JPS61248060A - Toner for developing electrostatic charge image - Google Patents
Toner for developing electrostatic charge imageInfo
- Publication number
- JPS61248060A JPS61248060A JP60088875A JP8887585A JPS61248060A JP S61248060 A JPS61248060 A JP S61248060A JP 60088875 A JP60088875 A JP 60088875A JP 8887585 A JP8887585 A JP 8887585A JP S61248060 A JPS61248060 A JP S61248060A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- group
- developer
- image
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- G03G9/09733—Organic compounds
- G03G9/09775—Organic compounds containing atoms other than carbon, hydrogen or oxygen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
- G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
- G03G15/0806—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller
- G03G15/0812—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller characterised by the developer regulating means, e.g. structure of doctor blade
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
- G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
- G03G15/0806—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller
- G03G15/0818—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller characterised by the structure of the donor member, e.g. surface properties
-
- 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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09783—Organo-metallic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は電子写真、”静電記録及び静電印刷等における
静電荷像を現像するための新規なトナーに関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.
[従来の技術]
従来、電子写真法としては米国特許第
2.2137.891号、特公昭42−23910号公
報及び特公昭43−24748号公報などに、種々の方
法が記載されているが、それらは要するに、光導電性絶
縁体層上に一様な静電荷を与え、該絶縁体層に光像を照
射することによって静電潜像を形成し、次いで該潜像を
当該技術でトナーと呼ばれる微粉末によって現像可視化
し、必要に応じて紙などに粉像を転写した後、加熱、加
圧、或いは溶剤蒸気などによって定着を行なうものであ
る。[Prior Art] Conventionally, various electrophotographic methods have been described in U.S. Pat. They essentially provide a uniform electrostatic charge on a photoconductive insulator layer, form an electrostatic latent image by irradiating the insulator layer with a light image, and then apply the latent image to a toner using the technique. After the powder image is developed and visualized using a so-called fine powder, if necessary, the powder image is transferred to paper or the like, and then fixed by heating, pressure, solvent vapor, or the like.
これらの電子写真法等に適用される現像方法としては、
大別して乾式現像法と湿式現像法とがある。前者は更に
、二成分系現像剤を用いる方法と、−成分系現像剤を用
いる方法に二分される。The developing methods applied to these electrophotographic methods include:
Broadly speaking, there are dry development methods and wet development methods. The former method is further divided into a method using a two-component developer and a method using a -component developer.
二成分系現像方法に属するものには、トナーを搬送する
キャリヤーの種類により、鉄粉キャリヤーを用いるマグ
ネットブラシ法、ビーズ・キャリヤーを用いるカスケー
ド法、ファーを用いるファーブラシ法等がある。Two-component developing methods include a magnetic brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using fur, etc., depending on the type of carrier for conveying the toner.
又、−成分系現像方法に属するものには、トナー粒子を
噴霧状態にして用いるパウダークラウド法、トナー粒子
を直接的に静電潜像面に接触させて現像する接触現像法
(コンタクト現像、又はトナー現像ともいう)、トナー
粒子を静電潜像面に直接接触させず、トナー粒子を荷電
して静電潜像の有する電界により該潜像面に向けて飛行
させるジャンピング現像法、磁性の導電性トナーを静電
潜像面に接触させて現像するマグネドライ法等がある。In addition, those belonging to the -component type development method include a powder cloud method in which toner particles are sprayed, and a contact development method (contact development, or (also referred to as toner development), jumping development method in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and flown toward the latent image surface by the electric field of the electrostatic latent image; and magnetic conductive method. There is the MagneDry method, which develops by bringing a toner into contact with the electrostatic latent image surface.
これらの現像法に適用するトナーとしては、従来、天然
あるいは合成樹脂中に染料、顔料を分散させた微粉末が
使用されている0例えば、ポリスチレンなどの結着樹脂
中に着色剤を分散させたものを1〜30ル程度に微粉砕
した粒子がトナーとして用いられている。磁性トナーと
してはマグネタイトなどの磁性粒子を含有したものが用
いられている。いわゆる二成分現像剤を用いる方式の場
合には、トナーは通常ガラスピーズ、鉄粉などのキャリ
ヤー粒子と混合されて用いられる。又、トナーは、現像
される静電潜像の極性に応じて正または負の電荷が保有
せしめられる。Conventionally, toners used in these development methods are fine powders in which dyes and pigments are dispersed in natural or synthetic resins. Finely pulverized particles of about 1 to 30 liters are used as toner. As the magnetic toner, one containing magnetic particles such as magnetite is used. In the case of a system using a so-called two-component developer, the toner is usually mixed with carrier particles such as glass beads and iron powder. Further, the toner is made to hold a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.
トナーに電荷を保有せしめるためには、トナーの成分で
ある樹脂の摩擦帯電性を利用することも出来るが、この
方法ではトナーの帯電性が小さいので、現像によって得
られる画像はカブリ易く、不鮮明なものとなる。そこで
、所望の摩擦帯電性をトナーに付与するために、帯電性
を付与する染料、顔料、更には荷電制御剤なるものを添
加することが行われている。In order to make the toner hold an electric charge, it is also possible to use the triboelectricity of the resin that is a component of the toner, but since the toner's chargeability is small with this method, the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart desired triboelectrification properties to toners, dyes and pigments that impart electrostatic properties, as well as charge control agents, are added.
今日、当該技術分野で知られている荷電制御剤としては
、以下のものがあげられる。Charge control agents known in the art today include the following:
(1)トナーを正荷電性に制御するものとして下記物質
がある。(1) The following substances can be used to control the toner to be positively charged.
ニグロシン、炭素数2〜1Bのアルキル基を含むアジン
系染料(特公昭42−1827号)、塩基性染料(例え
ば、C,1,Bagic Yellow 2 (C,1
,41000)、C,1,Ba5ic Yellow
3 、 C,1,Ba5ic Red 1(C,1,4
5180) 、 C,1,Ba5ic Red ill
(C,l−42500)、C,1,Ba5ic Vi
olet 1 (C,1,42535)、C,1,Ba
5ic Violet 3 (C,I−42555)
C,1,Ba5icViolet 10 (C,1,4
5170)、C,1,、Ba5ic Violet 1
4(C,1,4251G) 、 C,1,Ba5ic
Blue 1 (C,1゜42025)、C,1,Ba
5ic Blue 3 (C,1,51005)、C,
I。Nigrosine, azine dyes containing an alkyl group having 2 to 1B carbon atoms (Japanese Patent Publication No. 1827/1983), basic dyes (e.g., C,1, Basic Yellow 2 (C,1
, 41000), C, 1, Ba5ic Yellow
3, C,1,Ba5ic Red 1(C,1,4
5180), C,1,Ba5ic Red ill
(C,l-42500),C,1,Ba5ic Vi
olet 1 (C,1,42535), C,1,Ba
5ic Violet 3 (C, I-42555)
C,1,Ba5icViolet 10 (C,1,4
5170), C,1,, Ba5ic Violet 1
4(C,1,4251G), C,1,Ba5ic
Blue 1 (C, 1°42025), C, 1, Ba
5ic Blue 3 (C, 1, 51005), C,
I.
Bs1c Blue 5 (C,1,42140)、C
,1,Ba5ic Blua7 (C,1,42595
)、C,1,Ba5ic Blue 13 (C,I。Bs1c Blue 5 (C, 1, 42140), C
,1,Ba5ic Blua7 (C,1,42595
), C,1,Ba5ic Blue 13 (C,I.
52015)、C,1,Bagic Blua 24
(C,1,52030)、C,1,−Basic Bl
ue 25 (C,!、 52025)、C,1,Ba
5ic Blue2B (C,1,44045) 、
C,1,Ba5ic Green l (C,l−42
040)、C,L Ba5ic Green 4 (C
,1,42000)など)、これらの塩基性染料のレー
キ顔料、(レーキ化剤としては、りんタングステン酸、
りんモリブデン酸、りんタングステンモリブデン酸、タ
ンニン酸、ラウリン酸、没食子酸、フェリシアン化物、
フェロシアン化物なト、 ) 、C,1゜5olven
t Black 3 (C,I−28150) 、 ハ
ンザイエローG (C,1,11880)、C,1,
Mordant Black 11 。52015), C, 1, Basic Blue 24
(C,1,52030),C,1,-Basic Bl
ue 25 (C,!, 52025), C,1,Ba
5ic Blue2B (C, 1, 44045),
C,1,Ba5ic Green l (C,l-42
040), C, L Ba5ic Green 4 (C
, 1,42000), etc.), lake pigments of these basic dyes, (lake-forming agents include phosphotungstic acid,
Phosphormolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide,
Ferrocyanide, ), C, 1°5olven
t Black 3 (C, I-28150), Hansa Yellow G (C, 1, 11880), C, 1,
Mordant Black 11.
C,1,Pig+5ent Black 1、ギルツナ
イト、アスファルト等。C, 1, Pig+5ent Black 1, Gilt Night, Asphalt, etc.
第4級アンモニウム塩、例えばベンジルメチル−ヘキサ
デシルアンモニウムクロライド、デシル−トリメチルア
ンモニウムクロライド、ジブチルチンオキサイド等の有
機錫化合物、高級脂肪酸の金属塩、ガラス、雲母、酸化
亜鉛等の無機微粉末、EDTA、アセチルアセトンの金
属錯体等、アミン基を含有するビニル系ポリマー、アミ
ノ基を含有する縮合系ポリマー等のポリアミン樹脂。Quaternary ammonium salts, such as benzylmethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, inorganic fine powders such as glass, mica, and zinc oxide, EDTA, Polyamine resins such as metal complexes of acetylacetone, vinyl polymers containing amine groups, and condensation polymers containing amino groups.
(2)トナーを負荷電性に制御するものとして下記物質
がある。(2) The following substances can be used to control the negative chargeability of toner.
特公昭41−20153号、同43−275138号、
同44−8H7号、同45−28478号などに記載さ
れている七ノアゾ染料の金属錯塩。Special Publication No. 41-20153, No. 43-275138,
44-8H7, 45-28478, etc. Metal complex salts of heptanoazo dyes.
特開昭50−133338号に記載されているニトロフ
ミン酸及びその塩或いはC,1,14845などの染顔
料。Dyes and pigments such as nitrofumic acid and its salts or C, 1,14845 described in JP-A-50-133338.
特公昭55−42752号、特公昭58−41508号
、特公昭59−7384号、特公昭59−7385号な
どに記載されているサリチル酸、ナフトエ酸、グイカル
ボン酸のGo、 Cr、 Fe等の金属錯体、スルホン
化した銅フタロシアニン顔料、ニトロ基、ハロゲンを導
入したスチレンオリゴマー、塩素化パラフィン、メラミ
ン樹脂等。Metal complexes of salicylic acid, naphthoic acid, guicarboxylic acid such as Go, Cr, Fe, etc. described in Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 58-41508, Japanese Patent Publication No. 59-7384, Japanese Patent Publication No. 59-7385, etc. , sulfonated copper phthalocyanine pigments, nitro groups, styrene oligomers with halogens introduced, chlorinated paraffins, melamine resins, etc.
これらの荷電制御剤は染顔料から派生したものが多く、
一般的に構造が複雑でその多くが強い着色性をもってい
る。Many of these charge control agents are derived from dyes and pigments.
Generally, they have a complex structure, and many of them have strong coloring properties.
最近新たに提案されたものには、これらとは系統の異な
るものも見受けられるが、染顔料系統のものを総合性能
で上まわったものはなく、未だ不満足ながら染顔料類を
使用している例がほとんどである。Recently, there are some newly proposed products that are different from these, but none have superior overall performance to dyes and pigments, and examples of dyes and pigments still being used are still unsatisfactory. Most of them are.
これらは、通常熱可塑性樹脂に添加され、熱溶融分散し
1.これを微粉砕して、必要に応じて適当な粒径に調整
され使用される。These are usually added to thermoplastic resins and thermally melted and dispersed.1. This is finely pulverized and adjusted to an appropriate particle size as necessary for use.
しかしながら、これらの荷電制御剤としての染料は、構
造が複雑で性質が一定しておらず安定性に乏しい、また
、熱混練時の分解、機械的衝撃、摩擦、温湿度条件の変
化などにより分解又は変質し易く、荷電制御性が低下す
る現象を生じ易い。However, these dyes used as charge control agents have complex structures, inconsistent properties, and poor stability, and are susceptible to decomposition during thermal kneading, mechanical impact, friction, changes in temperature and humidity conditions, etc. Otherwise, it is likely to change in quality and cause a phenomenon in which charge controllability is deteriorated.
従って、これらの染料を荷電制御剤として含有したトナ
ーを複写機に用いて現像すると、複写回数の増大に伴い
、荷電制御剤が分解あるいは変質し、耐久中にトナーの
劣化を引き起こすことがある。Therefore, when a toner containing these dyes as a charge control agent is used for development in a copying machine, as the number of copies increases, the charge control agent decomposes or changes in quality, which may cause deterioration of the toner during durability.
又、これらの荷電制御剤は、熱可塑性樹脂中に均一に分
散する事が極めて困難であるため、粉砕して得られたト
ナー粒子間の摩擦帯電量に差異を生じるという致命的な
問題点を有している。このため、従来、分散をより均一
に行なうための種々の方法が行なわれている0例えば、
塩基性ニグロシン染料は、熱可塑性樹脂との相溶性を向
上させるために、高級脂肪酸と造塩して用いられるが、
しばしば未反応分の脂肪酸あるいは、塩の分散生成物が
、トナー表面に露出して、キ・ヤリャーあるいは、トナ
ー担持体を汚染し、トナーの流動性低下やカブリ、画像
濃度の低下を引き起こす原因と、 なっている、あるい
は、これらの荷電制御剤の樹脂中への分散向上のために
、あらかじめ、荷電制御剤粉末と樹脂粉末とを機械的に
粉砕混合してから熱溶融混練する方法もとられている。Furthermore, since it is extremely difficult to uniformly disperse these charge control agents in thermoplastic resins, they pose the fatal problem of causing differences in the amount of frictional charge between toner particles obtained by pulverization. have. For this reason, various methods have been used to achieve more uniform dispersion.
Basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve their compatibility with thermoplastic resins.
Dispersion products of unreacted fatty acids or salts are often exposed on the toner surface and contaminate the carrier or toner carrier, causing a decrease in toner fluidity, fogging, and a decrease in image density. Alternatively, in order to improve the dispersion of these charge control agents into the resin, methods are also used in which charge control agent powder and resin powder are mechanically pulverized and mixed in advance and then hot melt kneaded. ing.
しかし、本来の分散不良性は回避する事ができず、未だ
実用上充分な荷電の均一さは得られていないのが現状で
ある。However, the inherent poor dispersion cannot be avoided, and the current situation is that sufficient charge uniformity has not yet been obtained for practical use.
又、一般に荷電制御剤として知られている物質は、その
多くが暗色であり、鮮やかな有彩色現像剤に含有させる
ことができないという問題点がある。Moreover, most of the substances generally known as charge control agents have a dark color, and there is a problem in that they cannot be incorporated into bright chromatic color developers.
又、荷電制御剤は親水性のものが多く、これらの樹脂中
への分散不良のために、溶融混練後、粉砕した時に染料
がトナー表面に露出し、高湿条件下で、こ屁ら荷電制御
剤が親水性であるがために良質な画像が得られないとい
う欠点を有している。In addition, many charge control agents are hydrophilic, and due to poor dispersion in these resins, the dye is exposed on the toner surface when it is crushed after melt-kneading, and under high humidity conditions, the charge control agent is Since the control agent is hydrophilic, it has the disadvantage that good quality images cannot be obtained.
この様に、従来の荷電制御剤をトナーに用いた際には、
トナー粒子間に於いて、あるいはトナーとキャリヤー間
、トナーとスリーブのごときトナー担持体間に於いて、
トナー粒子表面に発生する電荷量にバラツキを生じ、現
像カブリ、トナー飛散、キャリヤー汚染等の障害が発生
し易い、またこの障害は、複写回数を多く重ねた際に顕
著な現象とな゛って現われ、実質上、複写機には適さな
い結果となる。In this way, when conventional charge control agents are used in toner,
Between toner particles, between toner and carrier, between toner and toner carrier such as a sleeve,
This causes variations in the amount of charge generated on the surface of toner particles, which tends to cause problems such as development fog, toner scattering, and carrier contamination, and these problems become more noticeable when copies are made many times. This results in a result that is virtually unsuitable for copying machines.
さらに、高湿条件下に於いては、トナー画像の転写効率
が著しく低下し、使用に耐えないものが多い、常温常湿
に於いてさえも、該トナーを長期保存した際には、用い
た荷電制御剤の不安定性のために、変質を起こし、荷電
性不良のために使用不可能になる場合が多い。Furthermore, under high humidity conditions, the transfer efficiency of toner images decreases significantly, making many toners unusable. Due to the instability of charge control agents, they often undergo deterioration and become unusable due to poor charging properties.
さらに従来の荷電制御剤をトナーに用いた際には、長期
間の使用により、感光体表面に荷電制御剤が付着ないし
トナーの付着を助長し、潜像形成に悪影響を与えたり(
フィルミング現象)、感光体表面又はクリーニングブレ
ード等のクリーニング部材にキズを生じせしめる或いは
該部材の摩耗を促進するもの等複写機のクリーニング工
程に悪い作用をもたらすものが少なくない。Furthermore, when conventional charge control agents are used in toner, long-term use may cause the charge control agents to adhere to the surface of the photoreceptor or promote toner adhesion, adversely affecting latent image formation (
There are many things that have a negative effect on the cleaning process of a copying machine, such as the filming phenomenon), those that cause scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, and those that accelerate wear of the members.
さらに従来の荷電制御剤をトナーに用いた際には、トナ
ーの熱溶融特性に大きな影響を与え定着性能を低下させ
るものも少なくない、特に高温時の耐オフセット性を悪
化させ、ヒートロール定着時の転写材のローラーへのま
きつき性を増す。Furthermore, when conventional charge control agents are used in toner, many of them have a large effect on the thermal melting properties of the toner and reduce fixing performance.In particular, they worsen offset resistance at high temperatures, and when heat roll fixing Increases the ability of the transfer material to cling to the roller.
ローラーの耐久寿命を低下させるもの等がみうけられる
。There are some things that reduce the durability life of the roller.
このように従来の荷電制御剤には多くの欠点がみられ、
これらを改良することが当該技術分野で強く要請され、
これまでにも幾多の改良技術が提案されてはいるが、い
まだ実用上総合的に満足できるものが見い出されていな
いのが実情である。As described above, conventional charge control agents have many drawbacks.
There is a strong demand in the technical field to improve these.
Although many improved techniques have been proposed so far, the reality is that no one has yet been found that is comprehensively satisfactory for practical use.
[発明が解決しようとする問題点]
本発明の目的は、かかる問題点を克服したトナーの荷電
制御の新しい技術を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a new technique for toner charge control that overcomes these problems.
本発明の他の目的は、トナー粒子間、またはトナーとキ
ャリヤー間、−成分現像の場合のトナーとスリーブの如
きトナー担持体との間等の摩擦帯電量が安定で、かつ庫
擦帯電量分布がシャープで均一であり、使用する現像シ
ステムに適した帯電量にコントロールできる現像剤の提
供にある。・さらに他の目的は、潜像に忠実な現像、及
び転写を行なわしめる現像剤、即ち、現像時のバックグ
ラウンド領域におけるトナーの付着即ち、カブリや潜像
のエツジ周辺へのトナーの飛び散りがなく、高い画像濃
度が得られ、ハーフトーンの再現性の良い現像剤の提供
にある。Another object of the present invention is to stabilize the amount of triboelectricity between toner particles, between a toner and a carrier, or between a toner and a toner carrier such as a sleeve in the case of component development, and to have a distribution of triboelectricity. The object of the present invention is to provide a developer that has a sharp and uniform charge and can be controlled to an amount of charge suitable for the developing system used.・Furthermore, another purpose is to develop a developer that is faithful to the latent image and to perform transfer, that is, toner adhesion in the background area during development, without fogging or toner scattering around the edges of the latent image. The object of the present invention is to provide a developer that provides high image density and good halftone reproducibility.
さらに他の目的は、現像剤を長期にわたり連続使用した
際も初期の特性を維持し、トナーの凝集や帯電特性の変
化のない現像剤の提供にある。Still another object is to provide a developer that maintains its initial characteristics even when the developer is used continuously over a long period of time, and that causes no toner aggregation or change in charging characteristics.
さらに他の目的は、温度、湿度の変化に影響を受けない
安定した画像を再現する現像剤、特に高湿時及び低湿時
の転写時の飛び散りゃ転写ぬけなどのない転写効率の高
い現像剤の提供にある。Another objective is to develop a developer that reproduces stable images that are not affected by changes in temperature and humidity, especially a developer that has high transfer efficiency and does not cause scattering or transfer dropouts during transfer at high or low humidity. On offer.
さらに他の目的は、鮮やかな有彩色現像剤の提供にある
。Still another object is to provide a bright chromatic developer.
さらに他の目的は、長期間の保存、でも初期の特性を維
持する保存安定性の優れた現像剤の提供にある。Still another object is to provide a developer with excellent storage stability that maintains its initial characteristics even during long-term storage.
さらに他の目的は、静電潜像面を汚したり、摩耗したり
、キズをつけたりしないクリーニング工程の容易な現像
剤の提供にある。Still another object is to provide a developer that does not stain, abrade, or scratch the electrostatic latent image surface and is easy to clean.
さらに他の目的は、良好な定着特性を有する現像剤、特
に高温オフセット等に問題のない現像剤の提供にある。Still another object is to provide a developer that has good fixing properties, particularly a developer that does not have problems such as high-temperature offset.
[問題点を解決するための手段及び作用]本発明は、静
電荷像の現像に供する電子写真用トナーであって、一般
式[IIで表わされるアリール化グアニジン類を含有す
ることを特徴とする静電荷像現像用トナー。[Means and effects for solving the problems] The present invention provides an electrophotographic toner for developing electrostatic images, which is characterized by containing an arylated guanidine represented by the general formula [II]. Toner for developing electrostatic images.
H
II H
Ar+−N−C−N−Arz [: I
][式中、Arl 、 Ar2は置換基としてハロゲン
原子。H II H Ar+-N-C-N-Arz [: I
] [In the formula, Arl and Ar2 are halogen atoms as substituents.
アルキル基、置換アルキル基、環状アルキル基。Alkyl group, substituted alkyl group, cyclic alkyl group.
アリール基、アラルキル基、アルコキシ基、アリールオ
キシ基、アラルキルオキシ基、アルキルチオ基、アリー
ルチオ基、アラルキルチオ基、アミノ基、ニトロ基を1
つ以上有していてもよいアリール基または水素原子を示
し、Ar1 、 Ar2は同じであっても異なっていて
もよい。(但し、Arl 。Aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, amino group, nitro group
represents an aryl group or hydrogen atom which may have more than one, and Ar1 and Ar2 may be the same or different. (However, Arl.
Ar2は同時に水素原子ではない、)]本発明者らは、
一般式[IIで表わされるアリール化グアニジン類が熱
的、時間的に安定であり、吸湿性も少なく、現像剤に含
有した場合、電子写真特性の優秀な現像剤を与える良質
な荷電制御剤であることを見い出した。Ar2 is not a hydrogen atom at the same time)] The present inventors
The arylated guanidines represented by the general formula [II are thermally and temporally stable, have low hygroscopicity, and are good charge control agents that, when included in a developer, provide a developer with excellent electrophotographic properties. I discovered something.
〒般式[IIにおいて、1つ以上の置換基を有していて
もよいアリール基の置換基としては、例えばフッ素原子
、塩素原子、臭素原子、沃素原子などのハロゲン原子:
メチル基、エチル基、プロピル基、ブチル基、ヘキシル
基、ドデシル基などの分岐していてもよいアルキル基:
メトキシエチル基、エトキシエチル基、ブトキシエチル
基、クロルエチル基、ジメチルアミノエチル基などの置
換アルキル基;フェニル基、トルイル基、ブチルフェニ
ル基、ブトキシフェニル基、クロルフェ−ニル基などの
7リール基又は置換アリール基;ベンジル基、フェネチ
ル基、メチルベンジル基などの7ラルキル基;メトキシ
基、エトキシ基、プロポキシ基、ブトキシ基、オクトキ
シ基などのアルコキシ基;フェノキシ基、メチルフェノ
キシ基、ブトキシフェノキシ基、クロルフェノキシ基な
どの7リールオキシ基又は置換アリールオキシ基;ベン
ジルオキシ基、メチルベンジルオキシ基、クロルベンジ
ルオキシ基、フェネチルオキシ基などのアラルキルオキ
シ基又は置換アラルキルオキシ基;メチルチオ基、プロ
ピルチオ基、ヘキシルチオ基などのフルキルチオ基;フ
ェニルチオ基、メチルフェニルチオ基、エチルフェニル
チオ基、クロルフェニルチオ基などの7リールチオ基又
は置換アリールチオ基;ベンジルチオ基、クロルベンジ
ルチオ基、メチルベンジルチオ基などの7ラルキルチオ
基又は置換アラルキルチオ基;アミノ基;ニトロ基:・
7シクロブチル基、シクロペンチル基、シクロヘキシル
基、シクロオクチル基などの環状アルキル基などが挙げ
られる。In the general formula [II, substituents for the aryl group which may have one or more substituents include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom:
Alkyl groups that may be branched such as methyl group, ethyl group, propyl group, butyl group, hexyl group, dodecyl group:
Substituted alkyl groups such as methoxyethyl group, ethoxyethyl group, butoxyethyl group, chloroethyl group, dimethylaminoethyl group; 7-aryl group or substituted such as phenyl group, tolyl group, butylphenyl group, butoxyphenyl group, chlorphenyl group Aryl group; heptaralkyl group such as benzyl group, phenethyl group, methylbenzyl group; alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, octoxy group; phenoxy group, methylphenoxy group, butoxyphenoxy group, chlorophenoxy 7-aryloxy group or substituted aryloxy group such as groups; aralkyloxy group or substituted aralkyloxy group such as benzyloxy group, methylbenzyloxy group, chlorobenzyloxy group, phenethyloxy group; methylthio group, propylthio group, hexylthio group, etc. Furkylthio group; 7-arylthio group or substituted arylthio group such as phenylthio group, methylphenylthio group, ethylphenylthio group, chlorphenylthio group; 7ralkylthio group or substituted such as benzylthio group, chlorobenzylthio group, methylbenzylthio group Aralkylthio group; Amino group; Nitro group:・
Examples include cyclic alkyl groups such as 7-cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.
一般式[I]で表わされるアリール化グアニジン類の代
表的な具体例としては、次のようなものがある。Typical specific examples of the arylated guanidines represented by the general formula [I] include the following.
[化合物例] これらの化合物は公知の方法で合成される。[Compound example] These compounds are synthesized by known methods.
すなわち、グアニジンに対応するクロロアリールを作用
させれば良い。That is, a chloroaryl corresponding to guanidine may be used.
例えば化合物例(1)は、グアニジンに1−クロロ、2
−エチルトルエンを作用させることで得られる。一般に
上記化合物は、平均粒径が10〜0.01.、特に5〜
0.1pの範囲の粒径としてトナー調整に供することが
好ましい。For example, compound example (1) has guanidine, 1-chloro, 2
- Obtained by reacting with ethyltoluene. Generally, the above compound has an average particle size of 10 to 0.01. , especially 5~
It is preferable to use the particle size in the range of 0.1p for toner adjustment.
上記化合物を現像剤に含有させる方法としては、現像剤
内部に添加する方法と外添する方法とがある。内添する
場合これら化合物の使用量は、結着樹脂の種類、必要に
応じて使用される添加剤の宥無、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、好ましくは結着樹脂100重量部
に対して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。Methods for incorporating the above compound into the developer include a method of adding it inside the developer and a method of adding it externally. When internally added, the amount of these compounds used is determined by the type of binder resin, the availability of additives used as necessary, and the toner manufacturing method including the dispersion method, and is uniquely limited. However, it is preferably 0.1 to 20 parts by weight (more preferably 0.5 to 20 parts by weight) per 100 parts by weight of the binder resin.
10 parts by weight).
又、外添する場合は、樹脂100重量部に対し、0.0
1−10重量部が望ましい。In addition, when externally added, 0.0 parts by weight per 100 parts by weight of resin.
1-10 parts by weight is desirable.
又、従来公知の荷電制御剤を本発明の荷電制御剤と組み
合わせて使用することもできる。Furthermore, conventionally known charge control agents can be used in combination with the charge control agent of the present invention.
本発明に使用される着色材としては、カーボンブラック
、ランプブラック、鉄黒、群青、ニグロレン染料、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、ハンザイエローG、ローダミン8G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、モノアゾ系、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あるいは混合して使用し得る。Colorants used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrolene dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 8G lake, calco oil blue, chrome yellow, and quinacridone. Any conventionally known dyes and pigments such as benzidine yellow, rose bengal, triallyl, methane dyes, monoazo dyes, disazo 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−ビニルトルエン共重合体、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。The binder resin used in the present invention includes polystyrene,
Monopolymers of styrene and its substituted products such as polyp-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers,
Styrene-vinyltoluene copolymer, 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 chloromethacrylate copolymer, styrene-acrylonitrile copolymer.
スチレン−ビニルメチルエーテル共重合体、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−7クリロニト
リル一インデン共重合体、スチレン−マレイン酸共重合
体、スチレン−マレイン醜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
ルメタクリレニド、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、単独或いは混合して使用で
きる。Styrene-vinyl methyl ether copolymer, styrene-
Vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-7crylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene - Styrenic copolymers such as maleic ugly ester copolymers: polymethyl methacrylate, polybutyl methacrylenide, polyvinyl chloride, polyvinyl acetate,
Polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated Examples include paraffin and paraffin wax, which can be used alone or in combination.
又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或いは混合して使用できる。In particular, as binder resins 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4弗化エチレンな
ど)、エポキシ樹脂、ポリエステル樹脂、スチレンーブ
・タジエン共重合体(モノマー比5〜30:95〜70
)、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、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。Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-tadiene copolymer (monomer ratio 5-30:95-70)
), olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic ester copolymer, ethylene-vinyl chloride copolymer, ethylene -vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.
さらに本発明のトナーは、二成分系現像剤として用いる
場合にはキャリヤー粉と混合して用いられる。Further, when the toner of the present invention is used as a two-component developer, it is used in combination with a carrier powder.
本発明に使用しうるキャリヤーとしては、公知のものが
すべて使用可能であり、例えば鉄粉。All known carriers can be used in the present invention, such as iron powder.
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。Examples include magnetic powders such as ferrite powder and nickel powder, glass beads, and those whose surfaces have been treated with resin or the like.
さらに本発明のトナーは更に、磁性材料を含有させ磁性
トナーとしても使用しうる0本発明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、バナジウム等の金属
との合金およびその混合物等が挙げられる。Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. Examples of the magnetic material contained in the magnetic toner of the present invention include magnetite, hematite,
Iron oxides such as ferrite, metals such as iron, cobalt, and nickel, or these metals such as aluminum, cobalt,
Examples include alloys with metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.
これらの強磁性体は平均粒径が0.1〜2ル程度のもの
が望ましく、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 fi重量部特に好
ましくは樹脂成分100重量部に対し約40〜150重
量部である。These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μl, and the amount to be included in the toner is about 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably about 20 to 200 parts by weight per 100 parts by weight of the resin component. It is about 40 to 150 parts by weight.
又本発明のトナーは、必要に応じて添加剤を混合しても
よい、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、あるいは例えば酸化セリウム、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ック、酸化スズ等の導電性
付与剤、あるいは例えば低分子量ポリエチレンなどの定
着助剤等がある。The toner of the present invention may also contain additives as required. Examples of additives include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide and silicon carbide, and colloidal additives. Fluidity imparting agents such as silica and aluminum oxide, anti-caking agents,
Alternatively, conductivity imparting agents such as carbon black and tin oxide, fixing aids such as low molecular weight polyethylene, etc. may also be used.
本発明に係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、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、捏和及び練肉して樹脂
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することにより、平均
粒径5〜20μのトナーを得ることが出来る。To prepare the toner for developing an electrostatic image according to the present invention, the charge control agent according to the present invention is added to a vinyl or non-vinyl thermoplastic resin, a pigment or dye as a coloring agent, and a magnetic material as necessary. The resins are thoroughly mixed using a ball mill or other mixer, and then melted, kneaded, and kneaded using a heat kneader such as a heated roll, kneader, or extruder to make the resins mutually dissolve. A toner having an average particle size of 5 to 20 μm can be obtained by dispersing or dissolving the pigment or dye, cooling and solidifying it, and then crushing and classifying it.
あるいは結着樹脂溶液中に材料を分散した後、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製造法等の方法が
適用出来る。Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as a polymerization method and a toner production method for obtaining a toner can be applied.
これらの方法により作成されたトナーは、従来公知の手
段で電子写真、静電記録及び静電印刷等における静電荷
像を顕像化するための現像用には全て使用出来るもので
下記の如き優れた効果を生ずるものである・
すなわちトナー粒子間の摩擦電荷量が均一であり、且つ
電荷量の制御が容易である。又使用中変質して摩擦電荷
量がバラツキ又は減少することがなく極めて安定したト
ナーである。このため前記した如き現像カブリ、トナー
飛散、電子写真感光材料及び複写機の汚染等の障害が除
去されると共に、従来大きな欠点であった保存中トナー
の凝集、塊状化及び、低温流動等の現象がおこらず長期
保存に耐えるトナーであり、且つトナー画像の耐摩耗性
、定着性及び接着性にもすぐれている。The toners prepared by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by conventionally known means, and have the following advantages: In other words, the amount of frictional charge between toner particles is uniform, and the amount of charge can be easily controlled. Furthermore, the toner is extremely stable, with no variation or decrease in the amount of triboelectric charge due to deterioration during use. Therefore, problems such as development fog, toner scattering, and contamination of electrophotographic photosensitive materials and copying machines as described above are eliminated, as well as phenomena such as toner aggregation, clumping, and low-temperature flow during storage, which were major drawbacks in the past. It is a toner that can withstand long-term storage without causing any problems, and also has excellent abrasion resistance, fixing properties, and adhesive properties of toner images.
このようなトナーの優れた効果は帯電、露光、現像、及
び転写の操作を連続してくりかえす反復転写式複写方式
に用いた場合更に拡大された効果を発揮するものである
。さらに荷電制御剤による色調障害がないのでカラー電
子写真用トナーとして使用することにより優れた色彩の
カラー像を形成することが出来るものである
[実施例J
以下本発明を実施例により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。These excellent effects of the toner are further magnified when used in a repetitive transfer copying system in which the operations of charging, exposure, development, and transfer are successively repeated. Furthermore, since there is no color tone disturbance caused by charge control agents, it is possible to form color images with excellent colors by using it as a toner for color electrophotography [Example J The present invention will be specifically explained below with reference to Examples. However, this does not limit the present invention in any way, and all parts in the following formulations are by weight.
実施例1
カーボンブラック(三菱1144) 10部低
分子量ポリエチレンワックス 2部化合物(1)
2部
上記材料をブレンダーでよく混合した後150℃に熱し
た2本ロールで混練した。混練物を自然放冷後、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粒
径5〜20#Lの微粉体を得た。Example 1 Carbon black (Mitsubishi 1144) 10 parts Low molecular weight polyethylene wax 2 parts Compound (1)
Two parts of the above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After the kneaded material is left to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 #L. I got it.
平均粒径50〜80JLの鉄粉キャリア 100部に対
し該微粉末5部の割合で混合して現像剤を作成した。A developer was prepared by mixing 5 parts of the fine powder with 100 parts of an iron powder carrier having an average particle size of 50 to 80 JL.
次いでOPC感光体上に従来公知の電子写真法により、
負の静電荷像を形成し、これを上記の現像剤を用い磁気
ブラシ法で粉体現像してトナー画像を作り、普通紙に転
写し加熱定着させた。得られた転写画像は濃度が充分高
く、かぶりも全くなく1画像周辺のトナーの飛び散りが
なく解像力の高い良好な画像が得られた。上記現像剤を
用いて連続して転写画像を作成し、耐久性を調べたが、
30 、000枚後の転写画像も初期の画像と比較し′
て、全く、そん色のない画像であった。Next, by a conventionally known electrophotographic method,
A negative electrostatic image was formed, and this was powder-developed using the above-mentioned developer using a magnetic brush method to create a toner image, which was transferred to plain paper and heat-fixed. The resulting transferred image had a sufficiently high density, no fogging, no toner scattering around one image, and a good image with high resolution was obtained. Transfer images were created continuously using the above developer to examine durability.
The transferred image after 30,000 sheets was compared with the initial image.
It was a completely unremarkable image.
又耐久時、感光体へのトナーに関わる前記のフィルミン
グ現象も全くみられずクリーニング工程での問題は何ら
見い出せなかった。又このとき定着工程でのトラブルも
’h < 、 30,000枚の耐久テストの終了時、
定着機を分解して観察したがローラーのキズ、いたみも
みられず、オフセットトナーによる汚れもほとんどなく
実用上全く問題がなかった。Further, during durability, the above-mentioned filming phenomenon related to toner on the photoreceptor was not observed at all, and no problems were found in the cleaning process. Also, at this time, troubles in the fixing process were also detected.
When the fixing device was disassembled and observed, there were no scratches or damage to the rollers, and there was almost no staining due to offset toner, so there was no practical problem at all.
また、環境条件を35℃、85%にしたところ、画像濃
度は常温常湿とほとんど変化がなく、カブリや飛び散り
もない鮮明な画像が得られ耐久性も30.000枚まで
ほとんど変化がなかった0次に15℃、10%の低温低
湿度において転写定着画像を得たところ画像濃度は充分
高く、ベタ黒も極めて滑らかに現像、転写され飛び散り
ゃ中抜けのない優秀な画像であった。この環境条件で耐
久を行なったが、連続、及び間けつでコピーしたが、や
はり3.0.000枚まで濃度変動は±0.2と実用上
充分であった。In addition, when the environmental conditions were set to 35°C and 85%, the image density was almost the same as at room temperature and humidity, clear images with no fogging or scattering were obtained, and the durability remained unchanged up to 30,000 sheets. When a transferred and fixed image was obtained at 15° C. and 10% low humidity, the image density was sufficiently high, solid black was developed and transferred very smoothly, and the image was excellent with no scattering or hollow spots. Durability was carried out under these environmental conditions, and even though copies were made continuously and intermittently, the density variation was ±0.2 up to 3.0,000 copies, which was sufficient for practical use.
比較例1
化合物(1)2部のかわりに、ニグロシン染料(オリエ
ント化学工業製ニグロシンベースEX) 2部を用いる
他は実施例1と同様にして現像剤を得、現像、転写、定
着を行ない同様に画像を得常温常温ではカブリは少ない
が画像濃度が1.06と低く線画も飛び散り、ベタ黒は
ガサツキが目立った。耐久性を調べたがao、ooo枚
時に濃度は0.83と低下した。Comparative Example 1 A developer was obtained in the same manner as in Example 1, except that 2 parts of nigrosine dye (Nigrosine Base EX manufactured by Orient Chemical Industry Co., Ltd.) was used instead of 2 parts of compound (1), and development, transfer, and fixing were carried out in the same manner. At room temperature, an image was obtained with little fog, but the image density was low at 1.06, and line drawings were scattered, and solid black was noticeably rough. Durability was investigated, and the density decreased to 0.83 when ao and ooo sheets were printed.
又耐久時、10,000枚前後から感光体表面上にトナ
ー材料かうすくスジ状に皮膜をつくり画像上に線となっ
てあられれだした。これはいわゆるフィルミングとよば
れるもので荷電制御剤がトナー粉体の潤滑性を変化させ
たためと考えられる。Also, during durability, after about 10,000 copies, the toner material formed a film in the form of thin stripes on the surface of the photoreceptor and began to appear as lines on the image. This is so-called filming, and is thought to be due to the charge control agent changing the lubricity of the toner powder.
又耐久時、定着工程で定着画像が定着ローラーにまき込
まれやすい傾向がみられ、ローラーに対する剥離性に難
があった。Furthermore, during durability, the fixed image tended to get caught up in the fixing roller during the fixing process, and there was difficulty in peeling it off from the roller.
35℃、85%の条件下で画像を得たところ画像濃度は
0,88と低くなりカブリ、飛び散り、ガサツキが増大
した。転写効率も低かった。When an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.88, and fogging, scattering, and roughness increased. Transfer efficiency was also low.
15℃、10%の条件下で画像を得たところ、画像濃度
は0.81と低く、飛び散り、カブリ、ガサツキがひど
く転写ぬけが目立った。連続画像出しを行なったが、3
0.Goo枚程度で濃度は0.53となり、実用不可と
なった。When an image was obtained under the conditions of 15° C. and 10%, the image density was as low as 0.81, and there was severe scattering, fogging, and roughness, and transfer omissions were noticeable. I tried to take continuous images, but 3
0. The density was 0.53 after only a few sheets, making it impractical.
実施例2
化合物(1)2部のかわりに、化合物(2)3部を用い
る他は実施例1と同様にして現像剤を得、現像1.転写
、定着を行い同様に画像を得た。Example 2 A developer was obtained in the same manner as in Example 1 except that 3 parts of compound (2) was used instead of 2 parts of compound (1), and development 1. Transfer and fixing were performed to obtain an image in the same manner.
詳細な結果は表1及び表2に示すが、実施例1とほぼ同
様な満足のいく結果が得られた。The detailed results are shown in Tables 1 and 2, and satisfactory results almost the same as in Example 1 were obtained.
実施例3
化合物(1)2部のかわりに、化合物(3)2部を用い
る他は実施例1と同様にして現像剤を得、現像、転写、
定着を行い同様に画像を得た。Example 3 A developer was obtained in the same manner as in Example 1 except that 2 parts of compound (3) was used instead of 2 parts of compound (1), and development, transfer, and
Fixation was performed and an image was obtained in the same manner.
詳細な結果は表1及び表2に示すが実施例1にほぼ同様
な満足のいく結果が得られた。The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 1 were obtained.
実施例4
化合物(1)2部のかわりに、化合物(4)2部を用い
る他は実施例1と同様にして現像剤を得、現像、転写、
定着を行い同様に画像を得た。Example 4 A developer was obtained in the same manner as in Example 1 except that 2 parts of compound (4) was used instead of 2 parts of compound (1), and development, transfer, and
Fixation was performed and an image was obtained in the same manner.
詳細な結果は表1及び表2に示すが実施例1にほぼ同様
な満足のいく結果が得られた。The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 1 were obtained.
実施例5
四三酸化鉄EPT−500(戸田工業製)80部低分子
量ポリプロピレンワックス 2部化合物(1)2部
上記材料をブレンダーでよく混合した後150℃に加熱
した2本ロールで混練した。混練物を自然放冷後、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
粒径5〜20ILの微粉体を得た。Example 5 Triiron tetroxide EPT-500 (manufactured by Toda Kogyo) 80 parts Low molecular weight polypropylene wax 2 parts Compound (1) 2 parts The above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After the kneaded material was left to cool naturally, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 IL. Ta.
次いで、該微粉末100部に疎水性コロイダルシリカR
−972(日本アエロジル社製)0.4部をサンプルミ
ルで混合し、−成分磁性トナーを作成した。Next, hydrophobic colloidal silica R was added to 100 parts of the fine powder.
0.4 part of -972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed in a sample mill to prepare a -component magnetic toner.
このトナーを市販の複写機(商品名MP−1502、キ
ャノン■製)に適用して画出ししたところ、実施例1と
ほぼ同様な良好な結果かえられた。When this toner was applied to a commercially available copying machine (trade name: MP-1502, manufactured by Canon ■) and an image was produced, good results similar to those of Example 1 were obtained.
実施例6
実施例5において、化合物(1)2部のかわりに、化合
物(2)3部を用いる他は実施例5と同様にして現像剤
を得、現像、転写、定着を行い同様に画像を得た。Example 6 A developer was obtained in the same manner as in Example 5, except that 3 parts of compound (2) was used instead of 2 parts of compound (1), and development, transfer, and fixing were carried out in the same manner. I got it.
詳細な結果は表1及び表2に示すが実施例5にほぼ同様
な満足のいく結果が得られた。The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 5 were obtained.
実施例7
実施例5において、化合物(1)2部のかわりに、化合
物(3)2部を用いる他は実施例5と同様にして現像剤
を得、現像、転写、定着を行い同様に画像を得た。Example 7 A developer was obtained in the same manner as in Example 5, except that 2 parts of compound (3) was used instead of 2 parts of compound (1), and development, transfer, and fixing were carried out in the same manner as in Example 5. I got it.
詳細な結果は表1及び表2に示すが実施例5にほぼ同様
な満足のいく結果が得られた。The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 5 were obtained.
比較例2
実施例5において化合物(1)2部のかわりに、ベンジ
ルメチル−ヘキサデシルアンモニウムクロライド2部を
用いる他は実施例5と同様に現像剤を得、同様に画像を
得た。常温常温ではカブリは少ないが画像濃度が0.8
1と低く線画も飛び散り、ベタ黒はガサツキが目立った
。耐久性を調べたが、30,000枚時に濃度は0.4
8と低下した。Comparative Example 2 A developer was obtained in the same manner as in Example 5, except that 2 parts of benzylmethyl-hexadecyl ammonium chloride was used instead of 2 parts of Compound (1) in Example 5, and an image was obtained in the same manner. At room temperature, there is little fog, but the image density is 0.8
1 and the line drawings were scattered, and the solid black was noticeably rough. I checked the durability, and the density was 0.4 after 30,000 sheets.
It dropped to 8.
又耐久時の前記フィルミング現象、定着工程での問題も
比較例1とほぼ同様の思わしくないものであったψ
35℃、85%の条件下で画像を得たところ画像濃度は
0.72と低くなりカブリ、飛び散り、ガサツキが増大
し、使用に耐えないものであった。転写効率も低かった
。15℃、10%の条件下で画像を得たところ、画像濃
度は0.73と低く、飛び散り、カブリ、ガサツキがひ
どく転写ぬけが目立った。連続画像出しを行なったが、
30.Goo枚時に濃度は0.58となり、実用不可
となった。In addition, the above-mentioned filming phenomenon during durability and problems in the fixing process were almost the same as those in Comparative Example 1. Images were obtained under the conditions of ψ 35°C and 85%, and the image density was 0.72. This resulted in increased fogging, scattering, and roughness, making it unusable. Transfer efficiency was also low. When an image was obtained under the conditions of 15° C. and 10%, the image density was as low as 0.73, and there was severe scattering, fogging, roughness, and transfer omissions were noticeable. I tried to take continuous images, but
30. The density was 0.58 at the time of Goo sheet, making it impractical.
実施例8
銅フタロシアニンブルー顔料 5部低分子量
ポリプロピレンワックス 2部化合物(1)2部
上記材料をブレンダーでよく混合した後150℃に熱し
た2本ロールで混練した。混練物を自然放冷後、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粒
径5〜20ルの微粉体を得た。Example 8 Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts Compound (1) 2 parts The above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After the kneaded material is left to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 l. Obtained.
次いで該微粉末100部に粒径50〜80井のキャリア
ー鉄粉50gを混合して現像剤とした。Next, 50 g of carrier iron powder having a particle size of 50 to 80 wells was mixed with 100 parts of the fine powder to prepare a developer.
この現像剤を用い、第1図に示す現像方法により、画出
しを行なったところ、鮮やかな青色を呈する良好な画像
が得られ、1500枚画出し後、トナー/キャリヤーが
10g 750gになったが、はとんど画像濃度に変動
は見られず、その後、トナーを補給しつつ30,000
万枚まで画出しを行なったが良好な画像が得られた。When this developer was used to develop an image using the developing method shown in Figure 1, a good image with a bright blue color was obtained. However, there was almost no change in the image density, and after that, while replenishing toner,
Even after printing up to 10,000 images, good images were obtained.
本現像方法について説明すると、第1図において、lは
静電像保持体、2はトナー担持体、3はホッパー、52
はキャリアートナー混合物により磁気ブラシ、58はト
ナー厚規制用ブレード、50は固定磁石、6は現像用バ
イアス、5はトナーを示す。To explain this developing method, in FIG. 1, l is an electrostatic image holder, 2 is a toner carrier, 3 is a hopper, and 52
5 is a magnetic brush made of a carrier toner mixture, 58 is a toner thickness regulating blade, 50 is a fixed magnet, 6 is a developing bias, and 5 is a toner.
即ち、トナー担持体2上に形成された磁気ブラシ52を
トナー担持体2を回転させることで循環させ、3のホッ
パ中のトナーをとり込んで2上に均一に薄層コートさせ
る0次いでトナー担持体2と静電像保持体lとをトナ一
層厚より大きな間隙で対向させ、z上のトナー5を1上
の静電荷像上へと飛翔現像させる。That is, the magnetic brush 52 formed on the toner carrier 2 is circulated by rotating the toner carrier 2, and the toner in the hopper 3 is taken in and coated in a thin layer uniformly on the hopper 2.Then, the toner is carried. The body 2 and the electrostatic image holding body 1 are opposed to each other with a gap larger than the thickness of the toner layer 1, and the toner 5 on the z layer is developed by flying onto the electrostatic charge image on the 1 layer.
トナ一層の厚さは、52の磁気ブラシの大きさ、即ちキ
ャリアの量及び58の規制ブレードで制御する。lと2
との間隙はトナ一層厚より大きめにとり、6の現像バイ
アスを印加しても良い。The thickness of the toner layer is controlled by the size of the magnetic brush 52, i.e. the amount of carrier, and the regulating blade 58. l and 2
A developing bias of 6 may be applied by making the gap between the toner and the toner layer larger than the thickness of the toner layer.
各実施例および比較例の評価結果を表1及び表2に示す
。The evaluation results of each example and comparative example are shown in Tables 1 and 2.
[発明の効果] 本発明によって得られる効果は次の如くである。[Effect of the invention] The effects obtained by the present invention are as follows.
(1)トナー粒子間またはトナーとキャリヤニ間、−成
分現像の場合のトナーとスリーブの如きトナー担持体と
の間などのまさつ帯電量が安定で、かつ摩擦帯電量分布
がシャープで均一であり、使用する現像システムに適し
た帯電量にコントロールできる現像剤である。(1) The amount of triboelectric charge between toner particles, between toner and carrier, or between toner and toner carrier such as a sleeve in the case of -component development is stable, and the distribution of triboelectricity is sharp and uniform. It is a developer that can control the amount of charge to suit the developing system used.
(2)潜像に忠実な現像及び転写ができ、しかも長期に
わたり連続使用した際も初期の特性を維持し、トナーの
凝集、帯電特性の変化のない現像剤である。(2) The developer is capable of faithfully developing and transferring a latent image, maintains its initial characteristics even when used continuously over a long period of time, and does not cause toner aggregation or change in charging characteristics.
(3)温度、湿度の変化に影響をうけない安定した画像
を再現でき、しかも鮮やかな有彩色の画像が得られる現
像剤である。(3) A developer that can reproduce stable images that are not affected by changes in temperature and humidity, and that can also produce images in vivid chromatic colors.
(4)静電潜像面を汚したり、摩擦したり、キズをつけ
たりしないクリーニング工程が容易でしかも定着特性の
すぐれた、特に高温オフセット等に問題のない現像剤で
ある。(4) It is a developer that does not stain, rub or scratch the electrostatic latent image surface, has an easy cleaning process, has excellent fixing properties, and has no problem with high-temperature offset, etc.
第1図は、本発明に係る正帯電性トナーが適用できる現
像装置の一例の説明図である。
1・・・静電像保持体、2・・・トナー担持体、5・・
・トナー、50・・・磁石、52・・・磁気ブラシ、5
8・・・規制ブレード。FIG. 1 is an explanatory diagram of an example of a developing device to which the positively chargeable toner according to the present invention can be applied. 1... Electrostatic image holder, 2... Toner carrier, 5...
・Toner, 50...Magnet, 52...Magnetic brush, 5
8...Regulation blade.
Claims (1)
般式[ I ]で表わされるアリール化グアニジン類を含
有することを特徴とする静電荷像現像用トナー。 ▲数式、化学式、表等があります▼[ I ] [式中、Ar_1、Ar_2は置換基としてハロゲン原
子、アルキル基、置換アルキル基、環状アルキル基、ア
リール基、アラルキル基、アルコキシ基、アリールオキ
シ基、アラルキルオキシ基、アルキルチオ基、アリール
チオ基、アラルキルチオ基、アミノ基、ニトロ基を1つ
以上有していてもよいアリール基または水素原子を示し
、Ar_1、Ar_2は同じであっても異なっていても
よい。(但し、Ar_1、Ar_2は同時に水素原子で
はない。)][Scope of Claims] An electrophotographic toner used for developing electrostatic images, characterized by containing an arylated guanidine represented by the general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, Ar_1 and Ar_2 are halogen atoms, alkyl groups, substituted alkyl groups, cyclic alkyl groups, aryl groups, aralkyl groups, alkoxy groups, and aryloxy groups as substituents. , represents an aryl group or a hydrogen atom which may have one or more aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, amino group, or nitro group, and Ar_1 and Ar_2 may be the same or different. Good too. (However, Ar_1 and Ar_2 are not hydrogen atoms at the same time.)]
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60088875A JPS61248060A (en) | 1985-04-26 | 1985-04-26 | Toner for developing electrostatic charge image |
US06/789,016 US4663263A (en) | 1984-10-19 | 1985-10-18 | Toner, charge-imparting material and composition containing substituted guanidine compound for electrophotography |
DE8585307587T DE3585769D1 (en) | 1984-10-19 | 1985-10-21 | TONER, CHARGE CONTROLLING MATERIAL AND COMPOSITION CONTAINING A POSITIVELY CHARGABLE CONNECTION. |
EP85307587A EP0178952B1 (en) | 1984-10-19 | 1985-10-21 | Toner, charge-imparting material and composition containing positively chargeable compound |
DE8585307588T DE3584942D1 (en) | 1984-10-19 | 1985-10-21 | TONER, CHARGE CONTROLLING MATERIAL AND COMPOSITION CONTAINING SUBSTITUTED GUANIDINE COMPOUNDS. |
EP85307588A EP0179642B1 (en) | 1984-10-19 | 1985-10-21 | Toner, charge-imparting material and composition containing substituted guanidine compound |
US07/552,859 US5071727A (en) | 1984-10-19 | 1990-07-11 | Positively chargeable electrostatic toner containing organic metal complex or organic nitrogen, phosphino or metal compound |
HK848/93A HK84893A (en) | 1984-10-19 | 1993-08-19 | Toner,charge-imparting material and composition containing substituted guanidine compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60088875A JPS61248060A (en) | 1985-04-26 | 1985-04-26 | Toner for developing electrostatic charge image |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61248060A true JPS61248060A (en) | 1986-11-05 |
Family
ID=13955178
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60088875A Pending JPS61248060A (en) | 1984-10-19 | 1985-04-26 | Toner for developing electrostatic charge image |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61248060A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03133950A (en) * | 1989-10-18 | 1991-06-07 | Canon Inc | Guanidine compound and guanidine compound-containing toner for development of electrostatic image |
-
1985
- 1985-04-26 JP JP60088875A patent/JPS61248060A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03133950A (en) * | 1989-10-18 | 1991-06-07 | Canon Inc | Guanidine compound and guanidine compound-containing toner for development of electrostatic image |
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