JP4136215B2 - Charge control agent for developing electrostatic image comprising polyaniline derivative transition metal complex, toner and charge imparting material using the charge control agent - Google Patents

Description

【０００７】
（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄は各々独立して水素原子、カルボキシル基を有していても良いアルキル基、アルコキシ基、アリール基、アミノ基又はカルボキシル基を表し、ｎは４以上の整数を表す。）
【０００８】
上記、Ｒ₁〜Ｒ₄においてカルボキシル基を有していても良いアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基等の炭素数１〜４の低級アルキル基が挙げられ、また、アルコキシ基としては、メトキシ基、エトキシ基等の低級アルコキシ基、アリール基としてはフェニル基等が挙げられる。ｎは４以上、好ましくは４〜５００である。
【０００９】
上記一般式で示される本発明金属錯体の製法は特に限定されるものではなく、一般的に採用されている電極酸化法を用いることができるが、電極酸化法以外の方法では、例えばアニリン誘導体を酸性条件下で過硫酸アンモニウム等の酸化剤によりポリアニリン誘導体を合成した後、室温下でＮ，Ｎ−ジメチルホルムアミド等の極性有機溶媒に溶解させ遷移金属のハロゲン化物と反応させることにより容易に得る事が出来る。
【００１０】
帯電性能に優れた本発明金属錯体からなる静電荷像現像用帯電制御剤（以下、帯電制御剤と称することもある）はトナーに有用であり、次に、本発明金属錯体を静電荷像現像用トナーに用いる場合について説明する。
本発明の静電荷像現像用トナーは、少なくとも該帯電制御剤、樹脂及び着色剤を含有する。
【００１１】
トナーに使用する樹脂成分としては、通常使用されている公知の樹脂が種々使用できる。具体的樹脂として、例えば、ポリスチレン、ポリクロロスチレン、スチレン−ブタジエン共重合体等のスチレン系樹脂；スチレン−アクリル酸エステル共重合体、スチレン−メタクリル酸エステル共重合体等のスチレンアクリル系共重合樹脂；ポリエステル系樹脂；エポキシ系樹脂、及びこれらの混合樹脂等が挙げられる。
【００１２】
トナーに使用する着色剤としては、公知の有機顔料、無機顔料及び染料から適宜選択して使用される。例えば、Ｃ．Ｉ．ピグメントレッド４８：１、Ｃ．Ｉ．ピグメントレッド５７：１、Ｃ．Ｉ．ピグメントレッド１２２、Ｃ．Ｉ．ピグメントイエロー１７、Ｃ．Ｉ．ピグメントイエロー９７、Ｃ．Ｉ．ピグメントイエロー１２、Ｃ．Ｉ．ピグメントブルー１５：１、Ｃ．Ｉ．ピグメントブルー１５：３、カーボンブラック、ニグロシン染料、金属錯塩染料、金属錯塩染料の誘導体、及びこれらの混合物等が挙げられる。
【００１３】
トナー中における本発明金属錯体の含有率は、樹脂１００重量部に対して０．１〜２０重量部が好ましく、より好ましくは０．１〜１０重量部である。
また、前記一般式で示される本発明金属錯体をトナーに含有させるに際し、これらの錯体を一種類でも二種類以上を併用して使用しても構わない。
【００１４】
本発明のトナーにおいては、上述した本発明金属錯体成分以外に必要に応じて他の帯電制御剤、更にはワックス、各種添加剤などを添加してもよい。他の帯電制御剤としては公知の化合物が使用され、例えば、ヒドロキシカルボン酸の金属錯体、アゾ化合物の金属錯体、ナフトール系化合物、ナフトール系化合物の金属化合物、ニグロシン系染料、第４級アンモニウム塩及びこれらの混合物が挙げられる。
【００１５】
ワックスとしては、離型性を有するものであればいかなるものも使用可能である。具体的には、カルナバワックス、ライスワックス等の植物系ワックス、アルキル変成シリコン等の固形シリコン系ワックス、ステアリン酸アミド等のアミド系ワックス、高級脂肪族アルコール系ワックス、高級脂肪酸エステル系ワックス、ポリエチレン、ポリプロピレン等の合成炭化水素系ワックス及びこれらの混合物が挙げられる。
【００１６】
本発明の静電荷像現像用トナーには、流動性や現像性を制御する為に公知の外添剤を添加しても良い。外添剤としては、シリカ、アルミナ、チタニア、等の各種無機酸化物粒子（必要に応じて疎水化処理する）ビニル系重合体粒子等が使用できる。外添剤の添加量は、トナー粒子に対して０．０５〜５重量部の範囲が好ましい。
【００１７】
本発明の静電荷像現像用トナーは、公知の現像法により現像する事ができる。例えば、カスケード法、磁気ブラシ法、マイクロトーニング法等の２成分現像法、導電性、絶縁性１成分現像法、非磁性１成分現像法等のいずれにも使用できる。
【００１８】
次に、本発明金属錯体を電荷付与材に用いる場合について説明する。電荷付与材は、本発明金属錯体を少なくともその母材表面の１部に有する。
ここで、電荷付与材とは、キャリア、現像スリーブ、層形成ブレード等の現像工程あるいは現像に先立つてトナーと接触して、トナーに対し現像のために必要な電荷を付与し、或いは電荷を補助的に付与し得る材料又は部材を総称するものであり、母材は該材料又は部材を意味する。
【００１９】
本発明金属錯体を、必要に応じてバインダー樹脂とともに、溶媒あるいは分散媒中に溶解または分散させて得た塗布液を電荷付与材の母材にディッピング、スプレー法、ハケ塗り等によって塗布するか、あるいは母材がキャリア粒子状である場合は、これを上記塗布液に浸漬混合したのち乾燥する方法、あるいは母材との直接混合物の流動化ベッドによる被覆の方法により、母材上に本発明金属錯体を含有する被覆層を形成させれば本発明の電荷付与材が得られる。また、バインダー樹脂と該金属錯体を直接溶融混練し、母材上に押し出しラミネートして電荷付与材を得ても良い。さらに成形可能な樹脂中に該金属錯体を含有させ、これをキャリア粒子、現像スリーブあるいは層形成ブレードの形状に成形して電荷付与材としても良い。
【００２０】
バインダー樹脂、或いは成形樹脂としては、通常使用されているものから適宜選ぶことが出来、例えば、ポリスチレン、ポリアクリル酸エステル、ポリメタクリル酸エステル、イソプレン又はブタジエン等のゴム系樹脂、ポリエステル、ポリウレタン、ポリアミド、エポキシ樹脂等が挙げられる。
【００２１】
本発明のポリアニリン誘導体の遷移金属錯体は、その優れた帯電特性を利用して上記静電荷像現像用帯電制御剤、並びにそれを用いたトナー及び静電荷像現像用トナーに電荷を付与する電荷付与材の用途に使用されるが、その他に例えば有機ＥＬ素子など各種電気・光学素子の電極材料、各種一次電池、二次電池の電極材料、電子写真感光体の導電性調節材料等としても有用である。
【００２２】
以下、本発明を合成例、実施例により更に詳細に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものでない。
なお、下記実施例中、単に「部」とあるは、「重量部」を意味する。
合成例
オルト−トルイジン８．５６ｇを１規定の塩酸水溶液１Ｌ(リットル)と４００ｍｌのエタノールからなる溶液に添加し、得られた溶液を−５℃に冷却した。この溶液中に過硫酸アンモニウム１．８ｇを添加した。−５℃で５時間反応を継続した後、室温にもどし反応溶液からの析出物を濾過し、オルト−トルイジンを繰り返し単位とする化合物を得た。この化合物を水洗した後、１規定の水酸化ナトリウム水溶液４００ｍｌで２時間処理し、その後、濾過、水洗を実施し６．５ｇの反応生成物を得た。
【００２３】
上記反応生成物６．５ｇと塩化バナジウム（III）４．７ｇを５００ｍｌのジメチルホルムアミドに添加し室温で錯体を形成させた。反応生成物を濾過、乾燥したところ、５．９ｇのポリオルト−トルイジンの塩化バナジウム錯体を得る事ができた。 この様にして得られた錯体の赤外吸収スペクトル測定(IR)及び元素分析を行った結果を以下に示す。
IR(KBr, cm^-1) : 3785, 3693, 3374, 1570, 1483, 1379, 1257, 1211, 1152, 1104, 999, 941, 805
元素分析 実測値； H:5.67, C:59.04, N:10.11, Cl:13.71%
【００２４】
実施例−１
平均粒径１０μｍのスチレンアクリル共重合樹脂（日本カーバイト（株）製；品番G-10）１００重量部と上記合成例により合成した錯体１重量部をコーヒーミルに入れ、１分間攪拌混合させた。この様にして調整したサンプル１重量部を鉄粉キャリア９９重量部と混合し、吸引ブロー法により、混合時間に対する帯電量を測定した。また錯体を添加しないスチレンアクリル共重合樹脂単独についても同様な測定を行った。その結果を以下の表１に示す。
【００２５】
【表１】

【００２６】
この結果、樹脂単独では帯電量は混合時間と共に大きく増大しているのに対して、錯体を添加したサンプルでは増大幅が非常に小さく、十分帯電性が制御されていることが判る。
【００２７】
実施例−２
ポリエステル系樹脂（三菱レイヨン社製 ＦＣ−０２３） １００部
カーボンブラック （三菱化学社製 ＭＡ−１００） ４部
合成例の錯体 ２部
上記材料を配合混練りし、粉砕分級して平均粒子径８．５ミクロンの黒色トナーを得た。このトナー５部と平均粒子径約９０ミクロンのフェライトキャリア（アクリルコート）９５部とを混合、攪拌して現像剤を作製した。次いでこの現像剤を負帯電性ＯＰＣ（積層系）を感光体とする複写機で実写したところ、鮮明なコピーが得られた。
【００２８】
実施例−３
ポリエステル系樹脂の代わりに、スチレン(St)／アクリル酸ブチル(BA)共重合樹脂（Ｓｔ／ＢＡ＝７／３、Ｓｐ＝約１４０℃）を使用する以外は、実施例−２と同様にして現像剤を調製し、実写したところ、実施例−２と同様に良好なコピーが得られた。
【００２９】
【発明の効果】
本発明の新規な金属錯体から成る静電荷像現像用帯電制御剤を用いた静電荷像現像用トナー及び電荷付与材は、安全性に優れ、かつ帯電性が良好で高品質な静電荷像現像用トナーおよび電荷付与材である。[0001]
BACKGROUND OF THE INVENTION
The present invention is a transition metal complex of the port Rianirin derivatives, for developing an electrostatic image charge control agent used in an electrophotographic copying machine or a laser printer or the like, as well as the toner used for developing the toner and electrostatic image using the same The present invention relates to a charge imparting material that imparts a charge.
[0002]
[Prior art]
The developer used in an electrophotographic copying machine or the like is once adhered to an image carrier such as a photoreceptor on which an electrostatic charge image is formed in the development process, and then transferred from the photoreceptor to a transfer paper in the transfer process. Then, it is fixed on the copy paper surface in a fixing step. At that time, as a developer for developing an electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toners are known.
[0003]
One of the important characteristics required of toner is chargeability. In particular, contact with the carrier or the wall of the developer tank produces an appropriate level of positive or negative charge, and the charge level is continuous. It is required to be almost stable over time even in use or in harsh environments.
The chargeability can be imparted to the toner with a resin or a colorant itself. However, it is difficult to obtain sufficient chargeability, and positive chargeability has been proposed as a material that imparts chargeability to a toner (charge control agent). There are known methods in which a nigrosine dye, a quaternary ammonium salt, a negatively charged metal-containing monoazo dye, a salicylic acid metal complex, a copper phthalocyanine pigment, and the like are contained in a toner.
[0004]
[Problems to be solved by the invention]
However, these conventional charge control agents have some problems in terms of charge imparting effect and other characteristics required for the toner. One of them is toner safety. As conventional charge control agents, particularly negative charge control agents, metal-containing dye types containing heavy metals such as chromium occupy most of them because of the high charge level to be applied. It is preferable to avoid the use of a metal such as chromium, which is questionable for safety, as a component of a material used in a place very close to the human body as a toner. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel charge control agent that does not contain a metal such as chromium that has a question of safety, a toner using the same, and a charge imparting material.
[0005]
[Means for Solving the Problems]
In order to overcome the drawbacks of the above charge control agents, the present inventors have conducted intensive studies on compounds that are safer and excellent in charge imparting performance, and as a result, found that metal complex compounds having a specific structure are useful. The present invention has been reached.
That is, the gist of the present invention, the general electrostatic image developing charge control agent consisting of transition metal complexes of reportage Rianirin derivative represented by formula, and the charging control agent The toner and charge with It exists in the grant material.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The transition metal complex of a polyaniline derivative (hereinafter abbreviated as the present metal complex) which is a charge control agent for developing an electrostatic image in the present invention is a compound represented by the following general formula.
[Chemical 2]

[0007]
(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group optionally having a carboxyl group, an alkoxy group, an aryl group, an amino group or a carboxyl group ; Represents an integer of 4 or more .)
[0008]
Examples of the alkyl group that may have a carboxyl group in R _{1 to} R ₄ include lower alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxy group include lower alkoxy groups such as methoxy group and ethoxy group, and examples of the aryl group include phenyl group . n is 4 or more, preferably 4 to 500.
[0009]
The process of the present invention the metal complex represented by the general formula is not particularly limited, may be used an electrode oxidation method which is commonly employed, in the method other than the electrode oxidation method, For example A aniline The derivative is synthesized by synthesizing a polyaniline derivative with an oxidizing agent such as ammonium persulfate under acidic conditions and then dissolved in a polar organic solvent such as N, N-dimethylformamide at room temperature and reacted with a transition metal halide. I can do it.
[0010]
A charge control agent for developing an electrostatic image comprising the metal complex of the present invention having excellent charging performance (hereinafter sometimes referred to as a charge control agent) is useful for a toner. Next, the metal complex of the present invention is developed for electrostatic image development. A case where the toner is used for toner will be described.
The toner for developing an electrostatic image of the present invention contains at least the charge control agent, a resin and a colorant.
[0011]
As the resin component used in the toner, various commonly used known resins can be used. Specific resins include, for example, styrene resins such as polystyrene, polychlorostyrene, and styrene-butadiene copolymers; styrene acrylic copolymers such as styrene-acrylate copolymers and styrene-methacrylate copolymers. Polyester resins; epoxy resins, and mixed resins thereof.
[0012]
The colorant used for the toner is appropriately selected from known organic pigments, inorganic pigments and dyes. For example, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, carbon black, nigrosine dye, metal complex dye, metal complex dye derivatives, and mixtures thereof.
[0013]
The content of the metal complex of the present invention in the toner is preferably from 0.1 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the resin.
In addition, when the metal complex of the present invention represented by the above general formula is contained in the toner, these complexes may be used alone or in combination of two or more.
[0014]
In the toner of the present invention, in addition to the above-described metal complex component of the present invention, other charge control agents, waxes, various additives and the like may be added as necessary. As other charge control agents, known compounds are used, for example, metal complexes of hydroxycarboxylic acid, metal complexes of azo compounds, naphthol compounds, metal compounds of naphthol compounds, nigrosine dyes, quaternary ammonium salts and These mixtures are mentioned.
[0015]
Any wax can be used as long as it has releasability. Specifically, plant waxes such as carnauba wax and rice wax, solid silicon waxes such as alkyl-modified silicon, amide waxes such as stearamide, higher aliphatic alcohol waxes, higher fatty acid ester waxes, polyethylene, Examples include synthetic hydrocarbon waxes such as polypropylene and mixtures thereof.
[0016]
A known external additive may be added to the toner for developing an electrostatic charge image of the present invention in order to control fluidity and developability. As the external additive, various inorganic oxide particles such as silica, alumina, titania, etc. (hydrophobized if necessary) vinyl polymer particles can be used. The addition amount of the external additive is preferably in the range of 0.05 to 5 parts by weight with respect to the toner particles.
[0017]
The toner for developing an electrostatic charge image of the present invention can be developed by a known development method. For example, it can be used for any of a two-component development method such as a cascade method, a magnetic brush method and a microtoning method, a conductive and insulating one-component development method, a non-magnetic one-component development method, and the like.
[0018]
Next, the case where the metal complex of the present invention is used as a charge imparting material will be described. The charge imparting material has the metal complex of the present invention at least at a part of the surface of the base material.
Here, the charge imparting material refers to a carrier, a developing sleeve, a layer forming blade, or the like, which is in contact with the toner prior to the development process or development, and imparts a charge necessary for development to the toner or assists the charge. The material or member that can be applied in a general manner is a generic term, and the base material means the material or member.
[0019]
The metal complex of the present invention is applied to the base material of the charge imparting material by dipping, spraying, brushing, or the like, by dissolving or dispersing the metal complex together with a binder resin, if necessary, in a solvent or dispersion medium, Alternatively, in the case where the base material is in the form of carrier particles, the metal of the present invention is applied onto the base material by a method of immersing and mixing the base material in the coating solution and then a method of coating with a fluidized bed of a direct mixture with the base material. If the coating layer containing a complex is formed, the charge-imparting material of the present invention can be obtained. Alternatively, the charge imparting material may be obtained by directly melt-kneading the binder resin and the metal complex and extruding and laminating them on the base material. Further, the metal complex may be contained in a moldable resin, and this may be molded into the shape of carrier particles, a developing sleeve or a layer forming blade to form a charge imparting material.
[0020]
The binder resin or molding resin can be appropriately selected from those usually used. For example, rubber resins such as polystyrene, polyacrylate ester, polymethacrylate ester, isoprene or butadiene, polyester, polyurethane, polyamide And epoxy resins.
[0021]
The transition metal complex of the polyaniline derivative of the present invention utilizes the excellent charging characteristics to provide the charge control agent for developing the electrostatic image, the toner using the same, and the charge imparting charge to the toner and the toner for developing the electrostatic image. It is also used as an electrode material for various electric / optical elements such as organic EL elements, various primary batteries, secondary battery electrode materials, and electroconductive photoreceptor conductivity adjusting materials. is there.
[0022]
EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
In the following examples, “parts” simply means “parts by weight”.
Synthesis Example Ortho-toluidine (8.56 g) was added to a solution composed of 1 L (liter) of 1N aqueous hydrochloric acid and 400 ml of ethanol, and the resulting solution was cooled to -5 ° C. 1.8 g of ammonium persulfate was added to this solution. After continuing the reaction at −5 ° C. for 5 hours, the reaction solution was returned to room temperature, and the precipitate from the reaction solution was filtered to obtain a compound having ortho-toluidine as a repeating unit. After washing this compound with water, it was treated with 400 ml of a 1N aqueous sodium hydroxide solution for 2 hours, and then filtered and washed with water to obtain 6.5 g of a reaction product.
[0023]
6.5 g of the above reaction product and 4.7 g of vanadium (III) chloride were added to 500 ml of dimethylformamide to form a complex at room temperature. When the reaction product was filtered and dried, 5.9 g of a polyortho-toluidine vanadium chloride complex could be obtained. The results of infrared absorption spectrum measurement (IR) and elemental analysis of the complex thus obtained are shown below.
IR (KBr, cm ^-1 ): 3785, 3693, 3374, 1570, 1483, 1379, 1257, 1211, 1152, 1104, 999, 941, 805
Elemental analysis Measured value; H: 5.67, C: 59.04, N: 10.11, Cl: 13.71%
[0024]
Example-1
100 parts by weight of a styrene acrylic copolymer resin (Nippon Carbite Corporation; product number G-10) having an average particle size of 10 μm and 1 part by weight of the complex synthesized by the above synthesis example were placed in a coffee mill and stirred and mixed for 1 minute. . 1 part by weight of the sample thus prepared was mixed with 99 parts by weight of an iron powder carrier, and the charge amount with respect to the mixing time was measured by a suction blow method. Moreover, the same measurement was performed also about the styrene acrylic copolymer resin single which does not add a complex. The results are shown in Table 1 below.
[0025]
[Table 1]

[0026]
As a result, the charge amount of the resin alone greatly increases with the mixing time, whereas the increase width is very small in the sample to which the complex is added, indicating that the chargeability is sufficiently controlled.
[0027]
Example-2
Polyester-based resin (FC-023 manufactured by Mitsubishi Rayon Co., Ltd.) 100 parts carbon black (MA-100 manufactured by Mitsubishi Chemical Corporation) 4 parts Complex of synthesis example 2 parts The above materials are blended and kneaded, pulverized and classified, and the average particle size is 8. A 5 micron black toner was obtained. 5 parts of this toner and 95 parts of ferrite carrier (acrylic coat) having an average particle diameter of about 90 microns were mixed and stirred to prepare a developer. Next, when the developer was photographed on a copying machine using a negatively chargeable OPC (lamination system) as a photoconductor, a clear copy was obtained.
[0028]
Example-3
Example 2 was used except that styrene (St) / butyl acrylate (BA) copolymer resin (St / BA = 7/3, Sp = about 140 ° C.) was used instead of the polyester resin. When a developer was prepared and photographed, a good copy was obtained as in Example-2.
[0029]
【The invention's effect】
The electrostatic image developing toner and the charge imparting material using the electrostatic charge image developing charge control agent comprising the novel metal complex of the present invention are excellent in safety, chargeability and high quality electrostatic image development. Toner and charge imparting material.

Claims (3)

A charge control agent for developing an electrostatic image, comprising a transition metal complex of a polyaniline derivative represented by the following general formula.

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group optionally having a carboxyl group, an alkoxy group, an aryl group, an amino group or a carboxyl group ; Represents an integer of 4 or more . ) An electrostatic image developing toner comprising a resin, a colorant, and the electrostatic charge image developing charge control agent according to claim 1 . An electrostatic charge image developing charge imparting material comprising the electrostatic charge image developing charge control agent according to claim 1 on at least a part of a surface of a base material.