JPS62210472A - Electrophotographic positively electrifiable toner - Google Patents
Electrophotographic positively electrifiable tonerInfo
- Publication number
- JPS62210472A JPS62210472A JP61052645A JP5264586A JPS62210472A JP S62210472 A JPS62210472 A JP S62210472A JP 61052645 A JP61052645 A JP 61052645A JP 5264586 A JP5264586 A JP 5264586A JP S62210472 A JPS62210472 A JP S62210472A
- Authority
- JP
- Japan
- Prior art keywords
- binder
- polymer
- meth
- acrylate
- toner
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011230 binding agent Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 22
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000003086 colorant Substances 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- -1 acrylate ester Chemical class 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 150000003839 salts Chemical group 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000009477 glass transition Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 43
- 239000003795 chemical substances by application Substances 0.000 description 16
- 108091008695 photoreceptors Proteins 0.000 description 12
- 238000002156 mixing Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 239000006247 magnetic powder Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920005992 thermoplastic 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
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-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
- 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 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- HPGIOSOCXHTQGW-UHFFFAOYSA-N 2-(dipropylamino)ethyl prop-2-enoate Chemical compound CCCN(CCC)CCOC(=O)C=C HPGIOSOCXHTQGW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical class CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- OPPHXULEHGYZRW-UHFFFAOYSA-N 4-methoxy-2,4-dimethyl-2-phenyldiazenylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC1=CC=CC=C1 OPPHXULEHGYZRW-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- HXWGXXDEYMNGCT-UHFFFAOYSA-M decyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)C HXWGXXDEYMNGCT-UHFFFAOYSA-M 0.000 description 1
- YSZAMQILQQDREB-UHFFFAOYSA-N decyl-hexyl-(2-phenylethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[NH+](CCCCCC)CCC1=CC=CC=C1 YSZAMQILQQDREB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DJLHXXNSHHGFLB-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C(C)=C DJLHXXNSHHGFLB-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- UXJXCZLHRLBCLF-UHFFFAOYSA-N n-ethylethanamine;ethyl 2-methylprop-2-enoate Chemical compound CCNCC.CCOC(=O)C(C)=C UXJXCZLHRLBCLF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08726—Polymers of unsaturated acids or derivatives thereof
- G03G9/08728—Polymers of esters
-
- 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
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08706—Polymers of alkenyl-aromatic compounds
- G03G9/08708—Copolymers of styrene
- G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、乾式電子写真法において静電荷潜像を可視像
とする際に用いる電子写真用正帯電トナーに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a positively charged toner for electrophotography, which is used to convert an electrostatic latent image into a visible image in dry electrophotography.
［従来の技術とその問題点］
乾式電子写真法において、静電荷潜像を可視像とする際
に用いられるトナーは、一般に熱可塑性樹脂、着色剤、
電荷制御剤、場合によっては磁性粉体、その他添加剤を
予備混合俊、溶融混線、粉砕、分級の工程を経て、所望
の粒子径を有する着色粒子（以下、トナー粒子と称する
）として製造されている。これらトナー粒子のうち、該
粒子中に磁性粉体を含まないトナー粒子は、二成分系ト
ナーと称され、別に準備された磁性粉体と混合撹拌され
ることによってトナー粒子表面に、−足固の正または負
の電荷が蓄積され、この帯電粒子が静電荷潜像の現像に
供される。また、磁性粉体をトナー粒子内に混合分散し
たトナー粒子の場合は、−成分系トナーと称され、トナ
ー粒子相互間あるいはトナー粒子とスリーブ間等との摩
擦によってトナー粒子表面に正または負の電荷を蓄積し
、上記二成分系トナーと同様に、静電荷潜像の現像に供
される。[Prior art and its problems] In dry electrophotography, the toner used to turn an electrostatic latent image into a visible image generally contains a thermoplastic resin, a colorant,
Colored particles (hereinafter referred to as toner particles) having a desired particle size are produced by premixing a charge control agent, magnetic powder in some cases, and other additives, melting, mixing, pulverizing, and classifying. There is. Among these toner particles, toner particles that do not contain magnetic powder are called two-component toners, and are mixed and stirred with separately prepared magnetic powder to form a -footprint on the surface of the toner particles. A positive or negative charge is accumulated, and the charged particles are used to develop an electrostatic latent image. In addition, in the case of toner particles in which magnetic powder is mixed and dispersed within the toner particles, it is called a -component toner, and the toner particles have positive or negative effects on their surfaces due to friction between the toner particles or between the toner particles and the sleeve. It accumulates charge and is used to develop an electrostatic latent image, similar to the two-component toner described above.
摩擦帯電によって、トナー粒子表面に蓄積される電荷は
、静電荷潜像の形成に用いられる光導電性感光体の種類
によって正または負のいずれかの電荷とする必要があり
、またその時の帯電量は静電荷潜像をより正確に可視像
化し得るような量とする必要がある。このため電荷制御
剤ないしは導電物質を結着剤中に混合分散し、トナー粒
子表面の電荷および帯電量を制御するのが一般的である
。The charge accumulated on the toner particle surface by triboelectric charging must be either positive or negative depending on the type of photoconductive photoreceptor used to form the electrostatic latent image, and the amount of charge at that time must be needs to be an amount that allows the electrostatic latent image to be visualized more accurately. For this reason, it is common to mix and disperse a charge control agent or a conductive substance in a binder to control the charge and amount of charge on the surface of toner particles.
近年、当業界においては、静電荷潜像形成のための光導
電性感光体としてセレン感光体に代えて、無害、低コス
ト、フリーメンテナンスの特＠を有する有機光導電性感
光体（以下、ＯＰＣ感光体と称する）の使用量が急激に
伸びており、このＯＰＣ感光体上に形成される静電荷潜
像の現像には、良好なる正帯電性トナーが望まれている
。また、セレン感光体を用いた場合でも反転現像には正
帯電トナーが必要であり、ざらにまた、特にカラーコピ
ー化への対応には特定色を有せず、無色透明で濁り等が
なく、任意の色調に着色可能な正帯電性トナーが望まれ
ている。In recent years, in the industry, organic photoconductive photoreceptors (hereinafter referred to as OPC), which have the characteristics of harmlessness, low cost, and free maintenance, have been used instead of selenium photoreceptors as photoconductive photoreceptors for forming electrostatic latent images. The usage of OPC photoreceptors (referred to as photoreceptors) is rapidly increasing, and a positively chargeable toner with good properties is desired for developing electrostatic latent images formed on these OPC photoreceptors. In addition, even when using a selenium photoreceptor, a positively charged toner is required for reversal development, and in addition, especially for color copying, it does not have a specific color, is colorless and transparent, and does not have any turbidity. A positively chargeable toner that can be colored into any color tone is desired.
トナー粒子は、結着剤中に、正電荷制御剤、着色剤、及
び必要に応じて磁性粉体、その他添加剤を混合分散する
ことによって製造されており、その際に使用される正電
荷制御剤としては、■アジン系のニグロシン、ニグロシ
ン塩基類、ニグロシン誘導体、
■ナフテン酸または高級脂肪酸の金属塩類、■アルコキ
シル化アミン、
■ベンジルメチルーヘキシルデシルアンモニウムクロラ
イド、デシル−トリメチルアンモニウムクロライド等の
４級アンモニウム塩、■アルキルアミド、
等が一般的でおる。Toner particles are manufactured by mixing and dispersing a positive charge control agent, a colorant, and, if necessary, magnetic powder and other additives in a binder. As agents, ■ azine-based nigrosine, nigrosine bases, nigrosine derivatives, ■ metal salts of naphthenic acid or higher fatty acids, ■ alkoxylated amines, ■ quaternary compounds such as benzylmethyl-hexyldecylammonium chloride, decyl-trimethylammonium chloride, etc. Ammonium salts, alkylamides, etc. are commonly used.
しかしながらこれらの正電荷制御剤は、構造が複雑であ
ると同時に、製造工程、精製工程が繁雑であるため、性
質が一定でなく、安定性、信頼性に劣るという欠点を有
し、例えば、結着剤となる熱可塑性樹脂中に混合分散し
てトナー粒子を製造する際の溶融混練、粉砕工程で熱的
、機械的影響を受けて分解、変質し、電荷制御性が低下
するという欠点があり、このため得られたトナー粒子の
トナー特性をいちじるしく低下させるという問題点があ
る。However, these positive charge control agents have a complicated structure, and at the same time, have complicated manufacturing and purification processes, so they have the drawbacks of inconsistent properties and poor stability and reliability. It has the disadvantage that it decomposes and changes in quality due to thermal and mechanical influences during the melt-kneading and pulverization processes when mixing and dispersing it in a thermoplastic resin that serves as an adhesive to produce toner particles, resulting in a decrease in charge controllability. Therefore, there is a problem that the toner characteristics of the obtained toner particles are significantly deteriorated.
また、これらの正電荷制御剤は、結着剤である熱可塑性
樹脂との相溶性を有しないため、透明性に乏しく、カラ
ーコピー化に対応させて任意に着色しようとした場合、
鮮明な色調のカラーコピーが得られないという大きな問
題がおる。In addition, these positive charge control agents are not compatible with the thermoplastic resin that is the binder, so they have poor transparency, and when attempting to arbitrarily color them for color copying,
A major problem is that color copies with clear tones cannot be obtained.
さらにまた、これらの正電荷制御剤は結着剤中に、着色
剤同様粒子状の分散状態で存在しているが、該電荷制御
剤は相溶性が悪く、結着剤に固定される要素を有してい
ないため、トナー粒子製造の際の粉砕工程でおるいは、
トナー粒子表面に電荷を蓄積する際の複写機内での流動
摩擦において、トナー粒子表面層に存在する電荷制御剤
の分散粒子に離脱が生じ、帯電量に変化を生じさせ、あ
るいは、トナー粒子例々の帯電性にバラツキを生じさせ
る等の欠点がある。特にこれらの欠点は、複写回数の増
大、すなわち流動摩擦の時間が長くなるにつれて増大す
るので、長期に亘って安定した帯電状態を維持すること
が困難であるという問題点を有している。かかる問題点
を解決するため、上記正電荷制御剤に高級脂肪酸等を反
応させることによって結着剤への相溶性を改良する方法
が提案ないし実施されているが、未だ満足し得るものか
えられていない。Furthermore, these positive charge control agents exist in a binder in a particulate dispersed state like colorants, but these charge control agents have poor compatibility and do not allow the elements fixed to the binder to Because it does not have any
During the flow friction inside the copying machine when charge is accumulated on the surface of the toner particles, the dispersed particles of the charge control agent present in the surface layer of the toner particles are detached, causing a change in the amount of charge, or causing a change in the amount of charge on the toner particles. There are drawbacks such as variations in charging properties. In particular, these drawbacks increase as the number of copies is increased, that is, as the time of fluid friction increases, so that it is difficult to maintain a stable charged state over a long period of time. In order to solve this problem, methods have been proposed or implemented to improve the compatibility with the binder by reacting the positive charge control agent with higher fatty acids, etc. However, no satisfactory method has been found yet. do not have.
上記正電荷制御剤の相溶性を改良するための他の方法と
しては、結着剤樹脂母格中に正電荷性の官能基（アミノ
基）を有するビニル重合性上ツマ−を共重合し、それ自
体で正帯電性結着剤とする方法（例えば特開昭５４−１
４３６４７号公報）、または、ジアルキルアミノメタク
リルアミドの重合体を４級塩とした正電荷制御剤を用い
る方法（例えば特開昭５８−１６２９５９号公報）等が
提案されているが、特開昭５４−１４３６４７号公報の
方法は、正電荷性官能基がアミノ基でおるため、酸化に
よる着色及び吸湿による帯電量の変化が生じるという欠
点があり、着色するという欠点は、カラートナー化した
場合、鮮明な色調が得られないという問題点となり、帯
電量の変化は、高品質、かつ均一なトナー画像が得られ
ないという問題点となる。また、特開昭５８−１６２９
５９号公報の方法は、必ずしも相溶性が充分改善された
とはいい難く、結着剤を白濁させるという欠点が必って
、濁りのない鮮明な色調のカラートナーとなり難いとい
う問題点がおるとともに、トナー粒子の耐湿性、帯電安
定性に劣るなどの問題点がある。Another method for improving the compatibility of the positive charge control agent is to copolymerize a vinyl polymerizable binder having a positively charged functional group (amino group) in the binder resin matrix, A method of using it as a positively chargeable binder (for example, JP-A-54-1
43647) or a method using a positive charge control agent using a quaternary salt of a polymer of dialkylaminomethacrylamide (for example, JP-A-58-162959). The method disclosed in Publication No. 143647 has the disadvantage that the positively charged functional group is an amino group, so that coloration due to oxidation and change in charge amount due to moisture absorption occur. This causes a problem in that a uniform color tone cannot be obtained, and a change in the amount of charge causes a problem in that a high quality and uniform toner image cannot be obtained. Also, JP-A-58-1629
The method of Publication No. 59 cannot be said to have sufficiently improved compatibility, and has the disadvantage that it inevitably makes the binder cloudy, making it difficult to produce a color toner with a clear tone without clouding. There are problems such as poor moisture resistance and charging stability of the toner particles.
［発明が解決しようとする問題点］
本発明は上記事情に基づいてなされたもので、正電荷制
御剤の有する問題点、すなわち、安定性に乏しく、結着
剤との相溶性に劣るという問題点を解決し、安定した帯
電性を有し、ざらには正電荷制御性が結着剤中へ無色ま
たは淡色透明状態で相溶し得るようにして、カラートナ
ーとしても好適に用いることのできる電子写真用正帯電
トナーを提供しようとするものである。[Problems to be Solved by the Invention] The present invention has been made based on the above circumstances, and solves the problems of positive charge control agents, namely, the problems of poor stability and poor compatibility with binders. By solving these problems, it has stable charging properties, and moreover, its positive charge control properties allow it to be compatible with the binder in a colorless or light-colored transparent state, making it suitable for use as a color toner. The present invention aims to provide a positively charged toner for electrophotography.
「問題点を解決するための手段］
本発明の電子写真用正帯電トナーは、
（Ａ）スチレン及び／またはα−メチルスチレンと、（
メタ）アクリル酸アルキルエステルの共重合体である結
着剤（以下、結着剤（Ａ＞と称する）、
（Ｂ）スチレン及び／またはα−メチルスチレンと、ジ
アルキルアミノアルキル（メタ）アクリレートの４＠塩
の共重合比（重量％）が９８：２〜８５：１５で、かつ
、その重量平均分子量（Ｍｗ）が２０００〜１００００
の重合体（以下、重合体（Ｂ）と称する）を、前記結着
剤（Ａ＞１００重量部に対し２〜１０重量部、及び、
（Ｃ）着色剤、その他添加剤
とからなることを特徴とするもので、これによって前記
従来の問題点を解決し得たものでおる。"Means for Solving the Problems" The positively charged toner for electrophotography of the present invention comprises (A) styrene and/or α-methylstyrene;
A binder that is a copolymer of alkyl meth)acrylate (hereinafter referred to as binder (A)), (B) styrene and/or α-methylstyrene, and dialkylaminoalkyl (meth)acrylate. @The copolymerization ratio (wt%) of the salt is 98:2 to 85:15, and the weight average molecular weight (Mw) is 2000 to 10000
(hereinafter referred to as polymer (B)), the binder (2 to 10 parts by weight for A>100 parts by weight), and (C) a coloring agent and other additives. This is a feature that solves the above-mentioned conventional problems.
本発明の電子写真用正帯電トナーは、前記組成の結着剤
（Ａ＞に前記特定組成の重合体（Ｂ）を組合せることか
らなっており、重合体（Ｂ）は結着剤（Ａ＞に耐久性、
安定性にすぐれた正帯電特性を付与し、同時に結着剤（
Ａ）中に透明ないし淡色透明な状態で相溶するので、カ
ラーコピーにも好適に対応し得るものでおる。The positively charged toner for electrophotography of the present invention is composed of a binder (A) having the above composition in combination with a polymer (B) having the above specific composition, and the polymer (B) is composed of a binder (A) having the above composition. ＞Durability,
Provides positive charging characteristics with excellent stability, and at the same time binder (
Since it is compatible with A) in a transparent or light-colored transparent state, it can be suitably used for color copying.
本発明でいう結着剤（Ａ）とは、スチレン及び／または
α−メチルスチレンと、（メタ）アクリル酸アルキルエ
ステル（例えばメチル（メタ）アクリレート、エチル（
メタ）アクリレート、ブチル（メタ）アクリレート、プ
ロピル（メタ）アクリレート、アミル（メタ）アクリレ
ート、２−エチルヘキシル（メタ）アクリレート、シク
ロヘキシル（メタ）アクリレート、ラウリル（メタ）ア
クリレート、ステアリル（メタ）アクリレート等の１種
または２種以上の単最体の混合物〉を常法に従って共重
合した重合体であって、該重合体のガラス転位温度（Ｔ
ｇ）が５０〜８０℃の範囲にある重合体を用いるのが好
ましい。またこの重合体には、架橋剤として共重合性不
飽和基を分子中に２個以上有するアルキレンジオール、
オキシアルキレンジオール、ポリオキシアルキレンジオ
ール等の多価アルコール類のジ（メタ）アクリレート類
、ジビニルベンゼン等を用いて重合した架橋部分を有す
るものであっても良い。The binder (A) in the present invention refers to styrene and/or α-methylstyrene, and alkyl (meth)acrylates (e.g., methyl (meth)acrylate, ethyl (meth)acrylate,
1 such as meth)acrylate, butyl(meth)acrylate, propyl(meth)acrylate, amyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, etc. species or a mixture of two or more monomers] according to a conventional method, the polymer has a glass transition temperature (T
It is preferred to use polymers having g) in the range from 50 to 80°C. In addition, this polymer contains an alkylene diol having two or more copolymerizable unsaturated groups in the molecule as a crosslinking agent,
It may have a crosslinked portion polymerized using di(meth)acrylates of polyhydric alcohols such as oxyalkylene diol and polyoxyalkylene diol, divinylbenzene, and the like.
上記結着剤（Ａ）に混合して使用する重合体（Ｂ）は、
スチレン及び／またはα−メチルスチレンと、ジアルキ
ルアミノアルキル（メタ）アクリレートの４級塩とを共
重合比（重量％）９８：２〜８５：１５、好ましくは９
７：３〜８７：１３で、かつ、そのＭＷが２０００〜１
００００の範囲となるように共重合させたものである。The polymer (B) used by mixing with the binder (A) is:
Copolymerization ratio (wt%) of styrene and/or α-methylstyrene and quaternary salt of dialkylaminoalkyl (meth)acrylate is 98:2 to 85:15, preferably 9
7:3 to 87:13 and its MW is 2000 to 1
0000 range.
共重合体（Ｂ）において、スチレン及び／またはα−メ
チルスチレンは、該重合体（Ｂ）を結着剤（Ａ）中に良
好に相溶させるための成分として好適で、スチレン及び
／またはα−メチルスチレンの使用量が９８重量％より
多くなると良好な相溶性が得られるが、トナー粒子とし
て必要な帯電特性を得るために結着剤（Ａ＞に混合する
量を多くしなければならず、定着性へ悪影響を及ぼし、
また８５重量％より少なくなると結着剤（Ａ）との相溶
性が悪化し、トナー粒子自体の耐湿性も悪化するので好
ましくない。In the copolymer (B), styrene and/or α-methylstyrene are suitable as components for making the polymer (B) well compatible with the binder (A). - Good compatibility is obtained when the amount of methylstyrene used is greater than 98% by weight, but the amount mixed with the binder (A>) must be increased in order to obtain the charging characteristics necessary for toner particles. , has a negative effect on fixation,
Further, if it is less than 85% by weight, the compatibility with the binder (A) will deteriorate and the moisture resistance of the toner particles themselves will also deteriorate, which is not preferable.
また、上記共重合体（Ｂ）のうち、スチレン及び／また
はα−メチルスチレンの使用量の２０重量％を越えない
範囲で（メタ）アクリル酸アルキルエステル類を共重合
成分とすることは、結着剤（Ａ＞との相溶性を改良する
上で有効であり、本発明の主旨に反するものではないが
、透明性及び帯電特性値が低下する傾向があるので１０
重量％以内とするのが好ましい。In addition, in the above copolymer (B), the use of (meth)acrylic acid alkyl esters as a copolymerization component in an amount not exceeding 20% by weight of the amount of styrene and/or α-methylstyrene used is Although it is effective in improving the compatibility with the adhesive (A>) and does not contradict the gist of the present invention, it tends to reduce the transparency and charging characteristic values.
It is preferably within % by weight.
本発明において重合体（８）の共重合成分として使用さ
れるジアルキルアミノアルキル（メタ）アクリレートの
４級塩としては、（メタ）アクリル酸ジメチルアミノエ
チル、（メタ）アクリル酸ジエチルアミノエチル、（メ
タ）アクリル酸ジプロピルアミノエチル、（メタ）アク
リル酸ジブチルアミノエチルをメチルクロライド、メチ
ルブロマイド、エチルクロライド、エチルブロマイド、
プロピルクロライド、プロピルブロマイド、ブチルクロ
ライド、ブチルブロマイドにて４級塩としたものである
。Examples of the quaternary salt of dialkylaminoalkyl (meth)acrylate used as a copolymerization component of polymer (8) in the present invention include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and (meth)acrylate. Dipropylaminoethyl acrylate, dibutylaminoethyl (meth)acrylate as methyl chloride, methyl bromide, ethyl chloride, ethyl bromide,
It is made into a quaternary salt with propyl chloride, propyl bromide, butyl chloride, and butyl bromide.
上記スチレンおよび／またはα−メチルスチレンと、ジ
アルキルアミノアルキル（メタ）アクリレートを共重合
させるに際して用いることのできる重合開始剤としては
、アゾ系開始剤、例えばアゾビスイソブチロニトリル、
アゾビスジメチルバレロニトリル、アゾビス（２，４−
ジメチル−４−メトキシバレロニトリル）、２−フェニ
ルアゾ（２，４−ジメチル−４−メトキシバレロニトリ
ル）等を、モノマー混合物に対し０．５〜５重量％の範
囲で用いるのが好ましい。Polymerization initiators that can be used in copolymerizing the above styrene and/or α-methylstyrene with dialkylaminoalkyl (meth)acrylate include azo initiators such as azobisisobutyronitrile,
Azobisdimethylvaleronitrile, Azobis(2,4-
Dimethyl-4-methoxyvaleronitrile), 2-phenylazo (2,4-dimethyl-4-methoxyvaleronitrile), etc. are preferably used in an amount of 0.5 to 5% by weight based on the monomer mixture.
重合体（Ｂ）を得るための重合法としては、溶液重合、
懸濁重合、塊状重合等いずれの方法を用いることも可能
であり、特に限定するものではないが、得られる重合体
（Ｂ）の重量平均分子量の制御が比較的容易であること
から、メタノール、イソプロパツール、ブタノール等の
低級アルコールを含む有機溶剤中で、七ツマー混合物を
共重合させる溶液重合法を採用するのが特に好ましい。Polymerization methods for obtaining the polymer (B) include solution polymerization,
It is possible to use any method such as suspension polymerization or bulk polymerization, and although there are no particular limitations, methanol, It is particularly preferable to employ a solution polymerization method in which the heptamer mixture is copolymerized in an organic solvent containing a lower alcohol such as isopropanol or butanol.
本発明における重合体（Ｂ）のＭＷが２０００より小さ
くなると、耐環境性に劣り、高湿度環境下で帯電性の低
下が大きく、また定着時にオフセットが発生し易くなる
。ＭＷが１００００より大きくなると結着剤（Ａ＞との
相溶性が悪化し、均一な分散が得られないため、カブ１
パ感光体汚染が認められるようになる。本発明にとって
重合体（Ｂ）の特に好ましいＭＷは、３０００〜８００
０である。If the MW of the polymer (B) in the present invention is less than 2000, the environmental resistance will be poor, the chargeability will be greatly reduced in a high humidity environment, and offset will easily occur during fixing. When the MW is greater than 10,000, the compatibility with the binder (A>) deteriorates and uniform dispersion cannot be obtained.
Contamination of the photoreceptor becomes apparent. A particularly preferable MW of the polymer (B) for the present invention is 3000 to 800.
It is 0.
本発明において重合体（Ｂ）は、結着剤（Ａ＞１００重
量部中に２〜１０重量部の範囲で混合して用いられる。In the present invention, the polymer (B) is mixed in the binder (A>100 parts by weight) in an amount of 2 to 10 parts by weight.
重合体（Ｂ）の使用量が２重量部より少ないと、必要と
する帯電量が得られないと同時に、トナー粒子間に帯電
量のバラツキが生じ定着画像が不鮮明となり、また、感
光体汚れが激しくなる等の欠点が生じ易い。反対に１０
重量部より多くなると、耐環境性の低下、相溶性の低下
、オフセット発生、感光体汚れなどの欠点が生じるよう
になる。If the amount of polymer (B) used is less than 2 parts by weight, the required amount of charge will not be obtained, and at the same time, the amount of charge will vary between toner particles, making the fixed image unclear, and the photoreceptor may become stained. Disadvantages such as increased intensity are likely to occur. 10 on the contrary
If the amount exceeds 1 part by weight, disadvantages such as decreased environmental resistance, decreased compatibility, generation of offset, and staining of the photoreceptor will occur.
本発明の電子写真用正帯電トナーは、上記結着剤（Ａ）
、重合体（Ｂ）、及び所望量の着色剤、その他添加剤（
Ｃ）を混合し、常法に従って溶融混練、粉砕、分級の工
程を経て製造することができる。The positively charged toner for electrophotography of the present invention has the above-mentioned binder (A).
, polymer (B), and desired amounts of colorants and other additives (
It can be produced by mixing C) and performing the steps of melt-kneading, pulverization, and classification according to conventional methods.
［実施例］
以下、実施例に基づいて本発明を具体的に説明する。な
お、実施例中の各成分の共重合比ないし混合比は重量比
で示した。[Example] Hereinafter, the present invention will be specifically described based on Examples. In addition, the copolymerization ratio or mixing ratio of each component in the examples is shown in weight ratio.
実施例−１
［結着剤（Ａ＞の製造］
スチレン／ｎ−ブチルメタクリレート＝６／４からなる
モノマー混合物を常法に従って共重合し、結着剤（Ａ＞
とした。この結着剤（共重合体）のＴｇは６３℃であっ
た。Example-1 [Production of binder (A>)] A monomer mixture consisting of styrene/n-butyl methacrylate = 6/4 was copolymerized according to a conventional method to produce a binder (A>).
And so. The Tg of this binder (copolymer) was 63°C.
［重合体（Ｂ）の製造］
撹拌機、コンデンサー、温度計、窒素導入管を付した２
Ｊ！フラスコにメタノール３００９、トルエン１００ｇ
、スチレン５７Ｑ９、ジメチルアミノエチルメタクリレ
ートのメチルクロライド４級塩３０ｙ、アゾビスジメチ
ルバレロニトリル１０３を仕込み、撹拌、窒素導入下６
５°Ｃで１０時間重合し、得られた重合体をフラスコか
ら取り出し、減圧乾燥侵、ジェットミルにて粉砕し、Ｍ
ｗ＝３３００の重合体（Ｂ）を製造した。[Production of polymer (B)] 2 equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube
J! Methanol 3009, toluene 100g in flask
, styrene 57Q9, methyl chloride quaternary salt of dimethylaminoethyl methacrylate 30y, and azobisdimethylvaleronitrile 103 were charged, stirred, and under nitrogen introduction.
Polymerization was carried out at 5°C for 10 hours, and the obtained polymer was taken out from the flask, dried under reduced pressure, and pulverized with a jet mill.
A polymer (B) with w=3300 was produced.
上記の結着剤（Ａ＞１００部と重合体（Ｂ）５部をミキ
サーにて１０分間混合後、ロールミルにて溶融混練し、
ジェットミルで微粉砕後、粒子径５〜２５μの粒子を風
力分級して無着色のトナー粒子を製造した。After mixing the above binder (A>100 parts and 5 parts of polymer (B) in a mixer for 10 minutes, melt-kneading in a roll mill,
After pulverization using a jet mill, the particles having a particle size of 5 to 25 μm were classified by air to produce uncolored toner particles.
上記で得た無着色のトナー粒子について、下記の方法で
評価し、その結果を表−２に示した。The uncolored toner particles obtained above were evaluated by the following method, and the results are shown in Table 2.
（１）相溶性：トナー粒子をメルトインデクサ−にて押
出し、約５Ｍφの円柱状に成形し、この成形体を側面か
ら目視観察し、透明性によって相溶性を評価した。(1) Compatibility: Toner particles were extruded using a melt indexer and formed into a cylindrical shape of approximately 5 Mφ, and the formed body was visually observed from the side to evaluate compatibility based on transparency.
（２）帯電性：トナー粒子と球状酸化鉄粉を３：９７の
比率で混合し一定時間（１０分、６０分、１８０分）摩
擦帯電（２０’ＣＸ６５％ＲＨ）させた後、東芝ケミカ
ル社製ブローオフ粉体帯電量測定装置を用いて帯Ｎ量（
μＣ／９）を測定した。(2) Charging property: After mixing toner particles and spherical iron oxide powder at a ratio of 3:97 and tribocharging (20'CX65%RH) for a certain period of time (10 minutes, 60 minutes, 180 minutes), Toshiba Chemical Co., Ltd. The charge N amount (
μC/9) was measured.
（３）帯電量残存率二上記（２）の１８０分間摩擦帯電
後のトナー粒子（帯電量ＣＯとする）を、３５°Ｃ×８
５％ＲＨの高湿度雰囲気下に１４時間放置した後、前記
同様に帯電量（μＣ／ｇ）を測定（この時の帯電量をＣ
１とする）し、次式によって帯電量残存率（％）を求め
た。(3) Residual charge rate 2 Toner particles after 180 minutes of frictional charging in (2) above (charge amount CO) were heated at 35°C x 8
After leaving it in a high humidity atmosphere of 5% RH for 14 hours, the amount of charge (μC/g) was measured in the same manner as above (the amount of charge at this time was
1), and the residual charge amount (%) was determined by the following formula.
帯電量残存率（％） ＝ −ｘ １００Ｏ
実施例−２
実施例−１で得た結着剤（Ａ＞１００部及び重合体（Ｂ
）４部に三菱カーボン＃４０を５部配合し、実施例−１
と同様にして粒子径５〜２５μのトナー粒子を得た。こ
のトナー粒子の帯電量及び帯電量残存率の測定を実施例
−１と同様に行った。Charge remaining rate (%) = -x 100O Example-2 The binder obtained in Example-1 (A>100 parts) and the polymer (B
) 4 parts and 5 parts of Mitsubishi Carbon #40 were mixed, Example-1
In the same manner as above, toner particles having a particle size of 5 to 25 μm were obtained. The charge amount and charge amount residual rate of this toner particle were measured in the same manner as in Example-1.
また、このトナー粒子の電子写真特性を下記の方法で評
価した。それらの評価結果を合わせて表−２に示した。Further, the electrophotographic properties of this toner particle were evaluated by the following method. The evaluation results are shown in Table 2.
（４）電子写真特性二市販の正帯電トナー用複写機を用
いて複写テストを行い、カブ１人感光体の汚れ、オフセ
ットの状態を目視により観察した。(4) Electrophotographic characteristics 2 A copying test was conducted using a commercially available copying machine for positively charged toner, and the state of dirt and offset on the photoreceptor was visually observed.
実施例−３
実施例−１の結着剤（Ａ）１００部、重合体（Ｂ）３部
、カヤセット レッド１３０（日本生薬社製）０．１部
を配合し、実施例−１と同様にして着色トナー粒子を製
造し、実施例−１及び２と同様に評価し、その結果を表
−２に示した。Example-3 100 parts of the binder (A) of Example-1, 3 parts of the polymer (B), and 0.1 part of Kayaset Red 130 (manufactured by Nippon Koyaku Co., Ltd.) were mixed, and the same procedure as in Example-1 was carried out. Colored toner particles were produced and evaluated in the same manner as in Examples 1 and 2, and the results are shown in Table 2.
また、このトナー粒子でＯＨＰ用透明ポリエステルシー
ト上にコピー画像を形成し、ＯＨＰスクリーンに投影し
たところ、ニゴリのない鮮明な色調の赤色画像が再現出
来た。Furthermore, when a copy image was formed on a transparent polyester sheet for OHP using the toner particles and projected onto an OHP screen, a red image with a clear tone and no staining could be reproduced.
実施例−４
［重合体（Ｂ）の製造］
スチレン８５部、ジエチルアミンエチルメタクリレート
のｎ−ブチルブロマイド４級塩１５部、重合開始剤１．
５部を実施例−１同様に共重合して、Ｍｗ＝４７００の
重合体（Ｂ）を得た。この重合体（Ｂ）２部、実施例−
１の結着剤（Ａ）１００部、カヤセエローＡＧ（日本生
薬社製）０゜１部にて、実施例−１同様に着色トナー粒
子を得、同様に評価し、その結果を表−２に示した。Example 4 [Production of Polymer (B)] 85 parts of styrene, 15 parts of n-butyl bromide quaternary salt of diethylamine ethyl methacrylate, 1. polymerization initiator.
5 parts were copolymerized in the same manner as in Example-1 to obtain a polymer (B) with Mw=4700. 2 parts of this polymer (B), Example-
Colored toner particles were obtained in the same manner as in Example-1 using 100 parts of the binder (A) of No. 1 and 0.1 part of Kayase Yellow AG (manufactured by Nippon Koyaku Co., Ltd.), and evaluated in the same manner. The results are shown in Table-2. Indicated.
実施例−５
実施例−１と同様の方法により、スチレン９８部、ジエ
チルアミノエチルメタクリレートのｎ −ブチルクロラ
イド４級塩２部、重合開始剤１．０部から、ＭＷ−８６
３０の重合体（Ｂ）を製造した。この重合体（８）１０
部と上記結着剤（Ａ）１００部、カヤセットブルーＮ（
日本生薬社製）０．０８部にて青色トナー粒子を得、次
いで評価し、その結果を表−２に示した。Example 5 Using the same method as in Example 1, MW-86 was prepared from 98 parts of styrene, 2 parts of n-butyl chloride quaternary salt of diethylaminoethyl methacrylate, and 1.0 part of a polymerization initiator.
30 polymers (B) were produced. This polymer (8) 10
100 parts of the above binder (A), Kayaset Blue N (
Blue toner particles were obtained at 0.08 parts (manufactured by Nippon Koyaku Co., Ltd.) and then evaluated, and the results are shown in Table 2.
実施例−６゛
実施例−１と同様の方法により、スチレン９０部、ジメ
チルアミノエチルメタクリレートのメチルクロ５４６４
級塩１０部、重合開始剤１．５部から、Ｍｗ＝５０００
の重合体（Ｂ）を製造した。Example-6 90 parts of styrene and methylchloride 5464 of dimethylaminoethyl methacrylate were prepared in the same manner as in Example-1.
From 10 parts of grade salt and 1.5 parts of polymerization initiator, Mw=5000
Polymer (B) was produced.
この重合体（Ｂ）７部と上記結着剤（Ａ＞１００部、カ
ヤセットブルーＮ０．０８部にて着色トナー粒子を得、
次いで評価し、その結果を表−２に示した。Colored toner particles were obtained using 7 parts of this polymer (B) and the above binder (A>100 parts, Kayaset Blue N 0.08 parts,
It was then evaluated and the results are shown in Table 2.
比較例１〜６
スチレンとジメチルアミンエチルメタクリレ−トのメチ
ルクロライド４級塩及び重合開始剤を下記表−１に示し
た比率で配合し、実施例−１と同様にして種々の重合体
（Ｂ）を製造し、次いでこの重合体（Ｂ）と上記の結着
剤（Ａ）及び着色剤（カヤセット、ブルーＮ０．０８部
）を表−１の混合比率で混合し、それぞれの重合体（Ｂ
）に対応する着色トナー粒子を製造した。得られたトナ
ー粒子の上記同様の評価結果を表−２に示した。Comparative Examples 1 to 6 Styrene, methyl chloride quaternary salt of dimethylamine ethyl methacrylate, and a polymerization initiator were blended in the ratios shown in Table 1 below, and various polymers ( B) was produced, and then this polymer (B) and the above binder (A) and colorant (Kayaset, Blue N 0.08 part) were mixed at the mixing ratio shown in Table 1 to produce each polymer ( B
) were prepared. Table 2 shows the results of the same evaluation of the obtained toner particles as described above.
（以下余白）
比較例−７
上記結着剤（Ａ）１００部、臭化セチルトリメチルアン
モニウム（無色の正電荷制御剤）１部、カヤセットブル
ーＮ０．０８部にて、実施例−１同様に着色トナー粒子
を得、同様に評価し、その結果を表−２に示した。(Space below) Comparative Example-7 Same as Example-1, using 100 parts of the above binder (A), 1 part of cetyltrimethylammonium bromide (colorless positive charge control agent), and 0.08 part of Kayaset Blue N. Colored toner particles were obtained and evaluated in the same manner, and the results are shown in Table 2.
（以下余白）
［発明の効果］
本発明によって提供される電子写真用正帯電トナーは、
安定した帯電特性を有し、環境変化によっても帯電量の
変化が小さく、優れた電子写真特性を有するものである
。(The following is a blank space) [Effects of the invention] The positively charged toner for electrophotography provided by the present invention has the following characteristics:
It has stable charging characteristics, shows little change in charging amount even with environmental changes, and has excellent electrophotographic characteristics.
また、結着剤と正電荷制御剤の混合においても無色ない
し淡色透明状態の相溶性が得られ、カラートナー化した
場合には、鮮明な色調の着色トナーが得られるなど、き
わめて優れた効果を有するものである。In addition, when the binder and positive charge control agent are mixed, compatibility in a colorless to light-colored transparent state can be obtained, and when made into a color toner, a colored toner with a vivid tone can be obtained, resulting in extremely excellent effects. It is something that you have.
Claims (1)
タ）アクリル酸アルキルエステルの共重合体からなる結
着剤、 （Ｂ）スチレン及び／またはα−メチルスチレンとジア
ルキルアミノアルキル（メタ）アクリレートの４級アン
モニウム塩との共重合比（重量％）が９８：２〜８５：
１５で、かつ、その重量平均分子量が２０００〜１００
００の重合体、を前記結着剤１００重量部に対し２〜１
０重量部、 （Ｃ）着色剤及びその他添加剤、 とからなることを特徴とする電子写真用正帯電トナー。[Scope of Claims] (A) A binder comprising a copolymer of styrene and/or α-methylstyrene and an alkyl (meth)acrylate ester, (B) Styrene and/or α-methylstyrene and dialkylaminoalkyl The copolymerization ratio (wt%) of (meth)acrylate with quaternary ammonium salt is 98:2 to 85:
15, and its weight average molecular weight is 2000 to 100
00 polymer in an amount of 2 to 1 per 100 parts by weight of the binder.
0 parts by weight; (C) a colorant and other additives; 1. A positively charged toner for electrophotography, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61052645A JPH083658B2 (en) | 1986-03-12 | 1986-03-12 | Positively charged toner for electrophotography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61052645A JPH083658B2 (en) | 1986-03-12 | 1986-03-12 | Positively charged toner for electrophotography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62210472A true JPS62210472A (en) | 1987-09-16 |
| JPH083658B2 JPH083658B2 (en) | 1996-01-17 |
Family
ID=12920576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61052645A Expired - Fee Related JPH083658B2 (en) | 1986-03-12 | 1986-03-12 | Positively charged toner for electrophotography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083658B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01144060A (en) * | 1987-12-01 | 1989-06-06 | Ricoh Co Ltd | Toner for electrostatic photography |
| JPH0315079A (en) * | 1989-06-13 | 1991-01-23 | Sanyo Chem Ind Ltd | Electrostatic charge controller |
| JPH05119513A (en) * | 1991-10-25 | 1993-05-18 | Fuji Xerox Co Ltd | Dry toner for developing electrostatic charge image |
| US6808854B2 (en) | 2001-04-27 | 2004-10-26 | Canon Kabushiki Kaisha | Polyhydroxyalkanoates having in its side chain phenylsulfinyl structure and/or phenyl sulfonyl structure and production process therefor; charge control agent, toner binder and toner containing same; and image forming method and image forming apparatus using the toner |
| WO2010072571A1 (en) | 2008-12-22 | 2010-07-01 | Basf Se | Method for producing polymeric, ionic imidazolium compounds |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54124731A (en) * | 1978-03-02 | 1979-09-27 | Xerox Corp | Electrophotographic toner and method of forming image |
| JPS6073630A (en) * | 1983-09-12 | 1985-04-25 | ゼロツクス コーポレーシヨン | Recognition of magnetic image character |
| JPS6193455A (en) * | 1984-08-30 | 1986-05-12 | ゼロツクス コ−ポレ−シヨン | Toner composition containing ammonium sulfate charging promoting additive |
| JPS61149969A (en) * | 1984-12-18 | 1986-07-08 | ゼロツクス コーポレーシヨン | Improved toner composition |
-
1986
- 1986-03-12 JP JP61052645A patent/JPH083658B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54124731A (en) * | 1978-03-02 | 1979-09-27 | Xerox Corp | Electrophotographic toner and method of forming image |
| JPS6073630A (en) * | 1983-09-12 | 1985-04-25 | ゼロツクス コーポレーシヨン | Recognition of magnetic image character |
| JPS6193455A (en) * | 1984-08-30 | 1986-05-12 | ゼロツクス コ−ポレ−シヨン | Toner composition containing ammonium sulfate charging promoting additive |
| JPS61149969A (en) * | 1984-12-18 | 1986-07-08 | ゼロツクス コーポレーシヨン | Improved toner composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01144060A (en) * | 1987-12-01 | 1989-06-06 | Ricoh Co Ltd | Toner for electrostatic photography |
| JPH0315079A (en) * | 1989-06-13 | 1991-01-23 | Sanyo Chem Ind Ltd | Electrostatic charge controller |
| JPH05119513A (en) * | 1991-10-25 | 1993-05-18 | Fuji Xerox Co Ltd | Dry toner for developing electrostatic charge image |
| US6808854B2 (en) | 2001-04-27 | 2004-10-26 | Canon Kabushiki Kaisha | Polyhydroxyalkanoates having in its side chain phenylsulfinyl structure and/or phenyl sulfonyl structure and production process therefor; charge control agent, toner binder and toner containing same; and image forming method and image forming apparatus using the toner |
| WO2010072571A1 (en) | 2008-12-22 | 2010-07-01 | Basf Se | Method for producing polymeric, ionic imidazolium compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH083658B2 (en) | 1996-01-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |