【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、負帯電性電荷交換制御剤及びそれを用いた
負帯電性現像剤組成物に関する。The present invention relates to a negatively chargeable charge exchange control agent and a negatively chargeable developer composition using the same.
更に詳しく言えば、この発明は電子写真、静電記録等に
おける電気的潜像や電気信号を可視化する負帯電性現像
剤組成物、特に帯電性、現像性、転写性に優れた負帯電
性現像剤組成物、及びその現像剤組成物に用いる負帯電
性電荷交換制御剤に関する。More specifically, the present invention relates to a negatively chargeable developer composition for visualizing an electric latent image or an electric signal in electrophotography, electrostatic recording, etc., and particularly, a negatively chargeable development excellent in chargeability, developability and transferability. The present invention relates to an agent composition and a negatively chargeable charge exchange control agent used in the developer composition.
電気的潜像や電気信号を可視化する現像剤（トナー）に
電荷を付与するための方法としては摩擦接触帯電法、イ
オン照射法、導電性を利用した静電誘導法、電荷注入法
等各種の方法が知られているが、最も利用しやすく、又
広く用いられているのが、摩擦接触帯電法である。Various methods such as a frictional contact charging method, an ion irradiation method, an electrostatic induction method utilizing conductivity, and a charge injection method are available as a method for applying an electric charge to a developer (toner) for visualizing an electric latent image or an electric signal. The method is known, but the most easily used and widely used is the friction contact charging method.
この摩擦接触帯電法には、トナーに電荷を付与するため
にトナーと逆極性に帯電するキヤリア粒子をトナーと混
合する二成分現像剤のほか、帯電ブレードや帯電ロール
等の帯電部材とトナーの摩擦帯電を利用したり、トナー
相互の摩擦帯電を利用する一成分現像剤も知られてい
る。In this friction contact charging method, in addition to a two-component developer in which carrier particles that are charged in the opposite polarity to the toner are mixed with the toner in order to impart an electric charge to the toner, friction between the charging member such as a charging blade or a charging roll and the toner A one-component developer that utilizes charging or triboelectric charging between toners is also known.
この様な接触帯電、摩擦帯電法でトナーを帯電する場
合、トナー側或いはキヤリア、ブレード等の電荷付与材
料側に、電子供与性の物質や電子吸引性の物質を添加し
て帯電性の制御を行う。摩擦帯電現像は複雑であり、そ
の機構は必ずしも明らかでないが、一般に電子供与性物
質は正に、電子吸引性物質は負に帯電する。When the toner is charged by such contact charging or friction charging method, the chargeability is controlled by adding an electron donating substance or an electron attracting substance to the toner side or the charge imparting material side such as the carrier or blade. To do. The triboelectrification development is complicated and its mechanism is not always clear, but generally, the electron-donating substance is positively charged and the electron-withdrawing substance is negatively charged.
従来、トナーの帯電制御を行うためには、 （ｉ） トナー中或いはトナー粒子表面に、染顔料、界
面活性剤、無機粉末等を添加混合する、 （ii） 結着樹脂として、−COOH、−CN、−Cl等のハロ
ゲン、−NO2、−NH2等の官能基を有する樹脂状物を用い
る等の手段が取られているが、トナー帯電性の経時的な
安定性、環境安定性の制御には成功しておらず、満足で
きるものではなかつた。Conventionally, in order to control the charging of the toner, (i) a dye or pigment, a surfactant, an inorganic powder or the like is added and mixed in the toner or on the surface of the toner particles, (ii) as a binder resin, -COOH,- CN, halogen -Cl etc., -NO2, but means such as a resin-like material having a functional group such as -NH2 have been taken, the toner charging property stability over time, the environmental stability The control was not successful and was not satisfactory.
また、無色もしくは淡色の、カラー現像に使用できる良
好な帯電制御剤も存在しなかつた。In addition, there is no good charge control agent which can be used for color development, which is colorless or light color.
従つて、本発明の目的は現像剤組成物における前述の問
題点を解消することのできる電荷交換制御剤を提供する
ことにある。Therefore, an object of the present invention is to provide a charge exchange control agent which can solve the above-mentioned problems in the developer composition.
また、本発明の目的は帯電の立上りが早く、帯電量及び
電荷分布の制御の容易な現像剤組成物を提供することに
ある。Another object of the present invention is to provide a developer composition in which charging rises quickly and the charge amount and charge distribution are easily controlled.
本発明の他の目的は、帯電性の環境安全性、経時安定性
にすぐれ、現像性、転写性が改善され、良好な画質の保
証とされる現像剤組成物を提供することにある。It is another object of the present invention to provide a developer composition which has excellent environmental safety of charging properties and stability over time, has improved developability and transferability, and guarantees good image quality.
本発明の更に他の目的は、帯電の立上りが早く、帯電
量、電荷分布の制御等が容易なカラー現像剤組成物を提
供することにある。Still another object of the present invention is to provide a color developer composition in which charging rises quickly and the amount of charge and charge distribution can be easily controlled.
本発明者等は鋭意検討を重ねた結果、ホウ素を含む有機
アニオン性成分（Ａ）と、前記有機アニオン性成分
（Ａ）より分子サイズの小さいカチオン性成分（Ｄ）と
から構成される有機ホウ素化合物（AD）を現像剤の電荷
交換制御剤として用いることにより、前記問題点が改善
克服できることを見出し、本発明を完了した。As a result of intensive studies by the present inventors, an organic boron composed of an organic anionic component (A) containing boron and a cationic component (D) having a smaller molecular size than the organic anionic component (A). The present invention has been completed by finding that the above problems can be improved and overcome by using the compound (AD) as a charge exchange control agent for a developer.
すなわち、ホウ素を含む有機アニオン性成分（Ａ）と、
前記有機アニオン性成分（Ａ）より分子サイズの小さい
カチオン性成分（Ｄ）とから構成される有機ホウ素化合
物（AD）からなることを特徴とする負帯電性電荷交換制
御剤、及びその負帯電性電荷交換制御剤を含有してなる
ことを特徴とする負帯電性現像剤組成物である。なお、
ここで分子サイズとはストークス半径で表わされるもの
である。That is, an organic anionic component (A) containing boron,
A negatively chargeable charge exchange control agent comprising an organic boron compound (AD) composed of a cationic component (D) having a smaller molecular size than the organic anionic component (A), and its negatively chargeable property A negatively chargeable developer composition comprising a charge exchange control agent. In addition,
Here, the molecular size is represented by the Stokes radius.
本発明で使用する有機ホウ素化合物（AD）の含ホウ素有
機アニオン性成分（Ａ）は一般式で示される。The boron-containing organic anionic component (A) of the organoboron compound (AD) used in the present invention has the general formula Indicated by.
式中、R1、R2、R3及びR4は互に独立した有機基であつ
て、それぞれは同一であつてもよく、またR1とR2及びR3
とR4はそれぞれが結合しているホウ素（Ｂ）と一緒にな
つて環を形成してもよい。In the formula, R1 , R2 , R3 and R4 are mutually independent organic groups, and each may be the same, and R1 , R2 and R3
And R4 may form a ring together with the boron (B) to which each is bonded.
このような含ホウ素有機アニオン性成分（Ａ）として
は、例えば以下のものが挙げられる。Examples of such a boron-containing organic anionic component (A) include the following.
式中、Ｒは有機基を表わす。 In the formula, R represents an organic group.
一方、カチオン性成分（Ｄ）は、Ｈ及びLi、Na、
Ｋ、Rb、Cs、Cu、Ag等のアルカリ金属カチオ
ン類、Be２、Mg２、Ca２、Zn２、Sr２、Cd
２、Ba２等のアルカリ土類金属カチオン類その他多
価金属カチオン類、アンモニウム、アルキルアンモニウ
ム、ピリジニウム、キノリニウム、イミダゾリニウム等
の有機アミン系カチオン類、スルホニウムカチオン類、
フオスホニウムカチオン類等から選択することが出来
る。On the other hand, the cationic component (D) is HAnd Li, Na,
K, Rb, Cs, Cu, AgAlkali metal cation such as
, BeTwo, MgTwo, CaTwo, ZnTwo, SrTwo, Cd
Two, BaTwoAlkaline earth metal cations such as
Valent metal cations, ammonium, alkylammonium
Aluminum, pyridinium, quinolinium, imidazolinium, etc.
Organic amine cations, sulfonium cations,
It can be selected from phosphonium cations, etc.
It
これら含ホウ素有機アニオン性成分（Ａ）とカチオン性
成分（Ｄ）との中和塩構造を有する有機ホウ素化合物
（AD）が、何故、電荷交換制御性に優れているのか、そ
の理由は必ずしも明らかではないが、（ｉ）ホウ素の電
子受容性、（ii）中和塩型の構造、（iii）有機官能基
の効果により、該化合物自体及び該化合物をポリマー等
に分散もしくは溶解した複合材料の電子及び／もしくは
イオンの交換、移動が促進されることによるものと推測
される。The reason why the organic boron compound (AD) having a neutralized salt structure of the boron-containing organic anionic component (A) and the cationic component (D) has excellent charge exchange controllability is always clear. However, due to (i) the electron accepting property of boron, (ii) the structure of a neutralized salt type, and (iii) the effect of an organic functional group, the compound itself and a composite material in which the compound is dispersed or dissolved in a polymer or the like It is presumed that this is due to the promotion of exchange and movement of electrons and / or ions.
また、前記一般式で示される含ホウ素有機アニオン性成分（Ａ）は有機官
能基中に、ベンゼン環、ナフタリン環等の芳香環を１つ
以上、好ましくは２つ以上有する場合に特に電荷交換性
の改善効果が大きい。In addition, the general formula The boron-containing organic anionic component (A) represented by the formula (A) has a particularly large effect of improving the charge exchange property when the organic functional group has at least one aromatic ring such as a benzene ring and a naphthalene ring, preferably at least two aromatic rings. .
本発明の負帯電電荷交換制御剤及び負帯電性現像剤組成
物は、前述の如く、ホウ素の電子受容性を活かした含ホ
ウ素有機アニオン成分を用い、カチオン成分として有機
アニオン性成分（Ａ）より分子サイズの小さいものを用
いた有機ホウ素化合物（AD）を電荷交換制御剤として用
いるところに主たる特徴がある。従つて主として、負帯
電性の制御及び負帯電性材料の電荷交換促進等に有効に
用いることが出来る。しかしながら使用法によつては正
帯電性材料にADで示される化合物に添加し、更に電荷交
換性を改善したり、更に材料の導電性の制御にも用いる
ことが出来る。As described above, the negatively-charged charge exchange control agent and the negatively-charged developer composition of the present invention use a boron-containing organic anion component that makes full use of the electron-accepting property of boron, and the organic anionic component (A) is used as the cation component. The main feature is that an organoboron compound (AD) having a small molecular size is used as a charge exchange control agent. Therefore, it can be effectively used mainly for controlling the negative charging property and promoting charge exchange of the negative charging material. However, depending on the method of use, it can be added to the compound represented by AD in a positively chargeable material to further improve the charge exchange property and further be used for controlling the conductivity of the material.
また、これら有機ホウ素化合物（AD）の帯電極性はそれ
ぞれ、化合物（AD）を形成する有機アニオン性成分Ａお
よびカチオン性成分Ｄの組成あるいは分子サイズによつ
て決まると考えられ、対カチオン性成分（Ｄ）の組成に
よつては、もしくは（Ｄ）の分子サイズが大きな場合に
は両者の中和塩型化合物である（AD）は、負帯電制御性
ではなく、むしろ正帯電制御性を発現しやすくなる。こ
のような場合は、（Ａ）成分よりも（Ｄ）成分によつて
その化合物の特徴が定まることになるが、本発明におい
ては、前述のような（Ｄ）成分として（Ａ）成分のホウ
素を含むアニオン性成分よりも分子サイズの小さいカチ
オン性成分使用することにより負帯電制御性を発現させ
るものである。The charge polarity of these organic boron compounds (AD) is considered to be determined by the composition or molecular size of the organic anionic component A and the cationic component D forming the compound (AD), respectively. Depending on the composition of D), or when the molecular size of (D) is large, both neutralizing salt type compounds (AD) exhibit positive charge controllability rather than negative charge controllability. It will be easier. In such a case, the characteristics of the compound are determined by the component (D) rather than the component (A), but in the present invention, the boron of the component (A) is used as the component (D) as described above. The negative charge controllability is exhibited by using a cationic component having a smaller molecular size than the anionic component containing a.
本発明の現像剤組成物に含有される有機ホウ素化合物
は、無色あるいは淡色のものが多く、しかも帯電制御性
に優れているので、黒色現像剤のほか、カラー現像剤の
ように着色をきらう材料の帯電制御に極めて良好に用い
ることができる。Many of the organoboron compounds contained in the developer composition of the present invention are colorless or light-colored and have excellent charge controllability. Therefore, in addition to a black developer, a material that is difficult to color like a color developer. It can be used very well for the charge control of.
本発明では使用する有機ホウ素化合物としては、融点も
しくは軟化点が約50℃以上の常温で固体状の物質を用い
ることが望ましい。しかしながら、現像剤の表面層のみ
を処理する場合等使用法によつては液状物質も使用でき
る。更に液状物質を無機微粉末、樹脂微粉末、多孔質物
質、ゲル化剤等に担持あるいは含浸させ、見かけ上固体
化して用いることもできる。As the organic boron compound used in the present invention, it is desirable to use a substance that is solid at room temperature and has a melting point or softening point of about 50 ° C. or higher. However, a liquid substance can also be used depending on the usage such as when only the surface layer of the developer is treated. Further, the liquid substance may be supported or impregnated with an inorganic fine powder, a resin fine powder, a porous substance, a gelling agent, etc., and apparently solidified before use.
有機ホウ素化合物を本発明の現像剤の帯電制御等のため
に電荷交換制御に用いる場合には、現像剤中約0.01重量
％から約10重量％、好ましくは約0.1重量％から約５重
量％添加することにより、極めて良好に現像剤の電気特
性を改善できる。When the organoboron compound is used for charge exchange control such as charge control of the developer of the present invention, about 0.01% by weight to about 10% by weight, preferably about 0.1% by weight to about 5% by weight is added to the developer. By doing so, the electrical characteristics of the developer can be improved very well.
現像剤への添加方法は、現像剤内部に分散もしくは溶解
させるだけでなく、現像剤表面層のみに選択的に添加し
たり、現像剤外部に添加混合してもよい。As a method of adding to the developer, not only dispersion or dissolution in the developer but also selective addition to the developer surface layer or addition to the outside of the developer may be carried out.
現像剤中に添加混合する場合、結着樹脂と共に溶解混
合、エマルジヨン混合、溶液混合等の方法で機械的に混
合するほか、本発明の有機ホウ素化合物存在下で、結着
樹脂を重合し、結着樹脂中に本発明の有機ホウ素化合物
を混合もしくは溶解させてもよい。この場合、本発明の
有機ホウ素化合物と結着樹脂、或いは現像剤中の他の添
加剤との間に化学結合が生じても良い。When added and mixed in the developer, in addition to mechanically mixing with a binder resin by a method such as dissolution mixing, emulsion mixing, and solution mixing, the binder resin is polymerized in the presence of the organoboron compound of the present invention to form a binder. The organoboron compound of the present invention may be mixed or dissolved in the resin. In this case, a chemical bond may occur between the organoboron compound of the present invention and the binder resin or other additive in the developer.
現像剤組成物の結着樹脂としては、従来周知のものを使
用することができる。例えばスチレン、クロルスチレ
ン、ビニルスチレン等のスチレン類；エチレン、プロピ
レン、ブチレン、イソブチレン等のモノオレフイン；酢
酸ビニル、プロピオン酸ビニル、安息香酸ビニル、酪酸
ビニル等のビニルエステル；アクリル酸メチル、アクリ
ル酸エチル、アクリル酸ブチル、アクリル酸ドデシル、
アクリル酸オクチル、アクリル酸フエニル、メタクリル
酸メチル、メタクリル酸エチル、メタクリル酸ブチル、
メタクリル酸ドデシル等のα−メチレン脂肪族モノカル
ボン酸のエステル；ビニルメチルエーテル、ビニルエチ
ルエーテル、ビニルブチルエーテル等のビニルエーテ
ル；ビニルメチルケトン、ビニルヘキシルケトン、ビニ
ルイソプロペニルケトン等のビニルケトン等の単独重合
体あるいは共重合体を例示することができ、特に代表的
な結着樹脂としては、ポリスチレン、スチレン−アクリ
ル酸アルキル共重合体、スチレン−メタクリル酸アルキ
ル共重合体、スチレン−アクリロニトリル共重合体、ス
チレン−ブタジエン共重合体、スチレン−無水マレイン
酸共重合体、ポリエレチン、ポリプロピレンを挙げるこ
とができる。As the binder resin of the developer composition, conventionally known ones can be used. For example, styrenes such as styrene, chlorostyrene and vinyl styrene; monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; methyl acrylate, ethyl acrylate. , Butyl acrylate, dodecyl acrylate,
Octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; homopolymers of vinyl ketone such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone. Alternatively, a copolymer can be exemplified, and as typical binder resins, polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Examples thereof include butadiene copolymer, styrene-maleic anhydride copolymer, polyeletin, and polypropylene.
更にポリエステル、ポリウレタン、エポキシ樹脂、シリ
コン樹脂、ポリアミド、変性ロジン、パラフイン、ワツ
クス類を挙げることができる。Further, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin, wax can be mentioned.
着色剤としては、カーボンブラツク、オイルブラツク、
黒鉛等の黒色系染顔料;C.I.Pigment Yellow1、同３、同
74、同97、同98等のアセト酢酸アリールアミド系モノア
ゾ黄顔料（フアストエロー系）;C.I.Pigment Yellow1
2、同13、同14等のアセト酢酸アリールアミド系ジスア
ゾ黄顔料;C.I.Solvent Yellow19、同77、同79、C.I.Dis
perse Yellow164等の黄染料;C.I.Pigment Red48、同49:
1、同53:1、同57:1、同81、同122、同５等の赤もしくは
紅顔料;C.I.Solvent Red52、同58、同８等の赤系染料;
C.I.Pigment Blue15:3 等銅フタロシアニン及びその誘
導体、変性体等の青系染顔料など、又有色もしくは無色
の昇華性染料等従来、印刷インクその他の着色用途で周
知の染顔料が使用できる。As a colorant, carbon black, oil black,
Black dyes and pigments such as graphite; CI Pigment Yellow 1, 3 and the same
74, 97, 98, etc. acetoacetic acid arylamide monoazo yellow pigments (Fast yellow); CI Pigment Yellow1
Acetoacetic acid arylamide disazo yellow pigments such as 2, 13, 13 and 14; CI Solvent Yellow 19, 77, 79, CIDis
Yellow dyes such as perse Yellow 164; CI Pigment Red 48, 49:
1, 53: 1, 57: 1, 81, 122, 5 and other red or red pigments; CISolvent Red52, 58, 8 and other red dyes;
CIPigment Blue15: 3, etc. Copper phthalocyanine and its derivatives, blue dyes and pigments such as modified products, and colored or colorless sublimable dyes, etc. Conventionally known dyes and pigments for coloring purposes such as printing inks can be used.
これら染顔料は単独でも２種以上混合して用いてもよ
い。勿論、体質顔料や白色顔料と混合し、色調を調整し
てもよい。更に又、結着材成分に対する分散性を改善す
るため、着色剤表面を界面活性剤、シランカツプリング
剤等のカツプリング剤、高分子材料で処理したり、高分
子染料や高分子グラフト顔料を用いてもよい。These dyes and pigments may be used alone or in combination of two or more. Of course, the color tone may be adjusted by mixing with an extender pigment or a white pigment. Furthermore, in order to improve the dispersibility in the binder component, the surface of the colorant is treated with a surfactant, a coupling agent such as a silane coupling agent, a polymer material, or a polymer dye or a polymer graft pigment is used. May be.
結着樹脂、着色剤は上述の例示したものに限定されるも
のでない。The binder resin and the colorant are not limited to those exemplified above.
また、本発明の現像剤組成物は、磁性材料（例えば、フ
エライト等）を内包せしめ磁性トナーとして用いること
もできる。The developer composition of the present invention can also be used as a magnetic toner by encapsulating a magnetic material (for example, ferrite).
その他、本発明の現像剤組成物には、他の添加剤として
従来公知の帯電制御剤を併用することもでき、また導電
性調整剤、金属酸化物等の無機物、補強充填剤、酸化防
止剤等をも使用することができる。In addition, in the developer composition of the present invention, a conventionally known charge control agent may be used in combination as another additive, and a conductivity adjusting agent, an inorganic substance such as a metal oxide, a reinforcing filler, an antioxidant. Etc. can also be used.
また、外添剤として、シリカ、カーボン、アルミナ、酸
化チタン、酸化亜鉛、樹脂微粉、酸化スズ、高級脂肪酸
及びその金属塩等の誘導体等従来公知のものが使用でき
る。As the external additive, conventionally known ones such as silica, carbon, alumina, titanium oxide, zinc oxide, resin fine powder, tin oxide, higher fatty acid and derivatives thereof such as metal salts can be used.
本発明の現像剤組成物は、混練粉砕法、スプレードライ
法、直接重合法等任意の方法で製造することができる。The developer composition of the present invention can be manufactured by any method such as a kneading and pulverizing method, a spray drying method, and a direct polymerization method.
現像剤組成物の粒度は、コールターカウンター法で測定
した平均粒度d50が１〜20μｍ、好ましくは５〜15μｍ
程度のものがよい。The particle size of the developer composition is such that the average particle size d50 measured by the Coulter counter method is 1 to 20 μm, preferably 5 to 15 μm.
Something good.
本発明の現像剤組成物は、キヤリアとトナーとを用い
る、いわゆる二成分現像剤としても、またキヤリアを用
いない、いわゆる一成分現像剤としても用いられる。The developer composition of the present invention can be used as a so-called two-component developer that uses a carrier and a toner, or as a so-called one-component developer that does not use a carrier.
本発明は、含ホウ素有機アニオン性成分と、前記有機ア
ニオン性成分（Ａ）より分子サイズの小さいカチオン性
成分（Ｄ）とから構成される有機ホウ素化合物（AD）か
らなる負帯電性電荷交換制御剤、及びその負帯電性電荷
交換制御剤を含有する負帯電性現像剤組成物を提供した
ものであり、本発明の負帯電性電荷交換制御剤を用いた
負帯電性現像剤組成物は帯電量及び電荷分布が容易に制
御でき、帯電の立上りが早く、現像性、転写性にすぐ
れ、またカラー現像剤としても好適である等の特長を有
する。The present invention provides a negatively chargeable charge exchange control comprising an organic boron compound (AD) composed of a boron-containing organic anionic component and a cationic component (D) having a smaller molecular size than the organic anionic component (A). The present invention provides a negatively chargeable developer composition containing an agent and a negatively chargeable charge exchange control agent thereof. The negatively chargeable developer composition using the negatively chargeable charge exchange control agent of the present invention is It has features that the amount and charge distribution can be easily controlled, the charge rises quickly, the developability and transferability are excellent, and it is also suitable as a color developer.
また本発明の電荷交換制御剤は、現像剤に添加して用い
るほか、トナーに電荷を付与するキヤリア、帯電ブレー
ド等の帯電部材、あるいはトナーと接触してトナーに電
気的影響を与える定着ロール、クリーニング部材、トナ
ーホツパーその他複写機プリンターの各構成部材等に添
加して用いることもできる。Further, the charge exchange control agent of the present invention is used by adding it to a developer, a carrier for imparting a charge to a toner, a charging member such as a charging blade, or a fixing roll for contacting the toner to electrically affect the toner, It can also be used by adding it to a cleaning member, a toner hopper and other components of a copying machine printer.
以下、実施例及び比較例を挙げて本発明の電荷交換制御
剤及び現像剤組成物を説明する。なお、下記の例中の部
は重量部を表わす。Hereinafter, the charge exchange control agent and the developer composition of the present invention will be described with reference to Examples and Comparative Examples. The parts in the following examples represent parts by weight.
比較例１ スチレン/n−ブチルメタクリレート共重合体（Tg65
℃、ｎ8,000、ｗ42,000） 100部 マゼンタ顔料（カーミン6B） ４部 を溶融混練、粉砕、分級し、平均粒径d5012μｍのト
ナーを得た。このトナーを平均粒径約100μｍの鉄粉キ
ヤリア（キヤリア／トナー重量比＝100/3）で混合し、
ブローオフトライボ法による平均帯電量、チヤージスペ
クトログラフ法による電荷分布等の帯電性の測定を、常
温常湿、高温高湿、低温低湿のそれぞれの環境で行つ
た。その結果を表１に示す。Comparative Example 1 Styrene / n-butyl methacrylate copolymer (Tg65
C., n8,000, w42,000) 100 parts 4 parts of magenta pigment (Carmine 6B) were melt-kneaded, pulverized and classified to obtain a toner having an average particle diameter d50 of 12 μm. This toner was mixed with an iron powder carrier (carrier / toner weight ratio = 100/3) with an average particle size of about 100 μm,
The chargeability such as the average charge amount by the blow-off tribo method and the charge distribution by the charge spectrograph method were measured under the conditions of normal temperature and normal humidity, high temperature and high humidity, and low temperature and low humidity. The results are shown in Table 1.
上表の如く、帯電量の環境による変動が大きく、又帯電
の立上り速度、逆極性トナー量も不満な状況であつた。 As shown in the above table, the amount of charge varied greatly depending on the environment, and the rising speed of charge and the amount of toner of opposite polarity were also unsatisfactory.
実施例１ スチレン/n−ブチルメタクリレート共重合体（比較例
１と同じ） 100部 マゼンタ顔料（比較例１と同じ） ４部 テトラフエニルホウ素ナトリウム １部 を比較例１と同様に、トナー化し（平均粒径d5012μ
ｍ）同様の方法で、帯電性を評価したところ表２の結果
を得た。Example 1 Styrene / n-butyl methacrylate copolymer (same as in Comparative Example 1) 100 parts Magenta pigment (same as in Comparative Example 1) 4 parts Sodium tetraphenylboron 1 part was converted into a toner in the same manner as in Comparative Example 1 ( Average particle size d50 12μ
m) When the charging property was evaluated by the same method, the results shown in Table 2 were obtained.
比較例と比べ、帯電量の環境安定性、帯電の立上り、電
荷分布のシヤープさが大幅に改善され、極めて良好な帯
電性を呈する様になつた。 Compared with the comparative example, the environmental stability of the charge amount, the rise of the charge, and the sharpness of the charge distribution were greatly improved, and an extremely good chargeability was exhibited.
このトナーに、更に疎水性シリカ微粉末0.7重量％、脂
肪酸金属塩0.8重量％を添加混合し、平均粒径約70μｍ
のフエライトキヤリアと組合せカラー現像剤とし、FX-2
300機（富士ゼロツクス社製）で5,000枚の連続複写テス
トを行つたところ、かぶりのない極めて鮮明なマゼンタ
色画像が安定に得られた。To this toner, 0.7% by weight of hydrophobic silica fine powder and 0.8% by weight of fatty acid metal salt were added and mixed, and the average particle size was about 70 μm.
FX-2 as a color developer combined with Ferrite Carrier of
When a continuous copying test of 5,000 sheets was performed with 300 machines (manufactured by Fuji Xerox Co., Ltd.), a very clear magenta image without fog was stably obtained.
実施例２ 実施例１のマゼンタ顔料４部を、それぞれシアン顔料
（銅フタロシアニン）４部、イエロー顔料（ジスアゾイ
エロー）４部、カーボンブラツク７部に置換し、同様の
方法で平均粒径d5012μｍのシアントナー、イエロー
トナー、黒色トナーを得た。Example 2 4 parts of magenta pigment of Example 1 were replaced with 4 parts of cyan pigment (copper phthalocyanine), 4 parts of yellow pigment (disazo yellow) and 7 parts of carbon black, respectively, and average particle diameter d50 12 μm was measured by the same method. Cyan toner, yellow toner and black toner were obtained.
これら３色のトナーについて、夫々実施例１と同様の方
法で帯電性評価を行つた。シアンの場合には全環境で、
−13μc/gから−17μc/g、イエローの場合には−12μc/
gから−15μc/g、黒色の場合には−14μc/g〜−17μc/g
と、環境に対して安定であり、かつ帯電の立上り、逆極
性トナー量も問題がなかつた。The charging properties of these three color toners were evaluated in the same manner as in Example 1. In the case of cyan, in all environments,
-13 μc / g to -17 μc / g, -12 μc / g for yellow
g to −15 μc / g, black −14 μc / g to −17 μc / g
As a result, it is stable to the environment, has a rise in charging, and has no problem with the amount of toner of opposite polarity.
実施例３ 架橋フエノール樹脂、補強剤及びカーボンブラツクから
なる電気抵抗率約1011Ωcmの表面層を有する直径20mmの
現像ロールと、現像ロール上にトナーを供給する導電性
ラバーからなるトナー供給ロールと、シリコンラバーと
補強剤及び帯電制御剤からなる表面層を有する、トナー
層厚を規制しかつトナーに電荷を付与するブレードとを
備え、トナー供給ロールにより主として機械的にトナー
が現像ロールに供給され、その後現像ロールに圧接した
ブレードによりトナーを帯電し、かつ現像ロール上ほゞ
単層のトナー層を形成して鏡像力で静電潜像部に搬送さ
れ、現像が行われる構成の一成分現像装置を組込んだ改
造FX-2300複写機（富士ゼロックス社製）で、トナーと
して実施例１のマゼンタトナーに疎水性シリカ微粉末1.
0重量％を外添混合したものをキヤリアを用いることな
く使用し、5000枚の連続複写テストを行ったところ、実
施例１と同様に極めて良好な画像を得た。Example 3 A developing roll having a diameter of 20 mm having a surface layer having an electric resistivity of about 1011 Ωcm, which is composed of a crosslinked phenolic resin, a reinforcing agent and a carbon black, and a toner supplying roll made of a conductive rubber for supplying the toner onto the developing roll. And a blade having a surface layer composed of a silicone rubber, a reinforcing agent and a charge control agent, for controlling the toner layer thickness and imparting an electric charge to the toner, and the toner is mainly mechanically supplied to the developing roll by the toner supply roll. After that, the blade is pressed against the developing roll to charge the toner, and a toner layer of almost a single layer is formed on the developing roll, and the toner layer is conveyed to the electrostatic latent image portion by the image force, and development is performed. A modified FX-2300 copier (manufactured by Fuji Xerox Co., Ltd.) incorporating the apparatus, the magenta toner of Example 1 was used as the toner, and the hydrophobic silica fine powder 1.
Using 0% by weight of externally added mixture without using a carrier and conducting a continuous copying test on 5,000 sheets, an extremely good image was obtained as in Example 1.
実施例４ ポリエステル樹脂（Tg60℃、クロロホルム不溶ゲル
分率15％） 100部 カーボンブラック 10部 ジカテコールボレートのテトラメチルアンモニウム塩
１部 を溶融混練、粉砕、分級し、d50９μｍのトナーを試
作し、粒径約80μｍのフエライトキヤリアと混合し（キ
ヤリア／トナー重量比＝100/3）、実施例１と同様の帯
電性評価を行つた。Example 4 Polyester resin (Tg 60 ° C., chloroform insoluble gel fraction 15%) 100 parts Carbon black 10 parts Tetramethylammonium salt of dicatecholborate 1 part Melt kneading, pulverizing and classifying to produce a toner of d50 9 μm Then, it was mixed with a ferrite carrier having a particle size of about 80 μm (carrier / toner weight ratio = 100/3), and the same charging property evaluation as in Example 1 was performed.
ブローオフ帯電量は、全環境で−17μc/gから−21μc/g
と安定であり、かつ帯電の立上りも早く、逆極性トナー
もほとんどみられなかつた。このトナーに0.7重量％の
疎水性シリカ微粉末、0.7重量％メチルメタクリレート
系樹脂微粉末を外添混合し、FX-2300複写機で10,000枚
の繰返しコピーテストを行つたところ極めて良好な画質
が得られた。Blow-off charge is -17 μc / g to -21 μc / g in all environments
The toner was stable, the charging started quickly, and almost no reverse polarity toner was seen. When 0.7% by weight of hydrophobic silica fine powder and 0.7% by weight methylmethacrylate resin fine powder were externally added and mixed to this toner and a repeated copy test of 10,000 sheets was conducted with the FX-2300 copying machine, extremely good image quality was obtained. Was given.
実施例５ スチレン／ブチルアクリレート共重合体（Tg60℃、
ｎ4,000、ｗ15,000） 50部 スチレン／ブチルアクリレート共重合体（Tg60℃、
ｎ16万、ｗ43万） 50部 低分子量ポリプロピレン ５部 γ−Fe2O3微粉末 100部 ジカテコールボレートのテトラメチルアンモニウム塩
２部 を溶融混練、粉砕、分級し、平均粒径d5012μｍのセ
ピア色の磁性トナーを得た。このトナーに、疎水化処理
アルミナ微粉末0.4重量％、酸化スズ微粉末0.1重量％を
外添混合し、磁性−成分現像機を実装した改造FX-2830
機で5,000枚の連続複写テストを行つたところ極めて鮮
明なセピア画像が得られた。Example 5 Styrene / butyl acrylate copolymer (Tg 60 ° C.,
n4,000, w15,000) 50 parts Styrene / butyl acrylate copolymer (Tg60 ℃,
n 160,000, w 430,000) 50 parts Low molecular weight polypropylene 5 parts γ-Fe2 O3 fine powder 100 parts Dicatecholborate tetramethylammonium salt 2 parts Melt kneading, crushing and classifying, sepia with average particle size d50 12 μm A colored magnetic toner was obtained. A modified FX-2830 in which 0.4% by weight of hydrophobized alumina fine powder and 0.1% by weight of tin oxide fine powder are externally added to this toner and a magnetic-component developing machine is mounted.
When a continuous copying test of 5,000 sheets was conducted with the machine, a very clear sepia image was obtained.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203507AJPH07104620B2 (en) | 1985-09-17 | 1985-09-17 | Charge exchange control agent and developer composition |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203507AJPH07104620B2 (en) | 1985-09-17 | 1985-09-17 | Charge exchange control agent and developer composition |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33592098ADivisionJP3019090B2 (en) | 1998-11-26 | 1998-11-26 | Charge exchange control agent and developer composition |
| JP33592198ADivisionJP3287400B2 (en) | 1985-09-17 | 1998-11-26 | Method for producing negatively chargeable developer composition |
| Publication Number | Publication Date |
|---|---|
| JPS6263941A JPS6263941A (en) | 1987-03-20 |
| JPH07104620B2true JPH07104620B2 (en) | 1995-11-13 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60203507AExpired - LifetimeJPH07104620B2 (en) | 1985-09-17 | 1985-09-17 | Charge exchange control agent and developer composition |
| Country | Link |
|---|---|
| JP (1) | JPH07104620B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01306861A (en)* | 1988-06-03 | 1989-12-11 | Japan Carlit Co Ltd:The | Toner for electrophotography |
| JPH02223958A (en)* | 1989-02-27 | 1990-09-06 | Fuji Xerox Co Ltd | Developer for electrophotography |
| JPH05224465A (en)* | 1992-02-14 | 1993-09-03 | Tomoegawa Paper Co Ltd | Dry developer for electrophotography |
| EP1059568B1 (en) | 1999-06-07 | 2007-02-14 | Canon Kabushiki Kaisha | Toner and image forming method |
| JP2007334163A (en) | 2006-06-16 | 2007-12-27 | Sharp Corp | Electrophotographic toner and method for producing electrophotographic toner |
| Publication number | Publication date |
|---|---|
| JPS6263941A (en) | 1987-03-20 |
| Publication | Publication Date | Title |
|---|---|---|
| US4767688A (en) | Charge controlling method and developers containing a charge-exchange control agent comprising organic boron compound | |
| JP3575061B2 (en) | Electrostatographic developer and image forming method using the same | |
| JPH07104620B2 (en) | Charge exchange control agent and developer composition | |
| JPH0727278B2 (en) | Non-magnetic one-component developer composition | |
| JP3287400B2 (en) | Method for producing negatively chargeable developer composition | |
| JP3214499B2 (en) | Image forming method | |
| JPS59102252A (en) | Toner for electrostatic charged image development | |
| JPH0810362B2 (en) | Developer for electrostatic image | |
| JP3019090B2 (en) | Charge exchange control agent and developer composition | |
| JP3633722B2 (en) | Positively chargeable charge control agent and toner for developing electrostatic image | |
| JP3475493B2 (en) | Liquid developer for electrostatography and image forming method using the same | |
| JPS63226661A (en) | Developer for electrostatic charge image | |
| JP3273387B2 (en) | Friction charging member for electrostatic image development | |
| JPH0740148B2 (en) | Positively charging non-magnetic toner for electrostatic image development | |
| JPS5848065A (en) | Method for developing electrostatic charge image | |
| JPH0257302B2 (en) | ||
| JPH0810361B2 (en) | Toner composition for developing electrostatic image | |
| JPH0810363B2 (en) | Developer for electrostatic image | |
| JPH0369107B2 (en) | ||
| JP2518227B2 (en) | Dry toner | |
| JPS63226664A (en) | Developer for electrostatic charge image | |
| JPH0383071A (en) | Toner for developing electrostatic charge image | |
| JPH0731421B2 (en) | Developer composition | |
| JPS63231357A (en) | Toner composition | |
| JPH05232739A (en) | Toner for development of electrostatic charge image |
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |