JPH04188147A - Rectifiable resin particle and electrophotographic toner using same - Google Patents
Rectifiable resin particle and electrophotographic toner using sameInfo
- Publication number
- JPH04188147A JPH04188147A JP2320159A JP32015990A JPH04188147A JP H04188147 A JPH04188147 A JP H04188147A JP 2320159 A JP2320159 A JP 2320159A JP 32015990 A JP32015990 A JP 32015990A JP H04188147 A JPH04188147 A JP H04188147A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- particles
- toner
- parts
- resin
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 title claims abstract description 58
- 239000011347 resin Substances 0.000 title claims abstract description 58
- 239000007771 core particle Substances 0.000 claims abstract description 74
- 239000011859 microparticle Substances 0.000 claims description 39
- 229920002545 silicone oil Polymers 0.000 claims description 25
- 239000012736 aqueous medium Substances 0.000 claims description 14
- 239000010419 fine particle Substances 0.000 abstract description 13
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 239000003921 oil Substances 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 3
- 239000003125 aqueous solvent Substances 0.000 abstract 3
- 229910052710 silicon Inorganic materials 0.000 abstract 3
- 239000010703 silicon Substances 0.000 abstract 3
- 238000007645 offset printing Methods 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 37
- 239000003795 chemical substances by application Substances 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000000725 suspension Substances 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 13
- -1 2-ethyl Chemical group 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000010558 suspension polymerization method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000012674 dispersion polymerization Methods 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- BHDDSIBLLZQKRF-UHFFFAOYSA-N 1-dodecylpiperidine Chemical compound CCCCCCCCCCCCN1CCCCC1 BHDDSIBLLZQKRF-UHFFFAOYSA-N 0.000 description 2
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 2
- PCUPXNDEQDWEMM-UHFFFAOYSA-N 3-(diethylamino)propyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C(C)=C PCUPXNDEQDWEMM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- RYNHNIDEKCRWHJ-QFIPXVFZSA-N (2s)-2-[(2-methyl-3-oxo-5,7-dipropyl-1,2-benzoxazol-6-yl)oxy]-2-(4-propan-2-ylphenyl)acetic acid Chemical compound C1([C@@H](C(O)=O)OC2=C(CCC)C3=C(C(N(C)O3)=O)C=C2CCC)=CC=C(C(C)C)C=C1 RYNHNIDEKCRWHJ-QFIPXVFZSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 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
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-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
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 description 1
- BXALRZFQYDYTGH-UHFFFAOYSA-N 1-oxoprop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C(=O)C=C BXALRZFQYDYTGH-UHFFFAOYSA-N 0.000 description 1
- GSSDUXHQPXODCN-UHFFFAOYSA-N 1-phenylethenylphosphonic acid Chemical compound OP(O)(=O)C(=C)C1=CC=CC=C1 GSSDUXHQPXODCN-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- UDWYGWMSVGVBCG-UHFFFAOYSA-N 2-(dimethylamino)prop-2-enoic acid Chemical compound CN(C)C(=C)C(O)=O UDWYGWMSVGVBCG-UHFFFAOYSA-N 0.000 description 1
- ULEVTQHCVWIDPC-UHFFFAOYSA-N 2-(methylamino)ethyl prop-2-enoate Chemical compound CNCCOC(=O)C=C ULEVTQHCVWIDPC-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- JFMYRCRXYIIGBB-UHFFFAOYSA-N 2-[(2,4-dichlorophenyl)diazenyl]-n-[4-[4-[[2-[(2,4-dichlorophenyl)diazenyl]-3-oxobutanoyl]amino]-3-methylphenyl]-2-methylphenyl]-3-oxobutanamide Chemical compound C=1C=C(C=2C=C(C)C(NC(=O)C(N=NC=3C(=CC(Cl)=CC=3)Cl)C(C)=O)=CC=2)C=C(C)C=1NC(=O)C(C(=O)C)N=NC1=CC=C(Cl)C=C1Cl JFMYRCRXYIIGBB-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-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
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical compound C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-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
- DEOCLXYPCQMPDP-UHFFFAOYSA-N 3-(2-aminoethylamino)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCNCCN DEOCLXYPCQMPDP-UHFFFAOYSA-N 0.000 description 1
- FGKYVGZYNGABJP-UHFFFAOYSA-N 3-(2-aminoethylamino)propyl prop-2-enoate Chemical compound NCCNCCCOC(=O)C=C FGKYVGZYNGABJP-UHFFFAOYSA-N 0.000 description 1
- XUYDVDHTTIQNMB-UHFFFAOYSA-N 3-(diethylamino)propyl prop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C=C XUYDVDHTTIQNMB-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- WOAMRAPSJUZQJV-UHFFFAOYSA-N 3-oxopent-4-ene-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)C(=O)C=C WOAMRAPSJUZQJV-UHFFFAOYSA-N 0.000 description 1
- JCYPECIVGRXBMO-UHFFFAOYSA-N 4-(dimethylamino)azobenzene Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1 JCYPECIVGRXBMO-UHFFFAOYSA-N 0.000 description 1
- NSWKKBKROCMOHA-UHFFFAOYSA-N 4-(naphthalen-1-yldiazenyl)naphthalen-1-ol Chemical compound Oc1ccc(N=Nc2cccc3ccccc23)c2ccccc12 NSWKKBKROCMOHA-UHFFFAOYSA-N 0.000 description 1
- DWDURZSYQTXVIN-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]aniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 DWDURZSYQTXVIN-UHFFFAOYSA-N 0.000 description 1
- JSEYDVLGSMLKDL-UHFFFAOYSA-N 4-[(4-ethoxyphenyl)diazenyl]naphthalen-1-ol Chemical compound C1=CC(OCC)=CC=C1N=NC1=CC=C(O)C2=CC=CC=C12 JSEYDVLGSMLKDL-UHFFFAOYSA-N 0.000 description 1
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 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
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- RCTGMCJBQGBLKT-PAMTUDGESA-N scarlet red Chemical compound CC1=CC=CC=C1\N=N\C(C=C1C)=CC=C1\N=N\C1=C(O)C=CC2=CC=CC=C12 RCTGMCJBQGBLKT-PAMTUDGESA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940033816 solvent red 27 Drugs 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- RBKBGHZMNFTKRE-UHFFFAOYSA-K trisodium 2-[(2-oxido-3-sulfo-6-sulfonatonaphthalen-1-yl)diazenyl]benzoate Chemical compound C1=CC=C(C(=C1)C(=O)[O-])N=NC2=C3C=CC(=CC3=CC(=C2[O-])S(=O)(=O)O)S(=O)(=O)[O-].[Na+].[Na+].[Na+] RBKBGHZMNFTKRE-UHFFFAOYSA-K 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は帯電性樹脂粒子およびこれを用いた電子写真用
トナーに関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to chargeable resin particles and an electrophotographic toner using the same.
〈従来の技術〉
電子写真法、静電印刷法、静電記録法等における現像方
法は、帯電、露光により感光体上に形成された静電潜像
をトナーで現像し、現像したトナー像を転写紙等の支持
体に転写すると共に、加熱ローラまたは加圧ローラによ
りトナー像を支持体上に定着させ、静電潜像を可視化し
ている。<Prior art> Development methods in electrophotography, electrostatic printing, electrostatic recording, etc. develop an electrostatic latent image formed on a photoconductor by charging and exposure with toner, and the developed toner image is The electrostatic latent image is visualized by transferring it to a support such as transfer paper and fixing the toner image onto the support using a heating roller or a pressure roller.
トナーを用いて、原稿画像を忠実に再現するためには、
各トナー粒子の帯電量を均一にして、未帯電粒子による
静電潜像以外へのトナーの移行や、過剰帯電粒子による
現像器内でのトナーの蓄積や、静電潜像へのトナーの付
着量の減少による画像濃度の低下を防止する必要がある
。In order to faithfully reproduce the original image using toner,
By making the amount of charge of each toner particle uniform, it prevents toner from moving to areas other than the electrostatic latent image due to uncharged particles, toner accumulation in the developing device due to excessively charged particles, and toner from adhering to the electrostatic latent image. It is necessary to prevent a decrease in image density due to a decrease in the amount.
従来のトナーは、一般に、定着用樹脂を電荷制御剤等の
添加剤と共に加熱溶融して混練し、冷却後、粉砕して分
級することによって製造されている。Conventional toners are generally manufactured by melting and kneading a fixing resin together with additives such as a charge control agent by heating, cooling, and then crushing and classifying the resin.
しかしながら、このような粉砕によって製造されたトナ
ーは、粒度の分布範囲が広く、比較的粒径の大きな粒子
か含まれるという欠点かある。また、トナーの摩擦帯電
性を制御するために、電荷制御剤か定着用樹脂中に添加
されているが、電荷制御剤は定着用樹脂中での分散性か
悪く、摩擦帯電性を支配する粒子表面に存在させるため
には、多量の電荷制御剤を添加する必要かあり、経済的
ではなかった。However, the toner produced by such pulverization has a drawback that it has a wide particle size distribution range and contains relatively large particles. In addition, in order to control the triboelectricity of toner, a charge control agent is added to the fixing resin, but the charge control agent has poor dispersibility in the fixing resin, and particles that control the triboelectricity are In order to make it exist on the surface, it is necessary to add a large amount of charge control agent, which is not economical.
そこで、このような問題を解消するために、重合法を利
用することにより、粉砕、分級等を行うことなく、その
まま用いることのできるように、懸濁重合法によるトナ
ーの製造方法か提案されている。懸濁重合法で得られる
トナーは、球形で流動性か良好で、摩擦帯電性にも優れ
ているという利点かある。しかし、帯電性向上のため、
ガラス転移温度（Ｔｇ）を小さくすると、プロソキンク
性か悪くなり、画質も低下するという欠点かある。Therefore, in order to solve this problem, a method of producing toner using a suspension polymerization method has been proposed so that the toner can be used as is without pulverization, classification, etc. There is. The toner obtained by the suspension polymerization method has the advantage of being spherical, having good fluidity, and having excellent triboelectric charging properties. However, in order to improve chargeability,
When the glass transition temperature (Tg) is decreased, the prosokink property deteriorates and the image quality also deteriorates.
そこで、特開昭６０−１０３３５５号公報に示されるよ
うなトナーか提案されている。このものは、懸濁重合法
により得られたトナーで、懸濁重合に際してカチオン性
重合体およびシリコーンオイルを含有させたものである
。ここで用いているシリコーンオイルは、モノマーに共
重合させたものではなくて、トナー中に内包させたもの
であるので、良好な剥離剤および溶剤として作用し、オ
フセント性を改善する作用を有すると記載されている。Therefore, a toner as disclosed in Japanese Patent Laid-Open No. 103355/1983 has been proposed. This toner is obtained by a suspension polymerization method, and contains a cationic polymer and silicone oil during suspension polymerization. The silicone oil used here is not copolymerized with monomers, but is encapsulated in the toner, so it acts as a good release agent and solvent, and has the effect of improving offset properties. Are listed.
〈発明か解決しようとする課題〉
しかしながら、上記提案のトナーは、トナーを構成して
いる重合体とシリコーンオイルとの相溶性か悪いために
、重合の進行に伴って相分離か生して、シリコーンオイ
ルか粒子外へ押し出され、重合体粒子の表面かノリコー
ンオイルで被覆された状態となってしまう。そのため得
られたトナーは、摩擦帯電特性に劣ると共に、紙との接
着性が悪く、定着性に劣ったものになるという問題があ
る。<Problem to be Solved by the Invention> However, in the toner proposed above, due to poor compatibility between the polymer constituting the toner and the silicone oil, phase separation occurs as the polymerization progresses. The silicone oil is pushed out of the particles, leaving the surface of the polymer particles coated with silicone oil. Therefore, the resulting toner has problems in that it has poor triboelectric charging properties, poor adhesion to paper, and poor fixing properties.
この発明の目的は、摩擦帯電性に優れると共に、離型性
にも優れ、オフセット性、ブロッキング性、定着性が改
善され、しかも耐湿性にも優れた帯電性樹脂粒子および
電子写真用トナーを提供することにある。An object of the present invention is to provide chargeable resin particles and toner for electrophotography that have excellent triboelectric charging properties, excellent mold release properties, improved offset properties, blocking properties, and fixing properties, and also excellent moisture resistance. It's about doing.
〈課題を解決するための手段および作用〉本発明の帯電
性樹脂粒子は、水系媒体中において正または負の電荷を
有する樹脂からなるコア粒子と、水系媒体中において前
記コア粒子と逆の電荷を有し、かつ重合性シリコーンオ
イルを含をすると共に、前記コア粒子よりも粒径か小さ
な樹脂の微小粒子とからなり、微小粒子か前記コア粒子
の表面に熱融着していることを特徴としている。<Means and effects for solving the problems> The chargeable resin particles of the present invention have a core particle made of a resin that has a positive or negative charge in an aqueous medium, and a core particle that has an opposite charge to the core particle in an aqueous medium. and contains polymerizable silicone oil, and microparticles of a resin having a smaller particle size than the core particles, and the microparticles are thermally fused to the surface of the core particles. There is.
また、上記微小粒子か、微小粒子１００重二部に対して
、重合性シリコーンオイルを１〜１０重量％含有してい
ることか好ましい。Further, it is preferable that the above-mentioned fine particles contain 1 to 10% by weight of polymerizable silicone oil based on 100 parts by weight of the fine particles.
本発明の電子写真用トナーは、かかる帯電性樹脂粒子を
用いたものである。The electrophotographic toner of the present invention uses such chargeable resin particles.
本発明のコア粒子と微小粒子とは、水系媒体中で互いに
逆の電荷を有するため、これらを水系媒体内で混合分散
すると、コア粒子の表面に微小粒子か適度に存在した状
態で電気的に付着する。従ってこの状態で、コア粒子と
微小粒子とを熱融着すれば、それらの付着か強固になり
、しかもコア粒子同士は電気的に互いに反発しあうため
、凝集するおそれもない。The core particles and microparticles of the present invention have opposite charges to each other in an aqueous medium, so when they are mixed and dispersed in an aqueous medium, an appropriate amount of microparticles is present on the surface of the core particle, and electrically adhere to. Therefore, if the core particles and the fine particles are thermally fused in this state, their adhesion becomes strong, and since the core particles electrically repel each other, there is no fear of agglomeration.
また、本発明におけるシリコーンオイルは、コア粒子の
表面を覆うのではなく、微小粒子の共重合体成分の１つ
として、微小粒子中に含有された、いわばコア粒子の表
面に偏在した状態にあるので、本発明の帯電性樹脂粒子
をトナーに使用する場合は、定着性に優れ、そかもノリ
コーンオイルの有する離型性により、耐オフセット性お
よび耐プロソキンク性に優れ、さらにｉ４ ／ｉ性にも
優れたものとなる。Moreover, the silicone oil in the present invention does not cover the surface of the core particle, but is contained in the microparticle as one of the copolymer components of the microparticle, so to speak, it is unevenly distributed on the surface of the core particle. Therefore, when the chargeable resin particles of the present invention are used in a toner, it has excellent fixing properties, and also has excellent offset resistance and prosokink resistance due to the release properties of Noricone oil, and also has excellent i4/i properties. will also be excellent.
さらに本発明の帯電性樹脂粒子をトナーとじて使用する
ときは、コア粒子の表面に付着した樹脂の微小粒子の正
または負の帯電により、帯電性の優れたものになる。Furthermore, when the chargeable resin particles of the present invention are used as a toner, the fine particles of resin attached to the surface of the core particles are positively or negatively charged, resulting in excellent chargeability.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
コア粒子
コア粒子を構成する樹脂粒子は、水系媒体中で正または
負の電荷を有するモノマーの単独重合体、または電荷を
有しない他の七ツマ−との共重合体からなる。Core particles The resin particles constituting the core particles are made of a homopolymer of a monomer that has a positive or negative charge in an aqueous medium, or a copolymer with another monomer that has no charge.
正の電荷を有する七ツマ−としては、例えば分子中に窒
素原子を有するもの等があげられる。また、負の電荷を
有するモノマーとしては、例えば分子中にスルホン酸基
−５Ｏ３Ｈ（たたし、式中の水素原子はナトリウム原子
、カリウム原子、カルシウム原子と置換されて塩を形成
してもよい）を有するもの等があげられる。Examples of positively charged heptadons include those having a nitrogen atom in the molecule. In addition, examples of monomers having a negative charge include, for example, a sulfonic acid group -5O3H in the molecule, and the hydrogen atom in the formula may be replaced with a sodium atom, potassium atom, or calcium atom to form a salt. ).
分子中に窒素原子を有するモノマーとしては、例えばジ
メチルアミノアクリレート、ジエチルアミノエチルアク
リレート、
ンメチルアミノエチルアクリレート、
ジエチルアミノプロビルアクリレート、Ｎ−アミノエチ
ルアミノプロピルアクリレート、ジメチルアミノメタク
リレート、
ジメチルアミノエチルメタクリレート、ジエチルアミノ
エチルメタクリレート、ジエチルアミノプロピルメタク
リレート、Ｎ−アミノエチルアミノプロピルメタクリレ
ート、ビニルピロリジン、２−ビニルイミダゾール、２
−ヒドロキシ−３−アクリルオキシプロピルメチルアン
モニウムクロライド、アクリルニトリル等の含窒素モノ
マーがあげられる。Examples of monomers having a nitrogen atom in the molecule include dimethylaminoacrylate, diethylaminoethyl acrylate, N-methylaminoethyl acrylate, diethylaminopropyl acrylate, N-aminoethylaminopropyl acrylate, dimethylaminomethacrylate, dimethylaminoethylmethacrylate, and diethylaminoethyl. Methacrylate, diethylaminopropyl methacrylate, N-aminoethylaminopropyl methacrylate, vinylpyrrolidine, 2-vinylimidazole, 2
Examples include nitrogen-containing monomers such as -hydroxy-3-acryloxypropylmethylammonium chloride and acrylonitrile.
スルホン酸基を有するモノマーとしては、例えばスチレ
ンスルホン酸、ビニルスルホン酸、アクリルアミドメチ
ルプロパンスルホン酸、メタクリルスルホン酸、アクリ
ルスルホン酸、アクリル−２−エチルスルホン酸、
メタクリル−２−エチルスルホン酸、さらにこれらのナ
トリウム、カリウム、カルシウム等の塩類かあげられる
。Examples of monomers having a sulfonic acid group include styrenesulfonic acid, vinylsulfonic acid, acrylamide methylpropanesulfonic acid, methacrylsulfonic acid, acrylsulfonic acid, acryl-2-ethylsulfonic acid, methacryl-2-ethylsulfonic acid, and these. Examples include salts such as sodium, potassium, and calcium.
正または負の電荷を有するモノマーと共重合するモノマ
ーしては、種々のラジカル重合性の七ツマ−があげられ
、例えばビニル芳香族モノマー、アクリル系モノマー、
ビニルエステル系モノマー、ビニルエーテル系モノマー
、ジオレフィン系モノマー、モノオレフィン系モノマー
等があげられる。Monomers that copolymerize with monomers having a positive or negative charge include various radically polymerizable monomers, such as vinyl aromatic monomers, acrylic monomers,
Examples include vinyl ester monomers, vinyl ether monomers, diolefin monomers, and monoolefin monomers.
ビニル芳香族モノマーとしては、下記一般式（１）（式
中、Ｒ１は水素原子、低級アルキル基またはハロゲン原
子、
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、ニトロ基あるいはビニル基を示す）
て表されるビニル芳香族炭化水素があげられ、例えばス
チレン、α−メチルスチレン、ビニルトルエン、ａ−ク
ロロスチレン、ｏ＋ ｍ ｔ ｐ−クロロスチレン
、ｐ−エチルスチレン、ジビニルベンゼン等の単独また
は２種以上の組み合わせかあげられる。The vinyl aromatic monomer has the following general formula (1) (wherein 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, a nitro group, or a vinyl group). Examples include styrene, α-methylstyrene, vinyltoluene, a-chlorostyrene, o+ m t p-chlorostyrene, p-ethylstyrene, divinylbenzene, etc. A combination of two or more types is possible.
アクリル系モノマーとしては、下記一般式（２）（式中
、Ｒ３は水素原子または低級アルキル基、
Ｒ４は水素原子、炭素数１〜１２の炭化水素基、ヒドロ
キシルアルキル基あるいはビニルエステル基を示す）
で表されるアクリル系モノマーかあげられ、例えばメチ
ルアクリレート、エチルアクリレート、ブチルアクリレ
ート、ヘキシルメタクリレート、２−エチルへキンルア
クリレート、
シクロへキシルアクリレート、
ツユニルアクリレート、メチルメタクリレート、゛エチ
ルメタクリレート、ブチルメタクリレート、２−エチル
へキシルメタクリレート、
エチル−β−ヒドロキシアクリレート、プロピル−γ〜
ヒドロキシアクリレート、ブチル−σ−ヒドロキシアク
リレート、エチル−β−ヒドロキシメタクリルレート、
エチレングリコールジメタクリレート、テトラエチレン
グリコールジメタクリレート等があげられる。The acrylic monomer is represented by the following general formula (2) (wherein R3 represents a hydrogen atom or a lower alkyl group, and R4 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a hydroxyalkyl group, or a vinyl ester group). Examples include acrylic monomers represented by methyl acrylate, ethyl acrylate, butyl acrylate, hexyl methacrylate, 2-ethyl hequinyl acrylate, cyclohexyl acrylate, tunily acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate. , 2-ethylhexyl methacrylate, ethyl-β-hydroxyacrylate, propyl-γ~
Hydroxyacrylate, butyl-σ-hydroxyacrylate, ethyl-β-hydroxymethacrylate,
Examples include ethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate.
ビニルエステル系モノマーとしては、下記一般式（３）
％式％
：
（式中、Ｒ５は水素原子または低級アルキル基を示す）
で表されるビニルエステルがあげられ、例えばギ酸ビニ
ル、酢酸ビニル、プロピオン酸ビニル等があげられる。Examples of vinyl ester monomers include vinyl esters represented by the following general formula (3) (in which R5 represents a hydrogen atom or a lower alkyl group), such as vinyl formate, vinyl acetate, and propion. Examples include vinyl acid.
ビニルエーテル系モノマーとしては、下記一般式（４）
％式％
（式中、Ｒ６は炭素数１〜１２の１価の炭化水素基を示
す）
で表されるビニルエーテルがあげられ、例えばビニル−
〇−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があげられる。Examples of vinyl ether monomers include vinyl ethers represented by the following general formula (4) % formula % (in the formula, R6 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms);
Examples include 〇-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether, and the like.
ジオレフィン糸上ツマ−としては、下記一般式（式中、
Ｒｙ 、 Ｒｓ 、Ｒ９は各々水素原子、低級アルキル
基またはハロゲン原子を示す）で表されるオレフィンが
あげられ、例えばブタジェン、イソプレン、クロロブレ
ン等があげられる。As a diolefin thread pick, the following general formula (in the formula,
Ry, Rs, and R9 each represent a hydrogen atom, a lower alkyl group, or a halogen atom), such as butadiene, isoprene, chlorobrene, and the like.
モノオレフィン系モノマーとしては、下記一般式（６）
（式中、ＲｌｏおよびＲ口は各々水素原子または低級ア
ルキル基を示す）
で表されるモノオレフィンがあげられ、例えばエチレン
、プロピレン、イソブチレン、ブテン−１、ペンテン−
１，４−メチルペンテン−１等があげられる。Examples of monoolefin monomers include monoolefins represented by the following general formula (6) (in the formula, Rlo and R each represent a hydrogen atom or a lower alkyl group), such as ethylene, propylene, isobutylene, butene, etc. -1, Penten-
Examples include 1,4-methylpentene-1.
これらのモノマーのうち、分子量分布の制御のうえで、
スチレン系モノマーやアクリル系モノマーを使用するの
が好ましい。Among these monomers, after controlling the molecular weight distribution,
It is preferable to use styrenic monomers or acrylic monomers.
モノマーの重合は、懸濁重合法、分散重合法等で行われ
、特に懸濁重合法を採用するのが好ましい。懸濁重合法
における分散媒としては、水またはアルコール類が使用
される。分散媒は、七ツマー１重合開始剤や添加剤等か
らなる樹脂成分の総量１００重量部に対して、通常５０
〜１０００重量部の割合で使用する。Polymerization of the monomer is carried out by a suspension polymerization method, a dispersion polymerization method, etc., and it is particularly preferable to employ a suspension polymerization method. Water or alcohols are used as a dispersion medium in the suspension polymerization method. The dispersion medium is usually used in an amount of 50 parts by weight per 100 parts by weight of the total resin component consisting of the 7-mer 1 polymerization initiator, additives, etc.
It is used in a proportion of ~1000 parts by weight.
モノマーの重合開始剤としては、２．２’ −アゾビス
（２，４−ジメチルバレロニトリル）、２．２′−アゾ
ビス（２−メチルブチロニトリル）、アゾビスイソブチ
ロニトリル（Ａ Ｉ ＢＮ）等のアゾ化合物、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、ジ
クミルペルオキシド、ジ−ｔ−ブチルペルオキシド、過
硫酸カリウム、過酸化ベンゾイル、過酸化ラウロイル等
の過酸化物等の油溶性の重合開始剤があげられる。また
、この他にγ線や加速電子線のようなイオン化放射線や
各種増感剤と組み合わせて使用してもよい。Examples of monomer polymerization initiators include 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), and azobisisobutyronitrile (A I BN). Oil-soluble polymerization initiators such as azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, peroxides such as potassium persulfate, benzoyl peroxide, and lauroyl peroxide. can be given. In addition, it may be used in combination with ionizing radiation such as gamma rays and accelerated electron beams, and various sensitizers.
重合開始剤は、一般にモノマーの総量１００重量部に対
して、０．１〜１０重量部の割合で使用され、好ましく
は０．５〜５重量部の割合で使用するのが好ましい。The polymerization initiator is generally used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of monomers.
また、コア粒子への他の添加剤としては、着色剤（顔料
や油溶性染料）があげられる。本発明の帯電性樹脂粒子
を電子写真用トナーとして用いる場合に使用される着色
剤としては、以下のものが例示される。Further, other additives to the core particles include colorants (pigments and oil-soluble dyes). Examples of the coloring agent used when the chargeable resin particles of the present invention are used as an electrophotographic toner include the following.
黒色
ファーネスブラック、チャンネルブラック、サーマル、
ガスブラック、オイルブラック、アセチレンブラック、
カーボンブラック、ランプブラック、アニリンブラック
黄色
黄鉛、亜鉛華、カドミウムイエロー、
黄色酸化鉄、ミネラルファストイエロー、ニッケルチタ
ンイエロー、ネーブルスイエロー、ナフトールイエロー
Ｓ２ハンザイエローＧ１ハンザイエロー１０Ｇ１ヘンジ
ジンイエローＧ１ベンジジンイエローＧＲ、タートラジ
ンレーキ、キノリンイエローレーキ、
パーマネントイエローＮＣＧ。Furnace black, channel black, thermal,
Gas black, oil black, acetylene black,
Carbon black, lamp black, aniline black yellow yellow lead, zinc white, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S2 Hansa Yellow G1 Hansa Yellow 10G1 Henzidine Yellow G1 Benzidine Yellow GR , Tartrazine Lake, Quinoline Yellow Lake, Permanent Yellow NCG.
Ｃ，１，ソルベントイエロー２、
Ｃ０１，ソルベントイエロー１４、
Ｃ，１，ソルベントイエロ−６０
橙色
モリブデンオレンジ、ベンジジンオレンジＧ、パーマネ
ントオレンジＧＴＲ，赤ロ黄鉛、ピラゾロンオレンジ、
パルカンオレンジ、インダンスレンブリリアントオレン
ジＲＫ。C,1, Solvent Yellow 2, C01, Solvent Yellow 14, C,1, Solvent Yellow-60 Orange Molybdenum Orange, Benzidine Orange G, Permanent Orange GTR, Red Yellow Yellow, Pyrazolone Orange,
Palkan Orange, Indanslen Brilliant Orange RK.
インダンスレンブリリアントオレンジＧＫＣ，１，ソル
ベントブルーフ
赤色
ベンガラ、カドミウムレッド、鉛丹、
硫化水銀カドミウム、パーマネントレッド４Ｒ。Indanthrene brilliant orange GKC, 1, solvent blue red red red iron, cadmium red, red lead, mercury cadmium sulfide, permanent red 4R.
リソールレッド、ピラゾロンレッド、 ウオッチングレッドカルシウム塩、 レーキレットＤ１ブリリアントカーミン６Ｂ。Lysol red, pyrazolone red, Watching red calcium salt, Lakelet D1 Brilliant Carmine 6B.
エオシンレーキ、ローダミンレーキＢ１アリザリンレー
キ、ブリリアントカーミン３Ｂ、Ｃ，１，ソルベントレ
ッド３、
Ｃ，１，ソルベントレッド２４、
Ｃ，１，ソルベントレッド２７
紫色
マンガン紫、ファーストバイオレットＢ１メチルバイオ
レットレーキ、
Ｃ，１，ソルベントバイオレット１３
青色
紺青、コバルトブルー、アルカリブルーレーキ、ビクト
リアブルーレーキ、フタロシアニンブルー、フタロシア
ニンブル一部分塩素化物、
無金属フタロシアニンブルー、
ファーストスカイブルー、
インダンスレンブル−ＢＣ。Eosin Lake, Rhodamine Lake B1 Alizarin Lake, Brilliant Carmine 3B, C,1, Solvent Red 3, C,1, Solvent Red 24, C,1, Solvent Red 27 Purple Manganese Purple, First Violet B1 Methyl Violet Lake, C,1 , Solvent Violet 13 Blue Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Phthalocyanine Blue Partially Chlorinated Compound, Metal-free Phthalocyanine Blue, Fast Sky Blue, Indan Stremburu-BC.
Ｃ，１，ソルベントブルーフ、
Ｃ，１，ソルベントブルー３５
緑色
酸化クロム、マラカイトグリーンレーキ、クロムグリー
ン、ピグメントグリーンＢ１ノアナルイエローグリーン
、
Ｃ１，ソルベントグリーン１５
茶色
Ｃ，１，ソルベントブラウン５
白色
亜鉛華、酸化チタン、アンチモン白、硫化亜鉛体質顔料
パライト粉、炭酸バリウム、クレー、シリカ、ホワイト
カーボン、タルク、アルミナホワイト導電性顔料
導電性カーボンブラック、アルミニウム粉等の各種金属
粉
磁性顔料
四三酸化鉄（マグネタイト−鉄黒）、
三二酸化鉄（γ−Ｆｅ２０．）、
酸化鉄亜鉛（ＺｎＦｅ２０４ ）、
酸化鉄イツトリウム（Ｙ ３ Ｆ ｅ ５０ ＋２）、
酸化鉄カドミウム（Ｃｄ Ｆ ｅ ２０ ＜ ）、酸化
鉄ガドリニウム（Ｇｄ３ Ｆ ｅ、０４ ）、酸化鉄銅
（ＣｕＦｅ２０４）、
酸化鉄錯（Ｐ ｂ Ｆ ｅ １２０１９）、酸化鉄ニッ
ケル（’ＮｉＦｅ２０４）、酸化鉄ネオジウム（Ｎ ｄ
Ｆ ｅ Ｏ３）、酸化鉄バリウム（Ｂ ａ Ｆ ｅ
１２０１９）、酸化鉄マグネシウム（ＭｇＦｅ２ｏ４）
、酸化鉄マンガン（ＭｎＦｅ２０ａ）、
酸化鉄ランタン（ＬａＦｅＯｉ ）、
［）、コバルト粉、ニッケル粉
光導電性顔料
酸化亜鉛、セレン、硫化カドミウム、セレン化カドミウ
ム
これらの着色剤は、１種または２種以上を混合して用い
られ、十分なトナー画像が得られる量、例えば樹脂成分
１００重量部に対して０．５〜３０重量部、特に１〜２
０重量部の割合で使用されるのが好ましい。C,1, Solvent Blue, C,1, Solvent Blue 35 Green chromium oxide, Malachite Green Lake, Chrome Green, Pigment Green B1 Noanal Yellow Green, C1, Solvent Green 15 Brown C,1, Solvent Brown 5 White Zinc White, Titanium oxide, antimony white, zinc sulfide extender pigment Palite powder, barium carbonate, clay, silica, white carbon, talc, alumina white Conductive pigment Conductive carbon black, aluminum powder and other various metal powders Magnetic pigment Triiron tetroxide (magnetite) - iron black), iron sesquioxide (γ-Fe20.), zinc iron oxide (ZnFe204), iron yttrium oxide (Y 3 Fe 50 +2),
Iron cadmium oxide (Cd Fe 20 < ), iron gadolinium oxide (Gd3 Fe, 04 ), iron copper oxide (CuFe204), iron oxide complex (P b Fe 12019), iron nickel oxide ('NiFe204), iron oxide Neodymium (Nd)
F e O3), barium iron oxide (B a F e
12019), magnesium iron oxide (MgFe2o4)
, iron manganese oxide (MnFe20a), lanthanum iron oxide (LaFeOi), [), cobalt powder, nickel powder photoconductive pigment zinc oxide, selenium, cadmium sulfide, cadmium selenide One or more of these colorants The amount used in the mixture is such that a sufficient toner image can be obtained, for example, 0.5 to 30 parts by weight, especially 1 to 2 parts by weight, per 100 parts by weight of the resin component.
Preferably, it is used in a proportion of 0 parts by weight.
また、電荷制御剤としては、それ自体公知の正電荷制御
剤や負電荷制御剤が使用される。正電荷制御剤としては
、塩基性窒素原子を有する有機化合物、例えば塩基性染
料、アミノピリン、ピリミジン化合物、多核ポリアミノ
化合物、アミノシラン類またはこれて表面処理された充
填剤類か使用される。また負電荷制御剤としては、カル
ボキシ基金を化合物、例えばアルキルサリチル酸金属キ
レート等が使用される。なかでも水系媒体中で電荷を示
さない含金属染料か特に好適に使用できる。Further, as the charge control agent, a positive charge control agent or a negative charge control agent that is known per se is used. As the positive charge control agent, organic compounds having a basic nitrogen atom, such as basic dyes, aminopyrine, pyrimidine compounds, polynuclear polyamino compounds, aminosilanes, or fillers surface-treated with these are used. Further, as the negative charge control agent, a compound containing a carboxy group such as an alkyl salicylic acid metal chelate is used. Among these, metal-containing dyes that exhibit no charge in an aqueous medium can be particularly preferably used.
かかる電荷制御剤の配合量は、コア粒子ノ樹脂成分１０
０重量部に対して、５重量部以下、好ましくは０．２〜
１重量部であり、電荷制御剤の配合量が５重量部より大
なるときは、電荷制御剤によるキャリアの汚染や、感光
体の汚染が生じ、好ましくない。The blending amount of the charge control agent is 10% of the resin component of the core particle.
5 parts by weight or less, preferably 0.2 to 0 parts by weight
If the amount of the charge control agent is more than 5 parts by weight, the charge control agent may contaminate the carrier or the photoreceptor, which is not preferable.
また、所望によりそれ自体公知のトナー配合剤を添加し
てもよい。トナー配合剤としては、例えば脂肪族系樹脂
、脂肪族金属塩類、高級脂肪酸類、脂肪酸エステル類、
その部分ケン化物類等の脂肪族系化合物からなる離型剤
（オフセット防止剤）をあげることができる。離型剤と
しては、特に低分子量（重量平均分子量か１０００〜１
００００）の脂肪族系樹脂か好適に使用される。具体的
には低分子量ポリプロピレン、低分子量ポリエチレン、
パラフィンワックス、炭素数４以上のオレフィン単体か
らなる低分子量オレフィン重合体等の１種または２種以
上の組み合わせやシリコーンオイル等の各種ワックス等
の使用することができる。ワックスの分子量は平均分子
量が２０００〜１５０００、特に３００〜１０００に範
囲内にあることが好ましい。これらのワックスは、一般
に樹脂成分１００重量部に対して１〜５重量部、特に１
．５〜３重量部の範囲内で使用することが好ましい。Further, if desired, toner compounding agents known per se may be added. Examples of toner compounding agents include aliphatic resins, aliphatic metal salts, higher fatty acids, fatty acid esters,
Examples include mold release agents (offset inhibitors) made of aliphatic compounds such as partially saponified products thereof. As a mold release agent, especially one with a low molecular weight (weight average molecular weight of 1000 to 1
0000) are preferably used. Specifically, low molecular weight polypropylene, low molecular weight polyethylene,
One type or a combination of two or more types of paraffin wax, a low molecular weight olefin polymer made of a simple olefin having 4 or more carbon atoms, and various waxes such as silicone oil can be used. The average molecular weight of the wax is preferably in the range of 2,000 to 15,000, particularly 300 to 1,000. These waxes are generally used in an amount of 1 to 5 parts by weight, especially 1 part by weight, based on 100 parts by weight of the resin component.
．． It is preferable to use it within the range of 5 to 3 parts by weight.
モノマーの懸濁重合に際しては、通常の懸濁安定剤を使
用することができる。かかる懸濁安定剤としては、カチ
オン系界面活性剤、アニオン系界面活性剤、水溶性の高
分子、難水溶性の粉末状無機化合物が使用される。During suspension polymerization of monomers, conventional suspension stabilizers can be used. As such suspension stabilizers, cationic surfactants, anionic surfactants, water-soluble polymers, and poorly water-soluble powdered inorganic compounds are used.
カチオン系界面活性剤としては、例えばアルキルアミン
、アルキルエチレンジアミン、アルキルトリメチルアン
モニウム、アルキルピリジニウム、アルキルジメチルベ
ンジルアンモニウム等があげられる。Examples of cationic surfactants include alkylamines, alkylethylenediamines, alkyltrimethylammoniums, alkylpyridiniums, and alkyldimethylbenzylammoniums.
アニオン系界面活性剤としては、例えばアルキル硫酸ナ
トリウム、ポリオキシエチレンアルキルアリルスルホン
酸ナトリウム、アルキルジフェニルエーテルジスルホン
酸ナトリウム、アルキルベンゼンスルホン酸ナトリウム
等があげられる。Examples of the anionic surfactant include sodium alkyl sulfate, sodium polyoxyethylene alkylaryl sulfonate, sodium alkyldiphenyl ether disulfonate, and sodium alkylbenzene sulfonate.
水溶性の高分子としては、例えばポリアクリル酸、ポリ
アクリル酸ソーダ、ゼラチン、トラガカントゴム、デン
プン、メチルセルロース、カルボキシメチルセルロース
、ポリビニルアルコール、ポリ塩化アリルにＮ−ドデシ
ルピペリジン、ジメチルドデシルアミンヤシメチルドデ
シルアミンやＮ−セチルピペリジン等を反応させたもの
等があげられる。Examples of water-soluble polymers include polyacrylic acid, sodium polyacrylate, gelatin, gum tragacanth, starch, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyallyl chloride, N-dodecylpiperidine, dimethyldodecylamine, coconut methyldodecylamine, and N-dodecylpiperidine. - Those reacted with cetylpiperidine, etc. can be mentioned.
難水溶性の粉末状無機化合物としては、例えば硫酸バリ
ウム、硫酸カルシウム、炭酸バリウム、炭酸カルシウム
、炭酸マグネシウム、リン酸カルシウム、タルク、ベン
トナイト、ケイソウ土、粘土等があげられる。Examples of poorly water-soluble powdered inorganic compounds include barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, calcium phosphate, talc, bentonite, diatomaceous earth, and clay.
懸濁安定剤の使用量は、通常樹脂成分１００重量部に対
して、３〜２０重量部の範囲内にあるのが適当である。The amount of the suspension stabilizer to be used is usually in the range of 3 to 20 parts by weight per 100 parts by weight of the resin component.
上記懸濁重合法における造粒は、ホモミキサーやホモジ
ナイザー等の高速剪断撹拌機によって行われ、コア粒子
を目的に応じた粒径に調整する。Granulation in the above suspension polymerization method is performed using a high-speed shearing stirrer such as a homomixer or a homogenizer, and the core particles are adjusted to a particle size depending on the purpose.
コア粒子をトナーとして使用する場合は、重合平均分子
量が３０００〜２００００００のものが好ましく、特に
１０００００〜１５０００００のものが好ましい。また
中心粒径は１〜１５μｍ程度に調整するのが好ましい。When the core particles are used as a toner, those having a polymerization average molecular weight of 3,000 to 2,000,000 are preferable, and those of 100,000 to 1,500,000 are particularly preferable. Moreover, it is preferable to adjust the center particle size to about 1 to 15 μm.
また、重合は通常、５０〜１００℃の温度下で、２〜１
２時間程度行われる。In addition, polymerization is usually carried out at a temperature of 50 to 100°C for 2 to 1
It will last about 2 hours.
なお、コア粒子は懸濁重合法に代えて、分散重合等の従
来より公知の樹脂粒子の製造方法により生成した熱可塑
性樹脂粒子や、熱可塑性樹脂を粉砕、分級あるいはスプ
レードライによって造粒した熱可塑性樹脂粒子を使用し
てもよい。In addition, instead of the suspension polymerization method, the core particles are thermoplastic resin particles produced by conventionally known resin particle manufacturing methods such as dispersion polymerization, or thermoplastic resin particles produced by pulverizing, classifying, or spray drying thermoplastic resin particles. Plastic resin particles may also be used.
また、コア粒子への電荷の付与は、懸濁重合あるいは分
散重合の重合時に、熱可塑性樹脂粒子の表面に電荷付与
剤を付着させて行ってもよいし、重合後に得られた熱可
塑性樹脂粒子と、電荷付与剤とを水系媒体中で混合して
、熱可塑性樹脂粒子の表面に電荷付与剤を付着させて行
ってもよい。In addition, charge may be imparted to the core particles by attaching a charge imparting agent to the surface of the thermoplastic resin particles during suspension polymerization or dispersion polymerization, or by attaching a charge imparting agent to the surface of the thermoplastic resin particles obtained after polymerization. and a charge imparting agent may be mixed in an aqueous medium to adhere the charge imparting agent to the surface of the thermoplastic resin particles.
二の場合、電荷付与剤としては、前述のカチオン ゛系
界面活性剤、アニオン系界面活性剤およびイオン性官能
基を有する水溶性の高分子等が使用できる。In the second case, as the charge imparting agent, the aforementioned cationic surfactants, anionic surfactants, water-soluble polymers having ionic functional groups, etc. can be used.
微小粒子
樹脂の微小粒子は前記コア粒子と逆の電荷を有する七ツ
マ−と重合性シリコーンオイルと、さらに必要に応じて
他のモノマーとの乳化共重合体から構成される。The microparticles of the microparticle resin are composed of an emulsion copolymer of a heptamer having an opposite charge to that of the core particle, a polymerizable silicone oil, and, if necessary, other monomers.
重合性シリコーンオイルと乳化共重合するモノマーとし
ては、前記コア粒子において例示したモノマーがいずれ
も使用可能でる。As the monomer that undergoes emulsion copolymerization with the polymerizable silicone oil, any of the monomers exemplified for the core particles can be used.
重合性シリコーンオイルとしては、下記一般式％式％
（式中、Ｒ２１は下記基：
／
Ｈ２−Ｃ
＼
−〇
＼
Ｑ ｆ１２３−
（式中、Ｒ”は水素原子または炭素数１〜６のアルキル
基、
Ｒ２３は炭素数２〜１ｏのアルキレン基を示す）を示し
、Ｒ２４は炭素数１〜６のアルキル基または上記Ｒ”を
示し、ｎは１〜５ｏの整数である）
で表される直鎖型のものや、下記一般式（８）（式中、
）は１〜１０の整数、Ｒ２１は前記と同じである）
で表される複鎖型のものが使用される。The polymerizable silicone oil has the following general formula: group, R23 represents an alkylene group having 2 to 1 o carbon atoms, R24 represents an alkyl group having 1 to 6 carbon atoms or the above R'', and n is an integer of 1 to 5 o). Chain-type ones, the following general formula (8) (in the formula,
) is an integer of 1 to 10, and R21 is the same as above.) A double-chain type is used.
重合性シリコーンオイルは、微小粒子に対して１〜１０
重量％含有させるのが好ましい。重合性シリコーンオイ
ルの含有量が１重量％より小なるときは、樹脂の離型性
および耐湿性が劣り、重合性シリコーンオイルの含有量
が１０重量％より大なるときは、摩擦帯電性および接着
性に劣り、好ましくない。Polymerizable silicone oil has a molecular weight of 1 to 10 for microparticles.
Preferably, the content is % by weight. When the content of polymerizable silicone oil is less than 1% by weight, the mold releasability and moisture resistance of the resin are poor, and when the content of polymerizable silicone oil is more than 10% by weight, the triboelectric charging properties and adhesion are poor. inferior to sex and undesirable.
重合性シリコーンオイルとモノマーとの共重合は、懸濁
重合法、分散重合法および乳化重合法を用いることがで
きるが、コア粒子の粒径よりも小さな粒径の微小粒子が
容易に得られる点で、乳化共重合が好適に採用される。Suspension polymerization, dispersion polymerization, and emulsion polymerization can be used for copolymerization of polymerizable silicone oil and monomer, but the key points are that fine particles with a particle size smaller than that of the core particles can be easily obtained. In this case, emulsion copolymerization is preferably employed.
乳化共重合は、水系媒体中で水溶性の開始剤を用いて、
乳化剤の存在下でモノマー重合を行うものであるが、乳
化剤が重合粒子表面に残留していると、乳化剤が水分を
吸収し、その吸湿性のために、重合体の帯電性が悪影響
を受けるため、乳化剤はできる限り除去する必要かある
。Emulsion copolymerization is carried out using a water-soluble initiator in an aqueous medium.
Monomer polymerization is carried out in the presence of an emulsifier, but if the emulsifier remains on the surface of the polymer particles, the emulsifier will absorb water and its hygroscopicity will adversely affect the chargeability of the polymer. It is necessary to remove as much emulsifier as possible.
従って、乳化重合に際しては、乳化剤を使用しない、い
わゆる無乳化剤乳化重合を行うのが好ましい。この重合
法は、
■反応性乳化剤を用いたり、
■比較的親水性のモノマーを過硫酸塩系の開始剤を使用
して無乳化重合を行ったり、
■水溶性ポリマー、オリゴマー（例えばポリビニルアル
コール等）を乳化剤の代わりに用いたり、■分解型乳化
剤を用いたり
して重合を行うものである。このうち、特に過硫酸塩系
の重合開始剤を使用する無乳化剤乳化重合法を採用する
のが好ましい。Therefore, in emulsion polymerization, it is preferable to perform so-called emulsifier-free emulsion polymerization without using an emulsifier. This polymerization method involves (1) using a reactive emulsifier, (2) non-emulsification polymerization of relatively hydrophilic monomers using a persulfate-based initiator, and (2) water-soluble polymers and oligomers (e.g. polyvinyl alcohol, etc.). ) in place of the emulsifier, or (2) a decomposable emulsifier is used to carry out the polymerization. Among these, it is particularly preferable to employ an emulsifier-free emulsion polymerization method using a persulfate-based polymerization initiator.
この微小粒子の重合平均分子量は、トナーとして使用す
る場合、５００００〜５００００００程度が好ましく、
中心粒径は０．０１〜２μｍ程度に調整するのか好まし
い。また必要に応じて、前述した着色剤や他の配合剤を
含有させてもよい。The polymerization average molecular weight of these fine particles is preferably about 50,000 to 5,000,000 when used as a toner.
It is preferable to adjust the center particle size to about 0.01 to 2 μm. Further, if necessary, the above-mentioned coloring agent and other compounding agents may be included.
重合は通常、５０−１００℃の温度下で、３〜２４時間
程度行われる。Polymerization is usually carried out at a temperature of 50-100°C for about 3-24 hours.
なお、樹脂の微小粒子への電荷の付与操作は、水系媒体
中で電荷を有する七ツマ−を使用して、重合体に電荷を
付与する代わりに、前記コア粒子の場合と同様に、重合
工程において微小粒子の表面に電荷付与剤を付着させて
行ってもよいし、重合後に電荷付与剤とを混合して、微
小粒子の表面に電荷付与剤を付着させて行ってもよい。Note that the operation of imparting electric charge to the resin microparticles is carried out in the polymerization step in the same way as in the case of the core particles, instead of imparting electric charge to the polymer using a seven-termer having an electric charge in an aqueous medium. In this step, a charge imparting agent may be attached to the surface of the microparticles, or the charge imparting agent may be mixed with the charge imparting agent after polymerization and the charge imparting agent is attached to the surface of the microparticles.
また、電荷を持たないモノマーを、重合開始剤として過
硫酸塩を用いて重合すると、水系媒体中で負電荷を付与
することができるので、このような方法で微小粒子を得
てもよい。Further, when a monomer having no charge is polymerized using a persulfate as a polymerization initiator, a negative charge can be imparted in an aqueous medium, and thus microparticles may be obtained by such a method.
帯電性樹脂粒子
前記コア粒子と微小粒子との付着は、熱融着によって行
う。すなわち、コア粒子の懸濁液と、微小粒子のエマル
ションとを混合し、コア粒子のガラス転移点温度以上の
温度で、熱処理を行って、コア粒子の表面に微小粒子を
付着させる。The chargeable resin particles The core particles and the fine particles are attached to each other by thermal fusion. That is, a suspension of core particles and an emulsion of microparticles are mixed and heat-treated at a temperature equal to or higher than the glass transition temperature of the core particles to adhere the microparticles to the surface of the core particles.
コア粒子の懸濁液と微小粒子のエマルションとの配合割
合は、双方の粒子の粒子径の比にもよるか、固形分に換
算して、１００：０．１〜１００：２０の範囲内にある
のが適当である。微小粒子の割合がこの範囲より大なる
ときは、微小粒子が余剰となり、その除去が煩雑である
ばかりでなく、コア粒子の表面に二層以上の微小粒子が
付着した場合には、静電引力が不十分であるために、ト
ナー化した後にトナーから剥離する付着力の弱いものと
なる。またこの範囲より小なるときは、１個のコア粒子
に付着する微小粒子の個数が不十分で、微小粒子による
コア粒子の粒子間架橋が生じ、凝集体が発生し、いずれ
の場合も好ましくない。The blending ratio of the core particle suspension and the fine particle emulsion depends on the ratio of the particle sizes of both particles, or is within the range of 100:0.1 to 100:20 in terms of solid content. It is appropriate that there be. When the proportion of microparticles is larger than this range, there will be a surplus of microparticles, and not only will their removal be troublesome, but if two or more layers of microparticles adhere to the surface of the core particle, electrostatic attraction will Because of insufficient adhesion, the toner peels off from the toner after being made into a toner, resulting in a weak adhesion force. If it is smaller than this range, the number of microparticles attached to one core particle will be insufficient, and interparticle crosslinking of the core particles will occur due to the microparticles, resulting in the formation of aggregates, which is undesirable in either case. .
コア粒子と微小粒子との熱処理は、両者を融着させるた
めに、コア粒子のガラス転移点温度の近傍、またはそれ
以上の温度で行うが、コア粒子に付着した微小樹脂同士
の凝集を防止するために、微小粒子のガラス転移点温度
以下の温度で行うのが好ましい。Heat treatment of the core particles and microparticles is carried out at a temperature near or above the glass transition temperature of the core particles in order to fuse them together, but this also prevents aggregation of the microscopic resins attached to the core particles. Therefore, it is preferable to carry out the treatment at a temperature equal to or lower than the glass transition temperature of the microparticles.
このようにして得られた帯電性樹脂粒子は、これを電子
写真用トナーとして使用する場合には、粒径３〜２５μ
ｍ１特に８〜２０μｍの複合球状粒子として使用するの
が好ましく、優れた流動性、帯電性、定着性およびクリ
ーニング性を有するものとなる。When the chargeable resin particles thus obtained are used as an electrophotographic toner, the particle size is 3 to 25 μm.
It is preferable to use composite spherical particles with m1 of 8 to 20 μm in particular, which have excellent fluidity, charging properties, fixing properties, and cleaning properties.
また、本発明にかかるトナーには、感光体を清浄化する
ための研磨剤を添加してもよい。研磨剤としては、例え
ばタルク、カオリン、硫酸バリウムの他、ケイ酸アルミ
ニウム、表面処理したケイ酸アルミニウム、二酸化チタ
ン、炭酸カルシウム、三酸化アンチモン、チタン酸バリ
ウム、チタン酸カルシウム、チタン酸ストロンチウム、
酸化マグネシウム、酸化亜鉛等が好ましく、特にコロイ
ド状シリカ、表面処理した疎水性シリカが好ましい。Furthermore, an abrasive for cleaning the photoreceptor may be added to the toner according to the present invention. Examples of abrasives include talc, kaolin, barium sulfate, aluminum silicate, surface-treated aluminum silicate, titanium dioxide, calcium carbonate, antimony trioxide, barium titanate, calcium titanate, strontium titanate,
Magnesium oxide, zinc oxide, etc. are preferred, and colloidal silica and surface-treated hydrophobic silica are particularly preferred.
研磨剤の添加、特に疎水性シリカを添加することにより
、トナー（現像剤）の流動性が向上する。Addition of an abrasive, particularly hydrophobic silica, improves the fluidity of the toner (developer).
研磨剤の平均粒径は１〜１１００ｎ、特に１０〜３０ｎ
ｍの範囲内にあるのか好ましい。また研磨剤の添加量は
、トナー１００重量部に対して、０．０１〜１重量部で
あるのが好ましい。研磨剤の添加量が０．０１重量部よ
り小なるときは、トナーの流動性が劣り、また１重量部
より大なるときは、感光体が傷付き易くなり、いずれも
好ましくない。The average particle size of the abrasive is 1 to 1100n, especially 10 to 30n
It is preferable if it is within the range of m. Further, the amount of the abrasive added is preferably 0.01 to 1 part by weight per 100 parts by weight of the toner. If the amount of the abrasive added is less than 0.01 part by weight, the fluidity of the toner will be poor, and if it is more than 1 part by weight, the photoreceptor will be easily damaged, both of which are undesirable.
また、トナーの電気抵抗を調整する目的で、トナーにカ
ーボンブラック、酸化アルミニウム等の電気抵抗調整剤
をまぶして使用してもよい。これらの電気抵抗調整剤は
、トナー１００重量部に対して、０．０１〜１重量部で
あるのが適当である。Further, for the purpose of adjusting the electrical resistance of the toner, the toner may be sprinkled with an electrical resistance adjusting agent such as carbon black or aluminum oxide. The amount of these electrical resistance adjusters is suitably 0.01 to 1 part by weight per 100 parts by weight of the toner.
なお、本発明の帯電性樹脂粒子は、静電潜像用トナーと
しての用途の他、例えば感光性トナーとして使用したり
、着色剤を含有させて静電塗装用の塗料としても使用す
ることができる。In addition to being used as a toner for electrostatic latent images, the chargeable resin particles of the present invention can also be used, for example, as a photosensitive toner, or as a paint for electrostatic painting by containing a colorant. can.
〈実施例〉
以下に実施例および比較例をあげて本発明の電子写真用
トナーを説明する。<Example> The electrophotographic toner of the present invention will be described below with reference to Examples and Comparative Examples.
負帯電性電荷制御共重合体１の合成
スチレン ６０重量部α−フェニ
ルビニルホスホン酸 ４０重量部２．２′−アゾビス（
２，４
一ジメチルバレロニトリル） １０重量部メチルアル
コール ４００重量部上記処方の各物質を混
合し、混合物を窒素雰囲気、緩攪拌下で８０℃にて、１
２時間重合反応を行った。次いで、得られた重合物をエ
バポレーションにより乾燥、粉末化し、負帯電性電荷制
御共重合体１を得た。Synthesis of negatively chargeable charge control copolymer 1 Styrene 60 parts by weight α-phenylvinylphosphonic acid 40 parts by weight 2.2'-azobis(
2,4-dimethylvaleronitrile) 10 parts by weight Methyl alcohol 400 parts by weight The substances in the above formulation were mixed, and the mixture was heated at 80°C under a nitrogen atmosphere with gentle stirring to 10 parts by weight.
The polymerization reaction was carried out for 2 hours. Next, the obtained polymer was dried and powdered by evaporation to obtain a negatively chargeable charge control copolymer 1.
負帯電性電荷制御共重合体２の合成
スチレン ９０重量部スチレンス
ルホン酸ナトリウム １０重量部アゾビスイソブチロニ
トリル １０．１量部ポリアクリル酸
１０重量部イソプロピルアルコール ６００重量
部水 ２００重量部上記処方
の各物質を混合し、混合物を窒素雰囲気、緩攪拌下で６
０℃にて、１２時間重合反応を行った。次いで、得られ
た重合物を遠心分離して媒体をメタノールに置換した後
、エバポレーションにより乾燥、粉末化して、負帯電性
電荷制御共重合体２を得た。Synthesis of negatively chargeable charge control copolymer 2 Styrene 90 parts by weight Sodium styrene sulfonate 10 parts by weight Azobisisobutyronitrile 10.1 parts by weight Polyacrylic acid
10 parts by weight Isopropyl alcohol 600 parts by weight Water 200 parts by weight The substances in the above formulation were mixed, and the mixture was heated under nitrogen atmosphere with gentle stirring for 60 minutes.
The polymerization reaction was carried out at 0°C for 12 hours. Next, the obtained polymer was centrifuged to replace the medium with methanol, and then dried and powdered by evaporation to obtain a negatively chargeable charge control copolymer 2.
正帯電コア粒子ｌ
スチレン ７５重量部２−エチル
ヘキシル
メタクリレート １５重量部ジメチルアミ
ノエチル
メタクリレート １０重量部ジビニルベン
ゼン ０．７重量部２−エチレングリコール
ジメタクリレート １．５重量部含金属染料（
電荷制御剤） ３重量部（オリエント化学社製の
ボントロンＳ−３４）
カーボンブラック ５重量部（三菱化成
社製のＭＡ−１００）
重合開始剤 ３重量部２．２′−
アゾビス（２，４
一ジメチルバレロニトリル）
重合開始剤 １重量部２．２′
−アゾビス（２
−メチルブチロニトリル）
上記処方の各物質を混合し、混合物を水８００重ｊ１部
とリン酸三カルシウム（太平化学産業社製のＴＣＰ−１
０，固形分濃度１０％）１００重量部とラウリル硫酸ナ
トリウム０．０１２重量部とからなる連続相に投入し、
ホモミキサーを用いて造粒し、緩攪拌下で８０℃にて、
８時間重合反応を行った。次いで、得られた重合物を水
洗、口過、再分散を３度繰り返すことにより正帯電コア
粒子１の懸濁液を得た。Positively charged core particle l Styrene 75 parts by weight 2-ethylhexyl methacrylate 15 parts by weight Dimethylaminoethyl methacrylate 10 parts by weight Divinylbenzene 0.7 parts by weight 2-ethylene glycol dimethacrylate 1.5 parts by weight Metallic dye (
Charge control agent) 3 parts by weight (Bontron S-34 manufactured by Orient Chemical Co., Ltd.) Carbon black 5 parts by weight (MA-100 manufactured by Mitsubishi Chemical Corporation) Polymerization initiator 3 parts by weight 2.2'-
Azobis(2,4-dimethylvaleronitrile) Polymerization initiator 1 part by weight 2.2'
-Azobis(2-methylbutyronitrile) The substances in the above formulation were mixed, and the mixture was mixed with 800 parts by weight of water and tricalcium phosphate (TCP-1 manufactured by Taihei Kagaku Sangyo Co., Ltd.).
0.0, solid content concentration 10%) into a continuous phase consisting of 100 parts by weight and 0.012 parts by weight of sodium lauryl sulfate,
Granulate using a homo mixer and at 80°C with gentle stirring.
The polymerization reaction was carried out for 8 hours. Next, the obtained polymer was washed with water, passed through the mouth, and redispersed three times to obtain a suspension of positively charged core particles 1.
正帯電コア粒子２
ジメチルアミノエチルメタクリレートの代わりに、ジエ
チルアミノプロピルメタクリレートを１０重量部用いた
他は、上記正帯電コア粒子１の合成と同様にして正帯電
コア粒子２の懸濁液を得た。Positively Charged Core Particles 2 A suspension of positively charged core particles 2 was obtained in the same manner as in the synthesis of positively charged core particles 1, except that 10 parts by weight of diethylaminopropyl methacrylate was used instead of dimethylaminoethyl methacrylate.
負帯電コア粒子３
スチレン ７５重量部２−エチル
ヘキシル
メタクリレート １５重量部負帯電性電
荷制御共重合体１ １０重量部ジビニルベンゼン
０．７重量部２−エチレングリコール
ジメタクリレート １．５重量部含金属染料（
電荷制御剤） ２重量部（オリエント化学社製の
ボントロンＮ−１１）
カーボンブラック ５重量部（三菱化成
社製のＭＡ−１（１０）
重合開始剤 ３重量部２．２′−
アゾビス（２，４
−ジメチルバレロニトリル）
重合開始剤 １重量部２．２′−
アゾビス（２
一メチルブチロニトリル）
上記処方の各物質を混合して、上記正帯電コア粒子１と
の合成と同様にして負帯電コア粒子３の懸濁液を得た。Negatively charged core particle 3 Styrene 75 parts by weight 2-ethylhexyl methacrylate 15 parts by weight Negatively chargeable charge control copolymer 1 10 parts by weight Divinylbenzene
0.7 parts by weight 2-ethylene glycol dimethacrylate 1.5 parts by weight Metal-containing dye (
Charge control agent) 2 parts by weight (Bontron N-11 manufactured by Orient Chemical Co., Ltd.) Carbon black 5 parts by weight (MA-1 (10) manufactured by Mitsubishi Chemical Corporation) Polymerization initiator 3 parts by weight 2.2'-
Azobis(2,4-dimethylvaleronitrile) Polymerization initiator 1 part by weight 2.2'-
Azobis(2-methylbutyronitrile) The substances in the above formulation were mixed to obtain a suspension of negatively charged core particles 3 in the same manner as in the synthesis with positively charged core particles 1 above.
負帯電コア粒子４
負帯電性電荷制御共重合体１の代わりに、負帯電性電荷
制御共重合体２を３重量部用いた他は、上記負帯電コア
粒子３の合成と同様にして負帯電コア粒子４の懸濁液を
得た。Negatively charged core particles 4 Negatively charged core particles 4 were produced in the same manner as in the synthesis of negatively charged core particles 3, except that 3 parts by weight of negatively chargeable charge control copolymer 2 was used instead of negatively chargeable charge control copolymer 1. A suspension of core particles 4 was obtained.
負帯電樹脂の微小粒子１
スチレン ７０重量部２−エチル
ヘキシル
メタクリレート ２５重量部スチレンスル
ホン酸ナトリウム ３重量部ラジカル重合性シリコー
ン ２重量部（信越化学社製）Ｘ−２２−１７４
Ｄ ）水 ９００重量部重
合開始剤（過硫酸カリウム） １重量部上記処方の各
物質を混合し、混合物を緩攪拌下で８０℃にて、６時間
重合反応を行い、負帯電性樹脂の微小粒子１のエマルシ
ョンを得た。Negatively charged resin microparticles 1 Styrene 70 parts 2-ethylhexyl methacrylate 25 parts Sodium styrene sulfonate 3 parts Radically polymerizable silicone 2 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-174
D) Water: 900 parts by weight Polymerization initiator (potassium persulfate): 1 part by weight The substances in the above formulation were mixed, and the mixture was subjected to a polymerization reaction at 80°C for 6 hours with gentle stirring to form a microscopically charged resin. An emulsion of particles 1 was obtained.
正帯電性樹脂の微小粒子２
ラジカル重合性シリコーンとして信越化学社製のＸ−２
２−１７４Ｄの代わりに、同社製のＸ−２２−５００４
Ｃを３重量部用い、スチレンスルホン酸ナトリウムの代
わりに、ジメチルアミノエチルメタクリレートを３重量
部用い、過硫酸カリウムの代わりに、アゾビス（２−ア
ミジニプロパン）塩酸塩を重合開始剤として１重量部用
いた他は、上記負帯電性樹脂の微小粒子１の合成と同様
にして、正帯電性樹脂の微小粒子２のエマルションを得
た。Microparticles of positively chargeable resin 2 X-2 manufactured by Shin-Etsu Chemical Co., Ltd. as a radically polymerizable silicone
Instead of 2-174D, use the company's X-22-5004
Using 3 parts by weight of C, 3 parts by weight of dimethylaminoethyl methacrylate instead of sodium styrene sulfonate, and 1 part by weight of azobis(2-amidinipropane) hydrochloride as a polymerization initiator instead of potassium persulfate. An emulsion of positively chargeable resin microparticles 2 was obtained in the same manner as in the synthesis of the negatively chargeable resin microparticles 1, except that the above-mentioned composition was used.
実施例１
正帯電コア粒子１の懸濁液１００重量部と、負帯電樹脂
の微小粒子１のエマルション３重量部とを混合し、この
混合液に１２Ｎの塩酸２０重量部を添加し、緩攪拌下で
７０℃にて、１時間熱処理を行うことにより、コア粒子
の表面に樹脂の微小粒子を固着させた。これを洗浄、口
過、乾燥、解砕することにより電子写真用トナーを得た
。Example 1 100 parts by weight of a suspension of positively charged core particles 1 and 3 parts by weight of an emulsion of negatively charged resin microparticles 1 were mixed, 20 parts by weight of 12N hydrochloric acid was added to this mixture, and the mixture was gently stirred. By performing heat treatment at 70° C. for 1 hour, the resin microparticles were fixed to the surface of the core particles. An electrophotographic toner was obtained by washing, rinsing, drying, and crushing this.
このトナーの粒度分布をコールタ−カウンターを用いて
測定した結果、体積基準のメジアン径［）ｓｏは１１．
１μｍで、シャープな粒度分布を有するものであった。As a result of measuring the particle size distribution of this toner using a Coulter counter, the volume-based median diameter [)so was 11.
It had a sharp particle size distribution of 1 μm.
また得られたトナー１００重量部に対して、０．１重量
部の疎水性シリカ微粉末を混合したものを、シリコーン
樹脂にて被覆されたフェライトキャリアと混合して、ト
ナー濃度か３．８％の現像剤を調製した。この現像剤を
、電子写真複写機（三田工業株式会社製のＤＣ−２５８
５を改造して定着ローラにシリコーンオイルが塗布され
ないようにしたもの）に充填し、１００００枚の原稿複
写を行い、以下のようにして現像剤の定着性、耐オフセ
ット性および定着ローラの汚れ具合を調べた。Further, 0.1 part by weight of hydrophobic silica fine powder was mixed with 100 parts by weight of the obtained toner, and a mixture was mixed with a ferrite carrier coated with silicone resin, resulting in a toner concentration of 3.8%. A developer was prepared. This developer was applied to an electrophotographic copying machine (DC-258 manufactured by Sanda Kogyo Co., Ltd.).
5 was modified to prevent silicone oil from being applied to the fixing roller), 10,000 originals were copied, and the developer fixability, offset resistance, and dirtiness of the fixing roller were evaluated as follows. I looked into it.
定着性の評価方法
１００００枚の複写を経て得られた複写画像のベタ画像
部分に、粘着テープを貼り付け、次に該テープを剥がし
て、テープの貼付前と剥離後との画像の濃度を反射濃度
計（東京電色社製のＴＣ−６Ｄ）を用いて測定し、下記
式
に従って定着率（％）を算出し、
定着率９５％以上を良
定着率９０％以上９５％未満をやや不良定着率９０％未
満を不良
として評価した。Fixability evaluation method: Adhesive tape is pasted on the solid image portion of the copied image obtained through 10,000 copies, then the tape is peeled off, and the density of the image before and after the tape is peeled off is reflected. Measure using a densitometer (TC-6D manufactured by Tokyo Denshokusha) and calculate the fixing rate (%) according to the formula below. If the fixing rate is 95% or more, the fixing rate is good.If the fixing rate is 90% or more and less than 95%, it is considered to be slightly poor fixing. A percentage of less than 90% was evaluated as poor.
耐オフセット性の評価方法
１００００枚の原稿複写を行っている間に、オフセット
現象か発生するか否かによフて行った。A method for evaluating offset resistance was carried out to determine whether an offset phenomenon occurred while copying 10,000 sheets of originals.
定着ローラの汚れの評価方法
１００００枚の複写後の定着熱ローラおよび定着圧ロー
ラの汚れの目視、および複写された紙の裏汚れを観察し
て行った。Method for evaluating stains on fixing rollers The stains on the fixing heat roller and fixing pressure roller after 10,000 sheets of copying were visually observed, and the stains on the back of the copied paper were observed.
上記各試験結果、実施例１のトナーは定着率か９５％以
上の「良」を示し、オフセット現象の発生も見られず、
定着σ−ラの汚れも殆どなかった。The above test results show that the toner of Example 1 had a "good" fixing rate of 95% or more, and no offset phenomenon was observed.
There was also almost no stain on the fixing σ-ra.
実施例２
正帯電コア粒子１の懸濁液の代わりに、正帯電コア粒子
２の懸濁液を１００重量部用いた他は、上記実施例１と
同様にしてトナーおよび現像剤を得た。得られたトナー
の粒度分布、定着性、耐オフセット性および定着ローラ
の汚れを調−・た。その結果を以下に記す。Example 2 A toner and a developer were obtained in the same manner as in Example 1, except that 100 parts by weight of a suspension of positively charged core particles 2 was used instead of the suspension of positively charged core particles 1. The particle size distribution, fixing properties, anti-offset properties, and staining of the fixing roller of the obtained toner were examined. The results are described below.
トナーの粒度分布：Ｉ）ｓｏか１１．２ｕｍ、シャープ
な粒度分布
定着性、良
耐オフセット性、良
定着ローラの汚れ 殆となし
実施例３
正帯電コア粒子１の懸濁液の代わりに、負帯電コア粒子
３の懸濁液を１００重量部用い、負帯電樹脂の微小粒子
１のエマルションの代わりに、正帯電樹脂の微小粒子２
のエマルションを３重量部用いた他は、上記実施例１と
同様にして電子写真用トナーを得た。Particle size distribution of toner: I) So or 11.2um, sharp particle size distribution fixing properties, good offset resistance, good fixing roller stains Almost none Example 3 Instead of a suspension of positively charged core particles 1, negatively charged core particles 1 were used. Using 100 parts by weight of a suspension of charged core particles 3, positively charged resin microparticles 2 were used instead of the emulsion of negatively charged resin microparticles 1.
An electrophotographic toner was obtained in the same manner as in Example 1 above, except that 3 parts by weight of the emulsion was used.
得られたトナーは、Ｄ、ｏか１０．０μｍでシャープな
粒度分布を有するものであった。The obtained toner had a sharp particle size distribution of D and O of 10.0 μm.
次に、得られたトナーを上記実施例１と同様に処理して
現像剤を調整し、電子写真方式プリンター（三田工業株
式会社製のＬＰＸ−１を改造して定着ローラにシリコー
ンオイルか塗布されないようにしたもの）に充填し、１
００００枚の原稿複写を行い、トナーの定着性、耐オフ
セット性等を調べｔ：。その結果、定着性および耐万フ
セッ］・性共に良好な結果を示し、定着ローラの汚れも
殆と見られなかった。Next, the obtained toner was processed in the same manner as in Example 1 above to prepare a developer, and an electrophotographic printer (LPX-1 manufactured by Sanda Industries Co., Ltd.) was modified so that no silicone oil was applied to the fixing roller. 1)
We made 0,000 copies of originals and examined toner fixability, offset resistance, etc. As a result, good results were obtained in terms of fixability and anti-stickiness, and almost no staining of the fixing roller was observed.
実施例４
正帯電コア粒子１の懸濁液の代わりに、負帯電コア粒子
４の懸濁液を１００重量部用い、負帯電樹脂の微小粒子
１のエマルションの代わりに、正帯電樹脂の微小粒子２
のエマルションを３重量部用いた他は、上記実施例１と
同様にして電子写真用トナーおよび現像剤を得た。得ら
れたトナーの粒度分布、および定着性と耐オフセット性
とを調べた。その結果、トナーはＤ５ｏか１０．６μｍ
でシャープな粒度分布を有するものであった。また、定
着性および耐オフセツト性共に良好な結果を示し、定着
ローラの汚れも殆ど見られなかった。Example 4 100 parts by weight of a suspension of negatively charged core particles 4 was used instead of the suspension of positively charged core particles 1, and positively charged resin microparticles were used instead of the emulsion of negatively charged resin microparticles 1. 2
An electrophotographic toner and developer were obtained in the same manner as in Example 1 above, except that 3 parts by weight of the emulsion was used. The particle size distribution, fixing properties, and anti-offset properties of the obtained toner were examined. As a result, the toner was D5o or 10.6 μm.
It had a sharp particle size distribution. Further, good results were shown in both fixing properties and offset resistance, and almost no staining of the fixing roller was observed.
比較例１
スチレン ８２重量部２−エチル
ヘキシル
メタクリレート １８重量部２−エチレ
ングリコール
ジメタクリレート １．５重量部非反応性シ
リコーンオイル １重量部（信越化学社製のＫＦ
９６−５０００Ｃ３）含金属染ｔ、４ （電荷制御剤）
１重量部（オリエント化学社製の
ホントロンＳ−３４）
カーホンブランク ５重量部（三菱化成
社製のＨＡ−１００）
重合開始剤 ３重量部２．２′−
アゾビス（２，４
一ジメチルバレロニトリル）
重合開始剤 １重量部アゾビスイ
ソブチロニトリル）
上記処方の各物質を混合し、混合物を水４００重量部と
リン酸カルシウム６重量部とドデシルベンゼンスルホン
酸ナトリウム００１重量部とからなる連続相に投入し、
ホモミキサーを用いて造粒し、緩攪拌下で８０℃にて、
８時間重合反応を行った。次いて、得られた重合物を希
酸処理、水洗、乾燥、解砕することにより、電子写真用
トナーを得た。Comparative Example 1 Styrene 82 parts by weight 2-ethylhexyl methacrylate 18 parts by weight 2-ethylene glycol dimethacrylate 1.5 parts by weight Non-reactive silicone oil 1 part by weight (KF manufactured by Shin-Etsu Chemical Co., Ltd.
96-5000C3) Metal-containing dye t, 4 (charge control agent)
1 part by weight (Hontron S-34 manufactured by Orient Chemical Co., Ltd.) Carphone blank 5 parts by weight (HA-100 manufactured by Mitsubishi Kasei Corporation) Polymerization initiator 3 parts by weight 2.2'-
Azobis(2,4-dimethylvaleronitrile) Polymerization initiator 1 part by weight azobisisobutyronitrile) Mix each substance in the above formulation and combine the mixture with 400 parts by weight of water, 6 parts by weight of calcium phosphate, and 0.1 parts by weight of sodium dodecylbenzenesulfonate. into a continuous phase consisting of parts by weight,
Granulate using a homo mixer and at 80°C with gentle stirring.
The polymerization reaction was carried out for 8 hours. Next, the resulting polymer was treated with a dilute acid, washed with water, dried, and crushed to obtain an electrophotographic toner.
二のよう１こして得られｔニトナーは、シリコーンオイ
ルかモノマーと反応するか、ポリマーとは相分離を生し
るため、シリコーンオイルを殆と含有せすに、シリコー
ンオイルかトナーの表面を覆った状態であった。そのた
め、このトナーは解砕しても直ぐに軟凝集を生じた。The toner obtained by filtration as shown in step 2 reacts with the silicone oil or monomer, or undergoes phase separation from the polymer. It was in a state of Therefore, even if this toner was crushed, soft aggregation occurred immediately.
このトナーの粒度分布をコールタ−カウンターを用いて
測定した結果、体積基準のメジアン径Ｉ）ｓｏは１０．
６μｍで、シャープな粒度分布を有するものであった。As a result of measuring the particle size distribution of this toner using a Coulter counter, the volume-based median diameter I)so was 10.
It was 6 μm and had a sharp particle size distribution.
また得られたトナーを上記実施例１と同様の方法で評価
したところ、帯電の立ち上がりが悪く、複写１００枚以
降でかぶりが発生した。また定着性にも劣り、複写８０
００枚以降に定着ローラに汚れが見られ、オフセット現
象が発生した。Furthermore, when the obtained toner was evaluated in the same manner as in Example 1, the charging start-up was poor and fogging occurred after the 100th copy. Also, the fixing properties are poor, and the copying rate is 80.
After the 00th sheet, stains were found on the fixing roller, and an offset phenomenon occurred.
比較例２
非反応性シリコーンオイルを使用しなかった他は、上記
比較例１と同様にして電子写真用トナーおよび現像剤を
得た。得られたトナーの粒度分布、定着性および耐オフ
セット性を調べた。その結果、トナーはり、。が１０，
９μｍでシャープな粒度分布を有するものであった。し
かしこのトナーは、定着性は「良」てあったか、複写１
０００枚以降に定着ローラに汚れか見られ、オフセット
現象か発生した。Comparative Example 2 An electrophotographic toner and developer were obtained in the same manner as in Comparative Example 1, except that non-reactive silicone oil was not used. The particle size distribution, fixing properties, and anti-offset properties of the obtained toner were examined. As a result, the toner beam. is 10,
It had a sharp particle size distribution of 9 μm. However, the fixing properties of this toner were "good", and the copy 1
After 000 copies, stains were seen on the fixing roller, and an offset phenomenon occurred.
〈発明の効果〉
以上のように、本発明の帯電性樹脂粒子は、微小樹脂粒
子がコア粒子の表面に強固に付着しているので、本発明
の帯電性樹脂粒子を電子写真用トナーとして使用する場
合は、樹脂の微小粒子の帯電により、帯電特性の優れた
ものになる。また、樹脂の微小粒子に含有される重合性
シリコーンオイルが離型性および耐湿性を向上させるの
で、定着性および耐オフセット性か向上する。<Effects of the Invention> As described above, in the chargeable resin particles of the present invention, the fine resin particles are firmly attached to the surface of the core particles, so that the chargeable resin particles of the present invention can be used as a toner for electrophotography. In this case, the fine particles of the resin are charged, resulting in excellent charging characteristics. Furthermore, since the polymerizable silicone oil contained in the resin microparticles improves mold release properties and moisture resistance, fixing properties and anti-offset properties are improved.
代 理 人 弁理士 亀 井 弘
勝（ばか２名）Agent: Patent attorney Hirokatsu Kamei (two idiots)
Claims (1)
からなるコア粒子と、 水系媒体中において前記コア粒子と逆の電荷を有し、か
つ重合性シリコーンオイルを含有すると共に、前記コア
粒子よりも粒径が小さな樹脂の微小粒子とからなり、 微小粒子が前記コア粒子の表面に熱融着していることを
特徴とする帯電性樹脂粒子。 ２、前記微小粒子が、微小粒子１００重量部に対して、
重合性シリコーンオイルを１〜１０重量％含有している
請求項１記載の帯電性樹脂粒子。 ３、水系媒体中において正または負の電荷を有する樹脂
からなるコア粒子と、 水系媒体中において前記コア粒子と逆の電荷を有し、か
つ重合性シリコーンオイルを含有すると共に、前記コア
粒子よりも粒径が小さな樹脂の微小粒子とからなり、 前記微小粒子が前記コア粒子の表面に熱融着してなる帯
電性樹脂粒子を用いた電子写真用トナー。[Claims] 1. A core particle made of a resin that has a positive or negative charge in an aqueous medium, and a core particle that has an opposite charge to the core particle in an aqueous medium and contains polymerizable silicone oil. , and microparticles of a resin having a particle size smaller than that of the core particles, and the microparticles are thermally fused to the surface of the core particles. 2. The microparticles contain 100 parts by weight of the microparticles,
The chargeable resin particles according to claim 1, containing 1 to 10% by weight of polymerizable silicone oil. 3. A core particle made of a resin that has a positive or negative charge in an aqueous medium, and a core particle that has a charge opposite to that of the core particle in the aqueous medium and contains polymerizable silicone oil, and has a higher charge than the core particle. 1. An electrophotographic toner comprising chargeable resin particles comprising resin microparticles having a small particle size, the microparticles being thermally fused to the surface of the core particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2320159A JPH04188147A (en) | 1990-11-21 | 1990-11-21 | Rectifiable resin particle and electrophotographic toner using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2320159A JPH04188147A (en) | 1990-11-21 | 1990-11-21 | Rectifiable resin particle and electrophotographic toner using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04188147A true JPH04188147A (en) | 1992-07-06 |
Family
ID=18118362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2320159A Pending JPH04188147A (en) | 1990-11-21 | 1990-11-21 | Rectifiable resin particle and electrophotographic toner using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04188147A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06295096A (en) * | 1993-04-07 | 1994-10-21 | Tomoegawa Paper Co Ltd | Electrophotographic toner |
| JP2007279504A (en) * | 2006-04-10 | 2007-10-25 | Casio Electronics Co Ltd | Oil-less process-compatible pulverized toner |
-
1990
- 1990-11-21 JP JP2320159A patent/JPH04188147A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06295096A (en) * | 1993-04-07 | 1994-10-21 | Tomoegawa Paper Co Ltd | Electrophotographic toner |
| JP2007279504A (en) * | 2006-04-10 | 2007-10-25 | Casio Electronics Co Ltd | Oil-less process-compatible pulverized toner |
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