JPS63106667A - Production of toner - Google Patents
Production of tonerInfo
- Publication number
- JPS63106667A JPS63106667A JP61307143A JP30714386A JPS63106667A JP S63106667 A JPS63106667 A JP S63106667A JP 61307143 A JP61307143 A JP 61307143A JP 30714386 A JP30714386 A JP 30714386A JP S63106667 A JPS63106667 A JP S63106667A
- Authority
- JP
- Japan
- Prior art keywords
- resin particles
- dye
- toner
- particle size
- producing
- 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 17
- 239000002245 particle Substances 0.000 claims abstract description 198
- 229920005989 resin Polymers 0.000 claims abstract description 107
- 239000011347 resin Substances 0.000 claims abstract description 107
- 239000000975 dye Substances 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 21
- 239000000057 synthetic resin Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000004043 dyeing Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012736 aqueous medium Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000009736 wetting Methods 0.000 claims description 16
- 239000000986 disperse dye Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000984 vat dye Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000980 acid dye Substances 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000000985 reactive dye Substances 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- 239000006185 dispersion Substances 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007771 core particle Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 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
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/09—Colouring agents for toner particles
- G03G9/0906—Organic dyes
Abstract
Description
【発明の詳細な説明】
童栗上皇剋朋公団
本発明は、電子写真や静電記録等における電気的潜像を
現像するためのトナーの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a toner for developing an electrical latent image in electrophotography, electrostatic recording, or the like.
従３４すえ肴
例えば、普通紙を記録紙として用いる静電式電子写真複
写機によれば、感光体の表面に帯電を行ない、露光、現
像、転写、分離及び定着の工程を経て、画像を普通紙上
に複写している。かかる電子写真複写機における現像法
としては、従来、キャリヤ粒子及びトナー粒子を用いる
２成分系の方法と、キャリヤ粒子を用いずにトナー粒子
のみを用いる１成分系の方法とが知られている。For example, according to an electrostatic electrophotographic copying machine that uses plain paper as recording paper, the surface of the photoreceptor is charged, and the image is normally printed through the steps of exposure, development, transfer, separation, and fixing. Copied on paper. Conventionally known developing methods for such electrophotographic copying machines include a two-component method using carrier particles and toner particles, and a one-component method using only toner particles without using carrier particles.
この２成分系の現像法においては、主として、磁気ブラ
シ現像法が採用されており、トナーとしては、従来、熱
可塑性樹脂にカーボンブラックのような顔料、荷電制御
剤及びその他の添加剤をボールミル、ロールミル等を用
いて混線分散させ、ハンマーミル、振動ミル等にて破砕
し、球状化や表面抵抗、ブロッキング等を減少させるた
めの表面処理を施し、或いは添加剤を添加した後、幅広
い粒径分布を有するトナー粒子を分級して、通常、粒径
５〜２０μｍの範囲のトナー粒子が製品として供されて
いる。In this two-component developing method, a magnetic brush developing method is mainly adopted, and the toner is conventionally prepared by adding a pigment such as carbon black, a charge control agent, and other additives to a thermoplastic resin using a ball mill. After cross-dispersing using a roll mill, etc., crushing with a hammer mill, vibration mill, etc., and applying surface treatment to reduce spheroidization, surface resistance, blocking, etc., or adding additives, a wide particle size distribution is achieved. Toner particles having a particle size of 5 to 20 μm are usually provided as products by classifying them.
従って、かかる従来の方法によれば、製造工程が極めて
多いうえに、例えば、分級工程において、相当量の中間
製品が失われて、歩留りが悪く、製品価格が高いものと
ならざるを得ない。Accordingly, such conventional methods involve an extremely large number of manufacturing steps, and, for example, in the classification step, a considerable amount of intermediate products are lost, leading to poor yields and high product prices.
そのために、最近、重合性単量体の懸濁重合時にカーボ
ンブラックを存在させ、直ちに着色された重合体粒子を
得る方法が提案されている。例えば、特開昭５６−１５
４７３８号公報には、スチレン、ｎ−ブチルアクリレー
ト及びジエチルアミノエチルメタクリレートのような混
合物からなる重合性単量体とカーボンブラックと重合開
始剤とコロイダルシリカを水に分散させ、撹拌下に加温
し、！！！濁重合させて、カーボンブラックを含む着色
核体粒子の水分散液を調製する方法が記載されｔいる。To this end, a method has recently been proposed in which carbon black is present during suspension polymerization of polymerizable monomers to immediately obtain colored polymer particles. For example, JP-A-56-15
No. 4738 discloses that a polymerizable monomer consisting of a mixture of styrene, n-butyl acrylate, and diethylaminoethyl methacrylate, carbon black, a polymerization initiator, and colloidal silica are dispersed in water, heated while stirring, ! ! ! A method for preparing an aqueous dispersion of colored core particles containing carbon black by turbidity polymerization is described.
この方法によれば、重合性単量体を重合させると同時に
、得られる核体粒子を着色することができるが、カーボ
ンブラックは上記懸濁重合において重合禁止剤としても
作用すると共に、非常に嵩高いために、カーボンブラッ
クを含む系の懸濁重合は容易ではなく、また、その後処
理も煩雑である。更に、均一な粒度分布を有する核体粒
子を得ることが困難である。According to this method, the resulting core particles can be colored at the same time as the polymerizable monomer is polymerized, but carbon black also acts as a polymerization inhibitor in the suspension polymerization and is extremely bulky. Due to the high carbon black content, suspension polymerization of systems containing carbon black is not easy, and post-treatment is also complicated. Furthermore, it is difficult to obtain core particles with a uniform particle size distribution.
しかも、このようにして得られる核体粒子はそのままで
はトナーとしては用いることができず、引き続いて、上
記分散液を加温し、水溶性染料にて上記着色核体粒子を
染色して、核体粒子の黒色度を高めた後、更に、トナー
としての所要の表面物性を与えるために、核体粒子の表
面上に樹脂を被覆することが必要である。従って、かか
る方法も、多数の工程を必要とする。Moreover, the nuclear particles obtained in this way cannot be used as a toner as they are, and the dispersion liquid is subsequently heated and the colored nuclear particles are dyed with a water-soluble dye. After increasing the blackness of the core particles, it is necessary to further coat the surface of the core particles with a resin in order to provide the required surface properties as a toner. Therefore, such a method also requires a large number of steps.
−、Ｂ （町 しよ゛ 。 古
本発明°は、上記したような従来のトナーの製造におけ
る問題を解決するためになされたものであって、合成樹
脂粒子を直接に染色することによって、簡単にして、且
つ、歩留りが極めて高く、従って、低度に高品質のトナ
ーを製造することができる方法を提供することを目的と
する。-, B (Shiyo Machi) This invention was made in order to solve the above-mentioned problems in the production of conventional toners. It is an object of the present invention to provide a method that can produce toner with an extremely high yield and, therefore, a low degree of high quality.
間 点を解ンするための手
本発明によるトナーの製造方法は、予め所定の粒子径又
は平均粒子径を有せしめた合成樹脂粒子を、この樹脂粒
子に対する重量比にて５以上であって、且つ、上記樹脂
粒子の軟化点以上、軟化点よりも４０℃高い温度以下に
加温した水性媒体中にて、撹拌下に染料にて染色し、脱
水し、乾燥することを特徴とする。A method for producing toner according to the present invention includes synthetic resin particles having a predetermined particle size or average particle size in a weight ratio of 5 or more to the resin particles, In addition, it is characterized in that it is dyed with a dye under stirring in an aqueous medium heated to a temperature above the softening point of the resin particles and below a temperature 40° C. higher than the softening point, dehydrated, and dried.
本発明の方法において用いる合成樹脂粒子は、染色に用
いる水性媒体に対して疎水性である樹脂からなる粒子で
あり、本発明の方法によれば、かかる樹脂粒子をその樹
脂の軟化点よりも高い温度に保持されている水性媒体中
にて激しい撹拌下に染色することによって、樹脂粒子の
相互の融着を防止し、粒子状の形態を保持させることが
できる。The synthetic resin particles used in the method of the present invention are particles made of a resin that is hydrophobic to the aqueous medium used for dyeing, and according to the method of the present invention, such resin particles are By dyeing in an aqueous medium maintained at a temperature with vigorous stirring, resin particles can be prevented from fusing with each other and their particulate morphology can be maintained.
本発明の方法においては、上記水性媒体としては、少量
の有機溶剤を含有していてもよい水が用いられる。従っ
て、本発明においては、合成樹脂粒子としては、例えば
、ポリエチレン、ポリスチレン、スチレンとアクリル酸
エステル、メタクリル酸エステル、アクリロニトリル、
メタクリロニトリル等のアクリル系単量体の１又は２以
上との共重合体、上記したアクリル系単量体の単独重合
体、エチレン−酢酸ビニル共重合体、ポリアミド、ポリ
エステル、ポリビニルブチラール、エポキシ樹脂、フェ
ノール樹脂や、これらの混合物のような樹脂からなる粒
子が好ましく用いられるが、これら例示に限定されるも
のではない。また、本発明においては、部分架橋された
合成樹脂粒子も用いることができる。In the method of the present invention, water, which may contain a small amount of organic solvent, is used as the aqueous medium. Therefore, in the present invention, the synthetic resin particles include, for example, polyethylene, polystyrene, styrene and acrylic ester, methacrylic ester, acrylonitrile,
Copolymers with one or more acrylic monomers such as methacrylonitrile, homopolymers of the above-mentioned acrylic monomers, ethylene-vinyl acetate copolymers, polyamides, polyesters, polyvinyl butyral, epoxy resins Particles made of resins such as , phenolic resins, and mixtures thereof are preferably used, but the particles are not limited to these examples. Further, in the present invention, partially crosslinked synthetic resin particles can also be used.
本発明において用いるこれら合成樹脂粒子は、軟化点が
５０〜８０℃、電気抵抗が１０”ΩＣｒｎ以上、特に、
１０′３Ωａ以上であるのが好ましい。These synthetic resin particles used in the present invention have a softening point of 50 to 80°C, an electrical resistance of 10"ΩCr or more, and in particular,
It is preferable that it is 10'3 Ωa or more.
尚、上記軟化点は、ガラス転移点でいえば、はぼ６０〜
１２０℃に相当する。In addition, the above-mentioned softening point is about 60 to 60 in terms of glass transition point.
Corresponds to 120°C.
本発明においては、かかる樹脂粒子は予め５〜２０μｍ
、好ましくは５〜１０μｍの粒子径又は平均粒子径を有
することが好ましい。樹脂粒子径が余りに大きいときは
、複写画像の解像力に劣り、他方、余りに小さいときは
、複写画像にかぶりを生じる等、複写品質に劣ることと
なる。上記のように、所定の粒子径又は平均粒子径を有
する樹脂粒子は、例えば、破砕され、分級されたもので
もよく、また、重合自体によって当初から上記の粒径を
有するように製造されたものであってもよい。In the present invention, such resin particles have a size of 5 to 20 μm in advance.
, preferably having a particle size or average particle size of 5 to 10 μm. If the resin particle diameter is too large, the resolution of the copied image will be poor, while if it is too small, the copy quality will be poor, such as fogging occurring in the copied image. As mentioned above, resin particles having a predetermined particle size or average particle size may be, for example, crushed and classified particles, or resin particles manufactured to have the above particle size from the beginning by polymerization itself. It may be.
本発明の方法は、かかる樹脂粒子を所定温度に加温した
水性媒体中にて、撹拌下に、好ましくは、「ホモミキサ
ー」のような市販されている高速攪拌機を用いる激しい
撹拌下に、染料にて直接に染色して、染色樹脂粒子とし
てトナーを得る。The method of the present invention involves dyeing the resin particles in an aqueous medium heated to a predetermined temperature under stirring, preferably under vigorous stirring using a commercially available high-speed stirrer such as "Homomixer". The toner is directly dyed in the form of dyed resin particles.
上記水性媒体としては、前述したように、通常、水が好
ましい。しかし、水性媒体が合成樹脂粒子に対する疎水
性を保持する限りは、必要に応じて、後述するような有
機溶剤を少量含有していてもよい。As mentioned above, water is usually preferred as the aqueous medium. However, as long as the aqueous medium maintains hydrophobicity toward the synthetic resin particles, it may contain a small amount of an organic solvent as described below, if necessary.
本発明の方法においては、一般に、水不溶性染料は、殆
どすべての樹脂粒子に適用することができる。かかる水
不溶性染料としては、例えば、分散染料、水不溶性合金
染料、バット染料、油溶性染料等を挙げることができる
。酸性染料、カチオン染料若しくは塩基性染料、水溶性
合金染料、反応性染料等の水溶性染料は、限られた樹脂
粒子にのみ適用することができる。しかし、水不溶性染
料を用いる場合であっても、本発明においては、染料は
、用いる樹脂にできるだけ高い親和性を有し、染色性の
よい染料を選択して、樹脂粒子を堅牢に染色することが
好ましく、通常、染料は、樹脂の化学組成に応じて、最
適に選択される。尚、用いる染料によっては、染色にお
いて、必要に応じて、助剤を用いてもよい。In the method of the invention, generally water-insoluble dyes can be applied to almost all resin particles. Examples of such water-insoluble dyes include disperse dyes, water-insoluble alloy dyes, vat dyes, and oil-soluble dyes. Water-soluble dyes such as acid dyes, cationic dyes or basic dyes, water-soluble alloy dyes, and reactive dyes can be applied only to limited resin particles. However, even when a water-insoluble dye is used, in the present invention, the dye has as high an affinity as possible for the resin used and has good dyeing properties to dye the resin particles in a durable manner. is preferred and the dye is usually optimally selected depending on the chemical composition of the resin. In addition, depending on the dye used, an auxiliary agent may be used in dyeing as necessary.
例えば、ポリスチレンには分散染料が、スチレン−アク
リル酸エステル共重合体、スチレン−アクリロニトリル
共重合体、ポリアクリル酸エステル、ポリメタクリル酸
エステルには分散染料、酸性染料、カチオン染料が、ポ
リアミドには酸性染料、含金属染料、カチオン染料、反
応性染料、バット染料が、ポリエステルには分散染料、
バット染料が、ポリビニルブチラールやエポキシ樹脂に
は分散染料が、それぞれ好ましく用いられる。しかし、
染料としては、特に、水不溶性の分散染料及び油溶性染
料が最も好ましく用いられる。驚くべきことに、本発明
の方法によれば、このような水不溶性染料によって樹脂
粒子を容易に堅牢に且つ濃色に染色することができるの
である。。尚、用いる染料によっては、染色助剤を用い
てもよい。For example, disperse dyes are used for polystyrene, disperse dyes, acid dyes, and cationic dyes are used for styrene-acrylic ester copolymers, styrene-acrylonitrile copolymers, polyacrylic esters, and polymethacrylic esters, and acidic dyes are used for polyamides. Dyes, metallized dyes, cationic dyes, reactive dyes, vat dyes, and disperse dyes for polyester.
Vat dyes are preferably used, and disperse dyes are preferably used for polyvinyl butyral and epoxy resins. but,
In particular, water-insoluble disperse dyes and oil-soluble dyes are most preferably used as the dye. Surprisingly, according to the method of the present invention, resin particles can be easily dyed in a fast and deep color with such water-insoluble dyes. . In addition, depending on the dye used, a dyeing aid may be used.
染料は、得られるトナーが実用的に十分な色濃度を有す
るように、樹脂粒子に対して２重量％以上用いることが
好ましく、特に、４重量％以上用いることが好ましい。The dye is preferably used in an amount of 2% by weight or more, particularly preferably 4% by weight or more, based on the resin particles so that the resulting toner has a practically sufficient color density.
本発明においては、粒子径が５μｍ以下、特に２μｍ以
下である微細な染料粉末、特に、水不溶性の染料粉末を
用いることは、樹脂粒子を特に容易に且つ濃色に染色す
るために好ましい。かかる微細な染料粒子は、何ら限定
されるものではないが、例えば、ボールミルやサンドミ
ルを用いることによって得ることができる。In the present invention, it is preferable to use a fine dye powder having a particle size of 5 μm or less, particularly 2 μm or less, especially a water-insoluble dye powder, in order to dye the resin particles particularly easily and in a deep color. Such fine dye particles can be obtained by using, for example, a ball mill or a sand mill, although there are no limitations at all.
他方、本発明においては、合成樹脂粒子としては、容易
に入手することができるところから、特に、ポリスチレ
ンやスチレン−アクリル酸エステル共重合体、スチレン
−アクリロニトリル共重合体等からなる樹脂粒子が好ま
しく用いられる。また、これらの樹脂粒子は、分散染料
にて容易に染色されるので、容易に所要の色濃度、例え
ば、マクベス色度図で１．２〜１．７を有するトナーを
得ることができる。On the other hand, in the present invention, resin particles made of polystyrene, styrene-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, etc. are preferably used as the synthetic resin particles because they are easily available. It will be done. Further, since these resin particles are easily dyed with a disperse dye, it is possible to easily obtain a toner having a desired color density, for example, 1.2 to 1.7 on the Macbeth chromaticity diagram.
本発明においては、染色媒体の温度は、用いる合成樹脂
粒子の軟化点以上であって、且つ、軟化点よりも４０℃
高い温度以下である。この媒体温度が用いる合成樹脂粒
子の軟化点よりも低いときは、樹脂粒子が所要の色濃度
を有するように染色することが困難であるか、又は可能
であるとしても、著しく長時間を必要とするので、実用
的でない。他方、媒体温度が用いる合成樹脂粒子の軟化
点よりも４０℃高い温度よりも更に高いときは、激しい
撹拌下における染色によっても、樹脂粒子が相互に融着
して、塊状物を形成し、本発明によるトナーを得ること
ができない。In the present invention, the temperature of the dyeing medium is equal to or higher than the softening point of the synthetic resin particles used, and 40° C. below the softening point.
below high temperature. When the temperature of this medium is lower than the softening point of the synthetic resin particles used, it is difficult to dye the resin particles so that they have the required color density, or even if it is possible, it requires a significantly longer time. Therefore, it is not practical. On the other hand, if the medium temperature is higher than 40°C higher than the softening point of the synthetic resin particles used, the resin particles will fuse together and form lumps even during dyeing under vigorous stirring, resulting in It is not possible to obtain toner according to the invention.
更に、本発明の方法においては、水性媒体中にて合成樹
脂粒子を染色するに際して、樹脂粒子と水性媒体との重
量比も重要であって、水性媒体は、合成樹脂粒子に対す
る重量比にて５以上用いることが必要である。上記水性
媒体量の合成樹脂粒子に対する重量比が５よりも小さい
ときは、媒体温度が合成樹脂粒子の軟化点以上の温度で
あるので、前述したように、激しい撹拌下に樹脂粒子の
染色を行なっても、尚、樹脂粒子が相互に融着し、塊状
物を形成して、本発明によるｌ・ナーを得ることができ
ないからである。特に好ましくは、上記重量比の範囲は
８〜４０である。水性媒体量の上限は特に限定されるも
のではないが、染色作業やその後の処理の容易性から、
通常、上記重量比にて１００までである。Furthermore, in the method of the present invention, when dyeing synthetic resin particles in an aqueous medium, the weight ratio of the resin particles to the aqueous medium is also important, and the aqueous medium has a weight ratio of 5 to the synthetic resin particles. It is necessary to use the above. When the weight ratio of the amount of the aqueous medium to the synthetic resin particles is less than 5, the medium temperature is above the softening point of the synthetic resin particles, so as mentioned above, dyeing of the resin particles is carried out under vigorous stirring. However, the resin particles still fuse together and form lumps, making it impossible to obtain the l-ner according to the present invention. Particularly preferably, the weight ratio ranges from 8 to 40. The upper limit of the amount of aqueous medium is not particularly limited, but from the viewpoint of ease of dyeing work and subsequent processing,
Usually, the above weight ratio is up to 100.
また、本発明の方法においては、適宜の添加剤、例えば
、荷電制御剤、流動化剤、四三酸化鉄粉末、充填剤等の
存在下に樹脂粒子を染色してもよい。１かかる添加剤と
しては、従来より知られているものを任意に珀いること
ができ、例えば、微粉無水シリカ、クレー、タルク、炭
酸カルシウムや、ニグロシンのような含金属錯体のよう
な荷電制御剤、金属石ケン、微粉無水シリカ等の流動化
剤等を挙げることができる。例えば、無水シリカ微粉は
、上記のように、荷電制御剤と流動化剤の両方の機能を
有するが、表面が疎水性であるために、染料によっては
染色されない。更に、無水シリカ微粉は、加温した染色
媒体中での樹脂粒子の染色において、樹脂粒子の相互の
融着をも有効に防止することができる。Further, in the method of the present invention, the resin particles may be dyed in the presence of appropriate additives such as a charge control agent, a fluidizing agent, triiron tetroxide powder, and a filler. 1 Such additives may include any conventionally known additives, such as finely divided anhydrous silica, clay, talc, calcium carbonate, and charge control agents such as metal-containing complexes such as nigrosine. , metal soap, and fluidizing agents such as finely powdered anhydrous silica. For example, anhydrous silica fine powder has the functions of both a charge control agent and a fluidizing agent as described above, but since its surface is hydrophobic, it is not dyed by dyes. Furthermore, the anhydrous silica fine powder can effectively prevent resin particles from fusing to each other during dyeing of resin particles in a heated dyeing medium.
従来より知られているトナーの製造方法によれば、無水
シリカは主として流動化剤としてトナーに配合されてい
るが、その配合量が１％を越えるときは、得られるトナ
ーの荷電量が高くなりすぎるために、通常、１％以下に
抑えられており、その結果、流動化効果が十分ではない
。他方、一般に、絶縁性樹脂粒子は、粒径が小さいほど
、正又は負のいずれかの帯電量が過大となるので、特に
、粒径の小さい樹脂粒子を用いる場合は、荷電制御剤の
併用が必要とされる。According to conventionally known toner manufacturing methods, anhydrous silica is mainly blended into toner as a fluidizing agent, but when the blending amount exceeds 1%, the amount of charge in the resulting toner increases. Therefore, it is usually suppressed to 1% or less, and as a result, the fluidization effect is not sufficient. On the other hand, in general, the smaller the particle size of insulating resin particles, the larger the amount of positive or negative charge. Needed.
本発明の方法によれば、微粉無水シリカを樹脂粒子重量
に対して１０％程度までを配合することによって、トナ
ーが鉄粉と混合されて、その間に摩擦を生じて生成され
るトナーの荷電量を所謂ブロー・オフ型の静電量測定器
（東芝ケミカル０菊製）による測定値にて、−１０μＣ
／■乃至−１００μＣ／■の任意の範囲に調整すること
ができる。According to the method of the present invention, by blending up to about 10% of finely powdered anhydrous silica based on the weight of resin particles, toner is mixed with iron powder, and friction is generated between them, resulting in the amount of charge on the toner. -10μC as measured by a so-called blow-off type electrostatic capacity measuring device (manufactured by Toshiba Chemical 0 Kiku)
It can be adjusted to any range from /■ to -100 μC/■.
更に、微粉無水シリカを例えば３％程度配合することに
よって、流動性も一層高められる。Furthermore, by blending, for example, about 3% of finely powdered anhydrous silica, fluidity can be further improved.
更に、本発明においては、樹脂粒子の染色に際して、カ
ーボンブラックを共存させてもよい。カーボンブラック
もまた、荷電制御剤及び流動化剤として作用するうえに
、得られるトナーの着色度を向上させ、或いは得られる
トナーの被覆力を冑める効果を有する。Furthermore, in the present invention, carbon black may be present in the dyeing of the resin particles. Carbon black also acts as a charge control agent and a fluidizing agent, and also has the effect of improving the coloring degree of the obtained toner or increasing the covering power of the obtained toner.
尚、上記添加剤は、樹脂粒子を後述するように染色し、
脱水、乾燥した後に、樹脂粒子に所定量配合してもよい
。In addition, the above additive dyes the resin particles as described below,
A predetermined amount may be added to the resin particles after dehydration and drying.
以上のようにして、樹脂粒子を染色した後、樹脂粒子を
染色媒体より分離し、乾燥し、必要に応じて、粉砕して
、分級すれば、本発明によるトナーを得ることができる
。尚、上記分離、乾燥及び粉砕の方法は、特に制限され
るものではなく、例えば、染色樹脂粒子を濾別し、常温
常圧又は加熱減圧下に適宜に乾燥すればよい。After dyeing the resin particles as described above, the resin particles are separated from the dyeing medium, dried, and optionally crushed and classified to obtain the toner according to the present invention. The methods of separation, drying and pulverization described above are not particularly limited; for example, the dyed resin particles may be filtered and dried as appropriate at room temperature and pressure or under heating and reduced pressure.
本発明の方法によれば、好ましい場合には、染色の段階
で樹脂粒子の融着が全く起こらないために、得られるト
ナーに当初に合成樹脂粒子が有する粒子径又は平均粒子
径をそのまま有せしめることができ、従って、染色後の
樹脂粒子の粉砕や分級を必要としない。According to the method of the present invention, in a preferable case, no fusion of the resin particles occurs during the dyeing stage, so that the resulting toner has the same particle size or average particle size as the synthetic resin particles initially have. Therefore, it is not necessary to crush or classify the resin particles after dyeing.
また、染色後の樹脂粒子の粉砕や分級を行なう場合にも
、本発明の方法によれば、予め゛所定の範囲の粒径を有
するように分級されている樹脂粒子を染色し、しかも、
この染色の過程で樹脂粒子の相互の融着は、起こっても
僅かであるので、染色後の樹脂粒子の粉砕や分級は軽度
のものでよく、しかも、これらによって失われる量は明
らかに僅かであるので、本発明の方法によれば、トナー
を高い歩留りにて得ることができる。Further, even when crushing or classifying resin particles after dyeing, according to the method of the present invention, resin particles that have been classified in advance to have a particle size within a predetermined range are dyed, and
In this dyeing process, mutual fusion of resin particles occurs only slightly, so the crushing and classification of the resin particles after dyeing only needs to be light, and the amount lost by this is clearly small. Therefore, according to the method of the present invention, toner can be obtained with a high yield.
更に、本発明の方法によれば、樹脂粒子を無水シリカの
存在下に染色する場合は、樹脂粒子と無水シリカ粉末と
を少量の有機溶剤と共に混合し、これらの緊密で且つ湿
潤した混合物とし、これを水性媒体に加え、加熱下及び
激しい撹拌下に樹脂粒子を染色することが好ましい。か
かる湿潤化は、例えば、樹脂粒子と無水シリカ粉末とに
少量の有機溶剤を混合し、これをロール、ペイント・シ
ェーカー、混練機等によって緊密に且つ一様な組成を有
するようにシェークし、或いは混練することによって得
ることができる。但し、湿潤化のための手段は何ら限定
されるものではない。Furthermore, according to the method of the present invention, when dyeing resin particles in the presence of anhydrous silica, the resin particles and anhydrous silica powder are mixed together with a small amount of an organic solvent to form an intimate and wet mixture thereof; It is preferable to add this to an aqueous medium and dye the resin particles under heating and vigorous stirring. Such wetting can be achieved, for example, by mixing a small amount of an organic solvent with the resin particles and anhydrous silica powder, and shaking the mixture with a roll, paint shaker, kneader, etc. so that the composition is intimately uniform; It can be obtained by kneading. However, the means for wetting is not limited at all.
上記湿潤化に用いる有機溶剤、即ち、湿潤化溶剤として
は種々のものを用いることができる。例えば、メタノー
ル、エタノール、イソプロパツール等の低級脂肪族アル
コール、酢酸、プロピオン酸等の低級脂肪族カルボン酸
、酢酸メチル、酢酸エチル等の低級脂肪族カルボン酸の
低級アルキルエステル、テトラヒドロフラン、ジオキサ
ン、ジイソプロピルエーテル等の脂肪族又は脂環式エー
テル、アセトン、メチルエチルケトン等のジアルキルケ
トン等を挙げることができる。かかる湿潤化溶剤は、好
ましくは、水溶性であって、用いる樹脂粒子及び染料に
対して親和性を有すると共に、比較的低温において揮発
性を有することが好ましく、従って、上記したなかでは
、特に、メタノールが好ましく用いられる。本発明にお
いては、湿潤化溶剤は、前述したように、樹脂粒子と無
水シリカ粉末との緊密で一様な混合物をつくり得るよう
に用いることが必要であり、従って、その量は、通常、
樹脂粒子１００重量部に対して１００〜４００ｍ１の範
囲である。Various organic solvents can be used for the above-mentioned wetting, that is, wetting solvents. For example, lower aliphatic alcohols such as methanol, ethanol, and isopropanol, lower aliphatic carboxylic acids such as acetic acid and propionic acid, lower alkyl esters of lower aliphatic carboxylic acids such as methyl acetate and ethyl acetate, tetrahydrofuran, dioxane, and diisopropyl. Examples include aliphatic or alicyclic ethers such as ethers, acetone, dialkyl ketones such as methyl ethyl ketone, and the like. Such wetting solvents are preferably water-soluble and have an affinity for the resin particles and dyes used, as well as being volatile at relatively low temperatures, and therefore, among the above, Methanol is preferably used. In the present invention, the wetting solvent needs to be used in such a way as to be able to create an intimate and uniform mixture of the resin particles and anhydrous silica powder, as described above, and therefore its amount is usually
The amount is in the range of 100 to 400 ml per 100 parts by weight of resin particles.
樹脂粒子及び無水シリカ粉末と共に染料粉末を上記のよ
うに少量の湿潤化溶剤を用いて、湿潤化し、これを水性
媒体に加えて、加熱下に樹脂粒子を染色することも好ま
しい。更に、無水シリカ粉末を用いない場合であっても
、樹脂粒子と染料粉末とを同様に湿潤化することも好ま
しい。このように樹脂粒子を予め湿潤化することによっ
て、水性媒体中において、樹脂粒子を染料によって一層
容易に且つ濃色に染色することができる。It is also preferred to moisten the dye powder together with the resin particles and anhydrous silica powder using a small amount of wetting solvent as described above and add this to the aqueous medium to dye the resin particles under heating. Furthermore, even when anhydrous silica powder is not used, it is also preferable to wet the resin particles and dye powder in the same way. By pre-wetting the resin particles in this way, the resin particles can be more easily dyed in a deep color with a dye in an aqueous medium.
上記したような樹脂粒子を含む湿潤化混合物を予め調製
し、これを水性媒体に加えて、樹脂粒子を染色すること
によって、樹脂粒子が容易に且つ濃色に染色される理由
は未だ明らかではなく、また、本発明は染色の機構や理
論によって何ら制限されるものではないが、湿潤化溶剤
、例えばメタノールは、樹脂粒子の表面に付着或いは吸
着し、かくして、染料が樹脂粒子の表面に容易に接触し
、或いは吸着されるためであるとみられる。また、染料
粉末を樹脂粒子と共に湿潤化するときは、この湿潤化に
よって、染料粉末が微細化されることも寄与していると
みられる。従って、染料を樹脂粒子と共に湿潤化しない
場合は、前述したように、粒子径５μｍ以下、より好ま
しくは２μｍ以下の微細染料粉末を用いることが推奨さ
れる。It is not yet clear why the resin particles are easily dyed in a deep color by preparing a wetting mixture containing resin particles as described above in advance and adding this to an aqueous medium to dye the resin particles. Furthermore, although the present invention is not limited in any way by the mechanism or theory of dyeing, the wetting solvent, such as methanol, adheres or adsorbs to the surface of the resin particles, and thus the dye is easily attached to the surface of the resin particles. This seems to be due to contact or adsorption. Furthermore, when the dye powder is moistened together with the resin particles, the wetting causes the dye powder to become finer, which also seems to contribute. Therefore, when the dye is not wetted together with the resin particles, it is recommended to use fine dye powder with a particle size of 5 μm or less, more preferably 2 μm or less, as described above.
溌」坏と丸末
以上のように、本発明の方法によれば、予め所定の範囲
の粒子径又は平均粒子径を有せしめた微細な樹脂粒子を
その軟化点以上の温度に加温した水性媒体中にて激しい
撹拌下に、染料にて染色してトナーを製造するので、従
来の方法におけるように、多くの工程を必要とせずして
トナーを製造することができる。特に、好ましい場合に
は、得られるトナーが当初に合成樹脂粒子が有する粒子
径又は平均粒子径をそのまま有するので、染色後の樹脂
粒子の粉砕や分級を必要としない。また、樹脂粒子が染
色の間に相互に融着するようなことがあっても、それは
極めて僅かであるので、染色後の樹脂粒子の粉砕や分級
を行なう場合にも、前述したように、これらは軽度のも
のでよく、しかも、これらによって失われる量は明らか
に僅かであるので、従って、本発明の方法によれば、ト
ナーを高い歩留りにて得ることができる。As described above, according to the method of the present invention, fine resin particles having a particle size or average particle size within a predetermined range are heated to a temperature above their softening point to form an aqueous resin. Since the toner is manufactured by dyeing with a dye under vigorous stirring in a medium, the toner can be manufactured without requiring many steps as in conventional methods. In particular, in a preferred case, the resulting toner has the same particle size or average particle size as the synthetic resin particles initially have, so there is no need to crush or classify the resin particles after dyeing. Furthermore, even if the resin particles fuse with each other during dyeing, it is extremely rare, so when crushing or classifying the resin particles after dyeing, as mentioned above, these The amount of toner particles may be light, and the amount lost by them is clearly small, so that the method of the present invention allows toner to be obtained with a high yield.
また、本発明の方法によれば、合成樹脂粒子として、破
砕によって微細化した不定形の粒子を用いる場合であっ
ても、樹脂粒子の軟化点以上に加温した水性媒体中にて
激しい撹拌下に疎水性の樹脂粒子を染色することによっ
て、樹脂粒子はこれに加えられる熱と機械的剪断力によ
って、相互の融着が阻止されつつ、その形状がほぼ球状
に整えられ、従って、本発明によれば、表面が清らがで
且つほぼ球状のトナーを得ることができる。Furthermore, according to the method of the present invention, even when using amorphous particles made fine by crushing as synthetic resin particles, the synthetic resin particles can be heated under vigorous stirring in an aqueous medium heated above the softening point of the resin particles. By dyeing the hydrophobic resin particles, the heat and mechanical shearing force applied to the resin particles prevents them from fusing with each other and makes them almost spherical in shape. Accordingly, it is possible to obtain toner having a clear surface and a substantially spherical shape.
更に、本発明の方法によって得られるトナーは、付加的
な着色なしにて、゛染料による染色のみにて十分な色濃
度を有し、かぶりが少なく、鮮明で、しかも、階調性に
すぐれた複写画像を与える。本発明によるトナーにて透
明なフィルム上に複写したときは、着色透明な複写画像
が得られるので、かかるフィルムはスライドに用いるこ
とができる。Furthermore, the toner obtained by the method of the present invention has sufficient color density only by dyeing without additional coloring, has little fogging, is clear, and has excellent gradation. Give a duplicate image. When copied onto a transparent film with the toner according to the invention, a colored and transparent reproduced image is obtained, so that such film can be used for slides.
また、本発明に従って、荷電制御剤としての所定量の無
水シリカの存在下に樹脂粒子を染色して得られるトナー
は、望ましい粒径分布と荷電量を有するのみならず、流
動性にもすぐれる。Further, according to the present invention, the toner obtained by dyeing resin particles in the presence of a predetermined amount of anhydrous silica as a charge control agent not only has a desirable particle size distribution and charge amount, but also has excellent fluidity. .
叉■±
以下に実施例を挙げて本発明によるトナーの製造方法を
説明する。EXAMPLES The method for producing toner according to the present invention will be described below with reference to Examples.
実施例１
懸濁重合によって予め造粒された平均粒子径約１０μｍ
のポリスチレン粒子（住友化学工業側製ＭＰＳ１２７５
、軟化点４５℃）５０ｇを水５゜Ｏｍｌに分散させた。Example 1 Average particle diameter of approximately 10 μm granulated in advance by suspension polymerization
Polystyrene particles (MPS1275 manufactured by Sumitomo Chemical Co., Ltd.)
, softening point: 45° C.) was dispersed in 5° Oml of water.
別に、黒色分散染料［カヤロン・ポリエステル・ブラッ
ク５−ｃｏｎｃ Ｊ （日本化薬■製）１０ｇを水１
００ｍ１に分散させ、これを上記樹脂粒子の水分散液に
加えた。Separately, add 10 g of black disperse dye [Kayalon Polyester Black 5-conc J (manufactured by Nippon Kayaku ■) to 1 part water.
00ml and added to the aqueous dispersion of the resin particles.
この混合分散液を磁気攪拌子にて激しく攪拌しながら、
２°Ｃ／分の速度にて媒体を温度７５℃まで加温し、こ
の温度に１時間保持した。この後、冷却し、樹脂粒子を
５号濾紙にて濾別し、蒸留水で洗浄した後、常温常圧下
に硫酸カルシウムを乾燥剤として２昼夜乾燥させた。こ
のようにして得た染色された樹脂粒子を２００メツシユ
篩にて通過分を集め、平均粒子径約１０μｍのトナーと
した。While stirring this mixed dispersion vigorously with a magnetic stirrer,
The medium was heated at a rate of 2°C/min to a temperature of 75°C and held at this temperature for 1 hour. Thereafter, it was cooled, and the resin particles were filtered out using No. 5 filter paper, washed with distilled water, and then dried for two days and nights at room temperature and pressure using calcium sulfate as a drying agent. The dyed resin particles thus obtained were collected through a 200 mesh sieve to obtain a toner having an average particle diameter of about 10 μm.
このトナーをキャリヤ粒子と共に現像剤とじて用いて、
市販の電子写真複写機にて普通紙上に複写を行なった。Using this toner together with carrier particles as a developer,
Copies were made on plain paper using a commercially available electrophotographic copying machine.
複写画像は白湯汚染がなく、解像力、階調性にもすぐれ
ていた。即ち、ファクシミリテストチャート隘１ （画
像電子学会）による色濃度（以下、同じ。）は１．５で
あり、諧調表現は、１５段階のうちの１０段階を達成し
た。The copied image was free from hot water contamination and had excellent resolution and gradation. That is, the color density (hereinafter the same applies) according to Facsimile Test Chart 1 (Image Electronics Engineers of Japan) was 1.5, and the gradation expression achieved 10 out of 15 levels.
比較例１
実施例１において、媒体温度を９０℃とした以外は、実
施例１と同様して、ポリスチレン粒子を染色したところ
、樹脂粒子が相互に融着して、塊状物を形成して、トナ
ーを得ることができなかった。Comparative Example 1 When polystyrene particles were dyed in the same manner as in Example 1 except that the medium temperature was 90°C, the resin particles fused to each other to form a lump. Couldn't get toner.
比較例２
実施例１において、染料として水溶性含金黒色染料「カ
ヤカラン・ブラック２ＲＬＪ （日本化架装）１０ｇ
を用いた以外は、実施例１と同様して、ポリスチレン粒
子を染色することを試みたが、樹脂粒子は殆ど染色され
ず、トナーを得ることができなかった。Comparative Example 2 In Example 1, 10 g of a water-soluble metal-containing black dye “Kayakaran Black 2RLJ (Nippon Kaso)” was used as the dye.
An attempt was made to dye polystyrene particles in the same manner as in Example 1, except that the resin particles were hardly dyed, and no toner could be obtained.
実施例２
破砕によって５〜２０μｍに分級したスチレン−アクリ
ル酸エステル共重合体粒子（三菱レーヨン■製ＦＢ２０
６、軟化点約５０℃、ガラス転移点６４℃）５０ｇを水
５００ｍ１に分散させた。Example 2 Styrene-acrylic acid ester copolymer particles classified into 5 to 20 μm by crushing (FB20 manufactured by Mitsubishi Rayon)
6. Softening point: about 50°C, glass transition point: 64°C) 50g was dispersed in 500ml of water.
別に、黒色分散染料「カヤロン・ポリエステル・ブラッ
クＥＸ−３Ｆ ２００Ｊ （日本化薬＠製）１０ｇを
水１００ｍ１に分散させ、東に、荷電制御剤及び流動化
剤としての粒径１５〜２０ｍμの無水シリカ「アエロジ
ルＲ９７２Ｊ （デグツサ社製）１．５ｇをメタノー
ル１０ｍ１にて湿潤化し、これを上記染料の分散液に加
えた。このようにして得られた染料と微粉末シリカとを
含む水性分散液を前記樹脂粒子の水分散液に加えた。Separately, 10 g of black disperse dye "Kayaron Polyester Black EX-3F 200J (manufactured by Nippon Kayaku @) was dispersed in 100 ml of water, and anhydrous silica with a particle size of 15 to 20 mμ was added as a charge control agent and a fluidizing agent. 1.5 g of Aerosil R972J (manufactured by Degutsusa) was moistened with 10 ml of methanol and added to the above dye dispersion. It was added to an aqueous dispersion of resin particles.
横揺れ式染色機にてこの混合分散液を２℃／分の速度で
８８℃に加温し、この温度で１時間保持した。この後、
冷却し、樹脂粒子を５号濾紙にて濾別し、蒸留水で洗浄
した後、常温常圧下に硫酸カルシウムを乾燥剤として２
昼夜乾燥させた。このようにして得た染色された樹脂粒
子を２００メツシユ篩にて通過分を集め、粒径５〜２０
μｍのトナーを得た。このトナーの荷電量は、前述した
「ブロー・オフ型」静電量測定器にて測定した結果、−
３０μＣ／ｍｇであった。尚、上記染色において、樹脂
粒子の融着が一部、認められた。This mixed dispersion was heated to 88° C. at a rate of 2° C./min using a horizontal shaking dyeing machine and held at this temperature for 1 hour. After this,
After cooling, the resin particles were filtered through No. 5 filter paper and washed with distilled water, and then dried with calcium sulfate as a drying agent at room temperature and pressure.
Dry day and night. The dyed resin particles thus obtained were collected through a 200-mesh sieve, and the particle size was 5 to 20.
A μm toner was obtained. The amount of charge on this toner was measured using the above-mentioned "blow-off type" capacitance meter, and it was found that -
It was 30μC/mg. In addition, in the above dyeing, some fusion of resin particles was observed.
このトナーによる複写画像は白湯汚染がなく、また、色
濃度は１．３、諧調表現は、１５段階のうちの１０段階
を達成した。Images copied using this toner were free from hot water stains, had a color density of 1.3, and achieved gradation of 10 out of 15 levels.
実施例３
実施例２におけると同じスチレン−アクリル酸エステル
共重合体粒子５０ｇを水５００ｍ１に分散させ、別に、
黒色分散染料［カヤロン・ポリエステル・ブルーＴＳＪ
（日本化薬■製）５ｇを水１００ｍ１に分散させ、
これを上記樹脂粒子の水分散液に加えた。Example 3 50 g of the same styrene-acrylic acid ester copolymer particles as in Example 2 were dispersed in 500 ml of water, and separately,
Black disperse dye [Kayalon Polyester Blue TSJ
(manufactured by Nippon Kayaku ■) 5g was dispersed in 100ml of water,
This was added to the aqueous dispersion of the resin particles.
この混合分散液をホモミキサーにて激しく攪拌しながら
、２℃／分の速度で９０℃に加温し、この温度で１時間
保持した。この後、冷却し、樹脂粒子を５号濾紙にて濾
別し、蒸留水で洗浄した後、常温常圧下に硫酸カルシウ
ムを乾燥剤として２昼夜乾燥させた。This mixed dispersion was heated to 90°C at a rate of 2°C/min while being vigorously stirred with a homomixer, and maintained at this temperature for 1 hour. Thereafter, it was cooled, and the resin particles were filtered out using No. 5 filter paper, washed with distilled water, and then dried for two days and nights at room temperature and pressure using calcium sulfate as a drying agent.
上記染色の間に樹脂粒子の融着は全く認められず、また
、用いた樹脂粒子は不定形であったが、得られたトナー
は、粒子径約１０μｍであって、角が取れたほぼ球形を
呈していた。Although no fusion of the resin particles was observed during the above dyeing process, and the resin particles used were irregular in shape, the obtained toner had a particle diameter of approximately 10 μm and was approximately spherical with rounded corners. It was exhibiting.
このトナーによる複写画像は白湯汚染がない鮮明な青色
であって、色濃度は１．３、諧調表現は、１５段階のう
ちの７段階を達成した。解像力は１０木／龍であったっ
実施例４
実施例２におけると同じスチレン−アクリル酸エステル
共重合体粒子５０ｇと実施例２におけると同じ無水シリ
カ粉末１ｇとをメタノール１００ｍ１と共にシェーカー
にて混合し、湿潤化混合物を得た。これを水５００ｍ１
中に加えた。The image reproduced with this toner was a clear blue color free from hot water stains, had a color density of 1.3, and achieved gradation of 7 out of 15 levels. The resolution was 10 mm.Example 4 50 g of the same styrene-acrylic acid ester copolymer particles as in Example 2 and 1 g of anhydrous silica powder as in Example 2 were mixed in a shaker with 100 ml of methanol. A moistened mixture was obtained. Add this to 500ml of water
Added inside.
別に、赤色分散染料「グイヤセリトン・ファスト・レッ
ド２Ｂ」 （三菱化成工業Ｇｌ製）４ｇを水１００ｍ１
に分散させ、これを上記樹脂分散液に加えた。Separately, add 4g of red disperse dye "Guiyaceritone Fast Red 2B" (manufactured by Mitsubishi Chemical Industries, Ltd.) to 100ml of water.
and added to the above resin dispersion.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で８０℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させた。これを分級して、粒子径５〜２０μｍ
のトナーを得た。このトナーは、荷電量−９３μＣ／ｍ
ｇを有した。While vigorously stirring the dispersion thus obtained,
It was heated to 80°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
Let dry for an hour. This is classified and the particle size is 5 to 20 μm.
I got the toner. This toner has a charge amount of -93 μC/m
It had g.
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．５、諧調表現は、１５段階の
うちの１２段階を達成した。Furthermore, the image copied using this toner was clear without hot water staining, had a color density of 1.5, and achieved gradation of 12 out of 15 levels.
実施例５
軟化点約６０℃のポリエステル樹脂粒子と実施例２にお
けると同じ無水シリカ粉末１ｇとをメタノール１００ｍ
１と共にシェーカーにて混合し、更に、これに粒子径２
．０μｍ以下の微細な赤色分散染料「グイヤセリトン・
ファスト・スカーレッ［・ＢＪ （三菱化成工業ａ菊
製）１．０ｇを含む溶液２．５ｇを加え、１０分間シェ
ークして、染料を含む湿潤化混合物を得た。これを水５
００ｍ１中に加えた。Example 5 Polyester resin particles with a softening point of about 60°C and 1 g of the same anhydrous silica powder as in Example 2 were mixed with 100 m of methanol.
1 in a shaker, and then add particle size 2 to this.
．． A fine red disperse dye of less than 0 μm "Guiyaceritone"
2.5 g of a solution containing 1.0 g of Fast Scarlet BJ (manufactured by Mitsubishi Kasei Corporation A Kiku) was added and shaken for 10 minutes to obtain a moistened mixture containing the dye. Add this to 5 liters of water.
00ml.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で８５℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させた。これを分級して、粒子径５〜２０μｍ
のトナーを得た。このトナーは、荷電：ｆＪ−２３μＣ
／ｍｇを有した。While vigorously stirring the dispersion thus obtained,
It was heated to 85°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
Let dry for an hour. This is classified and the particle size is 5 to 20 μm.
I got the toner. This toner has a charge: fJ-23μC
/mg.
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．７、諧調表現は、１３段階の
うちの１３段階を達成した。Furthermore, the image copied using this toner was clear and free of hot water stains, had a color density of 1.7, and achieved gradation of 13 out of 13 levels.
実施例６
軟化点６４℃のポリアミド樹脂粒子と実施例２における
と同じ無水シリカ粉末１ｇとをメタノール１００ｍ１と
共にシェーカーにて混合し、かくして得た湿潤化混合物
を水５００ｍ１に加えた。Example 6 Polyamide resin particles with a softening point of 64° C. and 1 g of the same anhydrous silica powder as in Example 2 were mixed in a shaker with 100 ml of methanol, and the moistened mixture thus obtained was added to 500 ml of water.
別に、赤色酸性染料「カヤノール・レッド・ＮＢＲＪ
（日本化薬■製）２ｇを水ｊｏＯｍｌに溶解させた水
溶液を上記樹脂粒子を含む水分散液に加えた。Separately, red acid dye “Kayanor Red NBRJ”
An aqueous solution in which 2 g (manufactured by Nippon Kayaku ■) was dissolved in 100 ml of water was added to the aqueous dispersion containing the resin particles.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で８０℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させた。これを分級して、粒子径５〜２０μｍ
のトナーを得た。このトナーは、荷電！−１０μＣ／ｒ
ｎｇを有した。While vigorously stirring the dispersion thus obtained,
It was heated to 80°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
Let dry for an hour. This is classified and the particle size is 5 to 20 μm.
I got the toner. This toner is charged! -10μC/r
ng.
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．３、諧調表現は、１３段階の
うちの８段階を達成した。Furthermore, the image copied using this toner was clear without hot water staining, had a color density of 1.3, and achieved gradation of 8 out of 13 levels.
実施例７
実施例６におけると同じボリア鱗ド樹脂粒子と実施例２
におけると同じ無水シリカ粉末１ｇと水不溶性合金染料
「エリオニル・ブラックＢ・リキッド」 （チバ・ガイ
ギー社製）２．５ｇとをメタノール１００ｍ１と共にシ
ェーカーにて混合し、かくして得た湿潤化混合物を水５
００ｍ１に加えた。Example 7 Same boria scaled resin particles as in Example 6 and Example 2
1 g of the same anhydrous silica powder and 2.5 g of the water-insoluble alloy dye "Elionil Black B Liquid" (manufactured by Ciba Geigy) were mixed in a shaker with 100 ml of methanol, and the thus obtained wetting mixture was mixed with 5 ml of water.
Added to 00ml.
このようにして得られた分散液を実施例６と同様に処理
して、粒子径５〜２０μｍのトナーを得た。このト、ナ
ーは、荷電量−１３μＣ／■を有した。The dispersion liquid thus obtained was treated in the same manner as in Example 6 to obtain a toner having a particle size of 5 to 20 μm. This toner had a charge amount of -13 μC/■.
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．２、諧調表現は、１５段階の
うちの１１段階を達成した。Furthermore, the image copied using this toner was clear without hot water staining, had a color density of 1.2, and achieved gradation of 11 out of 15 levels.
実施例８
実施例２におけると同じスチレン−アクリル酸エステル
共重合体粒子５０ｇと実施例２におけると同じ無水シリ
カ粉末１ｇとをメタノール１００ｍ１と共にシェーカー
にて混合し、湿潤化混合物を得た。これを水５００ｍ１
中に加えた。Example 8 50 g of the same styrene-acrylic acid ester copolymer particles as in Example 2 and 1 g of anhydrous silica powder as in Example 2 were mixed in a shaker with 100 ml of methanol to obtain a wetting mixture. Add this to 500ml of water
Added inside.
別に、赤色塩基性染料「アイゼン・ローダミンＢＪ
（保土谷化学工業ａｌ製）１．５ｇを水５００ｍ１に溶
解させ、この染料溶液に上記樹脂粒子を含む分散液を加
えた。Separately, red basic dye “Eisen Rhodamine BJ”
(manufactured by Hodogaya Chemical Industry Al) 1.5 g was dissolved in 500 ml of water, and the dispersion containing the resin particles was added to this dye solution.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で８０℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させた。これを分級して、粒子径５〜２０ＩＩ
ｍのトナーを得た。このトナーは、荷電１−１９μＣ／
■を有した。While vigorously stirring the dispersion thus obtained,
It was heated to 80°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
Let dry for an hour. This was classified and the particle size was 5 to 20 II.
m toner was obtained. This toner has a charge of 1-19μC/
■It had.
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．０、諧調表現は、１５段階の
うちの８段階を達成した。Furthermore, the image copied using this toner was free from hot water stains, was clear, had a color density of 1.0, and achieved gradation of 8 out of 15 levels.
実施例９
実施例２におけると同じスチレン−アクリル酸エステル
共重合体粒子５０ｇ、実施例２におけると同じ無水シリ
カ粉末１・ｇ、黄色油溶性染料「アイゼンＳＯＴ・イエ
ロー１」 （保土谷化学工業ｕ憤製）０．５ｇ及び青色
油溶性染料「アイゼンＳＯＴ・ブルー２」 （保土谷化
学工業！１１製）０．７５ｇをメタノール１００ｍ１と
共にシェーカーにて混合し、湿潤化混合物を得た。これ
を水５００ｍ１中に加えた。Example 9 50 g of the same styrene-acrylic acid ester copolymer particles as in Example 2, 1 g of anhydrous silica powder as in Example 2, yellow oil-soluble dye "Eisen SOT Yellow 1" (Hodogaya Chemical Co., Ltd.) 0.5 g of blue oil-soluble dye "Eisen SOT Blue 2" (manufactured by Hodogaya Chemical Industry! 11) were mixed in a shaker with 100 ml of methanol to obtain a moistened mixture. This was added to 500ml of water.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で８５℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させた。これを分級して、粒子径５〜２０μｍ
のトナーを得た。このトナーは、荷電量−２３μＣ／ｆ
ｆｇを有した。While vigorously stirring the dispersion thus obtained,
It was heated to 85°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
Let dry for an hour. This is classified and the particle size is 5 to 20 μm.
I got the toner. This toner has a charge amount of -23μC/f
It had fg.
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．５、諧調表現は、１５段階の
うちの１１段階を達成した。Furthermore, the image copied using this toner was clear and free of hot water stains, had a color density of 1.5, and achieved gradation of 11 out of 15 levels.
実施例１０
実施例２におけると同じスチレン−アクリル酸エステル
共重合体粒子５０ｇ、実施例２におけると同じ無水シリ
カ粉末１ｇ及び青色油溶性染料「アイゼンＳＯＴ・ブル
ー２」１ｇをメタノール１００ｍ１と共にシェーカーに
て１０分間混合し、湿潤化混合物を得た。これを水５０
０ｍ１中に加えた。Example 10 50 g of the same styrene-acrylic acid ester copolymer particles as in Example 2, 1 g of anhydrous silica powder as in Example 2, and 1 g of blue oil-soluble dye "Eisen SOT Blue 2" were combined with 100 ml of methanol in a shaker. Mixed for 10 minutes to obtain a moistened mixture. Add this to 50 ml of water
Added in 0ml.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で８５℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させた。これを分級して、粒子径５〜２０μｍ
のトナーを得た。このトナーは、荷電量−３３μＣ／■
を有した。While vigorously stirring the dispersion thus obtained,
It was heated to 85°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
Let dry for an hour. This is classified and the particle size is 5 to 20 μm.
I got the toner. This toner has a charge amount of -33μC/■
It had
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．３、諧調表現は、１５段階の
うちの１１段階を達成した。Furthermore, the image copied using this toner was clear without hot water staining, had a color density of 1.3, and achieved gradation of 11 out of 15 levels.
実施例１１
実施例２におけると同じスチレン−アクリル酸エステル
共重合・体粒子５０ｇ、実施例２におけると同じ無水シ
リカ粉末１ｇ及び平均粒子径約２μｍの微細青色バット
染料「ニホンスレン・ブルーＢＣＪ （住友化学工業
ａｌ製）４ｇをメタノール１００ｍ１と共にシェーカー
にて１０分間シェークし、湿潤化混合物を得、これを水
５００ｍ１中に加えた。Example 11 50 g of the same styrene-acrylic ester copolymer particles as in Example 2, 1 g of the same anhydrous silica powder as in Example 2, and a fine blue vat dye "Japanese Ren Blue BCJ" (Sumitomo Chemical) with an average particle size of about 2 μm. (Industrial Al) was shaken with 100 ml of methanol for 10 minutes in a shaker to obtain a moistened mixture, which was added to 500 ml of water.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で８５℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させた。これを分級して、粒子径５〜２０μｍ
のトナーを得た。このトナーは、荷電量−２８μＣ／
ｍｇを有した。While vigorously stirring the dispersion thus obtained,
It was heated to 85°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
Let dry for an hour. This is classified and the particle size is 5 to 20 μm.
I got the toner. This toner has a charge amount of -28μC/
It had mg.
また、このトナーによる複写画像は白湯汚染がなく、鮮
明であって、色濃度は１．１、諧調表現は、１５段階の
うちの１１段階を達成した。Furthermore, the image copied using this toner was clear and free of hot water stains, had a color density of 1.1, and achieved gradation of 11 out of 15 levels.
実施例１２
実施例２におけると同じスチレン−アクリル酸エステル
共重合体粒子５０ｇと実施例２におけると同じ無水シリ
カ粉末１ｇをメタノール１００ｍ１と共にシェーカーに
て１０分間シェークした。Example 12 50 g of the same styrene-acrylic acid ester copolymer particles as in Example 2 and 1 g of anhydrous silica powder as in Example 2 were shaken together with 100 ml of methanol in a shaker for 10 minutes.
別に、青色バット染料［二ホンスレン・ブルーＢＣＪを
含む水溶液５００ｍ１を調製し、これに上記湿潤化混合
物を加えた。Separately, 500 ml of an aqueous solution containing a blue vat dye [Nihonthrene Blue BCJ was prepared, and the above wetting mixture was added thereto.
このようにして得られた分散液を実施例１１と同様に処
理して、粒子径５〜２０μｍのトナーを得た。このトナ
ーが形成した複写画像は、白湯汚染がなく、鮮明であっ
て、色濃度は１．０、諧調表現は、１５段階のうちの１
１段階を達成した。The dispersion liquid thus obtained was treated in the same manner as in Example 11 to obtain a toner having a particle size of 5 to 20 μm. The copied image formed by this toner is clear and free of hot water contamination, has a color density of 1.0, and has a gradation level of 1 out of 15.
Achieved stage 1.
実施例１３
軟化点約６０℃、平均粒子径約ｌＯμｍのポリスチレン
樹脂粒子と実施例２におけると同じ無水シリカ粉末１ｇ
をメタノール１００ｎ＋１と共にシェーカーにて１０分
間シェークした。Example 13 Polystyrene resin particles with a softening point of about 60° C. and an average particle diameter of about 10 μm and 1 g of the same anhydrous silica powder as in Example 2
was shaken with 100n+1 methanol in a shaker for 10 minutes.
別に、赤色分散染料［グイヤセリトン・ファスト・スカ
ーレットＢＪ１．５ｇを水１００ｍ１に分散させ、この
分散液に上記湿潤化混合物を加え、これを更に水５００
ｍ１に加えた。Separately, 1.5 g of red disperse dye [Guiyaceritone Fast Scarlet BJ] was dispersed in 100 ml of water, the above wetting mixture was added to this dispersion, and this was further mixed with 500 ml of water.
Added to m1.
このようにして得られた分散液を激しく攪拌しながら、
２℃／分の速度で７５℃に加温し、この温度で１時間保
持した。この後、冷却し、樹脂粒子を５号濾紙にて濾別
し、蒸留水で洗浄した後、常圧下に４０℃の温度で２４
時間乾燥させて、平均粒子径１０μｍのトナーを得た。While vigorously stirring the dispersion thus obtained,
It was heated to 75°C at a rate of 2°C/min and held at this temperature for 1 hour. Thereafter, the resin particles were cooled, filtered through No. 5 filter paper, washed with distilled water, and heated to 40°C under normal pressure for 24 hours.
After drying for hours, a toner having an average particle size of 10 μm was obtained.
このトナーは、荷電量−２８μＣ／■を有した。This toner had a charge amount of -28 μC/■.
このトナーを用いて、実施例１と同様にして、透明なス
ライド用ポリエステルフィルム上に複写画像を形成させ
た。この複写画像は、着色透明であるのみならず、高度
に解像されており、白湯汚染がなく、鮮明であった。Using this toner, a copy image was formed on a transparent polyester film for slides in the same manner as in Example 1. This copied image was not only colored and transparent, but also highly resolved, free of hot water stains, and clear.
Claims (10)
成樹脂粒子を、この樹脂粒子に対する重量比にて５以上
であつて、且つ、上記樹脂粒子の軟化点以上、軟化点よ
りも４０℃高い温度以下に加温した水性媒体中にて、撹
拌下に染料にて染色し、脱水し、乾燥することを特徴と
するトナーの製造方法。(1) Synthetic resin particles having a predetermined particle size or average particle size in advance have a weight ratio of 5 or more to the resin particles, and are equal to or higher than the softening point of the resin particles and 40% lower than the softening point of the resin particles. 1. A method for producing a toner, which comprises dyeing with a dye in an aqueous medium heated to a temperature below 100° C. while stirring, dehydrating, and drying.
料又は油溶性染料であることを特徴とする特許請求の範
囲第１項記載のトナーの製造方法。(2) The method for producing a toner according to claim 1, wherein the dye is a water-insoluble disperse dye, a vat dye, a metal-containing dye, or an oil-soluble dye.
ン染料、含金染料又は反応性染料であることを特徴とす
る特許請求の範囲第１項記載のトナーの製造方法。(3) The method for producing a toner according to claim 1, wherein the dye is a water-soluble acid dye, a basic or cationic dye, a metal-containing dye, or a reactive dye.
下に染色することを特徴とする特許請求の範囲第１項記
載のトナーの製造方法。(4) The method for producing a toner according to claim 1, wherein the resin particles are dyed in the presence of a charge control agent and/or a fluidizing agent.
であることを特徴とする特許請求の範囲第４項記載のト
ナーの製造方法。(5) The method for producing a toner according to claim 4, wherein the charge control agent and/or fluidizing agent is an anhydrous silica fine powder.
を少量の有機溶剤と共に混合して湿潤化混合物とし、こ
れを水性媒体に加えることを特徴とする特許請求の範囲
第５項記載のトナーの製造方法。(6) The toner according to claim 5, characterized in that the resin particles and the anhydrous silica fine powder and/or the dye powder are mixed together with a small amount of an organic solvent to form a wetting mixture, and this is added to the aqueous medium. manufacturing method.
ルボン酸、低級脂肪族カルボン酸の低級アルキルエステ
ル、脂肪族若しくは脂環族エーテル又はジアルキルケト
ンであることを特徴とする特許請求の範囲第６項記載の
トナーの製造方法。(7) Claim 6, characterized in that the organic solvent is an aliphatic lower alcohol, a lower aliphatic carboxylic acid, a lower alkyl ester of a lower aliphatic carboxylic acid, an aliphatic or alicyclic ether, or a dialkyl ketone. Method for manufacturing the toner described in Section 1.
特徴とする特許請求の範囲第７項記載のトナーの製造方
法。(8) The method for producing a toner according to claim 7, wherein the aliphatic lower alcohol is methanol.
子径を有することを特徴とする特許請求の範囲第１項記
載のトナーの製造方法。(9) The method for producing a toner according to claim 1, wherein the resin particles have a particle diameter or an average particle diameter of 5 to 20 μm in advance.
子径を有することを特徴とする特許請求の範囲第１項記
載のトナーの製造方法。(10) The method for producing a toner according to claim 1, wherein the dye powder has a particle size or an average particle size of 5 μm or less in advance.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29177185 | 1985-12-23 | ||
| JP61-119598 | 1986-05-24 | ||
| JP60-291771 | 1986-05-24 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8136567A Division JP2676141B2 (en) | 1985-12-23 | 1996-05-30 | Manufacturing method of toner |
| JP15157798A Division JP2905477B2 (en) | 1985-12-23 | 1998-06-01 | Manufacturing method of toner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63106667A true JPS63106667A (en) | 1988-05-11 |
| JPH0752307B2 JPH0752307B2 (en) | 1995-06-05 |
Family
ID=17773207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61307143A Expired - Lifetime JPH0752307B2 (en) | 1985-12-23 | 1986-12-22 | Toner manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0752307B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2237653A (en) * | 1989-10-18 | 1991-05-08 | Ricoh Kk | Method of producing toner for developing latent electrostatic images |
| JPH03168653A (en) * | 1989-11-28 | 1991-07-22 | Mita Ind Co Ltd | Electrostatic charge image developing toner and manufacture of the same |
-
1986
- 1986-12-22 JP JP61307143A patent/JPH0752307B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2237653A (en) * | 1989-10-18 | 1991-05-08 | Ricoh Kk | Method of producing toner for developing latent electrostatic images |
| GB2237653B (en) * | 1989-10-18 | 1993-09-29 | Ricoh Kk | Method of producing toner for developing latent electro-static images |
| JPH03168653A (en) * | 1989-11-28 | 1991-07-22 | Mita Ind Co Ltd | Electrostatic charge image developing toner and manufacture of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0752307B2 (en) | 1995-06-05 |
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