JPH0815914A - Toner for developing electrostatic charge image and electrostatic charge image developer - Google Patents
Toner for developing electrostatic charge image and electrostatic charge image developerInfo
- Publication number
- JPH0815914A JPH0815914A JP6169057A JP16905794A JPH0815914A JP H0815914 A JPH0815914 A JP H0815914A JP 6169057 A JP6169057 A JP 6169057A JP 16905794 A JP16905794 A JP 16905794A JP H0815914 A JPH0815914 A JP H0815914A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- electrostatic charge
- charge image
- group
- developer
- 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
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- Developing Agents For Electrophotography (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、電子写真法により形成
される静電荷像の現像に有用なトナーおよび現像剤に関
する。FIELD OF THE INVENTION The present invention relates to toners and developers useful for developing electrostatic images formed by electrophotography.
【0002】[0002]
【従来の技術】電子写真法により、感光体を一様に帯電
させた後、原図に基づいた光像を前記感光体に露光し、
光照射部分の電荷を削減あるいは滅少させて感光体上に
原図に対応する静電荷像を形成させ、この静電荷像をキ
ャリア粒子とトナー粒子からなる、いわゆる二成分系現
像剤により顕像化して複写物を得る方法は、一般に、良
く知られている。2. Description of the Related Art A photoconductor is uniformly charged by an electrophotographic method, and then a photoimage based on an original image is exposed on the photoconductor.
An electrostatic charge image corresponding to the original image is formed on the photoconductor by reducing or reducing the charge in the light irradiation area, and this electrostatic charge image is visualized by a so-called two-component developer consisting of carrier particles and toner particles. The method of obtaining a copy by using the method is generally well known.
【0003】この二成分系現像剤は、比較的大きなキャ
リア粒子表面上に微小なトナー粒子が、両粒子の摩擦に
より発生した電気力により保持されており、かかる現像
剤を静電潜像に接近させると、静電潜像が形成する電界
のトナー粒子に対する潜像方向への吸引力が、トナー粒
子とキャリア粒子間の結合に打ち勝って、トナー粒子の
み静電潜像上に吸引付着されて静電潜像が可視化され
る。In this two-component developer, fine toner particles are held on the surface of a relatively large carrier particle by an electric force generated by friction between the particles, and the developer is brought close to an electrostatic latent image. Then, the attractive force of the electric field formed by the electrostatic latent image on the toner particles in the direction of the latent image overcomes the bond between the toner particles and the carrier particles, and only the toner particles are attracted and adhered onto the electrostatic latent image and statically absorbed. The latent image is visualized.
【0004】そして、このトナーに要求される特性とし
ては、帯電性、吸湿性、経時安定性、流動性等が挙げら
れるが、これらの特性のうち、帯電性、吸湿性、経時安
定性はトナー中に含有される荷電制御剤によって大きな
影響を受ける。従来、トナー用荷電制御剤としては、負
荷電制御剤として、含Cr、Co錯体(特開昭61−2
17061号公報、特開昭63−216061号公
報)、ニトロフミン酸類(特開昭50−133838号
公報)、フタロシアニン顔料(特開昭60−25856
0号公報)等が、また、正荷電制御剤としてニグロシン
系染料塩(特開昭56−22441号公報)、各種四級
アンモニウム塩(特開昭59−136747号公報)、
イミダゾール誘導体(特開平3−72373号公報)等
が知られているが、これらの制御剤を用いたトナーは帯
電性、吸湿性、経時安定性が充分でなく制御剤自身のバ
インダーとの相溶性も十分とは言い難い。例えば正荷電
制御剤として公知のニグロシン染料を用いたトナーは、
それ自体は比較的高い帯電力を有するが、基材(紙)に
対する付着力が劣り、また、それ自体が黒色であるため
適用範囲が限定された色相のトナーにしか使用できない
といった欠点がある。また、四級アンモニウム塩を用い
たトナーのなかには極めて吸湿性が高く、その結果、経
時安定性に欠け反復画像形成能が劣るという欠点がある
ものもある。The properties required for this toner include chargeability, hygroscopicity, stability over time, fluidity, and the like. Among these properties, the chargeability, hygroscopicity, and stability over time are toners. It is greatly affected by the charge control agent contained therein. Conventionally, as a charge control agent for toner, as a negative charge control agent, a Cr-containing or Co complex (Japanese Patent Application Laid-Open No. 61-2)
17061, JP-A-63-216061), nitrohumic acids (JP-A-50-133838), phthalocyanine pigments (JP-A-60-25856).
No. 0) and the like, and as a positive charge control agent, a nigrosine dye salt (JP-A-56-22441), various quaternary ammonium salts (JP-A-59-136747),
Although imidazole derivatives (Japanese Patent Laid-Open No. 3-72373) and the like are known, toners using these control agents have insufficient chargeability, hygroscopicity, and stability over time, and are compatible with the binder of the control agent itself. Is hard to say. For example, a toner using a known nigrosine dye as a positive charge control agent is
Although it itself has relatively high electric power, it has a drawback that it has poor adhesion to a substrate (paper) and can be used only for toner of a hue whose application range is limited because it is black in itself. Further, some of the toners using the quaternary ammonium salt have a very high hygroscopicity, and as a result, there is a defect that they lack stability over time and are inferior in repetitive image forming ability.
【0005】[0005]
【発明が解決しようとする課題】本発明は、上記事情に
鑑みてなされたもので、吸湿性が少なく経時安定性を有
し、その結果、反復画像形成性を有する等、環境性およ
び耐久性に優れた静電荷像現像用トナーおよび現像剤を
得ることを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has low hygroscopicity and stability over time, and as a result, has repetitive image forming properties, and is environmentally friendly and durable. It is an object of the present invention to obtain a toner and a developer for developing an electrostatic image which are excellent in
【0006】[0006]
【課題を解決するための手段】本発明によれば、樹脂お
よび着色剤を主成分とする静電荷像用トナーにおいて、
下記一般式(I)で示されるニッケルジチオラート錯体
を含有することを特徴とする静電荷像現像用トナーが提
供される。According to the present invention, in an electrostatic charge image toner containing a resin and a colorant as main components,
Provided is a toner for developing an electrostatic charge image, which comprises a nickel dithiolate complex represented by the following general formula (I).
【化1】 また、本発明によれば、上記のトナーとキャリアを含有
することを特徴とする静電荷像現像剤が提供される。Embedded image Further, according to the present invention, there is provided an electrostatic image developer containing the above-mentioned toner and carrier.
【0007】以下に本発明を詳細に説明する。本発明の
トナーに使用されるニッケルジチオラート錯体は、ま
ず、下記一般式(II)で示されるジチオラートナトリウ
ム塩と硝酸ニッケルを有機溶媒中で加熱還流して合成さ
れる中性ニッケル錯体を、ヨウ素酸化して、対応するオ
ニウム塩によって結晶化した後、カラムクロマトグラ
フ、あるいは再結晶によって得ることができる。The present invention will be described in detail below. The nickel dithiolate complex used in the toner of the present invention is a neutral nickel complex synthesized by heating and refluxing sodium dithiolate salt represented by the following general formula (II) and nickel nitrate in an organic solvent, It can be obtained by column chromatography or recrystallization after iodine oxidation and crystallization with the corresponding onium salt.
【化2】 (式中、R、R’は一般式(I)の化合物の場合と同じ
である) 一般式(I)における置換基RおよびR’の具体例とし
ては、メチル基、エチル基、n−プロピル基、i−プロ
ピル基、n−ブチル基、t−ブチル基、n−ヘキシル
基、シクロヘキシル基、n−オクチル基、n−ドデシル
基などのアルキル基、置換または無置換のフェニル基、
ベンジル基、アルコキシ基およびニトロ基、ニトリル
基、エステル基、メチルチオ基、フェニルチオ基、フッ
素原子、塩素原子、臭素原子、ヨウ素原子等を挙げるこ
とができる。また、フェニル基、ベンジル基に置換する
置換基としては、メチル基、エチル基、n−プロピル
基、n−ブチル基、t−ブチル基などのアルキル基、メ
トキシ基、エトキシ基、n−プロポキシ基、t−ブトキ
シ基などのアルコキシ基、ニトロ基、シアノ基、ハロゲ
ン原子ならびにこれらのアルキル基、アルコキシ基、ニ
トロ基、シアノ基、ハロゲン原子の一置換、二置換、三
置換体などが挙げられる。複素環としては、ピリジン、
ピロール、ピリミジン、イミダゾール、キノリン等が挙
げられる。また、カウンターのカチオン種X(+イオ
ン)としては、水素イオンのほか、アルカリ金属イオ
ン、種々の四級アンモニウム塩、ホスホニウム塩などが
挙げられる。Embedded image (In the formula, R and R ′ are the same as in the case of the compound of the general formula (I)) Specific examples of the substituents R and R ′ in the general formula (I) include a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group and other alkyl groups, substituted or unsubstituted phenyl group,
Examples thereof include benzyl group, alkoxy group and nitro group, nitrile group, ester group, methylthio group, phenylthio group, fluorine atom, chlorine atom, bromine atom, iodine atom and the like. Further, as the substituent for substituting the phenyl group and the benzyl group, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a t-butyl group, a methoxy group, an ethoxy group, an n-propoxy group. , An alkoxy group such as a t-butoxy group, a nitro group, a cyano group, a halogen atom, and an alkyl group, an alkoxy group, a nitro group, a cyano group, a mono-substituted, di-substituted or tri-substituted product of a halogen atom. As the heterocycle, pyridine,
Examples include pyrrole, pyrimidine, imidazole, quinoline and the like. Examples of the cation species X (+ ion) of the counter include hydrogen ions, alkali metal ions, various quaternary ammonium salts, phosphonium salts, and the like.
【0008】本発明の静電像現像用トナーおよび現像剤
は前記一般式(I)で示されるニッケルジチオラート錯
体を含有することから、繰り返しの連続複写を行っても
画像品質が低下せず、また温度や湿度等の環境が変化し
ても帯電特性の変動が少ないものである。Since the electrostatic image developing toner and developer of the present invention contain the nickel dithiolate complex represented by the general formula (I), the image quality does not deteriorate even when repeated continuous copying is performed. In addition, even if the environment such as temperature and humidity changes, the charging characteristic does not change much.
【0009】以下に本発明の負荷電荷制御剤であるニッ
ケルジチオラート錯体の具体例を挙けるが、本発明はこ
れらに限定されるものではない。Specific examples of the nickel dithiolate complex which is the load charge control agent of the present invention are listed below, but the present invention is not limited thereto.
【0010】[0010]
【表1−(1)】 [Table 1- (1)]
【0011】[0011]
【表1−(2)】 [Table 1- (2)]
【0012】[0012]
【表1−(3)】 [Table 1- (3)]
【0013】[0013]
【表1−(4)】 [Table 1- (4)]
【0014】次に本発明で用いることができる樹脂とし
ては、ポリスチレン樹脂、アクリル樹脂、スチレン−メ
タアクリル共重合体、エポキシ樹脂などが挙げられる。
また、着色剤としては、例えば、Kayaset Ye
llow E−L2R(日本化薬製、C.I.Pigm
ent Yellow 142)、Kayaset R
ed A−G(同、C.I.Solvent 17
9)、Kayaset Blue FR(同、C.I.
Solvent Blue 105)およびカーボンブ
ラック等が挙げられるが、これらに限定されるものでは
ない。本発明の前記化合物(1)の含有量は、樹脂成分
100重量部に対して0.5部〜30重量部、好ましく
は1〜10重量部である。0.5重量部以下では十分な
オフセット防止効果の点で問題を生じやすく、また、3
0重量部以上ではゲル化することがあるので好ましくな
い。また、ポリプロピレン、ポリエチレン、カルナウバ
ワックス等の定着性向上剤、疎水性シリカ、アルミナ、
硫化モリブデン、酸化チタン等の流動性向上剤、ステア
リン酸亜鉛、ステアリン酸マグネシウム、ラウリン酸亜
鉛等のクリーニング向上剤などの各種添加剤を加えるこ
とができる。キャリアとしては、鉄、ニッケル、コバル
ト、フェライト等の磁性材料が好ましく用いられる。Next, examples of resins that can be used in the present invention include polystyrene resins, acrylic resins, styrene-methacrylic copolymers, and epoxy resins.
Further, as the coloring agent, for example, Kayase Ye
low E-L2R (manufactured by Nippon Kayaku, CI Pigm
ent Yellow 142), Kayaset R
ed A-G (the same, CI Solvent 17
9), Kayase Blue FR (ibid., C.I.
Solvent Blue 105), carbon black, and the like, but are not limited thereto. The content of the compound (1) of the present invention is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin component. If it is less than 0.5 part by weight, a problem tends to occur in terms of sufficient offset prevention effect.
If it is 0 parts by weight or more, gelation may occur, which is not preferable. Further, fixability improvers such as polypropylene, polyethylene, carnauba wax, hydrophobic silica, alumina,
Various additives such as fluidity improvers such as molybdenum sulfide and titanium oxide, and cleaning improvers such as zinc stearate, magnesium stearate and zinc laurate can be added. As the carrier, magnetic materials such as iron, nickel, cobalt and ferrite are preferably used.
【0015】本発明のトナーは、上記の樹脂、着色剤、
電荷制御剤を加熱ニーダー、三本ロール等の加熱混合処
理可能な装置により、溶融、混練後、冷却固化したもの
をジェットミル、ボールミル等の粉砕機により1〜50
μmの粒径に粉砕することにより得ることができる。他
の方法としては、樹脂を溶解し、これに電荷制御剤を添
加し、撹拌処理の後、水に流し込み再沈殿させてから濾
別、乾燥してボールミルなどの粉砕機を使って1〜50
μmの粒径に粉砕することにより得ることができる。The toner of the present invention comprises the above resin, colorant,
The charge control agent is melted and kneaded by a device capable of heating and mixing such as a heating kneader and three rolls, and then cooled and solidified, and then the amount is 1 to 50 by a pulverizer such as a jet mill and a ball mill.
It can be obtained by pulverizing to a particle size of μm. As another method, a resin is dissolved, a charge control agent is added thereto, and after stirring treatment, it is poured into water for reprecipitation, followed by filtration and drying, and then using a pulverizer such as a ball mill for 1 to 50.
It can be obtained by pulverizing to a particle size of μm.
【0016】[0016]
【実施例】以下に本発明を実施例により具体的に説明す
るが、本発明はこれらに限定されるものではない。な
お、実施例中の部は重量部を表す。下記各処方を配合
し、熱ロールで混練後、粉砕、分級して平均粒径8.0
μmの実施例および比較例のトナーを作成した。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In addition, the part in an Example represents a weight part. Each of the following formulations is blended, kneaded on a hot roll, pulverized and classified to have an average particle size of 8.0.
The toners of Examples and Comparative Examples having a size of μm were prepared.
【0017】実施例1 〈トナーの処方〉 スチレン−メタクリレート樹脂 100部 ニッケルジチオラート錯体(例示化合物2) 5部 カーボンブラック 10部Example 1 <Toner formulation> Styrene-methacrylate resin 100 parts Nickel dithiolate complex (Exemplified compound 2) 5 parts Carbon black 10 parts
【0018】実施例2 〈トナーの処方〉 ポリエステル樹脂 100部 ニッケルジチオラート錯体(例示化合物6) 8部 カーボンブラック 10部Example 2 <Toner formulation> Polyester resin 100 parts Nickel dithiolate complex (Exemplified compound 6) 8 parts Carbon black 10 parts
【0019】実施例3 〈トナーの処方〉 エポキシ樹脂 100部 ニッケルジチオラート錯体(例示化合物12) 10部 カーボンブラック 10部Example 3 <Toner formulation> Epoxy resin 100 parts Nickel dithiolate complex (Exemplified compound 12) 10 parts Carbon black 10 parts
【0020】比較例 〈トナーの処方〉 スチレン−メタクリレート樹脂 100部 含金属モノアゾ染料 (保土谷化学社製 スピロンブラックTOH) 10部 カーボンブラック 10部Comparative Example <Prescription of Toner> Styrene-methacrylate resin 100 parts Metal-containing monoazo dye (Spirone Black TOH manufactured by Hodogaya Chemical Co., Ltd.) 10 parts Carbon black 10 parts
【0021】上記で得たトナーをEFV200〜300
メッシュ鉄粉(日本鉄粉社製)と混合し、撹拌してトナ
ー濃度7%の静電荷像現像剤をそれぞれ作成し、以下の
評価を行った。The toner obtained above is EFV200-300.
It was mixed with mesh iron powder (manufactured by Nippon Iron Powder Co., Ltd.) and stirred to prepare an electrostatic charge image developer having a toner concentration of 7%, and the following evaluations were performed.
【0022】1.耐久性試験 耐久性は、電子写真複写機(リコー製 FT4060)
で連続20000枚複写を行い、初期および複写後の現
像剤のトナー帯電量(μC/g)を測定し、画像評価を
行った。1. Durability test Durability is measured by an electrophotographic copying machine (FT4060 made by Ricoh).
Then, 20,000 sheets were continuously copied, and the toner charge amount (μC / g) of the developer at the initial stage and after the copying was measured to evaluate the image.
【0023】2.環境性試験 環境性については、トナーおよびキャリアを高湿条件
(30℃、湿度90%の雰囲気中に2時間)および低湿
条件(10℃、湿度30%の雰囲気中に2時間)で調湿
後、上記と同様にトナーとキャリアを混合、撹拌してそ
れぞれについて現像剤を作成し、現像剤のトナー帯電量
(μc/g)を測定し、高湿時と低湿時の変動率を評価
した。評価結果を表2に示す。2. Environmental test As for environmental test, after toner and carrier are conditioned under high humidity condition (30 ° C, 90% humidity for 2 hours) and low humidity condition (10 ° C, 30% humidity for 2 hours). The toner and the carrier were mixed and agitated in the same manner as above to prepare a developer for each, and the toner charge amount (μc / g) of the developer was measured, and the fluctuation rate at high humidity and low humidity was evaluated. Table 2 shows the evaluation results.
【0024】[0024]
【表2】 * :10000枚複写時点 **:地汚れの発生が著しい[Table 2] *: At the time of copying 10000 sheets **: Significant scumming occurs
【0025】[0025]
【発明の効果】本発明のニッケルジチオラート錯体を含
有した静電荷像現像用トナーおよび現像剤は、環境によ
る帯電特性の変動が少なく、また、繰り返しの連続複写
を行っても画像品質が低下しない。INDUSTRIAL APPLICABILITY The toner and developer for developing an electrostatic image containing the nickel dithiolate complex of the present invention have little fluctuation in charging characteristics due to the environment, and the image quality does not deteriorate even after repeated continuous copying. .
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松本 冬彦 東京都大田区中馬込1丁目3番6号 株式 会社リコー内 (72)発明者 丸山 勝次 東京都大田区中馬込1丁目3番6号 株式 会社リコー内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Fuyuhiko Matsumoto 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Katsuji Maruyama 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh
Claims (2)
像用トナーにおいて、下記一般式(I)で示されるニッ
ケルジチオラート錯体を含有することを特徴とする静電
荷像現像用トナー。 【化1】 1. A toner for developing an electrostatic charge image, which comprises a nickel dithiolate complex represented by the following general formula (I) in a toner for an electrostatic charge image containing a resin and a colorant as main components. Embedded image
することを特徴とする静電荷像現像剤。2. An electrostatic image developer containing the toner according to claim 1 and a carrier.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6169057A JPH0815914A (en) | 1994-06-28 | 1994-06-28 | Toner for developing electrostatic charge image and electrostatic charge image developer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6169057A JPH0815914A (en) | 1994-06-28 | 1994-06-28 | Toner for developing electrostatic charge image and electrostatic charge image developer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0815914A true JPH0815914A (en) | 1996-01-19 |
Family
ID=15879548
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6169057A Pending JPH0815914A (en) | 1994-06-28 | 1994-06-28 | Toner for developing electrostatic charge image and electrostatic charge image developer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0815914A (en) |
-
1994
- 1994-06-28 JP JP6169057A patent/JPH0815914A/en active Pending
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