JPH04291356A - Toner and production of toner - Google Patents
Toner and production of tonerInfo
- Publication number
- JPH04291356A JPH04291356A JP3057154A JP5715491A JPH04291356A JP H04291356 A JPH04291356 A JP H04291356A JP 3057154 A JP3057154 A JP 3057154A JP 5715491 A JP5715491 A JP 5715491A JP H04291356 A JPH04291356 A JP H04291356A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- toner
- resin
- inner core
- colorant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 106
- 239000011347 resin Substances 0.000 claims abstract description 106
- 239000002245 particle Substances 0.000 claims abstract description 89
- 239000003086 colorant Substances 0.000 claims abstract description 80
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000007771 core particle Substances 0.000 claims description 74
- 238000000034 method Methods 0.000 claims description 51
- 239000011247 coating layer Substances 0.000 claims description 25
- 238000011161 development Methods 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 abstract description 30
- 238000011282 treatment Methods 0.000 abstract description 17
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- 238000012546 transfer Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 9
- -1 etc. Polymers 0.000 description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 8
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- 238000004898 kneading Methods 0.000 description 3
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- 229910052793 cadmium Inorganic materials 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 2
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- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
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Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は電子写真法等に使用され
ている乾式現像用トナーに関し、さらに詳しくは多層構
造を有するトナーに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry developing toner used in electrophotography, and more particularly to a toner having a multilayer structure.
【０００２】0002
【従来の技術】従来の電子写真法としては、米国特許第
２，２９７，６９１に示されているカールソンプロセス
を基本として、これまでに多数の方法が提案されている
。一般には光導電性物質を用いた感光体上に静電気的潜
像を形成し、次に静電気的潜像に「トナー」と呼ばれる
微粉末を選択的に付着させて現像を行うことにより静電
気的潜像を顕像化させ、これを必要に応じて紙等の転写
材に転写した後、熱及び圧力、あるいは溶剤蒸気等によ
り定着させ、画像形成物を得るというものである。2. Description of the Related Art Many conventional electrophotographic methods have been proposed based on the Carlson process shown in US Pat. No. 2,297,691. Generally, an electrostatic latent image is formed on a photoreceptor using a photoconductive substance, and then a fine powder called "toner" is selectively attached to the electrostatic latent image and development is performed. The image is visualized, transferred to a transfer material such as paper as necessary, and then fixed by heat and pressure, solvent vapor, etc. to obtain an image-formed product.
【０００３】現像方法としては乾式現像方式と液体現像
方式に大別でき、さらに乾式現像方式としてはキャリア
を使用する二成分現像方式として磁気ブラシ現像法やカ
スケード現像法等が知られている。また一成分現像方式
としては、ジャンピング現像法、ＦＥＥＤ現像法及び磁
気ブラシ現像法等が知られている。これらの現像方式に
使用されるトナーはさらに絶縁性と導電性に分類される
。一般にこれらの現像方法に使用されるトナーとしては
、樹脂の中に染料や顔料等の着色剤及び帯電制御剤等を
分散させた約１０μｍの内核粒子の表面に種々の物質を
付着させたものが使用されている。[0003] Development methods can be broadly classified into dry development methods and liquid development methods. Further, as dry development methods, two-component development methods using a carrier such as a magnetic brush development method and a cascade development method are known. Further, as one-component development methods, there are known jumping development methods, FEED development methods, magnetic brush development methods, and the like. The toners used in these development methods are further classified into insulating and conductive toners. Generally, the toner used in these development methods is one in which various substances are attached to the surface of core particles of about 10 μm in which colorants such as dyes and pigments and charge control agents are dispersed in resin. It is used.
【０００４】トナーの製造方法としては、一般に混練粉
砕法、スプレードライ法及び重合法等が知られている。
また内核粒子の表面に種々の物質を付着させる方法とし
ては、流動乾燥炉等を使用して熱により付着させる方法
やボールミル等の混合機を用いて機械的な力により付着
させる方法等が知られている。詳しくは、着色剤と帯電
制御剤を含む内核粒子の表面に結着樹脂粉末を静電付着
させ、その後に結着樹脂粉末を熱溶融させ表面被覆を行
ったカラートナー（特開平１−２２７１６３）、着色剤
と磁性粉を含む内核粒子の表面に、熱可塑性樹脂微粒子
と帯電制御剤を乾式混合で外添させた後、融着で表面被
覆したトナー（特開昭６３−２５６６３）等がある。[0004] Generally known methods for producing toner include a kneading and pulverizing method, a spray drying method, and a polymerization method. In addition, there are known methods of attaching various substances to the surface of the inner core particles, such as a method of attaching them by heat using a fluidized drying oven, etc., and a method of attaching them by mechanical force using a mixer such as a ball mill. ing. Specifically, a color toner in which binder resin powder is electrostatically adhered to the surface of inner core particles containing a colorant and a charge control agent, and the binder resin powder is then thermally melted to cover the surface (Japanese Patent Application Laid-Open No. 1-227163). There is a toner (Japanese Unexamined Patent Publication No. 63-25663) in which fine thermoplastic resin particles and a charge control agent are externally added to the surface of an inner core particle containing a colorant and magnetic powder by dry mixing, and then the surface is coated by fusing. .
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前述の
トナーは内核粒子中に着色剤が入っているが、結着樹脂
等により着色剤が隠されてしまって色がはっきりと出な
くなるため、着色剤量を多くしなければならない。そう
すると着色剤により光が遮られてしまうので、カラート
ナー特性として必要である透明性が劣り、画像が不鮮明
になるという欠点を有している。さらに着色剤量が多い
と、二成分現像トナーとして使用する場合、連続印刷時
に磁性キャリア表面への着色剤の溶出、いわゆるブリー
ドアウトが起こりやすくなるため、トナー特性の劣化や
転写時に不良を引き起こすという欠点を有している。ま
たトナー表面の被覆を熱溶融法で行う場合、内核粒子は
外添した樹脂微粒子より軟化点が高いものでなければな
らず、材質や組み合わせ等が制限されるという欠点を有
している。また内核粒子の表面に種々の物質を付着させ
ただけのものでは、トナーの搬送中及び保存時に付着物
が容易に剥がれ落ち、トナー特性の劣化及び装置内部の
汚染等を引き起こすという欠点を有している。従って本
発明の目的は前記課題を解決するもので、少ない着色剤
量にも関わらず画像形成物が鮮明かつ透明性に優れてお
り、さらにトナー搬送中及び保存中に特性が劣化せず装
置内部を汚さないという特性を有するトナーとトナー製
造方法を提供するものである。[Problems to be Solved by the Invention] However, although the above-mentioned toner contains a coloring agent in the inner core particles, the coloring agent is hidden by a binder resin etc. and the color does not come out clearly. The quantity must be increased. In this case, since light is blocked by the colorant, transparency, which is necessary as a color toner characteristic, is poor and the image becomes unclear. Furthermore, if the amount of colorant is large, when used as a two-component developing toner, the colorant is likely to elute onto the magnetic carrier surface during continuous printing, so-called bleed-out, resulting in deterioration of toner properties and defects during transfer. It has its drawbacks. Furthermore, when the toner surface is coated by a thermal melting method, the inner core particles must have a higher softening point than the externally added fine resin particles, which has the disadvantage that materials, combinations, etc. are limited. In addition, if various substances are simply attached to the surface of the inner core particles, the attached substances easily peel off during toner transportation and storage, resulting in deterioration of toner properties and contamination inside the device. ing. Therefore, an object of the present invention is to solve the above-mentioned problems, and to provide an image formed product with excellent clarity and transparency despite the small amount of colorant, and to prevent the characteristics from deteriorating during toner transportation and storage, and to prevent the inside of the device from deteriorating. The purpose of the present invention is to provide a toner and a method for producing the toner that have the property of not staining the surface of the toner.
【０００６】[0006]
【課題を解決するための手段】本発明のトナーは、乾式
現像法に使用するトナーにおいて、少なくとも結着樹脂
より成る内核粒子の表面に、少なくとも着色剤と樹脂微
粒子を用いて樹脂被膜層を形成したことを特徴とする。[Means for Solving the Problems] The toner of the present invention is a toner used in a dry development method, in which a resin coating layer is formed using at least a colorant and fine resin particles on the surface of core particles made of at least a binder resin. It is characterized by what it did.
【０００７】また本発明のトナー製造方法は、前記内核
粒子の表面に、少なくとも着色剤と樹脂微粒子から成る
混合粒子を付着させ、次に前記樹脂微粒子を溶解させる
溶剤で処理することにより、少なくとも着色剤を含む樹
脂被膜層を形成することを特徴とする。Further, the toner manufacturing method of the present invention includes adhering mixed particles consisting of at least a coloring agent and fine resin particles to the surface of the inner core particles, and then treating the inner core particles with a solvent that dissolves the fine resin particles. It is characterized by forming a resin coating layer containing the agent.
【０００８】さらに本発明のトナー製造方法は、前記内
核粒子の表面への、少なくとも着色剤と樹脂微粒子から
成る混合粒子の付着を、乾式で行うことを特徴とする。Furthermore, the toner manufacturing method of the present invention is characterized in that the adhesion of mixed particles comprising at least a colorant and fine resin particles to the surface of the inner core particles is carried out in a dry manner.
【０００９】[0009]
【作用】本発明のトナーは、少なくとも結着樹脂から成
る内核粒子の表面に、少なくとも着色剤と樹脂微粒子を
用いて樹脂被膜層を形成している。すなわちトナーの表
面近くに着色剤が存在しているので、画像形成した際に
も画像の表面近くに着色剤が存在することになる。従っ
て結着樹脂等により着色剤がほとんど隠されることがな
いので、着色剤量が少ないにも関わらず鮮明な画像を形
成するものと思われる。さらに着色剤として黒色以外の
ものを用いたカラートナーでは、着色剤が少ないと透過
光を遮ることが少なくなるため、カラートナー特性とし
て重要である透明性のよい画像が得られる。[Operation] In the toner of the present invention, a resin coating layer is formed on the surface of the inner core particles made of at least a binder resin using at least a colorant and fine resin particles. That is, since the colorant is present near the surface of the toner, the colorant is also present near the surface of the image when an image is formed. Therefore, since the colorant is hardly hidden by the binder resin or the like, it is thought that a clear image is formed despite the small amount of colorant. Furthermore, in a color toner using something other than black as a colorant, the less the colorant, the less the transmitted light will be blocked, so an image with good transparency, which is an important characteristic of color toners, can be obtained.
【００１０】また本発明のトナーの製造方法では、内核
粒子の表面への着色剤や樹脂微粒子等の混合粒子の付着
を乾式で行っている。この方法の原理は、各粒子間に相
互衝突運動を繰り返させて、衝突時に与えられるエネル
ギーで局部的活性領域を形成し、そこで生じる物理的吸
着力あるいは化学的吸着力等により内核粒子の表面に着
色剤や樹脂微粒子等を付着させるというものである。こ
の時内核粒子の表面で着色剤や樹脂微粒子等の均一な分
散が生じ、樹脂微粒子や着色剤等の局部的な偏りのない
状態で内核粒子表面への付着が生じる。次に内核粒子表
面に付着させた樹脂微粒子を溶剤で溶解処理することに
より、内核粒子の表面に着色剤等を含む樹脂被膜層を形
成している。そのため内核粒子に対する樹脂被膜層の密
着性及び均一性が向上し、さらに着色剤等の添加物を固
着させて剥がれ落ちなくする。この時、溶剤の種類及び
粒子と溶剤との接触時間を選択して樹脂微粒子の溶解時
間を制御することにより、内核粒子にまで溶剤が浸透し
ないようにすることができる。従って、例えば内核粒子
が樹脂微粒子より軟化点が低く柔らかい場合でも、樹脂
被膜層を確実に形成させることができ、トナー同士の凝
集や造粒現象を抑えることができる。Further, in the toner manufacturing method of the present invention, mixed particles such as a colorant and fine resin particles are attached to the surface of the inner core particles in a dry manner. The principle of this method is to repeat mutual collision motion between each particle, form a local active region with the energy given at the time of collision, and use the physical adsorption force or chemical adsorption force generated there to attach to the surface of the inner core particle. This involves attaching coloring agents, resin particles, etc. At this time, uniform dispersion of the colorant, fine resin particles, etc. occurs on the surface of the inner core particle, and the fine resin particles, colorant, etc. adhere to the surface of the inner core particle without any local bias. Next, by dissolving the resin fine particles attached to the surface of the inner core particle with a solvent, a resin coating layer containing a coloring agent and the like is formed on the surface of the inner core particle. Therefore, the adhesion and uniformity of the resin coating layer to the inner core particles are improved, and furthermore, additives such as colorants are fixed and prevented from peeling off. At this time, by controlling the dissolution time of the resin fine particles by selecting the type of solvent and the contact time between the particles and the solvent, it is possible to prevent the solvent from penetrating into the inner core particles. Therefore, even if, for example, the inner core particles have a lower softening point and are softer than the fine resin particles, a resin coating layer can be reliably formed, and aggregation and granulation phenomena of toner particles can be suppressed.
【００１１】[0011]
【実施例】図１（ａ）に本発明のトナー製造方法のフロ
ーチャートを、また図１（ｂ）に本発明のトナーの模式
図を示す。トナー製造方法は、結着樹脂１等から成る原
料を用いて混練粉砕法、スプレードライ法、重合法等に
より内核粒子５を作製する。次に内核粒子５の表面に着
色剤２及び樹脂微粒子３等を付着させる外添処理６を行
って着色剤及び樹脂微粒子外添処理内核粒子７を作製す
る。次に着色剤及び樹脂微粒子外添処理内核粒子７に樹
脂微粒子を溶解する溶剤４を接触させ被膜化処理８を行
って内核粒子５の表面に樹脂被膜層９を形成させて、着
色剤含有樹脂被膜化トナー１０を作製するというもので
ある。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1(a) is a flowchart of the toner manufacturing method of the present invention, and FIG. 1(b) is a schematic diagram of the toner of the present invention. In the toner production method, the inner core particles 5 are produced by a kneading and pulverization method, a spray drying method, a polymerization method, etc. using raw materials including the binder resin 1 and the like. Next, an external addition treatment 6 is performed in which a colorant 2, fine resin particles 3, etc. are attached to the surface of the inner core particle 5, thereby producing an inner core particle 7 treated with the external addition of colorant and fine resin particles. Next, the colorant and resin fine particle external addition treatment inner core particles 7 are brought into contact with a solvent 4 that dissolves the resin fine particles, and a coating treatment 8 is performed to form a resin coating layer 9 on the surface of the inner core particles 5, and the colorant-containing resin is A coated toner 10 is produced.
【００１２】本発明に用いる内核粒子は少なくとも結着
樹脂から成っており、必要に応じてトナー成分を入れる
ことができる。トナー成分としては、無機物剤、電荷制
御剤、磁性粉、導電剤、離型剤、分散剤等から必要に応
じて一種類あるいは二種類以上選択できる。またこれら
を必要に応じて着色剤及び樹脂微粒子と共に内核粒子の
表面に付着させ、樹脂被膜層中に入れることもできる。
内核粒子の作製方法としては、一般に用いられている混
練粉砕法、スプレードライ法及び重合法等である。形状
は球形、不定型のどちらでもよく、粒径は一般に１〜４
０μｍのものを用いる。The inner core particles used in the present invention are made of at least a binder resin, and can contain toner components as required. As the toner component, one or more types can be selected from inorganic agents, charge control agents, magnetic powders, conductive agents, mold release agents, dispersants, etc., as required. Further, if necessary, these can be attached to the surface of the inner core particles together with a coloring agent and fine resin particles, and incorporated into the resin coating layer. Methods for producing the inner core particles include commonly used kneading and pulverization methods, spray drying methods, polymerization methods, and the like. The shape may be either spherical or irregular, and the particle size is generally 1 to 4.
Use one with a diameter of 0 μm.
【００１３】内核粒子表面に着色剤や樹脂微粒子等の混
合粒子を付着させる乾式の方法としては、通常の混合機
、例えばボールミルやＶ型混合機等も使用できるが、い
わゆる高速流動攪拌機を使用することが好ましい。高速
流動攪拌機としては、いわゆるヘンシェルミキサー、メ
カノフュージョンシステム（細川ミクロン）、ナラハイ
ブリタイゼーションシステム（奈良機械製作所）、メカ
ノミル（岡田精工）等を用いる。但し内核粒子の表面に
微粒子を付着させる装置としては決してこれらに限定さ
れるものではない。[0013] As a dry method for adhering mixed particles such as a coloring agent and fine resin particles to the surface of the inner core particles, ordinary mixers such as a ball mill or a V-type mixer can be used, but a so-called high-speed fluidized stirrer is used. It is preferable. As the high-speed fluidized stirrer, a so-called Henschel mixer, Mechano Fusion System (Hosokawa Micron), Nara Hybridization System (Nara Kikai Seisakusho), Mechano Mill (Okada Seiko), etc. are used. However, the device for adhering fine particles to the surface of the inner core particles is by no means limited to these.
【００１４】溶剤で処理して樹脂被膜層を形成させる方
法としては噴霧乾燥法や液浸法等があるが、接触時間を
制御できるものであれば何でもよい。好ましくは粉体コ
ーティング装置、例えばディスパーコート（日清製粉）
、コートマイザー（フロイント産業）等を使用する。Methods for forming a resin coating layer by treatment with a solvent include spray drying and immersion, but any method may be used as long as the contact time can be controlled. Preferably a powder coating device, such as Dispercoat (Nissin Seifun)
, use Coat Mizer (Freund Sangyo), etc.
【００１５】結着樹脂の原料としては特に限定されるも
のではなく、一般に用いられているものを用いることが
できる。詳しくは、ポリスチレン及びその共重合体とし
て水素添加スチレン樹脂、ＡＢＳ樹脂、ＡＳＡ樹脂、Ａ
Ｓ樹脂、ＡＡＳ樹脂、ＡＣＳ樹脂、ＡＥＳ樹脂、スチレ
ン−ｐ−クロロスチレン共重合体、スチレン−プロピレ
ン共重合体、スチレン−ブタジエン架橋重合体、スチレ
ン−ブタジエン−塩素化パラフィン共重合体、スチレン
−アリルアルコール共重合体、スチレン−ブタジエンゴ
ムエマルジョン、スチレン−マレイン酸エステル共重合
体、スチレン−イソブチレン共重合体、スチレン−無水
マレイン酸共重合体等、またアクリレート系樹脂あるい
はメタアクリレート系樹脂及びその共重合体等、またス
チレン−アクリル系樹脂及びその共重合体としてスチレ
ン−アクリル共重合体、スチレン−ジエチルアミノエチ
ルメタアクリレート共重合体、スチレン−ブタジエン−
アクリル酸エステル共重合体、スチレン−メチルメタア
クリレート共重合体、スチレン−ｎ−ブチルメタアクリ
レート共重合体、スチレン−メチルメタアクリレート−
ｎ−ブチルアクリレート共重合体、スチレン−メチルメ
タアクリレート−ブチルアリレート−Ｎ−（エトキシメ
チル）アクリルアミド共重合体、スチレン−グリシジル
メタアクリレート共重合体、スチレン−ブタジエン−ジ
メチルアミノエチルメタアクリレート共重合体、スチレ
ン−アクリル酸エステル−マレイン酸エステル共重合体
、スチレン−メタアクリル酸メチル−アクリル酸−２−
エチルヘキシル共重合体、スチレン−ｎ−ブチルアリレ
ート−エチルグリコールメタアクリレート共重合体、ス
チレン−ｎ−ブチルメタアクリレート−アクリル酸共重
合体、スチレン−ｎ−ブチルメタアクリレート−無水マ
レイン酸共重合体、スチレン−ブチルアクリレート−イ
ソブチルマレイン酸ハーフエステル−ジビニルベンゼン
共重合体等、またポリエステル及びその共重合体、ポリ
エチレン及びその共重合体、エポキシ樹脂、シリコーン
樹脂、ポリプロピレン及びその共重合体、フッ素樹脂、
ポリアミド樹脂、ポリビニールアルコール樹脂、ポリウ
レタン樹脂、ポリビニルブチラール樹脂等があり、これ
らを必要に応じて一種類あるいは二種類以上混合したも
のを用いることができる。また樹脂以外の物質としてワ
ックス等も用いることができる。詳しくはキャンデリラ
ワックス、カルナバワックス、ライスワックス等の植物
系天然ワックス、みつろう、ラノリン等の動物系天然ワ
ックス、モンタンワックス、オゾケライト等の鉱物系天
然ワックス、パラフィンワックス、マイクロクリスタリ
ンワックス、ペトロラタム等の天然石油系ワックス、ポ
リエチレンワックス、フィッシャー・トロプシュワック
ス等の合成炭化水素ワックス、モンタンワックス誘導体
、パラフィンワックス誘導体等の変性ワックス、硬化ひ
まし油、硬化ひまし油誘導体等の水素化ワックス、合成
ワックス等のワックス類、ステアリン酸、パルミチン酸
等の高級脂肪酸類、低分子量ポリエチレン、酸化ポリエ
チレン、ポリプロピレン等のポリオレフィン、エチレン
−アクリル酸共重合体、エチレン−アクリル酸エステル
共重合体、エチレン−酢酸ビニル共重合体等のオレフィ
ン共重合体等があり、これらを必要に応じて一種類ある
いは二種類以上を用いることができる。The raw material for the binder resin is not particularly limited, and commonly used materials can be used. In detail, polystyrene and its copolymers include hydrogenated styrene resin, ABS resin, ASA resin, A
S resin, AAS resin, ACS resin, AES resin, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene crosslinked polymer, styrene-butadiene-chlorinated paraffin copolymer, styrene-allyl Alcohol copolymers, styrene-butadiene rubber emulsions, styrene-maleic acid ester copolymers, styrene-isobutylene copolymers, styrene-maleic anhydride copolymers, etc., acrylate resins or methacrylate resins, and their copolymers. In addition, styrene-acrylic resins and their copolymers include styrene-acrylic copolymers, styrene-diethylaminoethyl methacrylate copolymers, styrene-butadiene-copolymers, etc.
Acrylic acid ester copolymer, styrene-methyl methacrylate copolymer, styrene-n-butyl methacrylate copolymer, styrene-methyl methacrylate
n-butyl acrylate copolymer, styrene-methyl methacrylate-butyl arylate-N-(ethoxymethyl) acrylamide copolymer, styrene-glycidyl methacrylate copolymer, styrene-butadiene-dimethylaminoethyl methacrylate copolymer, Styrene-acrylic acid ester-maleic acid ester copolymer, styrene-methyl methacrylate-acrylic acid-2-
Ethylhexyl copolymer, styrene-n-butyl arylate-ethyl glycol methacrylate copolymer, styrene-n-butyl methacrylate-acrylic acid copolymer, styrene-n-butyl methacrylate-maleic anhydride copolymer, styrene -butyl acrylate-isobutyl maleic acid half ester-divinylbenzene copolymer, etc., polyester and its copolymers, polyethylene and its copolymers, epoxy resins, silicone resins, polypropylene and its copolymers, fluororesins,
There are polyamide resins, polyvinyl alcohol resins, polyurethane resins, polyvinyl butyral resins, etc., and one type or a mixture of two or more of these can be used as required. Moreover, wax etc. can also be used as a substance other than resin. For more information, please see plant-based natural waxes such as candelilla wax, carnauba wax, and rice wax, animal-based natural waxes such as beeswax and lanolin, mineral-based natural waxes such as montan wax and ozokerite, and natural natural waxes such as paraffin wax, microcrystalline wax, and petrolatum. Petroleum waxes, polyethylene waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch waxes, modified waxes such as montan wax derivatives and paraffin wax derivatives, hydrogenated waxes such as hydrogenated castor oil and hydrogenated castor oil derivatives, waxes such as synthetic waxes, and stearin. acids, higher fatty acids such as palmitic acid, polyolefins such as low molecular weight polyethylene, polyethylene oxide, and polypropylene, olefin copolymers such as ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, and ethylene-vinyl acetate copolymers. There are polymers, etc., and one type or two or more types of these can be used as necessary.
【００１６】着色剤として詳しくは、カーボンブラック
、スピリットブラック、酸化銅、二酸化マンガン、アニ
リンブラック、活性炭、ニグロシン、黄鉛、亜鉛黄、カ
ドミウムイエロー、黄色酸化鉄、ミネラルファストイエ
ロー、ニッケルチタンイエロー、ネーブルスイエロー、
ナフトールイエローＳ、バンザーイエローＧ、バンザー
イエロー１０Ｇ、ベンジジンイエローＧ、ベンジジンイ
エローＧＲ、キノリンイエローレーキ、タートラジンレ
ーキ、パーマネントイエローＮＣＧ、赤口黄鉛、モリブ
デンオレンジ、ピラゾロンオレンジ、パーマネントオレ
ンジＧＴＲ、バルカンオレンジ、インダスレンブリリア
ントオレンジＲＫ、インダスレンブリリアントオレンジ
ＧＫ、ベンジジンオレンジＧ、ベンガラ、カドミウムレ
ッド、鉛丹、硫化水銀、カドミウム、パーマネントレッ
ド４Ｒ、リソールレッド、ピラゾロンレッド、レーキレ
ッドＤ、ブリリアントカーミン６Ｂ、ブリリアントカー
ミン３Ｂ、エオシンレーキ、ローダミンレーキＢ、アリ
ザリンレーキ、マンガン紫、ファストバイオレットＢ、
メチルバイオレットレーキ、コバルトブルー、アルカリ
ブルーレーキ、ビクトリアブルーレーキ、フタロシアニ
ンブルー、ファーストスカイブルー、インダスレンブル
ーＢＣ、ピグメントグリーンＢ、マラカイトグリーンレ
ーキ、ファナルイエローグリーンＧ、亜鉛華、酸化チタ
ン、硫化亜鉛、フタロシアニン、ローダミンＢレーキ、
ソーラピュアイエロー８Ｇ、キナクリドン、ポリタング
ストリン酸、メチレンブルー、ローズベンガル、スルホ
ンアミド誘導体、Ｃ．Ｉ．ダイレクトブラック１９、２
２、２８、１５４、１６８、Ｃ．Ｉ．ダイレクトイエロ
ー１２、２６、８６、８７、１３０、１４２、Ｃ．Ｉ．
ダイレクトレッド９、１３、１７、２３、Ｃ．Ｉ．ダイ
レクトブルー７８、８６、１９９、Ｃ．Ｉ．アッシドブ
ラック５２、１７２、２０８、Ｃ．Ｉ．アッシドイエロ
ー２３、２５、Ｃ．Ｉ．アッシドレッド５２、２５４、
２８９、Ｃ．Ｉ．アッシドブルー９、２５４、Ｃ．Ｉ．
フードブラック２、Ｃ．Ｉ．ソルベントイエロー２、６
、１４、１５、１６、１９、２１、３３、５６、６１、
８０、Ｃ．Ｉ．ソルベントオレンジ１、２、５、６、１
４、３７、４０、４４、４５、Ｃ．Ｉ．ソルベントレッ
ド１、３、８、２３、２４、２５、２７、３０、４９、
８１、８２、８３、８４、１００、１０９、１２１、Ｃ
．Ｉ．ディスパースレッド９、Ｃ．Ｉ．ソルベントバイ
オレット８、１３、１４、２１、２７、Ｃ．Ｉ．ディス
パースバイオレット１、Ｃ．Ｉ．ソルベントブルー２、
１１、１２、２５、３５、３６、５５、７３、Ｃ．Ｉ．
ソルベントグリーン３、Ｃ．Ｉ．ソルベントブラウン３
、５、２０、３７、Ｃ．Ｉ．ソルベントブラック３、５
、２２、２３等の染料または顔料があり、これらを必要
に応じて一種類あるいは二種類以上混合して用いること
ができる。[0016] In detail, the colorants include carbon black, spirit black, copper oxide, manganese dioxide, aniline black, activated carbon, nigrosine, yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel. Sue Yellow,
Naphthol Yellow S, Banzer Yellow G, Banzer Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Tartrazine Lake, Permanent Yellow NCG, Red Yellow Lead, Molybdenum Orange, Pyrazolone Orange, Permanent Orange GTR, Vulcan Orange, Indus Ren Brilliant Orange RK, Indus Thren Brilliant Orange GK, Benzidine Orange G, Red Garla, Cadmium Red, Red Lead, Mercury Sulfide, Cadmium, Permanent Red 4R, Lysol Red, Pyrazolone Red, Lake Red D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Manganese Purple, Fast Violet B,
Methyl violet lake, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, fast sky blue, industhrene blue BC, pigment green B, malachite green lake, final yellow green G, zinc white, titanium oxide, zinc sulfide, Phthalocyanine, rhodamine B lake,
Solar Pure Yellow 8G, quinacridone, polytungstophosphoric acid, methylene blue, rose bengal, sulfonamide derivative, C.I. I. Direct black 19, 2
2, 28, 154, 168, C. I. Direct Yellow 12, 26, 86, 87, 130, 142, C. I.
Direct Red 9, 13, 17, 23, C. I. Direct Blue 78, 86, 199, C. I. Assid Black 52, 172, 208, C. I. Ashido Yellow 23, 25, C. I. Ashido Red 52, 254,
289, C. I. Ashido Blue 9, 254, C. I.
Food Black 2, C. I. Solvent Yellow 2, 6
, 14, 15, 16, 19, 21, 33, 56, 61,
80,C. I. Solvent Orange 1, 2, 5, 6, 1
4, 37, 40, 44, 45, C. I. Solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49,
81, 82, 83, 84, 100, 109, 121, C
．． I. Disperse Red 9, C. I. Solvent Violet 8, 13, 14, 21, 27, C. I. Disperse Violet 1, C. I. Solvent Blue 2,
11, 12, 25, 35, 36, 55, 73, C. I.
Solvent Green 3, C. I. Solvent Brown 3
, 5, 20, 37, C. I. Solvent black 3, 5
, 22, 23, etc., and these can be used singly or in a mixture of two or more, if necessary.
【００１７】さらに分散剤として、金属石鹸、ポリエチ
レングリコール等を、また帯電制御剤として電子受容性
の有機錯体、塩素化ポリエステル、ニトロフニン酸、第
４級アンモニウム塩、ピリジニル塩等を必要に応じて添
加することができる。Further, as a dispersing agent, metal soap, polyethylene glycol, etc. are added, and as a charge control agent, an electron-accepting organic complex, chlorinated polyester, nitrofnic acid, quaternary ammonium salt, pyridinyl salt, etc. are added as necessary. can do.
【００１８】この他に磁性用トナーとして磁性粉末、詳
しくはＦｅ３Ｏ４、Ｆｅ２Ｏ３、Ｆｅ、Ｃｒ、Ｎｉ等を
用いることができる。In addition, magnetic powders such as Fe3O4, Fe2O3, Fe, Cr, Ni, etc. can be used as the magnetic toner.
【００１９】無機物微粒子としては、Ｓｉ０２、ＴｉＯ
２（ルチル、アナターゼ）、Ｚｎ０、Ａｌ２Ｏ３（α型
、β型）、ＴｉＯＮ、ＴｉＢａＯ３、ＭｇＯ、ＺｒＯ２
、ＣａＣＯ３、ＮｉＯ、ＳｎＯ、クレー、タルク、ケイ
砂、雲母、ＳｉＮ、ＳｉＣ、Ｂａ２ＳＯ４、カーボンブ
ラック等の微粒子を用いることができる。[0019] As the inorganic fine particles, Si02, TiO
2 (rutile, anatase), Zn0, Al2O3 (α type, β type), TiON, TiBaO3, MgO, ZrO2
, CaCO3, NiO, SnO, clay, talc, silica sand, mica, SiN, SiC, Ba2SO4, carbon black, and other fine particles can be used.
【００２０】樹脂微粒子としてはポリメチルメタアクリ
レート（ＰＭＭＡ）、ポリエチルメタアクリレート（Ｐ
ＥＭＡ）、ポリ−ｎ−ブチルメタアクリレート（ＰＢＭ
Ａ）、ポリエステル、スチレン−ブタジエン共重合体、
ポリ塩化ビニル（ＰＶＣ）、ポリビニルアルコール（Ｐ
ＶＡ）、ポリ酢酸ビニル（ＰＶＡｃ）、ポリ−γ−メチ
ルグルタメート、フッ素樹脂、フッ化ビニリデン樹脂、
ベンゾクアナミン樹脂、シリコーン樹脂、エポキシ樹脂
、ナイロン６６／６、ナイロン１１、ナイロン１２、ポ
リスチレン樹脂、架橋ポリスチレン樹脂、フェノール樹
脂、メラミン樹脂、ポリオレフィン樹脂、ポリエチレン
樹脂、セルロース等を用いることができる。 内核粒
子の表面を被膜化処理するときに用いる溶剤は、内核粒
子の表面に前記方法によって付着させた樹脂微粒子を溶
かすものならば特に制限されない。詳しくは、ｎ−ヘキ
サン、ヘプタン、シクロヘキサン、ベンゼン、トルエン
、キシレン、ジクロロメタン、クロロホルム、テトラク
ロロメタン、ジクロロエタン、クロロベンゼン、ニトロ
メタン、アセトニトリル、アクリロニトリル、テトラヒ
ドロフラン、ジオキサン、メチルセルソルブ、エチルア
セテート、ブチルアセテート、アセトン、メチルエチル
ケトン、メタノール、エタノール、プロパノール、ベン
ジルアルコール、ピリジン、ジエチルホルムアミド、ジ
メチルホルムアミド等があり、これらを必要に応じて一
種類あるいは二種類以上混合して用いることができる。Polymethyl methacrylate (PMMA) and polyethyl methacrylate (PMMA) are used as resin fine particles.
EMA), poly-n-butyl methacrylate (PBM
A), polyester, styrene-butadiene copolymer,
Polyvinyl chloride (PVC), polyvinyl alcohol (P
VA), polyvinyl acetate (PVAc), poly-γ-methylglutamate, fluororesin, vinylidene fluoride resin,
Benzoquanamine resin, silicone resin, epoxy resin, nylon 66/6, nylon 11, nylon 12, polystyrene resin, crosslinked polystyrene resin, phenol resin, melamine resin, polyolefin resin, polyethylene resin, cellulose, etc. can be used. The solvent used when coating the surface of the inner core particle is not particularly limited as long as it dissolves the fine resin particles attached to the surface of the inner core particle by the method described above. For details, see n-hexane, heptane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroform, tetrachloromethane, dichloroethane, chlorobenzene, nitromethane, acetonitrile, acrylonitrile, tetrahydrofuran, dioxane, methylcellosolve, ethyl acetate, butyl acetate, acetone. , methyl ethyl ketone, methanol, ethanol, propanol, benzyl alcohol, pyridine, diethyl formamide, dimethyl formamide, etc., and these can be used alone or in combination of two or more types as required.
【００２１】以上述べた原料を用い、かつ前記方法によ
って着色剤を含む樹脂被膜層を形成することにより、処
理後の分級等の操作を必要とせず、保存安定性が優れ、
さらに着色剤がトナーの表面近くにあるために、少ない
着色剤量で画像形成物が鮮明かつ透明性のよいトナーを
製造することができる。[0021] By using the raw materials described above and forming a resin coating layer containing a colorant by the method described above, there is no need for operations such as classification after treatment, and the product has excellent storage stability.
Furthermore, since the colorant is located near the surface of the toner, a toner with a clear image and good transparency can be produced with a small amount of colorant.
【００２２】以下に本実施例をより詳細に説明する。以
下の実施例と比較例中の数字は特に断りのない限り重量
部を示す。This embodiment will be explained in more detail below. The numbers in the following Examples and Comparative Examples indicate parts by weight unless otherwise specified.
【００２３】〔実施例１〕
＜内核粒子の作製＞原料としてスチレン−アクリル共重
合体を使用した。これをスクリュー押出機で溶融混練し
、冷却した後粗粉砕した。次にジェット粉砕機で微粉砕
し、分級して平均粒径９μｍ、粒径分布５〜２０μｍの
内核粒子を作製した。[Example 1] <Preparation of inner core particles> A styrene-acrylic copolymer was used as a raw material. This was melt-kneaded using a screw extruder, cooled, and then coarsely ground. Next, it was finely pulverized with a jet pulverizer and classified to produce inner core particles with an average particle size of 9 μm and a particle size distribution of 5 to 20 μm.
【００２４】＜着色剤と樹脂微粒子の付着＞前記内核粒
子と、樹脂微粒子としてＰＢＭＡ、着色剤としてコバル
トブルーを用いた。ＰＢＭＡはガラス転移点８３℃、粒
径０．４μｍのものを使用した。この樹脂微粒子と着色
剤と前記内核粒子を下記に示す組成に混合して、メカノ
フュージョンシステム（細川ミクロン製）を用いて内核
粒子の表面に付着させた。その組成と条件を以下に示す
。
ＰＢＭＡ微粒子・・・１５．０
内核粒子・・・８３．５
コバルトブルー・・・１．５
付着は回転数１５００ｒｐｍ、処理時間３０分の条件で
行った。得られた粒子は、樹脂微粒子と着色剤が内核粒
子の表面に剥がれずに付着していることが電子顕微鏡観
察により明らかとなった。また電子顕微鏡により断面観
察を行ったところ、内核粒子表面に樹脂微粒子が球形の
まま埋め込まれた状態にあることが観察された。<Attachment of Colorant and Resin Fine Particles> PBMA was used as the inner core particle and the resin fine particles, and cobalt blue was used as the colorant. The PBMA used had a glass transition point of 83° C. and a particle size of 0.4 μm. The resin fine particles, the colorant, and the inner core particles were mixed to have the composition shown below, and the mixture was attached to the surface of the inner core particles using a mechanofusion system (manufactured by Hosokawa Micron). Its composition and conditions are shown below. PBMA fine particles: 15.0 Inner core particles: 83.5 Cobalt blue: 1.5 Attachment was performed at a rotation speed of 1500 rpm and a processing time of 30 minutes. Observation with an electron microscope revealed that the resin fine particles and the colorant adhered to the surface of the inner core particles without peeling off. Further, when cross-sectional observation was performed using an electron microscope, it was observed that the resin fine particles were embedded in a spherical shape on the surface of the inner core particle.
【００２５】＜被膜化処理＞前記方法で作製した微粒子
外添内核粒子に対して被膜化処理を行った。溶剤として
アセトンを用いた。この溶剤の分散気流と粒子の分散気
流を接触時間が１．０秒になるように接触させ、その後
乾燥温度６０℃で噴霧乾燥してアセトンを蒸発させた。
この被膜化処理により得られた粒子は粒子同士の結着も
なく、粒子それぞれが独立した状態の集合体であった。
また本実施例で作製した粒子を電子顕微鏡により断面観
察したところ、内核粒子の表面に膜厚０．２μｍの樹脂
被膜層が形成されており、その中に着色剤が均一に分散
されているのが確認された。<Coating treatment> The inner core particles added to the outer part of the fine particles prepared by the above method were subjected to a coating treatment. Acetone was used as the solvent. This solvent dispersion air stream and particle dispersion air stream were brought into contact for a contact time of 1.0 seconds, and then spray-dried at a drying temperature of 60°C to evaporate acetone. The particles obtained by this coating treatment had no binding between particles, and each particle was an aggregate in an independent state. Furthermore, when the cross section of the particles produced in this example was observed using an electron microscope, it was found that a resin coating layer with a thickness of 0.2 μm was formed on the surface of the inner core particle, and the colorant was uniformly dispersed in the resin coating layer. was confirmed.
【００２６】以上の方法で作製したトナーを一成分非接
触型現像機とＯＰＣ感光体を有するレーザープリンタに
搭載して、トナー転写材として紙を用いて画像形成を行
ったところ、鮮明な画像を形成することができた。さら
にトナー転写材としてＯＨＰ用透明シートを用いて同様
なテストを行ったところ、透明性のよい鮮明な画像が形
成された。さらに３万枚の耐久テストを行ったところ、
初期と同様に鮮明な画像を得ることができた。また本実
施例で作製したトナーを容器に密閉し、温度３０℃で湿
度８０％の環境下に３ヶ月間保存した後同様なテストを
行ったが凝集等なく、初期と同様な鮮明画像を得ること
ができた。When the toner prepared by the above method was loaded into a laser printer equipped with a one-component non-contact developing machine and an OPC photoreceptor, and an image was formed using paper as the toner transfer material, a clear image was obtained. was able to form. Furthermore, when a similar test was conducted using an OHP transparent sheet as a toner transfer material, clear images with good transparency were formed. Furthermore, after conducting a durability test of 30,000 sheets,
I was able to obtain clear images just like in the beginning. In addition, the toner produced in this example was sealed in a container and stored for 3 months in an environment with a temperature of 30°C and a humidity of 80%, and then a similar test was performed, but there was no aggregation, and a clear image similar to the initial image was obtained. I was able to do that.
【００２７】〔比較例１〕
＜内核粒子の作製＞結着樹脂としてスチレン−アクリル
共重合体を、着色剤としてコバルトブルーを用いて内核
粒子を作製した。作製方法は実施例１と同様にした。[Comparative Example 1] <Preparation of inner core particles> Inner core particles were prepared using styrene-acrylic copolymer as a binder resin and cobalt blue as a coloring agent. The manufacturing method was the same as in Example 1.
【００２８】
スチレン−アクリル共重合体・・・９７．５コバルトブ
ルー・・・２．５
分級後の平均粒径は１０μｍ、粒径分布は６〜２１μｍ
であった。Styrene-acrylic copolymer...97.5 Cobalt blue...2.5 Average particle size after classification is 10 μm, particle size distribution is 6 to 21 μm
Met.
【００２９】＜樹脂微粒子の付着＞前記内核粒子と粒径
０．４μｍのＰＢＭＡを用いた。条件は実施例１と同様
にした。以下に組成を示す。<Attachment of fine resin particles> The inner core particles and PBMA having a particle size of 0.4 μm were used. The conditions were the same as in Example 1. The composition is shown below.
【００３０】
内核粒子・・・８５．０
ＰＢＭＡ微粒子・・・１５．０
得られた粒子を電子顕微鏡で観察したところ、実施例１
と同様な状態であった。Inner core particles...85.0 PBMA fine particles...15.0 When the obtained particles were observed with an electron microscope, it was found that Example 1
The situation was similar.
【００３１】＜被膜化処理＞実施例１と同様な方法で被
膜化処理を行った。得られた粒子を電子顕微鏡で観察し
たところ、実施例１と同様な状態であった。<Coating treatment> A coating treatment was performed in the same manner as in Example 1. When the obtained particles were observed with an electron microscope, they were found to be in the same state as in Example 1.
【００３２】以上の方法で作製したトナーを実施例１で
用いたレーザープリンタに搭載して画像形成を行ったと
ころ、着色剤量が実施例１より多いにも関わらず、色の
ぼやけた不鮮明な画像を形成した。When the toner prepared by the above method was loaded into the laser printer used in Example 1 and an image was formed, although the amount of colorant was larger than in Example 1, the color was blurred and unclear. An image was formed.
【００３３】〔実施例２〕 ＜内核粒子の作製＞内核粒子としてワックスを用いた。 その組成と方法を以下に示す。[Example 2] <Preparation of inner core particles> Wax was used as the inner core particles. Its composition and method are shown below.
【００３４】
パラフィンワックス・・・５０．０
ポリエチレンワックス・・・５０．０
上記組成物をバッチ式混練機で混練し、冷却した後粗粉
砕した。次にジェット粉砕機で微粉砕後、分級して平均
粒径１０μｍ、粒径分布５〜２５μｍの内核粒子を作製
した。Paraffin wax: 50.0 Polyethylene wax: 50.0 The above composition was kneaded using a batch kneader, cooled, and coarsely ground. Next, the mixture was finely pulverized using a jet pulverizer, and then classified to produce inner core particles having an average particle size of 10 μm and a particle size distribution of 5 to 25 μm.
【００３５】＜着色剤と樹脂微粒子の付着＞粒径０．４
μｍのＰＢＭＡと着色剤を使用して、実施例１と同様な
組成と方法で付着を行った。但し着色剤はソーラピュア
イエロー８Ｇを用いた。付着は、内核粒子が柔らかいた
め、回転数８００ｒｐｍ、処理時間１５分の条件で行っ
た。得られた粒子は実施例１と同様な状態であった。<Adhesion of colorant and resin fine particles> Particle size 0.4
Deposition was carried out using the same composition and method as in Example 1 using μm PBMA and colorant. However, the colorant used was Solar Pure Yellow 8G. Since the inner core particles are soft, the attachment was carried out at a rotation speed of 800 rpm and a processing time of 15 minutes. The obtained particles were in the same state as in Example 1.
【００３６】＜被膜化処理＞溶剤としてキシレンを用い
た。被膜化処理及び噴霧乾燥の条件は実施例１と同様に
した。得られた粒子は実施例１と同様に粒子同士の結着
もなく、粒子それぞれが独立した状態の集合体であった
。さらに得られたトナーを電子顕微鏡により断面観察し
たところ、内核粒子の表面に膜厚０．２μｍの樹脂被膜
層が形成され、その中に着色剤が均一に分散しているこ
とが確認された。<Coating treatment> Xylene was used as the solvent. The coating treatment and spray drying conditions were the same as in Example 1. As in Example 1, the obtained particles had no binding between the particles and were an aggregate of independent particles. Furthermore, when the obtained toner was cross-sectionally observed using an electron microscope, it was confirmed that a resin coating layer with a thickness of 0.2 μm was formed on the surface of the inner core particles, and the colorant was uniformly dispersed therein.
【００３７】以上の方法で作製したトナーを実施例１で
用いたレーザープリンタに搭載して、トナー転写材とし
て紙を用いて画像形成したところ、定着温度１２０℃と
いう低温で鮮明な画像を形成することができた。さらに
トナー転写材としてＯＨＰ用透明シートを用いて同様な
テストを行ったところ、透明性のよい鮮明な画像が定着
温度１２０℃で形成された。さらに３万枚の耐久テスト
を行ったところ、初期と同様に鮮明な画像を得ることが
できた。さらに本実施例で作製したトナーを容器に密閉
し、温度３０℃で湿度８０％の環境下に３ヶ月間保存し
て同様なテストを行ったが凝集等なく、初期と同様に鮮
明な画像を得ることができた。When the toner produced by the above method was loaded into the laser printer used in Example 1 and an image was formed using paper as the toner transfer material, a clear image was formed at a low fixing temperature of 120°C. I was able to do that. Furthermore, when a similar test was conducted using an OHP transparent sheet as a toner transfer material, clear images with good transparency were formed at a fixing temperature of 120°C. Furthermore, when we conducted a durability test of 30,000 sheets, we were able to obtain clear images just like the initial one. Furthermore, the toner produced in this example was sealed in a container and stored for 3 months in an environment with a temperature of 30°C and a humidity of 80%, and a similar test was performed, but there was no aggregation, and the image was as clear as the initial one. I was able to get it.
【００３８】〔実施例３〕 ＜内核粒子の作製＞内核粒子としてワックスを用いた。 その組成と方法を以下に示す。[Example 3] <Preparation of inner core particles> Wax was used as the inner core particles. Its composition and method are shown below.
【００３９】キャンデリラワックス・・・６５．０ポリ
エチレンワックス・・・３５．０
上記組成物を実施例２と同様な方法で混練粉砕処理した
。その後分級して平均粒径１１μｍ、粒径分布６〜２３
μｍの内核粒子を作製した。Candelilla wax: 65.0 Polyethylene wax: 35.0 The above composition was kneaded and pulverized in the same manner as in Example 2. After that, it was classified to have an average particle size of 11 μm and a particle size distribution of 6 to 23.
A μm-sized inner core particle was prepared.
【００４０】＜着色剤、樹脂微粒子及びトナー成分の付
着＞着色剤としてピラゾロンレッド、樹脂微粒子として
粒径０．４μｍのＰＢＭＡ、外添剤として粒径０．０６
μｍのＳｉＯ２を用いて、実施例２と同様な方法と条件
で付着を行った。用いたものの組成を以下に示す。<Adhesion of colorant, fine resin particles, and toner components> Pyrazolone red as the colorant, PBMA with a particle size of 0.4 μm as the resin particles, and particle size 0.06 as the external additive.
Deposition was carried out using the same method and conditions as in Example 2 using .mu.m SiO2. The composition of what was used is shown below.
【００４１】内核粒子・・・７４．０ 着色剤・・・１．０ 樹脂微粒子・・・１５．０ ＳｉＯ２・・・１０．０ 得られた粒子は実施例１と同様な状態であった。[0041] Inner core particle...74.0 Colorant...1.0 Resin fine particles...15.0 SiO2...10.0 The obtained particles were in the same state as in Example 1.
【００４２】＜被膜化処理＞溶剤としてキシレンを用い
た。被膜化処理及び噴霧乾燥の条件は実施例１と同様に
した。得られた粒子は流動性が非常によく、また粒子同
士の結着もなく、粒子それぞれが独立した状態の集合体
であった。さらに得られたトナーを電子顕微鏡により断
面観察したところ、内核粒子の表面に膜厚０．２μｍの
樹脂被膜層が形成され、その中に着色剤とトナー成分が
均一に分散していることが確認された。<Film forming treatment> Xylene was used as the solvent. The coating treatment and spray drying conditions were the same as in Example 1. The obtained particles had very good fluidity, and there was no binding between particles, and each particle was an aggregate in an independent state. Furthermore, when the obtained toner was cross-sectionally observed using an electron microscope, it was confirmed that a resin coating layer with a thickness of 0.2 μm was formed on the surface of the inner core particles, and the colorant and toner components were uniformly dispersed in the resin coating layer. It was done.
【００４３】以上の方法で作製したトナーを実施例１で
用いたレーザープリンタに搭載して、トナー転写材とし
て紙を用いて画像形成したところ、定着温度１１０℃と
いう低温で鮮明な画像を形成することができた。さらに
トナー転写材としてＯＨＰ用透明シートを用いて同様な
テストを行ったところ、透明性のよい鮮明な画像が定着
温度１１０℃で形成された。さらに３万枚の耐久テスト
を行ったところ、初期と同様に鮮明な画像を得ることが
できた。さらに本実施例で作製したトナーを容器に密閉
し、温度３０℃で湿度８０％の環境下に３ヶ月間保存し
て同様なテストを行ったが凝集等なく、初期と同様に鮮
明な画像を得ることができた。When the toner produced by the above method was loaded into the laser printer used in Example 1 and an image was formed using paper as the toner transfer material, a clear image was formed at a low fixing temperature of 110°C. I was able to do that. Furthermore, when a similar test was conducted using an OHP transparent sheet as a toner transfer material, clear images with good transparency were formed at a fixing temperature of 110°C. Furthermore, when we conducted a durability test of 30,000 sheets, we were able to obtain clear images just like the initial one. Furthermore, the toner produced in this example was sealed in a container and stored for 3 months in an environment with a temperature of 30°C and a humidity of 80%, and a similar test was performed, but there was no aggregation, and the image was as clear as the initial one. I was able to get it.
【００４４】〔実施例４〕
＜内核粒子の作製＞実施例１と同様な組成と方法で内核
粒子を作製した。分級後の平均粒径と粒径分布は実施例
１と同様であった。[Example 4] <Preparation of inner core particles> Inner core particles were prepared using the same composition and method as in Example 1. The average particle size and particle size distribution after classification were the same as in Example 1.
【００４５】＜着色剤、樹脂微粒子及びトナー成分の付
着＞着色剤としてカーボンブラック、樹脂微粒子として
粒径０．５μｍのＰＭＭＡ、トナー成分として磁性粉の
Ｆｅ３Ｏ４を用いた。その組成を以下に示す。ただし作
製の方法は実施例１と同様にした。<Attachment of Colorant, Fine Resin Particles, and Toner Components> Carbon black was used as the colorant, PMMA with a particle size of 0.5 μm was used as the resin particles, and magnetic powder Fe3O4 was used as the toner component. Its composition is shown below. However, the manufacturing method was the same as in Example 1.
【００４６】内核粒子・・・４９．５
ＰＭＭＡ・・・１０．０
Ｆｅ３Ｏ４・・・４０．０
カーボンブラック・・・０．５
得られた粒子を電子顕微鏡で観察したところ、内核粒子
の表面に樹脂微粒子とトナー成分と着色剤が均一に付着
していた。Inner core particles...49.5 PMMA...10.0 Fe3O4...40.0 Carbon black...0.5 When the obtained particles were observed with an electron microscope, it was found that on the surface of the inner core particles. The fine resin particles, toner components, and colorant were uniformly adhered.
【００４７】＜被膜化処理＞実施例１と同様にして被膜
化処理を行った。得られた粒子を電子顕微鏡で断面観察
したところ、内核粒子の表面に膜厚０．３μｍの樹脂被
膜層が形成され、さらに樹脂被膜層中に着色剤とトナー
成分が均一に分散されていることが確認された。<Coating treatment> A coating treatment was carried out in the same manner as in Example 1. When the obtained particles were cross-sectionally observed using an electron microscope, a resin coating layer with a thickness of 0.3 μm was formed on the surface of the inner core particle, and furthermore, the colorant and toner components were uniformly dispersed in the resin coating layer. was confirmed.
【００４８】以上の方法で作製したトナーを一成分磁気
ブラシ現像機とＯＰＣ感光体を有するレーザープリンタ
に搭載して、トナー転写材として紙を用いて画像形成し
たところ、鮮明な画像を形成することができた。さらに
３万枚の耐久テストを行ったところ、初期と同様に鮮明
な画像を得ることができた。さらに本実施例で作製した
トナーを容器に密閉し、温度３０℃で湿度８０％の環境
下に３ヶ月間保存して同様なテストを行ったが凝集等な
く、初期と同様に鮮明な画像を得ることができた。When the toner prepared by the above method was loaded into a laser printer having a one-component magnetic brush developer and an OPC photoreceptor and an image was formed using paper as a toner transfer material, a clear image was formed. was completed. Furthermore, when we conducted a durability test of 30,000 sheets, we were able to obtain clear images just like the initial one. Furthermore, the toner produced in this example was sealed in a container and stored for 3 months in an environment with a temperature of 30°C and a humidity of 80%, and a similar test was performed, but there was no aggregation, and the image was as clear as the initial one. I was able to get it.
【００４９】〔比較例２〕実施例１で作製した内核粒子
の表面に、着色剤としてカーボンブラック、トナー成分
として磁性分のＦｅ３Ｏ４及び樹脂微粒子として粒径０
．４μｍのＰＭＭＡ粒子を、実施例４と同様な組成と方
法で付着させただけのものを作製した。これを実施例１
で用いたレーザープリンタに搭載して、トナー転写材と
して紙を用いて画像形成を行ったところ、トナーの流動
性が悪く、さらに現像機内で凝集を起こし、地かぶりの
ある不鮮明な画像を形成した。さらに外添した微粒子が
剥がれ落ち、レーザープリンタ内部を汚すという悪影響
を及ぼした。[Comparative Example 2] On the surface of the inner core particles prepared in Example 1, carbon black was added as a coloring agent, Fe3O4 as a magnetic component was added as a toner component, and particle size 0 was added as fine resin particles.
．． A sample was prepared in which 4 μm PMMA particles were simply attached using the same composition and method as in Example 4. Example 1
When the toner was installed in a laser printer used in 2015 and used paper as the toner transfer material to form an image, the toner had poor fluidity and agglomerated in the developing machine, resulting in an unclear image with background fog. . Furthermore, the externally added fine particles peeled off and contaminated the inside of the laser printer, which had an adverse effect.
【００５０】〔実施例５〕
＜内核粒子の作製＞実施例１と同様な組成と方法で内核
粒子を作製した。分級後の平均粒径と粒径分布は実施例
１と同様であった。[Example 5] <Preparation of inner core particles> Inner core particles were prepared using the same composition and method as in Example 1. The average particle size and particle size distribution after classification were the same as in Example 1.
【００５１】＜着色剤と樹脂微粒子の付着＞着色剤とし
てコバルトブルー、ソーラピュアイエロー８Ｇ、ピラゾ
ロンレッドを用いて３色の粒子をそれぞれ作製した。そ
の組成を以下に示す。付着の条件は実施例１と同様にし
た。<Attachment of Colorant and Resin Fine Particles> Particles of three colors were prepared using cobalt blue, solar pure yellow 8G, and pyrazolone red as colorants. Its composition is shown below. The conditions for attachment were the same as in Example 1.
【００５２】
ＰＢＭＡ微粒子（粒径０．４μｍ）・・・１５．０内核
粒子・・・８３．５
着色剤・・・１．５
＜被膜化処理＞実施例１と同様にして樹脂の被膜化処理
を行った。得られた粒子は、３種類とも粒子同士の結着
もなく、粒子それぞれが独立した状態の集合体であった
。また本実施例で作製した粒子を電子顕微鏡により断面
観察したところ、３種類とも内核粒子の表面に膜厚０．
２μｍの樹脂被膜層が形成されており、その中に着色剤
が均一に分散しているのが確認された。PBMA fine particles (particle size 0.4 μm)...15.0 Inner core particles...83.5 Colorant...1.5 <Coating treatment> Coating with resin in the same manner as in Example 1 processed. The three types of particles obtained were aggregates in which each particle was independent, with no binding between particles. Further, when the cross-sections of the particles produced in this example were observed using an electron microscope, it was found that all three types had a film thickness of 0.5 mm on the surface of the inner core particles.
It was confirmed that a 2 μm resin coating layer was formed and the colorant was uniformly dispersed therein.
【００５３】以上の方法で作製した３色のトナーにそれ
ぞれキャリアを混合したものを、二成分磁気ブラシ型現
像機とＯＰＣ感光体を有するレーザープリンタで３回現
像と転写を繰り返して、フルカラーの画像を形成した。
トナーとキャリアの混合比はトナー１０．０重量部に対
し、キャリア９０．０重量部であった。トナー転写材と
して紙を用いてフルカラーの画像を形成したところ、３
色及び２色混色部分の色再現性のよい鮮明な画像が形成
された。またトナー転写材としてＯＨＰ用透明シートを
用いてフルカラーの画像を形成したところ、紙の時と同
じように、混色部分の色再現性と透明性のよい鮮明な画
像が形成された。さらに３万枚の耐久テストを行ったと
ころ、ブリードアウトが起こらず、初期と同様に鮮明な
画像を得ることができた。[0053] The three color toners prepared in the above manner were mixed with carriers, and then developed and transferred three times using a two-component magnetic brush developing machine and a laser printer equipped with an OPC photoreceptor, thereby producing a full-color image. was formed. The mixing ratio of toner and carrier was 10.0 parts by weight of toner and 90.0 parts by weight of carrier. When a full color image was formed using paper as a toner transfer material, 3
A clear image with good color reproducibility in the color and the two-color mixed portion was formed. Further, when a full-color image was formed using an OHP transparent sheet as a toner transfer material, a clear image with good color reproducibility and transparency in the mixed color portion was formed, just like when using paper. Furthermore, when we conducted a durability test of 30,000 sheets, no bleed-out occurred and we were able to obtain clear images just like the initial one.
【００５４】以上実施例を述べたが、本発明はこれらの
実施例に限定されるものではなく、さらに、樹脂被膜層
内にその他のトナー成分を添加することも可能である。Although the embodiments have been described above, the present invention is not limited to these embodiments, and it is also possible to add other toner components into the resin coating layer.
【００５５】[0055]
【発明の効果】以上述べたように本発明のトナー及びト
ナー製造方法によれば、内核粒子の表面に着色剤や樹脂
微粒子等を用いて樹脂被膜層を形成したトナー、詳しく
は着色剤や樹脂微粒子等の混合粒子を乾式で付着させ、
次に樹脂微粒子を溶解させる溶剤で処理して樹脂被膜層
を形成したトナーを用いれば、保存時に凝集を起こさず
、さらにトナー表面に固着した着色剤等が剥がれないの
で装置内部の汚染がなく、さらに着色剤量が比較的少な
いにも関わらず鮮明で、特に着色剤に黒色以外のものを
使用した場合透明性のよい画像を形成することができる
という効果を有する。また用いる着色剤量が少ないため
、連続印刷を行ってもブリードアウトが起こらず、トナ
ー特性の劣化及び転写時の不良を引き起こさないという
効果を有する。さらに本発明のトナー製造方法によれば
、内核粒子の組成や構造に関わらず、種々の樹脂成分と
着色成分から成る樹脂被膜層を均一に、かつ膜厚制御を
行って前記特性を満足するトナーを簡単に作製できるた
め、これまでの多層構造トナー作製方法に比べて多大の
効果を有する。従って本発明のトナー及びトナー製造方
法は、優れた機能を有する多層構造トナーの低コスト化
にさらに大きく貢献することができる。Effects of the Invention As described above, according to the toner and toner manufacturing method of the present invention, a toner in which a resin coating layer is formed on the surface of the inner core particles using a colorant, resin fine particles, etc. Mixed particles such as fine particles are attached by dry method,
Next, if you use a toner that has been treated with a solvent that dissolves resin particles to form a resin coating layer, it will not aggregate during storage, and furthermore, the coloring agent fixed on the toner surface will not peel off, so there will be no contamination inside the device. Further, despite the relatively small amount of coloring agent, it is possible to form an image that is clear and has good transparency, especially when a coloring agent other than black is used. Furthermore, since the amount of colorant used is small, bleed-out does not occur even when continuous printing is performed, and there is an effect that deterioration of toner characteristics and defects during transfer do not occur. Furthermore, according to the toner manufacturing method of the present invention, the resin coating layer made of various resin components and coloring components can be made uniform and the thickness can be controlled to produce a toner that satisfies the above characteristics, regardless of the composition and structure of the inner core particles. Because it can be easily produced, it has a great effect compared to conventional methods for producing multilayered toners. Therefore, the toner and toner manufacturing method of the present invention can further significantly contribute to cost reduction of multilayer structure toners having excellent functions.
【００５６】さらに本発明のトナー及びトナー製造方法
は、電子写真、静電記録、静電印刷、磁気記録法等を用
いた画像形成装置、つまり複写機、プリンター、ファク
シミリ等に広く応用することができる。Furthermore, the toner and toner manufacturing method of the present invention can be widely applied to image forming apparatuses using electrophotography, electrostatic recording, electrostatic printing, magnetic recording, etc., such as copying machines, printers, facsimile machines, etc. can.
【図１】図１（ａ）は本発明のトナー製造方法のフロー
チャートを示す図、図１（ｂ）は本発明のトナーの模式
図である。FIG. 1(a) is a diagram showing a flowchart of the toner manufacturing method of the present invention, and FIG. 1(b) is a schematic diagram of the toner of the present invention.
１ 結着樹脂
２ 着色剤
３ 樹脂微粒子
４ 溶剤
５ 内核粒子
６ 外添処理
７ 着色剤及び樹脂微粒子外添処理内核粒子８ 被
膜化処理
９ 樹脂被膜層
１０ 着色剤含有樹脂被膜化トナー1 Binder resin 2 Colorant 3 Resin fine particles 4 Solvent 5 Inner core particles 6 External addition treatment 7 Colorant and resin fine particle external addition treatment inner core particles 8 Coating treatment 9 Resin coating layer 10 Colorant-containing resin coating toner
Claims (3)
、少なくとも結着樹脂より成る内核粒子の表面に、少な
くとも着色剤と樹脂微粒子を用いて樹脂被膜層を形成し
たことを特徴とするトナー。1. A toner for use in a dry development method, characterized in that a resin coating layer is formed on the surface of core particles made of at least a binder resin using at least a colorant and fine resin particles.
色剤と樹脂微粒子から成る混合粒子を付着させ、次に前
記樹脂微粒子を溶解させる溶剤で処理することにより、
少なくとも着色剤を含む樹脂被膜層を形成することを特
徴とするトナー製造方法。2. By attaching mixed particles consisting of at least a colorant and fine resin particles to the surface of the inner core particles, and then treating with a solvent that dissolves the fine resin particles,
A method for producing a toner, comprising forming a resin coating layer containing at least a colorant.
着色剤と樹脂微粒子から成る混合粒子の付着を、乾式で
行うことを特徴とする請求項２記載のトナー製造方法。3. The toner manufacturing method according to claim 2, wherein the adhesion of the mixed particles consisting of at least a colorant and fine resin particles to the surface of the inner core particles is carried out in a dry manner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3057154A JPH04291356A (en) | 1991-03-20 | 1991-03-20 | Toner and production of toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3057154A JPH04291356A (en) | 1991-03-20 | 1991-03-20 | Toner and production of toner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04291356A true JPH04291356A (en) | 1992-10-15 |
Family
ID=13047649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3057154A Pending JPH04291356A (en) | 1991-03-20 | 1991-03-20 | Toner and production of toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04291356A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010085495A (en) * | 2008-09-29 | 2010-04-15 | Sharp Corp | Method for manufacturing toner, toner, developer, developing apparatus, and image forming apparatus |
| JP2010169771A (en) * | 2009-01-20 | 2010-08-05 | Sharp Corp | Method of manufacturing toner, toner, developer, developing device and image forming apparatus |
-
1991
- 1991-03-20 JP JP3057154A patent/JPH04291356A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010085495A (en) * | 2008-09-29 | 2010-04-15 | Sharp Corp | Method for manufacturing toner, toner, developer, developing apparatus, and image forming apparatus |
| JP2010169771A (en) * | 2009-01-20 | 2010-08-05 | Sharp Corp | Method of manufacturing toner, toner, developer, developing device and image forming apparatus |
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| JPH04307554A (en) | Production of toner for electrophotography |