JP3712434B2 - Method for producing liquid toner - Google Patents

Method for producing liquid toner Download PDF

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Publication number
JP3712434B2
JP3712434B2 JP04009495A JP4009495A JP3712434B2 JP 3712434 B2 JP3712434 B2 JP 3712434B2 JP 04009495 A JP04009495 A JP 04009495A JP 4009495 A JP4009495 A JP 4009495A JP 3712434 B2 JP3712434 B2 JP 3712434B2
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Japan
Prior art keywords
solvent
copolymer
resin
liquid toner
resin particles
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JPH08234502A (en
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康晴 須田
勝昭 槇野
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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Description

【0001】
【産業上の利用分野】
本発明は液体トナー及びその製造方法に関し、特に電子写真用,静電印刷用,情報記録用として適した液体トナー及びその製造方法に関する。
【0002】
【従来の技術】
従来、電子写真液体トナーは、電気絶縁性液体とそれに分散した粒径0.1〜1μmの着色剤粒子及び着色剤粒子の分散,定着,電荷調節を目的とした該電気絶縁性液体に可溶性の樹脂とからなるものが使用されている。この種の液体トナーは、粒径が小さく解像度が優れ、調製が比較的容易という長所を有する。
【0003】
【発明が解決しようとする課題】
しかしながら、従来の液体トナーはトナーの定着性が悪く、更に高濃度のトナーを補充しながら長期間使用をすると、電気絶縁性液体に溶解した樹脂濃度の変化による画質欠陥を生ずるという欠点がある。
【0004】
こうした欠点を改良するため、常温では電気絶縁性液体に不要の樹脂からなる樹脂粒子(着色剤を含む場合もある)を該電気絶縁性液体に分散させてなる液体トナーの提案例もある。しかし、樹脂粒子を重合法によって生成しようとすると重合条件の制約が多く、更に重合後に樹脂粒子表面に付着している開始剤,未反応モノマーなどを除去しなければ液体トナーとして適さない場合が多い。また、樹脂を溶媒中に一度加熱溶解した後、冷却析出して樹脂粒子を析出させる方法では粒子径を任意に調節しにくい等の問題を有する。
【0005】
本発明はこうした事情を考慮してなされたもので、樹脂粒子の粒径が任意でかつその粒度分布を狭いものとすることができ、また画像濃度,像のにじみ,像流れ等の画質がより改善された液体トナー及びその製造方法を提供することを目的とする。
【0006】
【課題を解決するための手段】
本発明者は、樹脂としてカルボキシ基又はエステル基を有するオレフィン系樹脂を使用し、該樹脂に対する溶解性において温度依存性が高く、かつ樹脂粒子の粒子径を任意に調節するために溶解度パラメータ(SP値)を調整した溶媒に加熱溶解した後、樹脂溶解液の樹脂の溶解度を下げることにより任意の粒径の粒度分布の狭い樹脂粒子を生成する方法を発明し、先に出願したが、更に該樹脂粒子を液体トナーとして用いて高画質の画像を出力するのに適した液体トナー及びその製造方法を提案するものである。
【0008】
本発明は、エチレン系共重合体単独又は着色剤を添加したエチレン系共重合体を、該共重合体に対する溶解性において、加熱時に該共重合体を溶解し、常温では実質的に該共重合体を溶解せず、かつ樹脂粒子の粒子径を任意に調節するために、該共重合体との溶解度パラメータの差を調整した溶媒に加熱溶解した後、リン酸エステル系界面活性剤の存在下、冷却して樹脂粒子を析出させると共に、溶媒を電気絶縁性液体に置換することを特徴とする液体トナーの製造方法である。
【0010】
本発明において、エチレン系共重合体としては、エチレン酢酸ビニル共重合体,エチレン酢酸ビニル共重合体の部分ケン化物,エチレンアクリル酸,エチレンアクリル酸エステルが挙げられる。これらの中から1種又は必要に応じて2種以上混合したものを使用することができる。
【0011】
本発明において、電気絶縁性液体としては、電気抵抗率1010Ω・cm以上、誘電率3以下の溶媒であり、またエチレン系共重合体の溶解度が小さいものが好ましい。例えば、エクソン化学株式会社製のアイソパーH,G,L,M等がある。
【0012】
本発明において、前記着色剤として用いる染顔料は従来公知ものもでさしつかせなく、カーボンブラック,フタロシアニンブルー、アルカリブルー,アゾ系顔料等が使用できる。前記着色剤は、予めエチレン系共重合体に加熱混練等の手段により添加しておくか、又は本発明の製造工程中の樹脂粒子析出前に着色剤を添加する等の手段を採用すればよい。
【0013】
本発明において、エチレン系共重合体を溶解するための溶媒は、加熱時に樹脂を溶解し、常温では実質的に樹脂を溶解しない溶媒である必要があり、樹脂溶解度の差が25℃と60℃で0.1g/溶媒100g以上,好ましくは1g/溶媒100g以上であればよい。また、前記溶媒は析出する樹脂粒子の粒子径を調節するためにSP値を調整した溶媒であり、樹脂自体のSP値と溶媒のSP値との差ΔSP値が小さい程樹脂粒子径を小さくすることができる。溶媒は単一溶媒でも混合溶媒でもよい。
【0014】
このような溶媒としては、例えば直鎖又は分岐鎖の脂肪族炭化水素,芳香族炭化水素,炭素数10以下の直鎖又は分岐鎖の脂肪族アルコール等が挙げられる。脂肪族炭化水素の具体例としては、炭素数6〜12の直鎖又は分岐鎖の脂肪族炭化水素,炭素数の異なる脂肪族炭化水素の混合物であるアイソパー(商品名,エクソン化学社製)等がある。芳香族炭化水素の具体例としては、ベンゼン,トルエン,キシレン,エチルベンゼン等が挙げられる。
次に、リン酸エステル系界面活性剤について説明する。本発明で用いるリン酸エステル系界面活性剤としては、下記「化2」に示される化合物が挙げられる。
【0015】
【化2】

Figure 0003712434
「化2」において、Rはアルキル又はアルキルアリル基,nはエチレンオキサイド付加モル数,R´はH又はR(CH2 CH2 O)n 基を示す。
【0016】
更に、好ましくはRがノニルフェノール,オクチルフェノール,ジノニルフェノール,ジスチリルフェノールであればよい。このようなリン酸エステル系界面活性剤としては、商品名であげると第一工業製薬(株)製プライサーフ・シリーズ、例えばA217E,A21G,A207H,AL等があるが、これらに限るものではない。前記リン酸エステル系界面活性剤は、顔料分散工程,顔料分散液,エチレン系共重合体溶解工程,樹脂粒子析出前段階のいずれかの段階で添加する(第1の製造法)か、又は溶媒置換後の樹脂分散液,最終の液体トナー中のいずれかの段階で添加する(第2の製造法)方法でよい。
【0017】
電荷調整剤としては、従来公知のものでさしつかえなく、レシチン,アマニ油,ナフテン酸コバルト,ナフテン酸亜鉛,ナフテン酸銅,ナフテン酸マンガン,ナフテン酸ジルコニウム,オクチル酸コバルト,オクチル酸ジルコニウムなど一般に使用されるものを、自由に使うことができる。
【0018】
【作用】
リン酸エステル系界面活性剤の分散効果により、トナー粒子間の過剰な凝集性が緩和された圧密性が良くなるため、現像部において感光体表面上に形成された画像はトナー粒子が緻密に積み重なった固形分濃度の高い画像となる。その結果、感光体表面から例えば紙面への画像の転写過程において像の流れ、像のにじみ等を抑制する効果があることが判明した。また、画像の固形分濃度が高くなることで紙面上の画像濃度が高くすることができる利点がある。
【0019】
また、エチレン系共重合体に対して溶解性を有する溶媒を用いた樹脂溶液を該リン酸エステル系界面活性剤の存在下、冷却して樹脂粒子を析出させる方法で液体トナーを製造する場合、その後の溶媒置換工程において過剰のリン酸エステル系界面活性剤が除去される結果、該リン酸エステル系界面活性剤の分散効果を十分に発揮させ、かつ粒子の帯電への影響はほとんど受けることなく、トナー粒子へ正又は負の帯電を任意に付与することが可能である。一方、樹脂粒子を析出させ、溶媒置換した後に該リン酸エステル系界面活性剤を添加する方法では、該リン酸エステル系界面活性剤はトナー粒子の分散性を改善するだけでなく、トナー粒子を帯電させる機能を有していることが判明した。
【0020】
エチレン系共重合体を溶解させる溶媒のSP値を調節することで、溶媒と該共重合体との親和性を変化させ、結果として析出する樹脂粒子の粒子径を任意に変えることができるという利点がある。エチレン系共重合体と溶媒のSP値の差ΔSP値が小さいほど、両者の親和性は強く、樹脂粒子径は小さくなり、逆にΔSPが大きいほど樹脂粒子径は大きくなる。特に、ΔSP値をほぼゼロにして析出させた樹脂粒子は粒度分布が狭く小粒径となることが判明した。
【0021】
【実施例】
以下、この発明の実施例について説明する。ここで、実施例中、部は重量部を%は重量%を表わすが、本発明を限定するものではない。実施例中の粒子径は(株)堀場製作所製レーザ回折式粒度分布計LA−700,画像濃度はマクベス濃度計を用いて測定した。画像の流れとにじみは市販の湿式電子写真複写機を用いて市販のコート紙上にコピーを行い、目視で評価した。トナーの電気特性としては大塚電子(株)製のレーザゼータ電位計LEZA−600を使用して、ゼータ電位を測定した。感光体表面の固形分濃度は複写機を停止して、紙への転写前の画像を感光体表面からすばやく掻き取り、110℃,2時間乾燥処理前後の重量差より求めた。
【0022】
(実施例1)
撹拌機,温度計,還流冷却器を備えた容器に、分岐鎖脂肪脂肪族炭化水素アイソパーG(エッソ石油製)72部,芳香族炭化水素トルエン(片山化学社製)48部,脂肪族アルコールエタノール(片山化学社製)30部を投入し、SP値9.18の非水溶媒とした。この中にエチレン・酢酸ビニル共重合体の部分ケン化物デュミランC−2280(武田薬品工業(株)製,SP値8.93)2部,着色剤フタロシアニンブルーNo1(大日精化工業(株)製)0.4部,リン酸エステル系界面活性剤プライサーフAL(第一工業製薬(株)製)0.24部を加えて70℃で1時間加熱撹拌し、デュミランを完全に溶解した後、室温放置し30℃まで放冷して着色樹脂粒子の析出させた。樹脂粒子径は2.70μmであった。この樹脂粒子分散液の混合溶媒をアイソパーGに置換し、帯電付与剤としてナフテン酸ジルコニウムを加えて正帯電液体トナー(固形分濃度3%)とした。トナーとしての物性,画質の評価結果を下記「表1」に示す。
【0023】
【表1】
Figure 0003712434
【0024】
次に、実施例1の比較例を示す。実施例1におけるリン酸エステル系界面活性剤プライサーフALを添加しない以外は同様にして液体トナーを調製した。評価結果を上記「表1」に示す。また、図1は、実施例1に係る樹脂粒子の粒度分布図を示す。図1において、メジアン径:2.701μm、粒子径(%):10.00μm=2.1%、比表面積:23464cm2 /cm3 、%粒子径:90.0%=1.555μmである。
【0025】
(実施例2)
実施例1におけるリン酸エステル系界面活性剤プライサーフALに代えて、プライサーフA207H(第一工業製薬(株)製)0.24部を使用した以外は同様にして液体トナーを調製した。評価結果を、上記「表1」に示す。また、図2は、実施例2係る樹脂粒子の粒度分布図を示す。図2において、メジアン径:2.331μm、粒子径(%):10.00μm=0.2%、比表面積:26504cm2 /cm3 、%粒子径:90.0%=1.482μmである。
【0026】
(実施例3)
実施例2におけるSP値9.18の非水溶媒の代わりに、アイソパーG45部、トルエン30部,エタノール75部を混合したSP値10.73の非水溶媒を使用した以外は同様にして液体トナーを調製した。評価結果を、上記「表1」に示す。また、図3は、実施例3係る樹脂粒子の粒度分布図を示す。図3において、メジアン径:7.904μm、粒子径(%):10.00μm=31.3%、比表面積:8633cm2 /cm3 、%粒子径:90.0%=3.949μmである。
【0027】
(実施例4)
実施例1のエチオレン系共重合体に代えて、エチレン酢酸ビニル共重合体エバフレックス220(三井デュポンケミカル(株)製)2部,及び着色剤としてカーミンB6(大日精化工業(株)製)0.4部を使用した以外は同様にして液体トナーを調製した。評価結果を、上記「表1」に示す。
【0028】
(実施例5)
撹拌機,温度計,還流冷却器を備えた容器に、分岐鎖脂肪脂肪族炭化水素アイソパーG72部,芳香族炭化水素トルエン48部,脂肪族アルコールエタノール30部を投入し、SP値9.18の非水溶媒とした。この中にエチレン・酢酸ビニル共重合体の部分ケン化物デュミランC−2280 2部,着色剤ベンジジンイエロー(大日精化工業(株)製)0.4部を加えて70℃で1時間加熱撹拌し、デュミランを完全に溶解した後、室温放置し30℃まで放冷して着色樹脂粒子を析出させた。この樹脂粒子分散液の混合溶媒をアイソパーGに置換した後、リン酸エステル系界面活性剤プライサーフA207H 0.24部を帯電付与剤オクチル酸ジルコニウムと共に加えて負帯電液体トナー(固形分3%)とした。トナーとしての物性,画質の評価結果を上記「表1」に示す。
【0029】
【発明の効果】
本発明による液体トナーを電子写真用として使用すると、リン酸エステル系界面活性剤の分散効果により、トナー粒子の圧密性が良くなるため感光体表面上にトナー粒子が緻密に積み重なった固形分濃度の高い画像を得ることができ、感光体から紙へのトナー転写時における像の流れ、にじみを抑制することができる。また、紙面上の画像の光学濃度を高くできるという利点がある。
【0030】
また、本発明の液体トナー製造法において、樹脂粒子を析出させる際にリン酸エステル系界面活性剤を存在させると、析出後の溶媒置換を経た後も該リン酸エステル系界面活性剤の分散効果を十分に発揮させ、かつトナー粒子への帯電付与に対してほとんど影響を受けないという利点がある。
【0031】
更に、本発明の液体トナーの製造法において、樹脂粒子析出及び溶媒置換の後にリン酸エステル系界面活性剤を添加する方法を用いると、該リン酸エステル系界面活性剤は分散性改善だけでなく粒子を帯電させる機能を有しており、優れた液体トナーとしえるものである。
【0032】
更には、本発明の液体トナーの製造法において、エチレン共重合体を溶解するための溶媒のSP値を調節することで溶媒と該共重合体との親和性を変化させ、結果として析出する樹脂粒子の粒子径を任意に変えることができる。
【図面の簡単な説明】
【図1】本発明の実施例1に係る樹脂粒子の粒度分布図。
【図2】本発明の実施例2に係る樹脂粒子の粒度分布図。
【図3】本発明の実施例3に係る樹脂粒子の粒度分布図。[0001]
[Industrial application fields]
The present invention relates to a liquid toner and a manufacturing method thereof, and more particularly to a liquid toner suitable for electrophotography, electrostatic printing, and information recording, and a manufacturing method thereof.
[0002]
[Prior art]
Conventionally, the electrophotographic liquid toner is soluble in the electrically insulating liquid for the purpose of dispersing, fixing, and controlling the charge of the electrically insulating liquid, the colorant particles dispersed in the particle having a particle diameter of 0.1 to 1 μm, and the colorant particles. What consists of resin is used. This type of liquid toner has the advantages of small particle size, excellent resolution, and relatively easy preparation.
[0003]
[Problems to be solved by the invention]
However, the conventional liquid toner has poor toner fixability, and has a drawback in that when it is used for a long period of time while replenishing a high concentration toner, an image quality defect is caused by a change in the resin concentration dissolved in the electrically insulating liquid.
[0004]
In order to remedy these drawbacks, there is also a proposal of a liquid toner in which resin particles (which may contain a colorant) made of an unnecessary resin in an electrically insulating liquid at room temperature are dispersed in the electrically insulating liquid. However, there are many restrictions on polymerization conditions when trying to produce resin particles by a polymerization method, and it is often not suitable as a liquid toner unless the initiator and unreacted monomers adhering to the surface of the resin particles are removed after polymerization. . Further, there is a problem that it is difficult to arbitrarily adjust the particle diameter by a method in which the resin particles are precipitated by cooling and precipitation after once dissolving the resin in a solvent.
[0005]
The present invention has been made in consideration of such circumstances, and the particle size of the resin particles can be arbitrarily set and the particle size distribution thereof can be narrowed, and the image quality such as image density, image blur, and image flow can be improved. It is an object of the present invention to provide an improved liquid toner and a manufacturing method thereof.
[0006]
[Means for Solving the Problems]
The present inventor uses an olefin-based resin having a carboxy group or an ester group as a resin, has a high temperature dependency in solubility in the resin, and has a solubility parameter (SP Invented a method of producing resin particles having a narrow particle size distribution of any particle size by lowering the solubility of the resin in the resin solution after heating and dissolving in a solvent having a value adjusted). The present invention proposes a liquid toner suitable for outputting a high-quality image using resin particles as a liquid toner, and a method for manufacturing the liquid toner.
[0008]
In the present invention, an ethylene copolymer alone or an ethylene copolymer to which a colorant is added is dissolved in the copolymer in terms of solubility in the copolymer. In order to arbitrarily adjust the particle size of the resin particles without dissolving the coalescence, after dissolving in a solvent in which the difference in solubility parameter from the copolymer is adjusted by heating, in the presence of a phosphate ester surfactant The liquid toner is produced by cooling and precipitating resin particles, and replacing the solvent with an electrically insulating liquid.
[0010]
In the present invention, the ethylene copolymer, ethylene-vinyl acetate copolymer, partially saponified ethylene-vinyl acetate copolymer, ethylene acrylic acid, ethylene acrylic acid ester. One of these or a mixture of two or more as required can be used.
[0011]
In the present invention , the electrically insulating liquid is preferably a solvent having an electrical resistivity of 10 10 Ω · cm or more and a dielectric constant of 3 or less, and preferably has a low solubility of the ethylene copolymer. For example, there are Isopar H, G, L, M, etc. manufactured by Exxon Chemical Co., Ltd.
[0012]
In the present invention , the dyes and pigments used as the colorant are not limited to those conventionally known, and carbon black, phthalocyanine blue, alkali blue, azo pigments and the like can be used. The colorant may be previously added to the ethylene copolymer by means such as heat kneading, or means such as adding a colorant before precipitation of resin particles during the production process of the present invention may be employed. .
[0013]
In the present invention , the solvent for dissolving the ethylene-based copolymer needs to be a solvent that dissolves the resin when heated and does not substantially dissolve the resin at room temperature, and the difference in resin solubility is 25 ° C. and 60 ° C. 0.1 g / solvent 100 g or more, preferably 1 g / solvent 100 g or more. The solvent is a solvent whose SP value is adjusted in order to adjust the particle diameter of the precipitated resin particles, and the smaller the difference ΔSP value between the SP value of the resin itself and the SP value of the solvent, the smaller the resin particle diameter. be able to. The solvent may be a single solvent or a mixed solvent.
[0014]
Examples of such a solvent include linear or branched aliphatic hydrocarbons, aromatic hydrocarbons, and linear or branched aliphatic alcohols having 10 or less carbon atoms. Specific examples of the aliphatic hydrocarbon include linear or branched aliphatic hydrocarbons having 6 to 12 carbon atoms, Isopar which is a mixture of aliphatic hydrocarbons having different carbon numbers (trade name, manufactured by Exxon Chemical Co., Ltd.), etc. There is. Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene and the like.
Next, the phosphate ester surfactant will be described. Examples of the phosphate ester surfactant used in the present invention include compounds represented by the following “Chemical Formula 2”.
[0015]
[Chemical formula 2]
Figure 0003712434
In “Chemical Formula 2”, R represents an alkyl or alkylallyl group, n represents the number of moles of ethylene oxide added, and R ′ represents H or R (CH 2 CH 2 O) n group.
[0016]
Furthermore, R may preferably be nonylphenol, octylphenol, dinonylphenol, or distyrylphenol . Examples of such phosphate ester surfactants include, but are not limited to, the Prisurf Series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., such as A217E, A21G, A207H, and AL. . The phosphate ester-based surfactant is added at any stage of the pigment dispersion process, the pigment dispersion, the ethylene copolymer dissolution process, and the stage before resin particle deposition (first production method), or a solvent. A method may be used in which the resin dispersion after replacement and the final liquid toner are added at any stage (second production method).
[0017]
As the charge control agent, a conventionally known one can be used. Lecithin, linseed oil, cobalt naphthenate, zinc naphthenate, copper naphthenate, manganese naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate and the like are generally used. Can use anything freely.
[0018]
[Action]
Due to the dispersion effect of the phosphoric ester surfactant, excessive cohesion between the toner particles is reduced and the compactness is improved, so that the toner particles are densely stacked on the image formed on the surface of the photoreceptor in the developing portion. The resulting solid content is high. As a result, it has been found that there is an effect of suppressing image flow, image blurring, and the like in the process of transferring an image from the photoreceptor surface to, for example, a paper surface. Further, there is an advantage that the image density on the paper surface can be increased by increasing the solid content density of the image.
[0019]
In the case of producing a liquid toner by a method in which a resin solution using a solvent that is soluble in an ethylene copolymer is cooled in the presence of the phosphate ester surfactant to precipitate resin particles, As a result of the removal of excess phosphate ester surfactant in the subsequent solvent replacement step, the dispersion effect of the phosphate ester surfactant is sufficiently exerted, and the particle charging is hardly affected. It is possible to arbitrarily impart positive or negative charge to the toner particles. On the other hand, in the method of depositing the resin particles and replacing the solvent after the solvent substitution, the phosphate ester surfactant not only improves the dispersibility of the toner particles but also the toner particles. It was found to have a charging function.
[0020]
By adjusting the SP value of the solvent in which the ethylene-based copolymer is dissolved, the affinity between the solvent and the copolymer can be changed, and as a result, the particle diameter of the resin particles deposited can be arbitrarily changed. There is. The smaller the difference ΔSP value between the SP value of the ethylene copolymer and the solvent, the stronger the affinity between them, and the smaller the resin particle diameter , and vice versa. In particular, it has been found that the resin particles precipitated with the ΔSP value almost zero have a narrow particle size distribution and a small particle size.
[0021]
【Example】
Examples of the present invention will be described below. Here, in the examples, “part” means “part by weight” and “%” means “% by weight”, but the present invention is not limited thereto. The particle size in the examples was measured using a laser diffraction particle size distribution analyzer LA-700 manufactured by Horiba, Ltd., and the image density was measured using a Macbeth densitometer. Image flow and blurring were visually evaluated by copying onto commercially available coated paper using a commercially available wet electrophotographic copying machine. As the electrical characteristics of the toner, the zeta potential was measured using a laser zeta electrometer LEZA-600 manufactured by Otsuka Electronics Co., Ltd. The solid content concentration on the surface of the photoreceptor was obtained from the weight difference between before and after the drying process at 110 ° C. for 2 hours after the copying machine was stopped and the image before transfer to paper was quickly scraped off from the photoreceptor surface.
[0022]
(Example 1)
In a vessel equipped with a stirrer, thermometer and reflux condenser, 72 parts of branched chain aliphatic aliphatic hydrocarbon isoper G (Esso Petroleum), 48 parts of aromatic hydrocarbon toluene (Katayama Chemical Co., Ltd.), aliphatic alcohol ethanol 30 parts (manufactured by Katayama Chemical Co., Ltd.) were added to obtain a non-aqueous solvent having an SP value of 9.18. 2 parts of ethylene / vinyl acetate copolymer partially saponified product Dumiran C-2280 (manufactured by Takeda Pharmaceutical Co., Ltd., SP value 8.93), colorant phthalocyanine blue No1 (manufactured by Dainichi Seika Kogyo Co., Ltd.) ) 0.4 part, 0.24 part of phosphate ester surfactant Surfsurf AL (Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred at 70 ° C. for 1 hour to completely dissolve dumilan. The mixture was allowed to stand at room temperature and allowed to cool to 30 ° C. to precipitate colored resin particles. The resin particle size was 2.70 μm. The mixed solvent of this resin particle dispersion was replaced with Isopar G, and zirconium naphthenate was added as a charge imparting agent to obtain a positively charged liquid toner (solid content concentration 3%). The evaluation results of physical properties and image quality as toner are shown in “Table 1” below.
[0023]
[Table 1]
Figure 0003712434
[0024]
Next, a comparative example of Example 1 is shown. A liquid toner was prepared in the same manner except that the phosphate ester surfactant Surfsurf AL in Example 1 was not added. The evaluation results are shown in the above “Table 1”. FIG. 1 is a particle size distribution diagram of resin particles according to Example 1. In FIG. 1, the median diameter is 2.701 μm, the particle diameter (%) is 10.00 μm = 2.1%, the specific surface area is 23464 cm 2 / cm 3 , and the% particle diameter is 90.0% = 1.555 μm.
[0025]
(Example 2)
A liquid toner was prepared in the same manner except that 0.24 part of PRISURF A207H (Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of the phosphate ester surfactant Surfsurf AL in Example 1. The evaluation results are shown in the above “Table 1”. FIG. 2 shows a particle size distribution diagram of the resin particles according to Example 2. In FIG. 2, the median diameter is 2.331 μm, the particle diameter (%) is 10.00 μm = 0.2%, the specific surface area is 26504 cm 2 / cm 3 , and the% particle diameter is 90.0% = 1.482 μm.
[0026]
(Example 3)
In the same manner as Example 2 except that a nonaqueous solvent having an SP value of 10.73 in which 45 parts of Isopar G, 30 parts of toluene and 75 parts of ethanol were mixed was used instead of the nonaqueous solvent having an SP value of 9.18. Was prepared. The evaluation results are shown in the above “Table 1”. FIG. 3 shows a particle size distribution diagram of the resin particles according to Example 3. In FIG. 3, the median diameter is 7.904 μm, the particle diameter (%) is 10.00 μm = 31.3%, the specific surface area is 8633 cm 2 / cm 3 , and the% particle diameter is 90.0% = 3.949 μm.
[0027]
(Example 4)
Instead of the ethylene copolymer of Example 1, 2 parts of ethylene vinyl acetate copolymer EVAFLEX 220 (manufactured by Mitsui DuPont Chemical Co., Ltd.) and Carmine B6 (manufactured by Dainichi Seika Kogyo Co., Ltd.) as a colorant A liquid toner was prepared in the same manner except that 0.4 part was used. The evaluation results are shown in the above “Table 1”.
[0028]
(Example 5)
A vessel equipped with a stirrer, a thermometer, and a reflux condenser was charged with 72 parts of branched chain aliphatic aliphatic hydrocarbon isopar G, 48 parts of aromatic hydrocarbon toluene and 30 parts of aliphatic alcohol ethanol, and had an SP value of 9.18. A non-aqueous solvent was used. In this, 2 parts of partially saponified product dumilane C-2280 of ethylene / vinyl acetate copolymer and 0.4 part of colorant benzidine yellow (manufactured by Dainichi Seika Kogyo Co., Ltd.) were added, and the mixture was heated and stirred at 70 ° C. for 1 hour. After complete dissolution of dumiran, it was allowed to stand at room temperature and allowed to cool to 30 ° C. to precipitate colored resin particles. After the mixed solvent of the resin particle dispersion was replaced with Isopar G, 0.24 part of phosphate ester surfactant Surfsurf A207H was added together with the charge-imparting agent zirconium octylate to give a negatively charged liquid toner (solid content 3%). It was. The above-mentioned “Table 1” shows the evaluation results of the physical properties and image quality as toner.
[0029]
【The invention's effect】
When the liquid toner according to the present invention is used for electrophotography, due to the dispersion effect of the phosphate ester-based surfactant, the compactness of the toner particles is improved. Therefore, the solid content concentration in which the toner particles are densely stacked on the surface of the photoreceptor is improved. A high image can be obtained, and the flow and blur of the image during toner transfer from the photoreceptor to paper can be suppressed. Further, there is an advantage that the optical density of the image on the paper can be increased.
[0030]
Further, in the liquid toner production method of the present invention, if a phosphate ester surfactant is present when the resin particles are precipitated, the dispersion effect of the phosphate ester surfactant even after the solvent substitution after the precipitation. Is sufficiently exerted, and there is an advantage that the toner particles are hardly affected by the charging.
[0031]
Furthermore, in the method for producing a liquid toner of the present invention, when a method of adding a phosphate ester surfactant after resin particle deposition and solvent replacement is used, the phosphate ester surfactant not only improves dispersibility. It has a function of charging particles and can be an excellent liquid toner.
[0032]
Furthermore, in the method for producing a liquid toner of the present invention, the resin that precipitates as a result of changing the affinity between the solvent and the copolymer by adjusting the SP value of the solvent for dissolving the ethylene copolymer. The particle diameter of the particles can be arbitrarily changed.
[Brief description of the drawings]
FIG. 1 is a particle size distribution diagram of resin particles according to Example 1 of the present invention.
FIG. 2 is a particle size distribution diagram of resin particles according to Example 2 of the present invention.
FIG. 3 is a particle size distribution diagram of resin particles according to Example 3 of the present invention.

Claims (1)

エチレン系共重合体単独又は着色剤を添加したエチレン系共重合体を、該共重合体に対する溶解性において、加熱時に該共重合体を溶解し、常温では実質的に該共重合体を溶解せず、かつ樹脂粒子の粒子径を任意に調節するために、該共重合体との溶解度パラメータの差を調整した溶媒に加熱溶解した後、リン酸エステル系界面活性剤の存在下、冷却して樹脂粒子を析出させると共に、溶媒を電気絶縁性液体に置換することを特徴とする液体トナーの製造方法。  The ethylene copolymer alone or the ethylene copolymer added with a colorant is dissolved in the copolymer in terms of solubility in the copolymer. When the copolymer is heated, the copolymer is substantially dissolved at room temperature. In order to arbitrarily adjust the particle size of the resin particles, after dissolving in a solvent adjusted for the difference in solubility parameter with the copolymer, it is cooled in the presence of a phosphate ester surfactant. A method for producing a liquid toner, wherein the resin particles are deposited and the solvent is replaced with an electrically insulating liquid.
JP04009495A 1995-02-28 1995-02-28 Method for producing liquid toner Expired - Fee Related JP3712434B2 (en)

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US5766818A (en) * 1997-10-29 1998-06-16 Xerox Corporation Toner processes with hydrolyzable surfactant
US5944650A (en) * 1997-10-29 1999-08-31 Xerox Corporation Surfactants
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