JPH09251214A - One-component developer and image forming method using the same - Google Patents
One-component developer and image forming method using the sameInfo
- Publication number
- JPH09251214A JPH09251214A JP5912796A JP5912796A JPH09251214A JP H09251214 A JPH09251214 A JP H09251214A JP 5912796 A JP5912796 A JP 5912796A JP 5912796 A JP5912796 A JP 5912796A JP H09251214 A JPH09251214 A JP H09251214A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- developer
- toner particles
- toner
- component developer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
- Dry Development In Electrophotography (AREA)
Abstract
(57)【要約】
【課題】 繰り返し使用時においても画像濃度が高くて
カブリが少ない一成分現像剤及び画像形成方法を提供す
る。
【解決手段】 少なくともバインダ樹脂と着色剤とを含
んでなる体積５０％径Ｄｔ50が５〜１２μｍでかつガラ
ス転移温度が６０℃以下であるトナー粒子と、外添剤と
から構成され、外添剤は脂肪酸金属塩粒子と流動性向上
剤とからなるものであって、外添剤が添加される前のト
ナー粒子の窒素吸着法による比表面積をＡ（ｍ2 ／ｇ）
とし、外添剤が添加された後のトナー粒子の窒素吸着法
による比表面積をＢ（ｍ2 ／ｇ）としたとき、下記式
（１）を満足することを特徴とする一成分現像剤。
【数１】
式（１） １．５≦Ｂ／Ａ≦３(57) An object of the present invention is to provide a one-component developer having high image density and less fog even after repeated use, and an image forming method. SOLUTION: The toner has a volume 50% diameter Dt 50 of 5 to 12 μm and contains a binder resin and a colorant and has a glass transition temperature of 60 ° C. or less, and an external additive. The agent is composed of fatty acid metal salt particles and a fluidity improver, and has a specific surface area of A (m 2 / g) of the toner particles by the nitrogen adsorption method before the external additive is added.
And a specific surface area of the toner particles after the addition of the external additive is determined to be B (m 2 / g) by a nitrogen adsorption method, the one-component developer satisfying the following formula (1). ## EQU1 ## Equation (1) 1.5 ≦ B / A ≦ 3
Description
【０００１】[0001]
【発明の属する技術分野】本発明、電子写真複写機やレ
ーザービームプリンタ等に用いられる一成分現像剤及び
それを用いる画像形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component developer used in electrophotographic copying machines, laser beam printers, etc., and an image forming method using the same.
【０００２】[0002]
【従来の技術】一成分現像剤を使用すると現像装置や画
像形成装置本体を小型化でき、また、これらの装置はメ
ンテナンス性等の信頼性にも優れるという利点を有する
ので、低速の画像形成装置を中心に近年その採用が活発
化している。前記した装置では、これらの一成分現像剤
を速やかに帯電させかつ現像剤の薄層を効率よく現像ス
リーブ上に形成させる目的で、現像スリーブに接触させ
た状態で層形状部材を設けることがよく行われている。
また、静電潜像を保持する感光体としては、材料の選択
等により種々の電気特性が得られること、材料としての
安全性が高いこと、ドラム、シート、ベルトなどへの加
工が容易であること等の理由から有機光導電体（ＯＰ
Ｃ）が多く使用され、紙等への被転写材への現像像転写
後の残存粒子のクリーニング方式としてはポリウレタン
等のクリーニングブレードの採用が一般的である。さら
に、被転写材上の現像剤は、熱ローラ方式等の熱的手段
により定着される。2. Description of the Related Art The use of a one-component developer makes it possible to reduce the size of a developing device and an image forming apparatus main body, and these devices have the advantage that they have excellent reliability such as maintainability. In recent years, its adoption has been active. In the above-mentioned apparatus, for the purpose of quickly charging these one-component developers and efficiently forming a thin layer of the developer on the developing sleeve, a layer-shaped member may be provided in contact with the developing sleeve. Has been done.
Further, as a photoreceptor for holding an electrostatic latent image, various electrical characteristics can be obtained by selecting materials, the safety as materials is high, and it can be easily processed into drums, sheets, belts, etc. For that reason, organic photoconductors (OP
C) is often used, and a cleaning blade made of polyurethane or the like is generally used as a cleaning method for residual particles after transfer of a developed image onto a transfer material such as paper. Further, the developer on the transfer material is fixed by a thermal means such as a heat roller system.
【０００３】一成分現像剤としては、現像剤中に磁性材
料を含有せしめた磁性一成分現像剤と磁性材料を含有し
ない非磁性一成分現像剤とが知られている。これらの現
像剤の製造方法としては、各構成材料を混合し、溶融混
練し、粉砕し、分級してトナー粒子を得るいわゆる粉砕
法が主流となっている。このトナー粒子に対して、その
流動性を向上させ、現像スリーブでのトナー層形成を容
易にするためにシリカ微粒子などの添加剤が外添によっ
て加えられ、一成分現像剤として調製される。As a one-component developer, a magnetic one-component developer containing a magnetic material in a developer and a non-magnetic one-component developer not containing a magnetic material are known. As a method for producing these developers, a so-called pulverization method in which respective constituent materials are mixed, melt-kneaded, pulverized, and classified to obtain toner particles has become the mainstream. Additives such as silica fine particles are externally added to the toner particles in order to improve the fluidity thereof and facilitate the formation of a toner layer on the developing sleeve, thereby preparing a one-component developer.
【０００４】[0004]
【発明が解決しようとする課題】現在、以下の課題を総
合的に解決するような提案が求められている。第１に、
一成分現像剤によって現像を行うときには、現像剤粒子
の均一な薄層を現像スリーブ上に形成することによって
現像剤に充分な帯電量を与えることが重要となるが、そ
れをいかにして達成するかという課題がある。第２に、
ＯＰＣ感光体はその表面は有機高分子材料で構成されて
おり、その硬度は無機系感光体に比して小さいので、現
像剤を介在するクリーニングブレードとの継続的な摺擦
によって表面の磨耗及び研磨筋が発生し易い。場合によ
っては、その研磨筋に現像剤が擦り込まれて点状やフィ
ルム状の欠陥が感光体上に発生する。また、クリーニン
グ不良も発生しやすい。このような表面の劣化は、感光
体の電気特性の著しい低下要因となるし、得られる画像
に致命的な汚染が生じることも改良すべき課題であっ
た。第３に、近年の省エネルギー化の世界的潮流から、
一成分現像剤を用いる画像形成装置においても低消費電
力、具体的には低エネルギー定着への要望が強まってお
り、その課題の解決が必要である。At present, there is a demand for a proposal that comprehensively solves the following problems. First,
When developing with a one-component developer, it is important to give a sufficient amount of charge to the developer by forming a uniform thin layer of developer particles on the developing sleeve, and how to achieve this. There is a problem. Second,
The surface of the OPC photosensitive member is composed of an organic polymer material, and its hardness is smaller than that of the inorganic photosensitive member. Grinding streaks are likely to occur. In some cases, the developer is rubbed into the polishing streaks, causing dot-like or film-like defects on the photoreceptor. In addition, poor cleaning is likely to occur. Such deterioration of the surface causes a remarkable decrease in the electrical characteristics of the photoreceptor, and it is a problem to be solved that fatal contamination occurs in the obtained image. Third, from the global trend of energy saving in recent years,
There is an increasing demand for low power consumption, specifically, low energy fixing in an image forming apparatus using a one-component developer, and it is necessary to solve the problem.
【０００５】まず、現像に関わる現像剤粒子の薄層形成
による帯電性の課題について述べる。一般に、現像スリ
ーブ上に現像剤の均一な薄層が形成できないと、現像剤
粒子の帯電が充分に行われないので、現像剤粒子の帯電
量は低く、またその帯電量分布も逆極性成分の多いもの
になりやすい。従って、得られる画像としては画像濃度
が低かったり、カブリが高い、またシャープネスが悪い
などの問題がある。さらに、連続実写や長期間の繰り返
し使用では、現像剤帯電性の低下が起こるので、そうい
った問題が一層顕在化しやすい。First, the problem of chargeability due to the formation of a thin layer of developer particles relating to development will be described. Generally, if a uniform thin layer of the developer cannot be formed on the developing sleeve, the developer particles are not sufficiently charged, so that the charge amount of the developer particles is low, and the charge amount distribution also has a reverse polarity component. It tends to be many. Therefore, the obtained image has problems such as low image density, high fog, and poor sharpness. Further, in continuous actual photography and repeated use for a long period of time, the chargeability of the developer is lowered, and such a problem is more likely to be manifested.
【０００６】均一な薄層形成を行って現像剤の帯電性を
高めるには、現像スリーブに対して接触押圧させた層形
成部材を設ける現像装置を用いれば現像剤を強制的に層
規制することができるから、比較的容易に現像剤薄層が
得られやすい。しかし、現像剤の流動性が悪化すると、
現像剤の薄層は得られてもその表面にはムラがあって均
一でないので、得られる画像も画像部にムラのある不鮮
明なものしか得られない。このような問題は、近年の高
画質化の市場要求に伴って現像剤粒子を小粒径化してい
くとますます顕在化しやすい。そこで、トナー粒子に、
シリカ微粒子などの無機物微粒子を始めとする流動性向
上剤を添加させて現像剤の流動性を向上させることによ
って、前記の問題を改善することがよく行われる。これ
らの流動性向上剤の添加により、薄層でしかも均一な現
像剤層が得られ、現像剤の帯電性を高めることができる
ので、画像濃度が高く、カブリが低く、ムラの少ない画
質が達成できる他、画像の文字部やライン部の中央部が
欠落する画像中抜けも発生しにくいという利点を有する
ので効果的である。従って、トナー粒子に対して、流動
性向上剤を積極的に添加することが望まれる。ただし、
シリカ微粒子等の流動性向上剤は、繰り返し使用により
現像剤から脱落し、飛散し、さらには現像剤粒子に埋没
するなど刻々と現像剤粒子表面での存在量が変化し、そ
のような状況は、現像剤粒子の帯電性を変動させるの
で、安定した画質が得られにくい問題がある。In order to form a uniform thin layer and enhance the chargeability of the developer, the developer is forcibly regulated by using a developing device provided with a layer forming member which is pressed against the developing sleeve. Therefore, it is relatively easy to obtain a thin developer layer. However, when the fluidity of the developer deteriorates,
Even if a thin layer of the developer is obtained, the surface thereof is uneven and not uniform, so that the obtained image is only an unclear image having an uneven image portion. Such problems are more likely to become apparent as the particle size of the developer particles is made smaller with the recent market demand for higher image quality. So, in the toner particles,
The above problems are often improved by adding a fluidity improver including fine inorganic particles such as silica fine particles to improve the fluidity of the developer. By adding these fluidity improvers, a thin and uniform developer layer can be obtained, and the chargeability of the developer can be enhanced, so that high image density, low fog, and uniform image quality can be achieved. In addition to this, it is effective because it has the advantage that it is less likely to cause a hollow image in which the character portion or the central portion of the line portion of the image is missing. Therefore, it is desired to positively add the fluidity improver to the toner particles. However,
The fluidity improver such as silica fine particles falls off from the developer by repeated use, scatters, and is further embedded in the developer particles such that the amount present on the surface of the developer particles changes every moment. However, since the chargeability of the developer particles is changed, it is difficult to obtain stable image quality.
【０００７】次に、現像剤粒子によるＯＰＣ上の汚染の
問題について述べる。トナー粒子へのシリカ微粒子等の
流動性向上剤の添加は、さらに以下の問題点も有してい
る。すなわち、ＯＰＣ感光体に対して、クリーニングブ
レードを接触押圧させて感光体のクリーニングを行うこ
とはよく行われるが、そのような工程を含む画像形成方
法においては、こうしたシリカ等の微粒子が感光体を傷
つけ、そこを起点に現像剤の固着や融着が起こって画像
の汚染を引き起こすことがある。従って、流動性向上剤
をトナーに添加することは、前述の層形成性の向上のた
めには良い結果となるが、ＯＰＣの汚染の面からは不都
合な結果となるので、このような相反する両方の性能を
満足するような提案が求められている。Next, the problem of contamination of the OPC by the developer particles will be described. The addition of the fluidity improver such as silica fine particles to the toner particles has the following problems. That is, it is often practiced to bring the cleaning blade into contact with the OPC photoconductor to press it to clean the photoconductor. In an image forming method including such a step, such fine particles of silica or the like cause the photoconductor to be damaged. The image may be damaged and the developer may be fixed or fused from the point of scratching to cause image contamination. Therefore, the addition of the fluidity improver to the toner gives good results for improving the above-mentioned layer forming property, but has an inconvenient result from the viewpoint of OPC contamination. Proposals that satisfy both performances are required.
【０００８】次に、低エネルギー定着に関する課題につ
いて述べる。定着工程での定着機の温度を下げること等
によって装置としての低エネルギー化は可能となるが、
現像剤はそのような低エネルギー定着に対応した特性を
有している必要がある。例えば、通常定着方式として多
用される熱ロール方式の場合、定着機温度の低下に伴っ
て定着強度の不足による紙からのトナーの剥離や定着ロ
ーラへのトナーの付着汚染の現象が見られるから、その
ような不具合が解消されるような現像剤が要求される。Next, the problems relating to low energy fixing will be described. It is possible to reduce the energy of the device by lowering the temperature of the fixing machine in the fixing process.
The developer needs to have characteristics corresponding to such low energy fixing. For example, in the case of a thermal roll method that is often used as a normal fixing method, a phenomenon of peeling of toner from paper due to insufficient fixing strength or adhesion of toner to the fixing roller due to a decrease in fixing machine temperature is observed. A developer that can solve such a problem is required.
【０００９】このように、一成分現像剤においてはいま
だ改良すべき課題が残っており、各々の課題については
それぞれ個別に提案もなされているが、上記した課題を
総合的に解決するような提案はなされていないのが現状
である。本発明は上記した現状に鑑み、その課題を解決
すべくなされたものであって、その目的は、繰り返し使
用時においても画像濃度が高くてカブリが少ない一成分
現像剤及び画像形成方法を提供することにある。As described above, there are still problems to be improved in the one-component developer, and each problem has been individually proposed. However, there is a proposal for solving the above problems comprehensively. It has not been done yet. The present invention has been made in view of the above circumstances and has been made to solve the problems, and an object thereof is to provide a one-component developer having a high image density and less fog even when repeatedly used, and an image forming method. Especially.
【００１０】本発明の他の目的は、画像ムラが少なく、
シャープネスがよく、画像中抜けが少ない等の優れた画
質が得られる一成分現像剤及び画像形成方法を提供する
ことにある。本発明の他の目的は、クリーニング不良や
ＯＰＣ感光体への現像剤の固着や融着現象による画像汚
染のない一成分現像剤及び画像形成方法を提供すること
にある。本発明の他の目的は、定着での画像剥離や定着
装置汚染がなく低エネルギー定着ができる一成分現像剤
及び画像形成方法を提供することにある。Another object of the present invention is to reduce image unevenness,
It is an object of the present invention to provide a one-component developer and an image forming method capable of obtaining excellent image quality such as good sharpness and little image dropout. Another object of the present invention is to provide a one-component developer and an image forming method which are free from image contamination due to poor cleaning, fixing of the developer to the OPC photosensitive member, and fusing phenomenon. Another object of the present invention is to provide a one-component developer and an image forming method capable of low-energy fixing without image peeling during fixing and contamination of the fixing device.
【００１１】本発明の他の目的は、各種の温度及び湿度
の組合せ環境条件下でも画質変化が少ない一成分現像剤
及び画像形成方法を提供することにある。本発明の他の
目的は、長期あるいは連続使用時においても画像濃度や
画質劣化が少なく耐久性、信頼性に優れた一成分現像剤
及び画像形成方法を提供することにある。本発明の他の
目的は、少ないトナー消費量で充分な画質が得られる一
成分現像剤及び画像形成方法を提供することにある。Another object of the present invention is to provide a one-component developer and an image forming method which cause little change in image quality even under combined environmental conditions of various temperatures and humidity. Another object of the present invention is to provide a one-component developer and an image forming method which have little deterioration in image density and image quality even during long-term use or continuous use and have excellent durability and reliability. Another object of the present invention is to provide a one-component developer and an image forming method capable of obtaining a sufficient image quality with a small amount of toner consumption.
【００１２】[0012]
【課題を解決するための手段】本発明者らはかかる目的
を達成すべく鋭意検討した結果、特定の熱特性を有する
トナー粒子に対して、外添剤として脂肪酸金属塩粒子と
流動性向上剤とが外添されており、その外添前後の現像
剤の比表面積の関係が特定式で表される一成分現像剤及
びそれを用いる画像形成方法により、上記目的が満足さ
れることを見出し本発明に到達した。Means for Solving the Problems As a result of intensive investigations by the present inventors in order to achieve such an object, fatty acid metal salt particles as an external additive and a fluidity improving agent are added to toner particles having specific thermal characteristics. It is found that the above objects are satisfied by a one-component developer in which the relationship between the specific surface area of the developer before and after the external addition is represented by a specific formula and the image forming method using the The invention was reached.
【００１３】すなわち、本発明の要旨は、少なくともバ
インダ樹脂と着色剤とを含んでなる体積５０％径Ｄｔ50
が５〜１２μｍでかつガラス転移温度が６０℃以下であ
るトナー粒子と、外添剤とから構成され、外添剤は脂肪
酸金属塩粒子と流動性向上剤とからなるものであって、
外添剤が添加される前のトナー粒子の窒素吸着法による
比表面積をＡ（ｍ2 ／ｇ）とし、外添剤が添加された後
のトナー粒子の窒素吸着法による比表面積をＢ（ｍ2 ／
ｇ）としたとき、下記式（１）を満足することを特徴と
する一成分現像剤に存する。That is, the gist of the present invention is a volume 50% diameter Dt 50 containing at least a binder resin and a colorant.
Of 5 to 12 μm and a glass transition temperature of 60 ° C. or lower, and an external additive, the external additive comprising fatty acid metal salt particles and a fluidity improver,
The specific surface area of the toner particles by the nitrogen adsorption method before the external additive is added is A (m 2 / g), and the specific surface area of the toner particles by the nitrogen adsorption method after the external additive is added is B (m 2 /
g), the one-component developer is characterized by satisfying the following formula (1).
【００１４】[0014]
【数５】 式（１） １．５≦Ｂ／Ａ≦３Equation (1) 1.5 ≦ B / A ≦ 3
【００１５】また、現像剤を保持するための現像スリー
ブと現像スリーブに押圧された層形成部材とを具備し、
層形成された現像剤を有機光導電体からなる感光体に現
像し、前記感光体から被転写材に転写を行った後、クリ
ーニングブレードで感光体のクリーニングを行い、被転
写材上の現像剤を熱的に定着する工程を含む電子写真画
像形成方法において、前記現像剤が、少なくともバイン
ダ樹脂と着色剤とを含んでなる体積５０％径Ｄｔ50が５
〜１２μｍでかつガラス転移温度が６０℃以下であるト
ナー粒子と、外添剤とから構成され、外添剤は脂肪酸金
属塩粒子と流動性向上剤とからなるものであって、外添
剤が添加される前のトナー粒子の窒素吸着法による比表
面積をＡ（ｍ2 ／ｇ）とし、外添剤が添加された後のト
ナー粒子の窒素吸着法による比表面積をＢ（ｍ2 ／ｇ）
としたとき、下記式（１）を満足する一成分現像剤であ
ることを特徴とする画像形成方法に存する。Further, it is provided with a developing sleeve for holding a developer and a layer forming member pressed against the developing sleeve,
After the layered developer is developed on the photoconductor made of an organic photoconductor and transferred from the photoconductor to the transfer material, the photoconductor is cleaned with a cleaning blade, and the developer on the transfer material is transferred. In the electrophotographic image forming method including the step of thermally fixing the toner, the developer has a volume 50% diameter Dt 50 of at least 5 including a binder resin and a colorant.
To 12 μm and having a glass transition temperature of 60 ° C. or lower, and an external additive. The external additive is composed of fatty acid metal salt particles and a fluidity improver. The specific surface area of the toner particles before addition by the nitrogen adsorption method is A (m 2 / g), and the specific surface area of the toner particles after addition of the external additive by the nitrogen adsorption method is B (m 2 / g)
Then, the image forming method is characterized by being a one-component developer satisfying the following formula (1).
【００１６】[0016]
【数６】 式（１） １．５≦Ｂ／Ａ≦３Equation (1) 1.5 ≦ B / A ≦ 3
【００１７】[0017]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明に用いられるトナーは、熱可塑性バインダ
樹脂、着色剤、必要に応じて帯電制御剤、離型剤、その
他の物質等を溶融混練し、粉砕し、分級した微粉末であ
る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The toner used in the present invention is a fine powder obtained by melt-kneading a thermoplastic binder resin, a colorant, and if necessary, a charge control agent, a release agent and other substances, pulverizing and classifying.
【００１８】前記トナー構成成分のうち、バインダ樹脂
としては、トナーに適した公知の種々のものが使用でき
る。例えば、ポリスチレン、ポリクロロスチレン、ポリ
−α−メチルスチレン、スチレン−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−ブタ
ジエン共重合体、スチレン−塩化ビニル共重合体、スチ
レン−酢酸ビニル共重合体、スチレン−アクリル酸エス
テル共重合体（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
共重合体及びスチレン−アクリル酸フェニル共重合体
等）、スチレン−メタクリル酸エステル共重合体（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−メタクリル酸オクチル共重合体及
びスチレン−メタクリル酸フェニル共重合体等）、スチ
レン−α−クロルアクリル酸メチル共重合体及びスチレ
ン−アクリロニトリル−アクリル酸エステル共重合体等
のスチレン系樹脂（スチレンまたはスチレン置換体を含
む単独重合体または共重合体）、塩化ビニル樹脂、ロジ
ン変性マレイン酸樹脂、フェノール樹脂、エポキシ樹
脂、飽和ポリエステル樹脂、不飽和ポリエステル樹脂、
低分子量ポリエチレン樹脂、低分子量ポリプロピレン樹
脂、アイオノマー樹脂、ポリウレタン樹脂、シリコーン
樹脂、ケトン樹脂、エチレン−エチルアクリレート共重
合樹脂、キシレン樹脂並びにポリビニルブチラール樹脂
等があり、それぞれ単独であるいは任意に併用して使用
しうるが、本発明に用いるのに好ましい樹脂としては、
スチレン系樹脂、飽和または不飽和ポリエステル樹脂等
を挙げることができる。Among the above-mentioned toner constituent components, various known binder resins suitable for toner can be used as the binder resin. For example, polystyrene, polychlorostyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer. Polymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer,
Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (styrene-methacrylic acid) Methyl acid copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-octyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-α-chloroacryl Styrene resins such as methyl acid copolymer and styrene-acrylonitrile-acrylic acid ester copolymer (homopolymers or copolymers containing styrene or styrene substitution products), vinyl chloride resin, rosin-modified maleic acid resin, phenol resin , Epoxy resin, saturated polyester Fat, unsaturated polyester resin,
There are low molecular weight polyethylene resin, low molecular weight polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene-ethyl acrylate copolymer resin, xylene resin, polyvinyl butyral resin, etc., and they are used alone or in any combination. However, as a preferred resin for use in the present invention,
Examples thereof include styrene resins, saturated or unsaturated polyester resins and the like.
【００１９】さらにまた、特公昭５１−２３３５４号公
報、特開昭５０−４４８３６号公報に記載されている架
橋系バインダ樹脂、あるいは特公昭５５−６８９５号公
報、特公昭６３−３２１８０号公報に記載されている非
架橋系バインダ樹脂も使用できる。Furthermore, the crosslinkable binder resins described in JP-B-51-23354 and JP-A-50-44836, or JP-B-55-6895 and JP-B-63-32180 are described. Non-crosslinked binder resins that have been used can also be used.
【００２０】そして、本発明のトナーのガラス転移温度
は６０℃以下である必要があり、より好ましくは５０〜
５８℃であるのがよいが、そのガラス転移温度を達成す
るためには、バインダ樹脂のガラス転移温度自体が、同
等の範囲であるのが望ましい。トナーのガラス転移温度
は、示差熱分析装置で測定したときの転移開始（変曲
点）の温度を求めること等により測定できる。ガラス転
移温度が前記範囲を超えて高い場合、低エネルギー定着
のために定着温度を低めた熱定着装置を用いる際、定着
強度の不足による紙からのトナーの剥離現象を招くので
使用上問題がある。樹脂のガラス転移温度を前記範囲と
するためには、樹脂製造時の使用モノマーの種類や配合
割合を適宜選択すればよい。また、該トナー用バインダ
樹脂の軟化点は、フローテスタ法で測定した値が１００
〜１８０℃であるのが好ましい。軟化点が１００℃未満
の場合、定着での汚れ（いわゆる「ホットオフセット」
現象）が発生し易く、１８０℃を超える場合は、定着強
度が悪化する傾向にあるので好ましくない。The glass transition temperature of the toner of the present invention needs to be 60 ° C. or lower, more preferably 50 to 50 ° C.
The temperature is preferably 58 ° C., but in order to achieve the glass transition temperature, it is desirable that the glass transition temperature itself of the binder resin is in the equivalent range. The glass transition temperature of the toner can be measured by, for example, obtaining the temperature of the transition start (inflection point) when measured by a differential thermal analyzer. When the glass transition temperature is higher than the above range, when a heat fixing device having a low fixing temperature is used for low energy fixing, the toner peeling phenomenon from the paper due to insufficient fixing strength is caused, which causes a problem in use. . In order to set the glass transition temperature of the resin within the above range, the type and blending ratio of the monomers used during resin production may be appropriately selected. The softening point of the binder resin for toner is 100 as measured by the flow tester method.
It is preferably ˜180 ° C. If the softening point is less than 100 ° C, stains on fixing (so-called "hot offset")
If the temperature exceeds 180 ° C., the fixing strength tends to deteriorate, which is not preferable.
【００２１】着色剤としては、従来から用いられるもの
であれば任意の適当な顔料や染料が使用できる。例え
ば、カーボンブラック、酸化チタン、亜鉛華、アルミナ
ホワイト、炭酸カルシウム、紺青などの無機顔料、モノ
アゾ顔料、ジスアゾ顔料、銅フタロシアニン顔料、キナ
クリドン顔料などの有機顔料、アントラキノン染料、ロ
ーダミン染料等の染料などを相当するトナーの色に合わ
せて単独または適宜混合して用いる。着色剤の含有量
は、非磁性一成分トナーの場合には、現像により可視像
を形成することができるようトナーを定着するに充分な
量であればよく、例えばバインダ樹脂１００重量部に対
して上記の着色剤３〜２０重量部とするのが好ましい。
なお、磁性一成分トナーの場合には、マグネタイト、γ
一酸化鉄等に代表される磁性酸化鉄類などの磁性を有す
る着色剤を含有せしめるが、この場合、その添加量はバ
インダ樹脂１００重量部に対して２０〜２００重量部と
するのがよく、特には３０〜１２０重量部とするのが望
ましい。As the colorant, any suitable pigment or dye can be used as long as it is conventionally used. For example, inorganic pigments such as carbon black, titanium oxide, zinc white, alumina white, calcium carbonate, navy blue, monoazo pigments, disazo pigments, copper phthalocyanine pigments, organic pigments such as quinacridone pigments, anthraquinone dyes, dyes such as rhodamine dyes, etc. The toners may be used alone or appropriately mixed depending on the color of the corresponding toner. In the case of a non-magnetic one-component toner, the content of the colorant may be an amount sufficient to fix the toner so that a visible image can be formed by development, and for example, with respect to 100 parts by weight of the binder resin. It is preferable to use 3 to 20 parts by weight of the above colorant.
In the case of magnetic one-component toner, magnetite, γ
A coloring agent having magnetism such as magnetic iron oxides typified by iron monoxide and the like is contained. In this case, the addition amount thereof is preferably 20 to 200 parts by weight with respect to 100 parts by weight of the binder resin, In particular, it is desirable to use 30 to 120 parts by weight.
【００２２】本トナーに用いられる帯電制御剤として
は、使用するバインダ樹脂の組成制御や現像剤を担持す
る現像スリーブの組成制御等の方策も考えられるが、通
常は正の帯電性を得るためには正の帯電制御剤を、負の
帯電性を得るためには負の帯電制御剤を用いてもよい。
これらは、各種公知のものの中から適宜選択すればよ
い。正の帯電制御剤としては、例えば、ニグロシン染料
及びその変性物、特公平１−５４６９４号公報、特公平
１−５４６９５号公報、特公平１−５４６９６号公報等
に記載の４級アンモニウム化合物、特開昭５１−４５５
号公報、特公昭６３−５７７８７号公報、特公表平２−
５０１５０６号公報等に記載のトリフェニルメタン化合
物、特開平３−１１９３６４号公報、特開平３−２０２
８５６号公報、特開平３−２１７８５１号公報等に記載
のイミダゾール誘導体やイミダゾール類の金属錯体等が
挙げられる。負の帯電制御剤としては、特公平３−３７
１８３号公報、特公平２−１６９１６号公報等に記載の
含金属アゾ染料や特公昭５５−４２７５２号公報等に記
載のサリチル酸類金属錯体、特開昭６３−１６３３７４
号公報等に記載のサリチル酸類金属塩、特開平５−１１
９５３５号公報等に記載の金属元素を含有しないカリッ
クスアレン化合物などが挙げられる。上記した帯電制御
剤をトナーに含有させる方法としては、トナー内部に添
加する方法と外添する方法とがある。内添する場合、こ
れらの化合物の使用量は、前記バインダ樹脂１００重量
部に対して、通常０．０５〜２０重量部がよく、より好
ましくは０．１〜１０重量部の範囲が望ましい。また、
外添する場合には、樹脂１００重量部に対して０．０１
〜１０重量部が好ましい。As the charge control agent used in the present toner, it is conceivable that the composition of the binder resin used and the composition of the developing sleeve carrying the developer may be controlled. A positive charge control agent may be used, and a negative charge control agent may be used to obtain a negative chargeability.
These may be appropriately selected from various known ones. Examples of the positive charge control agent include nigrosine dyes and modified products thereof, quaternary ammonium compounds described in Japanese Patent Publication No. 1-54694, Japanese Patent Publication No. 1-54695, Japanese Patent Publication No. 1-54696, and the like. Kaisho 51-455
Publication, Japanese Patent Publication No. 63-57787, Japanese Patent Publication No. 2-
Triphenylmethane compounds described in JP-A-501506, JP-A-3-119364, JP-A-3-202
Examples thereof include imidazole derivatives and metal complexes of imidazoles described in JP-A-856, JP-A-3-217851 and the like. As a negative charge control agent, Japanese Patent Publication No. 3-37
No. 183, Japanese Patent Publication No. 2-16916, etc., and metal salicylic acid metal complexes described in Japanese Patent Publication No. 55-42752 and Japanese Patent Publication No. 63-163374.
Salicylic acid metal salts described in Japanese Patent Application Laid-Open No. 5-11
Examples thereof include calixarene compounds containing no metal element described in Japanese Patent No. 9535 and the like. As a method of incorporating the above charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. When internally added, the amount of these compounds used is usually 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the binder resin. Also,
When added externally, 0.01 to 100 parts by weight of resin
-10 parts by weight is preferred.
【００２３】この他、熱特性や物理特性を改良する目的
でトナー中に内添しうる助剤としては、公知のものが使
用可能であるが、例えば、離型剤としてポリアルキレン
ワックス、パラフィンワックス、高級脂肪酸、脂肪酸ア
ミド等が挙げられる。その添加量は、バインダ樹脂１０
０重量部に対して、０．１〜１０重量部が好ましい。Other known auxiliary agents that can be internally added to the toner for the purpose of improving thermal characteristics and physical characteristics include, for example, polyalkylene wax and paraffin wax as release agents. , Higher fatty acids, fatty acid amides and the like. The amount of the binder resin 10
0.1 to 10 parts by weight with respect to 0 parts by weight is preferred.
【００２４】トナー粒子の製造方法としては、以下の方
法で行う。まず、トナーの構成材料であるバインダ樹
脂、着色剤、帯電制御剤等を所定割合で配合して混合す
る。この際の装置としては、Ｖブレンダー、ボールミル
等の重力落下式混合機やヘンシェルミキサー（三井三池
化工機社製）、スーパーミキサー（カワタ社製）等の高
速流動式混合機等が使用される。The method for producing the toner particles is as follows. First, a binder resin, a colorant, a charge control agent, and the like, which are constituent materials of the toner, are blended and mixed at a predetermined ratio. As a device at this time, a gravity drop mixer such as a V blender or a ball mill, a high-speed fluid mixer such as a Henschel mixer (manufactured by Mitsui Miike Kakoki) or a super mixer (manufactured by Kawata) is used.
【００２５】混合の後、混合物を溶融混練する。溶融混
練工程で使用される装置としては、２本あるいは３本ロ
ール、バンバリーミキサー、一軸あるいは二軸押し出し
機等が挙げられる。この工程において、バインダ樹脂と
の相溶性を有する成分は樹脂と溶融し、また、バインダ
樹脂との相溶性を有しない帯電制御剤等の成分は、溶融
した樹脂に分散される。After mixing, the mixture is melt-kneaded. Examples of the apparatus used in the melt-kneading step include a two- or three-roll mill, a Banbury mixer, a single-screw or twin-screw extruder, and the like. In this step, the component having compatibility with the binder resin is melted with the resin, and the component such as the charge control agent having no compatibility with the binder resin is dispersed in the melted resin.
【００２６】次に上記溶融混練物を冷却固化させた後、
粗粉砕、微粉砕および分級の各工程を経てトナー粒子が
製造される。粗粉砕にはハンマーミル、カッターミル等
が、微粉砕には高速回転式微粉砕機等の機械式粉砕機や
衝撃型ジェットミルや流動層式ジェットミル等のジェッ
ト粉砕機等が用いられ、分級には強制うず型遠心分級機
や慣性分級機等が用いられる。Next, after the melt-kneaded product is cooled and solidified,
The toner particles are manufactured through the steps of coarse pulverization, fine pulverization and classification. Hammer mills and cutter mills are used for coarse pulverization, and mechanical pulverizers such as high-speed rotary pulverizers and jet pulverizers such as impact-type jet mills and fluidized-bed jet mills are used for fine pulverization. For example, a forced vortex type centrifugal classifier or an inertial classifier is used.
【００２７】本発明の一成分現像剤に関わるトナー粒子
は、粉砕・分級後にその体積５０％径Ｄｔ50が５〜１２
μｍであれば、高画質の画像が得られるので好適であ
る。５μｍ未満の場合、トナー飛散が激しく、得られる
画像のカブリが悪化するので好ましくなく、また１２μ
ｍを超える場合には得られる画像のシャープネスが低下
する傾向を示すので好ましくない。The toner particles relating to the one-component developer of the present invention have a volume 50% diameter Dt 50 of 5 to 12 after pulverization and classification.
A micrometer is preferable because a high quality image can be obtained. When the thickness is less than 5 μm, toner scattering is severe and fogging of an obtained image is deteriorated.
If it exceeds m, the sharpness of the obtained image tends to decrease, which is not preferable.
【００２８】粒子径の測定は、レーザー回折式粒度分布
測定システムＨｅｒｏｓ ＆ Ｒｏｄｏｓ（独ＳＹＭＰ
ＡＴＥＣ社製）で以下の条件で行うのがよいが、他にコ
ールタカウンタ（米Ｃｏｕｌｔｅｒ社製）を用いて行っ
てもよい。 分散方式：流動式分散ユニット 分散空気圧：２ｂａｒ レンズ焦点距離：１００ｍｍ 測定時間：３秒 本発明の一成分現像剤は、これらのトナー粒子と脂肪酸
金属塩粒子と流動性向上剤とから成る。本発明におい
て、脂肪酸金属塩粒子の粒子径は以下の式（２）及び
（３）を満足するものであるのが望ましい。The particle size is measured by a laser diffraction type particle size distribution measuring system Heros & Rodos (SYMP, Germany).
ATEC Co., Ltd.) may be used under the following conditions. Alternatively, a Coulter Counter (Coulter Co., USA) may be used. Dispersion method: Flow type dispersion unit Dispersion air pressure: 2 bar Lens focal length: 100 mm Measurement time: 3 seconds The one-component developer of the present invention comprises these toner particles, fatty acid metal salt particles, and a fluidity improver. In the present invention, the particle size of the fatty acid metal salt particles preferably satisfies the following formulas (2) and (3).
【００２９】[0029]
【数７】 式（２） Ｄｓ50／Ｄｔ50≦０．５ 式（３） Ｄｓ84／Ｄｓ16≦４ ただし、式中、Ｄｔ50はトナー粒子の体積５０％径を表
し、Ｄｓ16、Ｄｓ50及びＤｓ84はそれぞれ脂肪酸金属塩
粒子の体積１６％径、５０％径及び８４％径を表す。Formula (2) Ds 50 / Dt 50 ≦ 0.5 Formula (3) Ds 84 / Ds 16 ≦ 4 where Dt 50 represents the 50% volume diameter of the toner particles, and Ds 16 and Ds 50 and Ds 84 represent the volume 16% diameter, 50% diameter and 84% diameter of the fatty acid metal salt particles, respectively.
【００３０】従来から、脂肪酸金属塩は電子写真プロセ
スにおける接触摺擦工程（感光体とクリーニングブレー
ド等）において、その減摩作用により摺擦をスムーズに
して粒子の摩擦熱等による付着の防止に効果のあること
が知られていた。本発明者らは、上記式（２）及び
（３）を満たす特別な粒度分布を有する脂肪酸金属塩粒
子を採用すれば、特に一成分現像剤において、上記の作
用の他にトナー粒子の帯電性を高め、帯電量分布の逆極
性部分を減らし、しかも帯電性の長期安定性も改善する
作用があることを知得した。上記の粒子径及び粒度分布
の測定は、前記した装置、条件で行うのが望ましい。Conventionally, a fatty acid metal salt is effective in preventing rubbing of particles due to frictional heat by smoothing rubbing due to its anti-friction action in the contact rubbing step (photoreceptor and cleaning blade, etc.) in the electrophotographic process. Was known to exist. When the fatty acid metal salt particles having a special particle size distribution satisfying the above formulas (2) and (3) are adopted, the inventors of the present invention, especially in a one-component developer, have the above-mentioned function and the charging property of the toner particles. It was found that there is an effect of increasing the chargeability, reducing the opposite polarity part of the charge amount distribution, and improving the long-term stability of the chargeability. It is desirable to measure the above-mentioned particle diameter and particle size distribution using the above-described apparatus and conditions.
【００３１】本発明に関わる脂肪酸金属塩粒子は、上記
式（２）及び（３）で示されるように、粒子径が小粒径
でしかもその粒度分布の範囲が狭いことを特徴とする。
式（２）において、Ｄｓ50／Ｄｔ50の値が０．５を超え
て大きい場合には、脂肪酸金属塩粒子の粒径はトナー粒
子の粒径に近づくか、それ以上に大きくなることを意味
するので、こうした大粒子は現像剤中から脱落して系外
に飛散しやすくなり装置を汚染するばかりか、画像上に
大粒状のカブリとして検出されるようになるので好まし
くない。また、式（３）において、粒子の粒度分布の幅
を表すＤｓ84／Ｄｓ16が４を超えて大きい場合には、粒
子の粒度が不揃いなので現像剤の帯電性を長期にわたっ
て安定に保つことが困難となり、画質の変動を抑制でき
ない。なお、脂肪酸金属塩粒子の粒度分布は一山分布で
あるのが望ましい。The fatty acid metal salt particles according to the present invention are characterized by a small particle size and a narrow particle size distribution range, as shown by the above formulas (2) and (3).
In the formula (2), when the value of Ds 50 / Dt 50 exceeds 0.5 and is large, it means that the particle size of the fatty acid metal salt particles is close to or larger than the particle size of the toner particles. Therefore, such large particles are not preferable because they are likely to fall out of the developer and scatter out of the system to contaminate the apparatus and also to be detected as large fog on the image. Further, in the formula (3), when Ds 84 / Ds 16 which represents the width of the particle size distribution of the particles is larger than 4, the particle sizes of the particles are not uniform, so that the electrostatic property of the developer can be kept stable for a long time. It becomes difficult and the fluctuation of the image quality cannot be suppressed. The particle size distribution of the fatty acid metal salt particles is desirably a single-peak distribution.
【００３２】本発明に用いられる脂肪酸金属塩粒子の脂
肪酸としては、酪酸、吉草酸、ラウリン酸、ミリスチン
酸、パルミチン酸、ステアリン酸及びモンタン酸等の一
価の飽和脂肪酸、アジピン酸、ピメリン酸、スベリン
酸、アゼライン酸及びセバシン酸等の多価の飽和脂肪
酸、クロトン酸及びオレイン酸等の一価の不飽和脂肪
酸、並びにマレイン酸及びシトラコン酸等の多価の不飽
和脂肪酸を挙げることができ、本発明には８〜３５個の
炭素元素を有する飽和または不飽和の脂肪酸の金属塩が
好ましく使用できるが、特にステアリン酸が望ましい。
金属塩としては、リチウム、ナトリウム、カリウム、
銅、ルビニウム、銀、亜鉛、マグネシウム、カルシウ
ム、ストロンチウム、アルミニウム、鉄、コバルト、ニ
ッケルの塩及びその混合物を含むがこれらには制限され
ない。上記した中でも、脂肪酸としてはステアリン酸が
より望ましく、金属としては亜鉛、マグネシウム、カル
シウム、アルミニウムの中から選ばれるものがより望ま
しい。その中でも、特にステアリン酸亜鉛を用いるのが
最適である。The fatty acid of the fatty acid metal salt particles used in the present invention includes butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, monic acid, and other monovalent saturated fatty acids, adipic acid, pimelic acid, Suberic acid, polyvalent saturated fatty acids such as azelaic acid and sebacic acid, monovalent unsaturated fatty acids such as crotonic acid and oleic acid, and polyvalent unsaturated fatty acids such as maleic acid and citraconic acid, In the present invention, a metal salt of a saturated or unsaturated fatty acid having 8 to 35 carbon elements can be preferably used, and stearic acid is particularly preferable.
Metal salts include lithium, sodium, potassium,
Salts of copper, rubinium, silver, zinc, magnesium, calcium, strontium, aluminum, iron, cobalt, nickel and mixtures thereof, but not limited thereto. Among the above, stearic acid is more preferable as the fatty acid, and a metal selected from zinc, magnesium, calcium, and aluminum is more preferable as the metal. Among them, it is particularly preferable to use zinc stearate.
【００３３】流動性向上剤としては、公知の各種のもの
が使用可能である。例えば、乾式製法または湿式製法に
よるシリカ、アルミナ、チタニア等の金属酸化物が挙げ
られる。中でもその平均一次粒子径が約５〜５０ｎｍで
あるものが好ましい。また、その表面が疎水化処理され
ているものが望ましい。疎水化処理剤の具体例としては
ヘキサメチルジシラザン、シリコンオイルが挙げられる
ものの中から選ばれる少なくとも一種の物質で疎水化処
理されたシリカ微粒子であるのが好適である。このよう
な微粒子は、凝集物による感光体傷の発生が極めて少な
く、従ってそれに付随して起こる各種の画像欠陥が出に
くい利点を有する。一方、疎水化処理剤としてジメチル
ジクロルシランで処理されている場合、得られる流動性
向上剤は、粗大な凝集物が残存しやすい傾向にあり、感
光体傷が発生する要因となるので好ましくない。As the fluidity improver, various known ones can be used. Examples thereof include metal oxides such as silica, alumina and titania produced by a dry method or a wet method. Among them, those having an average primary particle diameter of about 5 to 50 nm are preferable. Further, it is desirable that the surface is subjected to a hydrophobic treatment. As a specific example of the hydrophobizing agent, fine silica particles hydrophobized with at least one substance selected from those including hexamethyldisilazane and silicone oil are preferable. Such fine particles have an advantage that the photoconductor scratches due to agglomerates are extremely small, and therefore various image defects that accompany it are less likely to occur. On the other hand, when it is treated with dimethyldichlorosilane as a hydrophobizing agent, the resulting fluidity improver tends to leave coarse agglomerates, which may cause damage to the photoreceptor, which is not preferable. .
【００３４】トナー粒子への脂肪酸金属塩粒子及び流動
性向上剤の添加の方法は、高速流動式混合機等を用いて
外添するのが好ましい。また、必要に応じてこれらの添
加剤を事前に個別あるいは混合して解砕して、粗大凝集
物を除去してトナー粒子に外添してもよい。本発明で
は、外添剤が添加される前のトナー粒子の窒素吸着法に
よる比表面積をＡ（ｍ2 ／ｇ）とし、外添剤が添加され
た後のトナー粒子の窒素吸着法による比表面積を微（ｍ
2 ／ｇ）としたとき、前記の式（１）を満足することが
必要である。As a method of adding the fatty acid metal salt particles and the fluidity improver to the toner particles, it is preferable to add them externally by using a high speed fluid mixer or the like. Further, if necessary, these additives may be individually or mixed in advance and crushed to remove coarse aggregates and externally add the toner particles. In the present invention, the specific surface area of the toner particles before the addition of the external additive is A (m 2 / g), and the specific surface area of the toner particles after the addition of the external additive is the nitrogen adsorption method. Fine (m
2 / g), it is necessary to satisfy the above formula (1).
【００３５】[0035]
【数８】 式（１） １．５≦Ｂ／Ａ≦３Expression (1) 1.5 ≦ B / A ≦ 3
【００３６】一般に、外添剤が添加される前のトナー粒
子の比表面積より外添剤が添加された後のトナー粒子の
比表面積の方が数値的には大きくなるので、式（１）の
Ｂ／Ａが１以上の数値を取りうることは想定されうる。
しかし、本発明者らは、層形成部材が接触・押圧された
現像スリーブ上での層形成に着目したところ、式（１）
を満足すれば、特に均一な薄層形成が容易にできること
を確認した。なお、式（１）のＢ／Ａが前記範囲より小
さい場合は、均一な薄層が得られにくく、前記範囲より
大きい場合は、定着性に悪影響を及ぼして現像剤の定着
強度が低下するので好ましくない。窒素吸着法による比
表面積の測定には、フローソーブ２３００（島津製作所
製）を用いた。Generally, the specific surface area of the toner particles after the external additive is added is numerically larger than the specific surface area of the toner particles before the external additive is added. It can be assumed that B / A can take a numerical value of 1 or more.
However, when the present inventors paid attention to the layer formation on the developing sleeve in which the layer forming member was contacted and pressed, the formula (1)
It was confirmed that a particularly uniform thin layer can be easily formed if the above condition is satisfied. If B / A in the formula (1) is smaller than the above range, it is difficult to obtain a uniform thin layer, and if it is larger than the above range, the fixability is adversely affected and the fixing strength of the developer is lowered. Not preferable. Flowsorb 2300 (manufactured by Shimadzu Corporation) was used for measurement of the specific surface area by the nitrogen adsorption method.
【００３７】従って、前記外添剤粒子の添加量は、前記
の式（１）を満足するように、トナー粒子を加えればよ
いが、通常は、トナー粒子１００重量部に対して、脂肪
酸金属塩粒子を０．０１〜３重量部の範囲からの適当
量、流動性向上剤を０．５〜５重量部の範囲からの適当
量を添加させるのがよい。本発明に用いる一成分現像剤
は磁性一成分方式または非磁性一成分方式のいずれであ
ってもよい。また、カラー一成分現像剤として用いるに
も好適である。Therefore, the addition amount of the external additive particles may be such that the toner particles are added so as to satisfy the above-mentioned formula (1). Normally, the fatty acid metal salt is added to 100 parts by weight of the toner particles. It is preferable to add particles in an appropriate amount within the range of 0.01 to 3 parts by weight and a fluidity improver in an appropriate amount within the range of 0.5 to 5 parts by weight. The one-component developer used in the present invention may be either a magnetic one-component type or a non-magnetic one-component type. It is also suitable for use as a color one-component developer.
【００３８】以下、図１を例に本発明の画像形成方法を
説明する。本図は非磁性一成分現像剤を用いる場合の例
である。本発明に用いられる現像スリーブ１は、通常、
円柱状あるいは円筒状の形態の表面を現像剤を担持する
表面として用いる。材質は弾性体、剛体どちらでもよい
が、感光体と現像スリーブとが非磁性現像剤を介在して
接触する、いわゆる接触現像方法においては弾性体を用
いる方法が一般的である。また磁性現像剤を用いる場合
は、マグネットを内包する金属製の剛体スリーブを用い
るのが通例である。現像スリーブの表面は現像剤６の搬
送性を上げる目的で適度な表面粗さを与えてもよい。ま
たトナー粒子との適度な摩擦帯電が得られるような材質
を考慮しなければならない。非磁性一成分接触型現像の
場合、弾性体の現像スリーブの一般的な形態としては、
導電性ゴムローラ（ＮＢＲゴム、シリコーンゴムなどに
導電性粒子を分散含有させたものなど）を用いる。導電
性ゴムの表面に誘電体層を設ける場合もある。The image forming method of the present invention will be described below with reference to FIG. This figure shows an example in which a non-magnetic one-component developer is used. The developing sleeve 1 used in the present invention is usually
A cylindrical or cylindrical surface is used as the surface for carrying the developer. The material may be either an elastic body or a rigid body. However, in a so-called contact developing method in which the photosensitive member and the developing sleeve come into contact with a non-magnetic developer, a method using an elastic body is generally used. When a magnetic developer is used, a metal rigid sleeve containing a magnet is usually used. The surface of the developing sleeve may be provided with an appropriate surface roughness for the purpose of improving the transportability of the developer 6. Further, it is necessary to consider a material capable of obtaining an appropriate frictional charge with the toner particles. In the case of non-magnetic one-component contact developing, the general form of the elastic developing sleeve is
A conductive rubber roller (such as NBR rubber or silicone rubber in which conductive particles are dispersed and contained) is used. In some cases, a dielectric layer is provided on the surface of the conductive rubber.
【００３９】本発明に用いられる現像層形成部材２は、
角棒状の剛体、突起状の弾性体、板バネ状等のものの面
や先端を利用するもの、ローラ、その他、あるいはそれ
らの複合型など各種が挙げられる。層形成部材２はそれ
自身の弾性力あるいは現像スリーブ１の弾性力あるいは
外部からの力あるいはそれらの複合力によって、現像ス
リーブ１に直線上に押圧されている。層形成部材２の電
気特性については、絶縁性のもの、導電体のものに電圧
を印加する場合、あるいは導電体ではあるが電気的には
どこにも接続されずにフロートになっているものなど各
種であるが、絶縁体の場合や導電体でも電気的にフロー
トである場合、つまり層形成部材２と現像スリーブ１と
の間に電圧を印加しない場合には逆帯電トナーによるカ
ブリが発生しやすく、そうした場合、本発明は顕著に効
果を発揮する。現像スリーブ１をこの直線上押圧に対し
て直角方向に摺るように相対移動させることにより現像
剤粒子は押圧部を押し広げながら通過し、現像スリーブ
１上に均一に塗布されて現像剤層を形成する。この押圧
部の形態、圧力、組成、印加電圧によって、現像剤層
厚、トナーの帯電量はコントロールされる。大局的には
圧力が大きいほど塗布される現像剤層厚は薄く帯電量は
高くなるが、形態、圧力、組成、印加電圧については複
雑な物理、化学の現象となるので一概には議論できな
い。The developing layer forming member 2 used in the present invention is
There are various types such as a rectangular rod-shaped rigid body, a protruding elastic body, a leaf spring-shaped one, and the like using a surface or a tip, a roller, and others, or a composite type thereof. The layer forming member 2 is pressed linearly against the developing sleeve 1 by its own elastic force, the elastic force of the developing sleeve 1, an external force, or a combination thereof. Regarding the electrical characteristics of the layer forming member 2, there are various types such as a case where a voltage is applied to an insulating material, a conductive material, or a material which is a conductor but floats without being electrically connected to anywhere. However, when an insulator or a conductor is electrically floated, that is, when no voltage is applied between the layer forming member 2 and the developing sleeve 1, fog due to the oppositely charged toner is likely to occur, In such a case, the present invention exerts a remarkable effect. By relatively moving the developing sleeve 1 so as to slide in a direction perpendicular to the linear pressing, the developer particles pass while pressing and expanding the pressing portion, and are uniformly applied on the developing sleeve 1 to form a developer layer. I do. The thickness of the developer layer and the charge amount of the toner are controlled by the form, pressure, composition, and applied voltage of the pressing portion. Generally speaking, the greater the pressure, the thinner the applied developer layer and the higher the charge amount. However, since the form, pressure, composition, and applied voltage are complicated physical and chemical phenomena, they cannot be generally discussed.
【００４０】静電潜像を保持する感光体３は、その表面
に静電荷分布による静電潜像パターンを形成する。本発
明の画像形成方法では、感光体３としてＯＰＣが用いら
れる。その一般的な形態はアルミなどの金属製の円筒ま
たは薄膜からなる導電性基材表面にポリカーボネート樹
脂やアクリル樹脂等を含む有機感光材料を塗布して用い
る。感光層の比誘電率は１〜５程度であり、層厚１０〜
５０μｍ程度で使用されるのが一般的である。The photoconductor 3 holding the electrostatic latent image forms an electrostatic latent image pattern due to the electrostatic charge distribution on its surface. In the image forming method of the present invention, OPC is used as the photoconductor 3. In a general form, an organic photosensitive material containing a polycarbonate resin, an acrylic resin, or the like is applied to the surface of a conductive base made of a cylinder or a thin film made of metal such as aluminum and used. The relative permittivity of the photosensitive layer is about 1 to 5 and the layer thickness is 10 to 10.
It is generally used at about 50 μm.
【００４１】画像形成の工程は、一般に用いられている
ゼログラフィーの原理に従い、コロナチャージャーや接
触型のローラ方式やブラシ方式等の感光体帯電部材７に
よって均一帯電され、ランプやレーザー光等による露光
の手順などを経て感光体３上に静電荷分布の潜像を形成
する。このときの感光体３上の最大電位が、導電性基材
を基準に絶対値で１００〜１２００Ｖ程度、より好まし
くは３００〜９００Ｖ程度になるようにコントロールさ
れる。In the image forming process, according to the generally used principle of xerography, a photosensitive member 7 such as a corona charger, a contact type roller type or a brush type is uniformly charged and exposed by a lamp or a laser beam. A latent image having an electrostatic charge distribution is formed on the photoconductor 3 through the procedure described above. At this time, the maximum potential on the photoreceptor 3 is controlled so as to have an absolute value of about 100 to 1200 V, more preferably about 300 to 900 V, based on the conductive base material.
【００４２】一方、現像スリーブ１には前述のごとく、
現像剤層形成部材２によって現像剤６を塗布する。現像
スリーブ１と層形成部材２との間には、特に電圧をかけ
ない場合、短絡して同電位とする場合、５００Ｖ以下程
度の電圧をかける場合などがある。On the other hand, in the developing sleeve 1, as described above,
The developer 6 is applied by the developer layer forming member 2. Between the developing sleeve 1 and the layer forming member 2, there is a case where no voltage is applied, a case where a short circuit is made to have the same potential, and a case where a voltage of about 500 V or less is applied.
【００４３】また、現像スリーブ１の相対的移動方向の
現像剤層形成部材２より上流側に接触部材４を設けても
よい。接触部材４としては、現像剤６が自重と流動性に
よって現像スリーブ１に付着する力に加え積極的に現像
剤６が現像スリーブ１に向かうものを用いる。例えば、
スポンジ状やブラシ状の部材に現像剤６を含ませて現像
スリーブ１に摺り付ける方法が用いられる。このときの
摩擦を利用して現像剤６の摩擦帯電を促進してもよい。
この接触部材４に導電性の材料を用いて、現像剤６が現
像スリーブ１へ向かう静電気力を与えるように現像スリ
ーブとの間に電圧をかけてもよい。また一般的にはロー
ラ状のエンドレスな現像スリーブ１が用いられるので、
感光体３への現像を終えた残りの現像剤が付着した現像
スリーブ１がこの接触部材４の部分に戻ってくるので清
掃手段を兼ねさせることもできる。その効果を積極的に
利用したい場合には、逆に現像剤６が現像スリーブ１か
ら離れる方向に力が加わるように電圧をかけてもよい。
また、清掃と供給を兼ねる場合は現像剤６の帯電を上げ
る目的で交番電界を印加してもよい。Further, the contact member 4 may be provided on the upstream side of the developer layer forming member 2 in the relative movement direction of the developing sleeve 1. As the contact member 4, a member in which the developer 6 positively moves toward the developing sleeve 1 in addition to the force of the developer 6 adhering to the developing sleeve 1 due to its own weight and fluidity is used. For example,
A method is used in which the developer 6 is contained in a sponge-like or brush-like member and is slid on the developing sleeve 1. The frictional charging of the developer 6 may be promoted by utilizing the friction at this time.
By using a conductive material for the contact member 4, a voltage may be applied between the contact member 4 and the developing sleeve so that the developer 6 applies an electrostatic force toward the developing sleeve 1. Further, since the roller-shaped endless developing sleeve 1 is generally used,
Since the developing sleeve 1 to which the remaining developer after the development on the photoconductor 3 is adhered returns to the contact member 4, it can also serve as a cleaning means. If it is desired to utilize the effect positively, a voltage may be applied so that a force is applied in a direction in which the developer 6 is separated from the developing sleeve 1.
When cleaning and supply are performed, an alternating electric field may be applied to increase the charge of the developer 6.
【００４４】しかしながら、装置の低価格化を図る上で
は、現像スリーブ１と接触部材４との間に電圧を印加し
ない方法が好ましく、さらには接触部材４自体を使用し
ない方が好ましい。この場合には、トナー粒子の摩擦や
電荷注入による帯電の機会が減少するため、画像中抜け
やカブリなどの悪しき現象が発生しやすい。こうした場
合に本発明は顕著な効果を発揮する。However, in order to reduce the cost of the apparatus, it is preferable to apply no voltage between the developing sleeve 1 and the contact member 4, and it is more preferable not to use the contact member 4 itself. In this case, the chance of electrification due to friction of toner particles or charge injection is reduced, so that bad phenomena such as missing images and fog are likely to occur. In such a case, the present invention exerts a remarkable effect.
【００４５】また、図１〜２のような形態の現像器を用
いる場合、現像スリーブ１の下方間隙より現像剤６が漏
れる恐れがあるため、現像剤漏れシール部材５を付ける
ことが一般的である。以上の工程により、現像剤層を形
成した現像スリーブ１と潜像を形成した感光体３とを対
向させ、現像剤６中の少なくともトナー粒子を転移させ
潜像を顕像化する。この際、飛翔現像等の非接触現像に
おいては、５０〜５００μｍの間隙を形成させ静電気力
で転移させる。接触現像の場合は、現像剤層を介して押
圧され、潜像パターンに見合ったトナー粒子が静電気力
で転移される。トナーを転移させたい潜像電位と白地と
したい潜像電位との間の電位に現像スリーブ１の電位を
保つ方法が一般的である。When the developing device having the configuration shown in FIGS. 1 and 2 is used, since the developer 6 may leak from the lower gap of the developing sleeve 1, the developer leak seal member 5 is generally attached. is there. Through the above steps, the developing sleeve 1 having the developer layer formed thereon and the photoconductor 3 having the latent image formed thereon face each other, and at least the toner particles in the developer 6 are transferred to visualize the latent image. At this time, in non-contact development such as flight development, a gap of 50 to 500 μm is formed, and transfer is performed by electrostatic force. In the case of contact development, the toner particles are pressed through the developer layer, and the toner particles corresponding to the latent image pattern are transferred by electrostatic force. A general method is to keep the potential of the developing sleeve 1 at a potential between the potential of the latent image at which the toner is to be transferred and the potential of the latent image at which the toner is to be made white.
【００４６】潜像パターンに転移したトナーは、通常の
複写機やレーザープリンタの場合、転写部材８によって
紙やフィルムなどの被転写材へさらに転写される。この
転写工程においては、被転写材を感光体に接触させて、
背面よりコロナ放電により電荷を与える方法や導電性の
転写ローラを押圧し電圧を印加する方法などが一般的で
ある。ローラ転写等の圧力を加える転写工程の場合、画
像中抜けが発生しやすい。その場合、本発明は顕著に効
果を発揮する。In the case of an ordinary copying machine or laser printer, the toner transferred to the latent image pattern is further transferred by a transfer member 8 to a transfer material such as paper or film. In this transfer step, the material to be transferred is brought into contact with the photoreceptor,
A method of applying a charge from the back surface by corona discharge or a method of applying a voltage by pressing a conductive transfer roller are common. In the case of a transfer step in which pressure such as roller transfer is applied, image missing is likely to occur. In this case, the present invention exerts a remarkable effect.
【００４７】転写工程の後に、感光体上に残存する粒子
の除去が感光体に当接するポリウレタン等のクリーニン
グブレード９での摺擦によって行われる。この際、ＯＰ
Ｃ感光体を用いると、クリーニング不良や感光体表面の
研磨傷、さらには感光体への粒子の付着・固着が起きや
すく、そういった現象は画像上に致命的な欠陥として現
れる。ＯＰＣ感光体とブレードクリーニングを組み合わ
せて行った場合のこうした問題の発生機構としては以下
のように推定される。すなわち、ＯＰＣ感光体はその表
面が高分子材料等を主体とするものである。このような
高分子材料等は、第一にトナー粒子を介在するクリーニ
ングブレードの押圧で弾性変形しやすい傾向にある。そ
の場合はトナー粒子等のすり抜け現象を引き起こすので
クリーニング不良となって現れる。第二にその硬度が低
いので粒子を介在するクリーニングブレードとの継続的
な摺擦によって、その表面に擦り傷、研磨傷がでやす
く、また、それらの傷状欠陥にトナー粒子等が摩擦熱で
擦り込まれて点状やフィルム状の融着現象が発生するた
めに画像上の汚れとして検出されるものと考えられる。
本発明はこのような現象に対して顕著な改良効果を発揮
する。さらに、被転写材上の現像剤像は、熱ロール方式
等の熱定着機１０を通過することによって、被転写材上
に熱融着して、固定化される。After the transfer step, the particles remaining on the photoconductor are removed by rubbing with a cleaning blade 9 made of polyurethane or the like that contacts the photoconductor. At this time, OP
When the C photoconductor is used, cleaning failure, polishing scratches on the photoconductor surface, and particles adhering to and fixing to the photoconductor are likely to occur, and such a phenomenon appears as a fatal defect on the image. The mechanism of occurrence of such a problem when the OPC photosensitive member and the blade cleaning are performed in combination is estimated as follows. That is, the surface of the OPC photoreceptor is mainly composed of a polymer material or the like. First, such a polymer material or the like tends to be elastically deformed by the pressure of the cleaning blade with toner particles interposed. In that case, the phenomenon of toner particles slipping through is caused, resulting in poor cleaning. Secondly, because of its low hardness, continuous rubbing with a cleaning blade interposing particles easily causes scratches and polishing scratches on its surface, and toner particles and the like are rubbed into the scratch-like defects by friction heat. It is considered that the spot-like or film-like fusing phenomenon occurs and is detected as a stain on the image.
The present invention exerts a remarkable improvement effect on such a phenomenon. Further, the developer image on the transfer material passes through a heat fixing device 10 such as a hot roll system, and is thermally fused and fixed on the transfer material.
【００４８】[0048]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はその要旨を超えない限り、以下の実施例に
より限定されるものではない。なお、実施例及び比較例
中、単に「部」とあるのはいずれも「重量部」を表す。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” simply means “parts by weight”.
【００４９】実施例１ 以下に示す配合比により非磁性一成分現像剤を得た。 ポリエステル樹脂 １００部 （テレフタル酸とイソドデセニルコハク酸とトリメリト
酸とビスフェノールＡのプロピレンオキシド付加物との
縮合重合物、ガラス転移温度５５℃） 帯電制御剤 クロム含金アゾ染料 ２部 （ボントロンＳ−３４、オリエント化学社製） カーボンブラック ６部 （三菱カーボンブラックＭＡ１００、三菱化学社製） 低分子量ポリプロピレン ３部 （ビスコール５５０Ｐ、三洋化成社製）Example 1 A non-magnetic one-component developer was obtained with the following compounding ratio. Polyester resin 100 parts (condensation polymerization product of terephthalic acid, isododecenylsuccinic acid, trimellitic acid and propylene oxide adduct of bisphenol A, glass transition temperature 55 ° C) Charge control agent Chromium-containing azo dye 2 parts (Bontron S -34, manufactured by Orient Chemical Co., Ltd.) Carbon black 6 parts (Mitsubishi Carbon Black MA100, manufactured by Mitsubishi Chemical Co.) Low molecular weight polypropylene 3 parts (Viscor 550P, manufactured by Sanyo Chemical Co., Ltd.)
【００５０】製造は、上記の原材料を高速流動式混合機
で混合し、２軸押し出し機で溶融混練した後、ハンマー
ミルで粗粉砕し、機械式粉砕機クリプトロン（川崎重工
社製）で微粉砕した後、ジグザグ分級機（アルピネ社
製）で分級した。トナー粒子の平均粒径Ｄｔ50は８．５
μｍであり、ガラス転移温度は５６℃であった。このト
ナー粒子１００部に対して、平均粒径Ｄｓ50が２．９μ
ｍ、Ｄｓ84／Ｄｓ16が２．８であるステアリン酸亜鉛粒
子を０．３部とヘキサメチルジシラザンで疎水化処理さ
れた平均一次粒子径約１０ｎｍのシリカ微粒子１．５部
とを高速流動式混合機で外添して、一成分現像剤を作製
した。外添する前のトナー粒子の窒素吸着法による比表
面積Ａは１．７ｍ2 ／ｇであり、外添後のトナー粒子の
窒素吸着法による比表面積Ｂは４．３ｍ2 ／ｇであり、
Ｂ／Ａは２．５であった。The production was carried out by mixing the above raw materials with a high-speed fluid mixer, melt-kneading with a twin-screw extruder, coarsely crushing with a hammer mill, and finely crushing with a mechanical crusher Cryptron (Kawasaki Heavy Industries). After crushing, it was classified by a zigzag classifier (manufactured by Alpine). The average particle diameter Dt 50 of the toner particles is 8.5.
μm, and the glass transition temperature was 56 ° C. With respect to 100 parts of this toner particle, the average particle diameter Ds 50 is 2.9 μm.
m, Ds 84 / Ds 16 of 0.3 parts zinc stearate particles having a particle size of 2.8 and 1.5 parts of silica fine particles having an average primary particle diameter of about 10 nm that have been hydrophobized with hexamethyldisilazane and flow at high speed. A one-component developer was prepared by externally adding with a type mixer. The specific surface area A of the toner particles before external addition by the nitrogen adsorption method is 1.7 m 2 / g, and the specific surface area B of the toner particles after external addition by the nitrogen adsorption method is 4.3 m 2 / g.
B / A was 2.5.
【００５１】実写評価装置として、市販の非磁性一成分
現像方式を採用したプリンターを改造して用いた。この
プリンターの感光体は、表面層にポリカーボネート樹脂
が含有される直径２４ｍｍφのドラム状の積層型ＯＰＣ
であり、クリーニング部材としてウレタンゴムのクリー
ニングブレードが感光体に接触押圧されている。定着機
は熱ロール方式で、上ローラ（現像剤接触面）の表面は
フッ素系樹脂で被覆されており、下ローラはシリコンゴ
ム製である。また、現像装置は導電剤が含有されたゴム
性の現像スリーブに対して、金属製のブレード（現像剤
層形成部材）が押し当てられている。約１００００枚の
印字が可能となるよう前記一成分現像剤をこの現像装置
に一定量供給する。A commercially available printer adopting a non-magnetic one-component developing system was modified and used as an apparatus for evaluating real images. The photoreceptor of this printer is a drum-shaped laminated OPC with a diameter of 24 mm and containing a polycarbonate resin in the surface layer.
A urethane rubber cleaning blade is pressed against the photosensitive member as a cleaning member. The fixing device is a heat roll type, the surface of the upper roller (developer contact surface) is covered with a fluororesin, and the lower roller is made of silicon rubber. Further, in the developing device, a metal blade (developer layer forming member) is pressed against a rubber developing sleeve containing a conductive agent. A constant amount of the one-component developer is supplied to the developing device so that printing of about 10,000 sheets is possible.
【００５２】評価方法は、上記プリンターを温度２５
℃、相対湿度５５％の常温常湿雰囲気に設置し、連続実
写により行う。評価結果は優秀であり、１００００枚の
実写を通じて、画像中抜け、画像濃度、カブリ等の画質
は優秀であった。また、ＯＰＣ上でのクリーニング不良
や現像剤粒子等の融着現象が見られず、耐久性も十分で
あった。定着後の画像の定着強度も充分高く、一定の圧
力で画像ベタ部を折り曲げてもトナー像の剥離はほとん
ど見られなかった。The evaluation method is as follows.
It is installed in a normal temperature and normal humidity atmosphere at 55 ° C. and a relative humidity of 55%, and is performed by continuous actual photography. The evaluation result was excellent, and the image quality such as hollow image, image density, and fog was excellent after 10,000 actual copies. In addition, no poor cleaning on the OPC and no fusing phenomenon such as developer particles were observed, and the durability was sufficient. The fixing strength of the image after fixing was also sufficiently high, and peeling of the toner image was hardly seen even when the solid image portion was bent with a constant pressure.
【００５３】一方、本現像剤及びプリンターを温度３５
℃、相対湿度８５％の高温高湿条件に持ち込み、同様の
連続実写を行ったが、常温常湿環境での結果とほぼ同等
の結果を得た。さらに、本現像剤及びプリンターを温度
１０℃、相対湿度２０％の高温高湿条件に持ち込み、同
様の連続実写を行ったが、常温常湿環境での結果とほぼ
同等の結果を得た。On the other hand, the temperature of this developer and printer is set to 35
The same continuous shooting was carried out under high temperature and high humidity conditions of 85 ° C. and a relative humidity of 85%, but the result was almost the same as the result in a normal temperature and normal humidity environment. Further, the developer and the printer were brought into a high-temperature and high-humidity condition of a temperature of 10 ° C. and a relative humidity of 20%, and the same continuous actual photographing was performed. The result was almost the same as the result in a normal temperature and normal humidity environment.
【００５４】実施例２ トナー粒子の平均粒径Ｄｔ50が６．９μｍである以外
は、実施例１全く同様の処方及び製造方法でトナー粒子
を得た。次に、実施例１で用いたのと同じステアリン酸
亜鉛とシリカ微粒子とを同様に添加して一成分系現像剤
を作製した。外添する前のトナー粒子の窒素吸着法によ
る比表面積Ａは２．０ｍ2 ／ｇであり、外添後のトナー
粒子の窒素吸着法による比表面積Ｂは４．４ｍ2 ／ｇで
あり、Ｂ／Ａは２．２であった。以下、実写装置及び方
法は実施例１と同様にして行った。その結果、常温常湿
環境、高温高湿環境及び低温低湿環境のいずれも実施例
１と同様に良好な結果を得た。Example 2 Toner particles were obtained in the same manner as in Example 1 except that the average particle diameter Dt 50 of the toner particles was 6.9 μm. Next, the same zinc stearate and the silica fine particles used in Example 1 were added in the same manner to prepare a one-component developer. The specific surface area A of the toner particles before external addition by the nitrogen adsorption method is 2.0 m 2 / g, and the specific surface area B of the toner particles after external addition by the nitrogen adsorption method is 4.4 m 2 / g. / A was 2.2. Hereinafter, the photographing apparatus and method were the same as those in the first embodiment. As a result, good results were obtained in the same manner as in Example 1 in the normal temperature and normal humidity environment, the high temperature and high humidity environment, and the low temperature and low humidity environment.
【００５５】実施例３ 実施例１で作製したトナー粒子を用い、このトナー粒子
１００部に対して、平均粒径Ｄｓ50が４．７μｍ、Ｄｓ
84／Ｄｓ16が３．７であるステアリン酸亜鉛粒子を０．
３部とヘキサメチルジシラザンで疎水化処理された平均
一次粒子径約３０ｎｍのシリカ微粒子１．５部とを添加
する以外は、実施例１と同様にして一成分現像剤を作製
した。外添する前のトナー粒子の窒素吸着法による比表
面積Ａは１．７ｍ2 ／ｇであり、外添後のトナー粒子の
窒素吸着法による比表面積Ｂは３．０ｍ2 ／ｇであり、
Ｂ／Ａは１．８であった。以下、実写評価は実写装置及
び方法とも実施例１と同様にして行った。その結果、常
温常湿環境、高温高湿環境及び低温低湿環境のいずれも
実施例１と同様に良好な結果を得た。Example 3 Using the toner particles prepared in Example 1, 100 parts of the toner particles had an average particle diameter Ds 50 of 4.7 μm and Ds.
Zinc stearate particles having a 84 / Ds 16 of 3.7 were
A one-component developer was prepared in the same manner as in Example 1 except that 3 parts and 1.5 parts of silica fine particles having an average primary particle diameter of about 30 nm that had been hydrophobized with hexamethyldisilazane were added. The specific surface area A of the toner particles before external addition by the nitrogen adsorption method is 1.7 m 2 / g, and the specific surface area B of the toner particles after external addition by the nitrogen adsorption method is 3.0 m 2 / g,
B / A was 1.8. Hereinafter, the actual photographing evaluation was performed in the same manner as in Example 1 for the actual photographing apparatus and method. As a result, good results were obtained in the same manner as in Example 1 in the normal temperature and normal humidity environment, the high temperature and high humidity environment, and the low temperature and low humidity environment.
【００５６】実施例４ 実施例１で用いたトナー粒子１００部に対して、実施例
１で用いたステアリン酸亜鉛粒子０．３部とシリコーン
オイルで疎水化処理された平均一次粒子径約１０ｎｍの
シリカ微粒子２．０部とを添加する以外は実施例１と全
く同様にして一成分現像剤を作製した。外添する前のト
ナー粒子の窒素吸着法による比表面積Ａは１．７ｍ2 ／
ｇであり、外添後のトナー粒子の窒素吸着法による比表
面積Ｂは４．８ｍ2 ／ｇであり、Ｂ／Ａは２．８であっ
た。以下、実写評価は実写装置及び方法とも実施例１と
同様にして行った。その結果、常温常湿環境、高温高湿
環境及び低温低湿環境のいずれも実施例１と同様に良好
な結果を得た。Example 4 For 100 parts of the toner particles used in Example 1, 0.3 parts of the zinc stearate particles used in Example 1 and an average primary particle diameter of about 10 nm which was hydrophobized with silicone oil were used. A one-component developer was prepared in exactly the same manner as in Example 1 except that 2.0 parts of silica fine particles were added. The specific surface area A of the toner particles before external addition according to the nitrogen adsorption method is 1.7 m 2 /
The specific surface area B of the toner particles after external addition by the nitrogen adsorption method was 4.8 m 2 / g, and the B / A was 2.8. Hereinafter, the actual photographing evaluation was performed in the same manner as in Example 1 for the actual photographing apparatus and method. As a result, good results were obtained in the same manner as in Example 1 in the normal temperature and normal humidity environment, the high temperature and high humidity environment, and the low temperature and low humidity environment.
【００５７】比較例１ 実施例１で用いたトナー粒子１００部に対して、実施例
１で用いたステアリン酸亜鉛粒子０．３部とシリカ微粒
子０．４部とを添加する以外は実施例１と全く同様にし
て一成分現像剤を作製した。外添する前のトナー粒子の
窒素吸着法による比表面積Ａは１．７ｍ2 ／ｇであり、
外添後のトナー粒子の窒素吸着法による比表面積Ｂは
２．２ｍ2 ／ｇであり、Ｂ／Ａは１．３であった。以
下、実写評価は実写装置及び方法とも実施例１と同様に
して行った。その結果、常温常湿環境下での実写で、初
期からカブリが高くて画像中抜けが発生しており、また
繰り返し実写では画像濃度の低下も認められるようにな
り、約２０００枚以降で実用上使用に耐えなくなった。
また、高温高湿環境下の実写で、これらの画質の問題が
一層悪化することが観察された。Comparative Example 1 To 100 parts of the toner particles used in Example 1, 0.3 part of the zinc stearate particles used in Example 1 and 0.4 part of silica fine particles were added, except for adding 1 part of Example 1. A one-component developer was prepared in exactly the same manner as in. The specific surface area A of the toner particles before external addition by the nitrogen adsorption method is 1.7 m 2 / g,
The specific surface area B of the toner particles after external addition by the nitrogen adsorption method was 2.2 m 2 / g, and B / A was 1.3. Hereinafter, the actual photographing evaluation was performed in the same manner as in Example 1 for the actual photographing apparatus and method. As a result, in actual shooting under normal temperature and normal humidity, the fog was high from the beginning and image dropouts occurred, and in repeated actual shooting, a decrease in image density was also observed. It can no longer be used.
In addition, it was observed that these image quality problems were aggravated in actual shooting under a high temperature and high humidity environment.
【００５８】比較例２ 実施例１の処方において、樹脂を以下に示す樹脂に変更
する以外は同一の処方で、また実施例１と全く同様の製
造方法でトナーを作製した。 ポリエステル樹脂（テレフタル酸とトリメリト酸とビス
フェノールＡのプロピレンオキシド付加物との縮合重合
物、ガラス転移温度６５℃） トナー粒子の平均粒径Ｄｔ50は８．５μｍであり、ガラ
ス転移温度は６４℃であった。次に、実施例１で用いた
のと同じステアリン酸亜鉛とシリカ微粒子とを同様に添
加して一成分系現像剤を作製した。外添する前のトナー
粒子の窒素吸着法による比表面積Ａは１．８ｍ2 ／ｇで
あり、外添後のトナー粒子の窒素吸着法による比表面積
Ｂは４．３ｍ2 ／ｇであり、Ｂ／Ａは２．４であった。
以下、実写評価は実写装置及び方法とも実施例１と同様
にして行った。その結果、定着後に得られる画像は、画
像ベタ部を折り曲げると簡単に紙からトナーが剥離する
ことから、定着強度が低くて実用に耐えないことが判明
した。Comparative Example 2 A toner was prepared in the same manner as in Example 1 except that the resin was changed to the resin shown below. Polyester resin (condensation polymer of terephthalic acid, trimellitic acid and propylene oxide adduct of bisphenol A, glass transition temperature 65 ° C.) The average particle diameter Dt 50 of the toner particles is 8.5 μm, and the glass transition temperature is 64 ° C. there were. Next, the same zinc stearate and the silica fine particles used in Example 1 were added in the same manner to prepare a one-component developer. The specific surface area A of the toner particles before external addition by the nitrogen adsorption method is 1.8 m 2 / g, and the specific surface area B of the toner particles after external addition by the nitrogen adsorption method is 4.3 m 2 / g. / A was 2.4.
Hereinafter, the actual photographing evaluation was performed in the same manner as in Example 1 for the actual photographing apparatus and method. As a result, it was found that the image obtained after fixing has low fixing strength and cannot be put to practical use because the toner is easily peeled off from the paper when the solid image portion is bent.
【００５９】実施例５ 以下に示す配合比により磁性一成分現像剤を得た。 スチレン系樹脂 １００部 （モノマー重量比：スチレン／ｎ−ブチルメタクリレー
ト＝７５／２５、ガラス転移温度５５℃） 帯電制御剤 クロム含金アゾ染料 ２部 （ボントロンＳ−３４、オリエント化学社製） マグネタイト磁性粉 ６０部 （ＥＰＴ−５００、戸田工業社製） 低分子量ポリプロピレン ３部 （ビスコール５５０Ｐ、三洋化成社製）Example 5 A magnetic one-component developer was obtained with the following compounding ratio. Styrene resin 100 parts (monomer weight ratio: styrene / n-butyl methacrylate = 75/25, glass transition temperature 55 ° C.) Charge control agent Chromium-containing azo dye 2 parts (Bontron S-34, manufactured by Orient Chemical Co.) Magnetite magnetism Powder 60 parts (EPT-500, Toda Kogyo Co., Ltd.) Low molecular weight polypropylene 3 parts (Viscor 550P, Sanyo Chemical Co., Ltd.)
【００６０】製造は、上記の原材料を高速流動式混合機
で混合し、２軸押し出し機で溶融混練した後、ハンマー
ミルで粗粉砕し、機械式粉砕機クリプトロン（川崎重工
社製）で微粉砕した後、ジグザグ分級機（アルピネ社
製）で分級した。トナー粒子の平均粒径Ｄｔ50は８．０
μｍであり、ガラス転移温度は５４℃であった。このト
ナー粒子１００部に対して、平均粒径Ｄｓ50が２．９μ
ｍ、Ｄｓ84／Ｄｓ16が２．８であるステアリン酸亜鉛粒
子を０．３部とヘキサメチルジシラザンで疎水化処理さ
れた平均一次粒子径約１０ｎｍのシリカ微粒子１．３部
とを高速流動式混合機で外添して、一成分現像剤を作製
した。外添する前のトナー粒子の窒素吸着法による比表
面積Ａは２．０ｍ2 ／ｇであり、外添後のトナー粒子の
窒素吸着法による比表面積Ｂは４．０ｍ2 ／ｇであり、
Ｂ／Ａは２．０であった。In the production, the above raw materials were mixed by a high-speed fluid mixer, melt-kneaded by a twin-screw extruder, coarsely pulverized by a hammer mill, and finely pulverized by a mechanical pulverizer Cryptron (manufactured by Kawasaki Heavy Industries, Ltd.). After crushing, it was classified by a zigzag classifier (manufactured by Alpine). The average particle diameter Dt 50 of the toner particles is 8.0.
μm, and the glass transition temperature was 54 ° C. With respect to 100 parts of this toner particle, the average particle diameter Ds 50 is 2.9 μm.
m, Ds 84 / Ds 16 of 0.3 parts zinc stearate particles having a 2.8 and 1.3 parts of silica fine particles having an average primary particle diameter of about 10 nm that have been hydrophobized with hexamethyldisilazane, and flow at high speed A one-component developer was prepared by externally adding with a type mixer. The specific surface area A of the toner particles before external addition by the nitrogen adsorption method is 2.0 m 2 / g, and the specific surface area B of the toner particles after external addition by the nitrogen adsorption method is 4.0 m 2 / g,
B / A was 2.0.
【００６１】実写評価装置として、市販の磁性一成分現
像方式を採用したプリンターを改造して用いた。このプ
リンターの感光体は、表面層にポリカーボネート樹脂が
含有される直径３０ｍｍφのドラム状の積層型ＯＰＣで
あり、クリーニング部材としてウレタンゴムのクリーニ
ングブレードが感光体に接触押圧されている。定着機は
熱ロール方式で、上ローラ（現像剤接触面）の表面はフ
ッ素系樹脂で被覆されており、下ローラはシリコンゴム
製である。また、現像装置はマグネットが内包されたス
テンレス性の現像スリーブに対して、ウレタンゴム製の
ブレード（現像剤層形成部材）が押し当てられている。
約７０００枚の印字が可能となるよう前記一成分現像剤
をこの現像装置に一定量供給する。評価方法は、実施例
１に準じて行う。A commercially available printer using a magnetic one-component developing system was modified and used as a device for evaluating real images. The photoreceptor of this printer is a drum-shaped laminated OPC having a diameter of 30 mm with a surface layer containing a polycarbonate resin, and a urethane rubber cleaning blade as a cleaning member is pressed against the photoreceptor. The fixing device is a heat roll type, the surface of the upper roller (developer contact surface) is covered with a fluororesin, and the lower roller is made of silicon rubber. Further, in the developing device, a blade (developer layer forming member) made of urethane rubber is pressed against a stainless developing sleeve containing a magnet.
A constant amount of the one-component developer is supplied to the developing device so that printing of approximately 7,000 sheets can be performed. The evaluation method is carried out according to Example 1.
【００６２】その結果、常温常湿雰囲気下での評価結果
は優秀であり、７０００枚の実写を通じて、画像中抜
け、画像濃度、カブリ等の画質は優秀であった。また、
ＯＰＣ上でのクリーニング不良や現像剤粒子等の融着現
象が見られず、耐久性も十分であった。さらに、定着後
の画像の定着強度も充分高く、一定の圧力で画像ベタ部
を折り曲げてもトナー像の剥離はほとんど見られなかっ
た。また、高温高湿条件での実写においては、実使用上
さほど問題のない程度の画像濃度の若干の低下が見られ
た他は、常温常湿環境での結果とほぼ同等の結果を得
た。さらに、高温高湿条件での実写においても、常温常
湿環境での結果とほぼ同等の結果を得た。As a result, the evaluation result under the normal temperature and normal humidity atmosphere was excellent, and the image quality such as hollow image, image density, and fog was excellent through the actual copying of 7,000 sheets. Also,
No cleaning failure on OPC or fusion phenomenon of developer particles was observed, and the durability was sufficient. Further, the fixing strength of the image after fixing is sufficiently high, and even if the solid image portion is bent with a constant pressure, almost no peeling of the toner image is observed. In actual shooting under high-temperature and high-humidity conditions, the results were almost the same as those in a normal-temperature and normal-humidity environment, except for a slight decrease in image density, which was not so problematic in actual use. Furthermore, in actual shooting under high-temperature and high-humidity conditions, results almost equivalent to those in a normal-temperature and normal-humidity environment were obtained.
【００６３】[0063]
【発明の効果】本発明の一成分現像剤及びそれを用いる
画像形成方法により、以下の効果が得られるので、その
工業的利用価値は高い。 （１）画像濃度が高くて、カブリが少ない良好な画質が
得られる。 （２）画像ムラが少なく、シャープネスがよく、画像中
抜けが少ない等の優れた画質が得られる。 （３）クリーニング不良やＯＰＣ感光体汚染に伴う画像
欠陥がない。 （４）定着での画像剥離や定着装置汚染がなく、低エネ
ルギー定着ができる。 （５）各種の温度及び湿度の組合せ環境条件下でも画質
変化が少ない。 （６）長期あるいは連続使用時においても画像濃度や画
質劣化が少なく耐久性、信頼性が高い。 （７）少ないトナー消費量で充分な画質が得られる。According to the one-component developer of the present invention and the image forming method using the same, the following effects can be obtained, and the industrial use value thereof is high. (1) A high image density and good image quality with less fog can be obtained. (2) Excellent image quality such as little image unevenness, good sharpness, and few image dropouts can be obtained. (3) There is no image defect due to poor cleaning or OPC photoreceptor contamination. (4) Low energy fixing can be performed without image peeling and contamination of the fixing device during fixing. (5) There is little change in image quality even under various environmental conditions of a combination of temperature and humidity. (6) Even in long-term or continuous use, there is little deterioration in image density and image quality, and durability and reliability are high. (7) Sufficient image quality can be obtained with a small amount of toner consumption.
【図１】本発明に使用できる画像形成方法の一例を示す
図。FIG. 1 is a diagram illustrating an example of an image forming method that can be used in the present invention.
【図２】本発明に使用できる画像形成方法の他の一例を
示す図。FIG. 2 is a diagram illustrating another example of an image forming method that can be used in the present invention.
１ 現像スリーブ ２ 現像剤層形成部材 ３ 感光体 ４ 接触部材 ５ 現像剤漏れ防止シール部材 ６ 一成分現像剤 ７ 感光体帯電部材 ８ 転写部材 ９ クリーニング部材 １０ 定着機 REFERENCE SIGNS LIST 1 developing sleeve 2 developer layer forming member 3 photoreceptor 4 contact member 5 developer leakage prevention seal member 6 one-component developer 7 photoreceptor charging member 8 transfer member 9 cleaning member 10 fixing device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｇ 9/08 ３７５ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location G03G 9/08 375
Claims (16)
んでなる体積５０％径Ｄｔ50が５〜１２μｍでかつガラ
ス転移温度が６０℃以下であるトナー粒子と、外添剤と
から構成され、外添剤は脂肪酸金属塩粒子と流動性向上
剤とからなるものであって、外添剤が添加される前のト
ナー粒子の窒素吸着法による比表面積をＡ（ｍ2 ／ｇ）
とし、外添剤が添加された後のトナー粒子の窒素吸着法
による比表面積をＢ（ｍ2 ／ｇ）としたとき、下記式
（１）を満足することを特徴とする一成分現像剤。 【数１】 式（１） １．５≦Ｂ／Ａ≦３1. A toner particle comprising at least a binder resin and a colorant, having a volume 50% diameter Dt 50 of 5 to 12 μm and a glass transition temperature of 60 ° C. or less, and an external additive. The additive is composed of fatty acid metal salt particles and a fluidity improver, and has a specific surface area of A (m 2 / g) of the toner particles before addition of the external additive, which is measured by a nitrogen adsorption method.
And a specific surface area of the toner particles after the addition of the external additive is determined to be B (m 2 / g) by a nitrogen adsorption method, the one-component developer satisfying the following formula (1). ## EQU1 ## Equation (1) 1.5 ≦ B / A ≦ 3
０〜５８℃であることを特徴とする請求項１に記載の一
成分現像剤。2. The glass transition temperature of the binder resin is 5
The one-component developer according to claim 1, which has a temperature of 0 to 58 ° C.
％径、５０％径及び８４％径をそれぞれＤｓ16、Ｄｓ50
及びＤｓ84とするとき、以下の式（２）及び（３）を満
足するものであることを特徴とする請求項１または２に
記載の一成分現像剤。 【数２】 式（２） Ｄｓ50／Ｄｔ50≦０．５ 式（３） Ｄｓ84／Ｄｓ16≦４3. The fatty acid metal salt particles have a volume of 16
% Diameter, 50% diameter and 84% diameter are Ds 16 and Ds 50 , respectively.
And Ds 84 , the one-component developer according to claim 1 or 2, which satisfies the following formulas (2) and (3). ## EQU00002 ## Formula (2) Ds 50 / Dt 50 ≤0.5 Formula (3) Ds 84 / Ds 16 ≤4
鉛粒子であることを特徴とする請求項１ないし３に記載
の一成分現像剤。4. The one-component developer according to claim 1, wherein the fatty acid metal salt particles are zinc stearate particles.
５〜５０ｎｍであることを特徴とする請求項１ないし４
に記載の一成分現像剤。5. The fluidity-improving agent has an average primary particle diameter of about 5 to 50 nm.
The one-component developer described in 1.
ザン及びシリコンオイルの中から選ばれる少なくとも１
種の物質で疎水化処理されたシリカ微粒子であることを
特徴とする請求項１ないし５に記載の一成分現像剤。6. The fluidity improver is at least one selected from hexamethyldisilazane and silicone oil.
The one-component developer according to any one of claims 1 to 5, which is a silica fine particle that has been subjected to a hydrophobic treatment with one of the above substances.
性の粒子であることを特徴とする請求項１ないし６に記
載の一成分現像剤。7. The one-component developer according to claim 1, wherein the toner particles are non-magnetic particles containing no magnetic material.
有する粒子であることを特徴とする請求項１ないし６に
記載の一成分現像剤。8. The one-component developer according to claim 1, wherein the toner particles are magnetic particles containing a magnetic material.
現像スリーブに押圧された層形成部材とを具備し、層形
成された現像剤を有機光導電体からなる感光体に現像
し、前記感光体から被転写材に転写を行った後、クリー
ニングブレードで感光体のクリーニングを行い、被転写
材上の現像剤を熱的に定着する工程を含む電子写真画像
形成方法において、前記現像剤が、少なくともバインダ
樹脂と着色剤とを含んでなる体積５０％径Ｄｔ50が５〜
１２μｍでかつガラス転移温度が６０℃以下であるトナ
ー粒子と、外添剤とから構成され、外添剤は脂肪酸金属
塩粒子と流動性向上剤とからなるものであって、外添剤
が添加される前のトナー粒子の窒素吸着法による比表面
積をＡ（ｍ2 ／ｇ）とし、外添剤が添加された後のトナ
ー粒子の窒素吸着法による比表面積をＢ（ｍ2 ／ｇ）と
したとき、下記式（１）を満足する一成分現像剤である
ことを特徴とする画像形成方法。 【数３】 式（１） １．５≦Ｂ／Ａ≦３9. A developing sleeve for holding a developer and a layer forming member pressed against the developing sleeve, wherein the layered developer is developed on a photosensitive member made of an organic photoconductor, After the transfer from the body to the transfer material, cleaning the photoreceptor with a cleaning blade, in an electrophotographic image forming method including the step of thermally fixing the developer on the transfer material, the developer, A volume 50% diameter Dt 50 containing at least a binder resin and a colorant is 5
The toner is composed of toner particles having a diameter of 12 μm and a glass transition temperature of 60 ° C. or lower, and an external additive. The external additive is composed of fatty acid metal salt particles and a fluidity improver. The specific surface area of the toner particles by the nitrogen adsorption method before being treated is A (m 2 / g), and the specific surface area of the toner particles by the nitrogen adsorption method after the external additive is added is B (m 2 / g). An image forming method characterized by being a one-component developer satisfying the following formula (1). ## EQU00003 ## Formula (1) 1.5 ≦ B / A ≦ 3
５０〜５８℃であることを特徴とする請求項９に記載の
画像形成方法。10. The image forming method according to claim 9, wherein the binder resin has a glass transition temperature of 50 to 58 ° C.
６％径、５０％径及び８４％径をそれぞれＤｓ16、Ｄｓ
50及びＤｓ84とするとき、以下の式（２）及び（３）を
満足するものであることを特徴とする請求項９または１
０に記載の画像形成方法。 【数４】 式（２） Ｄｓ50／Ｄｔ50≦０．５ 式（３） Ｄｓ84／Ｄｓ16≦４11. The fatty acid metal salt particles have a volume of 1
6% diameter, 50% diameter and 84% diameter are Ds 16 and Ds, respectively.
50 or Ds 84 , the following expressions (2) and (3) are satisfied:
The image forming method described in 0. Formula (2) Ds 50 / Dt 50 ≦ 0.5 Formula (3) Ds 84 / Ds 16 ≦ 4
亜鉛粒子であることを特徴とする請求項９ないし１１に
記載の画像形成方法。12. The image forming method according to claim 9, wherein the fatty acid metal salt particles are zinc stearate particles.
約５〜５０ｎｍであることを特徴とする請求項９ないし
１２に記載の画像形成方法。13. The image forming method according to claim 9, wherein the average primary particle diameter of the fluidity improver is about 5 to 50 nm.
ラザン及びシリコンオイルの中から選ばれる少なくとも
１種の物質で疎水化処理されたシリカ微粒子であること
を特徴とする請求項９ないし１３に記載の画像形成方
法。14. The silica fine particles which have been hydrophobized with at least one substance selected from hexamethyldisilazane and silicone oil, as the fluidity improver. Image forming method.
磁性の粒子であることを特徴とする請求項９ないし１４
に記載の画像形成方法。15. The toner particles according to claim 9, wherein the toner particles are non-magnetic particles containing no magnetic material.
2. The image forming method according to 1.,
を有する粒子であることを特徴とする請求項９ないし１
４に記載の画像形成方法。16. The toner particles according to claim 9, wherein the toner particles are magnetic particles containing a magnetic material.
4. The image forming method according to item 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5912796A JP3637136B2 (en) | 1996-03-15 | 1996-03-15 | One-component developer and image forming method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5912796A JP3637136B2 (en) | 1996-03-15 | 1996-03-15 | One-component developer and image forming method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09251214A true JPH09251214A (en) | 1997-09-22 |
| JP3637136B2 JP3637136B2 (en) | 2005-04-13 |
Family
ID=13104342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5912796A Expired - Fee Related JP3637136B2 (en) | 1996-03-15 | 1996-03-15 | One-component developer and image forming method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3637136B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000089502A (en) * | 1998-09-11 | 2000-03-31 | Konica Corp | Toner and its production |
| JP2006301008A (en) * | 2005-04-15 | 2006-11-02 | Ricoh Co Ltd | Toner for electrophotography, manufacturing method thereof, developing method using the toner, and image forming apparatus |
| JP2007079304A (en) * | 2005-09-15 | 2007-03-29 | Ricoh Co Ltd | Toner for electrophotography, developing method, developing device, image forming method and image forming device |
| JP2007156099A (en) * | 2005-12-05 | 2007-06-21 | Ricoh Co Ltd | Image forming toner, developer, toner containing container, process cartridge, image forming apparatus, and image forming method |
| JP2014191215A (en) * | 2013-03-27 | 2014-10-06 | Mitsubishi Chemicals Corp | Image forming apparatus |
| WO2014175533A1 (en) * | 2013-04-23 | 2014-10-30 | (주)심원테크 | Waste-toner separation device and waste-toner recycling method using same |
-
1996
- 1996-03-15 JP JP5912796A patent/JP3637136B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000089502A (en) * | 1998-09-11 | 2000-03-31 | Konica Corp | Toner and its production |
| JP2006301008A (en) * | 2005-04-15 | 2006-11-02 | Ricoh Co Ltd | Toner for electrophotography, manufacturing method thereof, developing method using the toner, and image forming apparatus |
| JP2007079304A (en) * | 2005-09-15 | 2007-03-29 | Ricoh Co Ltd | Toner for electrophotography, developing method, developing device, image forming method and image forming device |
| JP2007156099A (en) * | 2005-12-05 | 2007-06-21 | Ricoh Co Ltd | Image forming toner, developer, toner containing container, process cartridge, image forming apparatus, and image forming method |
| JP2014191215A (en) * | 2013-03-27 | 2014-10-06 | Mitsubishi Chemicals Corp | Image forming apparatus |
| WO2014175533A1 (en) * | 2013-04-23 | 2014-10-30 | (주)심원테크 | Waste-toner separation device and waste-toner recycling method using same |
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| Publication number | Publication date |
|---|---|
| JP3637136B2 (en) | 2005-04-13 |
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