JPH1124308A - Toner for electrophotography and its production - Google Patents
Toner for electrophotography and its productionInfo
- Publication number
- JPH1124308A JPH1124308A JP18010197A JP18010197A JPH1124308A JP H1124308 A JPH1124308 A JP H1124308A JP 18010197 A JP18010197 A JP 18010197A JP 18010197 A JP18010197 A JP 18010197A JP H1124308 A JPH1124308 A JP H1124308A
- Authority
- JP
- Japan
- Prior art keywords
- release agent
- toner
- organic solvent
- wax
- weight
- 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
Landscapes
- Dry Development In Electrophotography (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、電子写真法で用い
られる静電荷像現像用のトナー及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image used in electrophotography and a method for producing the same.
【0002】[0002]
【従来の技術】従来電子写真で用いられている静電荷像
現像用のトナーの製造方法としては、混練粉砕法が知ら
れており、このトナーの配合成分を混練後に粉砕して所
望の粒径のトナーを得る方法である混練粉砕法のが一般
的であった。この混練粉砕法によって得られたトナーに
は、定着ローラーへトナーが残留するという、所謂オフ
セットを防止するために、トナー中に低分子量ポリオレ
フィン等のワックスが離型剤として添加されている。こ
の低分子量ワックス等の離型剤は、オフセット防止には
有効であるが、感光体やキャリアへ付着するフィルミン
グが発生し、クリーニング性、経時安定性に問題があっ
た。このフィルミングを防止するために、例えば、特開
昭62−143061号公報及び特開平3−14864
9号公報にはワックス等の離型剤の粒子径を小さくする
方法が提案されている。また、カラー用トナーとして
も、ポリエステルにポリオレフィンワックスを混練で分
散させたり(特開平3ー107869号公報)、OHP
の透過性改善のために結晶化度を低くしたポリアルキレ
ンを含有した懸濁重合法で作製したトナー(特開平5ー
197191号公報)が知られている。一方、離型剤の
形状を棒状または針状で樹脂組成物に分散後、ワックス
ドメインをせん断させることで、ワックスの分散性をあ
げたり(特開平6−289645号公報)、フィルミン
グ防止のために粉砕時のワックス分離を防ぐことを狙っ
て、ワックス形状を紡錘形にしたり(特開平7−161
144号公報、特開平7−161145号公報)、小粒
径の球状ワックス粒子を分散させる(特開平8−328
293号公報)などが行われている。2. Description of the Related Art A kneading and pulverizing method has been known as a method for producing a toner for developing an electrostatic image conventionally used in electrophotography. The kneading and pulverizing method, which is a method for obtaining the toner of the formula (1), was generally used. To the toner obtained by the kneading and pulverizing method, a wax such as a low-molecular-weight polyolefin is added as a release agent in the toner in order to prevent so-called offset in which the toner remains on the fixing roller. This release agent such as a low molecular weight wax is effective in preventing offset, but causes filming to adhere to a photoreceptor or a carrier, and has problems in cleaning properties and stability over time. To prevent this filming, for example, JP-A-62-143061 and JP-A-3-14864.
No. 9 proposes a method for reducing the particle size of a release agent such as wax. Also, as a color toner, polyolefin wax is dispersed in polyester by kneading (Japanese Patent Laid-Open No. 3-107869), or OHP is used.
A toner prepared by a suspension polymerization method containing a polyalkylene having a reduced crystallinity in order to improve the transparency (Japanese Patent Laid-Open No. 197191/1993) is known. On the other hand, after dispersing the release agent in a rod-like or needle-like shape in the resin composition, the wax domain is sheared to increase the dispersibility of the wax (Japanese Patent Application Laid-Open No. 6-289645), and to prevent filming. In order to prevent wax separation at the time of pulverization, the shape of wax is changed to a spindle shape (Japanese Patent Laid-Open No. 7-161).
144, JP-A-7-161145), and disperse spherical wax particles having a small particle size (JP-A-8-328).
No. 293).
【0003】しかしながら、前記ワックスを配合し、混
練粉砕法で製造したトナーは、得られた粒子表面に多量
にワックスが偏在するため、(1)トナーの帯電性、流
動性、寿命等が悪化する、(2)軟化点の低いワックス
の分散性が悪い、(3)粉砕可能な樹脂に制限があり、
例えばカラートナー用のシャープメルトの低分子ポリエ
ステル等が使えない、等の問題があった。一方、混練粉
砕法以外での前記の問題を改善するトナー粒子作製方法
として、ポリエステル樹脂を有機溶媒中に溶解させた油
相成分を無機分散剤を含有する水媒体中で造粒する方法
が知られている(特開平7−152202号公報、特開
平7−168395号公報、特開平7−168396号
公報)。これらの製造方法によれば、ワックスは表面に
露出しにくくなるものの、造粒工程でトナーに分散され
たワックスの分散単位が大きくなり、粒子の光透過性が
下がり、カラートナーとして用いた場合、発色性が低
く、OHP透明性が悪い等の欠点があった。また、表面
に露出するワックスが少ない場合は、ワックスによるオ
フセット性防止の効果が弱く、たとえば、トナー粒子の
中心部に偏在するようなワックスは、耐オフセットへの
寄与が少なく、より多くのワックスを添加する必要があ
った。一方、ワックス等の離型剤の分散方法としては、
攪拌や超音波処理などがあるが、これらを用いると、微
粒子化が不十分で、充分な分散が得られない。また、加
圧ホモジナイザー等で強いせん断、衝撃、キヤビテーシ
ョン等を加えると粒子径を小さくすることは可能である
が、粒子を球状化することができず、さらに温度が上昇
して離型剤の再凝集が起こり、必ずしも充分な離型剤の
分散が得られず、特に、融点の低い離型剤に対しては、
いっそう再凝集が進み、離型剤の分散が悪くなる欠点が
あった。However, in a toner prepared by kneading and pulverizing with the above-mentioned wax, a large amount of the wax is unevenly distributed on the surface of the obtained particles, so that (1) the toner's chargeability, fluidity, life and the like are deteriorated. (2) poor dispersibility of a wax having a low softening point;
For example, there is a problem that a low-molecular polyester of sharp melt for a color toner cannot be used. On the other hand, as a method of preparing toner particles that solves the above-mentioned problems other than the kneading and pulverizing method, there is known a method of granulating an oil phase component in which a polyester resin is dissolved in an organic solvent in an aqueous medium containing an inorganic dispersant. (JP-A-7-152202, JP-A-7-168395, and JP-A-7-168396). According to these manufacturing methods, although the wax is less likely to be exposed on the surface, the dispersion unit of the wax dispersed in the toner in the granulation step is increased, the light transmittance of the particles is reduced, and when used as a color toner, There were drawbacks such as low color development and poor OHP transparency. In addition, when the amount of wax exposed on the surface is small, the effect of preventing the offset property by the wax is weak. For example, a wax which is unevenly distributed in the center of the toner particles has a small contribution to the offset resistance, and more wax is used. It had to be added. On the other hand, as a dispersion method of a release agent such as wax,
Although there are stirring, ultrasonic treatment, and the like, when these are used, the fine particles are insufficiently formed and sufficient dispersion cannot be obtained. In addition, it is possible to reduce the particle size by applying strong shear, impact, cavitation, etc. with a pressure homogenizer, etc., but it is not possible to make the particles spherical, and the temperature rises further and the release agent Re-agglomeration occurs, and sufficient dispersion of the release agent is not always obtained, especially for a release agent having a low melting point.
There was a disadvantage that reaggregation further progressed and dispersion of the release agent became worse.
【0004】[0004]
【発明が解決しようとする課題】本発明は、上記課題に
鑑みてなされたものであり、トナー中に離型剤の球状微
粒子が分散したトナーであって、耐オフセット性、帯電
性、流動性、安定性に優れかつ良好な発色性、OHP透
明性を有する電子写真用トナー及びその製造方法を提供
することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and is directed to a toner in which spherical fine particles of a release agent are dispersed in a toner. The toner has offset resistance, chargeability, and fluidity. An object of the present invention is to provide an electrophotographic toner having excellent color stability and excellent transparency and OHP transparency, and a method for producing the same.
【0005】[0005]
【課題を解決するための手段】本発明の電子写真用トナ
ーは、結着樹脂を溶解する有機溶媒中に、少なくとも結
着樹脂、着色剤、及び離型剤を溶解ないし分散させて油
相成分を調製する工程と、該油相成分を水性媒体中に分
散させて造粒する工程を含む製造方法によって製造され
る電子写真用トナーにおいて、該離型剤が予め有機溶媒
中に溶解後析出せしめられた後、或いは予め有機溶媒中
に懸濁せしめられた後、メディアにて粉砕及び/又は分
散せしめて得られる離型剤の分散液であることを特徴と
する電子写真用トナー。The electrophotographic toner of the present invention comprises an oil phase component obtained by dissolving or dispersing at least a binder resin, a colorant, and a release agent in an organic solvent that dissolves the binder resin. And an electrophotographic toner produced by a production method comprising a step of granulating the oil phase component by dispersing the oil phase component in an aqueous medium, wherein the release agent is previously dissolved in an organic solvent and then precipitated. A toner for electrophotography, which is a dispersion of a release agent obtained by being pulverized and / or dispersed in a medium after being subjected to or after being suspended in an organic solvent in advance.
【0006】本発明において、トナー中に、離型剤の球
状微粒子を分散させる一方法としては、結着樹脂を溶解
する有機溶媒中に、少なくとも結着樹脂、着色剤、及び
離型剤を溶解ないし分散させて油相成分を調製する工程
と、該油相成分を水性媒体中に分散させて造粒する工程
を含む電子写真用トナーの製造方法において、該結着樹
脂を溶解する有機溶媒中に分散させる離型剤として、予
め有機溶媒中に溶解した後析出させ、或いは予め有機溶
媒中に懸濁させた後、メディアにて粉砕及び/又は分散
せしめて得られる離型剤の分散液を用いる方法が挙げら
れる。本発明のトナーは好ましくは、下記式(1)によ
って示される形状係数の条件を満たすことが望ましい。In the present invention, one method of dispersing the spherical fine particles of the release agent in the toner is to dissolve at least the binder resin, the colorant, and the release agent in an organic solvent in which the binder resin is dissolved. Or dispersing the oil phase component to prepare an oil phase component, and dispersing the oil phase component in an aqueous medium to granulate the electrophotographic toner. As a release agent to be dispersed in, a dispersion of the release agent obtained by dissolving in an organic solvent in advance and then precipitating or suspending in an organic solvent in advance and then pulverizing and / or dispersing with a medium is used. The method used is mentioned. The toner of the present invention preferably satisfies the condition of the shape factor represented by the following formula (1).
【数4】f≦1.25 ・・・ (1) (式中、f=a/bであり、aは離型剤粒子の長軸の平
均長さ、bは離型剤粒子の短軸の平均長さを表す。) また本発明においては、トナー中に分散する離型剤の球
状微粒子が、平均粒径が0.01ないし1.5μmの範
囲にあり、かつ形状が前記形状係数(f)、f≦1.2
5、の条件を満たす離型剤球状微粒子であることが望ま
しい。このようなトナーを製造する方法の一つとして
は、結着樹脂を溶解する有機溶媒中に、少なくとも結着
樹脂、着色剤、及び離型剤を溶解ないし分散させて油相
成分を調製する工程と、該油相成分を水性媒体中に分散
させて造粒する工程を含む電子写真用トナーの製造方法
において、該結着樹脂を溶解する有機溶媒中に分散させ
る離型剤として、予め有機溶媒中に溶解した後析出し、
或いは予め有機溶媒中に懸濁させた後、メデイアにて粉
砕及び/又は分散せしめて得られる離型剤の分散液を用
い、かつメディアにて粉砕及び/又は分散させる際、少
なくとも該離型剤及び該有機溶媒を含む分散液の温度
を、40℃以下とすることを特徴とする製造方法が挙げ
られる。分散液温度が40℃を越えると、球状かつ微粒
子化した離型剤が再凝集し、所望の離型剤球状微粒子を
得ることができなくなる。F ≦ 1.25 (1) (where f = a / b, a is the average length of the major axis of the release agent particles, and b is the minor axis of the release agent particles) In the present invention, the spherical fine particles of the release agent dispersed in the toner have an average particle diameter in the range of 0.01 to 1.5 μm and a shape having the shape factor ( f), f ≦ 1.2
It is desirable that the release agent spherical fine particles satisfy the conditions of 5. One of the methods for producing such a toner includes a step of dissolving or dispersing at least a binder resin, a colorant, and a release agent in an organic solvent that dissolves the binder resin to prepare an oil phase component. And a method for producing an electrophotographic toner comprising a step of dispersing the oil phase component in an aqueous medium and granulating, wherein an organic solvent is used in advance as a release agent for dispersing in an organic solvent in which the binder resin is dissolved. After dissolving in the precipitate
Alternatively, when using a dispersion of a release agent obtained by previously suspending in an organic solvent and then pulverizing and / or dispersing with a medium, and pulverizing and / or dispersing with a medium, at least the release agent is used. And the temperature of the dispersion containing the organic solvent is set to 40 ° C. or lower. If the temperature of the dispersion liquid exceeds 40 ° C., the release agent that has become spherical and fine particles reaggregates, and it becomes impossible to obtain the desired release agent spherical fine particles.
【0007】[0007]
【発明の実施の形態】以下に本発明をさらに詳細に説明
する。本発明のトナーは、少なくとも結着樹脂、着色剤
及び離型剤を含む。本発明に用いられる結着樹脂として
は例えば、スチレン、パラクロロスチレン、α−メチル
スチレン等のスチレン類、アクリル酸メチル、アクリル
酸エチル、アクリル酸n−プロピル、アクリル酸ラウリ
ル、アクリル酸2−エチルヘキシル、メタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸n−プロピル、
メタクリル酸ラウリル、メタクリル酸2−エチルヘキシ
ル等のビニル基を有するエステル類、アクリロニトリ
ル、メタクリロニトリル等のビニルニトリル類、ビニル
メチルエーテル、ビニルイソブチルエーテル等のビニル
エーテル類、ビニルメチルケトン、ビニルエチルケト
ン、ビニルイソプロペニルケトン等のビニルケトン類、
エチレン、プロピレン、ブタジエンなどのポリオレフィ
ン類などの単量体などの重合体またはこれらを2種以上
組み合せて得られる共重合体またはこれらの混合物、エ
ポキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポ
リアミド樹脂、セルロース樹脂、ポリエーテル樹脂等の
非ビニル縮合系樹脂、あるいはこれらと前記ビニル系樹
脂との混合物やこれらの共存下でビニル系単量体を重合
する際に得られるグラフト重合体等を挙げることができ
る。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The toner of the present invention contains at least a binder resin, a colorant and a release agent. Examples of the binder resin used in the present invention include styrenes such as styrene, parachlorostyrene and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. , Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
Lauryl methacrylate, esters having a vinyl group such as 2-ethylhexyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, and vinyl Vinyl ketones such as isopropenyl ketone,
Polymers such as monomers such as polyolefins such as ethylene, propylene and butadiene, or copolymers obtained by combining two or more thereof, or mixtures thereof, epoxy resins, polyester resins, polyurethane resins, polyamide resins, and cellulose resins And non-vinyl condensed resins such as polyether resins, and mixtures of these with the vinyl resins, and graft polymers obtained when polymerizing vinyl monomers in the presence of these.
【0008】また、前記ポリエステル樹脂は、アルコー
ル成分とカルボン酸成分との縮重合によって得られ、各
成分として以下のものが挙げられる。アルコール成分と
してはエチレングリコール、ジエチレングリコール、ト
リエチレングリコール、ポリエチレングリコール、プロ
ピレングリコール、ブタンジオール、ペンタンジオー
ル、ヘキサンジオール、シクロヘキサンジメタノール、
キシリレングリコール、ジプロピレングリコール、ポリ
プロピレングリコール、ビスフェノールA、水添ビスフ
ェノールA、ビスフェノールAエチレンオキサイド、ビ
スフェノールAプロピレンオキサイド、ソルビトール、
グリセリンなどの2価以上のアルコールおよびアルコー
ル誘導体が挙げられる。カルボン酸成分としては、マレ
イン酸、フマール酸、フタル酸、イソフタル酸、テレフ
タル酸、コハク酸、アジピン酸、トリメリット酸、ピロ
メリット酸、シクロペンタンジカルボン酸、無水コハク
酸、無水トリメリット酸、無水マレイン酸、ドデセニル
無水コハク酸などの2価以上のカルボン酸、カルボン酸
誘導体及びそれらの無水物などが挙げられる。アルコー
ル成分およびカルボン酸成分はそれぞれ2種類以上、組
み合せてもかまわない。The polyester resin is obtained by polycondensation of an alcohol component and a carboxylic acid component, and each component includes the following. As the alcohol component, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol,
Xylylene glycol, dipropylene glycol, polypropylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide, bisphenol A propylene oxide, sorbitol,
Dihydric or higher alcohols such as glycerin and alcohol derivatives are exemplified. As the carboxylic acid component, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, trimellitic acid, pyromellitic acid, cyclopentanedicarboxylic acid, succinic anhydride, trimellitic anhydride, anhydride Examples thereof include divalent or higher carboxylic acids such as maleic acid and dodecenyl succinic anhydride, carboxylic acid derivatives, and anhydrides thereof. Two or more alcohol components and two or more carboxylic acid components may be used in combination.
【0009】これらの結着樹脂を溶解し油相成分を構成
させる溶媒としては、各樹脂を溶解する通常の有機溶媒
が用いられる。例えば、トルエン、キシレン、ヘキサン
等の炭化水素、塩化メチレン、クロロホルム、ジクロロ
エタン等のハロゲン化炭化水素、メタノール、エタノー
ル等のアルコール、テトラヒドロフラン等のエーテル
類、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル
類、アセトン、メチルエチルケトン、シクロヘキサノン
等のケトン類が挙げられ、これらを単独にあるいは複数
の混合溶媒として用いても構わない。これらの溶媒と樹
脂との配合割合は、樹脂/溶媒=5/95〜50/50
が望ましい。As a solvent for dissolving the binder resin and constituting the oil phase component, a usual organic solvent for dissolving each resin is used. For example, hydrocarbons such as toluene, xylene and hexane, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, esters such as methyl acetate, ethyl acetate and butyl acetate. , Acetone, methyl ethyl ketone, cyclohexanone and the like, and these may be used alone or as a mixture of a plurality of solvents. The mixing ratio of these solvents and resin is such that resin / solvent = 5/95 to 50/50.
Is desirable.
【0010】本発明における離型剤としては、パラフィ
ンワックス、酸化パラフィンワックス、マイクロクリス
タリンワックスなどの石油ワックス、モンタンワックス
などの鉱物ワックス、カルナバワックスなどの動植物ワ
ックス、ポリオレフィンワックス、酸化ポリオレフィン
ワックス、フィッシャートロプシュワックスなどの合成
ワックスあるいはエステルワックス、エーテルワックス
などが挙げられる。離型剤の融点は120℃以下で、か
つより低いことがトナーの耐オフセット性の点からみて
望ましい。また、ハンドリング性、製造の簡便性、保存
性の観点から、融点が40〜120℃であることが好ま
しく、さらには、50〜100℃が好ましい。ただし、
常温で液状のワックス、すなわち、融点が40℃未満の
離型剤にも適用することができる。The release agent in the present invention includes petroleum wax such as paraffin wax, paraffin wax, microcrystalline wax, mineral wax such as montan wax, animal and plant wax such as carnauba wax, polyolefin wax, oxidized polyolefin wax, Fischer-Tropsch Examples thereof include synthetic wax such as wax, ester wax, and ether wax. It is desirable that the melting point of the release agent be 120 ° C. or lower and lower from the viewpoint of the offset resistance of the toner. In addition, the melting point is preferably from 40 to 120 ° C, and more preferably from 50 to 100 ° C, from the viewpoint of handling properties, production simplicity, and storage stability. However,
It can also be applied to wax that is liquid at room temperature, that is, a release agent having a melting point of less than 40 ° C.
【0011】本発明におけるトナーは、その中に離型剤
の球状微粒子を分散させていることを特徴としており、
その製造方法の1つは、離型剤を有機溶媒中に樹脂、着
色剤とともに分散して油相成分を調整する前に、あらか
じめ溶媒中に小さい分散単位で、かつ球形に分散させて
おくことを特徴とする。予め離型剤を小さい分散単位
で、かつ球形に分散させておくことにより、得られるト
ナー粒子中に分散される離型剤の粒子を小さい分散単位
で、かつ球形にすることができ、トナーのオフセット性
と定着性の双方を満足させることができる。離型剤分散
液中の離型剤粒子は、その平均粒径が0.01〜1.5
μmの範囲であり、かつ、前記形状係数(f)、f≦
1.25の条件を満たす、球状微粒子であることが好ま
しい。特に平均粒径0.1〜0.5μmの範囲にするこ
とが望ましい。離型剤の平均粒径が0.01μm未満で
あると耐オフセット性の改善効果が低下し、1.5μm
を超えるとOHPにおける透過性が低下し、フィルミン
グが生じやすくなるため好ましくない。離型剤粒子の平
均粒径は、レーザー回折/散乱式粒度分布測定装置(た
とえば、堀場製作所製、LA−700やLA−910)
等を用いて測定することができる。The toner of the present invention is characterized in that spherical fine particles of a release agent are dispersed therein.
One of the production methods is to disperse the release agent in a small dispersion unit and in a spherical form in the solvent before dispersing the release agent together with the resin and the colorant in the organic solvent to adjust the oil phase component. It is characterized by. By previously dispersing the release agent in a small dispersion unit and in a spherical shape, the particles of the release agent dispersed in the obtained toner particles can be formed in a small dispersion unit and in a spherical shape. Both the offset property and the fixing property can be satisfied. The release agent particles in the release agent dispersion have an average particle size of 0.01 to 1.5.
μm, and the shape factor (f), f ≦
Spherical fine particles satisfying the condition of 1.25 are preferred. In particular, the average particle diameter is desirably in the range of 0.1 to 0.5 μm. When the average particle size of the release agent is less than 0.01 μm, the effect of improving the offset resistance is reduced, and
If it exceeds, the transmittance in OHP is reduced, and filming is liable to occur. The average particle size of the release agent particles is determined by a laser diffraction / scattering type particle size distribution analyzer (for example, LA-700 or LA-910 manufactured by HORIBA, Ltd.).
And the like.
【0012】離型剤の球状微粒子分散液を製造する方法
としては、離型剤を予め有機溶媒中に溶解し析出させた
後、または予め有機溶媒中に懸濁させた後、すなわち離
型剤の粗分散液を製造した後、メデイアにて離型剤を粉
砕及び/又は分散させる方法が挙げられる。分散離型剤
粒子の平均粒径をさらに小さくするためには、メデイア
にて離型剤を粉砕及び/又は分散させる際、少なくとも
離型剤及び有機溶媒を含む分散液の温度を40℃以下と
する方法が挙げられる。前記の離型剤分散液の製造方法
において用いられる有機溶媒は、前記結着樹脂を溶解し
うる有機溶媒と同種のものを単独で、あるいは、複数種
を混合して用いることができる。離型剤の球状微粒子形
成に用いるこの有機溶媒と前記油相成分を構成する有機
溶媒とは必ずしも同一である必要はない。しかし、同一
のものを用いると、溶媒同士の相溶性を考慮する必要が
ない、油相成分を構成する有機溶媒の配合量の制御が容
易である、離型剤の分散系が安定なまま油相成分を調整
しうる、などの利点を有する。As a method for producing a dispersion of spherical fine particles of a release agent, the release agent is dissolved and precipitated in an organic solvent in advance, or after the suspension is previously suspended in an organic solvent, And then pulverizing and / or dispersing the release agent with a medium. In order to further reduce the average particle size of the dispersed release agent particles, when pulverizing and / or dispersing the release agent in a medium, the temperature of the dispersion containing at least the release agent and the organic solvent should be 40 ° C. or less. Method. As the organic solvent used in the method for producing a release agent dispersion, the same kind of organic solvent that can dissolve the binder resin can be used alone, or a plurality of kinds can be used as a mixture. The organic solvent used for forming the spherical fine particles of the release agent and the organic solvent constituting the oil phase component need not always be the same. However, if the same one is used, there is no need to consider the compatibility between the solvents, it is easy to control the blending amount of the organic solvent constituting the oil phase component, and the dispersion of the release agent is stable in the oil. It has the advantage that the phase components can be adjusted.
【0013】離型剤の微分散に用いられる有機溶媒の量
は、離型剤1重量部に対して、有機溶媒1〜20重量部
程度であることが好ましい。有機溶媒の量が少ないと均
一な微分散が得られず、多すぎると離型剤の分散密度が
低下し、油相成分に配合した際に、溶媒量が過多となり
生産性が低下する。The amount of the organic solvent used for finely dispersing the release agent is preferably about 1 to 20 parts by weight of the organic solvent per 1 part by weight of the release agent. If the amount of the organic solvent is small, uniform fine dispersion cannot be obtained, and if the amount is too large, the dispersion density of the release agent is reduced, and when mixed with the oil phase component, the amount of the solvent is excessive and the productivity is reduced.
【0014】離型剤の粗分散液を得る方法としては、離
型剤を、有機溶媒中に溶解した後析出させる方法、或い
は離型剤を有機溶媒中に懸濁させる方法が挙げられる
が、前者の方法としては、有機溶媒に離型剤を添加・攪
拌又は添加・攪拌・加熱などして、離型剤を有機溶媒に
溶解し、その後冷却して離型剤を析出させる方法などが
採られ、また、後者の方法としては、粒子状の離型剤を
有機溶媒に懸濁させる方法などが採られる。さらに、冷
却析出させる際、超音波処理などを併用しても構わな
い。As a method for obtaining a coarse dispersion of the release agent, a method in which the release agent is dissolved in an organic solvent and then precipitated, or a method in which the release agent is suspended in the organic solvent, may be mentioned. As the former method, a method in which the release agent is dissolved in the organic solvent by adding / stirring or adding / stirring / heating the organic solvent, and then cooled to precipitate the release agent is adopted. As the latter method, a method in which a particulate release agent is suspended in an organic solvent is used. Further, when cooling and precipitating, ultrasonic treatment or the like may be used in combination.
【0015】こうして得られた離型剤の粗分散液をメデ
イアを用いて粉砕及び/又は分散させて、球状微粒子の
離型剤を形成する。メデイアを用いる具体的な方法とし
ては、ボールミル、サンドミル、アトライター、コボー
ルミル、DCPミル、ファインミルなどのいわゆる、媒
体ミルや媒体撹拌ミルが挙げられる。離型剤粒子をより
小さい粒子、すなわち平均粒径が0.01ないし1.5
μmの範囲とし、かつ球形の粒子を得るためには、メデ
イアにて離型剤を粉砕及び/又は分散させる際、粉砕及
び/又は分散領域での分散液温度を40℃以下とするこ
とが必要であるが、このためには、粉砕及び/又は分散
領域において、分散処理による発熱を効果的に冷却する
必要があり、分散液を効果的に冷却できる機構をもつ装
置例えば、サンドミル、アトライター、コボールミル、
DCPミル、ファインミルなどを用いて粉砕及び/又は
分散が行われる。また、さらに小さい粒径でかつより球
状の離型剤を形成するためには、前記粉砕及び/又は分
散領域での分散液温度を20℃以下、最適には10℃以
下に制御する必要がある。分散液を効率良く冷却できる
機構を有する装置としては、例えばコボールミル、DC
Pミル、ファインミル等が好ましく、さらに好ましく
は、ローター・ステーター部も冷却可能なDCPミル、
ファインミルなどが用いられる。The coarse dispersion of the release agent thus obtained is pulverized and / or dispersed using a medium to form a release agent of spherical fine particles. As a specific method using a medium, a so-called medium mill or medium stirring mill such as a ball mill, a sand mill, an attritor, a co-ball mill, a DCP mill, and a fine mill can be used. The release agent particles are reduced to smaller particles, that is, having an average particle size of 0.01 to 1.5.
In order to obtain spherical particles in the range of μm, when the release agent is pulverized and / or dispersed in a medium, the temperature of the dispersion in the pulverized and / or dispersed region must be 40 ° C. or less. However, for this purpose, it is necessary to effectively cool the heat generated by the dispersion treatment in the pulverization and / or dispersion region, and a device having a mechanism capable of effectively cooling the dispersion liquid, for example, a sand mill, an attritor, Koball mill,
Grinding and / or dispersion is performed using a DCP mill, a fine mill, or the like. In order to form a release agent having a smaller particle size and a more spherical shape, it is necessary to control the temperature of the dispersion in the pulverization and / or dispersion region to 20 ° C. or lower, optimally 10 ° C. or lower. . Apparatuses having a mechanism capable of efficiently cooling a dispersion include, for example, a co-ball mill, DC
P mills, fine mills and the like are preferable, and more preferably, a DCP mill capable of cooling the rotor / stator portion,
A fine mill or the like is used.
【0016】本発明において離型剤の球状微粒子の分散
液を作成する際に用いられるメディアの形状は、円柱
状、球状などを用いることができるが、粉砕および分散
の効率、分散装置への適応性を考慮し、球状が好まし
い。球状メディアのサイズは直径0.1〜5mmが好ま
しいが、離型剤の形状を効果的に球状かつ微粒子化する
には直径0.1〜2mmが好ましい。また、前記有機溶
媒中に溶解または懸濁させた後、メディアにて離型剤を
粉砕及び/又は分散させる際、粉砕及び/又は分散領域
での分散液温度は40℃以下が良く、好ましくは20℃
以下が、最適には10℃以下が望ましい。分散液温度が
40℃を越えると、球状かつ微粒子化した離型剤が再凝
集し所望の離型剤球状微粒子を得ることができなくな
る。In the present invention, the medium used for preparing the dispersion liquid of the spherical fine particles of the release agent may be cylindrical, spherical, etc., but the efficiency of pulverization and dispersion and the adaptability to a dispersion apparatus can be used. Considering the properties, a spherical shape is preferable. The size of the spherical media is preferably from 0.1 to 5 mm in diameter, but is preferably from 0.1 to 2 mm in order to effectively make the shape of the release agent spherical and fine. When the release agent is pulverized and / or dispersed in a medium after being dissolved or suspended in the organic solvent, the temperature of the dispersion in the pulverized and / or dispersed region is preferably 40 ° C. or less, and is preferably 20 ° C
The following is optimally, and preferably 10 ° C. or less. If the temperature of the dispersion exceeds 40 ° C., the release agent which has become spherical and fine particles is reaggregated, and it becomes impossible to obtain the desired release agent spherical fine particles.
【0017】本発明の着色剤としては、公知の有機又は
無機の顔料や染料、油溶性染料を使用することができ
る。例えばC.I.ピグメントレッド48:1、C.
I.ピグメントレッド57:1、C.I.ピグメントレ
ッド122、C.I.ピグメントイエロー17、C.
I.ピグメントイエロー97、C.I.ピグメントイエ
ロー12、C.I.ピグメントブルー15:1、C.
I.ピグメントブルー15:3、ランプブラック(C.
I.No.77266)、ローズベンガル(C.I.N
o.45432)、カーボンブラック、アセチレンブラ
ック、アニリンブラック、ニグロシン染料(C.I.N
o.50415B)、金属錯塩染料、金属錯塩染料の誘
導体、及びこれらの混合物等を挙げることができる。こ
れらの着色剤は樹脂100重量部に対して、1〜50重
量部程度の割合で加え、好ましくは2〜20重量部が適
切である。As the coloring agent of the present invention, known organic or inorganic pigments and dyes, and oil-soluble dyes can be used. For example, C.I. I. Pigment Red 48: 1, C.I.
I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Yellow 17, C.I.
I. Pigment Yellow 97, C.I. I. Pigment Yellow 12, C.I. I. Pigment Blue 15: 1, C.I.
I. Pigment Blue 15: 3, Lamp Black (C.I.
I. No. 77266), Rose Bengal (C.I.N.
o. 45432), carbon black, acetylene black, aniline black, nigrosine dye (CIN)
o. 50415B), metal complex dyes, derivatives of metal complex salt dyes, and mixtures thereof. These colorants are added at a ratio of about 1 to 50 parts by weight with respect to 100 parts by weight of the resin, and preferably 2 to 20 parts by weight.
【0018】本発明の製造方法における油相成分の調製
は、前記結着樹脂を溶解する有機溶媒中に結着樹脂、着
色剤、離型剤等を溶解ないし分散させることにより行わ
れるが、油相成分に配合しうるその他の添加剤として、
トナー流動性調整剤、帯電制御剤等を挙げることがで
き、これらは、本発明の効果を損なわない範囲で任意に
添加することができる。トナーの流動性などを制御する
添加剤としては、シリカ、酸化アルミニウム、マグネタ
イトや各種フェライト類、酸化第二銅、酸化ニッケル、
酸化亜鉛、酸化ジルコニウム、酸化チタン及び酸化マグ
ネシウム等の種々の金属酸化物およびこれらの適宜の混
合物等を挙げることができる。これらの添加量として
は、結着樹脂に対して5重量%以下であることが好まし
く、さらに、0.05〜3重量%であることがより好ま
しい。The oil phase component in the production method of the present invention is prepared by dissolving or dispersing a binder resin, a colorant, a release agent, and the like in an organic solvent in which the binder resin is dissolved. As other additives that can be blended with the phase component,
Examples thereof include a toner fluidity adjusting agent and a charge controlling agent, and these can be arbitrarily added as long as the effects of the present invention are not impaired. Additives that control the fluidity of the toner include silica, aluminum oxide, magnetite and various ferrites, cupric oxide, nickel oxide,
Examples include various metal oxides such as zinc oxide, zirconium oxide, titanium oxide, and magnesium oxide, and appropriate mixtures thereof. The amount of these additives is preferably 5% by weight or less based on the binder resin, and more preferably 0.05 to 3% by weight.
【0019】また、本発明において使用できる帯電制御
剤としては、従来現像剤に用いられたものが使用できる
が、ゼログラフィー用粉体トナーにおいて使用されてい
る、安息香酸の金属塩、サリチル酸の金属塩、アルキル
サリチル酸の金属塩、カテコールの金属塩、含金属ビス
アゾ染料、テトラフェニルボレート誘導体、第四級アン
モニウム塩、アルキルピリジニウム塩からなる群より選
ばれる化合物、さらにこれらの適宣組合せたもの等が好
ましく使用できる。トナー固形分に対するこれら帯電制
御剤の添加量は、一般に10重量%以下の範囲でさら
に、0.01〜5重量%が好ましい。As the charge control agent that can be used in the present invention, those conventionally used in developers can be used, but the metal salts of benzoic acid and metal of salicylic acid used in powder toners for xerography can be used. Salts, metal salts of alkylsalicylic acid, metal salts of catechol, metal-containing bisazo dyes, tetraphenylborate derivatives, quaternary ammonium salts, compounds selected from the group consisting of alkylpyridinium salts, and the like, in addition to those suitably combined. It can be used preferably. The amount of the charge control agent to be added to the toner solid content is generally 10% by weight or less, and more preferably 0.01 to 5% by weight.
【0020】前記の如く、有機溶媒中に結着樹脂、着色
剤、離型剤等を含むトナー組成物を溶解ないし分散させ
て得られる油相成分は、その後、水性媒体中に混合攪拌
されて造粒され、トナー粒子が形成される。ここで用い
られる水性媒体は、主として水が用いられるが、水溶性
溶媒を混合して用いることができる。前記油相成分に対
する水性媒体の使用量は、油相/水性媒体=60/40
〜10/90の範囲であることが好ましく、さらに分散
性の観点からは50/50〜25/75の範囲であるこ
とが望ましい。油相成分を水性媒体中に分散させると
き、分散剤を添加しても構わない。分散剤を加えると、
得られるトナー粒子の粒径分布を狭くする効果がある。
分散剤としては、リン酸三カルシウム、ヒドロキシアパ
タイト、炭酸カルシウム、酸化チタン、水酸化アルミニ
ウム、水酸化マグネシウム、硫酸バリウム、シリカ、セ
ルロース、デンプン、ポリビニルアルコール、ポリアク
リル酸などが挙げられる。分散剤の量は、水性媒体10
0重量部に対して、20重量部以下が好ましい。造粒の
方法としては、油相成分を水性媒体中に混合撹拌する際
に、剪断を加えることが好ましく、ローターステーター
型の分散機、例えばコロイドミル等あるいはホモジナイ
ザー、クッキングミキサーなどの公知の攪拌機、混合
機、分散機を用いることができる。造粒は、0〜70℃
の温度範囲で剪断力をかけながら、1分から1時間に亘
って行うことが好ましい。As described above, the oil phase component obtained by dissolving or dispersing the toner composition containing a binder resin, a colorant, a release agent and the like in an organic solvent is then mixed and stirred in an aqueous medium. Granulated to form toner particles. As the aqueous medium used here, water is mainly used, but a water-soluble solvent may be mixed and used. The use amount of the aqueous medium with respect to the oil phase component is as follows: oil phase / aqueous medium = 60/40
The range is preferably from 10 to 90/90, and more preferably from 50/50 to 25/75 from the viewpoint of dispersibility. When dispersing the oil phase component in the aqueous medium, a dispersant may be added. When you add a dispersant,
This has the effect of narrowing the particle size distribution of the resulting toner particles.
Examples of the dispersant include tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, silica, cellulose, starch, polyvinyl alcohol, and polyacrylic acid. The amount of the dispersant depends on the aqueous medium 10
It is preferably 20 parts by weight or less based on 0 parts by weight. As a method of granulation, it is preferable to apply shearing when mixing and stirring the oil phase component in an aqueous medium, and a rotor-stator type disperser, for example, a colloid mill or a homogenizer, a known stirrer such as a cooking mixer, Mixers and dispersers can be used. Granulation is 0-70 ° C
It is preferable to perform the reaction for 1 minute to 1 hour while applying a shearing force in the temperature range described above.
【0021】造粒後に溶媒を除去し、さらに残留する分
散剤等を除去することにより、粒子内に離型剤の球状微
粒子が微分散された均一な粒径を有するトナー粒子を得
ることができる。得られたトナー粒子の離型剤平均分散
単位および離型剤の形状は、好ましくは前記のごとく粒
径が0.01ないし1.5μmの範囲内にあり、かつ、
形状が前記形状係数(f)、f≦1.25、の球状微粒
子であるが、この離型剤の分散状態は、トナー粒子の断
面を電子顕微鏡(TEM)写真にとり、離型剤の分散単
位断面の直径を計測することにより求めることができ
る。By removing the solvent after the granulation and further removing the remaining dispersant and the like, it is possible to obtain toner particles having a uniform particle diameter in which spherical fine particles of a release agent are finely dispersed in the particles. . The average dispersion unit of the release agent and the shape of the release agent of the obtained toner particles preferably have a particle diameter in the range of 0.01 to 1.5 μm as described above, and
The shape of the particles is spherical particles having the shape factor (f), f ≦ 1.25, and the dispersion state of the release agent is determined by taking a cross section of the toner particles in an electron microscope (TEM) photograph and examining the dispersion unit of the release agent. It can be obtained by measuring the diameter of the cross section.
【0022】本発明の製造方法により得られた電子写真
用トナーは水性媒体中で造粒されるため、形状の制御が
容易で球形の均一なトナー粒子も容易に得られる。ま
た、粒子中に離型剤が微分散されて内在していることか
ら、トナーの紙等の支持体に対する転写性および定着性
が良好で、定着ロールのオイルなしでもオフセットも見
られず、光透過性の高い優れた特性を有している。Since the toner for electrophotography obtained by the production method of the present invention is granulated in an aqueous medium, the shape can be easily controlled and uniform spherical toner particles can be easily obtained. In addition, since the release agent is finely dispersed and contained in the particles, the transferability and the fixability of the toner to a support such as paper are good, and no offset is observed without the oil of the fixing roll. It has excellent properties of high permeability.
【0023】本発明の電子写真用トナー粒子は、油相成
分を水性媒体中で造粒するため、離型剤と油相成分及び
離型剤と水性媒体との親和性の差異によって、離型剤が
表面に露出しにくく、さらに、トナー中に分散している
離型剤粒子を球状、好ましくは前記形状係数(f)、f
≦1.25、の球状微粒子にすることにより、トナー粒
子表面へ離型剤の露出がほとんどなくなり、トナー流動
性が向上し、かつ帯電性が良好となる。したがって、低
融点の離型剤を用いても、表面への露出が少なく、流動
性、保存性に問題がない。また、トナー中に離型剤を含
有することによってオイルなし定着が可能で、トナーの
発色性およびOHPの透過性に優れ、かつトナーの流動
性、保存性がよく、帯電性が良好となる。また、本発明
の電子写真用トナーにおいて、有機溶媒中に分散すべき
離型剤を、予め有機溶媒中に溶解し析出させた後、また
は予め有機溶媒中に懸濁させた後、メデイアにて離型剤
を粉砕及び/又は分散せしめて得られる離型剤の分散液
を用い、かつメディアにて粉砕及び/又は分散させる
際、少なくとも該離型剤及び該有機溶媒を含む分散液の
温度を40℃以下に維持する工程を含む製造方法によっ
て得られる電子写真用トナーは、トナー中離型剤が、分
散単位が平均0.01ないし1.5μmの範囲内であ
り、かつ形状が前記形状係数(f)、f≦1.25、を
満たす球状微粒子として分散している。その結果、この
トナーは、上で説明したトナーの有する特性に加え、離
型剤による光散乱を防ぐことができ、発色性及びOHP
の透明性が優れるという効果を有する。また、このトナ
ーは、離型剤の融解が速やかに起こることで、効率よく
離型剤性能を発現することができる。Since the toner particles for electrophotography of the present invention granulate the oil phase component in an aqueous medium, the difference in affinity between the release agent and the oil phase component and the affinity between the release agent and the aqueous medium causes the release. The releasing agent particles are hardly exposed on the surface, and the releasing agent particles dispersed in the toner are spherical, preferably the shape factors (f), f
By making the spherical fine particles of ≦ 1.25, the release agent is hardly exposed on the toner particle surface, the toner fluidity is improved, and the chargeability is improved. Therefore, even if a release agent having a low melting point is used, exposure to the surface is small, and there is no problem in fluidity and storage stability. Further, by containing a release agent in the toner, fixing without oil is possible, the toner has excellent coloring properties and OHP transparency, and has good fluidity and preservability of the toner, and good chargeability. Further, in the electrophotographic toner of the present invention, the release agent to be dispersed in the organic solvent, after previously dissolved and precipitated in the organic solvent, or after previously suspended in the organic solvent, in the medium When using a dispersion of the release agent obtained by pulverizing and / or dispersing the release agent and pulverizing and / or dispersing with a medium, the temperature of the dispersion containing at least the release agent and the organic solvent is adjusted. The toner for electrophotography obtained by the production method including the step of maintaining the temperature at 40 ° C. or lower is such that the release agent in the toner has a dispersion unit within the range of 0.01 to 1.5 μm on average, and the shape has the shape factor. (F), dispersed as spherical fine particles satisfying f ≦ 1.25. As a result, in addition to the properties of the toner described above, this toner can prevent light scattering by the release agent,
Has an effect of being excellent in transparency. In addition, the toner can efficiently exhibit the performance of the release agent because the release agent quickly melts.
【0024】本発明におけるトナー粒子の直径は特に限
定されるものではないが、得ようとするトナー粒子径を
より小さくする場合には、その中に分散する離型剤粒子
から粒径が1.5μmを超える大きな分散単位の離型剤
粒子をなくすことが望ましい。このようにすることによ
り、離型剤の粒子を球状化した効果が大きくなり、画質
の向上をねらいとした小粒径トナー、例えば6μm以下
の小粒径トナー粒子の場合においても優れた特性を得る
ことができる。The diameter of the toner particles in the present invention is not particularly limited, but when the diameter of the toner particles to be obtained is made smaller, the diameter of the release agent particles dispersed in the toner particles becomes 1. It is desirable to eliminate release agent particles of large dispersion units exceeding 5 μm. By doing so, the effect of spheroidizing the particles of the release agent is increased, and excellent characteristics are obtained even in the case of a small particle size toner which aims to improve image quality, for example, a small particle size toner particle of 6 μm or less. Obtainable.
【0025】さらに、本発明の電子写真用トナーは、像
担持体上に潜像を形成する工程と、該潜像を現像剤を用
いて現像する工程とを含む画像形成方法に用いられる現
像剤として適用することができる。Further, the toner for electrophotography of the present invention is a developer used in an image forming method including a step of forming a latent image on an image carrier and a step of developing the latent image using a developer. Can be applied as
【0026】[0026]
(実施例1)パラフィンワックス(商品名:HNP(高
純度精製パラフィンワックス)日本精蝋製、融点89
℃)30重量部を酢酸エチル250重量部に加え、73
℃で加熱溶解し、冷却析出させて得られた25℃のワッ
クス粗分散液を、直径0.5mmのジルコニア・メデイ
アと共に、DCPミルSF−12(日本アイリッヒ製)
に充填し、単位積算動力が0.50kWh/kgまで粉
砕及び/又は分散させてワックスの酢酸エチル分散液を
得た。このときの粉砕及び/又は分散領域でのワックス
分散液の温度は15℃であった。ワックスの平均粒子径
は、レーザー回折/散乱式粒度分布測定装置LA−91
0(堀場製作所製)で測定したところ0.90μmであ
った(LA−910測定の粒子径はいずれも体積基準で
50%頻度粒子径ーメジアン径ーを示す)。ワックス分
散液中のワックス形状を走査型電子顕微鏡(SEM)で
観察したところ、ワックスの長軸の平均長さ(a)が
0.95μm、ワックスの短軸の平均長さ(b)が0.
80μmであり、形状係数(f=a/b)は1.19で
あった。測定はSEM写真からワックス粒子の20個の
平均により求めた。(Example 1) Paraffin wax (trade name: HNP (high-purity purified paraffin wax) manufactured by Nippon Seisaku, melting point 89)
℃) 30 parts by weight to 250 parts by weight of ethyl acetate, 73
A wax dispersion at 25 ° C. obtained by heating and dissolving at 25 ° C. and precipitating by cooling is used together with zirconia media having a diameter of 0.5 mm in a DCP mill SF-12 (manufactured by Eirich Japan).
, And pulverized and / or dispersed to a unit integrated power of 0.50 kWh / kg to obtain a wax ethyl acetate dispersion. At this time, the temperature of the wax dispersion in the pulverization and / or dispersion region was 15 ° C. The average particle diameter of the wax is measured by a laser diffraction / scattering particle size distribution analyzer LA-91.
It was 0.90 μm when measured at 0 (manufactured by Horiba Seisakusho) (the particle size measured by LA-910 indicates 50% frequency particle size−median size−by volume). When the shape of the wax in the wax dispersion was observed with a scanning electron microscope (SEM), the average length (a) of the major axis of the wax was 0.95 μm, and the average length (b) of the minor axis of the wax was 0.
80 μm, and the shape factor (f = a / b) was 1.19. The measurement was obtained from an SEM photograph by averaging 20 wax particles.
【0027】ビスフェノールAプロピレンオキサイド付
加物、ビスフェノールAエチレンオキサイド付加物、コ
ハク酸誘導体からなるポリエステル樹脂(重量平均分子
量:15000、Tg64℃、Tm102℃)100重
量部、C.I.ピグメントブルー15:3を4重量部、
酢酸エチル80重量部をボールミルで10時間分散後、
ワックスの酢酸エチル分散液36重量部を加え、均一に
なるまでよく撹拌して油相成分を調製した。炭酸カルシ
ウム60重量部、水40重量部をボールミルで10時間
分散して炭酸カルシウム分散液を得た。この炭酸カルシ
ウム分散液7重量部とセロゲンBS−H(第一工業製薬
製)の2重量%水溶液100重量部をクッキングミキサ
ーMX−915C(松下電器製)に入れて、5分間混合
して水相液を作製する。この水相液に油相液100重量
部を加えて、クッキングミキサーで6分間混合後、40
℃湯浴中で加熱して有機溶媒を除去する。6N塩酸を1
00重量部加えて炭酸カルシウムを除去した後、水洗・
乾燥・分級して平均粒子径7.1μmの固形トナーを得
た。SEM写真をみると形状がほぼ球形をしている。ト
ナー中のワックス形状を確認するために、トナー粒子の
断面を電子顕微鏡(TEM)写真にとり、ワックスの分
散単位断面の直径を計測することにより、ワックスの長
軸の平均長さ(a)が1.20μm、ワックスの短軸の
平均長さ(b)が0.98μmであり、形状係数(f=
a/b)は1.22であった。トナー断面の透過型電子
顕微鏡(TEM)写真では、ワックスはトナー内部に分
散し、トナー粒子表面には見えなかった。100 parts by weight of a polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, and a succinic acid derivative (weight average molecular weight: 15,000, Tg 64 ° C., Tm 102 ° C.); I. 4 parts by weight of CI Pigment Blue 15: 3,
After dispersing 80 parts by weight of ethyl acetate in a ball mill for 10 hours,
36 parts by weight of an ethyl acetate dispersion of wax was added, and the mixture was stirred well until the mixture became uniform to prepare an oil phase component. 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours to obtain a calcium carbonate dispersion. 7 parts by weight of this calcium carbonate dispersion and 100 parts by weight of a 2% by weight aqueous solution of cellogen BS-H (manufactured by Daiichi Kogyo Seiyaku) are placed in a cooking mixer MX-915C (manufactured by Matsushita Electric), mixed for 5 minutes, and mixed with an aqueous phase. Make a liquid. 100 parts by weight of the oil phase liquid was added to this aqueous phase liquid, and mixed with a cooking mixer for 6 minutes.
Heat in a hot water bath to remove the organic solvent. 1N 6N hydrochloric acid
After removing calcium carbonate by adding 00 parts by weight,
After drying and classification, a solid toner having an average particle diameter of 7.1 μm was obtained. Looking at the SEM photograph, the shape is almost spherical. In order to confirm the shape of the wax in the toner, the cross section of the toner particles is taken with an electron microscope (TEM) photograph, and the average length (a) of the major axis of the wax is set to 1 by measuring the diameter of the dispersion unit cross section of the wax. .20 μm, the average length (b) of the minor axis of the wax was 0.98 μm, and the shape factor (f =
a / b) was 1.22. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was dispersed inside the toner and was not visible on the surface of the toner particles.
【0028】トナー100重量部にシリカR972(日
本エアロジル製)1重量部をサンプルミルで1分間混合
した。こうして得たシリカ外添トナーをA−color
935(富士ゼロックス製)を用い、定着ヒューザーオ
イルなしで画像形成の評価を行ない、その結果を表1に
示した。評価方法は以下の通りである。画質は初期およ
び1000枚コピー後の色調、画像濃度、かぶりの有
無、紙およびOHPとの定着性を目視で見た。オフセッ
トは初期および1000枚コピー後の定着ロールへのト
ナーの付着の有無を目視で確認した。OHPの光透過性
はOHPに、べたの画像を定着後、着色剤の吸収のない
波長の光透過率を測定した。トナー中のワックス径はト
ナー断面のTEM写真からランダムに選んだ10個の水
平方向径の平均値から求めた。保存性はトナーを50℃
において3時間放置後の凝集の有無を調べた。転写性は
紙への転写直後の感光体表面のトナーの有無を目視で確
認した。1 part by weight of silica R972 (manufactured by Nippon Aerosil) was mixed with 100 parts by weight of the toner for 1 minute using a sample mill. The thus-obtained silica externally added toner was subjected to A-color.
Using 935 (manufactured by Fuji Xerox), image formation was evaluated without fixing fuser oil, and the results are shown in Table 1. The evaluation method is as follows. As for the image quality, the color tone, the image density, the presence or absence of fog, and the fixability to paper and OHP were visually observed at the initial stage and after 1000 copies. For the offset, the presence or absence of toner attached to the fixing roll at the initial stage and after copying 1000 sheets was visually checked. The light transmittance of the OHP was measured by fixing a solid image to the OHP and then measuring the light transmittance at a wavelength at which the colorant was not absorbed. The wax diameter in the toner was determined from the average value of ten horizontal diameters randomly selected from a TEM photograph of the cross section of the toner. Storage stability is 50 ℃
Was examined for the presence or absence of aggregation after standing for 3 hours. The transferability was visually confirmed immediately after the transfer to paper by the presence or absence of toner on the surface of the photoreceptor.
【0029】(実施例2)DCPミルSF−12(日本
アイリッヒ製)で処理中のワックス分散液の温度が5.
0℃であること以外は、実施例1と同様にしてワックス
の酢酸エチル分散液を得た。ワックスの平均粒子径は、
レーザー回折/散乱粒度分布測定装置LA−910(堀
場製作所製)で測定したところ0.50μmであった。
ワックス分散液中のワックス形状を実施例1と同様に走
査型電子顕微鏡(SEM)で観察したところ、ワックス
の長軸の平均長さ(a)が0.55μm、ワックスの短
軸の平均長さ(b)が0.48μmであり、形状係数
(f=a/b)は1.15であった。ビスフェノールA
プロピレンオキサイド付加物、ビスフェノールAエチレ
ンオキサイド付加物、コハク酸誘導体からなるポリエス
テル樹脂(重量平均分子量:15000、Tg64℃、
Tm102℃)100重量部、C.I.ピグメントレッ
ド57を3重量部、酢酸エチル100重量部をサンドミ
ルで5時間分散後、ワックスの酢酸エチル分散液36重
量部を加え、均一になるまでよく撹拌して油相液を作製
した。炭酸カルシウム60重量部、水40重量部をボー
ルミルで10時間分散して炭酸カルシウム分散液を得
た。この炭酸カルシウム分散液6重量部とセロゲンBS
−H(第一工業製薬製)の2重量%水溶液100重量部
をクッキングミキサーMX−915C(松下電器製)に
入れて、5分間混合して水相液を作製した。この水相液
に油相液50重量部を加えて、クッキングミキサーで6
分間混合後、40℃湯浴中で加熱して有機溶媒を除去し
た。6N塩酸を100重量部加えて炭酸カルシウムを除
去した後、水洗・乾燥・分級して平均粒子径6.1μm
の固形トナーを得た。SEM写真を見ると形状がほぼ球
形をしていた。トナー中のワックス形状を確認するため
に、実施例1と同様にしてTEM写真で観察したとこ
ろ、ワックスの長軸の平均長さ(a)が0.68μm、
ワックスの短軸の平均長さ(b)が0.57μmであ
り、形状係数(f=a/b)は1.19であった。トナ
ー断面の透過型電子顕微鏡(TEM)写真では、ワック
スはトナー内部に分散し、トナー粒子表面には見えなか
った。トナー100重量部にシリカR972(日本エア
ロジル製)1重量部をサンプルミルで1分間混合して得
たシリカ外添トナーをA−color935(富士ゼロ
ックス製)を用い、定着ヒューザーオイルなしで画像評
価を行った結果を表1に示した。(Example 2) The temperature of the wax dispersion liquid being treated with DCP mill SF-12 (manufactured by Eirich Japan) was 5.
A wax dispersion in ethyl acetate was obtained in the same manner as in Example 1 except that the temperature was 0 ° C. The average particle size of the wax is
It was 0.50 μm when measured with a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.).
When the shape of the wax in the wax dispersion was observed with a scanning electron microscope (SEM) in the same manner as in Example 1, the average length (a) of the major axis of the wax was 0.55 μm, and the average length of the minor axis of the wax was (B) was 0.48 μm, and the shape factor (f = a / b) was 1.15. Bisphenol A
Polyester resin comprising propylene oxide adduct, bisphenol A ethylene oxide adduct, and succinic acid derivative (weight average molecular weight: 15,000, Tg 64 ° C,
Tm 102 ° C) 100 parts by weight, C.I. I. After 3 parts by weight of CI Pigment Red 57 and 100 parts by weight of ethyl acetate were dispersed in a sand mill for 5 hours, 36 parts by weight of a wax ethyl acetate dispersion was added, and the mixture was thoroughly stirred until the mixture became uniform to prepare an oil phase liquid. 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours to obtain a calcium carbonate dispersion. 6 parts by weight of this calcium carbonate dispersion and cellogen BS
100 parts by weight of a 2% by weight aqueous solution of -H (manufactured by Daiichi Kogyo Seiyaku) was put into a cooking mixer MX-915C (manufactured by Matsushita Electric) and mixed for 5 minutes to prepare an aqueous phase liquid. Add 50 parts by weight of the oil phase liquid to the aqueous phase liquid, and add
After mixing for minutes, the mixture was heated in a water bath at 40 ° C. to remove the organic solvent. After 100 parts by weight of 6N hydrochloric acid was added to remove calcium carbonate, the particles were washed with water, dried and classified to have an average particle diameter of 6.1 μm.
Was obtained. The SEM photograph showed that the shape was almost spherical. In order to confirm the shape of the wax in the toner, it was observed with a TEM photograph in the same manner as in Example 1. As a result, the average length (a) of the major axis of the wax was 0.68 μm,
The average length (b) of the minor axis of the wax was 0.57 μm, and the shape factor (f = a / b) was 1.19. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was dispersed inside the toner and was not visible on the surface of the toner particles. 100 parts by weight of toner was mixed with 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) for 1 minute using a sample mill. The results obtained are shown in Table 1.
【0030】(実施例3)マイクロクリスタリンワック
ス(商品名:Hi−Mis−3080、日本精蝋製、融
点84℃)30重量部に酢酸エチル250重量部を加
え、73℃で加熱溶解した後、65℃に保持しワックス
を冷却析出させ、ワックス粗分散液を得た。このワック
ス粗分散液を直径0.5mmのジルコニア・メデイアと
共に、DCPミルSF−12(日本アイリッヒ製)に充
填し粉砕及び/又は分散させながら、単位積算動力が
0.20kWh/kgになるまで分散液温度を5℃まで
冷却し、その後分散液温度5℃で単位積算動力が0.6
5 kWh/kgになるまで粉砕及び/又は分散させて
ワックスの酢酸エチル分散液を得た。ワックスの平均粒
子径はレーザー回折/散乱粒度分布測定装置LA−91
0(堀場製作所製)で測定したところ、0.58μmで
あった。ワックス分散液中のワックス形状を実施例1と
同様に走査型電子顕微鏡(SEM)で観察したところ、
ワックスの長軸の平均長さ(a)が0.64μm、ワッ
クスの短軸の平均長さ(b)が0.55μmであり、形
状係数(f=a/b)は1.16であった。(Example 3) 250 parts by weight of ethyl acetate was added to 30 parts by weight of microcrystalline wax (trade name: Hi-Mis-3080, manufactured by Nippon Seisaku, melting point: 84 ° C), and the mixture was heated and dissolved at 73 ° C. While maintaining the temperature at 65 ° C., the wax was precipitated by cooling to obtain a crude wax dispersion. This crude wax dispersion is mixed with zirconia media having a diameter of 0.5 mm in a DCP mill SF-12 (manufactured by Nippon Eirich Co.) and dispersed until the unit integrated power becomes 0.20 kWh / kg while pulverizing and / or dispersing. The liquid temperature is cooled to 5 ° C., and then the unit integrated power is 0.6 at the dispersion temperature of 5 ° C.
The wax was ground and / or dispersed until it became 5 kWh / kg to obtain a wax ethyl acetate dispersion. The average particle diameter of the wax is measured by a laser diffraction / scattering particle size distribution analyzer LA-91.
When measured at 0 (manufactured by Horiba, Ltd.), it was 0.58 μm. When the shape of the wax in the wax dispersion was observed with a scanning electron microscope (SEM) in the same manner as in Example 1,
The average length (a) of the major axis of the wax was 0.64 μm, the average length (b) of the minor axis of the wax was 0.55 μm, and the shape factor (f = a / b) was 1.16. .
【0031】スチレン−ブチルアクリレート80対20
の共重合樹脂(重量平均分子量:40000、数平均分
子量:15000)100重量部、C.I.ピグメント
イエロー17を6重量部、トルエン1000重量部をサ
ンドミルで5時間分散後、ワックスの酢酸エチル分散液
72重量部を加え、均一になるまでよく撹拌して油相液
を作製した。炭酸カルシウム60重量部、水40重量部
をボールミルで10時間分散して炭酸カルシウム分散液
を得た。この炭酸カルシウム分散液6重量部とセロゲン
BS−H(第一工業製薬株)の2重量%水溶液100重
量部を卓上コロイドミル(日本精機製作所製)で、50
00rpm、5分間混合して水相液を作製した。この水
相液に油相液50重量部を加え、8000rpmで20
分間混合後、25℃水浴中で減圧下、有機溶媒を除去す
る。6N塩酸を100重量部加えて、炭酸カルシウムを
除去した後、水洗・乾燥・分級して平均粒子径7.4μ
mの固形トナーを得た。SEM写真をみると形状がほぼ
球形をしていた。トナー中のワックス形状を確認するた
めに、実施例1と同様にしてTEM写真で観察したとこ
ろ、ワックスの長軸の平均長さ(a)が0.70μm、
ワックスの短軸の平均長さ(b)が0.58μmであ
り、形状係数(f=a/b)は1.21であった。トナ
ー断面の透過型電子顕微鏡(TEM)写真では、ワック
スはトナー内部に分散し、トナー粒子表面には見えなか
った。 トナー100重量部にシリカR972(日本エ
アロジル製)1重量部をサンプルミルで1分間混合して
得たシリカ外添トナーをA−color935(富士ゼ
ロックス製)を用い、定着ヒューザーオイルなしで画像
評価を行った結果を表1に示した。Styrene-butyl acrylate 80:20
100 parts by weight of a copolymer resin (weight average molecular weight: 40000, number average molecular weight: 15000), C.I. I. 6 parts by weight of Pigment Yellow 17, after 5 hours dispersed 1000 parts by weight of toluene in a sand mill, adding ethyl acetate dispersion 72 parts by weight of the word box, to prepare an oil phase liquid stirred well until uniform. 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours to obtain a calcium carbonate dispersion. 6 parts by weight of this calcium carbonate dispersion and 100 parts by weight of a 2% by weight aqueous solution of cellogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.) were subjected to a tabletop colloid mill (manufactured by Nippon Seiki Seisakusho) to obtain 50 parts by weight.
An aqueous phase solution was prepared by mixing at 00 rpm for 5 minutes. 50 parts by weight of the oil phase liquid is added to this aqueous phase liquid,
After mixing for minutes, the organic solvent is removed under reduced pressure in a water bath at 25 ° C. After 100 parts by weight of 6N hydrochloric acid was added to remove calcium carbonate, the particles were washed with water, dried, and classified to have an average particle size of 7.4 μm.
m of solid toner was obtained. Looking at the SEM photograph, the shape was almost spherical. In order to confirm the shape of the wax in the toner, it was observed with a TEM photograph in the same manner as in Example 1. As a result, the average length (a) of the major axis of the wax was 0.70 μm,
The average length (b) of the minor axis of the wax was 0.58 μm, and the shape factor (f = a / b) was 1.21. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was dispersed inside the toner and was not visible on the surface of the toner particles. 100 parts by weight of toner was mixed with 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) for 1 minute with a sample mill, and the image was evaluated using A-color 935 (manufactured by Fuji Xerox) without using a fuser oil. The results obtained are shown in Table 1.
【0032】(実施例4)パラフィンワックス(商品
名:HNP(高純度精製パラフィンワックス)日本精蝋
製、融点89℃)30重量部を酢酸エチル250重量部
に73℃で加熱溶解し、その後60℃に保持してワック
スを析出させて得たワックス粗分散液を超音波処理(超
音波発振周波数28±2kHz、超音波発振出力密度
0.601W/cm2 )してワックス粗分散液を得た。
25℃のワックス粗分散液を、直径0.3mmのジル
コニア・メデイアと共に、DCPミルSF−12(日本
アイリッヒ製)に充填し、単位積算動力が0.70kW
h/kgになるまで、粉砕及び/又は分散させてワック
スの酢酸エチル分散液を得た。このときの粉砕及び/又
は分散領域でのワックス分散液の温度は5℃であった。
ワックスの平均粒子径は、レーザー回折/散乱式粒度分
布測定装置LA−910(堀場製作所製)で測定したと
ころ0.40μmであった。ワックス分散液中のワック
ス形状を走査型電子顕微鏡(SEM)で観察したとこ
ろ、ワックスの長軸の平均長さ(a)が0.45μm、
ワックスの短軸の平均長さ(b)が0.39μmであ
り、形状係数(f=a/b)は1.15であった。Example 4 30 parts by weight of paraffin wax (trade name: HNP (high-purity purified paraffin wax), manufactured by Nippon Seiro, melting point: 89 ° C.) was dissolved by heating at 73 ° C. in 250 parts by weight of ethyl acetate, and then 60 parts by weight. The wax coarse dispersion obtained by precipitating the wax while maintaining the temperature at ° C. was subjected to ultrasonic treatment (ultrasonic oscillation frequency 28 ± 2 kHz, ultrasonic oscillation output density 0.601 W / cm 2 ) to obtain a coarse wax dispersion. .
A 25 ° C. crude wax dispersion was charged into a DCP mill SF-12 (manufactured by Eirich Japan) together with zirconia media having a diameter of 0.3 mm, and the unit integrated power was 0.70 kW.
h / kg to obtain a wax-ethyl acetate dispersion. At this time, the temperature of the wax dispersion in the pulverization and / or dispersion region was 5 ° C.
The average particle size of the wax was 0.40 μm as measured with a laser diffraction / scattering type particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). When the shape of the wax in the wax dispersion was observed with a scanning electron microscope (SEM), the average length (a) of the major axis of the wax was 0.45 μm,
The average length (b) of the minor axis of the wax was 0.39 μm, and the shape factor (f = a / b) was 1.15.
【0033】スチレン−ブチルアクリレート80対20
の共重合樹脂(重量平均分子量:40000、数平均分
子量:15000)100重量部、カーボンブラック5
重量部、及び酢酸エチル1000重量部をサンドミルで
5時間分散後、ワックスの酢酸エチル分散液42重量部
を加え、均一になるまでよく撹拌して油相液を作製し
た。炭酸カルシウム60重量部、水40重量部をボール
ミルで10時間分散後炭酸カルシウム分散液を得た。こ
の炭酸カルシウム分散液6重量部とセロゲンBS−H
(第一工業製薬製)の2重量%水溶液100重量部を卓
上コロイドミル(日本精機製作所製)で、5000rp
m、5分間混合して水相液を作製した。この水相液に油
相液50重量部を加え、8000rpmで、20分間混
合後、25℃水浴中で減圧下で有機溶媒を除去する。6
N塩酸を100重量部加えて、炭酸カルシウムを除去し
た後、水洗・乾燥・分級して平均粒子径7.4μmの固
形トナーを得た。SEM写真をみると形状がほぼ球形を
していた。トナー中のワックス形状を確認するために、
実施例1と同様にして、TEM写真で観察したところ、
ワックスの長軸の平均長さ(a)が0.56μm、ワッ
クスの短軸の平均長さ(b)が0.48μmであり、形
状係数(f=a/b)は1.17であった。トナー断面
の透過型電子顕微鏡(TEM)写真では、ワックスはト
ナー内部に分散し、トナー粒子表面には見えなかった。
トナー100重量部にシリカR972(日本エアロジル
製)1重量部をサンプルミルで1分間混合して得たシリ
カ外添トナーをA−color935(富士ゼロックス
製)を用いて、定着ヒューザーオイルなしで画像評価を
行った結果を表1に示した。Styrene-butyl acrylate 80:20
100 parts by weight of a copolymer resin (weight average molecular weight: 40000, number average molecular weight: 15000), carbon black 5
After dispersing 5 parts by weight of ethyl acetate and 1000 parts by weight of ethyl acetate in a sand mill for 5 hours, 42 parts by weight of a wax ethyl acetate dispersion were added, and the mixture was stirred well until uniform to prepare an oil phase liquid. 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours to obtain a calcium carbonate dispersion. 6 parts by weight of this calcium carbonate dispersion and cellogen BS-H
100 parts by weight of a 2% by weight aqueous solution (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was 5,000 rpm by a tabletop colloid mill (manufactured by Nippon Seiki Seisakusho).
m for 5 minutes to prepare an aqueous phase liquid. After adding 50 parts by weight of the oil phase liquid to the aqueous phase liquid and mixing at 8000 rpm for 20 minutes, the organic solvent is removed under reduced pressure in a 25 ° C. water bath. 6
After 100 parts by weight of N hydrochloric acid was added to remove calcium carbonate, the solid was washed with water, dried and classified to obtain a solid toner having an average particle diameter of 7.4 μm. Looking at the SEM photograph, the shape was almost spherical. To check the wax shape in the toner,
When observed with a TEM photograph in the same manner as in Example 1,
The average length (a) of the major axis of the wax was 0.56 μm, the average length (b) of the minor axis of the wax was 0.48 μm, and the shape factor (f = a / b) was 1.17. . In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was dispersed inside the toner and was not visible on the surface of the toner particles.
100 parts by weight of toner and 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) were mixed for 1 minute by a sample mill, and an external silica-added toner was evaluated using A-color 935 (manufactured by Fuji Xerox) without fixing fuser oil. Table 1 shows the results obtained.
【0034】(実施例5)パラフィンワックス(商品
名:HNP(高純度精製パラフィンワックス)日本精蝋
製、融点89℃)30重量部を酢酸エチル250重量部
を加え73℃で加熱溶解し、冷却析出させて得られた2
5℃のワックス粗分散液を、DCPミルの粉砕及び/又
は分散領域でのワックス分散液の温度が55℃であるこ
と以外は、実施例1同様にしてワックスの酢酸エチル分
散液を得た。このときのワックスの平均粒子径は、レー
ザー回折/散乱式粒度分布測定装置LA−910(堀場
製作所製)で測定したところ2.0μmであった。ワッ
クス分散液中のワックス形状を走査型電子顕微鏡(SE
M)で観察したところ、ワックスの長軸の平均長さ
(a)が2.20μm、ワックスの短軸の平均長さ
(b)が1.44μmであり、形状係数(f=a/b)
は1.53であった。以下、実施例1とワックス分散液
が異なるほかは同様に行った結果、平均粒子径7.3μ
mの固形トナーを得た。トナー中のワックス形状をTE
M写真で観察したところ、ワックスの長軸の平均長さ
(a)が2.57μm、ワックスの短軸の平均長さ
(b)が1.59μmであり、形状係数(f=a/b)
は1.62であった。トナー断面の透過型電子顕微鏡
(TEM)写真では、ワックスはトナー内部に分散し、
トナー粒子表面には見えなかった。(Example 5) 30 parts by weight of paraffin wax (trade name: HNP (high-purity purified paraffin wax), manufactured by Nippon Seiro, melting point: 89 ° C) was added to 250 parts by weight of ethyl acetate, dissolved by heating at 73 ° C, and cooled. 2 obtained by precipitation
A wax crude dispersion at 5 ° C. was obtained in the same manner as in Example 1 except that the temperature of the wax dispersion in the pulverization and / or dispersion region of the DCP mill was 55 ° C. to obtain an ethyl acetate dispersion of wax. The average particle diameter of the wax at this time was 2.0 μm when measured with a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). Scanning electron microscope (SE)
M), the average length (a) of the major axis of the wax was 2.20 μm, the average length (b) of the minor axis of the wax was 1.44 μm, and the shape factor (f = a / b)
Was 1.53. Hereinafter, the same operation as in Example 1 was performed except that the wax dispersion was different, and as a result, the average particle diameter was 7.3 μm.
m of solid toner was obtained. TE shape of wax in toner
Observation with an M photograph showed that the average length (a) of the major axis of the wax was 2.57 μm, the average length (b) of the minor axis of the wax was 1.59 μm, and the shape factor (f = a / b)
Was 1.62. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax is dispersed inside the toner,
It was not visible on the surface of the toner particles.
【0035】トナー100重量部にシリカR972(日
本エアロジル社製)1重量部をサンプルミルで1分間混
合して得たシリカ外添トナーをA−color935
(富士ゼロックス製)を用いて、定着ヒューザーオイル
なしで画像評価を行った結果を表1に示した。A-color 935 was prepared by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of the toner in a sample mill for 1 minute and then adding silica.
Table 1 shows the results of image evaluation using (manufactured by Fuji Xerox) without fixing fuser oil.
【0036】(比較例1)スチレン−ブチルアクリレー
ト80対20共重合樹脂(重量平均分子量:4000
0、数平均分子量:15000)100重量部、C.
I.ピグメントレッド57を3重量部、パラフィンワッ
クス(商品名:HNP(高純度精製パラフィンワック
ス)日本精蝋製、融点89℃)3重量部を加え混練機で
混練粉砕後、分級して平均粒子径7.8μmの固形トナ
ーを得た。トナー中のワックス形状をTEM写真で観察
したところ、ワックスの長軸の平均長さ(a)が2.7
1μm、ワックスの短軸の平均長さ(b)が0.91μ
mであり、形状係数(f=a/b)は2.98であっ
た。トナー断面の透過型電子顕微鏡(TEM)写真で
は、ワックスはトナー粒子表面に一部露出していた。ト
ナー100重量部にシリカR972(日本エアロジル
製)1重量部をサンプルミルで1分間混合して得たシリ
カ外添トナーを、A−color935(富士ゼロック
ス製)を用いて、定着ヒューザーオイルなしで画像評価
を行った結果を表1に示した。Comparative Example 1 Styrene-butyl acrylate 80:20 copolymer resin (weight average molecular weight: 4000)
0, number average molecular weight: 15000) 100 parts by weight, C.I.
I. 3 parts by weight of CI Pigment Red 57 and 3 parts by weight of paraffin wax (trade name: HNP (high-purity purified paraffin wax) manufactured by Nippon Seisu, melting point: 89 ° C.) A solid toner of 0.8 μm was obtained. When the shape of the wax in the toner was observed with a TEM photograph, the average length (a) of the major axis of the wax was 2.7.
1 μm, the average length (b) of the minor axis of the wax is 0.91 μm
m and the shape factor (f = a / b) was 2.98. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was partially exposed on the surface of the toner particles. An external silica toner obtained by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil) with 100 parts by weight of the toner in a sample mill for 1 minute is used to fix an image without fixing fuser oil using A-color 935 (manufactured by Fuji Xerox). The results of the evaluation are shown in Table 1.
【0037】(比較例2)実施例5のワックス粗分散液
を、ゴーリンホモジナイザー15MRー8TA(同榮商
事)を用いて圧力500kg/cm2 、パス回数2回で
処理したこと以外は、比較例1と同様にして、ワックス
の酢酸エチル分散液を得た。なお、ゴーリンホモジナイ
ザー処理の際のワックス分散液の温度は、パス回数1回
及び2回とも処理前が5℃、処理後が45℃であった。
このときのワックスの平均粒子径は、レーザー回折/散
乱式粒度分布測定装置LA−910(堀場製作所製)で
測定したところ0.65μmであった。ワックス分散液
中のワックス形状を走査型電子顕微鏡(SEM)で観察
したところ、ワックスの長軸の平均長さ(a)が1.1
5μm、ワックスの短軸の平均長さ(b)が0.46μ
mであり、形状係数(f=a/b)は2.50であっ
た。以下、実施例1とワックス分散液が異なるほかは同
様に行った結果、平均粒子径8.1μmの固形トナーを
得た。トナー中のワックス形状をTEM写真で観察した
ところ、ワックスの長軸の平均長さ(a)が1.22μ
m、ワックスの短軸の平均長さ(b)が0.54μmで
あり、形状係数(f=a/b)は2.26であった。ト
ナー断面の透過型電子顕微鏡(TEM)写真では、ワッ
クスはトナー粒子表面に一部露出していた。(Comparative Example 2) A comparative example was carried out except that the crude wax dispersion of Example 5 was treated with a Gaulin homogenizer 15MR-8TA (Doei Shoji) at a pressure of 500 kg / cm 2 and two passes. In the same manner as in 1, a wax dispersion of ethyl acetate was obtained. The temperature of the wax dispersion during the Gaulin homogenizer treatment was 5 ° C. before the treatment and 45 ° C. after the treatment in both the first and second pass.
The average particle diameter of the wax at this time was 0.65 μm as measured with a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). When the shape of the wax in the wax dispersion was observed with a scanning electron microscope (SEM), the average length (a) of the major axis of the wax was 1.1.
5 μm, average length (b) of the minor axis of the wax is 0.46 μm
m, and the shape factor (f = a / b) was 2.50. Hereinafter, a solid toner having an average particle diameter of 8.1 μm was obtained in the same manner as in Example 1 except that the wax dispersion was different. When the shape of the wax in the toner was observed with a TEM photograph, the average length (a) of the major axis of the wax was 1.22 μm.
m, the average length (b) of the minor axis of the wax was 0.54 μm, and the shape factor (f = a / b) was 2.26. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was partially exposed on the surface of the toner particles.
【0038】トナー100重量部にシリカR972(日
本エアロジル製)1重量部をサンプルミルで1分間混合
して得たたシリカ外添トナーをA−color935
(富士ゼロックス製)を用いて、定着ヒューザーオイル
なしで画像評価を行った結果を表1に示した。A-color 935 was obtained by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil) with 100 parts by weight of toner with a sample mill for 1 minute.
Table 1 shows the results of image evaluation using (manufactured by Fuji Xerox) without fixing fuser oil.
【0039】(比較例3)実施例5のワックス粗分散液
を、ナノメーカー200(ナノマイザー製)を用いて圧
力500kg/cm2 、パス回数3回で処理したこと以
外は、実施例5と同様にして、平均粒子径8.5μmの
固形トナーを得た。なお、ナノメーカー処理の際のワッ
クス分散液の温度は、パス回数1回ないし3回いずれも
処理前が5℃、処理後が48℃であった。ワックスの平
均粒子径は3.28μmで、長軸の平均長さ(a)が
3.90μm、ワックスの短軸の平均長さ(b)が2.
45μmであり、形状係数(f=a/b)は1.59で
あった。Comparative Example 3 Same as Example 5 except that the crude wax dispersion of Example 5 was treated using Nanomaker 200 (manufactured by Nanomizer) at a pressure of 500 kg / cm 2 and three passes. Thus, a solid toner having an average particle size of 8.5 μm was obtained. The temperature of the wax dispersion during the nano maker treatment was 5 ° C. before the treatment and 48 ° C. after the treatment in any of the first to third passes. The average particle diameter of the wax is 3.28 μm, the average length (a) of the major axis is 3.90 μm, and the average length (b) of the minor axis of the wax is 2.
45 μm, and the shape factor (f = a / b) was 1.59.
【0040】スチレン−ブチルアクリレート80対20
の共重合樹脂(重量平均分子量:40000、数平均分
子量:15000)50重量部、C.I.ピグメントイ
エロー17を6重量部、トルエン500重量部をサンド
ミルで5時間分散後、ワックスの酢酸エチル分散液30
7.7重量部を加え、均一になるまでよく撹拌して油相
液を作製した。炭酸カルシウム60重量部、水40重量
部をボールミルで10時間分散して炭酸カルシウム分散
液を得た。この炭酸カルシウム分散液6重量部とセロゲ
ンBS−H(第一工業製薬製)の2重量%水溶液100
重量部を卓上コロイドミル(日本精機製作所製)で、5
000rpmで、5分間混合して水相液を作製した。こ
の水相液に油相液50重量部を加え8000rpmで、
20分間混合後、25℃水浴中で減圧下で有機溶媒を除
去した。6N塩酸100重量部を加えて、炭酸カルシウ
ムを除去した後、水洗・乾燥・分級して平均粒子径7.
8μmの固形トナーを得た。SEM写真をみると、形状
がほぼ球形をしていた。トナー中のワックスの長軸の平
均長さ(a)が3.25μm、ワックスの短軸の平均長
さ(b)が1.31μmであり、形状係数(f=a/
b)は2.48であった。トナー断面の透過型電子顕微
鏡(TEM)写真では、ワックスはトナー内部に分散
し、トナー粒子表面には見えなかった。Styrene-butyl acrylate 80:20
50 parts by weight of a copolymer resin (weight average molecular weight: 40000, number average molecular weight: 15000) of C.I. I. 6 parts by weight of CI Pigment Yellow 17 and 500 parts by weight of toluene are dispersed in a sand mill for 5 hours.
7.7 parts by weight were added, and the mixture was stirred well until it became uniform to prepare an oil phase liquid. 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours to obtain a calcium carbonate dispersion. 6 parts by weight of this calcium carbonate dispersion and a 2% by weight aqueous solution of cellogen BS-H (manufactured by Daiichi Kogyo Seiyaku) 100
5 parts by weight in a desktop colloid mill (Nippon Seiki Seisakusho)
The mixture was mixed at 000 rpm for 5 minutes to prepare an aqueous phase liquid. 50 parts by weight of the oil phase liquid was added to this aqueous phase liquid, and at 8000 rpm,
After mixing for 20 minutes, the organic solvent was removed under reduced pressure in a water bath at 25 ° C. After removing calcium carbonate by adding 100 parts by weight of 6N hydrochloric acid, the particles were washed, dried, and classified to have an average particle diameter of 7.
An 8 μm solid toner was obtained. Looking at the SEM photograph, the shape was almost spherical. The average length (a) of the major axis of the wax in the toner is 3.25 μm, the average length (b) of the minor axis of the wax is 1.31 μm, and the shape factor (f = a /
b) was 2.48. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was dispersed inside the toner and was not visible on the surface of the toner particles.
【0041】トナー100重量部にシリカR972(日
本エアロジル製)1重量部をサンプルミルで1分間混合
して得たシリカ外添トナーをA−color935(富
士ゼロックス製)を用いて、定着ヒューザーオイルなし
で画像評価を行った結果を表1に示した。A silica R972 (manufactured by Nippon Aerosil) was mixed with 1 part by weight of silica R972 (manufactured by Nippon Aerosil) in a sample mill for 1 minute. Table 1 shows the results of image evaluation.
【0042】[0042]
【表1】 [Table 1]
【0043】[0043]
【発明の効果】以上述べたように、この発明によれば、
トナーの耐オフセット性、帯電性、流動性、定着性、サ
イクル安定性にすぐれ、かつ良好な発色性、OHP透明
性を有し、良好な画質が得られるという効果を奏する。
また、同時にトナーの形状制御が可能で、球状の粒子が
容易にでき、転写性、クリーニング性のよいトナーが得
られた。As described above, according to the present invention,
The toner has excellent effects such as offset resistance, chargeability, fluidity, fixability, and cycle stability, and has good color developing properties and OHP transparency, and good image quality can be obtained.
At the same time, the shape of the toner could be controlled, spherical particles could be easily formed, and a toner having good transferability and cleaning properties was obtained.
Claims (11)
くとも結着樹脂、着色剤、及び離型剤を溶解ないし分散
させて油相成分を調製する工程と、該油相成分を水性媒
体中に分散させて造粒する工程を含む製造方法によって
製造される電子写真用トナーにおいて、該離型剤が予め
有機溶媒中に溶解後析出せしめられた後、或いは予め有
機溶媒中に懸濁せしめられた後、メディアにて粉砕及び
/又は分散せしめて得られる離型剤の分散液であること
を特徴とする電子写真用トナー。1. a step of dissolving or dispersing at least a binder resin, a colorant, and a release agent in an organic solvent in which a binder resin is dissolved to prepare an oil phase component; In a toner for electrophotography manufactured by a manufacturing method including a step of granulating by dispersing the release agent in an organic solvent, the release agent is previously dissolved and then precipitated in an organic solvent or suspended in an organic solvent in advance. A toner for electrophotography, which is a dispersion of a release agent obtained by pulverizing and / or dispersing in a medium after being subjected to the treatment.
01ないし1.5μmの範囲にあり、かつ形状が下記式
(1)の形状係数(f)を満たす球状微粒子であること
を特徴とする、請求項1に記載の電子写真用トナー。 【数1】f≦1.25 ・・・(1) (式中、f=a/bであり、aは離型剤粒子の長軸の平
均長さ、bは離型剤粒子の短軸の平均長さを表す。)2. The spherical fine particles of the release agent have an average particle diameter of 0.1.
2. The electrophotographic toner according to claim 1, wherein the toner is spherical fine particles having a shape in a range of from 01 to 1.5 [mu] m and satisfying a shape factor (f) of the following formula (1). F ≦ 1.25 (1) where f = a / b, a is the average length of the major axis of the release agent particles, and b is the minor axis of the release agent particles. Represents the average length.)
1ないし0.5μmの範囲にあり、かつ形状が下記式
(1)の形状係数(f)を満たす球状微粒子であること
を特徴とする、請求項1に記載の電子写真用トナー。 【数2】f≦1.25 ・・・(1) (式中、f=a/bであり、aは離型剤粒子の長軸の平
均長さ、bは離型剤粒子の短軸の平均長さを表す。)3. The spherical fine particles of the release agent have an average particle diameter of 0.3.
2. The electrophotographic toner according to claim 1, wherein the spherical fine particles are in a range of 1 to 0.5 [mu] m and have a shape satisfying a shape factor (f) of the following formula (1). F ≦ 1.25 (1) (where f = a / b, a is the average length of the major axis of the release agent particles, and b is the minor axis of the release agent particles. Represents the average length.)
を特徴とする、請求項1に記載の電子写真用トナー。4. The electrophotographic toner according to claim 1, wherein the binder resin is a polyester resin.
を特徴とする、請求項1に記載の電子写真用トナー。5. The electrophotographic toner according to claim 1, wherein the melting point of the release agent is 120 ° C. or less.
いし15重量部の離型剤が含有されていることを特徴と
する、請求項1に記載の電子写真用トナー。6. The electrophotographic toner according to claim 1, wherein the release agent is contained in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the binder resin.
くとも結着樹脂、着色剤、及び離型剤を溶解ないし分散
させて油相成分を調製する工程と、該油相成分を水性媒
体中に分散させて造粒する工程を含む電子写真用トナー
の製造方法において、該結着樹脂を溶解する有機溶媒中
に分散させる離型剤が、予め有機溶媒中に溶解後析出せ
しめられた後、或いは予め有機溶媒中に懸濁せしめられ
た後、メディアにて粉砕及び/又は分散せしめて得られ
る離型剤の分散液であることを特徴とする電子写真用ト
ナーの製造方法。7. A step of dissolving or dispersing at least a binder resin, a colorant, and a release agent in an organic solvent for dissolving the binder resin to prepare an oil phase component, and adding the oil phase component to an aqueous medium. In a method for producing an electrophotographic toner including a step of dispersing and granulating in a toner, a release agent to be dispersed in an organic solvent in which the binder resin is dissolved is preliminarily dissolved and then precipitated in an organic solvent. Or a dispersion of a release agent obtained by previously suspending in an organic solvent and then pulverizing and / or dispersing with a medium.
散せしめる際、少なくとも離型剤及び有機溶媒を含む分
散液の温度を40℃以下に保つことを特徴とする、請求
項7に記載の電子写真用トナーの製造方法。8. The method according to claim 7, wherein the temperature of the dispersion containing at least the release agent and the organic solvent is kept at 40 ° C. or less when the release agent is pulverized and / or dispersed in the medium. A method for producing an electrophotographic toner.
て得られる離型剤分散液の離型剤の微粒子が、平均粒径
が0.01ないし1.5μmの範囲にあり、かつ形状が
下記式(1)の形状係数(f)を満たす球状微粒子であ
ることを特徴とする、請求項7に記載の電子写真用トナ
ーの製造方法。 【数3】f≦1.25 ・・・(1) (式中、f=a/bであり、aは離型剤粒子の長軸の平
均長さ、bは離型剤粒子の短軸の平均長さを表す。)9. The release agent fine particles of the release agent dispersion obtained by pulverizing and / or dispersing in a medium have an average particle size in the range of 0.01 to 1.5 μm and a shape of: The method for producing an electrophotographic toner according to claim 7, wherein the particles are spherical fine particles satisfying a shape factor (f) of the formula (1). F ≦ 1.25 (1) (where f = a / b, a is the average length of the long axis of the release agent particles, and b is the short axis of the release agent particles) Represents the average length.)
分散させる工程において、離型剤1重量部に対して1な
いし20重量部の有機溶媒を用いることを特徴とする請
求項7に記載の電子写真用トナーの製造方法。10. The method according to claim 7, wherein in the step of pulverizing and / or dispersing the release agent in the medium, 1 to 20 parts by weight of an organic solvent is used per 1 part by weight of the release agent. A method for producing an electrophotographic toner.
潜像を現像剤を用いて現像する工程、現像によって形成
されたトナー像を転写体上に転写する工程を含む画像形
成方法において、該現像剤が、請求項1ないし6のいず
れか1に記載のトナーを含むことを特徴とする画像形成
方法。11. An image forming method including a step of forming a latent image on an image carrier, a step of developing the latent image using a developer, and a step of transferring a toner image formed by development onto a transfer body An image forming method according to claim 1, wherein the developer contains the toner according to any one of claims 1 to 6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18010197A JP3456372B2 (en) | 1997-07-04 | 1997-07-04 | Electrophotographic toner and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18010197A JP3456372B2 (en) | 1997-07-04 | 1997-07-04 | Electrophotographic toner and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH1124308A true JPH1124308A (en) | 1999-01-29 |
JP3456372B2 JP3456372B2 (en) | 2003-10-14 |
Family
ID=16077456
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18010197A Expired - Fee Related JP3456372B2 (en) | 1997-07-04 | 1997-07-04 | Electrophotographic toner and method for producing the same |
Country Status (1)
Country | Link |
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JP (1) | JP3456372B2 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000305309A (en) * | 1999-04-19 | 2000-11-02 | Tomoegawa Paper Co Ltd | Electrophotographic toner |
JP2002139861A (en) * | 2000-10-31 | 2002-05-17 | Kyocera Mita Corp | Toner for full color development |
JP2002351123A (en) * | 2001-03-21 | 2002-12-04 | Konica Corp | Electrostatic image developing toner and method for forming image |
JP2004318064A (en) * | 2002-11-08 | 2004-11-11 | Canon Inc | Method for manufacturing toner particles |
JP2004326030A (en) * | 2003-04-28 | 2004-11-18 | Canon Inc | Method for manufacturing toner particle and method for manufacturing toner |
JP2005338133A (en) * | 2004-05-24 | 2005-12-08 | Canon Inc | Method for manufacturing polymerized toner |
JP2006071697A (en) * | 2004-08-31 | 2006-03-16 | Canon Inc | Method for manufacturing toner |
JP2008040464A (en) * | 2006-07-10 | 2008-02-21 | Seiko Epson Corp | Method for manufacturing toner |
JP2015114666A (en) * | 2013-12-10 | 2015-06-22 | ゼロックス コーポレイションXerox Corporation | Emulsion aggregation toner |
US10859934B2 (en) | 2018-12-27 | 2020-12-08 | Ricoh Company, Ltd. | Yellow toner, developer, process cartridge, image forming apparatus, and image forming method |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8309290B2 (en) | 2006-09-15 | 2012-11-13 | Ricoh Company, Ltd. | Toner and method of manufacturing the same |
JP5494097B2 (en) | 2010-03-25 | 2014-05-14 | 株式会社リコー | Toner for electrostatic charge development |
-
1997
- 1997-07-04 JP JP18010197A patent/JP3456372B2/en not_active Expired - Fee Related
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000305309A (en) * | 1999-04-19 | 2000-11-02 | Tomoegawa Paper Co Ltd | Electrophotographic toner |
JP2002139861A (en) * | 2000-10-31 | 2002-05-17 | Kyocera Mita Corp | Toner for full color development |
JP2002351123A (en) * | 2001-03-21 | 2002-12-04 | Konica Corp | Electrostatic image developing toner and method for forming image |
JP2004318064A (en) * | 2002-11-08 | 2004-11-11 | Canon Inc | Method for manufacturing toner particles |
JP2004326030A (en) * | 2003-04-28 | 2004-11-18 | Canon Inc | Method for manufacturing toner particle and method for manufacturing toner |
JP2005338133A (en) * | 2004-05-24 | 2005-12-08 | Canon Inc | Method for manufacturing polymerized toner |
JP2006071697A (en) * | 2004-08-31 | 2006-03-16 | Canon Inc | Method for manufacturing toner |
JP2008040464A (en) * | 2006-07-10 | 2008-02-21 | Seiko Epson Corp | Method for manufacturing toner |
JP2015114666A (en) * | 2013-12-10 | 2015-06-22 | ゼロックス コーポレイションXerox Corporation | Emulsion aggregation toner |
US10859934B2 (en) | 2018-12-27 | 2020-12-08 | Ricoh Company, Ltd. | Yellow toner, developer, process cartridge, image forming apparatus, and image forming method |
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