JPH02223961A - Production of polymerized toner - Google Patents
Production of polymerized tonerInfo
- Publication number
- JPH02223961A JPH02223961A JP1045663A JP4566389A JPH02223961A JP H02223961 A JPH02223961 A JP H02223961A JP 1045663 A JP1045663 A JP 1045663A JP 4566389 A JP4566389 A JP 4566389A JP H02223961 A JPH02223961 A JP H02223961A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- toner
- suspension
- polymerization
- polymerized 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
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 19
- 239000007900 aqueous suspension Substances 0.000 claims description 7
- 239000007970 homogeneous dispersion Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 48
- 239000000725 suspension Substances 0.000 abstract description 19
- 239000006185 dispersion Substances 0.000 abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 235000012216 bentonite Nutrition 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- 238000005406 washing Methods 0.000 description 3
- 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-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
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- HTMIBDQKFHUPSX-UHFFFAOYSA-N methdilazine Chemical group C1N(C)CCC1CN1C2=CC=CC=C2SC2=CC=CC=C21 HTMIBDQKFHUPSX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は懸濁重合法を利用した、電子写真用トナーの製
造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing an electrophotographic toner using a suspension polymerization method.
（従来の技術）
エチレン性不飽和二重結合を有する単量体に、顔料や添
加剤を混合分散し、ついで該分散体を水性懸濁浴中で懸
濁重合する電子写真用トナーの製造方法に関する特許や
報文は、これまでに多数発表されているが（例えば、特
公昭５５−５０９６４、特公昭５６−５０８８３、特開
昭５６−１１０９４５号公報など）それらのいずれも、
得られる重合体粒子は球状のものであった。(Prior Art) A method for producing an electrophotographic toner, which comprises mixing and dispersing a pigment and additives in a monomer having an ethylenically unsaturated double bond, and then suspension-polymerizing the dispersion in an aqueous suspension bath. Although many patents and reports related to this have been published so far (for example, Japanese Patent Publication No. 55-50964, Japanese Patent Publication No. 50883-1983, Japanese Patent Application Laid-open No. 110945-1987, etc.), none of them
The resulting polymer particles were spherical.
（発明が解決しようとする問題点）
これらの球状の重合体粒子は、所望の粒形に分球されて
電子写真用トナーとして使用されるが、この上）な方法
で得られる球状のトナー粒子は、時には５０００〜１０
０００枚の複写でクリーニング性が不良となる問題が生
じてくることが判り、この原因が、複写機のクリーニン
グ工程で、ドラムに付着している残存トナーをブレード
で掻！１落とす際に、トナーが球状であるが故に転がる
ため摩擦力が小さく、艮時闇使用しているうちにブレー
ドと感光ドラムの闇に入り込み、クリーニングされなく
なってくることが判明した。(Problems to be Solved by the Invention) These spherical polymer particles are divided into desired particle shapes and used as toner for electrophotography. is sometimes 5000-10
It has been found that after making 1,000 copies, a problem arises in which the cleaning performance is poor.The cause of this problem is that the remaining toner adhering to the drum is scraped off with a blade during the cleaning process of the copying machine. It was found that when dropping the toner, the frictional force is small as it rolls because it is spherical, and as the toner is used, it gets stuck in the blade and photosensitive drum, making it impossible to clean it.
（問題点を解決するための手段）
本発明者等はこの点に着目し、鋭意検討を重ねた結果、
懸濁重合で得られた重合トナーに、更に、懸濁重合に使
用した単量体とは異種のエチレン性不飽和二重結合を有
する単量体又は、懸濁重合に使用したものと同種の単量
体と異種の単量体との混合物を重合することにより、得
られる粒子は不定形となりトナーとして使用すると、従
来の重合トナーを使用する場合に比ベクリー二ング性が
着しく向上することを見いだし、本発明に到達した。(Means for solving the problem) The inventors of the present invention focused on this point, and as a result of intensive studies,
The polymerized toner obtained by suspension polymerization is further added with a monomer having an ethylenically unsaturated double bond different from the monomer used in suspension polymerization, or a monomer of the same type as that used in suspension polymerization. By polymerizing a mixture of monomers and different types of monomers, the particles obtained become irregularly shaped and when used as a toner, the cleaning properties are significantly improved compared to when using conventional polymerized toners. They discovered this and arrived at the present invention.
即ち、本発明の目的は、クリーニング性に優れた重合ト
ナーを製造する方法に関するものであり、そして本発明
のか）る目的は、エチレン性不飽和二重結合を有する単
量体、顔料及び添加剤からなる均一分散体を、水性懸濁
洛中で懸濁重合することにより得られた重合トナーに、
更に、懸濁重合に使用したエチレン性不飽和二重結合を
有する単量体とは異種の単量体、または懸濁重合に使用
したものと同種の単量体と異種の単量体との混合物を重
合させることにより、容易に達成される。That is, an object of the present invention relates to a method for producing a polymerized toner having excellent cleaning properties, and an object of the present invention is to provide a method for producing a polymerized toner having excellent cleaning properties. A polymerized toner obtained by suspension polymerizing a homogeneous dispersion consisting of
Furthermore, a monomer of a different type from the monomer having an ethylenically unsaturated double bond used in the suspension polymerization, or a monomer of the same type and a different type used for the suspension polymerization. This is easily achieved by polymerizing the mixture.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において用いられるエチレン性不飽和二重結合を
有する単量体とは、トナーを製造する際に用いられるも
のであれば特に限定されるものではなく、具体的にはス
チレン系単量体あるいはアクリル酸基単量体が用いられ
る。スチレン系単量体としては、スチレン、ビニルトル
エン、エチルスチレン、μｍクロルスチレン、９ｆｌ−
ブチルスチレン等が帯げられ、好ましくはスチレン又は
ビニルトルエンが用いられる。アクリル酸系単敬体とし
ては、アクリル酸エチル、メタクリル酸エチル、アクリ
ル酸ブチル、メタクリル酸ブチル、アクリル酸メチル、
メタクリル酸メチル、アクリル酸プロピル等が挙げられ
、好ましくはアクリル酸−ｎ−ブチル、メタクリル酸−
ｎ−ブチル又はメタクリル酸メチルが用いられる。なお
、これらの単量体は各々単独でもまた混合してもよく、
更に必要ならばＮ、Ｎ−ツノチル７ミノエチル／タクリ
レー）、Ｎ、Ｎ−ノエチル７ミノエチルメタクリレート
、ビニルピリジン等のカチオン性の単量体を併用しても
よい。The monomer having an ethylenically unsaturated double bond used in the present invention is not particularly limited as long as it is used in manufacturing toner, and specifically, styrene monomer or An acrylic acid group monomer is used. Styrene monomers include styrene, vinyltoluene, ethylstyrene, μm chlorostyrene, 9fl-
Butylstyrene and the like are used, preferably styrene or vinyltoluene. Acrylic acid-based monomers include ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, methyl acrylate,
Methyl methacrylate, propyl acrylate, etc., preferably n-butyl acrylate, methacrylate-
n-Butyl or methyl methacrylate is used. Note that these monomers may be used alone or in combination,
Furthermore, if necessary, a cationic monomer such as N,N-noethyl 7minoethyl/tacryl), N,N-noethyl 7minoethyl methacrylate, or vinylpyridine may be used in combination.
顔料としては、従来のトナーで用いられているものであ
れば特に限定なく用いることができ、具体的にはカーボ
ンブラック、酸化鉄、酸化亜鉛、酸化チタン等を用いる
ことができる。カーボンブラックとしては、チャンネル
ブラックあるいは７Ｔ−ネスブラツク等の通常トナーに
使用されるものであって、粒径１５〜８０ミリミクロン
程度であるようなものがよい、その添加量としては重合
性単量体に対して１〜１０重量％、好ましくは３〜７重
量％であればよく、１重量％未満であると黒度が十分に
出す、又１０重量％をこえても黒皮の顕著な向上がみち
れず経済的ではない。As the pigment, any pigment used in conventional toners can be used without particular limitation, and specifically, carbon black, iron oxide, zinc oxide, titanium oxide, etc. can be used. The carbon black used in normal toners, such as channel black or 7T-Nes black, with a particle size of about 15 to 80 millimicrons is preferable, and the amount added is based on the polymerizable monomer. It is sufficient that the amount is 1 to 10% by weight, preferably 3 to 7% by weight, and if it is less than 1% by weight, the blackness will be sufficiently obtained, and even if it exceeds 10% by weight, there will be no noticeable improvement in blackness. Michiru is not economical.
添加剤としては、帯電制御剤及びワックスが用いられ、
帯電制御剤は通常使用されるものでよく、例えばニグロ
シン、７ニリンブルー、７タロンア二ンプルー、７ゾ系
合金染料、クロムイエロー等が挙げられる。帯電制御剤
としてニグロシンを用いる場合には、分散暗闇を短縮す
るために、粒径の小さいものが好ましく、具体的には３
〜３０μ−程度のものが用いられる。その添加量は、重
合性単量体に対して１〜５重量％、好ましくは２〜３重
量％とするのがよい、１重量％未満ではトナーの帯電制
御剤が不十分で、安定した画像が得られない、又５重量
％を越えても特性の顕著な向上が見られないことから好
ましくない。As additives, charge control agents and wax are used.
The charge control agent may be one commonly used, and examples thereof include nigrosine, 7-niline blue, 7-talonine blue, 7zo-based alloy dye, and chrome yellow. When using nigrosine as a charge control agent, in order to shorten dispersion darkness, it is preferable to use nigrosine with a small particle size.
A material having a diameter of about 30μ is used. The amount added is preferably 1 to 5% by weight, preferably 2 to 3% by weight based on the polymerizable monomer. If it is less than 1% by weight, the charge control agent for the toner will be insufficient, resulting in a stable image. is not obtained, and even if it exceeds 5% by weight, no significant improvement in properties is observed, which is not preferable.
ワックスとしでは、トナーに離型性を付与するものであ
れば特に限定されるものではなく、例えに使用されるワ
ックスが畢げられる。その添加量としては、重合性単量
体に対して１〜５重量％、好ましくは２〜３重量％とす
るのがよい、１重量％未満では離型性が不十分であり、
又５重量％を越えても離型性の顕著な向上が見られない
ことから好ましくない。The wax is not particularly limited as long as it imparts releasability to the toner, and for example, wax used may be used. The amount added is preferably 1 to 5% by weight, preferably 2 to 3% by weight based on the polymerizable monomer. If it is less than 1% by weight, the mold releasability is insufficient.
Moreover, even if it exceeds 5% by weight, no significant improvement in mold releasability is observed, which is not preferable.
重合トナーの製造では、上記の各種成分を均一に分散さ
せて懸濁重合を行うが、その際、重合物が所望のゲル化
率となるように、架橋剤を重合性単量体に対して０．１
〜２重量％添加するのがよい、デル化率としては、樹脂
分総量に対してテトラヒドロ７ランに不溶の樹脂分含量
が５０重量％以下、好ましくは４５重量％以下とするの
がよい。In the production of polymerized toner, the above-mentioned various components are uniformly dispersed and suspension polymerization is performed. At this time, a crosslinking agent is added to the polymerizable monomer so that the polymer has the desired gelation rate. 0.1
It is preferable to add up to 2% by weight, and the delification rate is such that the content of resins insoluble in tetrahydro-7 run is 50% by weight or less, preferably 45% by weight or less, based on the total resin content.
デル化率が５０重量％を越えると、得られるトナーの軟
化魚が高くなりすぎ、トナーを使用する際に定着するた
めの熱エネルギーを多く必要とするので好ましくない、
かかる架橋剤としては、通常使用されているものであれ
ばよく、例えばノビニルベンゼン、ジビニルナフタレン
、エチレングリコールジメタクリレート、ノビニルエー
テル等の２個のビニル基を有する化合物、あるいはトリ
ノチロールプロパントリアクリレート等の３個のビニル
基を有する化合物７ｙ挙げられ、これらは各々単独に、
あるいはこれらを混合して用いられる。If the delification rate exceeds 50% by weight, the softening rate of the obtained toner becomes too high and a large amount of thermal energy is required for fixation when the toner is used, which is undesirable.
Such a crosslinking agent may be any commonly used one, such as a compound having two vinyl groups such as novinylbenzene, divinylnaphthalene, ethylene glycol dimethacrylate, novinyl ether, or trinotyrolpropane triacrylate. Compound 7y having three vinyl groups, each of which is independently
Alternatively, a mixture of these may be used.
尚、更に該分散体には重合開始剤が添加される。Additionally, a polymerization initiator is further added to the dispersion.
重合開始剤としても通常使用されているものであればよ
く、例えばアゾビスイソブチロニトリル、アゾビス−２
，４−ノメチルパレロこトリル等が用いられる。Any commonly used polymerization initiator may be used, such as azobisisobutyronitrile, azobis-2
, 4-nomethylparerocotolyl, etc. are used.
重合トナーの製造では、これらの各種成分を均一に分散
させることが重要であり、かかる均一な分散体を調製す
るためには、重合性単量体、顔料及び添加剤を混合して
おき、不活性〃スの雰囲気下で、強力な撹拌機または分
散機、例えばホモミキサー、ホモジナイザーまたはディ
スパーサ−等を用い、回転数４０００〜１００００回転
で１０〜６０分間強力に分散することにより達成される
。In the production of polymerized toner, it is important to uniformly disperse these various components, and in order to prepare such a uniform dispersion, the polymerizable monomer, pigment, and additives are mixed, and the This is achieved by vigorously dispersing in an active gas atmosphere using a powerful stirrer or dispersion machine, such as a homomixer, homogenizer, or disperser, at a rotational speed of 4,000 to 10,000 rpm for 10 to 60 minutes.
尚、該分散体を調製する際の各種成分の添加順序は、特
に限定されるものではなく、順次−品づつ添加してもよ
いし、−括で添加してもよい、＊た分散時の温度は、室
温でも若干加温しながらでも、また冷却しながらでもよ
いが、加温する場合には、重合開始剤の分解温度に達し
ないような温度で行うか、または重合開始剤のみを、分
解終了後分解温度以下に冷却してから添加し、再度分散
するのが好ましい、更に、分散中に発熱する場合には、
冷却しながら分散するのが好ましく、この場合にも、重
合開始剤は分散終了間際に添加するのが望ましい。The order of addition of the various components when preparing the dispersion is not particularly limited, and they may be added one by one or all at once. The temperature may be at room temperature, while being slightly heated, or while being cooled, but when heating, it should be done at a temperature that does not reach the decomposition temperature of the polymerization initiator, or only the polymerization initiator may be heated. After completion of decomposition, it is preferable to cool down to below the decomposition temperature before adding and redispersing.Furthermore, if heat is generated during dispersion,
It is preferable to disperse while cooling, and in this case as well, it is desirable to add the polymerization initiator just before the completion of dispersion.
このようにして得られた分散体は、水性懸温浴に注下し
て、ホモミキサーやホモジナイザー等で強力攪拌し、所
望の粒径の懸濁粒子を形成させた後、ゆっくり撹拌しな
がら所定温度まで昇温し懸濁重合を行うが、撹拌機はホ
モミキサーやホモジナイザー等で１０００ｒｐ＋ｓ以下
の低速で継続してもよく、又その他の撹拌機に交換して
懸濁重合してもよい。The dispersion thus obtained is poured into an aqueous suspension bath and stirred vigorously using a homomixer, homogenizer, etc. to form suspended particles of the desired particle size, and then heated to a predetermined temperature while being slowly stirred. Suspension polymerization may be carried out by raising the temperature to 100 mL, but the stirrer may be a homomixer, homogenizer, etc., and the stirring may be continued at a low speed of 1000 rp+s or less, or another stirrer may be used for suspension polymerization.
水性懸温浴とは、通常ｍ濁重合に使用される無機系及び
有機系の懸濁安定剤、例えばシリカ粉末、ベントナイト
、リン酸カルシウム、ポリビニルアルクール、ヒドロキ
シエチルセルロース、メチルヒドロキシエチルセルロー
ス、ゼラチン等の懸濁安定剤０．００１へ、５重ｆＩ！
、部を、水１００重Ｉｔ部に均一に分散させたものであ
る。これらの懸濁安定剤は、各々単独または２種以上の
混合物としても使用でき、更に界面活性Ｍ、例えば２ウ
リル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナト
リウム等を、水１００重量部に対し０．００１〜５重量
部併用してもよい。Aqueous suspension bath refers to inorganic and organic suspension stabilizers normally used in turbidity polymerization, such as silica powder, bentonite, calcium phosphate, polyvinyl alcohol, hydroxyethylcellulose, methylhydroxyethylcellulose, gelatin, etc. To 0.001, quintuple fI!
, parts were uniformly dispersed in 100 parts by weight of water. Each of these suspension stabilizers can be used alone or as a mixture of two or more. Furthermore, a surface active M such as sodium diuryl sulfate, sodium dodecylbenzenesulfonate, etc. can be used in an amount of 0.001 to 100 parts by weight of water. 5 parts by weight may be used together.
注下する分散体は、水性懸温浴１００重量部に対し１０
〜１００重量部、好ましくは２０〜５０重量部とし、又
重合条件としては不活性ガス雰囲気下５０〜９０℃、６
〜１０時間程時間子えばよい、得られるトナー粒子の粒
径は攪拌速度によって異なるが、通常４０００〜８００
０ ｒｐｍの攪拌速度で、５〜２５μ論の真球状のトナ
ー粒子とするのがよい、懸濁重合反応終了後は、反応液
を室温まで冷却後トナー粒子を濾過、乾燥したものを二
段階目の重合に供してもよく、また懸濁重合反応終了後
、引ト続いて二段階目の重合に供してもよいが、連続し
て操作で終るところから後者の方が経済的である。The dispersion to be poured is 10 parts by weight per 100 parts by weight of the aqueous suspension bath.
~100 parts by weight, preferably 20 to 50 parts by weight, and the polymerization conditions are 50 to 90°C under an inert gas atmosphere, 6
The particle size of the toner particles obtained varies depending on the stirring speed, but is usually 4000 to 800.
It is best to form toner particles in the perfect spherical shape of 5 to 25 micrometers at a stirring speed of 0 rpm. After the suspension polymerization reaction is completed, the reaction solution is cooled to room temperature, and the toner particles are filtered and dried for the second stage. Alternatively, after the completion of the suspension polymerization reaction, it may be subjected to a second stage of polymerization, but the latter is more economical since it is a continuous operation.
かくして得られた重合トナーは、第２図に示す如く球状
の形態を示す。The polymerized toner thus obtained has a spherical shape as shown in FIG.
次に二段階目の重合について説明する。Next, the second stage of polymerization will be explained.
上記のようにして得られた懸濁重合トナーに、更に、エ
チレン性二重結合を有する単量体を重合するが、二段階
目の重合に用いられるエチレン性不飽和二重結合を有す
る単量体とは、トナーを製造する際に用いられるもので
あれば特に限定されるものではなく、具体的にはスチレ
ン系単量体あるいはアクリル酸系単量体が用いられる。The suspension polymerized toner obtained as described above is further polymerized with a monomer having an ethylenically unsaturated double bond. The material is not particularly limited as long as it is used in producing toner, and specifically, styrene monomers or acrylic acid monomers are used.
スチレン系単量体としては、スチレン、ビニルトルエン
、エチルスチレン、ｐ−クロルスチレン、ｐｎ−ブチル
スチレン等が挙げられ、好ましくはスチレン又はビニル
トルエンが用いられる。アクリル酸系単量体としては、
アクリル酸エチル、メタクリル酸エチル、アクリル酸ブ
チル、メタクリル酸ブチル、アクリル酸メチル、メタク
リル酸メチル、アクリル酸プロピル等が挙げられ、好ま
しくはアクリル酸−ｎ−ブチル、メタクリル酸−ｎ−ブ
チル又はメタクリル酸メチルが用いられる。なお、これ
らの単量体は各々単独でもまた混合してもよく、更に必
要ならばＮ、Ｎ−ツメチルアミノエチルメタクリレ−）
、Ｎ、Ｎ−ノエチル７ミノエチルメタクリレート、ビニ
ルピリジン等のカチオン性の単量体を併用してもよい。Examples of the styrene monomer include styrene, vinyltoluene, ethylstyrene, p-chlorostyrene, pn-butylstyrene, etc., and preferably styrene or vinyltoluene is used. As an acrylic acid monomer,
Examples include ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, propyl acrylate, etc., preferably n-butyl acrylate, n-butyl methacrylate, or methacrylic acid. Methyl is used. These monomers may be used alone or in combination, and if necessary, N,N-trimethylaminoethyl methacrylate)
, N,N-noethyl 7minoethyl methacrylate, vinylpyridine, and other cationic monomers may be used in combination.
二段階目の重合に使用する単量体の量は、懸濁重合によ
り得られた球状の重合トナー１００重量部に対し、１０
〜１００重量部、好ましくは２０〜７５重を部とするの
がよい、単量体の量が１０重量部以下では、トナー粒子
の不定形化が不十分で、クリーニング性の大幅な改良が
なされない。The amount of monomer used in the second stage polymerization is 10 parts by weight per 100 parts by weight of the spherical polymerized toner obtained by suspension polymerization.
The amount of the monomer is preferably 100 parts by weight or less, preferably 20 to 75 parts by weight. If the amount of the monomer is less than 10 parts by weight, the toner particles will not be sufficiently shaped and the cleaning properties will not be significantly improved. Not done.
また、単量体の量が１００重量部を越えると、粒子が粗
大化して収率が悪くなり、更に二段階目の重合に使用す
る単量体のみの重合物の生成が増加するため好ましくな
い、ここで重要なことは、二段階目の重合に使用する単
量体中に、懸濁重合トナーの原料として用いた単量体を
使用する場合、該単量体の含有量は二段階目の重合に使
用する単量体量の５０％以下、好ましくは３０％以下と
するのがよい、二段階目の重合に使用する単量体中の、
懸濁重合トナーの原料として用いた単量体の含有量が多
すぎると、懸濁重合トナー粒子表面で二段階目の重合が
進行する際、粒子の表面を均一に覆い易く、粒子表面で
の重合の局在化が妨げられ、突起状重合物の形成がされ
難くなり、その結果粒子の不定形化度が小さくなり、元
の粒子の球状の形状を保持したまま、粒径のみが成長す
るため好ましくない、この意味では二段階目の重合に使
用する単量体又はその組合せは、それらから得られる重
合体が一段階目の重合体との相溶性が無いか小さいもの
が好適に選択される。In addition, if the amount of monomer exceeds 100 parts by weight, the particles become coarse and the yield deteriorates, and furthermore, the formation of a polymer containing only the monomer used in the second stage polymerization increases, which is undesirable. What is important here is that when the monomer used as the raw material for the suspension polymerized toner is used in the second stage polymerization, the content of the monomer in the second stage polymerization is The amount of monomers used in the second stage polymerization is preferably 50% or less, preferably 30% or less of the amount of monomers used in the second stage polymerization.
If the content of the monomer used as a raw material for the suspension polymerized toner is too high, when the second stage of polymerization proceeds on the surface of the suspension polymerized toner particles, the surface of the particles is likely to be uniformly covered, resulting in The localization of polymerization is hindered, making it difficult to form protruding polymers, and as a result, the degree of amorphousness of the particles is reduced, and only the particle size grows while retaining the spherical shape of the original particles. In this sense, the monomers or combinations thereof used in the second stage polymerization are preferably selected so that the polymer obtained from them has little or no compatibility with the first stage polymer. Ru.
また、二段階目の重合に用いる単量体中には、通常トナ
ーの製造に用いられる顔料、帯電制御剤、離型剤等の添
加剤も併用できる。Furthermore, additives such as pigments, charge control agents, and mold release agents, which are commonly used in toner production, can also be used in the monomers used in the second stage polymerization.
顔料としてはカーボンブラック、酸化チタン、酸化亜鉛
等が挙げられる。また、帯電制御剤としてはニグロシン
、クロムイエロー、７ニリンブル、７タロシアニンブル
ー及び７ゾ系合金染料等が挙げられる。更に、離型剤と
してはポリプロピレンワックス、ポリエチレンワックス
、マイクロクリスタリンワッメーが李げられる。これら
の添加量は該単量体に対し、それぞれ５％以下とするの
がよい。Examples of pigments include carbon black, titanium oxide, zinc oxide, and the like. Further, examples of the charge control agent include nigrosine, chrome yellow, 7-nirimble, 7-talocyanine blue, and 7-zo alloy dyes. Furthermore, as a mold release agent, polypropylene wax, polyethylene wax, and microcrystalline wax can be used. It is preferable that the amount of each of these added is 5% or less based on the monomer.
これらの添加剤を併用する場合には、サンドグラインド
ミル、ホモゾナイザー及びダイスパーサ−等の強力な剪
段力を有する混合機で、該単量体中に十分に分散してお
く必要がある。When these additives are used in combination, they must be sufficiently dispersed in the monomer using a mixer having a strong shearing force, such as a sand grind mill, homozonizer, or die parser.
二段階目の重合に使用する単量体には、エチレン性二重
結合を１個有する単量体の他に、架橋剤を二段階目の重
合に使用する単量体に対し、０．１〜２％添加してもよ
い、かかる架橋剤としては、通常使用されているもので
あればよく、例えばノビニルベンゼン、ノビニルナフタ
レン、エチレングリコールノメタクリレート、ジビニル
エーテル等の２個のビニル基を有する化合物、あるいは
トリノチロールプロパントリアクリレート等の３個のビ
ニル基を有する化合物が挙げられ、これらは各々単独に
、あるいはこれらを混合して用いることができる。In addition to the monomer having one ethylenic double bond, the monomer used in the second stage polymerization contains a crosslinking agent of 0.1 Such a crosslinking agent, which may be added in an amount of ~2%, may be any commonly used crosslinking agent, such as novinylbenzene, novinylnaphthalene, ethylene glycol no methacrylate, divinyl ether, etc. and compounds having three vinyl groups such as trinotylolpropane triacrylate, which can be used alone or in combination.
二段階目の重合の開始剤としては、水溶性の重合開始剤
で通常使用されているものでよく、例えば過硫酸カリウ
ム、過硫酸アンモニウム、過硫酸ナトリウム、２，２°
−アゾビス（２−アミツノプロパン）・二塩酸塩（和光
紬薬製、商品名Ｖ−５０）等が挙げられる。The initiator for the second stage polymerization may be a water-soluble polymerization initiator that is commonly used, such as potassium persulfate, ammonium persulfate, sodium persulfate, 2.2°
-Azobis(2-amitsunopropane) dihydrochloride (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd., trade name V-50), and the like.
二段階目の重合は４０〜８０℃で４〜１０時間、５００
〜１０００ｒｐ輪で攪拌しながら行なうが、単量体の添
加方法としては、マイクロポンプ等で徐々に滴下しても
よく、又、浴中に乳化分散しておいてもよい、単量体を
徐々に滴下する場合には、充分に硬化させるために単量
体の滴下終了後、２時開以上重合を継続するのがよい、
又単量体を洛中に乳化分散する方法としては、単量体重
ｆｉｌに対し水１〜５倍量、界面活性剤例えばラウリル
硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウ
ム、ポリスチレンスルホン酸ナトリウム、アルキルフェ
ノールエト斗シレート型ノニオン界面活性剤等の単独、
または混合物をｏ、ｏ ｏ ｏ ｓ〜０．０５倍を混合
し、ホモミキサーやホモジナイザーあるいはディスパー
サ−の様な強力な分散機で乳化したものを二段階目の重
合浴に添加してもよいし、あるいは、この乳化浴へ、乾
燥した重合トナーを分散させてもよい。The second stage polymerization was carried out at 40-80°C for 4-10 hours at 500°C.
The monomer is added while stirring at ~1000 rpm, but the monomer can be added gradually by dropping it using a micro pump, etc., or it can be emulsified and dispersed in the bath. When dropping the monomer dropwise, it is recommended to continue the polymerization for at least 2 o'clock after dropping the monomer to ensure sufficient curing.
In addition, as a method for emulsifying and dispersing the monomer in a liquid, water is added in an amount of 1 to 5 times the weight of the monomer, a surfactant such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polystyrene sulfonate, or alkylphenol ethyl sylate. Single type nonionic surfactant, etc.
Alternatively, the mixture may be mixed in an amount of 0.05 times to 0.05 times, emulsified using a strong dispersion machine such as a homomixer, homogenizer, or disperser, and then added to the second-stage polymerization bath. Alternatively, a dried polymerized toner may be dispersed in this emulsification bath.
二段階目の重合浴の１ｌｌ１９Ｉは、乾燥した重合トナ
ーの場合と、懸濁重合トナー製造工程に続いて二段階目
の重合をする場合とで若干具なるが、浴液量は重合トナ
ー重量に対し２〜２０倍量、好ましくは４〜１０倍量が
よい、浴液ｌが２倍量より少ない場合には、粒子の凝集
、あるいは融着が起こり易くなり、又、２０倍量より多
い場合には単位作業中に製造できる二段階目の重合トナ
ーの量が少ないため、又、使用した単量体がトナー粒子
と接触しにく（なり、二段階目の重合がトナー粒子表面
で有効に起こらないため、好ましくない。The amount of 1 liter 19 I in the second-stage polymerization bath varies depending on whether the polymerized toner is dried or the second-stage polymerization is performed following the suspension polymerization toner manufacturing process, but the amount of bath liquid depends on the weight of the polymerized toner. 2 to 20 times the amount, preferably 4 to 10 times the amount. If the bath solution is less than 2 times the amount, particle agglomeration or fusion tends to occur, and if it is more than 20 times the amount. Because the amount of second-stage polymerized toner that can be produced during a unit operation is small, and the monomer used has difficulty in contacting the toner particles (this makes it difficult for the second-stage polymerization to occur effectively on the toner particle surface). This is not desirable because it does not happen.
懸濁重合トナーの製造に続いて二段階目の重合をする場
合には、浴液中に懸濁安定剤例えばシリカ粉末、ベント
ナイト、リン酸カルシウム、ポリビニルアルコール、ヒ
ドロキシエチルセルロース、メチルヒドロキシエチルセ
ルロース、ゼラチン等を含んでいるが、浴液中の懸濁安
定剤の量は２％以下、好ましくは１％以下となるように
水で希釈して調製する必要がある。懸濁安定剤の量が２
％を越えると、粒子表面の懸濁安定剤の濃度が高いため
、重合性単量体と粒子との接触が妨げられ、二段階目の
重合が十分に進行せず、期待どうりの不定形トナーが得
られない。When performing a second stage of polymerization following the production of a suspension polymerized toner, suspension stabilizers such as silica powder, bentonite, calcium phosphate, polyvinyl alcohol, hydroxyethylcellulose, methylhydroxyethylcellulose, gelatin, etc. may be included in the bath solution. However, it is necessary to prepare the suspension stabilizer by diluting it with water so that the amount of suspension stabilizer in the bath solution is 2% or less, preferably 1% or less. The amount of suspension stabilizer is 2
%, the concentration of the suspension stabilizer on the particle surface is high, which prevents the contact between the polymerizable monomer and the particles, and the second stage polymerization does not proceed sufficiently, resulting in an unexpectedly amorphous shape. I can't get toner.
又、乾燥工程まで進めた重合トナーを二段階目の重合の
原料トナー粒子とする場合には、通常使用される攪拌機
で攪拌しながら重合トナーを浴中へ分散させるが、この
重合トナーの浴への分散性を高めるため、ホモジナイザ
ーやホモミキサーのような分散機を使用してもよい。又
この際、水浴中に２％以下の通常懸濁重合に使用される
無１ｆ１１％及び有機系の懸濁安定剤、例えばシリカ粉
末、ベントナイト、リン酸カルシウム、ポリビニルアル
コール、ヒドロキシエチルセルロース、メチルヒドロキ
シエチルセルロース、ゼラチン等を含んでいてもよい、
更に、分散性を向上させるために界面活性剤、例えばフ
ッリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナ
トリウム等を１％以下併用してもよい。In addition, when the polymerized toner that has proceeded to the drying process is used as the raw material toner particles for the second stage of polymerization, the polymerized toner is dispersed into the bath while stirring with a commonly used stirrer; In order to improve the dispersibility, a dispersing machine such as a homogenizer or a homomixer may be used. At this time, in the water bath, 11% or less of 1F, which is usually used in suspension polymerization, and an organic suspension stabilizer such as silica powder, bentonite, calcium phosphate, polyvinyl alcohol, hydroxyethyl cellulose, methylhydroxyethyl cellulose, gelatin are added. May include, etc.
Furthermore, in order to improve dispersibility, a surfactant such as sodium furyl sulfate, sodium dodecylbenzenesulfonate, etc. may be used in combination in an amount of 1% or less.
二段階目の重合反応終了後は、反応液を室温まで冷却後
トナー粒子を濾過、乾燥し第１図に示す如く、目的の不
定形化されたトナー粒子が得られる。After the second stage polymerization reaction is completed, the reaction solution is cooled to room temperature, and the toner particles are filtered and dried to obtain the desired amorphous toner particles as shown in FIG.
（本発明の効果）
本発明によれば、球状の重合トナー粒子表面に突起を形
成させ、不定形のトナー粒子を製造することができる。(Effects of the Present Invention) According to the present invention, irregularly shaped toner particles can be manufactured by forming protrusions on the surface of spherical polymerized toner particles.
＊た、この不定形化されたトナー粒子によれば、従来の
球状トナー粒子に比べ、クリーニング性が着しく向上す
る。*Furthermore, the amorphous toner particles significantly improve cleaning performance compared to conventional spherical toner particles.
（実施例）
以下、実施例にで本発明を具体的に説明するが、本発明
は、以下の実施例に限定されるものではな＋１１゜
実施例１
スチレン７９．５部、１１−ブチル７クリレート２０部
、ノビニルベンゼン０．５部、ポリプロピレンワックス
（５５０Ｐ 三洋化成社）２部、ニグロシン２部、カー
ボンブラック５部および２，２゜−７／ｌ：’ス（２，
４−ツメチルバレロニトリル）５部を分散容器に取り、
窒素雰囲気下ホモジナイザーにより６５００回転で３０
分間分散した０次いで得られた分散体を、分散体１に対
して３倍量のポリビニルアルコール１％水溶液を入れた
水性懸濁浴中へ注下し、続いて窒素雰囲気下ホモミキサ
ーによＱ６０００回松で２０分間分散して懸濁微粒子を
形成させた。この懸濁微粒子は、顕微ａｍ寮によるとほ
ぼ２５μ−以下の粒形であった０次いで攪拌機を平羽根
攪拌機に交換し、窒素雰囲気下６００回転で攪拌しなが
ら、６５℃に昇温して重合を行った。このまま６時間重
合を続けて硬化させ、トナー粒子を製造した後、水性懸
温浴に対して同量の脱塩水及び０．００５倍量の２，２
゛アゾビス（２−７ミノノプロパン）・二塩酸塩（和光
紬薬製Ｖ−５０）を加え７０℃に昇温しな１次いで懸濁
重合に続いて窒素雰囲気下６００回松２攪拌を続けなが
ら、別に混合分散しておいた二段階目の重合用単量体混
合物（メチルメタクリレート７３部、＋１−ブチルメタ
クリレート２４部、ニグロシン１部、カーボンブラック
１部及びＮ、Ｎ−ノエチルアミノエチルメタクリレー）
１ｆｆｌをサンドグラインドミルで混合分散）をトナー
粒子重量に対し０．５倍量用意し、マイクロポンプで２
時間かけて滴下して二段階目の重合を行った。顕微鏡観
察によると、トナー粒子表面に多数の突起が形成されて
いるのが確認された。このまま６時間重合を続け、完全
に硬化させた後冷却、濾過、洗浄及び乾燥の後、分級機
により５〜２５μ−の不定形化されたトナー粒子を得た
。このトナー粒子を鉄粉と混合して現像剤を調製し、有
機光半導体からなる感光体（いわゆるＯＰＣ感光体）を
用いた複写機で評価したところ、２万枚複写してもクリ
ーニング性は良好であった。(Example) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples. 20 parts of acrylate, 0.5 part of novinylbenzene, 2 parts of polypropylene wax (550P Sanyo Chemical Co., Ltd.), 2 parts of nigrosine, 5 parts of carbon black and 2,2°-7/l:'s (2,
4-trimethylvaleronitrile) in a dispersion container,
30 at 6500 rpm with a homogenizer under nitrogen atmosphere
The resulting dispersion was then poured into an aqueous suspension bath containing a 1% aqueous solution of polyvinyl alcohol in an amount 3 times the amount of the dispersion 1, and then Q6000 was added to the homomixer under a nitrogen atmosphere. Dispersion was carried out for 20 minutes using a spinning wheel to form suspended fine particles. The suspended fine particles had a particle size of approximately 25μ or less according to the microscopic AM research.Next, the stirrer was replaced with a flat blade stirrer, and while stirring at 600 rpm in a nitrogen atmosphere, the temperature was raised to 65°C to polymerize. I did it. After continuing polymerization for 6 hours to harden toner particles, add the same amount of demineralized water to the aqueous suspension bath and 0.005 times the amount of 2,2
Azobis (2-7 minonopropane) dihydrochloride (V-50 manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was added and the temperature was raised to 70°C.Next, suspension polymerization was carried out, and stirring was continued for 600 times under a nitrogen atmosphere. , a monomer mixture for the second stage polymerization that had been mixed and dispersed separately (73 parts of methyl methacrylate, 24 parts of +1-butyl methacrylate, 1 part of nigrosine, 1 part of carbon black, and N,N-noethylaminoethyl methacrylate) )
Prepare 0.5 times the amount of toner particles by mixing and dispersing 1 ffl with a sand grind mill, and mix and disperse with a micro pump.
A second stage of polymerization was carried out by dropping the mixture over a period of time. According to microscopic observation, it was confirmed that many protrusions were formed on the surface of the toner particles. Polymerization was continued for 6 hours, and after being completely cured, the mixture was cooled, filtered, washed and dried, and amorphous toner particles of 5 to 25 .mu.m were obtained using a classifier. A developer was prepared by mixing these toner particles with iron powder, and it was evaluated using a copying machine that uses a photoconductor (so-called OPC photoconductor) made of an organic photosemiconductor, and the cleaning performance was good even after 20,000 copies were made. Met.
実施例２
実施例１と同様にして懸濁重合によるトナー粒子を製造
し、二段階目の重合に供さないでこのまま冷却、濾過、
洗浄及び乾燥を行った。この重合トナー１重量に対し、
４倍量の０．２％ポリビニルアルコール水溶液を二段階
口の重合槽に用意し、この溶液中に重合トナーを５００
回転で撹拌しながら分散した。更に重合トナー量に対し
０．００５倍量の２，２゛−アゾビス（２−アミジノプ
ロパン）二塩酸塩を添加し溶解した。別にメチルメタク
リレート７３部、＋１−ブチルメタクリレート２４部、
ニグロシン１部、カーボンブラック１部及びＮ、Ｎ−ジ
エチルアミノエチルメタクリレ−１１部をサンドグライ
ンドミルで混合分散して、二段階目の重合用単量体混合
物を１ｌ１９１シた。次に別の容器に重合トナー１重量
に対し、二段階目の重合用単量体混合物０．２５倍量、
水２倍量、ドデシルベンゼンスルホン
びノニルフェノールのエチレ．ンオキサイド付加物（平
均付加モル数：２０）０．０１倍量を取り、ディスパー
サ−で８０００回松で２Ｏ分乳化分散し、次いで該乳化
物を二段階目の重合槽へ添加して混合し、十分に窒素五
換した後７０℃に昇温して重合した．顕微鏡観察による
と、トナー粒子表面に多数の突起が形成されているのが
確認された。このまま８時間重合を続けて完全に硬化さ
せた後、冷却、濾過、洗浄及び乾燥の後、分級して５〜
２５μ輪の不定形化されたトナー粒子を得た．このトナ
ー粒子を実施例１と同様に評価したところ、２万枚複写
してもクリーニング性は良好であった。Example 2 Toner particles were produced by suspension polymerization in the same manner as in Example 1, and without being subjected to the second stage of polymerization, they were cooled, filtered, and
Washing and drying were performed. For 1 weight of this polymerized toner,
Prepare 4 times the volume of 0.2% polyvinyl alcohol aqueous solution in a two-stage polymerization tank, and add 500% of polymerized toner to this solution.
Disperse while stirring by rotation. Further, 2,2'-azobis(2-amidinopropane) dihydrochloride was added and dissolved in an amount of 0.005 times the amount of the polymerized toner. Separately, 73 parts of methyl methacrylate, 24 parts of +1-butyl methacrylate,
1 part of nigrosine, 1 part of carbon black, and 11 parts of N,N-diethylaminoethyl methacrylate were mixed and dispersed using a sand grind mill to obtain 1 liter of a monomer mixture for second stage polymerization. Next, in another container, 0.25 times the amount of the monomer mixture for second stage polymerization per 1 weight of polymerized toner,
Double the amount of water, ethylene of dodecylbenzenesulfonylphenol. Take 0.01 times the amount of the carbon oxide adduct (average number of moles added: 20), emulsify and disperse it 8000 times with a disperser for 2O, and then add the emulsion to the second stage polymerization tank and mix. After sufficient nitrogen exchange, the temperature was raised to 70°C for polymerization. According to microscopic observation, it was confirmed that many protrusions were formed on the surface of the toner particles. After continuing to polymerize for 8 hours and completely curing, after cooling, filtering, washing and drying, it was classified and
Amorphous toner particles with a 25μ ring were obtained. When this toner particle was evaluated in the same manner as in Example 1, the cleaning performance was good even after 20,000 copies were made.
比較例１
実施例１と同様にして懸濁重合によるトナー粒子を製造
し、このまま冷却、濾過、洗浄及び乾燥した後、分級し
て５〜２５μ論の真球状の重合トナー粒子を得た．この
トナー粒子を実施例１と同様にして評価したところ、１
万枚複写したところでクリー二ング不良が発生した。Comparative Example 1 Toner particles were produced by suspension polymerization in the same manner as in Example 1, and after cooling, filtering, washing and drying, they were classified to obtain perfectly spherical polymerized toner particles with a diameter of 5 to 25 μm. When this toner particle was evaluated in the same manner as in Example 1, it was found that 1
After making 10,000 copies, a cleaning failure occurred.
以上のように、重合トナーに更にエチレン性二重結合を
有する単量体を重合させることにより、不定形化された
重合トナーが得られ、更に、該不定形化された重合トナ
ーによれば、球状の重合トナーに比べ着しくクリーニン
グ性が向上する。As described above, by further polymerizing the polymerized toner with a monomer having an ethylenic double bond, an amorphous polymerized toner can be obtained, and further, according to the amorphous polymerized toner, Cleanability is improved compared to spherical polymerized toner.
第１図は、本発明方法により得られた重合トナーの一例
につき、その粒子構造を示した写真であり、第２図は、
懸濁重合後のトナーの一例につ柊その粒子構造を示した
写真である。FIG. 1 is a photograph showing the particle structure of an example of a polymerized toner obtained by the method of the present invention, and FIG.
This is a photograph showing the particle structure of Tsuhiragi, an example of a toner after suspension polymerization.
Claims (1)
及び添加剤からなる均一分散体を、水性懸濁浴中で懸濁
重合することにより得られた重合トナーに、更に、懸濁
重合に使用した単量体とは異種のエチレン性不飽和二重
結合を有する単量体、又は、懸濁重合に使用したものと
同種の単量体と異種の単量体との混合物を、重合させる
ことを特徴とする重合トナーの製造方法。(1) A homogeneous dispersion consisting of a monomer having an ethylenically unsaturated double bond, a pigment, and an additive is suspended in a polymerized toner obtained by suspension polymerization in an aqueous suspension bath. A monomer having an ethylenically unsaturated double bond different from the monomer used in the polymerization, or a mixture of the same type of monomer and a different type of monomer as used in the suspension polymerization, A method for producing a polymerized toner, which comprises polymerizing the toner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1045663A JP2850350B2 (en) | 1989-02-27 | 1989-02-27 | Method for producing polymerized toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1045663A JP2850350B2 (en) | 1989-02-27 | 1989-02-27 | Method for producing polymerized toner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02223961A true JPH02223961A (en) | 1990-09-06 |
| JP2850350B2 JP2850350B2 (en) | 1999-01-27 |
Family
ID=12725621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1045663A Expired - Fee Related JP2850350B2 (en) | 1989-02-27 | 1989-02-27 | Method for producing polymerized toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2850350B2 (en) |
-
1989
- 1989-02-27 JP JP1045663A patent/JP2850350B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2850350B2 (en) | 1999-01-27 |
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