤の種類や処理量に
依存するだけではなく、カーがンブラックそのものの表
面の化学的及び物理的特性にも大きく依存すると共に、
定着用樹脂との混合操作によっても影響されることから
、従来の手段では十分満足し得る成果を挙げるに至って
いない。If the dispersion of carbine black in the fixing resin medium is non-uniform, the degree of blackness and coloring power will be poor, resulting in a decrease in image density. Furthermore, the effect of treating carbon black with a coupling agent does not simply depend on the type and amount of the coupling agent used, but also greatly depends on the chemical and physical properties of the surface of the carbon black itself. ,
Since it is also affected by the mixing operation with the fixing resin, conventional means have not achieved sufficiently satisfactory results.
（問題点を解決するための手段）
本発明者等は、トナー用のカーメンブラックとして比較
的比表面が小さく、−値の低いカーボンブラックを、選
択すること；このカービンブラックをアルミニウムカッ
プリング剤で処理すること；及びこの特定のカービンブ
ラックとラジカル重合性単量体とを含む重合性組成物を
水性媒体中に懸濁させて球状粒子への重合を行うことが
、定着用樹脂媒質中にカービンブラックを一様に分散さ
れた球状トナー粒子を得る上で重要であることを見出し
た。(Means for Solving the Problems) The present inventors selected a carbon black with a relatively small specific surface and a low value as carmen black for toner; and suspending this particular polymerizable composition comprising carbine black and a radically polymerizable monomer in an aqueous medium to polymerize it into spherical particles. It has been found that this is important in obtaining spherical toner particles in which black is uniformly dispersed.
本発明によれば、ラジカル重合性単量体及びアルミニウ
ムカップリング剤で処理された比表面積３００ｍ２／ｇ
以下かつｐＨ７，０以下のカービンブラ、りから成る組
成物を水性媒体中に懸濁させ、懸濁粒子なう・ゾカル開
始剤の存在下に重合させ、該単量体の重合で生成する定
着用樹脂とその中に分散されたカービンブラックとから
成る球状粒子を分離することから成る静電荷像用トナー
の製法が提供される。According to the present invention, the specific surface area treated with a radically polymerizable monomer and an aluminum coupling agent is 300 m2/g.
A fixing agent formed by polymerizing the monomers by suspending a composition consisting of Carbinbra and chlorine having a pH of 7.0 or less in an aqueous medium and polymerizing the suspended particles in the presence of a zocal initiator. A method of making an electrostatic toner is provided which comprises separating spherical particles comprising a resin and carbine black dispersed therein.
（作用）
本発明において、トナー用のカーがンブラックとして比
較的比表面積の小さい、即ち比表面積（ＢＥＴ）が３０
０ ｍ２７１７以下で一値７．０以下のものを用いるの
が第一の特徴である。カーメンブラックの内位とは、カ
ービンブラックの水性懸濁液の−のことであり、−値の
低いカービンブラックは、その製法、処理法に由来して
、炭素、水素と相当量の酸素（一般に２乃至１２重量％
）とを含有することが特徴である。この酸素はカーボン
ブラック粒子光面に極性基として存在するものと認めら
れるが、これらの極性基の存在がアルミニウムカップリ
ング剤との協働作用により、カー？ンブラック粒子を定
着樹脂用単量体中に一様に微粒化分散させるものと認め
られる。(Function) In the present invention, as a car black for toner, the specific surface area is relatively small, that is, the specific surface area (BET) is 30.
The first feature is to use a material with a value of 0 m2717 or less and a single value of 7.0 or less. The internal value of carmen black refers to the - value of an aqueous suspension of carbine black, and carbine black with a low - value is derived from its manufacturing and processing methods, and contains carbon, hydrogen, and a considerable amount of oxygen (generally 2 to 12% by weight
). It is recognized that this oxygen exists as a polar group on the optical surface of the carbon black particle, but the existence of these polar groups, due to the cooperative action with the aluminum coupling agent, causes carbon black particles to become carbon black particles. It is recognized that the black particles are uniformly atomized and dispersed in the fixing resin monomer.
このカービンブラックは３００ ｍ ／ｌ／以下の比表
面積を有することも重要であυ、比表面積がこの範囲を
越えて大きくなると、アルミニウムカップリング剤と組
合せて用いたとしても、定着樹脂用単量体中に一様に微
粒化分散させることが困難となり、更に単量体の重合体
への転化率や重合速度も低下する傾向が表われる。これ
は比表面積が大きい程、表面活性が大となり粒子相互の
凝集傾向が大となること、及びアルミニウムカップリン
グ剤の効果が十分に及ばなくなることと関連していると
思われる。It is also important that this carbine black has a specific surface area of 300 m/l/or less; if the specific surface area exceeds this range, even if it is used in combination with an aluminum coupling agent, the monomer for the fixing resin will be It becomes difficult to uniformly atomize and disperse the monomer into the polymer, and the conversion rate of the monomer to the polymer and the polymerization rate also tend to decrease. This seems to be related to the fact that the larger the specific surface area, the greater the surface activity, the greater the tendency for particles to agglomerate, and the less effective the aluminum coupling agent is.
本発明の目的に適したチャンネル型カーゲンブラックハ
、スペシャル・ブラック４．スペシャル・ブラック５、
ＭＡ−１００等として入手し得るが。Channel-type Cargen Black Ha, Special Black, suitable for the purpose of the present invention4. special black 5,
It is available as MA-100 etc.
勿論これらに限定されない。Of course, it is not limited to these.
本発明によれば、この特定のカーピンブランクをアルミ
ニウム系カップリング剤で表面処理する。According to the invention, this particular carpin blank is surface treated with an aluminum-based coupling agent.
従来、カップリング剤としては、アルミニウム系以外の
もめとして、シラン系及びチタン系のカップリング剤が
多数知られており、また各方面にも広く使用されている
。しかしながら、本発明者等の研究によると、シラン系
カップリング剤やチタン系カップリング剤をこの目的に
使用したのでは殆んど効果が得られず、前述した種々の
作用はアルミニウム系カップリング剤に特有のものであ
る。Conventionally, many coupling agents other than aluminum-based coupling agents, such as silane-based and titanium-based coupling agents, have been known and are widely used in various fields. However, according to the research conducted by the present inventors, the use of silane coupling agents and titanium coupling agents for this purpose has little effect, and that the various effects described above are caused by the use of aluminum coupling agents. It is unique to
アルミニウム系カップリング剤の適当な例は、これに限
定されないが、アセトアルコキシアルミニウムジイソゾ
ロピレートである。A suitable example of an aluminum-based coupling agent is, but is not limited to, acetalkoxyaluminum diisozolopyrate.
カーボンブラックに対するアルミニウム系カップリング
剤の処理量は、カーボンブラック当り０．１乃至３０重
量％、特に１０乃至３０重量％の範囲内にあることが望
ましい。即ち、この量が上記範囲よりも少ないと分散性
向上等に対する十分な効果が得られず、一方上記範囲よ
りも多くても格別の効果の上積みは期待できず、経済的
にはかえって不利となる。The amount of aluminum-based coupling agent treated with respect to carbon black is desirably in the range of 0.1 to 30% by weight, particularly 10 to 30% by weight, based on carbon black. That is, if the amount is less than the above range, sufficient effects such as improving dispersibility cannot be obtained, while if it is more than the above range, no particular additional effect can be expected, which is economically disadvantageous. .
カーボンブラックの表面処理は、アルミニウム系カップ
リング剤を溶解可能な有機溶剤、例えばトルエン、キシ
レン、ヘキサン等に溶解させ、この溶液にカーフにンブ
ラックを浸漬し、これを乾燥することによっても行うこ
とができる。しかしながら、本発明においては、アルミ
ニウムカップリング剤処理カーボンブラックが、アルミ
ニウム力、ｆ リｙグ成分が難溶な有機溶媒、例えばメ
タノール、アセトン等でカーボンブラックを湿潤させ、
この系にアルミニウムカップリング剤を滴下、攪拌する
ことにより得られたものであることが望ましい。この方
法によれば、前者の方法に比して、カーボンブラック粒
子の表面がむしろ一様にアルミニウムカップリング剤で
表面処理され、操作も著しく簡単に行われることがわか
った。Surface treatment of carbon black can also be carried out by dissolving the aluminum coupling agent in an organic solvent such as toluene, xylene, hexane, etc., immersing the carbon black in this solution, and drying it. Can be done. However, in the present invention, carbon black treated with an aluminum coupling agent is obtained by moistening the carbon black with an organic solvent in which the aluminum coupling agent is poorly soluble, such as methanol, acetone, etc.
It is preferable that the aluminum coupling agent be obtained by dropping an aluminum coupling agent into this system and stirring. It has been found that according to this method, the surface of the carbon black particles is treated with the aluminum coupling agent more uniformly than in the former method, and the operation is significantly easier.
本発明においては、上記カップリング剤処理カーボンブ
ラック及び定着用樹脂単量体を含む組成物を水性媒体中
に懸濁させ、この懸濁粒子をラジカル開始剤の存在下に
重合させることが第二の特徴である。In the present invention, the second step is to suspend the composition containing the coupling agent-treated carbon black and the fixing resin monomer in an aqueous medium, and to polymerize the suspended particles in the presence of a radical initiator. It is a characteristic of
即ち、この手段を採用することにより、定着用樹脂の重
合工程でトナーに適した粒度の樹脂−カー？ンブラック
組成物の球状粒子が一挙に製造されるという利点が得ら
れるはかりではなく、カーぎンブラック粒子の樹脂中へ
の分散が極めて、微細になるという利点がある。That is, by adopting this method, a resin-carrier having a particle size suitable for the toner can be used in the polymerization process of the fixing resin. This scale does not have the advantage that spherical particles of the Cargin black composition are produced all at once, but has the advantage that the dispersion of the Cargin black particles in the resin is extremely fine.
一般に定着用樹脂単量体中にカーボンブラックを添加す
ると、その重合速度は小さくなシ、また重合体への転化
率も小さくなる傾向が認められる。Generally, when carbon black is added to the fixing resin monomer, the polymerization rate tends to be low and the conversion rate to the polymer tends to be low as well.
これはカーボンブラック表面にキノイド状酸素があり、
これが重合禁止作用を示すためと考えられる。本発明に
よれば、カーボンブラックとして比表面積の比較的小さ
いカーボンブラックを使用し。This is because there is quinoidal oxygen on the carbon black surface.
This is thought to be because it exhibits a polymerization inhibiting effect. According to the present invention, carbon black having a relatively small specific surface area is used as carbon black.
しかもカーボンブラックをアルミニウムカップリング剤
で表面処理することにより、重合速度及び重合体への転
化率をも高いレベルに維持することが可能となるもので
ある。Moreover, by surface-treating carbon black with an aluminum coupling agent, it is possible to maintain the polymerization rate and the conversion rate to a polymer at a high level.
本発明において、表面処理カーボンブラックは、単量体
当り１乃至２０重蓋チ、特に２乃至ｌＯ重ｔ％の量で用
いるのがよい。In the present invention, the surface-treated carbon black is preferably used in an amount of 1 to 20% by weight, particularly 2 to 10% by weight, per monomer.
本発明において、使用する単量体はラジカル重合性のも
のであり、しかも生成重合体がトナーに要求される定着
性と検電性を有するものであシ、エチレン系不飽和を有
する単量体の１種又は２種以上の組合せが前述した制限
のもとに使用される。In the present invention, the monomer used is one that is radically polymerizable, and the resulting polymer has the fixing properties and electrodetection properties required for a toner. One or a combination of two or more of these may be used subject to the above-mentioned limitations.
このような単量体の適当な例は、モノビニル芳香族単量
体、アクリル系単量体、ビニルエステル系単量体、ビニ
ルエーテル系単量体、ジオレフィン系単量体、モノオレ
フィン系単量体等である。Suitable examples of such monomers include monovinyl aromatic monomers, acrylic monomers, vinyl ester monomers, vinyl ether monomers, diolefin monomers, and monoolefin monomers. body etc.
モノビニル芳香族単量体としては、
式
式中、Ｒ１は水素原子、低級アルキル基又はハロゲン原
子であｐ、Ｒ２は水素原子、低級アルキル基、ハロゲン
原子、アルコキシ基、アミン基、ニトロ基、ビニル基或
いはカルブキシル基である、のモノビニル芳香族炭化水
素、例えばスチレン、α−メチルスチレン、ビニルトル
エン、α−クロロスチレン、０−１ｍ−１ｐ−クロロス
チレ／、ｐ−エチルスチレン、ステンンスルホンａｆｔ
’）ラム、ジビニルベンゼンの単独又は２種以上の組合
せを挙げることができ、更に前述した他の単量体として
は以下のものが夫々挙げられる。As a monovinyl aromatic monomer, in the formula, R1 is a hydrogen atom, a lower alkyl group, or a halogen atom, and R2 is a hydrogen atom, a lower alkyl group, a halogen atom, an alkoxy group, an amine group, a nitro group, or a vinyl atom. monovinyl aromatic hydrocarbons, such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, 0-1m-1p-chlorostyrene/, p-ethylstyrene, stainless sulfone aft
') Lamb and divinylbenzene may be used alone or in combination of two or more, and the other monomers mentioned above include the following, respectively.
式
％式％（２）
式中、Ｒ３は水素原子又は低級アルキル基、Ｒ４は水素
原子、炭素数１２迄の炭化水素基、ヒドロキシアルキル
基、ビニルエステル基又はアミノアルキル基である、
のアクリル系単量体、例えばアクリル酸、メタクリル酸
、アクリル酸メチル、アクリル酸エチル、アクリル酸ブ
チル、アクリル酸−２−エチルヘキシル、アクリル酸シ
クロヘキシル、アクリル酸フェニル、メタクリル酸メチ
ル、メタクリル酸ヘキシル、メタクリル酸−２−エチル
ヘキシル、β−ヒドロキシアクリル酸エチル、γ−ヒド
ロキシアクリル酸プロピル、δ−ヒドロキシアクリル酸
ブチル、β−ヒドロキシメタクリル酸エチル、γ−アミ
ノアクリル酸プロピル、γ−Ｎ、Ｎ−ジエチルアミンア
クリル酸グロビル、エチレングリコールジメタクリル酸
エステル、テトラエチレングリコールジメタクリル酸エ
ステル等。Formula % Formula % (2) In the formula, R3 is a hydrogen atom or a lower alkyl group, and R4 is a hydrogen atom, a hydrocarbon group having up to 12 carbon atoms, a hydroxyalkyl group, a vinyl ester group, or an aminoalkyl group. Monomers such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, 2-methacrylate -Ethylhexyl, β-ethyl hydroxyacrylate, γ-propyl hydroxyacrylate, δ-butyl hydroxyacrylate, β-hydroxyethyl methacrylate, γ-aminopropyl acrylate, γ-N,N-diethylamine globil acrylate, ethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc.
式 ％式％ 式中、Ｒ５は水素原子又は低級アルキル基である。formula %formula% In the formula, R5 is a hydrogen atom or a lower alkyl group.
のビニルエステル、例えばイ酸ビニル、酢酸ビニル、グ
ロピオン酸ビニル等。vinyl esters, such as vinyl iorate, vinyl acetate, vinyl glopionate, etc.
式、 ＣＨ２＝ＣＨ ０−Ｒ６・・・・・・（４） 式中、Ｒ６は炭素数１２迄の１価炭化水素基である、 のビニルエーテル、例エバビニルメチルエーテル。formula, CH2=CH 0-R6...(4) In the formula, R6 is a monovalent hydrocarbon group having up to 12 carbon atoms, vinyl ethers, e.g. eva vinyl methyl ether.
ビニルエチルエーテル、ビニル−ｎ−ブチルエーテル、
ビニルフェニルエーテル、ビニルシクロヘキシルエーテ
ル等。vinyl ethyl ether, vinyl-n-butyl ether,
Vinyl phenyl ether, vinyl cyclohexyl ether, etc.
式、
ＣＨ２＝ Ｃ−Ｃ＝ ＣＨ−Ｒ９・・・・・・（５）式
中、Ｒ７、Ｒ８、Ｒ７の各々は水素原子、低級アルキル
基又はノ・ログン原子である、
のジオレフィン類、特にブタジェン、イソグレン、クロ
ロプレン等。Diolefins of the formula, CH2= C-C= CH-R9... (5) In the formula, each of R7, R8, and R7 is a hydrogen atom, a lower alkyl group, or a nologne atom, Especially butadiene, isogren, chloroprene, etc.
式、
ＣＨ２＝Ｃ−Ｒ１１・・・・・・（６）式中、Ｒｌｏ、
Ｒ１１の各々は水素原子又は低級アルキル基である、
のモノオレフィン類、特にエチレン、プロピレン、イン
ブチレン、ブテン−１、ペンテン−１，４−メチルペン
テン−１等。Formula, CH2=C-R11...(6) In the formula, Rlo,
Each of R11 is a hydrogen atom or a lower alkyl group, monoolefins such as ethylene, propylene, imbutylene, butene-1, pentene-1,4-methylpentene-1, etc.
本発明においては、上述した必須成分以外にトナーに含
有させることが望ましい添加剤成分を、重合に先立って
重合系中に配合しておくことができる。In the present invention, in addition to the above-mentioned essential components, additive components that are desirable to be included in the toner can be blended into the polymerization system prior to polymerization.
例えば、二成分系顔料としての用途には、それ自体公知
の荷電？ｌ１１１＃剤、例えばニグロシンペース（ＣＩ
５０４５）オイルブラック（ＣＩ２６１５０）、スピ
ロンブラック等の油溶性染料や、ナフテン酸金属塩、脂
肪金属石鹸、樹脂酸石鹸等を、配合することができ、ま
たトナーにオフセット防止効果を付加するために、低分
子量ポリエチレン、低分子量ポリプロピレン、各種ワッ
クス、シリコーン油等の離型剤を含有させることができ
る。For example, when used as a two-component pigment, it may be necessary to use a charge that is known per se. l111# agents, such as nigrosin pace (CI
5045) Oil-soluble dyes such as oil black (CI26150) and spirone black, naphthenic acid metal salts, fatty metal soaps, resin acid soaps, etc. can be blended, and in order to add an anti-offset effect to the toner. , low molecular weight polyethylene, low molecular weight polypropylene, various waxes, silicone oils, and other mold release agents can be contained.
本発明方法では、前述した原料を水中に懸濁させる。水
中での懸濁状態を安定化させるため、有機又は無機の分
散剤を一般に使用する。In the method of the present invention, the above-mentioned raw materials are suspended in water. Organic or inorganic dispersants are generally used to stabilize the suspension in water.
有機分散剤としては、ゼラチン、澱粉、水溶性ｍ粉誘導
体、カル？キシメチルセルロースやエトセル等の水溶性
セルロース誘導体、ポリビニルアルコール、水溶性アク
リル樹脂、ビニルエーテル・マレイン酸共重合体等の水
溶性高分子や、アニオン系、ノニオン系、カチオン系或
いは両性系の界面活性剤が挙げられる。Examples of organic dispersants include gelatin, starch, water-soluble M powder derivatives, and Cal? Water-soluble cellulose derivatives such as xymethylcellulose and etocel, water-soluble polymers such as polyvinyl alcohol, water-soluble acrylic resin, vinyl ether/maleic acid copolymer, and anionic, nonionic, cationic, or amphoteric surfactants. Can be mentioned.
無機系分散剤としては、難溶性の無機微粒子、例えば炭
酸カルシウム、炭酸マグネシウム、リン酸マグネシウム
、硫酸バリウム、シリカ、アルミナ、メルク、ベントナ
イト等の各種クレイ、ケイソウ土等を挙げることができ
る。Examples of the inorganic dispersant include poorly soluble inorganic fine particles such as calcium carbonate, magnesium carbonate, magnesium phosphate, barium sulfate, silica, alumina, Merck, various clays such as bentonite, diatomaceous earth, and the like.
これらの無機或いは有機の分散剤は単独でも或いは２８
１以上の組合せでも用いることができる。These inorganic or organic dispersants may be used alone or in combination with 28
Combinations of one or more can also be used.
本発明の場合、一般に必要でないが、所望によっては、
媒体比重、表面張力、粘度等の調整の目的で、上記分散
剤以外に、ＮａＣ１，ＫＣｌ、 Ｎａ２８０４等の水溶
性塩類を用いることもできる。In the case of the present invention, if desired, although generally not necessary,
In addition to the above-mentioned dispersants, water-soluble salts such as NaCl, KCl, Na2804, etc. can also be used for the purpose of adjusting the specific gravity, surface tension, viscosity, etc. of the medium.
重合開始剤としては、アゾビスイソブチロニトリル等の
アゾ化合物や、クメンヒドロペルオキシド、ｔ−ブチル
ヒドロペルオキシド、過酸化ベンゾイル、過酸化ラウロ
イル等の過酸化物など単量体に可溶なものが使用される
。Polymerization initiators include those soluble in the monomer, such as azo compounds such as azobisisobutyronitrile, and peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, and lauroyl peroxide. used.
単量体と水との比は、かなり大幅に変化させ得るが、一
般に１：９９乃至５０：５０、特に５：９５乃至３０ニ
ア０の重量比で用いるのがよい。The ratio of monomer to water can vary quite widely, but it is generally preferred to use a weight ratio of 1:99 to 50:50, especially 5:95 to 30:0.
分散剤の使用量は種類によっても相違するが、水溶性高
分子分散剤は、水当り０．１乃至１０重量％。Although the amount of the dispersant used varies depending on the type, the water-soluble polymer dispersant is used in an amount of 0.1 to 10% by weight based on water.
特に０．５乃至５重量％で用いるのがよく、また無機分
散剤は単量体当り０，０１乃至１０重量％、特に０１乃
至５重ｉ％の量で用いるのがよい。界面活性剤を使用す
る場合には、懸濁粒子がエマルノヨンサイズになるよう
な量で使用してはならない。In particular, it is preferably used in an amount of 0.5 to 5% by weight, and the inorganic dispersant is preferably used in an amount of 0.01 to 10% by weight, particularly 0.1 to 5% by weight, based on the monomer. If surfactants are used, they should not be used in amounts such that the suspended particles are emulsion-sized.
ラジカル重合開始剤は単量体当り０．１乃至１０重量％
、特に０．５乃至５重ｔ％の量で用いるのがよい。The radical polymerization initiator is 0.1 to 10% by weight per monomer.
It is particularly preferable to use it in an amount of 0.5 to 5% by weight.
重合温度は一般に４０乃至１００℃、特に５０乃至９０
℃の範囲が適当であり１重合時間は単量体の種類によっ
ても相違するが、２乃至２０時間の範囲から重合が完結
する時間を選ぶのがよい。The polymerization temperature is generally 40 to 100°C, particularly 50 to 90°C.
C., and the time required for one polymerization to complete polymerization is preferably selected from a range of 2 to 20 hours, although it varies depending on the type of monomer.
本発明によれば、下記式、
ｒｚ
式中、ｒｚはトナー粒子の長径を表わし、ｒ９はトナー
粒子の短径を表わす、
で定義される真円度（Ｄ）が０．９以上、特に０．９５
乃至１の範囲内にある真球状の粒子が得られる。また、
本発明によれば、上記条件下に重合を行うことにより、
生成重合体粒子、即ちトナー粒子の粒径な１乃至３０μ
ｍ、特に５乃至２０μｍの範囲に制御することが容易で
あり、しかもその粒度分布は極めてシャープであり、そ
の標準偏差は一般に３以内である。生成粒子は反応媒質
から分離し、必要により洗浄等の精製操作を行い、乾燥
してトナー製品とする。According to the present invention, the circularity (D) defined by the following formula: rz where rz represents the major axis of the toner particle and r9 represents the minor axis of the toner particle is 0.9 or more, particularly 0. .95
True spherical particles within the range of 1 to 1 are obtained. Also,
According to the present invention, by performing polymerization under the above conditions,
The particle size of the produced polymer particles, i.e., toner particles, is 1 to 30μ.
m, particularly in the range of 5 to 20 μm, is easy to control, and its particle size distribution is extremely sharp, and its standard deviation is generally within 3. The generated particles are separated from the reaction medium, subjected to purification operations such as washing if necessary, and dried to produce a toner product.
このトナー用着色粒子には、必要により、カーボンブラ
ック、疎水性シリカ等をまぶして、最終トナーとする。The colored particles for toner are sprinkled with carbon black, hydrophobic silica, etc., if necessary, to form a final toner.
（発明の効果）
本発明によれば、カーぜンブラックを定着用樹脂媒質中
に完全に一様に微粒化分散させることにより、トナーの
黒色度及び着色度を高め、高濃度の画像形成を行うこと
ができる。また、このトナーは真球状で且つトナー中に
残存モノマーが含有されていないことから、流動性に優
れており、現像に際してブロッキング傾向も殆んどない
。(Effects of the Invention) According to the present invention, by completely and uniformly atomizing and dispersing Curzen Black in the fixing resin medium, the degree of blackness and coloring of the toner is increased, and high-density image formation is possible. It can be carried out. Further, since this toner is perfectly spherical and contains no residual monomer, it has excellent fluidity and has almost no blocking tendency during development.
また、定着用樹脂の重合工程で一挙に所定粒度の球状ト
ナー粒子が得られ、収率が高く、生産性も高いという利
点を有する・
本発明の実施例を下記に示すがこれにより本発明が限定
されるものではない。In addition, it has the advantage that spherical toner particles of a predetermined particle size can be obtained at once in the polymerization process of the fixing resin, resulting in a high yield and high productivity. Examples of the present invention are shown below. It is not limited.
実施例−１
カービンプラック：ＭＡ−１００（比表面積１３４ ｍ
２／９、−値３．０）ｌ：三菱化成工業（株）製〕５重
址部にアルミニウムカップリング剤：ＡＬ−Ｍ（アセト
アルコキシアルミニウムジイングロピレート）〔味の素
（株）製〕１重量部を添加し得られたこの混合物を、ア
セトン２０重量部中に浸漬させ、マグネテックスクーラ
ーで攪拌した後、減圧乾燥し、アルミニウムカップリン
グ剤処理カーボンブラックを得た−
上記ＡＬ−Ｍ処理カーデンブラック５重清部に、スチレ
ン７０重量部、ｎ−ブチルメタクリレート３０重量部を
加えて、ＴＫホモミキサー〔特殊機化工業（株）製〕を
用いて、３０００ ｒｐｍにて５分間攪拌することによ
りカービンプラック分散液を得た。この得られたカーピ
ンブラック分散液を光学顕微鏡（Ｘ６００）にて観察し
たところカーボンブラックの凝集物は認められず、分散
性は良好であった。Example-1 Carbine plaque: MA-100 (specific surface area 134 m
2/9, -value 3.0) L: Manufactured by Mitsubishi Chemical Industries, Inc.] Aluminum coupling agent in the 5-layer part: AL-M (acetalkoxyaluminum diinglopyrate) [manufactured by Ajinomoto Co., Inc.] 1 The resulting mixture was immersed in 20 parts by weight of acetone, stirred in a magnetic cooler, and then dried under reduced pressure to obtain aluminum coupling agent-treated carbon black. By adding 70 parts by weight of styrene and 30 parts by weight of n-butyl methacrylate to the heavy liquid part of Black 5, and stirring at 3000 rpm for 5 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). A carbine plaque dispersion was obtained. When the obtained carpin black dispersion was observed under an optical microscope (X600), no carbon black aggregates were observed, and the dispersibility was good.
このカービンプラック分散液に、荷電制御剤ピントロン
５−３４［オリエント化学（株）製〕２重址部、離型剤
ビスコール５５０Ｐ［三洋化成（株）製〕２重量部、重
合開始剤２．２′−アゾビス−（２，４ツメチルバレロ
ニトリル）５重一部を加えて、充分に分散させた。次に
、２重１ｔ９６のポリビニルアルコール水溶液中に上記
分散物を添加し、ＴＫホモミキサーを用い６０００ ｒ
ｐｍにて、１０分間攪拌し、油滴を得た。この油滴は非
常に安定で、光学顕微鏡で観察した結果、油滴中には、
カーボンブラック等の特性付与剤が均一に分散していた
。To this Carbin Plaque dispersion, 2 parts by weight of the charge control agent Pintron 5-34 [manufactured by Orient Chemical Co., Ltd.], 2 parts by weight of the mold release agent Viscoel 550P [manufactured by Sanyo Chemical Co., Ltd.], and 2.2 parts by weight of the polymerization initiator were added. 5 parts of '-azobis-(2,4-methylvaleronitrile) were added and thoroughly dispersed. Next, the above dispersion was added to a double 1t96 aqueous polyvinyl alcohol solution, and heated at 6000 r using a TK homomixer.
pm for 10 minutes to obtain oil droplets. These oil droplets are very stable, and as a result of observing them with an optical microscope, it was found that there were
Characteristic agents such as carbon black were uniformly dispersed.
その後、通常攪拌機で６ Ｏｒｐｍの攪拌速度で、窒素
気流下７０℃で５時間に２重合反応を完結させた。Thereafter, the double polymerization reaction was completed in 5 hours at 70° C. under a nitrogen stream using a regular stirrer at a stirring speed of 6 Orpm.
重合反応終了後、脱水、洗浄を繰り返し乾燥させ、平均
粒径１２μｍの本発明のトナーを得た。After the polymerization reaction was completed, dehydration and washing were repeated and dried to obtain a toner of the present invention having an average particle size of 12 μm.
上記の如くして得られたトナーを用いて、電子写真複写
機ＤＣ−１００１（：三田工業（株）製〕にて、画像形
成させたところ、カプリが少なく、高い黒化度を有する
画像が得られ、これを反射濃度計で測定し次ところ、力
ノリ濃度０．００３、黒ペタ部の画像濃度１．６と、良
好な結果が得られた。When an image was formed using the toner obtained in the above manner using an electrophotographic copying machine DC-1001 (manufactured by Sanda Kogyo Co., Ltd.), an image with less capri and a high degree of blackening was obtained. The resulting image was measured with a reflection densitometer, and good results were obtained, with a force-glue density of 0.003 and an image density of the black peta portion of 1.6.
実施例−２
実施例−１でアルミニウムカップリング剤の処理に用い
次アセトンの代わりに、メタノール２０重蓋部を用いて
、実施例−１と同一の手法により、カーボンブラック：
ＭＡ−１００（比表面積１３４ｍ２／Ｉ、ＰＨ値３．０
）［三菱化成工業（株）製〕を処理し、油滴形成を行っ
た。得られた油滴は非常に安定で、光学顕微鏡で観察し
た結果、油滴中には、カーボンブラック等の特性付与剤
が均一に分散してい次。その後、通常攪拌機で６ Ｏｒ
ｐｍの攪拌速度で、窒素気流下７０℃で５時間に２重合
反応を完結させた。重合反応終了後、脱水、洗浄を繰り
返し、乾燥させることにより、平均粒径１２μｍの本発
明のトナーを得た。Example 2 Carbon black was prepared in the same manner as in Example 1, using a 20-layer methanol lid instead of the acetone used to treat the aluminum coupling agent in Example 1:
MA-100 (specific surface area 134m2/I, PH value 3.0
) [manufactured by Mitsubishi Chemical Industries, Ltd.] to form oil droplets. The resulting oil droplets were very stable, and observation under an optical microscope revealed that the property-imparting agent, such as carbon black, was uniformly dispersed within the oil droplets. After that, use a regular stirrer for 6 Or
The bipolymerization reaction was completed in 5 hours at 70° C. under a nitrogen stream at a stirring speed of pm. After the polymerization reaction was completed, the toner of the present invention having an average particle size of 12 μm was obtained by repeating dehydration, washing, and drying.
上記の如くして得られたトナーを用いて、ＤＣ−１００
１にて、画像形成させたところ、カプリが少なく、高い
黒化度を有する画像が得られ、これを反射濃度計で測定
したところ、カプリ濃度０．００２、黒ペタ部の画像濃
度１．６と良好な結果が得られた。Using the toner obtained as above, DC-100
When an image was formed using No. 1, an image with less capri and a high degree of blackening was obtained, and when this was measured with a reflection densitometer, the capri density was 0.002, and the image density in the black peta area was 1.6. Good results were obtained.
比較例−ｌ
カーボンブラック：ゾリンテックスしく比表面８ｔｌ
５０ｍ／１１．ｐＨ値８．５）［：デグサ社製］を５部
用いて、実施例−１と、同一の方法でアルミニウムカッ
プリング剤ＡＬ−Ｍにて処理し、油滴形成を行った結果
油滴中には、１〜２μｍ程のカーボンブラックの凝集物
が見られた。この懸濁液を実施例−１と同一の手法によ
シトナー合成し、ＤＣ−１００１にて画像形成したとこ
ろカプリ濃度０．０２、画像濃度１．１となシ、十分な
画像濃度が得られなかった。Comparative example-l Carbon black: Zolintex specific surface 8tl
50m/11. pH value 8.5) [manufactured by Degussa] was treated with aluminum coupling agent AL-M in the same manner as in Example-1 to form oil droplets. Carbon black aggregates of about 1 to 2 μm in size were observed. This suspension was synthesized with a toner using the same method as in Example 1, and an image was formed using DC-1001, resulting in a capri density of 0.02 and an image density of 1.1. Sufficient image density was obtained. There wasn't.
比較例−２
実施例に於ける、アセト／、メタノール等のカップリン
グ剤が難溶な有機溶媒の代りに、カップリング剤が可溶
であるトルエン１に２０重量部用いて、力−ゼンブラッ
ク：ＭＡ−１００を実施例−１と同一の手法によシ処理
し油滴形成を行った。Comparative Example 2 Instead of the organic solvent in which the coupling agent is poorly soluble, such as acetate/methanol, in the example, 20 parts by weight of toluene 1, in which the coupling agent is soluble, was used, :MA-100 was treated in the same manner as in Example-1 to form oil droplets.
この得られた油滴は、安定であり、光学顕微鏡観察の結
果、カーボンブラックの微分散性は、実施例−１，２に
比べて劣るものであった。その後、通常攪拌機で６ Ｏ
ｒｐｍの攪拌速度で、窒素気流下７０℃で５時間に２重
合反応を完結させた。The obtained oil droplets were stable, and as a result of optical microscopic observation, the fine dispersibility of carbon black was inferior to that in Examples 1 and 2. After that, add 6 O using a regular stirrer.
The bipolymerization reaction was completed in 5 hours at 70° C. under a nitrogen stream at a stirring speed of rpm.
重合反応終了後、脱水、洗浄を繰シ返し乾燥させ、平均
粒径１２μｍの本発明のトナーを得た。After the polymerization reaction was completed, dehydration and washing were repeated and dried to obtain a toner of the present invention having an average particle size of 12 μm.
上記の如くして得られたトナーを用いて、ＤＣ−１００
１にて１画像形成させたところ、カプリが少なく、高い
黒化度を有する画像が得られたが実施例−１，２に比べ
ると多少劣るものであり、反射濃度計にて測定したとこ
ろ、カプリ濃度０．００２、画像濃度１．４であった。Using the toner obtained as above, DC-100
When one image was formed using Example 1, an image with less capri and a high degree of blackening was obtained, but it was somewhat inferior to Examples 1 and 2, and when measured with a reflection densitometer, Capri density was 0.002 and image density was 1.4.
比較例−３
カーボンブラック：プリンテックスしく比表面積１５０
ｍ２／ １１、−値８．５）（デグサ社製〕を５部用
いて、比較例−２と同一の手法により、アルミニウムカ
ップリング剤ＡＬ−Ｍで処理し、油滴形成を行った結果
、油滴中には、２〜３μｍ程の、カーピンブラックの凝
集物が見られた。この懸濁液を実施例−１と同一の手法
によりトナー合成し、ＤＣ−１００１にて画像形成した
ところ、カブリ濃度が０．０２、画像濃度０．９であっ
た。Comparative example-3 Carbon black: Printex specific surface area 150
m2/11, -value 8.5) (manufactured by Degussa) was treated with aluminum coupling agent AL-M in the same manner as in Comparative Example-2 to form oil droplets. Carpin black aggregates of approximately 2 to 3 μm in size were observed in the oil droplets. This suspension was synthesized into a toner using the same method as in Example 1, and an image was formed using DC-1001. , fog density was 0.02, and image density was 0.9.
比較例−４
アルミニウムカップリング剤で処理を行っていないカー
メンブラックＭＡ−１００（比表面積１３４ｍ／Ｉ、Ｐ
Ｆ′１値３．０）［三菱化成工業（株）製］５重量部を
用いて、実施例−１と同一の方法で、油滴形成を行った
結果、油滴中には、５〜１０μｍ程のカーピンブラック
の凝集物が見られ、この懸濁液を実施例１と同一の手法
によシ、トナー合成し、ＤＣ−１００１で画像形成した
ところ、カプリ濃度が０．０２、画像濃度が０９７５で
あった。Comparative Example-4 Carmen Black MA-100 (specific surface area 134 m/I, P
F'1 value 3.0) [manufactured by Mitsubishi Chemical Industries, Ltd.] Oil droplets were formed in the same manner as in Example-1 using 5 parts by weight. Aggregates of carpin black about 10 μm in size were observed, and when this suspension was synthesized into a toner using the same method as in Example 1 and an image was formed using DC-1001, the capri density was 0.02 and the image was The concentration was 0,975.
上記、実施例１．２、比較例１〜４の結果を表１にまと
めた。The results of the above Examples 1.2 and Comparative Examples 1 to 4 are summarized in Table 1.
Claims (2)
ング剤で処理された比表面積３００ｍ＾２／ｇ以下かつ
ｐＨ値７．０以下のカーボンブラックから成る組成物を
水性媒体中に懸濁させ、 懸濁粒子をラジカル開始剤の存在下に重合させ、該単量
体の重合で生成する定着用樹脂とその中に分散されたカ
ーボンブラックとから成る球状粒子を分離することから
成る静電荷像用トナーの製法。(1) A composition consisting of carbon black treated with a radically polymerizable monomer and an aluminum coupling agent and having a specific surface area of 300 m^2/g or less and a pH value of 7.0 or less is suspended in an aqueous medium. A toner for electrostatic images comprising polymerizing cloudy particles in the presence of a radical initiator and separating spherical particles consisting of a fixing resin produced by the polymerization of the monomer and carbon black dispersed therein. manufacturing method.
クが、アルミニウムカップリング成分が難溶な有機溶媒
でカーボンブラックを湿潤させ、この系にアルミニウム
カップリング剤を滴下、攪拌することにより得られたも
のである特許請求の範囲第１項記載の製法。(2) A patent in which aluminum coupling agent-treated carbon black is obtained by wetting carbon black with an organic solvent in which the aluminum coupling component is poorly soluble, and adding the aluminum coupling agent dropwise to this system and stirring. The manufacturing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62043070A JPS63210852A (en) | 1987-02-27 | 1987-02-27 | Manufacture of toner for electrostatic charge image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62043070A JPS63210852A (en) | 1987-02-27 | 1987-02-27 | Manufacture of toner for electrostatic charge image |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63210852A true JPS63210852A (en) | 1988-09-01 |
Family
ID=12653592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62043070A Pending JPS63210852A (en) | 1987-02-27 | 1987-02-27 | Manufacture of toner for electrostatic charge image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210852A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03171144A (en) * | 1989-11-30 | 1991-07-24 | Mita Ind Co Ltd | Electrostatic charge image developing toner and manufacture of same |
| JPH04145450A (en) * | 1990-10-05 | 1992-05-19 | Mita Ind Co Ltd | Toner for electrophotography |
| WO2016158288A1 (en) * | 2015-03-31 | 2016-10-06 | 日本ゼオン株式会社 | Method for manufacturing negatively chargeable toner and negatively chargeable toner |
-
1987
- 1987-02-27 JP JP62043070A patent/JPS63210852A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03171144A (en) * | 1989-11-30 | 1991-07-24 | Mita Ind Co Ltd | Electrostatic charge image developing toner and manufacture of same |
| JPH04145450A (en) * | 1990-10-05 | 1992-05-19 | Mita Ind Co Ltd | Toner for electrophotography |
| WO2016158288A1 (en) * | 2015-03-31 | 2016-10-06 | 日本ゼオン株式会社 | Method for manufacturing negatively chargeable toner and negatively chargeable toner |
| CN107430364A (en) * | 2015-03-31 | 2017-12-01 | 日本瑞翁株式会社 | The manufacture method and negatively charged toner of negatively charged toner |
| JPWO2016158288A1 (en) * | 2015-03-31 | 2018-01-25 | 日本ゼオン株式会社 | Method for producing negatively chargeable toner and negatively chargeable toner |
| US10353306B2 (en) | 2015-03-31 | 2019-07-16 | Zeon Corporation | Method for producing negatively chargeable toner, and negatively chargeable toner |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6268103B1 (en) | Toner processes | |
| JPH02259657A (en) | Production of electrophotographic toner excellent in cleaning characteristic | |
| JPS63210852A (en) | Manufacture of toner for electrostatic charge image | |
| JP2588886B2 (en) | Method for producing toner for developing electrostatic images | |
| JP2001092184A (en) | Method for manufacturing polymerization process toner | |
| JPH0814715B2 (en) | Method of manufacturing toner for developing electrostatic image | |
| JPH0663387A (en) | Production of blended particles | |
| JPH01260461A (en) | Production of electrostatic charge image developing toner | |
| JPS63113559A (en) | Production of toner for electrophotography | |
| JPH0438348B2 (en) | ||
| JP2005078006A (en) | Method for manufacturing toner particles | |
| JPS63313168A (en) | Electrostatic charge image developing toner and preparation of same | |
| JP2699361B2 (en) | Method for producing toner for electrostatic image | |
| JPH01244471A (en) | Production of electrostatic latent image developing toner | |
| JPS63210850A (en) | Electrophotographic toner and its manufacture | |
| JPH02223960A (en) | Production of toner | |
| JPH0257303B2 (en) | ||
| JPH01250962A (en) | Production of electrostatic latent image developing toner | |
| JPH03171144A (en) | Electrostatic charge image developing toner and manufacture of same | |
| JPH01306864A (en) | Production of toner for development of electrostatic latent image | |
| JPH02273758A (en) | Production of polymerized toner | |
| JPH01250964A (en) | Production of electrostatic latent image developing toner | |
| JPS61255357A (en) | Toner for developing electrostatic charge image and its production | |
| JPH01217466A (en) | Production of electrostatic charge image developing toner | |
| JPH0315859A (en) | Production of polymerized toner |