JPH11167225A - Production of binder resin for electrostatic charge image developing toner - Google Patents
Production of binder resin for electrostatic charge image developing tonerInfo
- Publication number
- JPH11167225A JPH11167225A JP34870997A JP34870997A JPH11167225A JP H11167225 A JPH11167225 A JP H11167225A JP 34870997 A JP34870997 A JP 34870997A JP 34870997 A JP34870997 A JP 34870997A JP H11167225 A JPH11167225 A JP H11167225A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- molecular weight
- toner
- solvent
- emulsified dispersion
- 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
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は電子写真、静電記録、静
電印刷などにおける静電荷像を現像するためのトナー用
結着樹脂の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a binder resin for toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like.
【0002】[0002]
【従来の技術】静電荷像を現像する方法として、近年、
乾式現像方式の技術開発が急速に進められてきた。乾式
現像において定着する方法としては種々のものが知られ
ているが、特に加熱ロ−ラ定着機に代表される接触加熱
定着方式は、熱板定着器などの無接触加熱定着方式に比
して熱効率が高く、特に高速度定着及び低温度定着が可
能である点で優れている。2. Description of the Related Art In recent years, as a method of developing an electrostatic charge image,
Technical development of the dry development method has been rapidly advanced. Various methods are known for fixing in dry development. In particular, a contact heat fixing method represented by a heat roller fixing machine is compared with a non-contact heat fixing method such as a hot plate fixing device. It is excellent in that it has high thermal efficiency, and particularly enables high-speed fixing and low-temperature fixing.
【0003】加熱ロ−ラ−定着法では、静電記録体(感
光ドラム)上に現像によって得られたトナ−像を一旦紙
などの転写シ−トに転写した後、該転写シ−トを加熱圧
着を行う定着ロ−ラ−に通すことによりトナ−像をシ−
トに融着させて定着が行なわれる。しかしながら、従来
のトナーを使用して加熱ロ−ラ−定着法により定着を行
うと、熱ロール表面とトナーが溶融状態で接触するた
め、トナーが熱ロール表面に付着転移し、次の被定着シ
ートにこれが再転移して汚す、即ちオフセット現象を起
こすという問題点があった。In the heating roller fixing method, a toner image obtained by development on an electrostatic recording medium (photosensitive drum) is temporarily transferred to a transfer sheet such as paper, and then the transfer sheet is transferred. The toner image is sealed by passing it through a fixing roller that performs heat compression.
The fixing is carried out by fusing the sheet. However, when the toner is fixed by the heat roller fixing method using the conventional toner, the toner is brought into contact with the surface of the hot roll in a molten state, so that the toner adheres and transfers to the hot roll surface, and the next sheet to be fixed is fixed. However, there is a problem that this is re-transferred and soiled, that is, an offset phenomenon is caused.
【0004】一般に、静電荷像現像用トナ−は樹脂成
分、顔料や磁性粉もしくは染料からなる着色剤成分およ
び離型剤、電荷制御剤等の添加成分によって構成されい
るが、上記問題点を解決するために、定着温度において
確実に定着が達成される目的で、トナー用結着樹脂中に
低分子量重合体を含有させ、トナ−粘度を下げると共
に、接触加熱ロ−ラにトナ−の一部が付着することによ
るオフセット現象を防止する目的で、当該トナー用結着
樹脂中に高分子量重合体を含有させトナ−弾性率を上げ
る方法が検討されてきた。Generally, the toner for developing an electrostatic image is composed of a resin component, a colorant component composed of a pigment, a magnetic powder or a dye, and additional components such as a release agent and a charge control agent. For the purpose of ensuring the fixing at the fixing temperature, a low molecular weight polymer is contained in the binder resin for toner to lower the toner viscosity, and a part of the toner is supplied to the contact heating roller. For the purpose of preventing the offset phenomenon due to the adhesion of the toner, a method of increasing the toner elastic modulus by including a high molecular weight polymer in the binder resin for toner has been studied.
【0005】これら低分子量重合体と高分子量重合体と
の複合体であるトナー用結着樹脂としては、主にスチレ
ン系樹脂が多く使われており、種々の製造方法が検討さ
れてきた。例えば、特開平2-48657号公報には、多官能
性開始剤を用い、懸濁重合法により高分子量の重合体を
製造し、この高分子量の重合体の存在下に、さらに低分
子量の重合体を製造し、得られた重合体を乾燥して無溶
媒の高分子量及び低分子量の重合体混合物を得、トナー
用結着樹脂として使用することを検討している。As a binder resin for a toner, which is a composite of a low molecular weight polymer and a high molecular weight polymer, a styrene resin is mainly used in many cases, and various production methods have been studied. For example, Japanese Patent Application Laid-Open No. 2-48657 discloses that a high molecular weight polymer is produced by a suspension polymerization method using a polyfunctional initiator, and a low molecular weight polymer is produced in the presence of the high molecular weight polymer. We are studying the preparation of a coalesced polymer, drying the obtained polymer to obtain a solvent-free high-molecular weight and low-molecular weight polymer mixture, and using it as a binder resin for toner.
【0006】しかしながら、一般に懸濁重合法により重
合する場合、ジビニルベンゼン、ジエチレングリコール
ジメタクリレート、トリメチロールプロパンジメタクリ
レートなどの架橋剤を用いることにより、比較的容易に
高分子量の重合体を得ることが可能であるが、低分子量
体を製造する段階で問題が多い。すなわち、懸濁重合で
低分子量の重合体を得るためには、多量の連鎖移動剤、
例えばメルカプタン類やハロゲン化化合物を用いる必要
があり、連鎖移動剤を用いた場合、所望されない臭気
や、残存ハロゲン化化合物を除去するために、重合後処
理を必要とし、コスト高になるという問題があった。更
に、未反応の重合性単量体を除去することが難しいとい
う問題も有している。However, in general, when polymerizing by a suspension polymerization method, a high molecular weight polymer can be obtained relatively easily by using a crosslinking agent such as divinylbenzene, diethylene glycol dimethacrylate, and trimethylolpropane dimethacrylate. However, there are many problems at the stage of producing a low molecular weight compound. That is, in order to obtain a low molecular weight polymer by suspension polymerization, a large amount of chain transfer agent,
For example, it is necessary to use a mercaptan or a halogenated compound, and when a chain transfer agent is used, an undesired odor or a residual post-polymerization treatment is required in order to remove a residual halogenated compound. there were. Further, there is a problem that it is difficult to remove unreacted polymerizable monomers.
【0007】特開平2-48675号公報には、溶液重合法に
より得た低分子量の重合体を高分子量重合体を製造する
ための重合性単量体に溶解させ、多官能性(三官能性以
上)開始剤を用いて高分子量重合体を重合し、トナー用
結着樹脂を製造するという技術が開示されている。しか
し、溶液重合法による高分子量樹脂の製造は、ワイゼン
ベルグ効果(攪拌棒に樹脂が巻きつく現象)によるトラ
ブルが発生し製造が困難であるという問題があった。ま
た、USP5,084,368号公報には、溶液重合で得た低分
子量重合体と塊状重合で得た高分子量重合体とを有機溶
媒中で溶解混合し、しかる後に溶媒を真空除去して高分
子量重合体と低分子量重合体の混合物を得る方法が開示
されている。[0007] JP-A-2-48675 discloses that a low-molecular-weight polymer obtained by a solution polymerization method is dissolved in a polymerizable monomer for producing a high-molecular-weight polymer, and a polyfunctional (trifunctional) polymer is prepared. A technique has been disclosed in which a high molecular weight polymer is polymerized using an initiator to produce a binder resin for a toner. However, the production of a high-molecular-weight resin by the solution polymerization method has a problem that a trouble occurs due to the Weissenberg effect (a phenomenon in which the resin is wound around a stirring rod), and the production is difficult. Further, US Pat. No. 5,084,368 discloses that a low molecular weight polymer obtained by solution polymerization and a high molecular weight polymer obtained by bulk polymerization are dissolved and mixed in an organic solvent, and then the solvent is removed in vacuo to obtain a high molecular weight polymer. A method for obtaining a mixture of a coalesced and low molecular weight polymer is disclosed.
【0008】しかしながら、上記いずれの溶液重合によ
る製造方法の場合においても、無溶媒の樹脂混合物を得
るためには、脱溶剤する必要があり、手間がかかってコ
スト高になる。However, in any of the above-described production methods by solution polymerization, it is necessary to remove the solvent in order to obtain a solvent-free resin mixture, which is troublesome and costly.
【0009】更に、特開平2-118583号公報には低分子量
重合体、高分子量重合体及び着色剤を配合、混合した
後、混練することによって静電荷像現像用トナーを製造
する技術も開示されている。しかしながら、一般に分子
量が大きく異なり、更に樹脂組成の異なった重合体は相
溶性が乏しいため、低分子量の欠点であるオフセット性
の発生、高分子量体の欠点である低温度での定着不足
が、重ねて発生するという欠点を有している。Further, Japanese Patent Application Laid-Open No. Hei 2-18583 discloses a technique for producing a toner for developing an electrostatic image by mixing, mixing and kneading a low molecular weight polymer, a high molecular weight polymer and a colorant. ing. However, in general, polymers having different molecular weights are largely different from each other, and polymers having different resin compositions have poor compatibility. Therefore, occurrence of offset property, which is a drawback of low molecular weight, and insufficient fixing at low temperature, which is a drawback of high molecular weight polymer, are repeated. It has the disadvantage that it occurs.
【0010】[0010]
【発明が解決しようとする課題】本発明の目的は、トナ
ー用結着樹脂成分である低分子量重合体、高分子量重合
体が均一に相溶分散した、耐オフセット性、定着性、製
造時の粉砕性、保存時の耐ブロッキング性(非凝集
性)、像形成時の現像性等において良好な特性を有す
る、臭気の少ない静電荷像現像トナーを製造し得るトナ
ー用結着樹脂を効率的に、且つ安価に製造する方法を提
供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a binder resin component for a toner in which low-molecular-weight polymer and high-molecular-weight polymer are uniformly compatible and dispersed, and have offset resistance, fixing property, Efficiently develop a binder resin for toner capable of producing an electrostatic image developing toner with low odor, which has good characteristics such as pulverizability, anti-blocking property during storage (non-aggregation property), and developability during image formation. It is another object of the present invention to provide a method for manufacturing the semiconductor device at low cost.
【0011】[0011]
【課題を解決するための手段】本発明者等は、鋭意研究
を行った結果、無溶媒樹脂と、樹脂乳化分散液とを特定
の条件下に、攪拌混合する処理し、更に水分除去処理を
施すことにより、上記の目的を達成することができるこ
とを見いだし、本発明を完成するに到った。即ち、本発
明は、樹脂乳化分散液と無溶媒樹脂とを共存せしめ、パ
ドルを固定した回転軸を胴体内部に有し、その空隙率が
50%以上である回転式乾燥機により、混合処理を施し、
並行して又はその後に水分除去処理を施して無溶媒樹脂
混合組成物を製造する工程を含むことを特徴とするトナ
ー用結着樹脂の製造方法を提供する。好ましくは、上記
混合処理及び水分除去処理の時間が10分以上であり、好
ましくは、上記回転式乾燥機が1軸又は2軸の回転式乾
燥機であり、好ましくは、上記無溶媒樹脂が塊状重合で
得られた重合体の乳化分散液であり、好ましくは、上記
樹脂乳化分散液が乳化重合で得られた重合体の乳化分散
液であり、好ましくは、上記無溶媒樹脂のGPC分子量
ピークMpが1,500〜30,000で且つその重量平均分子量
(Mw)/数平均分子量(Mn)が4.0未満であり、上
記樹脂乳化分散液中の樹脂のGPC分子量ピーク(M
p)が300,000〜3,000,000であるトナー用結着樹脂の製
造方法を提供する。更に本発明は、樹脂乳化分散液と無
溶媒樹脂とを共存せしめ、パドルを固定した回転軸を胴
体内部に有し、その空隙率が50%以上である回転式乾燥
機により、混合処理を施し、並行して又はその後に水分
除去処理を施して無溶媒樹脂混合組成物を製造する工程
を経て得られたトナー用結着樹脂と顔料とを含有する静
電荷像現像用トナーを提供する。Means for Solving the Problems As a result of diligent research, the present inventors have conducted a process of stirring and mixing a solventless resin and a resin emulsified dispersion under specific conditions, and furthermore, a process of removing water. It has been found that the above object can be achieved by performing the method, and the present invention has been completed. That is, the present invention allows a resin emulsified dispersion and a solventless resin to coexist, has a rotating shaft with a fixed paddle inside the body, and has a porosity of
The mixing process is performed by a rotary dryer that is 50% or more.
A method for producing a binder resin for a toner, which comprises a step of producing a solventless resin mixture composition by performing a water removal treatment in parallel or thereafter. Preferably, the time of the mixing treatment and the water removal treatment is 10 minutes or more, preferably, the rotary dryer is a single-screw or twin-screw rotary dryer, and preferably, the solvent-free resin is a lump. It is an emulsified dispersion of the polymer obtained by polymerization, preferably, the resin emulsified dispersion is an emulsified dispersion of the polymer obtained by emulsion polymerization, preferably, the GPC molecular weight peak Mp of the solventless resin. Is 1,500 to 30,000 and the weight average molecular weight (Mw) / number average molecular weight (Mn) is less than 4.0, and the GPC molecular weight peak (M
A method for producing a binder resin for a toner, wherein p) is 300,000 to 3,000,000. Further, in the present invention, the resin emulsified dispersion and the solvent-free resin are allowed to coexist, and the mixing process is performed by a rotary dryer having a rotary shaft having a paddle fixed inside the body and having a porosity of 50% or more. The present invention provides an electrostatic image developing toner containing a binder resin for a toner and a pigment obtained through a step of producing a solventless resin mixture composition by performing a water removal treatment in parallel or thereafter.
【0012】しかして、本発明によれば、無溶媒樹脂
と、樹脂乳化分散液とを共存せしめ、攪拌混合処理と、
それと並行又はその後に水分除去処理を施すことによ
り、静電荷像現像用トナー用結着樹脂を効率的に、且つ
安価に製造することができる。更に、残存するモノマー
は、水分が蒸発により除去される際に随伴して効果的に
系外に除去されるので、極めて微量となり、臭気がほと
んど感じられない無溶媒樹脂混合組成物を得ることがで
きる。Thus, according to the present invention, the solvent-free resin and the resin emulsified dispersion are allowed to coexist, and the mixture is stirred and mixed.
By performing the water removal treatment concurrently or thereafter, the binder resin for the toner for developing an electrostatic image can be efficiently and inexpensively manufactured. Furthermore, since the remaining monomer is effectively removed from the system accompanying the removal of water by evaporation, it is possible to obtain a solventless resin mixture composition in which the amount is extremely small and almost no odor is felt. it can.
【0013】そして本発明の製造方法により得られる低
分子量樹脂と高分子量樹脂との無溶媒樹脂混合組成物を
結着樹脂として使用した静電荷現像用トナーは、(a)
低分子量樹脂と高分子量樹脂とが均一に分散し、(b)
非オフセット性、定着性、製造時の粉砕性、保存時の耐
ブロッキング性(非凝集性)、像形成時の現像性等にお
いて良好であり、しかも(c)臭気が少ない、という顕
著な優れた特性を有する。以下、本発明の静電荷像現像
用トナー用結着樹脂の製造方法について詳述する。[0013] The toner for electrostatic charge development using a solventless resin mixture of a low molecular weight resin and a high molecular weight resin obtained by the production method of the present invention as a binder resin comprises (a)
(B) the low molecular weight resin and the high molecular weight resin are uniformly dispersed;
It has excellent non-offset properties, fixing properties, pulverizability during production, blocking resistance during storage (non-agglomeration), developability during image formation, etc., and (c) low odor. Has characteristics. Hereinafter, the method for producing the binder resin for a toner for developing an electrostatic image of the present invention will be described in detail.
【0014】本発明の静電荷像現像用トナー用結着樹脂
の製造方法は、無溶媒樹脂と、樹脂乳化分散液とを共存
せしめ、攪拌混合処理を施し、それと並行又はその後に
水分除去処理を特定の装置により施す工程を含むことを
特徴とする。上記無溶媒樹脂と、樹脂乳化分散液とを共
存せしめて施す攪拌混合処理とは、無溶媒樹脂と、樹脂
乳化分散液とを、機械的その他の方法で攪拌混合する操
作を行うことである。In the method for producing a binder resin for a toner for developing an electrostatic image according to the present invention, a solventless resin and a resin emulsified dispersion are allowed to coexist, and the mixture is stirred and mixed. It is characterized in that it includes a step of applying with a specific device. The stirring and mixing treatment performed by coexisting the solventless resin and the resin emulsified dispersion is to perform an operation of stirring and mixing the solventless resin and the resin emulsified dispersion by mechanical or other methods.
【0015】上記攪拌混合処理は、好ましくは上記無溶
媒樹脂のガラス転移点以上の温度、更に好ましくは該ガ
ラス転移点よりも20℃以上の温度で行うことにより、得
られる無溶媒樹脂と樹脂乳化分散液中の樹脂との混合物
の組成が均一になり、該混合物を用いて作成したトナー
の諸物性が向上する。上記攪拌混合処理による上記利点
は、該攪拌混合処理中に、樹脂乳化分散液中の樹脂粒子
が無溶媒樹脂に接触し、樹脂乳化分散液中の樹脂粒子が
無溶媒樹脂中に分散された状態で無溶媒樹脂と合一する
作用が、上記温度で促進されるためと考えられる。攪拌
混合処理は常圧で行われても、或いは水分の蒸発揮散を
抑制するために圧力を加えた状態で行ってもよい。The stirring and mixing treatment is preferably carried out at a temperature higher than the glass transition point of the solventless resin, more preferably at a temperature higher than 20 ° C. than the glass transition point, so that the resulting solventless resin and the resin emulsified resin are emulsified. The composition of the mixture with the resin in the dispersion becomes uniform, and the various physical properties of the toner produced using the mixture are improved. The advantage of the stirring and mixing treatment is that, during the stirring and mixing treatment, the resin particles in the resin emulsified dispersion contact the solventless resin, and the resin particles in the resin emulsified dispersion are dispersed in the solventless resin. It is considered that the action of coalescence with the solvent-free resin is promoted at the above temperature. The stirring and mixing treatment may be performed at normal pressure, or may be performed in a state where pressure is applied in order to suppress evaporation of water.
【0016】上記水分除去処理は、上記攪拌混合処理に
よって生成した組成物から水分を蒸発により除去する処
理であり、この処理の結果、大部分の水分が除去された
無溶媒樹脂混合組成物が得られる。このとき、上記混合
物中に例えば残留モノマー、有機溶媒等の揮発性不純物
が存在していれば、該揮発性不純物を同時に除去するこ
とができる。水分除去処理は、上記混合物を混合物中の
水の蒸発平衡温度以上に加熱することにより行うことが
でき、さらに加熱下に減圧にすることによりより効率的
に行うことができる。水分除去を常圧で行う場合には、
混合物の温度は、無溶媒樹脂と樹脂乳化分散液とを混合
した当初は100℃近辺に設定されればよいが、水分の除
去の進行と共に高温となる。The water removal treatment is a treatment for removing water from the composition produced by the stirring and mixing treatment by evaporation. As a result of this treatment, a solventless resin mixed composition from which most of the water has been removed is obtained. Can be At this time, if volatile impurities such as residual monomers and organic solvents are present in the mixture, the volatile impurities can be removed at the same time. The water removal treatment can be performed by heating the mixture to a temperature equal to or higher than the evaporation equilibrium temperature of water in the mixture, and can be performed more efficiently by reducing the pressure while heating. When removing water at normal pressure,
The temperature of the mixture may be set at around 100 ° C. at the beginning when the solventless resin and the resin emulsified dispersion are mixed, but the temperature becomes higher as the removal of water proceeds.
【0017】上記水分除去処理は、上記攪拌混合処理終
了後に行うことができるが、両者を並行してに行うこと
ができる。そして両者を並行して行うことが効率的であ
り、好ましい。水分除去処理の開始とともに混合物の水
分の低下が始まり、最終的に大部分の水分が除去される
が、攪拌混合処理と並行して行う場合には攪拌混合処理
の開始とともに混合物中の水分の蒸発が始まり、水分の
低下が始まる。The water removal treatment can be carried out after the completion of the stirring and mixing treatment, but both can be carried out in parallel. It is efficient and preferable to perform both in parallel. At the start of the water removal process, the water content of the mixture begins to decrease, and most of the water is eventually removed.However, when the process is performed in parallel with the stirring and mixing process, the water in the mixture evaporates with the start of the stirring and mixing process. Begins, and the decrease in moisture begins.
【0018】さらに、無溶媒樹脂と樹脂乳化分散液中の
樹脂との混合物の組成を高度に均一とする場合には、攪
拌混合処理及び水分除去処理の後に、更に混練処理を施
すことが好ましい。本発明において混練りとは、大部分
の水分が除去された無溶媒樹脂混合組成物を更に機械的
に練り合わせることを言う。この場合少量の水分を更に
除去する条件下で混練りが行われても良い。混練処理
は、無溶媒樹脂と樹脂乳化分散液中の樹脂の少なくとも
一方の樹脂の溶融状態で行われると、より均一な組成の
混合物が得られるために好ましい。Further, when the composition of the mixture of the solventless resin and the resin in the resin emulsified dispersion is highly uniform, it is preferable to further perform a kneading treatment after the stirring and mixing treatment and the water removing treatment. In the present invention, kneading means mechanically kneading the solventless resin mixture composition from which most of the water has been removed. In this case, kneading may be performed under the condition that a small amount of water is further removed. The kneading treatment is preferably performed in a molten state of at least one of the solventless resin and the resin in the resin emulsified dispersion, since a mixture having a more uniform composition is obtained.
【0019】本発明においては、パドルを固定した回転
軸を胴体内部に有し、その空隙率が50%以上である回
転式乾燥機により、上記無溶媒樹脂と、上記樹脂乳化分
散液を共存せしめ、攪拌混合処理、水分除去処理及び必
要に応じて混練処理を行う。In the present invention, the solventless resin and the resin emulsified dispersion are allowed to coexist by a rotary dryer having a rotary shaft having a paddle fixed inside the body and having a porosity of 50% or more. Then, a stirring and mixing process, a water removing process and, if necessary, a kneading process are performed.
【0020】上記パドルは胴体内部に添加された原材料
を攪拌混合する構造を有し、連続処理する場合は、排出
口への搬送性を有するものが用いられる。又更に胴体壁
面の樹脂を掻き取る構造のものが好適に用いられる。回
転軸内部には熱媒を通じても良く、又更に回転軸面の樹
脂を掻き取る構造のものが好適に用いられる。The paddle has a structure in which the raw materials added to the inside of the body are stirred and mixed. When the paddle is continuously processed, a material having a transportability to a discharge port is used. Further, those having a structure for scraping off the resin on the body wall surface are preferably used. A heat medium may be passed through the inside of the rotating shaft, and one having a structure for scraping off the resin on the rotating shaft surface is preferably used.
【0021】空隙率とは、胴体内部の全容積から回転軸
及びパドル等の容積を引いた有効空間容積を、胴体内部
の全容積で除した割合を%で示した値であり、50〜90%
が好ましく、55〜85%が更に好ましく、60〜80%が特に
好ましい。空隙率が上記範囲より大きいと、攪拌効率が
落ちて、無溶媒の樹脂と樹脂乳化分散液中の樹脂とが充
分均一に混合されない。空隙率が上記範囲より小さい
と、樹脂の処理量が少なくなり処理効率が低下する。The porosity is a value obtained by dividing the effective volume of the space obtained by subtracting the volume of the rotary shaft and the paddle from the total volume of the inside of the body by the total volume of the inside of the body, and is expressed as a percentage. %
Is preferably, more preferably 55 to 85%, particularly preferably 60 to 80%. If the porosity is larger than the above range, the stirring efficiency is reduced, and the resin in the solventless and the resin in the resin emulsified dispersion are not sufficiently uniformly mixed. If the porosity is smaller than the above range, the processing amount of the resin decreases, and the processing efficiency decreases.
【0022】上記装置で混合処理、水分除去処理及び必
要に応じて混練処理する処理時間は、好ましくは10分以
上、更に好ましくは15分以上、特に好ましくは20分以上
であると、効率的に処理することができる。The processing time for the mixing, water removal and, if necessary, kneading in the above apparatus is preferably at least 10 minutes, more preferably at least 15 minutes, particularly preferably at least 20 minutes. Can be processed.
【0023】上記機能を有する好ましい装置としては、
(株)奈良機械製の「パドルドライヤー」、ホソカワミ
クロン(株)製の「ドーラス・ディスク」、LIST社
製の「DISCOTHERM」等を挙げることができ
る。連続的に処理ができ、混合攪拌混合処理、水分除去
処理及び無溶媒樹脂と樹脂乳化分散液中の樹脂をより均
一に分散させることが可能な混練処理を一つの装置で効
率的に行える点でパドルに搬送性を持たせ、強制搬出装
置を付帯した装置が好ましい。Preferred devices having the above functions include:
"Paddle dryer" manufactured by Nara Machinery Co., Ltd., "Dorus Disc" manufactured by Hosokawa Micron Corporation, "DISCOTHERM" manufactured by LIST, and the like can be mentioned. It can be processed continuously, and can be efficiently mixed and stirred with a single device, and can perform mixing, stirring, mixing, moisture removal, and kneading that can disperse the solvent-free resin and the resin in the resin emulsified dispersion more uniformly. It is preferable that the paddle be provided with a transporting property and be attached with a forced unloading device.
【0024】上記装置により、攪拌混合処理及び混練処
理は上記装置の攪拌軸に固定されたデスクあるいはバド
ルの回転により混合物を攪拌混合して施すことができ
る。また、水分除去処理は胴体部分あるいは回転軸中に
通常装備されている加熱ジャケットあるいは電熱ヒータ
ーで混合物を前記混合物中の水の蒸発平衡温度以上に加
熱する、あるいは加熱に加えて装置内を減圧にすること
によってより効率的に行うことができる。また水分除去
処理を行う別法として、例えば上記混合物を必要に応じ
て加熱後、減圧域に導入し水分を蒸発させる、所謂それ
自体公知のフラッシュ法によって実質的に無溶媒の状態
とする方法を挙げることができる。With the above apparatus, the mixing and kneading treatment can be performed by stirring and mixing the mixture by rotating a desk or a paddle fixed to the stirring shaft of the above apparatus. In addition, the water removal treatment is performed by heating the mixture to a temperature equal to or higher than the evaporation equilibrium temperature of the water in the mixture by using a heating jacket or an electric heater usually provided in the body or the rotating shaft, or by reducing the pressure in the apparatus in addition to the heating. By doing so, it can be performed more efficiently. As another method of performing the water removal treatment, for example, a method of heating the above-described mixture as necessary, introducing the mixture into a reduced pressure region and evaporating the water, and a method of substantially eliminating the solvent by a so-called flash method known per se. Can be mentioned.
【0025】上記攪拌混合処理及び水分除去処理は単一
の装置で行うこともできるし、別々の装置で行うことも
できるが、単一の装置で行うことが好ましい。更に混練
処理を行う場合には、攪拌混合処理、水分除去処理及び
混練処理をそれぞれ別々の装置で行うこともできるし、
攪拌混合処理及び水分除去処理を単一の第1の装置で行
い、混練処理を別の第2の装置で行う、若しくは攪拌混
合処理を第1の装置で行い、水分除去処理及び混練処理
を別の第2の装置で行うこともできるし、攪拌混合処
理、水分除去処理及び混練処理を単一の装置で行うこと
ができるが、特に均一な無溶媒樹脂混合組成物を得る場
合には攪拌混合処理及び水分除去処理を単一の第1の装
置で行い、混練処理を別の第2の装置で行うのが好まし
く、特に作業性を良好に行う場合には攪拌混合処理、水
分除去処理及び混練処理を単一の装置で行うことが好ま
しい。The stirring and mixing treatment and the water removal treatment can be performed by a single device or by separate devices, but are preferably performed by a single device. Further, when performing the kneading process, the stirring and mixing process, the water removal process and the kneading process can be performed in separate devices, respectively,
The stirring and mixing process and the water removing process are performed by a single first device, and the kneading process is performed by another second device. The stirring and mixing process is performed by the first device. The mixing and stirring, the water removal and the kneading can be performed by a single device. In particular, when a uniform solventless resin mixture composition is obtained, the stirring and mixing are performed. It is preferable that the treatment and the water removal treatment are performed by a single first device, and the kneading treatment is performed by another second device. In particular, when the workability is good, the stirring and mixing treatment, the water removal treatment and the kneading are performed. Preferably, the processing is performed in a single device.
【0026】攪拌混合処理及び水分除去処理を単一の第
1の装置で行い、混練処理を別の第2の装置で行う場
合、攪拌混合処理及び水分除去処理を終えての第1の装
置の排出口から得られる無溶媒樹脂混合組成物の水分含
有率は20重量%以下が好ましく、5重量%以下がより
好ましい。When the stirring and mixing process and the water removing process are performed by a single first device and the kneading process is performed by another second device, the first device after the stirring and mixing process and the water removing process are completed. The water content of the solvent-free resin mixture composition obtained from the outlet is preferably 20% by weight or less, more preferably 5% by weight or less.
【0027】図1には、好ましい2軸回転式乾燥機の構
造が模式的に示されている。図1の(イ)は概略側面
図、(ロ)は断面図である。図1に従って、2軸回転式
乾燥機を用いて、攪拌混合処理、水分除去処理を並行し
て施し、更に混練処理を行う態様を説明する。FIG. 1 schematically shows the structure of a preferred twin-screw rotary dryer. 1A is a schematic side view, and FIG. 1B is a cross-sectional view. Referring to FIG. 1, an embodiment will be described in which a stirring and mixing process and a water removing process are performed in parallel using a twin-screw rotary dryer, and a kneading process is further performed.
【0028】上記2軸回転式乾燥機は多数のパドル
(1)を固定した2本の回転軸(2)が設けられてお
り、モーター(3)によって回転する。この回転運動に
より、連続的に投入口(4)から供給される無溶媒樹脂
と樹脂乳化分散液とを、無溶媒樹脂のガラス転移点以上
の温度で、攪拌、混合しつつ、排出口(5)方向にこれ
らの樹脂を移動させる。The two-shaft rotary dryer has two rotating shafts (2) to which a number of paddles (1) are fixed, and is rotated by a motor (3). By this rotational movement, the solvent-free resin and the resin emulsified dispersion continuously supplied from the inlet (4) are stirred and mixed at a temperature equal to or higher than the glass transition point of the solvent-free resin, and the resin is discharged from the outlet (5). ) To move these resins.
【0029】上記パドル1及び回転軸は内部が中空とな
っており、入り口側ロータリージョイント(6)の熱媒
体入り口(7)から導入された熱媒体は、回転軸(2)
の中空部分を通り、パドル(1)の中空部分を経た後、
出口側ロータリージョイント(8)の熱媒体出口(9)
より排出される。更に、別系統の熱媒体は、胴体部熱媒
体入り口(10)より導入され、胴体部ジャケット(1
1)を通った後、胴体部熱媒体出口(12)より排出さ
れる。The paddle 1 and the rotary shaft are hollow inside, and the heat medium introduced from the heat medium inlet (7) of the inlet side rotary joint (6) is supplied to the rotary shaft (2).
After passing through the hollow part of the paddle (1),
Heat medium outlet (9) of outlet side rotary joint (8)
Is more exhausted. Further, the heat medium of another system is introduced from the body heat medium inlet (10), and the body jacket (1) is introduced.
After passing through 1), it is discharged from the body-portion heat medium outlet (12).
【0030】投入口(4)から供給される無溶媒樹脂と
樹脂乳化分散液は混合されながら胴体部を移動する過程
で、パドル表面及びジャケット表面と接触し、加熱され
て水分が蒸発する。加熱により蒸発した水分は、キャリ
ヤーガス入り口(13)より導入されたわずかな量のキ
ャリヤーガス(空気、不活性ガス等)により胴体内部の
上部を流れて蒸発口(14)より排出される。The solventless resin and the resin emulsified dispersion supplied from the charging port (4) come into contact with the paddle surface and the jacket surface during the movement of the body while being mixed, and are heated to evaporate water. Moisture evaporated by heating flows through the upper portion of the inside of the body by a small amount of carrier gas (air, inert gas, etc.) introduced from the carrier gas inlet (13), and is discharged from the evaporation port (14).
【0031】投入口(4)近辺では水分が多量に存在す
るため、混合物の温度は100〜110℃であるが、水分の減
少と共に混合物の温度は上昇し、最終的に混合物中の大
部分の水分が除去され、その後、好ましくは無溶媒樹脂
が溶融する温度で、混練処理が行われる。この混練処理
により、無溶媒樹脂と樹脂乳化分散液中の樹脂はより一
層均一に分散される。混練処理が行われる樹脂溶融領域
においても残留水分は蒸発して蒸発口(7)から排出さ
れる。又、必要に応じて乾燥機内を減圧にして処理する
ことができる。排出口(5)から得られた樹脂は目的と
する用途によって、更に連続的に他の装置に導入しペレ
ット状、パウダー状、フレーク状等に加工することもで
きる。The temperature of the mixture is 100 to 110 ° C. due to the presence of a large amount of water near the inlet (4). However, the temperature of the mixture increases as the amount of water decreases, and finally, most of the water in the mixture is mixed. After the water is removed, a kneading treatment is performed preferably at a temperature at which the solventless resin melts. By this kneading treatment, the solvent-free resin and the resin in the resin emulsified dispersion are more uniformly dispersed. Even in the resin melting region where the kneading process is performed, the residual moisture evaporates and is discharged from the evaporation port (7). Further, if necessary, the inside of the dryer can be treated under reduced pressure. The resin obtained from the discharge port (5) can be further continuously introduced into another device and processed into a pellet, powder, flake, or the like, depending on the intended use.
【0032】上記のような1軸回転式乾燥機を用いて攪
拌混合処理、水分除去処理及び混練処理を行う場合、ジ
ャケットの加熱温度、攪拌混合処理、水分除去処理及び
混練処理を行うための滞留時間、その他の条件等は、無
溶媒樹脂及び樹脂乳化分散液中の樹脂の種類、樹脂乳化
分散液の水分量、排出口(5)から得られる無溶媒樹脂
混合組成物の、意図する無溶媒樹脂と樹脂乳化分散液の
状態及び水分量、装置の処理能力、その他の要因によっ
て一概に述べることはできない。しかしながら当業者に
とって、上記の要因が特定されれば、理論的にかつ実験
的に、上記の諸条件を設定することは容易である。In the case of performing the stirring and mixing process, the water removing process and the kneading process by using the above-described single-shaft rotary dryer, the heating temperature of the jacket, the stirring and mixing process, the residence time for performing the water removing process and the kneading process, and the like. The time, other conditions, etc. are determined based on the types of the solvent-free resin and the resin in the resin emulsified dispersion, the water content of the resin emulsified dispersion, and the intended solvent-free resin mixed composition obtained from the outlet (5). It cannot be described in a general manner depending on the state and water content of the resin and the resin emulsified dispersion, the processing capacity of the apparatus, and other factors. However, if the above factors are specified, it is easy for those skilled in the art to set the above conditions theoretically and experimentally.
【0033】一般的には、加熱温度を上げる等の方法に
より水分除去速度を高めると、攪拌混合処理及び水分除
去処理を行う時間及び装置内の領域が短縮され、混練処
理を行う時間及び装置内の領域が拡大される。In general, when the moisture removal rate is increased by, for example, increasing the heating temperature, the time for performing the stirring and mixing process and the moisture removal process and the area within the device are shortened, and the time for performing the kneading process and the device. Is expanded.
【0034】無溶媒樹脂及び樹脂乳化分散液中の樹脂
が、例えばポリスチレン樹脂の場合、ジャケットの温度
を120〜300℃、好ましくは160〜250℃に設定し、投入口
4から排出口5までの滞留時間を、装置の混練能力、そ
の他の要因にもよるが、通常10〜90分、好ましくは15〜
60分となるように設定することができる。When the solvent-free resin and the resin in the resin emulsified dispersion are, for example, a polystyrene resin, the temperature of the jacket is set to 120 to 300 ° C., preferably 160 to 250 ° C. The residence time depends on the kneading capacity of the apparatus and other factors, but is usually 10 to 90 minutes, preferably 15 to 90 minutes.
Can be set to be 60 minutes.
【0035】上記装置の如き水分の蒸発口(14)を有
する装置においては、胴体上部に設けられている投入口
(4)と蒸発口(14)の開口面積の和が、胴体の長さ
と幅(各々図1のLとDに相当)の積の30〜50%の範囲
にあることが、水分除去処理を効率的に行う観点から、
好ましい。この場合ジャケットは胴体上部に存在せず、
胴体下部に設けられるか、ジャケットを設けずに回転軸
内あるいはパドル内に熱媒体を循環させる。In an apparatus having a water evaporation port (14) such as the above apparatus, the sum of the opening areas of the input port (4) and the evaporation port (14) provided in the upper part of the body is determined by the length and width of the body. (Each corresponding to L and D in FIG. 1) is in the range of 30 to 50% from the viewpoint of efficiently performing the water removal processing.
preferable. In this case, the jacket does not exist on the upper body,
The heat medium is circulated in the rotating shaft or the paddle provided at the lower part of the body or without a jacket.
【0036】本発明において、本発明の静電荷像現像用
トナーの結着樹脂の製造方法で混合される無溶媒樹脂と
は、フレーク状、粉体状、粒状、ブロック状、溶融状態
等の樹脂であって、水又は有機溶剤の含有率が10重量%
以下、好ましくは5重量%以下、特に好ましくは実質的
に水又は有機溶剤を含有しない樹脂を意味する。In the present invention, the solvent-free resin to be mixed in the method for producing a binder resin of the toner for developing an electrostatic image of the present invention refers to a resin in the form of flakes, powders, granules, blocks, melts, or the like. Wherein the content of water or organic solvent is 10% by weight
Below, preferably 5% by weight or less, particularly preferably a resin containing substantially no water or organic solvent.
【0037】本発明の静電荷像現像用トナーの結着樹脂
の製造において、上記無溶媒樹脂は、トナー結着樹脂中
の低分子量の重合体成分として使用することが好まし
い。In the production of the binder resin of the toner for developing an electrostatic image of the present invention, the solventless resin is preferably used as a low molecular weight polymer component in the toner binder resin.
【0038】上記トナー結着樹脂中の低分子量の重合体
成分として使用される無溶媒樹脂の分子量は、ゲルパー
ミエーションクロマトグラフィー(GPC)の測定チャ
ートにおける最大値を示す分子量(分子量ピーク)Mp
で表すと1,500〜30,000が好ま しく、更に好ましくは、
2,000〜20,000である。Mpが上記下限値未満であると
定着性は良好であるが、現像機中でトナ−が凝集し易く
現像剤の寿命が短い。又、トナ−の保存安定性が悪く、
高温保存時に固まる。又、Mpが上記上限値を越える
と、スペント化及び微細化は起きにくいが低温領域での
定着性は不良となり、定着下限温度が上昇し、かつコ−
ルド・オフセット温度も不良となり好ましくない。The molecular weight of the solvent-free resin used as the low-molecular-weight polymer component in the toner binder resin is the molecular weight (molecular weight peak) Mp showing the maximum value in a measurement chart of gel permeation chromatography (GPC).
When represented by 1,500 to 30,000 are preferred, and more preferably,
2,000 to 20,000. When Mp is less than the above lower limit, the fixability is good, but the toner easily aggregates in the developing machine and the life of the developer is short. Also, the storage stability of the toner is poor,
Hardens when stored at high temperatures. On the other hand, if Mp exceeds the above upper limit, spent and miniaturization hardly occur, but the fixability in a low temperature region becomes poor, the minimum fixing temperature rises, and
The offset / offset temperature is also poor, which is not preferable.
【0039】上記低分子量の重合体成分として使用され
る樹脂の重量平均分子量MWは、1,000〜200,000が好ま
しく、更に好ましくは1,000〜100,000;特に好ましくは
1,000〜40,000である。MWが上記下限値未満であると定
着性は良好であるが、現像機中でトナ−が凝集し易く現
像剤の寿命が短い。又、トナ−の保存安定性が悪く、高
温保存時に固まる。又、MWが上記上限値を越えると、
スペント化及び微細化は起きにくいが低温領域での定着
性は不良となり、定着下限温度が上昇し、かつコ−ルド
・オフセット温度も不良となり好ましくない。又、重量
平均分子量MWと数平均分子量MNとの比MW/MNが4未
満であることが好ましい。MW/MNが上記上限値以上で
あると定着性が不良となり好ましくない。The weight average molecular weight MW of the resin used as the low molecular weight polymer component is preferably from 1,000 to 200,000, more preferably from 1,000 to 100,000;
1,000 to 40,000. If the MW is less than the lower limit, the fixability is good, but the toner easily aggregates in the developing machine and the life of the developer is short. Further, the storage stability of the toner is poor, and the toner hardens during high-temperature storage. When MW exceeds the upper limit,
Spent formation and miniaturization are unlikely to occur, but the fixability in a low temperature region is poor, the minimum fixing temperature is increased, and the cold offset temperature is also poor. Further, the ratio MW / MN of the weight average molecular weight MW to the number average molecular weight MN is preferably less than 4. If MW / MN is higher than the above upper limit value, the fixing property becomes poor, which is not preferable.
【0040】上記無溶媒樹脂は、トナーの結着樹脂とし
て使用される樹脂であれば特に制限はなく、どのような
樹脂であっても良く、例えば、アクリル系樹脂、スチレ
ン系樹脂、エポキシ樹脂、ポリエステル樹脂、スチレン
ーブタジエン樹脂等が挙げられるが、トナーとしての性
能が得られやすい観点からスチレン系樹脂が好ましい。The solvent-free resin is not particularly limited as long as it is a resin used as a binder resin of the toner, and may be any resin, for example, an acrylic resin, a styrene resin, an epoxy resin, Examples thereof include a polyester resin and a styrene-butadiene resin, and a styrene-based resin is preferable from the viewpoint of easily obtaining performance as a toner.
【0041】上記スチレン系樹脂とはスチレン系単量体
を主成分とする(共)重合体であり、スチレン系単量体
の例としては、スチレン、o−メチルスチレン、m−メ
チルスチレン、p−メチルスチレン、α−メチルスチレ
ン、p−エチルスチレン、2,4−ジメチルスチレン、
p−n−ブチルスチレン、p−tert−ブチルスチレン、
p−n−ヘキシルスチレン、p−n−オクチルスチレ
ン、p−n−ノニルスチレン、p−n−デシルスチレ
ン、p−n−ドデシルスチレン、p−メトキシスチレ
ン、p−フェニルスチレン、p−クロルスチレン、3,
4−ジクロルスチレンなどを挙げることができるが、こ
のうちスチレンが最も好ましい。The styrene resin is a (co) polymer having a styrene monomer as a main component. Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene. -Methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
pn-butylstyrene, p-tert-butylstyrene,
p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, Three,
Examples thereof include 4-dichlorostyrene, and among them, styrene is most preferable.
【0042】上記スチレン系単量体と共重合することの
できる他の単量体としては、スチレン系単量体と共重合
が可能な単量体であれば特に制限はないが、アクリル系
単量体が好ましく、アクリル系単量体としては、例え
ば、アクリル酸メチル、アクリル酸エチル、アクリル酸
n−ブチル、アクリル酸イソブチル、アクリル酸エチル
ヘキシル、メタアクリル酸メチル、メタクリル酸エチ
ル、メタクリル酸nブチル、メタクリル酸イソブチル、
メタクリル酸ラウリル、メタクリル酸ステアリル等があ
り、特にアクリル酸nブチル、アクリル酸エチルヘキシ
ル、メタクリル酸n−ブチル、メタクリル酸ラウリル等
が挙げられる。このアクリル系成分は、前記スチレン系
成分のモノマ−と通常の条件下で重合せしめて得られる
共重合体のガラス転移温度が40〜80℃の範囲内にあるこ
とが好ましく、更に好ましくは、ガラス転移温度が50〜
70℃の範囲内にあることが好ましい。The other monomer that can be copolymerized with the styrene monomer is not particularly limited as long as it is a monomer that can be copolymerized with the styrene monomer. Is preferred. Examples of the acrylic monomer include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and nbutyl methacrylate. , Isobutyl methacrylate,
Examples thereof include lauryl methacrylate and stearyl methacrylate, and particularly include n-butyl acrylate, ethylhexyl acrylate, n-butyl methacrylate, and lauryl methacrylate. The acrylic component preferably has a glass transition temperature of a copolymer obtained by polymerizing the monomer of the styrene component with a monomer under ordinary conditions in the range of 40 to 80 ° C., more preferably glass. Transition temperature 50 ~
Preferably it is in the range of 70 ° C.
【0043】トナー結着樹脂中の低分子量の重合体成分
として使用される上記の無溶媒樹脂は、縮合重合、付加
重合、ビニル単量体の塊状重合等で直接塊状樹脂を得る
方法;樹脂溶液、樹脂乳化分散液等から溶媒を除去して
塊状樹脂を得る方法等が挙げられるが、ビニル単量体の
塊状重合による方法が好ましい。The above-mentioned solvent-free resin used as a low molecular weight polymer component in the toner binder resin may be obtained by a method of directly obtaining a bulk resin by condensation polymerization, addition polymerization, bulk polymerization of vinyl monomers, or the like; And a method in which a solvent is removed from a resin emulsified dispersion to obtain a bulk resin, and the like, and a method by bulk polymerization of a vinyl monomer is preferable.
【0044】上記塊状重合は、上記単量体と該単量体に
溶解する触媒とを共存せしめ、実質上溶剤や分散剤・乳
化剤等が存在しない原料混合物を重合温度に加熱するこ
とにより行うことができる。バッチ単位で重合しても、
又原料添加、重合及び重合体の取り出しを連続的に行っ
ても良いが、連続的に塊状重合を行い、直接前記着色剤
との混合装置に添加すると、効率的で好ましい。The above-mentioned bulk polymerization is carried out by coexisting the above-mentioned monomer and a catalyst which dissolves in the monomer, and heating a raw material mixture substantially free of solvents, dispersants, emulsifiers and the like to the polymerization temperature. Can be. Even when polymerizing in batch units,
Although the addition of raw materials, polymerization and removal of the polymer may be continuously performed, it is efficient and preferable to continuously perform bulk polymerization and directly add the mixture to the mixing device with the colorant.
【0045】上記塊状重合の重合温度は130〜250℃が好
ましく、更に好ましくは170〜250℃、特に好ましくは19
0〜230℃である。反応温度が上記下限の温度未満である
と反応速度が遅く、また得られた重合体の分子量ピーク
Mpが高くなり好ましくない。又、反応温度が上記上限
の温度を超えるとと重合反応と共に、重合体の分解反応
が起り、分子量500以下のオリゴマーが増大し、得られ
る樹脂を配合してトナーを作成すると、トナーの保存性
及びスペント化・微細化を起し易い。The polymerization temperature of the bulk polymerization is preferably 130 to 250 ° C., more preferably 170 to 250 ° C., and particularly preferably 19 to 250 ° C.
0-230 ° C. If the reaction temperature is lower than the lower limit, the reaction rate is low, and the molecular weight peak Mp of the obtained polymer is undesirably high. If the reaction temperature exceeds the above upper limit temperature, a polymerization reaction and a decomposition reaction of the polymer occur, and an oligomer having a molecular weight of 500 or less increases. In addition, it tends to cause spent and miniaturization.
【0046】塊状重合に使用される触媒は、任意の従来
の油溶性開始剤が使用できる。一群の適当な開始剤は、
ベンゾイルパーオキサイド、t-ブチルハイドロパーオキ
サイド、ジ-t-ブチルハイドロパーオキサイド、クメン
ハイドロパーオキサイド、t-ヘキシルハイドロパーオ
キサイド、p-メンタンハイドロパーオキサイド、ジ-ア
ゾビスイソブチロニトリルが挙げられる。特に反応温度
が170℃以上と高いため、好適な開始剤としては、t
-ブチルハイドロパーオキサイド、ジ-t-ブチルハイド
ロパーオキサイドが挙げられる。フリーラジカル開始剤
の使用量は、前記単量体の重量に基づいて、0〜5%の
量が好ましく、0.03%〜3%の量が更に好ましく、0.05
%〜1%の量が特に好ましい。As the catalyst used for the bulk polymerization, any conventional oil-soluble initiator can be used. A group of suitable initiators are
Benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, di-azobisisobutyronitrile . Particularly, since the reaction temperature is as high as 170 ° C. or higher, a preferable initiator is t
-Butyl hydroperoxide and di-t-butyl hydroperoxide. The amount of the free radical initiator used is preferably from 0 to 5%, more preferably from 0.03% to 3%, more preferably from 0.05 to 3%, based on the weight of the monomer.
% To 1% are particularly preferred.
【0047】上記の如くして得られるスチレン系低分子
量重合体は、転換率が90%以上、好ましくは95%以上、
更に好ましくは97%以上の転換率となる様に反応温度と
反応滞留時間を設置するのが好ましく、必要に応じて薄
膜蒸留装置などにより、残存単量体の回収を行うことが
できる。かくして得られる塊状重合低分子量重合体は特
にトナーの帯電性の保持性が高く又、臭気が少なく好ま
しい。The styrene type low molecular weight polymer obtained as described above has a conversion of 90% or more, preferably 95% or more,
More preferably, the reaction temperature and the reaction residence time are preferably set so as to obtain a conversion of 97% or more. If necessary, the residual monomer can be recovered by a thin film distillation apparatus or the like. The bulk polymerized low molecular weight polymer thus obtained is particularly preferred because it has a high toner chargeability and low odor.
【0048】本発明の静電荷像現像用トナーの結着樹脂
の製造において、前記樹脂乳化分散液中の樹脂は、トナ
ー結着樹脂中の高分子量重合体成分として使用され、前
記低分子量の重合体成分として使用される無溶媒樹脂と
組み合わせて使用されるのが好ましい。従って、樹脂乳
化分散液中の樹脂の重量平均分子量は、無溶媒樹脂のそ
れよりも大であることが好ましい。In the production of the binder resin of the toner for developing an electrostatic image of the present invention, the resin in the resin emulsified dispersion is used as a high molecular weight polymer component in the toner binder resin, and the low molecular weight polymer is used. It is preferably used in combination with a solventless resin used as a coalescing component. Therefore, the weight average molecular weight of the resin in the resin emulsified dispersion is preferably larger than that of the solventless resin.
【0049】トナー結着樹脂中の高分子量の重合体成分
として使用される樹脂乳化分散液中の樹脂の分子量は、
GPCの測定チャートにおける前記ピーク位置分子量M
pで表して、 300,000〜 3,000,000が好ましく、更に好
ましくは 500,000〜 2,000,000、特に好ましくは 600,0
00〜 1,000,000のものが使用される。上記Mpが上記下
限値未満であると定着性は良好であるがホット・オフセ
ットが発生しやすくなり定着可能温度幅が狭くなり好ま
しくない。更に上記高分子量の重合体成分として使用さ
れる上記樹脂の分子量は、重量平均分子量Mwで表すと
100,000以上が好ましく、更に好ましくは 200,000以
上、特に好ましくは 300,000以上である。又、必要に応
じて架橋構造を持たせることができる。The molecular weight of the resin in the resin emulsified dispersion used as the high molecular weight polymer component in the toner binder resin is as follows:
The peak position molecular weight M in the GPC measurement chart
p, preferably from 300,000 to 3,000,000, more preferably from 500,000 to 2,000,000, particularly preferably from 600,0
00-1,000,000 are used. If the Mp is less than the lower limit, the fixing property is good, but hot offset is apt to occur, and the fixing temperature range is undesirably narrow. Further, the molecular weight of the resin used as the high molecular weight polymer component is represented by a weight average molecular weight Mw.
It is preferably at least 100,000, more preferably at least 200,000, particularly preferably at least 300,000. Further, a cross-linked structure can be provided if necessary.
【0050】上記樹脂乳化分散液の樹脂の種類は前記ト
ナー結着樹脂中の低分子量の重合体成分として使用され
る樹脂と同一のものを挙げることができ、特にポリスチ
レン系樹脂が好ましい。The type of the resin in the resin emulsified dispersion may be the same as the resin used as the low molecular weight polymer component in the toner binder resin, and a polystyrene resin is particularly preferable.
【0051】上記樹脂乳化分散液は、樹脂が乳化状態に
分散されたものであって、樹脂が乳化状態に分散された
ものであれば特に制限はなく、いずれのものでも良い
が、例えば、樹脂を水中に強制乳化分散させた樹脂乳化
分散液、乳化重合で得られる樹脂乳化分散液等が挙げら
れるが、保存時及び無溶媒着色剤分散樹脂との混合時に
安定であるという観点から、乳化重合で得られた樹脂乳
化分散液が好ましい。さらには樹脂粒子が、樹脂自体の
持つ極性によって自己安定化した、乳化剤が使用されて
いない樹脂粒子であっても良い、The resin emulsified dispersion described above is not particularly limited as long as the resin is dispersed in an emulsified state and is not particularly limited as long as the resin is dispersed in an emulsified state. Emulsified dispersion in water, resin emulsified dispersion obtained by emulsion polymerization, and the like.Examples include emulsion polymerization from the viewpoint of stability during storage and mixing with a solventless colorant-dispersed resin. Is preferred. Furthermore, the resin particles may be resin particles that are self-stabilized by the polarity of the resin itself and that do not use an emulsifier.
【0052】樹脂乳化分散液を乳化重合で得るための乳
化重合の方法は、公知の乳化重合の方法を用いることが
できる。A known emulsion polymerization method can be used as the emulsion polymerization method for obtaining the resin emulsified dispersion by emulsion polymerization.
【0053】上記の如くし得られたペレット状、フレー
ク状等の混合樹脂組成物に、着色剤、必要に応じて帯電
制御剤、磁性体、離型剤等の添加剤を配合して均一に混
合溶融し、溶融混合物を冷却後必要に応じ粗砕した上ジ
ェットミル等で微粉砕のち、分級機で分級することによ
り、所望の粒子径の静電荷像現像用トナーを得ることが
できる。The mixed resin composition in the form of pellets or flakes obtained as described above is blended with additives such as a coloring agent and, if necessary, a charge controlling agent, a magnetic substance, and a release agent, to obtain a uniform mixture. After mixing and melting, the molten mixture is cooled, then finely crushed as necessary, finely crushed by a jet mill or the like, and then classified by a classifier, whereby a toner for developing an electrostatic charge image having a desired particle diameter can be obtained.
【0054】上記着色剤の使用量は混合樹脂組成物100
重量部に対して1〜200重量部が好ましく、3〜150重量
部が更に好ましい。上記着色剤としては、無機顔料、有
機顔料及び合成染料を挙げることができ、無機顔料また
は有機顔料が好ましく用いられ、また、一種若しくは二
種以上の顔料及び/または一種若しくは二種以上の染料
を組み合わせて用いることもできる。The amount of the coloring agent used is 100
The amount is preferably 1 to 200 parts by weight, more preferably 3 to 150 parts by weight with respect to parts by weight. Examples of the colorant include inorganic pigments, organic pigments, and synthetic dyes. Inorganic pigments or organic pigments are preferably used, and one or more pigments and / or one or more dyes may be used. They can be used in combination.
【0055】上記無機顔料としては、金属粉系顔料、金
属酸化物系顔料、カ−ボン系顔料、硫化物系顔料、クロ
ム酸塩系顔料、フェロシアン化塩系顔料を挙げることが
できる。Examples of the inorganic pigments include metal powder pigments, metal oxide pigments, carbon pigments, sulfide pigments, chromate pigments, and ferrocyanide pigments.
【0056】上記金属粉系顔料の例としては、例えば、
亜鉛粉、鉄粉、銅粉等を挙げることができる。上記金属
酸化物系顔料としては、例えば、マグネタイト、フェラ
イト、ベンガラ、酸化チタン、亜鉛華、シリカ、酸化ク
ロム、ウルトラマリ−ン、コバルトブル−、セルリアン
ブル−、ミラネルバイオレット、四酸化三鉛等を挙げる
ことができる。Examples of the metal powder pigments include, for example,
Zinc powder, iron powder, copper powder and the like can be mentioned. Examples of the metal oxide pigments include magnetite, ferrite, red iron oxide, titanium oxide, zinc white, silica, chromium oxide, ultramarine, cobalt blue, celerian blue, Milanel violet, and trilead tetroxide. Can be mentioned.
【0057】上記カ−ボン系顔料としては、例えば、カ
−ボンブラック、サ−マトミックカ−ボン、ファ−ネス
ブラック等を挙げることができる。上記硫化物系顔料と
しては、例えば、硫化亜鉛、カドミウムレッド、セレン
レッド、硫化水銀、カドミウムイエロ−等を挙げること
ができる。Examples of the above-mentioned carbon pigments include carbon black, thermoplastic carbon, furnace black and the like. Examples of the sulfide pigment include zinc sulfide, cadmium red, selenium red, mercury sulfide, and cadmium yellow.
【0058】上記クロム酸塩系顔料としては、例えば、
モリブデンレッド、バリウムイエロ−、ストロンチウム
イエロ−、クロムイエロ−等を挙げることができる。フ
ェロシアン化化合物系顔料としては、例えば、ミロリブ
ル−等を挙げることができる。The chromate pigments include, for example,
Molybdenum red, barium yellow, strontium yellow, chrome yellow and the like can be mentioned. Examples of the ferrocyan compound pigments include, for example, miroribble.
【0059】また、上記有機顔料としては、アゾ系顔
料、酸性染料系顔料及び塩基性染料系顔料、媒染染料系
顔料、フタロシアニン系顔料、並びにキナクドリン系顔
料及びジオキサン系顔料等を挙げることができる。上記
アゾ系顔料としては、例えば、ベンジジンイエロ−、ベ
ンジジンオレンジ、パ−マネントレッド4R、ピラゾロ
ンレッド、リソ−ルレッド、ブリリアントスカ−レット
G、ボンマル−ンライト等を挙げることができる。Examples of the organic pigment include azo pigments, acid dye pigments and basic dye pigments, mordant dye pigments, phthalocyanine pigments, quinacdrine pigments and dioxane pigments. Examples of the azo pigments include, for example, benzidine yellow, benzidine orange, permanent red 4R, pyrazolone red, lithol red, brilliant scarlet G, and bommarnlite.
【0060】上記酸性染料系顔料及び塩基性染料系顔料
としては、例えば、オレンジII、アシットオレンジR、
エオキシン、キノリンイエロ−、タ−トラジンイエロ
−、アシッドグリ−ン、ピ−コックブル−、アルカリブ
ル−等の染料を沈澱剤で沈澱させたもの、あるいはロ−
ダミン、マゼンタ、マカライトグリ−ン、メチルバイオ
レット、ビクトリアブル−等の染料をタンニン酸、吐酒
石、リンタングステン酸、リンモリブデン酸、リンタン
グステンモリブデン酸などで沈澱させたもの等を挙げる
ことができる。Examples of the acid dye-based pigment and the basic dye-based pigment include Orange II, Acid Orange R,
Dyes such as eoxin, quinoline yellow, tartrazine yellow, acid green, peak blue, alkali blue, etc., precipitated with a precipitant, or
Dyes such as damine, magenta, makalite green, methyl violet, and victoria blue are precipitated with tannic acid, tartarite, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, and the like. .
【0061】上記媒染染料系顔料としては、例えば、ヒ
ドロキシアントラキノン類の金属塩類、アリザリンマ−
ダ−レ−キ等を挙げることができる。上記フタロシアニ
ン系顔料としては、例えば、フタロシアニンブル−、ス
ルホン化銅フタロシアニン等を挙げることができる。上
記キナクリドン系顔料及びジオキサン系顔料としては、
例えば、キナクリドンレッド、キナクリドンバイオレッ
ト、カルバゾ−ルジオキサンバイオレット等を挙げるこ
とができる。Examples of the mordant dye-based pigments include metal salts of hydroxyanthraquinones and alizarinmer.
Drake and the like can be mentioned. Examples of the phthalocyanine pigment include phthalocyanine blue and sulfonated copper phthalocyanine. As the quinacridone pigment and dioxane pigment,
For example, quinacridone red, quinacridone violet, carbazole-dioxane violet and the like can be mentioned.
【0062】上記合成染料としては、アクリジン染料、
アニリン黒、アントラキノン染料、アジン染料、アゾ染
料、アゾメチン染料、ベンゾ及びナフトキノン染料、イ
ンジゴ染料、インドフェノール、インドアニリン、イン
ダミン、ロイコ建染メ染料エステル、ナフタールイミド
染料、ニグロシン、インジュリン、ニトロ及びニトロソ
染料、オキサジン及びジオキサジン染料、酸化染料、フ
タロシアニン染料、ポリメチン染料、キノフタロン染
料、硫化染料、トリ及びジアリルメタン染料、チアジン
染料、キサンテン染料等を挙げることができるが、好ま
しくは、アニリン黒、ニグロシン染料、アゾ染料が用い
られ、さらに好適なものとしては、アゾ染料のうち分子
中にサリチル酸、ナフトエ酸または8−オキシキノリン
残基を有し、クロム、銅、コバルト、鉄、アルミニウム
等の金属と錯塩を形成するものが用いられる。As the above synthetic dyes, acridine dyes,
Aniline black, anthraquinone dye, azine dye, azo dye, azomethine dye, benzo and naphthoquinone dye, indigo dye, indophenol, indoaniline, indamine, leuco vat dye ester, naphthalimide dye, nigrosine, indulin, nitro and nitroso dye, Oxazine and dioxazine dyes, oxidation dyes, phthalocyanine dyes, polymethine dyes, quinophthalone dyes, sulfur dyes, tri and diallyl methane dyes, thiazine dyes, xanthene dyes and the like can be mentioned, preferably aniline black, nigrosine dye, azo dye More preferably, among azo dyes, having a salicylic acid, naphthoic acid or 8-oxyquinoline residue in the molecule, forms a complex salt with a metal such as chromium, copper, cobalt, iron, and aluminum. Those that are used.
【0063】上記帯電制御剤としては、プラス用として
ニグロシン系の電子供与性染料、その他、ナフテン酸ま
たは高級脂肪酸の金属塩、アルコキシル化アミン、4級
アンモニウム塩、アルキルアミド、キレ−ト、顔料、フ
ッ素処理活性剤等を挙げることができ、また、マイナス
用として電子受容性の有機金属錯体、キレート化合物そ
の他、塩素化パラフィン、塩素化ポリエステル、酸基過
剰のポリエステル、銅フタロシアニンのスルホニルアミ
ン等を挙げることができる。Examples of the charge control agent include a nigrosine-based electron-donating dye for plus, a metal salt of naphthenic acid or a higher fatty acid, an alkoxylated amine, a quaternary ammonium salt, an alkylamide, a chelate, a pigment, and the like. Fluorinated activators and the like can be mentioned, and for minus, electron-accepting organometallic complexes, chelate compounds and the like, chlorinated paraffins, chlorinated polyesters, polyesters with excess acid groups, sulfonylamines of copper phthalocyanine, etc. be able to.
【0064】上記離型剤としてはパラフィンワックス及
びその誘導体、マイクロクリスタリンワックス及びその
誘導体、フィッシャートロプシュワックス及びその誘導
体、ポリオレフィンワックス及びその誘導体、カルナバ
ワックス及びその誘導体等が挙げられる。誘導体は、酸
化物、ビニル系モノマーとのブロック共重合体、ビニル
系モノマーとのグラフト変成物も含む。Examples of the release agent include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, and the like. The derivatives also include oxides, block copolymers with vinyl monomers, and graft modified products with vinyl monomers.
【0065】その他、アルコール、脂肪酸、酸アミド、
エステル、ケトン、硬化ひまし油及びその誘導体、植物
系ワックス、動物系ワックス、鉱物系ワックス、ペトロ
ラクタムも利用できる。In addition, alcohols, fatty acids, acid amides,
Esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, and petrolactam can also be used.
【0066】上記トナーに更に流動性向上剤を添加して
用いてもよい。流動性向上剤としては、トナー粒子に添
加することにより、流動性が添加前後を比較すると増加
しうるものであれば、使用可能である。例えば、疎水性
コロイダルシリカ微粉体、コロイダルシリカ微粉体、疎
水性酸化チタン微粉体、酸化チタン微粉体、疎水性アル
ミナ微粉体、アルミナ微粉体、それらの混合粉体等が挙
げられる。A fluidity improver may be further added to the above toner. Any fluidity improver can be used as long as it can be added to toner particles to increase the fluidity before and after the addition. Examples thereof include hydrophobic colloidal silica fine powder, colloidal silica fine powder, hydrophobic titanium oxide fine powder, titanium oxide fine powder, hydrophobic alumina fine powder, alumina fine powder, and a mixed powder thereof.
【0067】上記の如くして製造されたトナーは、鉄粉
或いはガラスビ−ズなどより成るキャリアが前記トナ−
に混合されたいわゆる二成分系現像剤を用いる現像法に
おいて、樹脂被覆層を有するキャリアを使用する現像剤
に好適に用いられる。更に、二成分系現像剤のみに限定
するものではなく、キャリアを用いない一成分系現像
剤、例えばトナ−中に磁性粉を含有した磁性一成分トナ
−、トナ−中に磁性粉を含有しない非磁性一成分トナ−
についても適用できる。In the toner produced as described above, the carrier made of iron powder or glass beads is used as the toner.
In a developing method using a so-called two-component developer mixed with the above, it is suitably used for a developer using a carrier having a resin coating layer. Further, the present invention is not limited to the two-component developer alone, and is not limited to a one-component developer using a carrier, for example, a magnetic one-component toner containing a magnetic powder in the toner, and no magnetic powder in the toner. Non-magnetic one-component toner
Is also applicable.
【0068】樹脂被覆層を有するキャリアとしては、一
般に鉄、ニッケル、フエライト、ガラスビ−ズより成る
核体粒子の表面を絶縁性樹脂の被覆層により被覆したキ
ャリアが代表的なものであり、絶縁性樹脂材料として
は、一般にフッ素樹脂、シリコン樹脂、アクリル樹脂、
スチレンアクリル共重合樹脂、ポリエステル樹脂、ポリ
ブタジエン樹脂が代表的なものとして挙げられる。本発
明により得られる静電荷像現像用トナ−と樹脂被覆層を
有するキャリアとを成分とする現像剤を用いた場合、キ
ャリア粒子の表面にトナ−粒子が付着して汚染されるス
ペントが著しく少ない、キャリアとトナ−の摩擦帯電特
性を制御することが可能であり、耐久性に優れ使用寿命
が長い点で特に高速の電子写真機に好適である。また、
本発明の製造方法により得られる結着樹脂以外に他のス
チレン系樹脂、ポリエステル系樹脂等の結着樹脂を補助
的にブレンドして使用してもよいが、全結着樹脂中に補
助的に用いられる上記結着樹脂が占める割合は30重量
%以下が好ましい。As a carrier having a resin coating layer, a carrier in which the surface of core particles made of iron, nickel, ferrite, and glass beads are generally coated with a coating layer of an insulating resin is typical. As a resin material, generally, a fluorine resin, a silicone resin, an acrylic resin,
Styrene acrylic copolymer resin, polyester resin and polybutadiene resin are typical examples. When a developer containing the toner for developing an electrostatic charge image obtained by the present invention and a carrier having a resin coating layer as components is used, the spent particles which adhere to the toner particles on the surface of the carrier particles and are contaminated are extremely small. It is possible to control the triboelectric charging characteristics of the carrier and the toner, and is particularly suitable for a high-speed electrophotographic machine in that it has excellent durability and a long service life. Also,
In addition to the binder resin obtained by the production method of the present invention, other styrene-based resins, a binder resin such as a polyester-based resin may be used as an auxiliary blend, but may be used as an auxiliary in all the binder resins. The proportion occupied by the binder resin used is preferably 30% by weight or less.
【0069】更に、本発明の製造方法により静電荷像現
像用トナー用結着樹脂を製造する際に、無溶媒樹脂及び
樹脂乳化分散液と共に、上記の各種添加剤を配合して、
直接トナーを製造することもできる。Further, when the binder resin for a toner for developing an electrostatic charge image is produced by the production method of the present invention, the above-mentioned various additives are blended together with the solventless resin and the resin emulsified dispersion.
The toner can also be directly manufactured.
【0070】以下、本発明を実施例、比較例により具体
的に説明する。Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
【実施例】以下の実施例で使用する各試験方法を以下に
説明する。 〔残存単量体測定法〕無溶媒樹脂混合組成物中の各単量
体の残存単量体量は、ガスクロマトグラフィー(GC)
に、カラム(25%Thermon1000)を装着した装置を用い
て、試料をクロロホルムに2.5wt%の濃度で溶解し、濾
過した抽出液を3μl注入して測定を行った。なお、試
料の濃度測定に際しては、各単量体の検量線より算出し
た。EXAMPLES Each test method used in the following examples is described below. [Residual monomer measurement method] The residual monomer amount of each monomer in the solvent-free resin mixture composition was determined by gas chromatography (GC).
Then, using a device equipped with a column (25% Thermon1000), the sample was dissolved in chloroform at a concentration of 2.5 wt%, and 3 μl of the filtered extract was injected, followed by measurement. In measuring the concentration of the sample, the concentration was calculated from the calibration curve of each monomer.
【0071】〔分子量測定法〕各種樹脂の分子量分布測
定は、ゲルバーミエーションクロマトグラフィー(GP
C)に、カラム(東ソー(株)製:GMH×3本)を装
着した装置を用いて、試料をテトラヒドロフラン(TH
F)の0.2wt%の濃度で溶解し、温度20℃ において1ml
/minの流速で測定を行った。なお、試料の分子量測定
に際しては、該試料の有する分子量が、数種の単分散ポ
リスチレン標準試料により作成された検量線の分子量の
対数とカウント数が直線となる範囲内に包含される測定
条件を選択した。[Molecular Weight Measurement Method] The molecular weight distribution of various resins was measured by gel permeation chromatography (GP).
C), and using a device equipped with a column (manufactured by Tosoh Corporation: GMH × 3), the sample was treated with tetrahydrofuran (TH
F) at a concentration of 0.2 wt%, and at a temperature of 20 ° C., 1 ml
The measurement was performed at a flow rate of / min. When measuring the molecular weight of a sample, a measurement condition in which the molecular weight of the sample is included in a range in which the logarithm of the molecular weight and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples are linear is used. Selected.
【0072】〔粒子径測定法〕エマルジョンの粒子径測
定は、光散乱(日機装(株)製マイクロトラック)2よ
り測定した。[Particle Size Measurement Method] The particle size of the emulsion was measured by light scattering (Microtrack, manufactured by Nikkiso Co., Ltd.) 2.
【0073】実施例1 (無溶媒樹脂の調整)210℃にコントロールされた攪拌
機、加熱装置、冷却装置、温度計及び滴下ポンプを備え
たオートクレーブ中に、スチレン100重量部とジ・ター
シャリー・ブチル・パーオキサイド0.5重量部とを均一
に混合した単量体混合液を30分で連続添加し、更に温度
210℃に保った状態で、30分保持し、残存モノマーを除
去して、無溶媒樹脂を得た。得られた無溶媒樹脂は、分
子量ピークMpが4,500で重量平均分子量Mwが5,100で
あった。Example 1 (Preparation of solvent-free resin) 100 parts by weight of styrene and di-tert-butyl were placed in an autoclave equipped with a stirrer controlled at 210 ° C, a heating device, a cooling device, a thermometer and a dropping pump.・ Continuously add a monomer mixture obtained by uniformly mixing 0.5 part by weight of peroxide and 30 minutes.
While maintaining the temperature at 210 ° C., the temperature was maintained for 30 minutes to remove the residual monomer, thereby obtaining a solventless resin. The obtained solvent-free resin had a molecular weight peak Mp of 4,500 and a weight average molecular weight Mw of 5,100.
【0074】(樹脂乳化分散液の調整)攪拌機と滴下ポ
ンプを備えた容器に、脱イオン水27重量部及びアニオン
性乳化剤(花王(株)製:商品名ネオゲンR)1重量部
を仕込み、攪拌溶解した後、スチレン75重量部、アクリ
ル酸ブチル25重量部、ジビニルベンゼン0.05重量部から
なる単量体混合液を攪拌滴下し、単量体乳化分散液を得
た。(Preparation of Resin Emulsion Dispersion) In a container equipped with a stirrer and a dropping pump, 27 parts by weight of deionized water and 1 part by weight of an anionic emulsifier (manufactured by Kao Corporation, trade name: Neogen R) were charged and stirred. After dissolution, a monomer mixture composed of 75 parts by weight of styrene, 25 parts by weight of butyl acrylate, and 0.05 parts by weight of divinylbenzene was added dropwise with stirring to obtain a monomer emulsified dispersion.
【0075】次に、攪拌機、圧力計、温度計及び滴下ポ
ンプを備えた耐圧反応容器に、脱イオン水120重量部を
仕込み、窒素置換した後、80℃に昇温し、上記単量体乳
化分散液の5重量%を耐圧反応容器へ添加し、さらに、
2重量%過硫酸カリウム水溶液1重量部を添加し、80℃
で初期重合を行った。初期重合終了後、85℃に昇温して
残りの単量体乳化分散液及び2重量%過硫酸カリウム4
重量部を3時間で添加し、その後、同温度にて2時間保
持し、粒子径0.15μm固形分濃度40%のスチレン系樹脂
乳化分散液を得た。Next, 120 parts by weight of deionized water was charged into a pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, and a dropping pump, and after purging with nitrogen, the temperature was raised to 80 ° C. 5% by weight of the dispersion is added to the pressure-resistant reaction vessel,
Add 1 part by weight of 2% by weight aqueous potassium persulfate solution,
Was used to carry out the initial polymerization. After completion of the initial polymerization, the temperature was raised to 85 ° C., and the remaining monomer emulsified dispersion and 2% by weight potassium persulfate 4
Parts by weight were added in 3 hours and then kept at the same temperature for 2 hours to obtain a styrene resin emulsified dispersion having a particle diameter of 0.15 μm and a solid concentration of 40%.
【0076】得られた樹脂乳化分散液は重合転換率も高
く、安定に重合可能であった。樹脂乳化分散液を超遠心
分離器で、樹脂を分離後、分子量を分析した結果、重量
平均分子量Mwは950,000、分子量ピークMpは700,000
であった。The resulting resin emulsified dispersion had a high polymerization conversion rate and could be polymerized stably. The resin emulsified dispersion was separated by an ultracentrifuge to separate the resin, and the molecular weight was analyzed. As a result, the weight average molecular weight Mw was 950,000, and the molecular weight peak Mp was 700,000.
Met.
【0077】(無溶媒樹脂混合組成物の調製)210℃に
溶融した上記無溶媒の樹脂100重量部と上記樹脂乳化分
散液135重量部とを図1に示した(株)奈良機械製の
「パドルドライヤー」(空隙率:約70%)を用いジャ
ケット温度200℃にて、連続的に混合操作、加熱して水
分を蒸発による除去処理及び混練操作を20分間行い、水
分が0.1重量%以下の、均一に混合された無溶媒樹脂混
合組成物を得た。得られた無溶媒樹脂混合組成物の残存
単量体は100ppmであった。(Preparation of Solvent-Free Resin Mixed Composition) 100 parts by weight of the solvent-free resin melted at 210 ° C. and 135 parts by weight of the resin emulsified dispersion shown in FIG. Using a “paddle dryer” (porosity: about 70%), the jacket is continuously heated at a temperature of 200 ° C. by mixing and heating to remove water by evaporation and kneading for 20 minutes. And a solventless resin-mixed composition uniformly mixed were obtained. The residual monomer in the obtained solvent-free resin mixed composition was 100 ppm.
【0078】(トナーの調製)上記無溶媒樹脂混合組成
物100重量部、カーボンブラック(三菱化学(株)製:
商品名カーボンブラックMA-100)6重量部、ポリプロピ
レンワックス(三洋化成(株)製:商品名ビスコール55
0P)2重量部、ニグロシン染料(オリエント化学(株)
製:商品名ボントロンN-01)2重量部をボールミルで粉
砕混合した後、140℃の熱ロールで30分間よく混練し
た。冷却後、ハンマーミルで粗砕し、次いでジェットミ
ルで微粉砕を行った。更に得られた微粉砕粉体を風力分
級機にて分級を行い5〜20μmの粒子を得た後、疎水性
シリカ(日本エアロジル(株)製:商品名R-972 )0.2
重量部を加えて混合し、平均粒子径10μmのトナーを得
た。(Preparation of Toner) 100 parts by weight of the solventless resin mixture composition, carbon black (manufactured by Mitsubishi Chemical Corporation):
6 parts by weight of carbon black MA-100 (trade name), polypropylene wax (manufactured by Sanyo Chemical Co., Ltd .: Viscol 55 trade name)
0P) 2 parts by weight, Nigrosine dye (Orient Chemical Co., Ltd.)
(Trade name: Bontron N-01) 2 parts by weight were pulverized and mixed by a ball mill, and then kneaded well with a hot roll at 140 ° C. for 30 minutes. After cooling, the mixture was roughly crushed by a hammer mill and then finely crushed by a jet mill. Further, the obtained finely pulverized powder was classified with an air classifier to obtain particles of 5 to 20 μm, and then hydrophobic silica (trade name: R-972, manufactured by Nippon Aerosil Co., Ltd.) 0.2
Parts by weight were added and mixed to obtain a toner having an average particle diameter of 10 μm.
【0079】上記トナーとシリコン樹脂被覆キャリアを
用いて複写機で複写試験を行ったところ、画像の定着は
140℃から可能となり225℃においても加熱定着ロールへ
のトナーのオフセットによる汚れはなく100,000枚の複
写後もキャリアへのトナー・スペントがなく初期と同
様、汚れカブリのない鮮明な画像が得られた。When a copying test was performed with a copying machine using the above toner and the silicone resin-coated carrier, the image was fixed.
It became possible from 140 ° C, and even at 225 ° C, there was no stain due to offset of the toner on the heat fixing roll, and after copying 100,000 sheets, there was no toner spent on the carrier, and a clear image with no stain fog was obtained as in the initial stage. .
【0080】実施例2 (無溶媒の樹脂の調整)単量体混合物として、スチレン
87重量部、アクリル酸ブチル13重量部及びジ・ターシャ
リ・ブチル・パーオキサイド0.1重量部を均一に混合し
た単量体混合液、反応温度を200℃、添加時間を30分と
する以外は実施例1と同様にして重合を行った。得られ
た無溶媒の樹脂の分子量ピークは10,000、重量平均分子
量は13,000であった。Example 2 (Preparation of solvent-free resin) As a monomer mixture, styrene was used.
Example 1 except that 87 parts by weight, 13 parts by weight of butyl acrylate and 0.1 part by weight of di-tert-butyl peroxide were mixed uniformly, the reaction temperature was 200 ° C., and the addition time was 30 minutes. Polymerization was carried out in the same manner as in Example 1. The molecular weight peak of the obtained solvent-free resin was 10,000, and the weight average molecular weight was 13,000.
【0081】(樹脂乳化分散液の調整)単量体混合物を
スチレン70量部、アクリル酸ブチル20重量部、メタアク
リル酸ブチル10重量部及び1−6ヘキサンジオール・ジ
アクリレート0.1重量部の単量体混合物を使用し、乳化
剤をネオゲンR(花王(株)製)1.2重量部とした以外
は、実施例1と同様にして重合を行い、重量平均分子量
(MW)850,000、分子量ピーク(Mp)650,000、粒子
径0.1μm、固形分濃度40%のスチレン系重合体樹脂乳化
分散液を得た。(Preparation of Resin Emulsion Dispersion) A monomer mixture of 70 parts by weight of styrene, 20 parts by weight of butyl acrylate, 10 parts by weight of butyl methacrylate, and 0.1 part by weight of 1-6 hexanediol / diacrylate Polymerization was carried out in the same manner as in Example 1 except that the emulsifier was changed to Neogen R (manufactured by Kao Corporation) at 1.2 parts by weight, and the weight average molecular weight (MW) was 850,000 and the molecular weight peak (Mp) was 650,000. A styrene polymer resin emulsified dispersion having a particle diameter of 0.1 μm and a solid content of 40% was obtained.
【0082】(無溶媒樹脂混合組成物の調整)200℃に
溶融した上記無溶媒の樹脂100重量部と上記樹脂乳化分
散液107重量部とを実施例1と同様に処理し、無溶媒樹
脂混合組成物を得た。得られた無溶媒樹脂混合組成物の
残存単量体は110ppmであった。 (トナーの調整)実施例1と同様に上記無溶媒樹脂混合
樹脂を用いてトナーを得、同様の複写試験を行ったとこ
ろ、画像の定着は140℃より可能となり、225℃において
もオフセットによる汚れはなく、100,000枚の複写後も
初期と同様汚れかぶりのない鮮明な画像が得られた。(Preparation of Solventless Resin Mixed Composition) 100 parts by weight of the solventless resin melted at 200 ° C. and 107 parts by weight of the resin emulsified dispersion were treated in the same manner as in Example 1, and the solventless resin mixed was prepared. A composition was obtained. The residual monomer in the obtained solvent-free resin mixture composition was 110 ppm. (Adjustment of Toner) Toner was obtained using the solventless resin-mixed resin in the same manner as in Example 1, and a similar copy test was performed. As a result, the image could be fixed at 140 ° C. No clear image was obtained after 100,000 copies, as in the initial case.
【0083】実施例3 (無溶媒樹脂混合組成物の調整)210℃に溶融した実施
例1で調整した無溶媒の樹脂100重量部と実施例1で調
整した樹脂乳化分散液135重量部とをLIST社製の
「DISCOTHERM」(空隙率:約80%)でジャ
ケット温度200℃にて、混合処理及び加熱して水分除去
処理し、水分が0.1重量%以下の、均一に相溶分散した
無溶媒樹脂混合組成物を得た。得られた混合樹脂組成物
の残存単量体は200ppmであった。実施例1と同様に上記
混合樹脂を用いてトナーを得、同様の複写試験を行った
ところ、画像の定着は150℃より可能となり、220℃にお
いてもオフセットによる汚れはなく、50,000枚の複写後
も初期と同様汚れかぶりのない鮮明な画像が得られた。Example 3 (Preparation of Solvent-Free Resin Mixed Composition) 100 parts by weight of the solvent-free resin prepared in Example 1 melted at 210 ° C. and 135 parts by weight of the resin emulsified dispersion prepared in Example 1 LIST's "DISCOTHERM" (porosity: about 80%), at a jacket temperature of 200 ° C, mixed and heated to remove water, and has a water content of 0.1% by weight or less and is uniformly compatible and dispersed without solvent. A resin mixture composition was obtained. The residual monomer in the obtained mixed resin composition was 200 ppm. A toner was obtained using the above-mentioned resin mixture in the same manner as in Example 1, and the same copy test was performed. As a result, the image could be fixed at 150 ° C., and there was no stain due to offset even at 220 ° C. In the same manner as in the initial stage, a clear image with no fog was obtained.
【0084】比較例1 (懸濁重合分散液の調製)撹拌機と滴下ポンプを備えた
容器に、脱イオン水200重量部及びポリビニルアルコー
ル〔(株)クラレ製:商品名PVA117〕1重量部を仕込
み、撹拌溶解した後、スチレン75重量部、アクリル酸ブ
チル25重量部、ジ−t−ブチルパーオキシヘキサヒドロ
テレフタレート(日本化薬(株)製:商品名カヤエステ
ルHTP)0.15重量部からなる単量体混合液を添加し
た。撹拌下に単量体混合物を分散しつつ、90℃で5時間
重合し、懸濁重合樹脂分散液を得た。次に、上記懸濁重
合樹脂分散液からスチレン・アクリル酸ブチル共重合樹
脂を分離した後、乾燥して該共重合樹脂を得た。得られ
た上記共重合樹脂の平均粒子径は250μmであり、重量
平均分子量Mwは 690,000、ピーク位置分子量Mpは 5
50,000であった。Comparative Example 1 (Preparation of Suspension Polymerization Dispersion) In a vessel equipped with a stirrer and a dropping pump, 200 parts by weight of deionized water and 1 part by weight of polyvinyl alcohol [manufactured by Kuraray Co., Ltd., trade name: PVA117] were placed. After charging and stirring and dissolving, 75 parts by weight of styrene, 25 parts by weight of butyl acrylate, and 0.15 part by weight of di-t-butylperoxyhexahydroterephthalate (trade name: Kayaester HTP, manufactured by Nippon Kayaku Co., Ltd.) A monomer mixture was added. Polymerization was conducted at 90 ° C. for 5 hours while dispersing the monomer mixture under stirring to obtain a suspension polymerization resin dispersion. Next, a styrene / butyl acrylate copolymer resin was separated from the suspension polymer resin dispersion and dried to obtain the copolymer resin. The average particle diameter of the obtained copolymer resin was 250 μm, the weight average molecular weight Mw was 690,000, and the peak position molecular weight Mp was 5 μm.
It was 50,000.
【0085】(無溶媒樹脂混合組成物の調製)配合する
樹脂として、実施例1の無溶媒樹脂100重量部と上記懸
濁重合して得られた樹脂重量52重量部を使用する以外
は、実施例1の無溶媒樹脂混合組成物の調製と全く同様
にして無溶媒樹脂混合組成物の調製を行った。(Preparation of Solvent-Free Resin Mixed Composition) The procedure was the same as in Example 1 except that 100 parts by weight of the solvent-free resin of Example 1 and 52 parts by weight of the resin obtained by the above suspension polymerization were used. A solventless resin mixture composition was prepared in exactly the same manner as in the preparation of the solventless resin mixture composition of Example 1.
【0086】(トナーの調製)上記無溶媒樹脂混合組成
物を結着樹脂として100重量部使用する以外は実施例1
と同様にしてトナーの調整を行った。平均粒子径10μm
のトナーを得、同様の複写試験を行ったところ、画像の
定着は加熱ロールへのオフセットが激しく、又画質のカ
ブリの多いものであった。(Preparation of Toner) Example 1 was repeated except that 100 parts by weight of the solventless resin mixture composition was used as a binder resin.
The toner was adjusted in the same manner as described above. Average particle size 10μm
The toner was obtained and the same copying test was carried out. As a result, it was found that the fixing of the image was severely offset to the heating roll, and that the image was fogged.
【0087】[0087]
【発明の効果】本発明の静電荷像現像用トナー用結着樹
脂の製造方法は、樹脂乳化分散液と無溶媒樹脂とを共存
せしめ、パドルを固定した回転軸を胴体内部に有し、そ
の空隙率が50%以上である回転式乾燥機により、混合処
理を施し、並行して又はその後に水分除去処理を施して
無溶媒樹脂混合組成物を製造する工程を含む事を特徴と
するものである。According to the method for producing a binder resin for a toner for developing an electrostatic image of the present invention, a resin emulsified dispersion and a non-solvent resin are allowed to coexist, and a rotary shaft having a paddle fixed therein is provided inside the body. It is characterized by including a step of producing a solvent-free resin mixed composition by performing a mixing treatment by a rotary dryer having a porosity of 50% or more and performing a water removal treatment in parallel or thereafter. is there.
【0088】本発明によれば、無溶媒樹脂及び樹脂乳化
分散液から均一に混合された無溶媒樹脂混合組成物を製
造後、粉砕することにより静電荷像現像用トナー用結着
樹脂を効率的に、且つ安価に製造することができる。ま
た、本発明の製造方法により得られた静電荷像現像用ト
ナー用結着樹脂使用してトナーを製造すると、低分子量
重合体、高分子量重合体及び着色剤が、均一に相溶分散
した、非オフセット性、定着性、製造時の粉砕性、保存
時の耐ブロッキング性(非凝集性)、像形成時の現像性
等において良好であり、臭気の少ない静電荷像現像トナ
ーを製造することができる。According to the present invention, a solventless resin-mixed composition uniformly mixed from a solventless resin and a resin emulsified dispersion is produced and then pulverized to efficiently produce a binder resin for a toner for developing an electrostatic image. And can be manufactured at low cost. Further, when a toner is produced using the binder resin for electrostatic charge image developing toner obtained by the production method of the present invention, the low molecular weight polymer, the high molecular weight polymer and the colorant are uniformly compatible and dispersed. It has good non-offset properties, fixing properties, pulverizability during production, anti-blocking properties during storage (non-agglomeration), developability during image formation, etc., and can produce an electrostatic image developing toner with little odor. it can.
【図面の簡単な説明】[Brief description of the drawings]
【図1】無溶媒樹脂と樹脂乳化分散液とを共存せしめ、
混合処理及び水分除去処理を施すのに好ましい2軸回転
式乾燥機であり、(イ)はその側面図であり、(ロ)は
その断面図である。FIG. 1 shows the coexistence of a solventless resin and a resin emulsified dispersion,
This is a preferred twin-screw rotary dryer for performing a mixing process and a water removing process, wherein (a) is a side view and (b) is a cross-sectional view.
1.パドル 2.回転軸 3.モーター 4.材料の投入口 5.混合生成物の排出口 6.入り口側ロータリージョイント 7.ロータリージョイントの熱媒体入り口 8.出口側ロータリージョイント 9.ロータリージョイントの熱媒体出口 10.胴体部熱媒体入り口 11.胴体部ジャケット 12.胴体部熱媒体出口 13.キャリヤーガス入り口 14.蒸発口 15.上部カバー 16.軸受けブラケット 1. Paddle 2. Rotation axis 3. Motor 4. 4. Material input port 5. outlet for mixed product Entrance side rotary joint 7. 7. Heat medium inlet of rotary joint Outlet side rotary joint 9. 9. Heat medium outlet of rotary joint 10. Body heat medium inlet Torso jacket 12. Body part heat medium outlet 13. 13. Carrier gas inlet Evaporation port 15. Top cover 16. Bearing bracket
Claims (9)
せしめ、パドルを固定した回転軸を胴体内部に有し、そ
の空隙率が50%以上である回転式乾燥機により、混合
処理を施し、並行して又はその後に水分除去処理を施し
て無溶媒樹脂混合組成物を製造する工程を含む事を特徴
とするトナー用結着樹脂の製造方法。1. A resin emulsified dispersion and a non-solvent resin are allowed to coexist, and a mixing process is performed by a rotary drier having a rotating shaft having a paddle fixed inside the body and having a porosity of 50% or more. A method of producing a solvent-free resin mixture composition by performing a water removal treatment in parallel or thereafter, thereby producing a binder resin for toner.
が10分以上である請求項1に記載のトナー用結着樹脂の
製造方法。2. The method for producing a binder resin for a toner according to claim 1, wherein the time of the mixing treatment and the water removing treatment is 10 minutes or more.
転式乾燥機である請求項1又は2のいずれかに記載のト
ナー用結着樹脂の製造方法。3. The method for producing a binder resin for a toner according to claim 1, wherein the rotary dryer is a single-axis or two-axis rotary dryer.
重合体である請求項1〜3のいずれかに記載のトナー用
結着樹脂の製造方法。4. The method for producing a binder resin for a toner according to claim 1, wherein the solventless resin is a polymer obtained by bulk polymerization.
れる請求項1〜4のいずれかに記載のトナー用結着樹脂
の製造方法。5. The method according to claim 1, wherein the emulsified resin dispersion is obtained by emulsion polymerization.
0,000以下のスチレン系樹脂であり、上記樹脂乳化分散
液中の樹脂の重量平均分子量が50,000以上であるスチレ
ン系樹脂である請求項1〜5に記載のトナー用結着樹脂
の製造方法。6. The solvent-free resin having a weight average molecular weight of 20
The method for producing a binder resin for a toner according to any one of claims 1 to 5, wherein the resin is a styrene resin having a weight average molecular weight of 50,000 or more in the resin emulsified dispersion of not more than 000.
Mpが1,500〜30,000で且つその重量平均分子量(M
w)/数平均分子量(Mn)が4.0未満であり、上記樹
脂乳化分散液中の樹脂のGPC分子量ピーク(Mp)が
300,000〜3,000,000である請求項1〜6のいずれかに記
載のトナー用結着樹脂の製造方法。7. The solvent-free resin having a GPC molecular weight peak Mp of 1,500 to 30,000 and a weight average molecular weight (M
w) / number average molecular weight (Mn) is less than 4.0, and the GPC molecular weight peak (Mp) of the resin in the resin emulsified dispersion is
The method for producing a binder resin for a toner according to any one of claims 1 to 6, wherein the amount is from 300,000 to 3,000,000.
せしめ、パドルを固定した回転軸を胴体内部に有し、そ
の空隙率が50%以上である回転式乾燥機により、混合処
理を施し、並行して又はその後に水分除去処理を施して
無溶媒樹脂混合組成物を製造する工程を経て得られたト
ナー用結着樹脂と顔料とを含有する静電荷像現像用トナ
ー。8. A resin emulsified dispersion and a non-solvent resin are allowed to coexist, and a mixing process is performed by a rotary dryer having a rotary shaft having a paddle fixed inside the body and having a porosity of 50% or more. A toner for developing an electrostatic image, comprising a binder resin for a toner and a pigment obtained through a step of producing a solventless resin mixture composition by performing a water removal treatment in parallel or thereafter.
Mpが1,500〜30,000で且つその重量平均分子量(M
w)/数平均分子量(Mn)が4.0未満であり、上記樹
脂乳化分散液中の樹脂のGPC分子量ピーク(Mp)が
300,000〜3,000,000である請求項8に記載の静電荷像現
像用トナー。9. The solvent-free resin having a GPC molecular weight peak Mp of 1,500 to 30,000 and a weight average molecular weight (M
w) / number average molecular weight (Mn) is less than 4.0, and the GPC molecular weight peak (Mp) of the resin in the resin emulsified dispersion is
9. The electrostatic image developing toner according to claim 8, wherein the amount is from 300,000 to 3,000,000.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34870997A JP3429442B2 (en) | 1997-12-04 | 1997-12-04 | Method for producing binder resin for toner for developing electrostatic images |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34870997A JP3429442B2 (en) | 1997-12-04 | 1997-12-04 | Method for producing binder resin for toner for developing electrostatic images |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11167225A true JPH11167225A (en) | 1999-06-22 |
JP3429442B2 JP3429442B2 (en) | 2003-07-22 |
Family
ID=18398845
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP34870997A Expired - Lifetime JP3429442B2 (en) | 1997-12-04 | 1997-12-04 | Method for producing binder resin for toner for developing electrostatic images |
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Country | Link |
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JP (1) | JP3429442B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7955755B2 (en) | 2006-03-31 | 2011-06-07 | Quantumsphere, Inc. | Compositions of nanometal particles containing a metal or alloy and platinum particles |
JP2011240334A (en) * | 2010-05-19 | 2011-12-01 | Xerox Corp | Screw extruder for continuous and solvent-free resin emulsification |
-
1997
- 1997-12-04 JP JP34870997A patent/JP3429442B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7955755B2 (en) | 2006-03-31 | 2011-06-07 | Quantumsphere, Inc. | Compositions of nanometal particles containing a metal or alloy and platinum particles |
JP2011240334A (en) * | 2010-05-19 | 2011-12-01 | Xerox Corp | Screw extruder for continuous and solvent-free resin emulsification |
Also Published As
Publication number | Publication date |
---|---|
JP3429442B2 (en) | 2003-07-22 |
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