JPS62245267A - Electrostatic charge image developing agent - Google Patents
Electrostatic charge image developing agentInfo
- Publication number
- JPS62245267A JPS62245267A JP61089378A JP8937886A JPS62245267A JP S62245267 A JPS62245267 A JP S62245267A JP 61089378 A JP61089378 A JP 61089378A JP 8937886 A JP8937886 A JP 8937886A JP S62245267 A JPS62245267 A JP S62245267A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- particle size
- image
- particles
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
１亙豆ｊ
本発明は電子写真、静電記録、静電印刷等に於ける静電
荷像を現像するための現像剤に関し、更に詳しくは、直
接又は間接電子写真現像方法に於いて、均一に強く正に
帯電し、負静電荷像を可視化して又は正静電荷像を反転
現像により可視化して、高品質な画像を与える正荷電性
現像剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., and more specifically, to a developer for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a positively charged developer which is uniformly and strongly positively charged, and which visualizes a negative electrostatic charge image or visualizes a positive electrostatic charge image by reversal development to give a high quality image.
ＩＬＩ！
近年、電子写真複写機等の画像形成装置によって形成さ
れた画像の画質に対する要求は著じるしいものがある。ILI! In recent years, there has been a significant demand for the quality of images formed by image forming apparatuses such as electrophotographic copying machines.
このため、形成される可視画像の画質に重大な影響を及
ぼすトナー粒径分布に関する提案も多くなされており、
例えば特開昭５４−１３４６３６号公報、特開昭５４−
７２０５４号公報、特開昭５８−１２９４３７号公報、
特開昭５９−４５４５２号公報、特開昭５９−３３４５
９号公報には、いずれも小粒径のトナー分布をもつ現像
剤が提案されている。For this reason, many proposals have been made regarding toner particle size distribution, which has a significant effect on the quality of the visible image formed.
For example, JP-A-54-134636, JP-A-54-
No. 72054, Japanese Unexamined Patent Publication No. 129437/1983,
JP-A-59-45452, JP-A-59-3345
No. 9 proposes a developer having a toner distribution with a small particle size.
しかしながら、これらの提案におけるトナーは小粒径で
あるために、トナー中に通常含有される電萄制御剤の分
散不良の影響を受は易く、これに伴い、トナー間の荷電
分布の不均一性により画像濃度の変動、かぶり等が生じ
るようになり、更に、トナー飛散も生じ易い傾向がある
。However, since the toners in these proposals have small particle sizes, they are easily affected by poor dispersion of the charge control agent normally contained in the toners, and as a result, non-uniform charge distribution among the toners occurs. This tends to cause fluctuations in image density, fogging, etc., and also tends to cause toner scattering.
このような荷電分布の不均一性は、ディジタル信号によ
って形成された潜像を現像する際には、特に問題となる
。この場合、現像特性を示す潜像電位−画像濃度（Ｖｓ
Ｉ）ｐ）曲線の傾きが小さくなること、及びその傾
きが変動することに起因して、画像濃度が低下し、解像
力、シャープネスも低い不良画像しか得られず、また、
ベタ黒画像や線画像の所謂チリチリ画像（本来均一にト
ナーが乗るべき黒画像に、微小な点状の白、又は灰色の
画像抜けのある画＊）が生じ易い傾向がある。Such non-uniformity in charge distribution poses a particular problem when developing a latent image formed by a digital signal. In this case, latent image potential - image density (Vs
I)p) Due to the decrease in the slope of the curve and the fluctuation of the slope, only defective images with low image density and low resolution and sharpness are obtained, and
There is a tendency for solid black images and line images to produce so-called dusty images (images* in which minute white or gray spots are missing in a black image where toner should originally be uniformly applied).
画像信号がディジタル信号の場合、潜像は一定電位のド
ツトが集って形成され、ベタ部、ハーフトーン部および
ライト部は各々ドツトの密度をかえることによって表現
されている。従ってどの部分も、ｚ値の場合は基本的に
ほぼ同じ電位の静電潜像から形成されることになる。When the image signal is a digital signal, the latent image is formed by a collection of dots with a constant potential, and solid areas, halftone areas, and light areas are each expressed by changing the density of the dots. Therefore, any part is basically formed from an electrostatic latent image having approximately the same potential in terms of z value.
この方法においても、最近更に画質向上の要求が高まり
、前述した白黒２値のディザ法から、３値あるいは４値
による多値ディザ法を用いて階調再現性の向上を図る必
要が生じてきた。この多値ディザ法は、ハイライト部に
発生し易い偽輪郭を除去する場合、あるいは中間調とラ
イン画像の混在した画像を同時に再現する際１階調性を
低下させずに、１画素のマトリックスサイズを小さくし
て解像度を向上させる場合にも必須な技術である。Even in this method, there has been an increasing demand for improved image quality recently, and it has become necessary to improve gradation reproducibility by using a 3-value or 4-value multi-value dither method instead of the black-and-white binary dither method mentioned above. . This multi-level dithering method can be used to remove false contours that tend to occur in highlight areas, or to simultaneously reproduce images with a mixture of halftones and line images. This technology is also essential when reducing size and improving resolution.
この多値ディザ法におけるディザマトリックスの概念を
第１図（ａ）及び（ｂ）を参照しながら説明する。第１
図（ａ）は２×２の３値のディザマトリックスであり、
領域Ｓ□、Ｓ２．Ｓ、はそれぞれ白、グレイ、黒の３値
の濃度レベルを表わしている。また、第１図（ｂ）は２
×２の４値のディザマトリックスであり、領域Ｓｉ、Ｓ
２．Ｓ、。The concept of a dither matrix in this multilevel dither method will be explained with reference to FIGS. 1(a) and 1(b). 1st
Figure (a) is a 2×2 ternary dither matrix,
Area S□, S2. S represents the three-value density level of white, gray, and black, respectively. Also, Fig. 1(b) shows 2
×2 four-valued dither matrix, with areas Si, S
2. S.
Ｓ４はそれぞれ白、薄いグレイ、濃いグレイ、黒の４値
の濃度レベルを表わしている。ドツトサイズは例えば１
６ドツト／腸腸である。S4 represents four density levels of white, light gray, dark gray, and black, respectively. For example, the dot size is 1
6 dots/intestine.
第２図（ａ）、（ｂ）及び第３図（ａ）、（ｂ）は、光
走査型の電子写真プリンタにおいて、３値記録を行なう
場合の露光強度分布（第２図（ａ）、第３図（ａ））と
、それに対応する静電潜像の電位分布（第２図（ｂ）、
第３図（ｂ））とを表わしたものである。第２図（ａ）
及び第３図（ａ）の破線は多値の潜像を形成するための
光ビームを出力させる信号出力を表わしたもので、第２
図（ａ）はレーザ出力を制御する輝度変調によって第１
図（ａ）の５２に相当するグレイＯレベル（以後「Ｍレ
ベル」とする）と、Ｓ３に相当する黒レベル（以後「Ｈ
レベル」とする）とを得る方式である。これは、例えば
ＭレベルはＨレベルの１／２のレーザ出力で得るもので
ある。一方、第３図（ａ）はレーザ出力時間を制御する
パルス巾変調によってＭレベルとＨレベルとを得る方式
である。これは、例えばＭレベルはＨレベルの１／２の
パルス巾とすることによって得られる。Figures 2 (a), (b) and 3 (a), (b) show the exposure intensity distribution (Figure 2 (a), Figure 3 (a)) and the corresponding potential distribution of the electrostatic latent image (Figure 2 (b),
FIG. 3(b)) is shown. Figure 2(a)
The broken line in FIG. 3(a) represents the signal output for outputting a light beam for forming a multivalued latent image.
Figure (a) shows that the first
The gray O level (hereinafter referred to as "M level") corresponding to 52 in Figure (a), and the black level (hereinafter referred to as "H level") corresponding to S3.
level). This means that, for example, the M level can be obtained with a laser output that is 1/2 that of the H level. On the other hand, FIG. 3(a) shows a method for obtaining the M level and H level by pulse width modulation that controls the laser output time. This can be obtained, for example, by setting the M level to 1/2 the pulse width of the H level.
第２図（ａ）及び第３図（ａ）の露光強度分布を有する
光ビームによる潜像の電位分布は、それぞれ第２図（ｂ
）及び第３図（ｂ）のようになるが、特に第３図（ｂ）
のパルス巾変調によるＭレベルの潜像コントラストは、
潜像のＭＴＦ（変調伝達関数）の低下により、Ｈレベル
に比べて小さくなる傾向がある。従って、このＭレベル
の現像後の画像濃度は、輝度変調による第２図（ｂ）の
Ｍレベルの画像濃度とほぼ同じグレイとなる。The potential distributions of the latent images created by the light beams having the exposure intensity distributions shown in FIGS. 2(a) and 3(a) are shown in FIG. 2(b), respectively.
) and Figure 3(b), especially Figure 3(b)
The M-level latent image contrast by pulse width modulation is
Due to a decrease in the MTF (modulation transfer function) of the latent image, it tends to be smaller than the H level. Therefore, the image density of this M level after development becomes almost the same gray as the image density of the M level shown in FIG. 2(b) due to brightness modulation.
第４図は多値の潜像を現像する場合の現像特性（Ｖｓ−
Ｄｐ特性）を示しており、第２図（ｂ）及び第３図（ｂ
）のＭレベル及びＨレベルの潜像（それぞれの電位コン
トラストを［相］、■で表わす）を再現するには、特に
Ｈレベルが十分高くとれない場合は、比較的ガンマ（潜
像電位Ｖｓに対する画像濃度り、の傾き）が大きいｖｓ
−Ｉ）ｐ特性（図中実線■で示す）が要求される。しか
しながら。Figure 4 shows the development characteristics (Vs-
2(b) and 3(b).
) to reproduce M-level and H-level latent images (respective potential contrasts are represented by [phase] and Image density (slope) is large vs.
-I) p characteristics (indicated by solid line ■ in the figure) are required. however.
従来の小粒径トナーないし現像剤を使用すると。When using conventional small particle size toner or developer.
多くの場合実線■で示すような現像特性を示す傾向があ
り、その場合１画像部度、シャープネスの低下等の種々
の問題を生ずる。In many cases, there is a tendency to exhibit development characteristics as shown by the solid line (■), and in this case, various problems such as a decrease in sharpness occur in one image area.
また、ディジタルなドツトの密度により表現されている
潜像を現像する際は、従来のアナログ潜像に比べてこの
Ｖｓ−Ｄ、曲線の精密な制御が必要とされる。１つはデ
ィジタル潜像を現像するにはＶｓ−Ｄ、曲線の傾き（ガ
ンマ）を従来よりは大きくする必要があり、さらにこの
傾きが変動しないように制御する必要がある。しかし、
従来の荷電制御剤を用いた小粒径トナーに生じる電荷の
不均一性は、ｖｓ−Ｄ、曲線の傾きを大きくするのに障
害となり、又この傾きが変動し易い状態を生じさせる。Furthermore, when developing a latent image expressed by the density of digital dots, more precise control of the Vs-D and curve is required than in conventional analog latent images. One is that in order to develop a digital latent image, it is necessary to make Vs-D and the slope (gamma) of the curve larger than in the past, and it is also necessary to control this slope so that it does not fluctuate. but,
The non-uniformity of charge that occurs in small particle size toners using conventional charge control agents becomes an obstacle to increasing the slope of the vs-D curve, and also causes the slope to fluctuate easily.
従来の小粒径トナーに生じる電荷の不均一性は、前述し
たようにベタ黒部及び、線画のチリチリ画像を生じさせ
るが、この電荷の不均一性が画質に与える影響について
、第５図を参照しつつ説明する。As mentioned above, the non-uniformity of charge that occurs in conventional small particle size toners causes solid black areas and scratchy line images, but see Figure 5 for the effect that this non-uniformity of charge has on image quality. I will explain as I go along.
第５図は荷電制御剤を小粒径トナー中に分散させた場合
の、トナー粒子１側当たりのトリポ電荷と、その電荷を
もつトナー粒子の個数との関係（トナーのトリボ電荷分
布）を示すグラフである。第５図を参照して、曲線Ａは
、従来の荷電制御剤をトナー中に分散させた従来のトナ
ーにおける電荷分布を示す、従来の荷電制御剤は小粒径
トナーに対する分散性が悪く、又それ自体の荷電制御性
も低いため、従来の小粒径トナーは１曲線Ａに示すよう
なブロードな荷電分布を示す。Figure 5 shows the relationship between the tribocharge per side of a toner particle and the number of toner particles with that charge (toner tribocharge distribution) when a charge control agent is dispersed in a small particle size toner. It is a graph. Referring to FIG. 5, curve A shows the charge distribution in a conventional toner in which a conventional charge control agent is dispersed in the toner. Since the charge controllability of the toner itself is low, the conventional small particle size toner exhibits a broad charge distribution as shown in curve 1 A.
曲線Ａ下部の斜線部分■は、トリボ電荷の特に低いトナ
ーに対応する部分であり、この部分のトナーは、現像部
電界において、現像方向に対し負になる潜像面（通常現
像においては潜像電位の低い部分、反転現像においては
潜像電位の高い部分）にも付着し易いトナーであり、従
ってかぶりの原因となるトナーである。The shaded area ■ at the bottom of curve A corresponds to toner with particularly low triboelectric charge, and toner in this area has a latent image surface that becomes negative with respect to the development direction in the developing section electric field (latent image surface in normal development). It is a toner that tends to adhere to areas of low potential (or areas of high latent image potential in reversal development), and therefore causes fogging.
一方、斜線部分■は、トリポ電荷の特に高いトナーに対
応する部分であり、トリポ電荷が高すぎるためトナーと
キャリアとの間の電気的接着力が強すぎて、キャリアか
ら離れず、従って現像に寄与しないトナーの部分である
。On the other hand, the shaded area ■ corresponds to toner with a particularly high tripo charge, and because the tripo charge is too high, the electrical adhesion between the toner and the carrier is too strong, and it does not separate from the carrier, thus preventing development. This is the part of the toner that does not contribute.
更に斜線部分■は、適正なトリポ電荷をもつトナーに対
応する部分であり１Ｍレベル及びＨレベルの潜像電位部
をともに良好に現像するトナーの部分である。Further, the shaded area (3) corresponds to toner having an appropriate tripo charge, and is a toner area that satisfactorily develops both the 1M level and H level latent image potential areas.
また、斜線部分の、■は、適正電荷を有するトナーと、
その他のトナーとの中間領域にあるトナーに対応する部
分であり、現像電界条件により適正に現像されるか、又
はカブリとなりもしくは現像されないトナーの部分であ
る。In addition, the shaded area ■ indicates toner having an appropriate charge;
This is a portion corresponding to toner in an intermediate region with other toners, and is a portion of toner that is either properly developed depending on the developing electric field conditions, or is a portion of toner that becomes foggy or is not developed.
ここで、曲線Ａのような電荷分布を有するトナー（従来
の小粒径トナー）でディジタル潜像を現像すると、前述
したようなチリチリ画像やカブリが発生する。Here, when a digital latent image is developed with a toner having a charge distribution as shown by curve A (conventional small particle diameter toner), a dusty image or fog as described above occurs.
また、高湿下においては、トナートリボ電荷も全体的に
減少して第５図の破線Ｂに示すようになり、チリチリ画
像やカブリの発生は、より顕著になる。Furthermore, under high humidity conditions, the toner triboelectric charge decreases as a whole, as shown by the broken line B in FIG. 5, and the occurrence of dusty images and fog becomes more noticeable.
更に、従来のトナーに用いられていた荷電制御剤は、ニ
グロシンに代表されるように通常は濃色を呈しているた
め、例えば鮮やかな有彩色トナーを得るには、その濃色
が大きな障害となっていた。Furthermore, the charge control agents used in conventional toners usually have a dark color, as typified by nigrosine, so the dark color is a major hindrance to obtaining bright chromatic toners, for example. It had become.
患」ＬΩ」Ｌ酌
本発明は、上述の欠点を解消し、高画質の画像を与える
小粒径トナー分布をもったトナーを含有する現像剤を提
供するものである。The present invention eliminates the above-mentioned drawbacks and provides a developer containing a toner having a small particle size toner distribution that provides high quality images.
すなわち１本発明の目的は、鮮鋭性および階調性が高く
、従って高画質の可視画像を形成することのできる静電
荷像用現像剤を提供することにある。That is, one object of the present invention is to provide a developer for electrostatic images that has high sharpness and gradation and is therefore capable of forming high-quality visible images.
本発明の他の目的は、耐久性のよい静電荷像用現像剤を
提供することにある。Another object of the present invention is to provide a developer for electrostatic images with good durability.
本発明の更に他の目的は、特にディジタル信号によって
形成された潜像を忠実に現像することができる現像剤、
即ち、現像時のＶｓ −Ｄ、曲線の傾きが大きい現像特
性を示し、画像ドツト間の濃度差を大きくすることが可
能で、ドツトの縁部をシャープに再現でき、且つ、チリ
チリ画像を除去することが可清な現像剤を提供すること
にある。Still another object of the present invention is to provide a developer capable of faithfully developing a latent image formed by a digital signal;
That is, Vs-D during development exhibits a development characteristic in which the slope of the curve is large, it is possible to increase the density difference between image dots, it is possible to reproduce sharp edges of dots, and it is possible to remove dusty images. The objective is to provide a clear developer.
本発明の他の目的は、温度、湿度の変化に影響を受けず
に安定した画像を再現することができる現像剤を提供す
ることにある。Another object of the present invention is to provide a developer that can reproduce stable images without being affected by changes in temperature and humidity.
本発明の更に他の目的は、鮮やかな有彩色画像を与える
ことができる現像剤を提供することにある。Still another object of the present invention is to provide a developer capable of producing vivid chromatic images.
ヱ」ＬのＩ！
本発明の現像剤は上記目的達成のために開発されたもの
であり、酸化電位が７５０■Ｖ以下、白色度Ｗが０．５
以上、且つ平均粒径が３．０終■以下の正荷電性化合物
を含有するトナーであって、重量分布による平均粒径が
３〜ｌ０ＪＬＩ１．個数分布における最多数粒子の粒径
が１〜８ＩＬｍ、且つ粒径１６ｐｍを越える粒子数が全
粒子数の２％以下である粒子群からなるトナーを含有す
ることを特徴とするものである。ヱ”L’s I! The developer of the present invention was developed to achieve the above objectives, and has an oxidation potential of 750 V or less and a whiteness W of 0.5.
A toner containing a positively charged compound having the above properties and an average particle size of 3.0JLI1. The toner is characterized by containing a particle group in which the largest number of particles in the number distribution has a particle size of 1 to 8 ILm, and the number of particles having a particle size exceeding 16 pm is 2% or less of the total number of particles.
すなわち１本発明者らは、高い正荷電性を有し、且つ良
好な白色度を有する特定の正荷電性化合物を、更に極め
て小さい微粒子状としてトナー中に含有せしめることに
より、小粒径であって。That is, the present inventors have created a toner with a small particle size by further incorporating a specific positively charged compound having high positive chargeability and good whiteness into the toner in the form of extremely small particles. hand.
しかも、高く均一な摩擦帯電特性を有するトナーが実現
可能であることを見出し、更にこの小粒径トナーを用い
ることにより、上述の目的達成のために極めて効果的な
特性を有する正荷電性現像剤が得られることを知見して
、本発明を完成したものである。Moreover, it has been discovered that it is possible to create a toner with highly uniform triboelectric charging characteristics, and furthermore, by using this small particle size toner, a positively charged developer with extremely effective characteristics for achieving the above-mentioned purpose can be created. The present invention was completed by discovering that the following can be obtained.
このような本発明の現像剤におけるトナーのトリボ電荷
の分布を第５図の曲線Ｃに示す、この第５図を見れば１
本発明に用いるトナーが小粒径であるにもかかわらず、
従来の小粒径トナー（曲線Ａないし破線Ｃ）と比べて均
一性が向上したトリポ電荷分布を示し、カブリのない鮮
鋭な高画質画像を与えることが理解できよう。The distribution of triboelectric charges of the toner in the developer of the present invention is shown in curve C of FIG.
Although the toner used in the present invention has a small particle size,
It can be seen that this toner exhibits a tripocharge distribution with improved uniformity compared to the conventional small particle size toner (curve A to dashed line C) and provides sharp, high-quality images without fogging.
なお、本発明者らの実験によると、潜像電位の比較的低
い部分では、トリボ電荷の高いトナーが付着する傾向、
すなわち、Ｍレベルの潜像電位には第５図の■の部分に
対応するトナーが付着する傾向があった。ここで、第５
図の曲線Ａのようなトリボ電荷分布を示す従来の小粒径
トナーでディジタル潜像を現像した場合、本来Ｈレベル
に現像されるべきトナー量の相対的減少によりチリチリ
画像が生じるものと推定されるが、これに対して、曲線
Ｃのようなトリポ電荷分布を示す本発明にかかわるトナ
ーを用いれば、上記のようなＨレベル潜像へのトナー付
着量の相対的減少、すなわちチリチリ画像の発生も有効
に抑制されるものと推定される。According to experiments conducted by the present inventors, toner with a high triboelectric charge tends to adhere to areas where the latent image potential is relatively low;
That is, there was a tendency for the toner corresponding to the area marked ■ in FIG. 5 to adhere to the M level latent image potential. Here, the fifth
It is estimated that when a digital latent image is developed with a conventional small particle size toner that exhibits a triboelectric charge distribution as shown by curve A in the figure, a dusty image will occur due to a relative decrease in the amount of toner that should originally be developed to the H level. On the other hand, if the toner of the present invention exhibiting a tripo charge distribution as shown by curve C is used, the amount of toner adhering to the H-level latent image as described above will be relatively reduced, that is, the generation of a dusty image. It is estimated that this will also be effectively suppressed.
以下、本発明を更に詳細に説明するが、まず本発明の現
像剤中のトナー構成要素である正荷電性化合物について
説明する。The present invention will be described in more detail below, but first, the positively charged compound that is a toner component in the developer of the present invention will be explained.
本発明に用いる正荷電性化合物としては、四級アンモニ
ウム塩やピリジニウム塩を除く有機溶媒に可溶な化合物
であり、飽和カロメロ電極に対する酸化電位が、７５０
ｍＶ以下であるものな使用する。すなわち酸化電位が
低い正荷電性化合物は、自ら電子を放出し易く、正荷電
に帯電し易い特性を淘するため、これを静電荷像現像用
トナーに含有せしめた場合、充分な摩擦帯電量を有し、
しかもトナー粒子間に均一に荷電を与え得る極めて良質
な荷電制御剤となる。The positively charged compound used in the present invention is a compound that is soluble in organic solvents, excluding quaternary ammonium salts and pyridinium salts, and has an oxidation potential of 750
Use one whose voltage is below mV. In other words, a positively charged compound with a low oxidation potential easily emits electrons by itself and eliminates the property of being easily charged to a positive charge. Therefore, when this compound is included in a toner for developing an electrostatic image, a sufficient amount of triboelectric charge can be generated. have,
Moreover, it becomes an extremely high-quality charge control agent that can uniformly impart charges between toner particles.
本発明において重要なことは、充分な摩擦帯電量をトナ
ー粒子の個々に、均一に与えることである。もし現像に
充分な摩擦帯電量をトナーに与えるだけであれば、（後
述の実施例で述べるように）ａＯＯ■Ｖ程度の酸化電位
を有する化合物でも充分であるが、そのような化合物は
、若干でもトナー粒子間の分散にバラツキがあると、そ
れが直接トナー粒子間の摩擦帯電量のバラツキとなり、
画像特性、特にｖｓ−Ｄ、特性とトナーのトリボ分布に
影響が現れる。これに対して、酸化電位が７５０■Ｖ以
下、特に７００■Ｖ以下の正荷電性化合物は、トナー粒
子間の分散に若干のバラツキが生じたとしても、該化合
物自身の摩擦帯電能が高いために、直接、画像特性に影
響を与えるような摩擦帯電量のバラツキを、トナー粒子
間に生じさせる傾向は極めて少ない。What is important in the present invention is to uniformly apply a sufficient amount of triboelectric charge to each toner particle. If the amount of triboelectric charge sufficient for development is simply given to the toner, a compound with an oxidation potential of about aOO■V is sufficient (as described in the examples below), but such a compound has a slight However, if there is variation in the dispersion between toner particles, this will directly lead to variation in the amount of triboelectric charge between toner particles.
Image characteristics, especially vs-D characteristics, and toner tribo distribution are affected. On the other hand, positively charged compounds with an oxidation potential of 750 ■V or less, especially 700 ■V or less, have a high triboelectric charging ability of the compound itself, even if slight variations occur in the dispersion between toner particles. Furthermore, there is very little tendency to cause variations in the amount of triboelectric charge between toner particles that would directly affect image characteristics.
尚、本発明において、酸化電位の測定は、試料極および
対極は白金、参照極は飽和カロメロ電極、支持電解質と
しては、０．ＩＮのｎ−テトラブチルアンモニウムパー
クロライドを用いて行なう、もちろん、本発明における
測定法を参照しながら他の測定方法の適用も可能である
。溶媒としては、化合物を溶解し得るものをその都度選
択する。In the present invention, the oxidation potential is measured using platinum as the sample electrode and the counter electrode, a saturated Calomero electrode as the reference electrode, and 0.05 mm as the supporting electrolyte. It is of course possible to apply other measurement methods while referring to the measurement method according to the present invention, which is carried out using IN n-tetrabutylammonium perchloride. As the solvent, one that can dissolve the compound is selected each time.
次に、第６図（ａ）に、上記測定法を用いた際のジ（０
−イソプロピルフェニル）グアニジンの電位−電流曲線
を示し、第６図（ｂ）にジフェニルグアニリノの電位−
電流曲線を示す０本発明においては、酸化ピークの延長
線と横軸との交点を酸化電位とする。なお、この結果は
、塩化メチレンを溶媒として用いて測定した際のもので
ある。Next, FIG. 6(a) shows the di(0) when using the above measurement method.
-isopropylphenyl)guanidine, and Figure 6(b) shows the potential-current curve of diphenylguanilino.
In the present invention, the intersection of the extension line of the oxidation peak and the horizontal axis is defined as the oxidation potential. Note that this result was measured using methylene chloride as a solvent.
第７図には、この酸化電位と、トナー（スチレン−アク
リル樹脂１００重量部と正荷電性化合物２重量部からな
る）のブローオフトリボとの関係を示したが、この両者
にはきれいな相関があり、酸化電位が低い物質を含有し
たトナーはど、摩擦帯電量は増加している。Figure 7 shows the relationship between this oxidation potential and the blow-off trigger of the toner (consisting of 100 parts by weight of styrene-acrylic resin and 2 parts by weight of a positively charged compound), and there is a clear correlation between the two. , the amount of triboelectric charge increases in toners containing substances with low oxidation potential.
なお、本発明における帯電量測定は、被検物質を２００
７３００メツシユの粒径を有する鉄粉キャリアとｔｏ
： ９０の割合で混合した混合物０．５〜１．５ｇを精
秤し、エレクトロメーターと接続された金属製４００メ
ツシユスクリーン上で、２５ｃｍＨ２Ｏの圧力により吸
引し、その時分離吸引された被検物質と、その電荷量よ
り、単位ｆＬ量当りの帯電量を求める方法による。In addition, in the measurement of the amount of charge in the present invention, the test substance is
An iron powder carrier with a particle size of 7300 mesh and to
: Precisely weigh 0.5 to 1.5 g of the mixture mixed at a ratio of 90%, and suction it with a pressure of 25cmH2O on a metal 400 mesh screen connected to an electrometer, and then separate and suck the test substance. Then, from the amount of charge, the amount of charge per unit fL amount is determined.
上述したように１本発明においては酸化電位が７５０ｍ
Ｖ以下、好ましくは７００層Ｖ以下を示す正荷電性化合
物が使用できる。As mentioned above, in the present invention, the oxidation potential is 750 m
Positively charged compounds exhibiting V or less, preferably 700 layers or less, can be used.
本発明では、上記特性を有する正荷電性化合物を、更に
微粒子状として用いる。すなわち、該化合物の平均粒径
は３終曹以下、好ましくは２終腸以下であって、更には
、上記平均粒径は、この化合物が適用されるトナーの平
均粒径の１１５以下であることが好ましい。In the present invention, the positively charged compound having the above characteristics is further used in the form of fine particles. That is, the average particle size of the compound is 3 or less, preferably 2 or less, and furthermore, the average particle size is 115 or less of the average particle size of the toner to which this compound is applied. is preferred.
この正荷電性化合物としては１粒径ｌ終■以下の粒子を
４０個数％以上、特に５０個数％以上含有するものがよ
り好ましく用いられる。As this positively charged compound, one containing 40% by number or more, particularly 50% by number or more of particles having a particle size of 1 or less is more preferably used.
正荷電性化合物の平均粒径が３終部以上の場合には、該
化合物の有する帯電能が十分発揮されず、ｖｓ−ｎ、特
性及びトナートリポ分布が好ましい状態を示さない傾向
が顕著になる他、チリチリ画像が生じてくる。When the average particle size of the positively charged compound is 3 or more, the charging ability of the compound is not sufficiently exhibited, and the vs-n, characteristics, and toner lipo distribution tend to be unfavorable. , a flickering image appears.
本発明者等は後述する実施例−１で使用したグアニジン
系の含チツ素化合物を微粉砕及び必要に応じて分級して
、種々の平均粒径を有する正荷電性化合物の試料を作成
して、この試料を含有し。The present inventors finely pulverized the guanidine-based nitrogen-containing compound used in Example 1 described later and classified it as necessary to prepare samples of positively charged compounds having various average particle sizes. , containing this sample.
且つ１本発明にかかるトナー粒度分布を有するトナーを
作り、アモルファスシリコン感光体を用いたレーザーコ
ピア（商品名ＮＰ−９０３０キャノン■製）に適用して
画像出しを行ったところ、初期状態では大きな差がなか
ったが、数１００枚から１０００枚程度のくり返し時に
、平均粒径３ｐ■以上の正荷電性化合物の試料を含有す
るトナーは、Ｈコントラストにおける画像濃度の低下が
認められた。上記試料の平均粒径と、５００枚時におけ
るＨコントラストの画像濃度との関係を第８図に示す。In addition, when a toner having the toner particle size distribution according to the present invention was made and applied to a laser copier (product name: NP-9030 manufactured by Canon ■) using an amorphous silicon photoreceptor to produce images, there was no significant difference in the initial state. However, when the toner contained a sample of a positively charged compound with an average particle size of 3p■ or more, a decrease in image density in H contrast was observed when the toner was repeatedly printed on several hundred to 1000 sheets. FIG. 8 shows the relationship between the average particle diameter of the sample and the image density of H contrast when 500 sheets were printed.
このような関係が生ずるのは、本発明に用いる正荷電性
化合物の粒度が、トナー表面における該化合物の存在確
率と密接に関係し、この化合物が微細粒子状であるほど
そのトナー表面の存在確率が増加し、潜在的能力をより
顕著に発揮できる状態になっているためと推測される。Such a relationship occurs because the particle size of the positively charged compound used in the present invention is closely related to the probability of the compound's presence on the toner surface, and the finer the particle size of the compound, the higher the probability of its presence on the toner surface. This is presumed to be due to an increase in the number of children, and they are now in a state where they can more clearly demonstrate their potential.
正荷電性化合物が所望の粒度を満たさない時は、必要に
応じてＪｅｔ Ｍｉｌ＋等の微粉砕機によって該化合物
を微粉砕し、使用することが好ましい。When the positively charged compound does not satisfy the desired particle size, it is preferable to pulverize the compound using a pulverizer such as Jet Mil+ as necessary and use it.
ここに、本発明に用いる正荷電性化合物及びトナーの粒
度は、コールタ−カウンターｔｙｐｅ Ｈを使ってその
個数を基準として求めたものである。Here, the particle size of the positively charged compound and toner used in the present invention is determined based on the number of particles using a Coulter counter type H.
ここで使用されるアパーチャー径・試料分散方法等は対
象試料物によって適宜選択することができる０例えばｌ
０ＪＬＩＩ程度のトナーであれば１００ルアパーチヤー
を使い、５〜２０％の試料濃度の分散液を５分位超音波
分散した後測定することができ、＊ＩＬｍ程度の化合物
であれば３０＃Ｌアパーチヤーを用い、試料濃度１０〜
２０％、超音波分散時間約１５分後で測定することがで
きる。The aperture diameter, sample dispersion method, etc. used here can be selected as appropriate depending on the target sample.
If the toner is about 0JLII, it can be measured using a 100#L aperture and after ultrasonically dispersing a dispersion liquid with a sample concentration of 5 to 20%, and if it is a compound about *ILm, a 30#L aperture can be used. sample concentration of 10~
20%, which can be measured after about 15 minutes of ultrasonic dispersion time.
本発明に用いる正荷電性化合物は、上記特性を有する他
、更に実質的に無色または白色とみなせるほどの白色度
（Ｗ）をもっているものである。In addition to having the above characteristics, the positively charged compound used in the present invention has a degree of whiteness (W) that is substantially colorless or white.
摩擦帯電性と上記化合物の色について１本発明者らの知
見によれば、一般に、摩擦帯電能の大きい（酸化電位の
低い）化合物は、多くの場合濃色系であり、例えば、鮮
明なカラートナーには適用できない場合が多い。Regarding triboelectric chargeability and the color of the above-mentioned compounds 1.According to the findings of the present inventors, in general, compounds with high triboelectricity (low oxidation potential) are often dark-colored, such as vivid colors. It is often not applicable to toner.
ここに、固体物質の摩擦帯電機構を考えると。Now, consider the triboelectric charging mechanism of solid materials.
接触過程と分離過程に大別できる。接触過程は。It can be broadly divided into contact process and separation process. What is the contact process?
物質間で電気二重層が形成され、電荷のやりとりを行う
過程であり、帯電符号はこの過程で決定される。一方、
分離過程は接触していた物質が分離していく過程で、こ
こでは電荷の漏洩が起こる。It is a process in which an electric double layer is formed between substances and charges are exchanged, and the charge sign is determined in this process. on the other hand,
The separation process is a process in which substances that have been in contact separate, and charge leakage occurs here.
今、接触過程を中心に摩擦帯電量を考えると、その大き
さは、化合物がいかに電荷の授受をしやすいか、またい
かに物質間での接触点を多く有しているかに依存する。Now, when we consider the amount of triboelectric charge with a focus on the contact process, its magnitude depends on how easily a compound can transfer and receive charge, and how many contact points there are between substances.
後者の接触点の数は、前述した物質の粒径に依存したも
のであり、前者の電荷の授受のし易さは、一般に、物質
の色と相関のあることが多い。The number of contact points in the latter depends on the particle size of the substance described above, and the ease with which charges can be transferred in the former is generally correlated with the color of the substance.
すなわち、物質が正に帯電するには、何らかの形でエネ
ルギーを吸収し、電子を放出することが必要である。従
って、正に帯電し易い物質には、低エネルギーで電子を
放出し、その後安定に存在し得る性質が望まれる。In other words, for a substance to become positively charged, it must somehow absorb energy and emit electrons. Therefore, it is desirable for a substance that is easily charged to be positively charged to have the property of emitting electrons at low energy and then being able to exist stably.
この２つの性質を化合物の構造と結び付けて考えると、
低エネルギーで電子を放出するには、バンドギャップ（
あるいは仕事関数）が小さいことが必要であり、電子放
出後も安定に存在するには、電子放出後生じた電荷のか
たよりを非局在化することが必要である。すなわち、こ
のような°２つの特性を同時に有する化合物の多くは、
共役二重結合を多数有する。従って、そのような化合物
の多くは、濃色物質であり、淡色物質は非常に少ないの
が現状である。If we consider these two properties in conjunction with the structure of the compound,
To emit electrons at low energies, the band gap (
In addition, in order to exist stably even after electron emission, it is necessary to delocalize the charge bias generated after electron emission. In other words, many of the compounds that have these two properties at the same time are
It has many conjugated double bonds. Therefore, at present, many of such compounds are dark-colored substances, and there are very few light-colored substances.
本発明者らは、鋭意研究した結果、Ｓ色を示す程度に共
役二重結合を有していなくとも、電荷のかたよりを安定
化し得る物質があり、このような物質は濃色性を示さな
いことを知見した。As a result of intensive research, the present inventors found that there are substances that can stabilize the charge shift even if they do not have conjugated double bonds to the extent that they exhibit S color, and such substances do not exhibit hyperchromic properties. I found out that.
本発明においては、下記式で定義される白色度Ｗが０．
５以上、好ましくは０．５５以上である正荷電性化合物
を使用する。尚、下記式は、色彩科学ハンドブック（株
式会社南江堂発行）２３７頁右欄７行目に記載されてい
る。In the present invention, the whiteness W defined by the following formula is 0.
A positively charged compound with a charge of 5 or more, preferably 0.55 or more is used. The following formula is described in the 7th line of the right column on page 237 of the Color Science Handbook (published by Nankodo Co., Ltd.).
本発明において、Ｃ及びＶとはＪＩＳ Ｚ８７２１に
定められた色の三属性による表示方法における彩度（Ｃ
ｈｒｏｍａ）及び明度（Ｖａｌｕｅ）を表わす。In the present invention, C and V refer to the saturation (C
hroma) and brightness (Value).
本発明における正荷電性化合物の彩度（Ｃ）及び明度（
Ｖ）は、以下のようにして求めることができる。すなわ
ち、正荷電性化合物を少量透明なビニール袋に採取し試
料とする。一方、標準色票としてＪＩＳ ２８７２１
に準拠した標準色票の光沢板（日本規格協会発行）を使
用し、試料と標準色票とをＪＩＳ Ｚ８７２３で定め
られた表面色の比較方法に準じた方法によって比較し、
（精度を上げる為に、マスクの使用、及び試料を採取し
たビニール袋と同一のビニール袋を標準色票にかぶせる
等は好ましい方法である。）、彩度（Ｃ）。The chroma (C) and brightness (
V) can be determined as follows. That is, a small amount of a positively charged compound is collected in a transparent plastic bag and used as a sample. On the other hand, JIS 28721 is used as a standard color chart.
Using a standard color chart gloss plate (published by the Japanese Standards Association) in accordance with
(To improve accuracy, it is preferable to use a mask and cover the standard color chart with the same plastic bag as the one in which the sample was taken.), Saturation (C).
明度（ｖ）必要ならば色相（Ｈ）を決定する。Determine brightness (v) and hue (H) if necessary.
本発明に用いる正荷電性化合物がトナーの色に与える影
響においては、該化合物の白色度だけでなく、多量の場
合はその添加量も重要である。Regarding the influence of the positively charged compound used in the present invention on the color of the toner, not only the whiteness of the compound but also the amount added is important if a large amount is used.
トナーに内添する際の正荷電性化合物の使用量は、結着
樹脂の種類、必要に応じて使用される添加剤の有無、分
散方法を含めたトナー製造方法によって決定されるもの
で、一義的に限定されるものでは無いが、他の性能をも
考慮すると、好ましくは結着樹脂１００重量部に対して
正荷電性化合物０．１〜２０重量部（より好ましくは０
．５〜１０重量部）の範囲で用いられる。The amount of positively charged compound used when internally added to toner is determined by the toner manufacturing method, including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method. Although not limited to this, in consideration of other properties, it is preferable to use 0.1 to 20 parts by weight (more preferably 0.1 to 20 parts by weight) of the positively charged compound to 100 parts by weight of the binder resin.
．． (5 to 10 parts by weight).
この程度の添加量の範囲においては、白色度ＷＯ０５以
上、好ましく彩度（Ｃ）がｌθ以下であり、且つ白色度
Ｗが０．５５以上、より好ましくは０．６以上である場
合、上記化合物の添加は、実質的にトナーの色に悪影響
を及ぼさない。In this range of addition amount, when the whiteness is WO05 or more, preferably the saturation (C) is lθ or less, and the whiteness W is 0.55 or more, more preferably 0.6 or more, the above compound The addition of does not substantially adversely affect the color of the toner.
上述したように、本発明に使用される荷電制御剤は、■
酸化電位が７５０ｍＶ以下であり、■３絡−以下の平均
粒径を有し、■白色度Ｗが０．５以上である条件を満足
する正荷電性化合物である。As mentioned above, the charge control agent used in the present invention is
It is a positively charged compound that satisfies the following conditions: 1) has an oxidation potential of 750 mV or less; 1) has an average particle size of 3 circuits or less; and 2) has a whiteness W of 0.5 or more.
このような正荷電性化合物は、■含窒素有機化合物、■
含リン有機化合物、■金属錯体および■有機金属化合物
等に見い出される。さらに具体的には、含窒素有機化合
物としては、アリール基で置換されたアミノ基を１個以
上有する化合物、含リン有機化合物としては、アリール
基で置換されたホスフィノ基を１個以上有する化合物、
金属錯体としては、カルボキシル基とアミ７基を配位子
として有するある種の金属錯体、アミ７基と水酸基を配
位子として有するある種の金属錯体、有機金属化合物と
しては、アリール基が直接結合した金属化合物、等が挙
げられる。Such positively charged compounds include ■ nitrogen-containing organic compounds, ■
It is found in phosphorus-containing organic compounds, (1) metal complexes, (2) organometallic compounds, etc. More specifically, the nitrogen-containing organic compound is a compound having one or more amino groups substituted with an aryl group, and the phosphorus-containing organic compound is a compound having one or more phosphino groups substituted with an aryl group.
Examples of metal complexes include certain metal complexes that have a carboxyl group and an amine 7 group as ligands, certain metal complexes that have an amine 7 group and a hydroxyl group as ligands, and organometallic compounds that have an aryl group directly bonded metal compounds, and the like.
尚、本発明におけるトナーに悪影響を与えない限り、従
来公知の荷電制御剤を１本発明に用いる荷電制御剤たる
上記正荷電性化合物と組み合わせて使用することもでき
る。しかしこの場合には。It should be noted that a conventionally known charge control agent may be used in combination with the positively charged compound used as the charge control agent used in the present invention, as long as it does not adversely affect the toner used in the present invention. But in this case.
公知の荷電制御剤の添加量は１本発明で使用する正荷電
性化合物の添加量より少ない場合に、好ましい結果を得
ることができる。又、本発明に用いる正荷電性化合物は
白色度が高い為、所望の色のトナーを得たい場合、併用
する公知の着色剤の色をひきたたせるばかりか、その着
色剤の添加量を少なくすることも可撤である。Favorable results can be obtained when the amount of the known charge control agent added is less than the amount of the positively charged compound used in the present invention. In addition, since the positively charged compound used in the present invention has a high degree of whiteness, when it is desired to obtain a toner of a desired color, it not only makes the color of a known colorant used in combination stand out, but also reduces the amount of the colorant added. It is also removable to do so.
本発明に使用される着色剤としては、カーボンブラック
、ランプブラック、鉄黒１群青、アニリンブルー、フタ
ロシアニンブルー、フタロシアニングリーン、ハンサイ
エローＧ、 ローダミン６Ｇレーキ、カルコオイルブ
ルー、クロムイエロー、キナクリドン、ベンジジンイエ
ロー、ローズベンガル、トリアリルメタン系染料、七ノ
アゾ系、ジスアゾ系染顔料等、従来公知のいかなる染顔
料をも、単独であるいは混合して使用し得る。Coloring agents used in the present invention include carbon black, lamp black, iron black 1 ultramarine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 6G lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow. , rose bengal, triallylmethane dyes, heptanoazo dyes, disazo dyes and pigments, any conventionally known dyes and pigments can be used alone or in combination.
本発明に使用される結着樹脂としては、ポリスチレン、
ポリ−ｐ−クロロスチレン、ポリビニルトルエンなどの
スチレン及びその置換体の単重合体；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−ビニルトルエン共ｆｆｌ 合体、スチレン
−ビニルナフタレン共重合体、スチレン−アクリル酸メ
チル共重合体、スチレン−アクリル酸エチル共重合体、
スチレン−アクリル酸ブチル共重合体、スチレン−アク
リル酸オクチル共重合体、スチレン−メタクリル酸メチ
ル共重合体、スチレン−メタクリル酸エチル共重合体、
スチレン−メタクリル酸ブチル共重合体、スチレン−α
−クロルメタクリル酸メチル共重合体、スチレン−アク
リロニトリル共重合体、スチレン−ビニルメチルエーテ
ル共重合体。The binder resin used in the present invention includes polystyrene,
Monopolymers of styrene and its substituted products such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene co-ffl polymers, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer,
Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer,
Styrene-butyl methacrylate copolymer, styrene-α
- Methyl chlormethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer.
スチレン−ビニルエチルエーテル共重合体、スチレン−
ビニルメチルケトン共重合体、スチレン−ブタジェン共
重合体、スチレン−イソプレン共重合体、スチレン−ア
クリロニトリル−インデン共重合体、スチレン−マレイ
ン酸共重合体、スチレンーヤレイン酸エステル共重合体
などのスチレン系共重合体：ポリメチルメタクリレート
、ポリブチルメタクリレート、ポリ塩化ビニル、ポリ酢
酸ビニル、ポリエチレン、ポリプロピレン、ポリエステ
ル、ポリウレタン、ポリアミド、エポキシ樹脂、ポリビ
ニルブチラール、ポリアクリル酸樹脂、ロジン、変性ロ
ジン、テルペン樹脂、フェノール樹脂、脂肪族又は脂環
族炭化水素樹脂、芳香族系石油樹脂、塩素化パラフィン
、パラフィンワックスなどがあげられ、単独で或いは混
合して使用できる。Styrene-vinylethyl ether copolymer, styrene-
Styrenes such as vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-yaleate copolymer System copolymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, Examples include phenol resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, etc., which can be used alone or in combination.
また、特に圧力定着用に好適な結着樹脂として限定して
あげると、下記のものが単独で或いは混合して使用でき
る。Further, as binder resins particularly suitable for pressure fixing, the following can be used alone or in combination.
ポリオレフィン（低分子量ポリエチレン、低分子量ポリ
プロピレン、酸化ポリエチレン、ポリ四弗化エチレンな
ど）、エポキシ樹脂、ポリエステル樹脂、スチレン−ブ
タジェン共重合体（モノマー比５〜３０ ： ９５〜７
０）、オレフィン共重合体（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−メタクリル酸共重合体、エチレン−メタクリル酸エ
ステル共重合体、エチレン−塩化ビニル共重合体。Polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resins, polyester resins, styrene-butadiene copolymers (monomer ratio 5-30:95-7)
0), olefin copolymers (ethylene-acrylic acid copolymers, ethylene-acrylic ester copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic ester copolymers, ethylene-vinyl chloride copolymers.
エチレン−酢酸ビニル共重合体、アイオノマー樹脂）、
ポリビニルピロリドン、メチルビニルエーテル−無水マ
レイン酸共重合体、マレイン酸変性フェノール樹脂、フ
ェノール変性テルペン樹脂。ethylene-vinyl acetate copolymer, ionomer resin),
Polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.
本発明の現像剤を二成分系現像剤として用いる場合には
、上記正荷電性化合物を含有するトナーとキャリア粉と
を混合して現像剤とする。When the developer of the present invention is used as a two-component developer, the toner containing the positively charged compound and carrier powder are mixed to form the developer.
この際トナーには、トナー重量に対して６０重量％、好
ましくは３０重量％までの磁性体を含有させ得る。In this case, the toner may contain a magnetic material in an amount of 60% by weight, preferably up to 30% by weight based on the weight of the toner.
本発明に使用しうるキャリアとしては、公知のものがす
べて使用可能であり、例えば鉄粉、フェライト粉、ニッ
ケル粉の如き磁性を有する粉体、ガラスピーズ等及びこ
れらの表面を樹脂等で処理したものなどがあげられる。All known carriers can be used in the present invention, such as magnetic powders such as iron powder, ferrite powder, nickel powder, glass beads, etc., and carriers whose surfaces are treated with resin etc. Things can be given.
また、本発明の現像剤は、上記トナーに更に磁性材料を
含有させて、−成分磁性トナーからなる現像剤としても
よい、この際の磁性トナー中に含まれる磁性材料として
は、マグネタイト、ヘマタイト、フェライト等の酸化鉄
；鉄、コバルト、ニッケルのような金属或いはこれらの
金属のアルミニウム、コバルト、銅、鉛、マグネシウム
、スズ、亜鉛、アンチモン、ベリリウム、ビスマス、カ
ドミウム、カルシウム、マンガン、セレン、チタン、タ
ングステン、バナジウムのような金属の合金およびその
混合物等が挙げられる。Further, the developer of the present invention may be made of a -component magnetic toner by further containing a magnetic material in the above toner. In this case, the magnetic material contained in the magnetic toner may include magnetite, hematite, Iron oxides such as ferrite; metals such as iron, cobalt, and nickel, or these metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, Examples include alloys of metals such as tungsten and vanadium, and mixtures thereof.
これらの強磁性体は、平均粒径が０．１〜２μ腸程度の
ものが好ましく、トナー中に含有させる量としては、樹
脂成分１００重量部に対し約２０〜２００重量部、特に
好ましくは、樹脂成分１００重量部に対し４０−１５０
重量部である。These ferromagnetic substances preferably have an average particle size of about 0.1 to 2 μm, and are contained in the toner in an amount of about 20 to 200 parts by weight based on 100 parts by weight of the resin component, particularly preferably, 40-150 per 100 parts by weight of resin component
Parts by weight.
又１本発明に用いるトナーに、必要に応じて添加剤を混
合した場合、よりよい結果が得られる。Furthermore, better results can be obtained if additives are mixed into the toner used in the present invention, if necessary.
添加剤としては、例えばテフロン、ステアリン酸亜鉛の
如き滑剤、あるいは酸化セリウム、炭化ケイ素等の研摩
剤、あるいは例えばコロイダルシリカ、酸化アルミニウ
ム等の流動性付与剤、ケーキング防止剤、あるいは例え
ばカーボンブラー２り、酸化スズ等の導電性付与剤、あ
るいは低分子量ポリエチレンなどの定着助剤等がある。Examples of additives include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide and silicon carbide, flow agents such as colloidal silica and aluminum oxide, anti-caking agents, and carbon blur 2. , conductivity imparting agents such as tin oxide, and fixing aids such as low molecular weight polyethylene.
これらの添加剤はトナーと同極性もしくはほとんど帯電
を示さないものを使用した時に、本発明の効果を一層ひ
きたたせる０例えばコロイダルシリカの場合には、キャ
リヤーあるいはスリーブと摩擦して負帯電性を示すシリ
カは好ましくない。When these additives are used with the same polarity as the toner or exhibit almost no charge, the effects of the present invention are further enhanced. For example, in the case of colloidal silica, it rubs against the carrier or sleeve to create negative chargeability. The silica shown is not preferred.
本発明に用いる静電荷像現像用トナーを作製するには、
前記本発明に“係る荷電制御剤をビニル系ないし非ビニ
ル系熱可塑性樹脂、及び着色剤としての顔料又は染料、
必要に応じて磁性材料、添加剤等をボールミルその他の
混合機により充分混合してから加熱ロール、ニーダ−、
エクストルーダー等の熱混練機を用いて熔融、混線及び
練肉して樹脂類を互に相溶せしめた中に顔料又は染料を
分散又は溶解せしめ、冷却固化後、粉砕及び分級して本
発明にかかる粒度分布のトナーを得ることが出来る。To prepare the electrostatic image developing toner used in the present invention,
The charge control agent according to the present invention is a vinyl or non-vinyl thermoplastic resin, a pigment or dye as a coloring agent,
If necessary, magnetic materials, additives, etc. are thoroughly mixed using a ball mill or other mixer, then heated rolls, kneaders, etc.
The pigment or dye is dispersed or dissolved in the resin by melting, mixing and kneading using a heat kneader such as an extruder, and after cooling and solidifying, it is pulverized and classified. A toner having such a particle size distribution can be obtained.
あるいは、結着樹脂溶液中に所定の材料を分散した後、
噴霧乾燥することにより得る方法、あるいは、結着樹脂
を構成すべき単量体に所定材料を混合して乳化懸濁液と
した後に重合させてトナーを得る重合法トナー、あるい
は芯及び殻からなるカプセルトナー等の方法を応用して
本発明に用いるトナーを得てもよい。Alternatively, after dispersing a predetermined material in a binder resin solution,
A method of obtaining a toner by spray drying, or a polymerization method of obtaining a toner by mixing a specified material with the monomer that constitutes the binder resin to form an emulsified suspension and then polymerizing the toner, or a toner consisting of a core and a shell. The toner used in the present invention may be obtained by applying a method such as capsule toner.
次に１本発明にかかるトナーを二成分現像剤として用い
たときのキャリアについて述べる。Next, the carrier when the toner according to the present invention is used as a two-component developer will be described.
本発明にかかるトナーと共に、使用されるキャリアの粒
径は、一般に使用されている５０〜１２０弘■のものも
用いられ得るが、本発明の効果をより高めるためには、
これより小粒径の５〜５０終腸、再には５〜３０終會の
ものを用いることが好ましい。The particle size of the carrier used in conjunction with the toner according to the present invention may be the commonly used carrier particle size of 50 to 120 hiromu, but in order to further enhance the effect of the present invention,
It is preferable to use a smaller particle size of 5 to 50 endomeres, and more preferably 5 to 30 endomeres.
更に、現像剤担持体（現像スリーブ等）と、潜像相持体
（感光面等）との間のリークの防止と、潜像担持体面に
付着したキャリア粒子による潜像担持体面の傷つきを防
止するため、キャリアは、その表面を樹脂で被覆させる
か、又は、磁性体粒子を樹脂中に分散含有せしめたもの
であることが好ましく、また、キャリアの抵抗率は１０
・ΩＣ履以上、特に１０１３Ωｃｌ１以上が好ましい。Furthermore, it prevents leakage between the developer carrier (developing sleeve, etc.) and the latent image carrier (photosensitive surface, etc.), and prevents the surface of the latent image carrier from being damaged by carrier particles adhering to the surface of the latent image carrier. Therefore, it is preferable that the surface of the carrier is coated with a resin or that magnetic particles are dispersed in the resin, and the resistivity of the carrier is 10.
- ΩC or more, especially 1013 Ωcl1 or more is preferable.
更に、キャリア粒子は、球形（長軸／短軸く３）である
方が、現像剤層の均一化のために好ましい。Further, it is preferable that the carrier particles have a spherical shape (major axis/minor axis (3)) in order to make the developer layer uniform.
キャリアとトナーの混合比は、キャリア１００重量部に
対して、トナーが通常３〜５０重量部、好ましくは５〜
３０重量部である。The mixing ratio of carrier and toner is usually 3 to 50 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of carrier.
It is 30 parts by weight.
＆１立皇】
上述したように本発明によれば、小粒径でしかも高く且
つ均一な摩擦帯電量分布を示すトナーを含有する現像特
性に優れた静電荷像現像用現像剤が得られる。&1 Rikuo] As described above, according to the present invention, a developer for developing electrostatic images containing a toner having a small particle size and a high and uniform triboelectric charge amount distribution and having excellent development characteristics can be obtained.
本発明の現像剤を用いることにより、鮮鋭性および階調
性が高く、しかもカブリやチリチリ画像のない高画質画
像を種々の条件下で得ることが可能となり、特にディジ
タル信号によって形成される静電ＮＩ像をも忠実に現像
することが可能となる。By using the developer of the present invention, it is possible to obtain high-quality images with high sharpness and gradation, and without fogging or dusting, under various conditions. It becomes possible to faithfully develop even NI images.
更に１本発明の現像剤を用いれば、白色度の高い荷電制
御剤の特性に基づき、鮮明な有彩色画像が得られる。Furthermore, by using the developer of the present invention, a clear chromatic image can be obtained based on the characteristic of the charge control agent having a high degree of whiteness.
見ム３
以下本発明を実施例により、更に具体的に説明するが、
これは本発明をなんら限定するものではない、なお以下
の配合における部数はすべて重量部である。View 3 The present invention will now be explained in more detail with reference to Examples.
This is not intended to limit the invention in any way, and all parts in the following formulations are by weight.
０℃に熱した２本ロールで混練した。混線物を自然放冷
して、カッターミルで粗粉砕した後。The mixture was kneaded using two rolls heated to 0°C. After allowing the mixed material to cool naturally and coarsely pulverizing it with a cutter mill.
ジェット気流を用いた微粉砕機を用いて粉砕し、さらに
風力分級機を用いて分級して重量平均粒径７ＩＬｍ１個
数分布における最多数粒子の粒径が４ｇｍ、１６ＩＬｓ
を越える粒径の粒子数が全粒子数の１％の微粉体を得た
。Grinding using a pulverizer using a jet stream and further classifying using a wind classifier, the weight average particle size is 7ILm1 The particle size of the largest number of particles in the number distribution is 4gm, 16ILs
A fine powder was obtained in which the number of particles having a particle size exceeding 1% of the total number of particles was obtained.
平均粒径２０〜３０ＩＬｌの樹脂被覆球形鉄粉キャリア
（抵抗率１０１３０ｃ１０ｌ３０部に対し、トナーとし
ての上記微粉末を１０部の割合で混合して現像剤を作成
した。A developer was prepared by mixing 10 parts of the above fine powder as a toner with 30 parts of resin-coated spherical iron powder carrier (resistivity 10130c10l) having an average particle size of 20 to 30 ILl.
なお、トリーＰ−）リルグアニジンは、微粉砕機により
微粉砕しさらに分級したもので、酸化電位５３０ｍＶ（
溶媒：塩化メチレン）、白色度０゜９、平均粒径１．３
＃Ｌｌｌ（粒度分布は、１ｇ１以下の粒子を６０個数％
以上含む）を有する含チツソ有機化合物である。In addition, Tory P-)ylguanidine is finely pulverized using a pulverizer and further classified, and has an oxidation potential of 530 mV (
Solvent: methylene chloride), whiteness 0°9, average particle size 1.3
#Lll (Particle size distribution is 60% by number of particles of 1g1 or less)
(including the above).
第９図に本発明の現像剤を適用し得る電子写真プリンタ
の一実施例を示す、第９図を参照して、レーザ変調ユニ
ット１に入力された電気信号は。Referring to FIG. 9, which shows an embodiment of an electrophotographic printer to which the developer of the present invention can be applied, the electrical signals input to the laser modulation unit 1 are as follows.
変調されたレーザ光として出力され、スキャナ・ミラー
２とｆ・θレンズ３によって感光ドラム４の長手方向を
走査する。感光ドラム４は矢印方向に回転し、レーザビ
ームを二次元的に走査することを可能ならしめる。The laser beam is output as a modulated laser beam, and is scanned in the longitudinal direction of the photosensitive drum 4 by the scanner mirror 2 and the f/θ lens 3. The photosensitive drum 4 rotates in the direction of the arrow, making it possible to scan the laser beam two-dimensionally.
感光体としては、アモルファスシリコン、セレン、Ｃｄ
Ｓ、有機感光体等が用いられ、例えば半導体レーザの波
長（７８０ｎｍ〜ａ ＯＯｎｍ）に感度を持つように増
感されている。このような感光体として、本実施例では
アモルファスシリコン感光体を用い、ＡＣ除電器５で感
光体表面の電位を平準化した後、帯電器６で３８０Ｖに
帯電する。その後、レーザビーム露光を行なって、感光
体にイメージ・スキャン方式により、３値のディザ法に
よるドツト潜像を形成する。３値のＭレベルは第３図（
ａ）のようにレーザ光のパルス巾変調によって形成され
る。ＷＩ像電位はＨレベルが２５０ｖ、Ｍレベルが１２
０ｖであった。As a photoreceptor, amorphous silicon, selenium, Cd
S, an organic photoreceptor, etc. are used, and are sensitized to have sensitivity to the wavelength of a semiconductor laser (780 nm to aOOnm), for example. In this embodiment, an amorphous silicon photoreceptor is used as such a photoreceptor, and after leveling the potential on the surface of the photoreceptor with an AC static eliminator 5, it is charged to 380V with a charger 6. Thereafter, laser beam exposure is performed to form a dot latent image on the photoreceptor by an image scanning method using a ternary dither method. The ternary M level is shown in Figure 3 (
It is formed by pulse width modulation of laser light as shown in a). WI image potential is 250v for H level and 12v for M level.
It was 0v.
このようなドツト潜像を、前述したトナーを含む本発明
の現像剤を収容した現像器９あるいは１０によって反転
現像せしめた。この時、現像バイアスは、直流分として
２８０ｖを印加した。Such a latent dot image was subjected to reversal development using the developing device 9 or 10 containing the developer of the present invention containing the above-mentioned toner. At this time, a developing bias of 280 V was applied as a DC component.
このように現像された画像は、次に転写帯電器１１によ
って転写紙１２上に転写され、定着器１３によって転写
紙１２に定着された。また、転写されないで感光ドラム
４上に残ったトナーはクリーナ１４で補集される。こう
して転写紙上に形成された画像は、Ｈレベルで画像濃度
１．３４、Ｍレベルで０．６９を示し、ベタ部の画像濃
度が十分高く、ドツトの切れがシャープであり、且つ中
間調の再現の目安としての写真画像もきれいに再現され
、更に、チリチリ画像も見られなかった。この時のＶｓ
−Ｄ、特性を第１０図に示す。The thus developed image was then transferred onto the transfer paper 12 by the transfer charger 11 and fixed onto the transfer paper 12 by the fixing device 13. Further, toner remaining on the photosensitive drum 4 without being transferred is collected by a cleaner 14. The image thus formed on the transfer paper has an image density of 1.34 at the H level and 0.69 at the M level, and the image density in the solid area is sufficiently high, the dots are sharp, and the midtones are reproduced well. The photographic image used as a guideline was also reproduced clearly, and furthermore, no scratchy images were observed. Vs at this time
-D, the characteristics are shown in FIG.
又、１万枚の複写をくり返し行なったが、得られた画像
濃度において、Ｈレベルの変動が±０．０７以内、Ｍレ
ベルの変動が±０．１５以内であリ、ｖｓ −Ｄ、特性
に大きな変化が認められなかった。更に、環境条件を３
５℃、８５％及び１５℃、１０％にしたところ、いずれ
も常温常湿と同様に良好な画像が得られ、これらは１万
枚のくり返しの使用においても大きな変化が認められな
かった。In addition, although 10,000 copies were repeatedly made, the variation in the H level was within ±0.07 and the variation in the M level was within ±0.15 in the obtained image density. No major changes were observed. Furthermore, the environmental conditions were
When the temperature was set to 85% at 5°C and 10% at 15°C, good images were obtained in both cases, similar to those at normal temperature and humidity, and no major changes were observed even after repeated use of 10,000 sheets.
又、この現像剤を半年間保存したが初期の特性から大き
な変化を起していなかった。Furthermore, although this developer was stored for half a year, there were no major changes in its initial characteristics.
支１■二」
実施例１で使用したトリーＰ−１リルグアジン７部の代
わりに、１．８−ジアミノナフタレンを配位子とするＣ
Ｏ錯体を５部用いる他は、実施例−１と同様にしてトナ
ーおよび現像剤を得、更に実施例１と同様にして画像を
得た。得られた画像は、画像濃度において、Ｈレベルで
１．３２、Ｍレベルで０．６５を示し、ベタ部の画像濃
度が十分高く、ドツトの切れがシャープであり、中間調
の再現の目安としの写真画像もきれいに再現され且つ、
チリチリ画像も見られなかった。Support 1 and 2” Instead of 7 parts of tri-P-1 lylguazine used in Example 1, C with 1,8-diaminonaphthalene as a ligand
A toner and a developer were obtained in the same manner as in Example 1, except that 5 parts of the O complex was used, and an image was obtained in the same manner as in Example 1. The image density of the obtained image was 1.32 at the H level and 0.65 at the M level, and the image density in the solid area was sufficiently high and the dots were sharp, making it suitable for use as a guide for midtone reproduction. The photographic image of is also beautifully reproduced, and
I couldn't even see the crisp images.
又１万枚の複写をくり返し行なったが、得られた画像濃
度において、Ｈレベルの変動が±０．０７以内、Ｍレベ
ルの変動が±０．１５以内であり、ｖｓ −Ｄｐ特性に
実用上変化が認められなかった。さらに環境条件を３５
℃、８５％及び１５℃、１０％にしたところ、いずれも
常温常湿と同様に良好な画像が得られ、これらは１万枚
のくり返しの使用においても実用上変化が認められなか
った。In addition, after 10,000 copies were repeatedly made, the variation in the H level was within ±0.07 and the variation in the M level was within ±0.15 in the obtained image density, which was not practical for the vs-Dp characteristics. No change was observed. Furthermore, 35 environmental conditions
When the temperature was set to 85% at 15°C and 10% at 15°C, images as good as those at normal temperature and humidity were obtained, and no practical changes were observed even after repeated use of 10,000 sheets.
なお、１．８−ジアミノナフタレンを配位子とするＣＯ
錯体は、微粉砕したものであり、酸化電位４２０ｍＶ、
白色度０．６．平均粒径１．２ＩＬｍ（粒度分布は、１
ル■以下の粒子を６０個数％以上含む）を有する金属錯
体である。In addition, CO with 1,8-diaminonaphthalene as a ligand
The complex was finely ground and had an oxidation potential of 420 mV,
Whiteness 0.6. Average particle size: 1.2ILm (particle size distribution: 1
It is a metal complex having 60 number % or more of particles with the following characteristics.
工笠１」
トリーｐ−トリルグアニジン７部の代わりに酢酸セリウ
ムを７部用いる他は、実施例−１と同様にしてトナーお
よび現像剤を得、実施例１と同様に画像を得た。A toner and a developer were obtained in the same manner as in Example 1, except that 7 parts of cerium acetate was used instead of 7 parts of tri-p-tolylguanidine, and an image was obtained in the same manner as in Example 1.
得られた画像は、画像濃度において、初期からＨレベル
０．３、Ｍレベルで０．２１と実用に供し難いものであ
り１画像もチリチリ画像であった。The image density of the obtained image was 0.3 at the H level and 0.21 at the M level from the beginning, which was difficult to put to practical use, and each image was a dusty image.
なお、使用した酢酸セリウムは、酸化電位８５０ｍＶ、
白色度０．９、平均粒径１．９１Ｌｍ（粒度分布は、Ｉ
ＩＬ以下の粒子を５０個数％以上含む）を有する金属塩
である。The cerium acetate used had an oxidation potential of 850 mV,
Whiteness 0.9, average particle size 1.91Lm (particle size distribution is I
50% or more by number of particles below IL).
０℃に加熱した２本ロールで混練した。混線物を自然放
冷し、カッターミルで粗粉砕した後、ジェット気流を用
いた微粉砕機を用いて粉砕し、さらに風力分級機を用い
て分級して重量平均粒径７終薦１個数分布における最多
数粒子の粒径が５μｍ、１６ＩＬ■を越える粒径の粒子
数が全粒子数の０％の微粉体を得た。The mixture was kneaded using two rolls heated to 0°C. The mixed material is left to cool naturally, coarsely pulverized with a cutter mill, then pulverized with a pulverizer using a jet stream, and further classified using an air classifier to obtain a weight average particle size of 7, with a number distribution of 7. A fine powder was obtained in which the particle size of the largest number of particles was 5 μm, and the number of particles with a particle size exceeding 16 IL2 was 0% of the total number of particles.
次いで、上記微粉末１００部に、アミンシリコンオイル
で処理した疎水性コロイダルシリカ（日本アエロジル社
製）０．４部をサンプルミルで混合し、本発明の現像剤
たる一成分磁性トナーを作成した。Next, 0.4 parts of hydrophobic colloidal silica (manufactured by Nippon Aerosil Co., Ltd.) treated with amine silicone oil was mixed with 100 parts of the fine powder using a sample mill to prepare a one-component magnetic toner serving as the developer of the present invention.
このトナーを市販のレーザーコピア（商品名′ＮＰ−９
０３０．キャノン■製）に適用して画像出しした。Apply this toner to a commercially available laser copier (product name: NP-9).
030. The image was created by applying it to a camera (manufactured by Canon ■).
得られた画像は１画像源度においてＨレベルで１．４１
、Ｍレベルで０．６５を示し、ベタ部の画像濃度が十分
高く、ドツトの切れがシャープであり、中間調の再現の
目安としての写真画像もきれいに再現された。The obtained image has an H level of 1.41 at 1 image source intensity.
, the M level was 0.65, the image density in solid areas was sufficiently high, the dots were sharp, and the photographic image, which serves as a guide for halftone reproduction, was also clearly reproduced.
又１万枚の複写をくり返し行なったが、画像濃度におい
てＨレベルの変動が±０ 、０７以内、Ｍレベルの変動
が±０．１５以内であり、Ｖｓ−Ｄｐ特性に実用上変化
が認められなかった。さらに環境条件を３５℃、８５％
及び１５℃、１０％にしたところいずれも常温常湿と同
様良好な画像が得られ、これらは１万枚のくり返しの使
用においても実用上変化が認められなかった。In addition, after 10,000 copies were repeatedly made, the H level variation in image density was within ±0.07, the M level variation was within ±0.15, and no practical changes were observed in the Vs-Dp characteristics. There wasn't. Furthermore, the environmental conditions were changed to 35℃ and 85%.
and 15° C. and 10%, good images were obtained in both cases, similar to those obtained at room temperature and room humidity, and no practical changes were observed even after repeated use of 10,000 sheets.
なお、Ｎ 、 Ｎ ′、 Ｎ ” −トリナフチルグア
ニジンは微粉砕分級を行なったものであり、酸化電位３
５０ｍＶ、白色度０．９１粒径１．２１Ｌｓ（粒度分布
は、１＃Ｌｍ以下の粒子を７０個数％以上含む）を有す
る含チツソ有機化合物である。Note that N, N', N''-trinaphthylguanidine is finely pulverized and classified, and has an oxidation potential of 3.
It is a titanium-containing organic compound having a brightness of 50 mV, a whiteness of 0.91, and a particle size of 1.21 Ls (particle size distribution includes 70 number % or more of particles of 1 #Lm or less).
１１■二」
Ｎ、Ｎ・′、 Ｎ ” −）リナフチルグアニジン３部
の代わりに４．４′−ビス〔２，４−ジクミジノー１．
３．５−１リアシリル−６−アミノコ−ジフェニルメタ
ンを５部用いる他は、実施、例−３と同様にしてトナー
を得、更に実施例３と同様にして画像を得た。11■2''N,N・',N''-) 4,4'-bis[2,4-dicumidino 1.
3. A toner was obtained in the same manner as in Example 3, except that 5 parts of 5-1lyasilyl-6-aminocodediphenylmethane was used, and an image was obtained in the same manner as in Example 3.
得られた画像は、画像濃度においてＨレベルで１．３８
、Ｍレベルで０．６０を示し、ベタ部の画像濃度が十分
高く、ドツトの切れがシャープであり、中間調の再現の
目安としての写真画像もきれいに再現され、チリチリ画
像も見られなかった。The image density of the obtained image was 1.38 at H level.
, the M level was 0.60, the image density in the solid area was sufficiently high, the dots were sharp, the photographic image as a guide for the reproduction of halftones was clearly reproduced, and there were no dusty images.
又１万枚の複写をくり返し行なったが、得られた画像濃
度においてＨレベルの変動が１０．０７以内、Ｍレベル
の変動が±０．１５以内であり、ＶＳ−Ｄｐ特性に実用
上変化が認められなかった。さらに環境条件を３５℃、
８５％及び１５℃、１０％にしたところいずれも常温常
温と同様良好な画像が得られ、これらは１万枚のくり返
しの使用においても実用上変化が認められなかった。Furthermore, after 10,000 copies were repeatedly made, the H level variation in the obtained image density was within 10.07, and the M level variation was within ±0.15, indicating that there was no practical change in the VS-Dp characteristics. I was not able to admit. Furthermore, the environmental conditions were changed to 35℃,
When the temperature was set to 85%, 15° C., and 10%, images as good as those at room temperature were obtained, and no change was observed in practical use even after repeated use of 10,000 sheets.
なお、４．４′−ビス〔２，４−ジクミジノ−１，３，
５−）リアシリル−６−７ミノ〕−ジフェニルメタンは
微粉砕し分級を行ったものであり、酸化電位３９０ｍＶ
、白色度０．８．平均粒径１、ＩＩＬｍ（粒度分布はｌ
＃Ｌ以下の粒子を６０個数％以上含む）を有する含チツ
ソ有機化合物である。In addition, 4,4'-bis[2,4-dicumidino-1,3,
5-) Reasilyl-6-7mino]-diphenylmethane is finely pulverized and classified, and has an oxidation potential of 390 mV.
, whiteness 0.8. Average particle size 1, IILm (particle size distribution is l
It is a titanium-containing organic compound containing 60% or more of particles of #L or less).
止Ｊし隨λ
Ｎ、Ｎ′、Ｎ″−トリナフチルグアニジンを３部の代わ
りに、ジ−ｏ−トリルグアニジンを７部用いる他は、実
施例−３と同様にしてトナーを得、更に実施例３と同様
にして画像を得た。A toner was obtained in the same manner as in Example 3, except that 7 parts of di-o-tolylguanidine was used instead of 3 parts of N,N',N''-trinaphthylguanidine, and further carried out. Images were obtained in the same manner as in Example 3.
得られた画像は、初期においては２画像源度でＨレベル
で１．３２．Ｍレベルで０．６１を示し、良好であった
が、複写回数をくり返すに従って、著しく画像濃度が低
下し、複写枚数５００枚では、Ｈレベルで０．６３．Ｍ
レベルで０．４１となり、カブリも多く、チリチリ画像
も見られ、実用に供し難いものであった。The obtained image initially had an H level of 1.32. The M level showed 0.61, which was good, but as the number of copies was repeated, the image density decreased significantly, and after 500 copies, the H level showed 0.63. M
The level was 0.41, there was a lot of fog, and a dusty image was observed, making it difficult to put it to practical use.
また、３５℃、８０％の環境条件下では、初期の画像か
ら１画像源度においてＨレベルで０．７１、Ｍレベルで
０．３８であり、使用に耐えないものであった。Further, under the environmental conditions of 35° C. and 80%, the H level was 0.71 and the M level was 0.38 in one image source from the initial image, which was not usable.
なお、ジー０−）リルグアニジンは、酸化電位６００
ｍＶ、白色度０．９、平均粒径３．３＃Ｌｍ（粒度分布
は、２＃Ｌ−以下の粒子が３０％以下である）を有する
含チツソ有機化合物である。In addition, di0-)ylguanidine has an oxidation potential of 600
mV, whiteness of 0.9, and average particle size of 3.3 #Lm (particle size distribution is 30% or less of particles of 2 #L- or less).
０℃に熱した２本ロールで混練した。混線物を自然放冷
し、カッターミルで粗粉砕した後、ジェット気流を用い
た微粉砕機を用いて粉砕し、さらに風力分級機を用いて
分級して重量平均粒径６μｍ、個数分布における最多数
粒子の粒径が４７ＬＩＩ、１６μ腸を越える粒径の粒子
数が全粒子数の１％の微粉体トナーを得た。The mixture was kneaded using two rolls heated to 0°C. The mixed material was left to cool naturally, coarsely pulverized with a cutter mill, then pulverized with a fine pulverizer using a jet stream, and further classified using an air classifier to obtain a weight average particle size of 6 μm and the highest particle size in the number distribution. A fine powder toner was obtained in which the majority particles had a particle size of 47 LII and the number of particles having a particle size exceeding 16 μm was 1% of the total number of particles.
次いで上記トナー微粉末１００部に、粒径３０〜５０終
−の樹脂被覆球形キャリア９００部を混合して現像剤と
した。Next, 900 parts of a resin-coated spherical carrier having a particle size of 30 to 50 mm was mixed with 100 parts of the fine toner powder to prepare a developer.
このトナーを市販のレーザービームプリンターに適用し
て画像出しをおこなったところ、画像濃度１．３５の鮮
やかな青色画像が得られ、カブリもなく、画像の鮮鋭さ
も充分満足し得るものであった、又、２０００枚の複写
をくり返し行なったが、画像濃度１．３３とほとんど変
動はなく、画像の鮮鋭さの低下も認められなかった。さ
らに複写環境を３５℃、８５％及び１５℃、１０％にし
たが、いずれも常温、常湿と同様に良好な画像が得られ
た。When this toner was applied to a commercially available laser beam printer to produce an image, a bright blue image with an image density of 1.35 was obtained, there was no fogging, and the sharpness of the image was sufficiently satisfactory. Further, although 2,000 copies were repeatedly made, the image density remained almost unchanged at 1.33, and no deterioration in image sharpness was observed. Further, although the copying environment was set to 35° C., 85% and 15° C., 10%, good images were obtained in both cases, as in normal temperature and normal humidity.
なお、トリス（２、４、６−ドリメチルフエニル）ビス
マスは、微粉砕したものであり、酸化電位６８０ｍＶ、
白色度０．９、平均粒径０ 、９ ＪＬＩ（粒度分布は
、ｌ＃Ｌ■以下の粒子を５０個％以上含む）を有する有
機金属化合物である。Note that tris(2,4,6-drimethylphenyl)bismuth is finely ground and has an oxidation potential of 680 mV,
It is an organometallic compound having a whiteness of 0.9 and an average particle size of 0.9 JLI (particle size distribution includes 50% or more of particles of 1#L■ or less).
を狡遣」
トリス（２，４，６−）リメチルフェニル）ビスマス７
部の代わりに、２−アミノ−５−メチルフェノールのＺ
ｎ錯体を５部用いる他は、実施例−５と同様にしてトナ
ーを得、更に実施例５と同様にして画像を得た。Tris(2,4,6-)limethylphenyl) bismuth 7
Z of 2-amino-5-methylphenol instead of part
A toner was obtained in the same manner as in Example 5, except that 5 parts of the n-complex was used, and an image was obtained in the same manner as in Example 5.
得られた画像の画像濃度は、１．３０と良好↑あったが
、画像の色調は、２−アミノ−５−メチルフェノールの
Ｚｎ錯体の影響で黒青色であり、鮮鋭さに欠ける画像で
あった。The image density of the obtained image was 1.30, which was good↑, but the color tone of the image was black-blue due to the influence of the Zn complex of 2-amino-5-methylphenol, and the image lacked sharpness. Ta.
なお、該Ｃｏ錯体は、酸化電位５２０ｍＶ、白色度０．
４、平均粒径３．７終■を有する金属錯体である。The Co complex has an oxidation potential of 520 mV and a whiteness of 0.
4. It is a metal complex having an average particle size of 3.7 mm.
第１図（ａ）、（ｂ）は多値ディザマトリックスの概念
を示す図であり、第２図（ａ）、（ｂ）及び第３図（ａ
）、（ｂ）は３値記録を行なう場合の露光強度分布と静
電潜像の電位分布を示す特性グラフであり・、第４図は
多値の潜像の現像特性を示すグラフであり、第５図は、
トナー粒子ｌ側当りのトリボ電荷とその電荷を有するト
ナー粒子の個数との関係を示すトリボ電荷分布図であり
、第６図（ａ）、（ｂ）は本発明に用いる正荷電性化合
物の酸化電位にかかわる電位−電流曲線を示す図であり
、第７図は本発明に用いる正荷電性化合物にかかわる酸
化電位−トナートリボ曲線を示す図であり、第８図は本
発明に用いる正荷電性化合物にかかわる化合物の粒度−
画像濃度曲線を示す図であり、第９図は本発明の現像剤
を適用する電子写真プリンターの具体例を概略的に示す
図であり、第１０図は本発明現像剤の現像特性を示すグ
ラフである。
１・・・レーサ変調ユニット
２・・・スキャナ・ミラー
３・・・ｆ・θレンズ
４・・・感光ドラム
５．６・・・コロナ放電器
９・・・第１現像器
１０・・・第２現像器
ｆ！ＵＬ５＝第５図
第５図
トソ次−ｔＡ
（）−ナー、ｆｔ＋＋４ｒＩｉ’ｔ５）Ｘ７図Figures 1(a) and (b) are diagrams showing the concept of a multivalued dither matrix, and Figures 2(a) and (b) and Figure 3(a) are diagrams showing the concept of a multilevel dither matrix.
), (b) are characteristic graphs showing the exposure intensity distribution and potential distribution of an electrostatic latent image when performing three-value recording, and FIG. 4 is a graph showing the development characteristics of a multi-valued latent image. Figure 5 shows
6 is a triboelectric charge distribution diagram showing the relationship between the triboelectric charge per toner particle side and the number of toner particles having that charge, and FIGS. 6(a) and 6(b) show the oxidation of the positively charged compound used in the present invention. FIG. 7 is a diagram showing a potential-current curve related to potential, FIG. 7 is a diagram showing an oxidation potential-toner ribo curve related to a positively charged compound used in the present invention, and FIG. 8 is a diagram showing a positively charged compound used in the present invention. Particle size of compounds involved in -
FIG. 9 is a diagram schematically showing a specific example of an electrophotographic printer to which the developer of the present invention is applied, and FIG. 10 is a graph showing the development characteristics of the developer of the present invention. It is. 1...Laser modulation unit 2...Scanner mirror 3...F/θ lens 4...Photosensitive drum 5.6...Corona discharger 9...First developer 10...No. 2 developer f! UL5=Figure 5Figure 5Toso next -tA ()-ner, ft++4rIi't5)X7Figure
Claims (1)
つ平均粒径が３．０μｍ以下の正荷電性化合物を含有す
るトナーであって、重量分布による平均粒径が３〜１０
μｍ、個数分布における最多数粒子の粒径が１〜８μｍ
、且つ粒径１６μｍを越える粒子数が全粒子数の２％以
下である粒子群からなるトナーを含有することを特徴と
する正荷電性現像剤。A toner containing a positively charged compound having an oxidation potential of 750 mV or less, a whiteness W of 0.5 or more, and an average particle size of 3.0 μm or less, the average particle size according to weight distribution being 3 to 10 μm.
μm, the particle size of the largest number of particles in the number distribution is 1 to 8 μm
, and the number of particles having a particle size exceeding 16 μm is 2% or less of the total number of particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089378A JPH07117775B2 (en) | 1986-04-18 | 1986-04-18 | Developer for electrostatic image development |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089378A JPH07117775B2 (en) | 1986-04-18 | 1986-04-18 | Developer for electrostatic image development |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62245267A true JPS62245267A (en) | 1987-10-26 |
| JPH07117775B2 JPH07117775B2 (en) | 1995-12-18 |
Family
ID=13969017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61089378A Expired - Fee Related JPH07117775B2 (en) | 1986-04-18 | 1986-04-18 | Developer for electrostatic image development |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07117775B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02877A (en) * | 1988-02-24 | 1990-01-05 | Canon Inc | Nonmagnetic toner |
| JPH0253076A (en) * | 1988-08-18 | 1990-02-22 | Canon Inc | Magnetic toner for developing electrostatic charge image |
| JPH0273260A (en) * | 1988-09-09 | 1990-03-13 | Canon Inc | Magnetic toner for electrostatic charge image development |
| JPH0273261A (en) * | 1988-09-09 | 1990-03-13 | Canon Inc | Magnetic toner for electrostatic charge image development |
| JPH02277075A (en) * | 1989-04-19 | 1990-11-13 | Canon Inc | Electrostatic charge image developing toner |
| JPH02287365A (en) * | 1989-04-28 | 1990-11-27 | Canon Inc | Image forming method |
| JPH02287366A (en) * | 1989-04-28 | 1990-11-27 | Canon Inc | Image forming method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5933459A (en) * | 1982-08-20 | 1984-02-23 | Konishiroku Photo Ind Co Ltd | Electrostatic image developing toner |
-
1986
- 1986-04-18 JP JP61089378A patent/JPH07117775B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5933459A (en) * | 1982-08-20 | 1984-02-23 | Konishiroku Photo Ind Co Ltd | Electrostatic image developing toner |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02877A (en) * | 1988-02-24 | 1990-01-05 | Canon Inc | Nonmagnetic toner |
| JPH0253076A (en) * | 1988-08-18 | 1990-02-22 | Canon Inc | Magnetic toner for developing electrostatic charge image |
| JPH0273260A (en) * | 1988-09-09 | 1990-03-13 | Canon Inc | Magnetic toner for electrostatic charge image development |
| JPH0273261A (en) * | 1988-09-09 | 1990-03-13 | Canon Inc | Magnetic toner for electrostatic charge image development |
| JPH02277075A (en) * | 1989-04-19 | 1990-11-13 | Canon Inc | Electrostatic charge image developing toner |
| JPH02287365A (en) * | 1989-04-28 | 1990-11-27 | Canon Inc | Image forming method |
| JPH02287366A (en) * | 1989-04-28 | 1990-11-27 | Canon Inc | Image forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07117775B2 (en) | 1995-12-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |