JP2004287270A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method which has excellent low temperature fixing capability, twine resistance and reliability of the fixing device, has excellent color developing property of a full color picture, transparency of an OHP picture and reproducibility of high resolution picture, has excellent anti-blocking property and does not cause picture defects due to the change of toner property due to a stress etc. in the developing device. <P>SOLUTION: An image is formed by using an image fixing apparatus composed of a heating fixing roller having a surface layer of fluororesin and a rubber elastic layer between the surface layer and a core, and a pressurizing member which is abutted on the heating fixing roller and forms a fixing nip for fixing the toner to an image carrier. The image is formed further by using the toner containing binder resin, a colorant and a releasing agent. The average value of pressure applied to the fixing nip part is 0.8-2.0 kg/cm<SP>2</SP>. The toner is designed so as to satisfy the following conditions; the glass transition temperature (Tg) of the toner is 45-55°C, the endothermic peak temperature of the releasing agent is 65-90°C and the endothermic amount at the endothermic peak of the releasing agent is 8-30 J/g. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０１０１】
（現像剤の調整）
得られたトナー１〜２８それぞれに、トナー１００質量部に対して、１．５質量部の疎水性シリカ（ＴＳ７２０）を、ヘンシェルミキサーで混合した。この外添トナーを、メタアクリレート（綜研化学社製）を１質量％被覆した平均粒径５０μｍのフェライトキャリアに対してトナー濃度が５質量％になるように秤量し、ボールミルで５分間攪拌・混合して現像剤１〜２８を得た。
【０１０２】
（定着器１）
ＤＰＣ ２２００定着器を改造し、定着ニップ部の平均圧力が１．６ｋｇ／ｃｍ^２になるように、エンドレスベルトの加熱ロールへの応圧加重を調整した。また、エンドレスベルト内部に配置した、加圧パッドは、２分割してあり、入り口側のパッドには、シリコーンゴムを用い、出口側のパッドには、アルミニウムを用い、その高さを調整することで、出口側の圧力を、入り口側の圧力に対して２．５倍に設定した。また、加熱ロールは、鉄製の０．５ｍｍのコア上に、厚さ０．３ｍｍのシリコーンゴム弾性層を設け、その上にＰＦＡチューブ（厚さ２０μｍ）を被覆したものを用い、行った。加圧ベルトは、１００μｍの厚さのポリイミド基材上に、ＰＦＡを粉体コートし焼成する事により、厚さ４０μｍの表面層を設けたエンドレスベルトを使用し、定着器１とした。
【０１０３】
（定着器２）
ＤＰＣ ２２００定着器を改造し、定着ニップ部の平均圧力が０．７ｋｇ／ｃｍ^２になるように、エンドレスベルトの加熱ロールへの応圧加重を調整した。また、エンドレスベルト内部に配置した、加圧パッドは、シリコーンゴムを用い、出口側と入口側の圧力が等しくなるように設定した。加熱ロールは、鉄製の０．５ｍｍのコア上に、ＰＦＡチューブ（厚さ２０μｍ）を被覆したものを用い、行った。加圧ベルトは、１００μｍの厚さのポリイミドのエンドレスベルトを使用し、定着器２とした。
【０１０４】
（定着器３）
定着ニップ部の平均圧力が２．４ｋｇ／ｃｍ^２になるように、エンドレスベルトの加熱ロールへの応圧加重を調整した以外は、定着器１と同様の設定にし、定着器３とした。
【０１０５】
（定着器４）
定着ニップ部の平均圧力が１．８ｋｇ／ｃｍ^２になるように、エンドレスベルトの加熱ロールへの応圧加重を調整し、出口側の圧力を、入り口側の圧力に対して４倍に設定した以外は、定着器１と同様の設定にし、定着器４とした。
【０１０６】
（定着器５）
定着ニップ部の平均圧力が１．０ｋｇ／ｃｍ^２になるように、エンドレスベルトの加熱ロールへの応圧加重を調整し、出口側の圧力を、入り口側の圧力に対して１．５倍に設定した以外は、定着器１と同様の設定にし、定着器５とした。
尚、出口側の圧力の、入り口側の圧力に対する倍率は、タクタイルセンサー（ニッタ製）を用い、定着ニップ部の圧力分布相対値を測定し、定着ニップの中心位置から入り口側ニップ開始位置までの平均値（Ｐｉｎ）と、定着ニップの中心位置から出口側ニップ終了位置までの平均値（Ｐｏｕｔ）を用い、Ｐｏｕｔ／Ｐｉｎであらわされる。
【０１０７】
＜実施例１＞
得られた現像剤１〜４を用い、定着器１による、最低定着試験、ホットオフセット開始温度、定着装置の耐久性試験、定着ロールへの巻付き性試験、画出し試験を行った。又、得られた現像剤１〜４から、２次色（Ｒｅｄ）、２次色（Ｇｒｅｅｎ）、２次色（Ｂｌｕｅ）及び３次色（Ｂｌａｃｋ）についても同様に評価した。
尚、２次色（Ｒｅｄ）は、画像密度１００％のＹｅｌｌｏｗトナー像の上に、画像密度１００％のＭａｇｅｎｔａトナー像を重ねる事により、画像を作成した。２次色（Ｇｒｅｅｎ）画像密度１００％のＹｅｌｌｏｗトナー像の上に、画像密度１００％のＣｙａｎトナー像を重ねることにより、画像を作成した。２次色（Ｂｌｕｅ）は、画像密度１００％のＭａｇｅｎｔａトナー像上に、画像密度１００％のＣｙａｎトナー像を重ねることにより、画像を作成した。３次色（Ｂｌａｃｋ）は、画像密度１００％のＹｅｌｌｏｗトナー像の上に、画像密度１００％のＭａｇｅｎｔａトナー像を重ね、さらに画像密度１００％のＣｙａｎトナー像を重ねることり、画像を作成した。
【０１０８】
最低定着温度とホットオフセット開始温度は、１１０℃〜２００℃の温度範囲で５℃おきに、温度調整し、富士ゼロックス製Ｐ紙に対する定着性試験により測定した。尚、最低定着温度は、得られた定着画像をＰ紙で摺擦し、摺擦したＰ紙側にトナーの転移が無い最低温度とした。ホットオフセット開始温度は、定着像の残像の発生を観察することにより行った。
定着装置の耐久性試験、定着ロールへの巻付き性試験、画出し試験は、定着器の加熱ロールの表面温度を、ロール軸方向の中心位置に温度センサーを配置しその情報から、フィードバックにより、１４５℃となるように制御し、富士ゼロックス製、ＤＰＣ ２２００改造機を用いて、Ｐ紙上に逐次作製した未定着画像を、連続で定着器から出力することにより実施した。その結果を表２に示す
【０１０９】
尚、前記画出し試験として、下記の基準で発色性、ＯＨＰ透明性、画像欠陥、細線の再現性、両面プリント時の裏面の画質の試験を行なった。
（発色性）
◎：紙上に、所望の色が鮮やかに再現される。
○：紙上に、所望の色が再現される。
△：わずかに色に濁りがあり、紙上で所望の色が再現されにくい。
×：色に濁りがあり、紙上で所望の色が再現されない。
【０１１０】
（ＯＨＰ透明性）
◎：ＯＨＰ透過像が、所望の色で鮮やかに再現される。
○：ＯＨＰ透過像が、所望の色で再現される。
×：ＯＨＰ透過像に濁りがあり、所望の色が再現されない。
【０１１１】
（細線の再現性）
◎：解像度６００ｄｐｉの１ｄｏｔライン細線が、鮮明に再現する。
○：解像度６００ｄｐｉの１ｄｏｔライン細線が、再現する。
×：解像度６００ｄｐｉの１ｄｏｔライン細線が、かすれ再現しない。
【０１１２】
（両面プリント時の裏面の画質）
○：オフセットが発生せず、表面と裏面の画像の光沢差がほとんど無い。
△：表面と裏面の画像の光沢差が発生する。
×：オフセットが発生した。
【０１１３】
【表２】

【０１１４】
＜実施例２＞
現像剤１〜４を現像剤５〜８に変更すること以外、実施例１と同様に評価した。
その結果を表３に示す。
【０１１５】
【表３】

【０１１６】
＜実施例３＞
現像剤１〜４を現像剤１３〜１６に変更すること以外、実施例１と同様に評価した。その結果を表４に示す。
【０１１７】
【表４】

【０１１８】
＜実施例４＞
現像剤１〜４を現像剤１７〜２０に変更すること以外、実施例１と同様に評価した。その結果を表５に示す。
【０１１９】
【表５】

【０１２０】
＜実施例５＞
現像剤１〜４を、現像剤２１〜２４に変更すること以外、実施例１と同様に評価した。その結果を表６に示す。
【０１２１】
【表６】

【０１２２】
＜実施例６＞
定着器１を定着器４に変更すること以外、実施例１と同様に評価した。その結果を表７に示す。
【０１２３】
【表７】

【０１２４】
＜実施例７＞
定着器１を定着器５に変更すること以外、実施例１と同様に評価した。その結果を表８に示す。
【０１２５】
【表８】

【０１２６】
＜実施例８＞
現像剤１〜４を現像剤５〜８に、定着器１を定着器５に変更すること以外、実施例１と同様に評価した。その結果を表９に示す。
【０１２７】
【表９】

【０１２８】
＜比較例１＞
現像剤１〜４を現像剤９〜１２に、定着器１を定着器２に変更すること以外、実施例１と同様に評価した。その結果を表１０に示す。
【０１２９】
【表１０】

【０１３０】
＜比較例２＞
定着器１を定着器３に変更すること以外、実施例１と同様に評価した。その結果を表１１に示す。
【０１３１】
【表１１】

【０１３２】
＜比較例３＞
現像剤１〜４を現像剤２５〜２８に変更すること以外、実施例１と同様に評価した。その結果を表１２に示す。
【０１３３】
【表１２】

【０１３４】
＜比較例４＞
現像剤１〜４を現像剤９〜１２に変更すること以外、実施例１と同様に評価した。その結果を表１３に示す。
【０１３５】
【表１３】

【０１３６】
表２〜表１３より、前記定着ニップ部にかかる圧力の平均値が０．８ｋｇ／ｃｍ^２〜２．０ｋｇ／ｃｍ^２であり、トナーＴｇが４５℃〜５５℃、前記離型剤の吸熱ピーク温度が６５℃〜９０℃、及び前記離型剤の吸熱ピークの吸熱量が８Ｊ／ｇ〜３０Ｊ／ｇの各条件を満たすトナーを用いた本発明の画像形成方法は、最低定着試験、ホットオフセット開始温度、定着装置の耐久性試験、定着ロールへの巻付き性試験、画出し試験の全てが良好であることがわかる。
【０１３７】
【発明の効果】
本発明は、低温定着性、耐巻き付性及び定着器の信頼性に優れ、フルカラー画像の発色性、ＯＨＰ画像の透明性、高精細な画像再現に優れ、耐ブロッキング性に優れ、現像器内のストレス等によるトナー性状の変化による画像欠陥が生じない画像形成方法を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an image forming method in which a formed image is heated and pressed on a recording material using a toner for electrostatic charge development used in an electrophotographic method, an electrostatic recording method, or the like in a copying machine, a printer, a facsimile, or the like.
[0002]
[Prior art]
Methods for visualizing image information via an electrostatic image, such as electrophotography, are currently used in various fields. In electrophotography, an electrostatic image is formed on a photoreceptor by a charging and exposing process, an electrostatic latent image is developed with a developer containing a toner, and visualized through a transfer and fixing process. As the developer used here, a two-component developer including a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone are known. For the production of such toners, usually, a kneading and pulverizing method is used in which a thermoplastic resin is melt-kneaded together with a releasing agent such as a pigment, a charge controlling agent, and wax, and after cooling, finely pulverized and classified. In these toners, inorganic or organic fine particles may be added to the surface of the toner particles, if necessary, for the purpose of improving fluidity and cleaning properties. Although these methods can produce excellent toners, they have the following problems.
[0003]
With the ordinary kneading and pulverizing method, the toner shape and the surface structure of the toner are indefinite, and they vary subtly depending on the pulverizability of the materials used and the conditions of the pulverizing process, making it difficult to actively control the toner shape and the surface structure It is. In addition, in the kneading and pulverizing method, there is a limitation on a selection range of materials. Specifically, the resin / colorant dispersion must be sufficiently brittle and finely pulverized by an economically feasible manufacturing apparatus. However, if the resin / colorant dispersion is made brittle, it may be subjected to mechanical shearing force or the like in a developing machine to generate fine powder or change the shape of the toner. As a result, in the case of the two-component developer, the fine powder adheres to the carrier surface to accelerate the deterioration of the chargeability of the developer, and in the case of the one-component developer, the particle size distribution is enlarged and toner scattering occurs, or the toner shape changes. Deterioration in image quality is likely to occur due to a decrease in developability.
[0004]
Also, the pressure heating method using a heat roller, which is the most commonly used fixing method at present, has extremely good thermal efficiency, can perform fixing quickly, and is very effective in high-speed electrophotographic copying machines. . When fixing a toner by this method, a method using a toner containing a release agent such as wax in the toner is used for the reliability of the fixing device and the simplification of the device. As described above, the toner in which a large amount of a release agent such as a wax is internally added often affects the exposure of the release agent to the toner surface depending on the combination with the thermoplastic resin. In particular, in the case of a combination of a resin whose elasticity is increased due to a high molecular weight component and is hardly pulverized and a brittle wax such as polyethylene, polyethylene is often exposed on the toner surface. Although this is advantageous for releasability at the time of fixing and cleaning of untransferred toner from the photoreceptor, the polyethylene on the surface layer is easily transferred by mechanical force and easily contaminates the developing roll, photoreceptor, and carrier. , Leading to lower reliability.
[0005]
Further, if the toner shape becomes irregular, even if a flow aid is added, sufficient fluidity cannot be ensured, and fine particles on the toner surface move to the toner concave portion due to mechanical shearing force during use. As a result, the fluidity is reduced with time, or the fluidity aid is buried in the toner, thereby deteriorating the developability, transferability and cleaning property. Further, when the toner collected by the cleaning is returned to the developing machine and used again, the image quality is further likely to deteriorate. If the flow aid is further increased to prevent these problems, problems such as generation of black spots on the photoreceptor and scattering of the aid particles will occur.
[0006]
In recent years, a method for producing a toner by an emulsion polymerization aggregation method has been proposed as a method for positively controlling the toner shape and surface structure. These generally prepare a resin fine particle dispersion by emulsion polymerization or the like, on the other hand, prepare a colorant dispersion liquid in which a colorant is dispersed in a solvent and mix both to form aggregated particles corresponding to the toner particle size, This is a method in which the toner is fused and united by heating to produce a toner. According to this emulsion polymerization aggregation method, the toner shape can be arbitrarily controlled from an irregular shape to a spherical shape by selecting a heating temperature condition. (See, for example, Patent Documents 1 and 2).
[0007]
Further, after forming the aggregated particles of the resin, the colorant, and the release agent, by additionally adding a resin fine particle dispersion, a resin layer is formed on the particle surface, thereby further exposing the surface of the colorant and the release agent. A suppression method has also been proposed (for example, see Patent Document 3).
[0008]
However, even with the toners of these methods, in order to sufficiently obtain offset properties, wrap resistance, and low-temperature fixing properties at the time of oilless fixing, and to obtain high color developing properties and OHP transparency, it is necessary to use a heating roll of a fixing device. It is necessary to apply a high pressure between the pressure rolls to promote the release of the release agent at the time of fixing, and to enhance the releasability between the heating roll and the toner layer. As described above, when a high pressure is applied between the heating roll and the pressure roll, the stress applied to the roll surface increases, and the abrasion of the surface is promoted, so that there is a problem in the maintainability of the fixing device. Further, when a fluororesin having a high releasability is used for the surface layer in order to perform oilless fixing, the resin itself is relatively soft, so that abrasion becomes remarkable. In addition, when the heating roll has an elastic layer, elasticity is likely to progress due to stress caused by heat and high pressure, and the pressure of the fixing nip decreases over time, or the elastic layer is cracked, The reliability of the fixing device is impaired. In particular, when fixing a full-color toner, unlike the case of fixing a single-color toner, it is necessary to sufficiently mix a plurality of color toners to enhance the color developing property. In this case, in order to enhance the color developability at a low temperature, it is necessary to further increase the nip pressure at the time of fixing, and the reliability of the fixing device is further reduced (for example, see Patent Document 4).
[0009]
To solve the problem of the reliability of the fixing device, it is necessary to coat the roller surface with a thin film of an anti-offset agent and a liquid having good releasability such as silicone oil in order to prevent fatigue of the roller surface. However, since a device for supplying the liquid for preventing offset is required, there is a problem that the fixing device becomes complicated.
In recent years, there has been an increasing demand for higher image quality, and in particular, in color image formation, the toner tends to have a smaller diameter in order to realize a high-definition image. However, in the case of a simple size reduction with the conventional particle size distribution, problems such as carrier and photoconductor contamination and toner scattering become remarkable due to the presence of the fine powder side toner, thereby realizing high image quality and high reliability at the same time. It was difficult. In order to solve this, it is important to sharpen the particle size distribution and reduce the particle size.
[0010]
Further, in a digital full-color copying machine or printer, a color image original is subjected to color separation by B (blue), R (red), and G (green) filters, and then a latent image having a dot diameter of 20 to 70 μm corresponding to the original original. The image is developed using the subtractive color mixing action using each of the Y (yellow), M (magenta), C (cyan) and Bk (black) developers. Compared to a conventional black-and-white copying machine, a digital full-color copying machine or the like needs to transfer a large amount of developer and needs to correspond to a small dot diameter. For this reason, in order to obtain high-definition image reproducibility, it is necessary to suppress image disturbance in the electrophotographic process, particularly when the toner layer thickness becomes large during color superposition. For this reason, uniform chargeability, persistence, toner strength, sharpness of particle size distribution, small particle size, and spherical toner shape become more and more important. Further, in order to respond to speeding up and energy saving performance of these machines, further low-temperature fixing property is required. In particular, when a document reading device such as a digital full-color copying machine is provided, the power consumption of the multi-color reading device is relatively large, so that it is necessary to further reduce the power of the fixing device, and it is desired to improve the low-temperature fixing performance. . In consideration of these points, the toner produced by the agglomeration / fusion coalescence method, which has a sharp particle size distribution and is suitable for producing small particle diameters, has excellent characteristics.
[0011]
As described above, in the electrophotographic process, it is necessary to suppress the exposure of the release agent to the toner surface in order to stably maintain the characteristics even under various mechanical stresses. Furthermore, in order to obtain the reliability of the fixing device and the low-temperature fixing property, the toner has sufficient fixing property even under low temperature and low pressure, and in order to maintain the winding resistance and the hot offset resistance, the toner melting property and the like. It is necessary to control the exudation of the release agent. Further, to achieve full-color high image quality, it is necessary to sharpen the particle size distribution of the toner, reduce the particle size, and make the toner spherical.
[0012]
[Patent Document 1]
JP-A-63-282752
[Patent Document 2]
JP-A-6-250439
[Patent Document 3]
Japanese Patent No. 3141783
[Patent Document 4]
JP-A-4-35657
[0013]
[Problems to be solved by the invention]
An object of the present invention is to solve the above problems. That is, it has excellent low-temperature fixability, wrap resistance and reliability of the fixing device, excellent color development of a full-color image, transparency of an OHP image, high-definition image reproduction, excellent blocking resistance, and stress in a developing device. It is an object of the present invention to provide an image forming method which does not cause an image defect due to a change in toner properties due to the above.
[0014]
[Means for Solving the Problems]
The present invention has solved the above problems by the following present invention. That is, the present invention
<1> A heat fixing roll having a surface layer made of a fluororesin and having a rubber elastic layer between the surface layer and the core, and a fixing nip for fixing the toner on the image carrier by pressing the heat fixing roll against the heat fixing roll. A pressure member to be formed, and an image forming method for forming an image using at least a binder resin, a toner containing a colorant and a release agent, the image forming method including: The average value of the pressure is 0.8 kg / cm ² ~ 2.0kg / cm ² Further, the toner has a toner Tg of 45 ° C. to 55 ° C., an endothermic peak temperature of the release agent of 65 ° C. to 90 ° C., and an endothermic amount of an endothermic peak of the release agent of 8 J / g to 30 J. / G which is a toner satisfying each condition.
[0015]
<2> The image forming method according to <1>, wherein the toner has a flow tester viscosity at 100 ° C of 10000 Pa · s to 30000 Pa · s.
<3> The image forming method according to <1> or <2>, wherein the release agent is a paraffin-based wax.
[0016]
<4> The toner according to any one of <1> to <3>, wherein the toner satisfies the conditions of a volume average particle diameter of 4 to 9 μm and an average circularity of 0.978 or more. It is an image forming method described in the above.
<5> The toner according to any one of <1> to <4, wherein the toner satisfies a condition that a volume particle size distribution index (GSDv) is 1.25 or less and a number particle size distribution index (GSDp) is 1.3 or less. > The image forming method according to any one of the above.
[0017]
<6> At least, a dispersion of fine particles of the binder resin, a dispersion of the colorant of the colorant, and a dispersion of the release agent are mixed, and a dispersion of aggregated particles of the resin fine particles and the colorant is mixed. The toner according to any one of <1> to <5>, wherein the toner is produced by a production method having a step of fusing and coalescing, after forming, heating this to a temperature not lower than the endothermic peak temperature of the release agent. An image forming method according to any one of the above.
<7> The image forming method according to any one of <1> to <6>, wherein the surface layer of the heat fixing roll is a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer.
[0018]
<8> The method according to any one of <1> to <7>, wherein the pressing member has a surface layer of a tetrafluoroethylene perfluoroalkylvinyl ether copolymer, and the base member is an endless belt made of a polyimide resin. An image forming method according to any one of the above.
<9> The image forming method according to any one of <1> to <8>, wherein in the pressure distribution of the fixing nip, the pressure on the outlet side is higher than the pressure on the inlet side.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The image forming method of the present invention will be described.
In the image forming method of the present invention, the surface layer is made of a fluororesin, and a heat-fixing roll having a silicone rubber elastic layer between the surface layer and the core; An image forming method for forming an image using a toner containing at least a binder resin, a colorant, and a release agent, using an image fixing device having a pressure member that forms a fixing nip for fixing the toner to the toner. The average value of the pressure applied to the fixing nip is 0.8 kg / cm. ² ~ 2.0kg / cm ² Wherein the toner satisfies each condition of Tg of 45 ° C. to 55 ° C., endothermic peak temperature of 65 ° C. to 90 ° C., and endothermic peak endothermic amount of 8 J / g to 30 J / g. And
[0020]
The heat fixing roll according to the present invention has a surface layer made of a fluororesin, and has a rubber elastic layer between the surface layer and the core. When fixing the toner on the image carrier, it is necessary to suppress the adhesion of the toner to the heat fixing roll. However, since the surface energy of the fluororesin is low, by using the fluororesin for the surface layer, the hot offset resistance is reduced. Is improved. Among the fluororesins, tetrafluoroethylene copolymers and tetrafluoroethylene perfluoroalkylvinyl ether copolymers are preferred because of their particularly low surface energy. Further, a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer is more preferable because it has excellent durability when used continuously in a high temperature range and also has excellent workability. Particularly, a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer in which a polymerization end is fluorinated is preferable.
[0021]
Further, the thickness of the surface layer is preferably 10 μm or more from the viewpoint of abrasion resistance and the strength of the surface layer, and the adhesion to the toner image at the time of fixing becomes better, so that heat transfer can be performed more efficiently. It is more preferable that the thickness be 50 μm or less from the viewpoint of the capability.
[0022]
By providing a rubber elastic layer on the heat fixing roll, the adhesiveness when the heat roll is pressed against the toner is improved, and heat can be uniformly supplied to the toner. In the present invention, the rubber elastic layer is preferably a silicone rubber elastic layer using silicone rubber from the viewpoint of heat resistance. The rubber hardness (JIS-A) used for the rubber elastic layer is preferably 15 to 45 degrees from the viewpoint of sufficient deformation under low pressure and durability due to pressure stress. From the viewpoint of thermal conductivity, a material in which a heat conductive material such as alumina is dispersed in a rubber elastic layer such as a silicone rubber elastic layer is preferable. The rubber elastic layer preferably has a thickness of 0.2 mm to 1.0 mm from the viewpoint of efficient heat transfer and adhesion to the toner layer.
[0023]
As the material of the core in the heat fixing roll, a material such as an aluminum alloy, an iron alloy, and a copper alloy can be used in view of strength, heat capacity, and thermal conductivity. From the viewpoint of the warm-up time and strength of the fixing device, it is preferable to use a high-tensile steel pipe having a wall thickness of 0.1 mm to 0.5 mm as the core material.
[0024]
The pressure member can use a pressure roll, a pressure belt, a pressure pad, and the like.However, a method in which an endless belt is used as a pressure belt and a nip is formed by a pad from the inside of the pressure belt, Even if the heat fixing roll has a small diameter, a wide nip width can be obtained in combination with the heat fixing roll, which is preferable in that the fixing device can be reduced in size and weight. It is also preferable to use an endless belt as a pressure belt in that the pressure distribution can be freely controlled by designing the pad.
[0025]
As a material of the endless belt, a polyimide-based material is preferable in terms of heat resistance and mechanical strength. Further, a pressing member having a surface layer of a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer and having a substrate made of a polyimide resin is preferable. With the above configuration, the effect of suppressing the back surface offset at the time of double-sided fixing becomes remarkable.
[0026]
In the present invention, the pressure applied to the fixing nip is 0.8 kg / cm. ² ~ 2kg / cm ² And preferably 1.0 to 1.8 kg / cm ² It is. The pressure applied to the fixing nip is 0.8 kg / cm ² When the value is less than the above range, the melting of the toner in the fixing nip portion becomes insufficient, so that the color developability is deteriorated and the image becomes uneven. On the other hand, the pressure applied to the fixing nip is 2 kg / cm. ² When the value exceeds the above, the wear of the surface layer is rapidly promoted or the rubber elastic layer is deteriorated due to the stress of the heating roll surface layer and the rubber elastic layer received at the fixing nip portion and the stress of the pressing member surface.
[0027]
Further, the pressure distribution of the fixing nip portion is set such that the pressure on the exit side is set higher than the pressure on the entrance side with respect to the nip center, so that the angle between the paper discharge direction and the rotation direction of the heating roll can be widened. It is preferable from the viewpoint of winding resistance. More preferably, the pressure on the outlet side is preferably at least twice the pressure on the inlet side. Further, since local stress on the elastic layer increases, the pressure on the outlet side is more preferably 5 times or less the pressure on the inlet side.
[0028]
The toner according to the present invention has a toner Tg (glass transition temperature) of 45C to 55C. When the toner Tg is lower than 45 ° C., the low-temperature fixability is good, but the blocking resistance is deteriorated. On the other hand, when the toner Tg is higher than 55 ° C., the minimum fixing temperature becomes higher. From the relationship between the blocking resistance and the minimum fixing temperature, the preferred toner Tg is 48 ° C. to 53 ° C.
[0029]
In the toner according to the present invention, the endothermic peak temperature of the release agent internally added to the toner is 65 ° C to 90 ° C. When the endothermic peak temperature is less than 65 ° C., the dispersion domain of the release agent inside the toner becomes large, and the OHP transparency and the blocking resistance deteriorate. On the other hand, if the endothermic peak temperature exceeds 90 ° C., the winding resistance deteriorates on the low temperature side of the effective swing width of the control temperature of the heating roll generated during long-term running. This tendency is not remarkable at first, but becomes remarkable when the surface layer of the heating roll receives stress due to long-term running. The preferred endothermic peak temperature is in the range of 70C to 80C.
[0030]
The endothermic amount of the endothermic peak of the release agent is 8 J / g to 30 J / g. When the heat absorption is less than 8 J / g, the effect of the release agent cannot be sufficiently exhibited at the time of fixing, and the winding resistance and the hot offset resistance deteriorate. On the other hand, if the heat absorption exceeds 30 J / g, the ratio of the release agent domain in the toner becomes too large, which impairs OHP permeability and color development. The preferable range of the endothermic amount is 13 J / g to 23 J / g.
[0031]
The viscosity of the flow tester at 100 ° C. of the toner according to the present invention is preferably 10,000 Pa · s to 30,000 Pa · s. When the viscosity of the flow tester is lower than 10,000 Pa · s, the self-aggregation property of the toner itself in a high temperature range is reduced, so that the hot offset resistance may be deteriorated. On the other hand, when the flow tester viscosity is higher than 30,000 Pa · s, the release resistance of the release agent is not sufficient on the low temperature side of the effective swing width of the control temperature of the heating roll generated during long-term running, so that the winding resistance is low. May worsen. This tendency does not appear initially, but may appear when the surface layer of the heating roll is stressed by long-term running.
[0032]
The toner according to the present invention contains at least a binder resin, a colorant, and a release agent. Hereinafter, the toner according to the present invention will be described.
The toner according to the present invention preferably satisfies the conditions that the volume average particle diameter is 4 to 9 μm and the average circularity is 0.978 or more.
When the volume average particle size is 4 μm or more, generation of a free release agent is suppressed, and the fluidity and blocking resistance of the toner are further improved. When the volume average particle size is 9 μm or less, higher definition image reproduction can be obtained. In particular, in order to faithfully reproduce a high-resolution latent image for writing by using a laser or an LED, a volume average particle diameter of 1/4 or less of the major axis of the photosensitive image writing spot is preferable.
Further, when the average circularity is 0.978 or more, the effect of suppressing image disturbance occurring at the time of development or transfer becomes more remarkable. The average circularity is preferably 0.980 or more, more preferably 0.980.
[0033]
Further, the toner according to the present invention preferably satisfies the conditions that the volume particle size distribution index (GSDv) is 1.25 or less and the number particle size distribution index (GSDp) is 1.3 or less.
The volume particle size distribution index of the toner is more preferably 1.23 or less. When the volume particle size distribution index is 1.25 or less, the effect of obtaining smooth image reproduction and fine line reproducibility is remarkable.
On the other hand, the number particle size distribution index of the toner according to the present invention is more preferably 1.28 or less. When the number particle size distribution index is 1.30 or less, the effect of suppressing carrier contamination during development and sleeve contamination of the developing device becomes remarkable.
[0034]
Examples of the binder resin include a thermoplastic binder resin, and specifically, homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene (styrene-based resins). Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, methacryl Homopolymers or copolymers of vinyl group-containing esters such as 2-ethylhexyl acid (vinyl resin); Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl resin); Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether Homopolymer or copolymer (vinyl resin); Homopolymer or copolymer of vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone (vinyl resin); ethylene, propylene, butadiene, isoprene Homopolymers or copolymers of olefins (olefin resins) such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, non-vinyl condensation resins such as polyether resins, and non-vinyl condensation thereof And a graft polymer of a vinyl resin and a vinyl monomer. These resins may be used alone or in combination of two or more.
Among these resins, styrene-based resins, vinyl-based resins, polyester resins, and olefin-based resins are preferable, and copolymers of styrene and n-butyl acrylate, n-butyl acrylate, and bisphenol A / fumaric acid copolymer A copolymer of styrene and olefin is particularly preferred from the viewpoint of the stability of the dispersion.
[0035]
When a vinyl monomer is used as the binder resin component, a resin particle dispersion can be prepared by performing emulsion polymerization using an ionic surfactant or the like, and using other resins. If the solvent is oily and soluble in a solvent with relatively low solubility in water, dissolve the resin into those solvents and mix it with water using a homogenizer or other dispersing machine together with an ionic surfactant or polymer electrolyte. The resin dispersion can be prepared by dispersing the solvent into fine particles and then evaporating the solvent by heating or reducing the pressure. The particle size of the obtained resin fine particle dispersion is measured by, for example, a laser diffraction type particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).
[0036]
As the release agent, a low-molecular-weight polyolefin such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, and low-molecular-weight polybutene as long as the endothermic peak temperature when added to the toner is in the range of 65 ° C to 90 ° C; Silicones having a melting point depending on the type; fatty acid amides such as oleamide, erucamide, ricinoleamide, and stearamide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc. Vegetable wax; animal wax such as beeswax; minerals such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, microcrystalline wax, Fischer-Tropsch wax, petroleum wax; and modified products thereof. use Kill. Among these waxes, paraffin-based wax has an appropriate viscosity in a toner fixing temperature region, so that it excels in exuding property, and has a toner winding property in a low temperature range and a hot offset resistance in a high temperature range. preferable.
[0037]
The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in a toner. For example, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite. Examples of the yellow pigment include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hanza yellow, Hanza yellow 10G, benzidine yellow G, benzidine yellow GR, sllen yellow, quinoline yellow, and permanent yellow NCG.
[0038]
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, induslen brilliant orange RK, induslen brilliant orange GK and the like.
Red pigments include red, red, cadmium red, lead red, mercury sulfide, watch young red, permanent red 4R, lithol red, brilliantamine 3B, brilliantamine 6B, Dupont oil red, pyrazolone red, rhodamine B lake, lake red C, Rose Bengal, Eoxin Red, Alizarin Lake and the like. Blue pigments include navy blue, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxa. Rates and the like.
[0039]
Examples of the purple pigment include manganese purple, fast violet B, and methyl violet lake. Examples of the green pigment include chromium oxide, chrome green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of the white pigment include zinc white, titanium oxide, antimony white, and zinc sulfide. Examples of the extender include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Examples of the dye include various dyes such as basic, acidic, dispersion, and direct dyes, for example, nigrosine, methylene blue, rose bengal, quinoline yellow, ultramarine blue, and the like.
[0040]
These colorants can be used alone or as a mixture, or even in the form of a solid solution. These colorants are dispersed in a dispersion in a known manner together with an ionic surfactant, a polymer acid or a polymer electrolyte such as a polymer base in water, for example, a rotary shearing homogenizer or a ball mill. , A sand mill, an attritor and the like, and a high pressure opposed collision type disperser are preferably used. The particle size of the obtained colorant particle dispersion is measured by, for example, a laser diffraction type particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).
[0041]
The content of the colorant is preferably in the range of 1 to 20 parts by mass in terms of solid content based on 100 parts by mass of the binder resin. When a magnetic material is used as the black colorant, it is preferable that the magnetic material be contained in the range of 30 to 100 parts by mass, unlike other colorants.
Further, when the toner is used as a magnetic toner, a magnetic powder may be contained. As the magnetic powder, a substance magnetized in a magnetic field is used, and a ferromagnetic powder such as iron, cobalt, and nickel, or a compound such as ferrite and magnetite is used. In the present invention, since the toner is manufactured in the aqueous phase, it is necessary to pay attention to the transferability of the magnetic substance to the aqueous phase, and the surface of the magnetic substance is subjected to a hydrophobic treatment to modify the surface. Is preferred.
[0042]
In the toner according to the present invention, a charge control agent can be used in order to further improve and stabilize the chargeability. As the charge control agent, a commonly used charge control agent such as a quaternary ammonium salt compound, a nigrosine compound, a dye composed of a complex of aluminum, iron, chromium or the like, or a triphenylmethane pigment can be used. From the viewpoint of controlling the ionic strength that affects the stability at the time of mixing and reducing the pollution of wastewater, a material that is difficult to dissolve in water is preferable.
[0043]
Further, the toner according to the present invention may contain inorganic fine particles in a wet manner in order to stabilize the charging property. Examples of the inorganic fine particles to be added include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, which are usually added externally to the toner surface, and are used with an ionic surfactant, a polymer acid, It can be used by being dispersed in a molecular base.
[0044]
Further, for the purpose of imparting fluidity to the toner and improving the cleaning property, after drying the toner in the same manner as a normal toner, inorganic particles such as silica, alumina, titania, calcium carbonate, fine particles of a vinyl resin, polyester, silicone Resin fine particles such as the above can be used by adding to the toner surface by shearing in a dry state.
[0045]
As a method for producing the toner according to the present invention, an emulsion polymerization aggregation method is preferable. The method for producing a toner by the emulsion polymerization coagulation method, at least, a fine particle dispersion comprising fine particles of the binder resin, a colorant dispersion comprising the colorant, a mixture of a release agent dispersion, the resin This is a production method comprising a step of forming an aggregated particle dispersion of fine particles and a colorant, heating the same to a temperature equal to or higher than the endothermic peak temperature of the release agent, and fusing and coalescing.
[0046]
In the emulsion polymerization coagulation method, the resin average dispersion diameter of the resin fine particle dispersion liquid including the binder resin fine particles is preferably 1 μm or less, since the internal dispersibility of the colorant and the release agent can be further improved. 5 μm or less is more preferable. The average dispersion diameter of the colorant in the colorant dispersion is preferably 0.5 μm or less, more preferably 0.3 μm or less, from the viewpoint of further improving the color developability and OHP permeability. Further, from the viewpoint of the efficiency of producing the aggregated particles, the thickness is more preferably 0.05 μm or more. The average dispersion diameter of the release agent of the release agent dispersion is preferably 0.5 μm or less, more preferably 0.3 μm or less, from the viewpoints of color development and OHP permeability. Further, from the viewpoint of the efficiency of producing the aggregated particles, the thickness is more preferably 0.05 μm or more.
From the above points, the method for producing the toner according to the present invention includes at least a fine particle dispersion comprising fine particles of the binder resin having an average dispersion diameter of 1 μm or less, and a colorant having an average dispersion diameter of 0.5 μm or less. Is mixed with a release agent dispersion having an average dispersion diameter of 0.5 μm or less to form an aggregated particle dispersion of fine resin particles and a colorant, which is then absorbed by the release agent. It is more preferable that the production method has a step of heating to a temperature equal to or higher than the peak temperature and fusing / unifying.
[0047]
Further, in the emulsion polymerization and aggregation method, the resin fine particle dispersion, the colorant dispersion and the release agent dispersion are mixed, and after forming aggregated particles, the resin fine particle dispersion is additionally added, so that toner is added. The particle surface can be coated with resin fine particles. This method is preferable because the concentration of the colorant and the concentration of the release agent on the surface can be suppressed lower. After the aggregated particles are formed, the particles are sufficiently fused, and the release agent easily leaks out into the particles.To obtain an appropriate release agent domain structure, the release agent endothermic peak temperature of the toner must be higher than the temperature. It is preferred to heat and fuse. More preferably, the fusion is performed at a temperature higher by at least 10 ° C. than the endothermic peak temperature of the release agent.
[0048]
The dispersion of the release agent (eg, waxes) is dispersed in water together with an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base by a known method, and a homogenizer or a pressure discharge type disperser is used. The particles can be finely divided by applying strong shearing while heating to a temperature higher than the melting point, and a dispersion of fine particles of 1 μm or less can be prepared. The average dispersion diameter of the obtained release agent particle dispersion is measured by, for example, a laser diffraction type particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).
[0049]
In the method for producing a toner according to the present invention, examples of surfactants used for emulsion polymerization, colorant dispersion, resin fine particle dispersion, release agent dispersion, aggregation, or stabilization thereof include, for example, a sulfate ester salt and a sulfonate. Surfactants, phosphate ester-based, soap-based anionic surfactants, cationic surfactants such as amine salt type and quaternary ammonium salt type, polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based It is also effective to use a nonionic surfactant such as the above in combination. As a dispersing means, a rotary shearing homogenizer, a ball mill having a media, a sand mill, a dyno mill, or the like can be used.
[0050]
When using a composite comprising a resin and a colorant, a method of dissolving and dispersing the resin and the colorant in a solvent, dispersing the resin and the appropriate dispersant in water, and removing the solvent by heating and reducing the pressure. Alternatively, it can be prepared and prepared by a method of applying a mechanical shear force to the surface of resin fine particles prepared by emulsion polymerization, or a method of electrically adsorbing and fixing. These methods are effective for suppressing the release of the colorant as additional particles and improving the colorant dependence of the chargeability.
[0051]
After completion of the polymerization, a desired toner is obtained through an optional washing step, solid-liquid separation step, and drying step. In the washing step, it is preferable to perform sufficient replacement washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration and the like are preferred from the viewpoint of productivity. The drying step is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration type fluidized drying and the like are preferably used from the viewpoint of productivity.
[0052]
As described above, according to the image forming method of the present invention, the average value of the pressure applied to the fixing nip is 0.8 kg / cm. ² ~ 2.0kg / cm ² The toner Tg satisfies the conditions of 45 ° C. to 55 ° C., the endothermic peak temperature of the release agent of 65 ° C. to 90 ° C., and the endothermic amount of the endothermic peak of the release agent of 8 J / g to 30 J / g. By using the toner, it is possible to achieve both the reliability of the image fixing device and a high-quality image.
[0053]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
(Preparation of resin fine particle dispersion 1)
Styrene: 300 parts by mass
n-butyl acrylate: 100 parts by mass
Acrylic acid: 6 parts by mass
Dodecanethiol: 20 parts by mass
Carbon tetrabromide: 4 parts by mass
The above components were mixed and dissolved, while 6 g of nonionic surfactant Nonipol 400 (manufactured by Kao Corporation) and 10 g of anionic surfactant Neogen SC (manufactured by Daiichi Kogyo Seiyaku) were dissolved in 500 g of ion-exchanged water. Was placed in a flask, and the above mixed solution was added to disperse and emulsify. 4 g of ammonium persulfate was dissolved while slowly stirring and mixing for 10 minutes. Further, 50 g of an ion exchange aqueous solution was added. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated to 70 ° C. in an oil bath while stirring, and the emulsion polymerization was continued for 5 hours. Thus, an anionic resin particle dispersion liquid 1 having a center particle diameter of the resin particles of 210 nm, a glass transition point of 53 ° C., and a weight average molecular weight Mw of 32,000 was obtained.
The central particle diameter of the resin particles was measured with a laser diffraction type particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The glass transition temperature was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50) at a heating rate of 3 ° C./min. The weight average molecular weight was measured by gel permission chromatography.
The same measurement was performed for the following resin dispersions.
[0054]
(Preparation of resin fine particle dispersion liquid 2)
Styrene: 330 parts by mass
n-butyl acrylate: 70 parts by mass
Acrylic acid: 6 parts by mass
Dodecanethiol: 20 parts by mass
Carbon tetrabromide: 4 parts by mass
The above components were mixed and dissolved, while 6 g of nonionic surfactant Nonipol 400 (manufactured by Kao Corporation) and 10 g of anionic surfactant Neogen SC (manufactured by Daiichi Kogyo Seiyaku) were dissolved in 500 g of ion-exchanged water. Was placed in a flask, and the above-mentioned mixed solution was added to disperse and emulsify. While slowly stirring and mixing for 10 minutes, 50 g of an ion exchange aqueous solution in which 4 g of ammonium persulfate was dissolved was added. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated to 70 ° C. in an oil bath while stirring, and the emulsion polymerization was continued for 5 hours. Thus, an anionic resin particle dispersion liquid 2 having a resin particle center particle diameter of 240 nm, a glass transition point of 50 ° C., and a weight average molecular weight Mw of 38500 was obtained.
[0055]
(Preparation of resin fine particle dispersion 3)
Styrene: 370 parts by mass
n-butyl acrylate: 30 parts by mass
Acrylic acid: 8 parts by mass
Dodecanethiol: 30 parts by mass
Carbon tetrabromide: 4 parts by mass
The above components were mixed and dissolved, while 6 g of nonionic surfactant Nonipol 400 (manufactured by Kao Corporation) and 10 g of anionic surfactant Neogen SC (manufactured by Daiichi Kogyo Seiyaku) were dissolved in 500 g of ion-exchanged water. Was placed in a flask, and the above-mentioned mixed solution was added to disperse and emulsify. While slowly stirring and mixing for 10 minutes, 50 g of an ion exchange aqueous solution in which 4 g of ammonium persulfate was dissolved was added. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated to 70 ° C. in an oil bath while stirring, and the emulsion polymerization was continued for 5 hours. Thus, an anionic resin particle dispersion liquid 3 having a resin particle center diameter of 180 nm, a glass transition point of 60 ° C., and a weight average molecular weight Mw of 19000 was obtained.
[0056]
(Preparation of resin fine particle dispersion 4)
Styrene: 340 parts by mass
n-butyl acrylate: 60 parts by mass
Acrylic acid: 8 parts by mass
Dodecanethiol: 25 parts by mass
Carbon tetrabromide: 4 parts by mass
The above components were mixed and dissolved, while 4 g of nonionic surfactant Nonipol 400 (manufactured by Kao Corporation) and 8 g of anionic surfactant Neogen SC (manufactured by Daiichi Kogyo Seiyaku) were dissolved in 500 g of ion-exchanged water. Was placed in a flask, and the above-mentioned mixed solution was added to disperse and emulsify. While slowly stirring and mixing for 10 minutes, 50 g of an ion exchange aqueous solution in which 4 g of ammonium persulfate was dissolved was added. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated to 70 ° C. in an oil bath while stirring, and the emulsion polymerization was continued for 5 hours. Thus, an anionic resin particle dispersion liquid 4 having a resin particle center diameter of 430 nm, a glass transition point of 55.2 ° C., and a weight average molecular weight Mw of 22,000 was obtained.
[0057]
(Preparation of resin fine particle dispersion liquid 5)
Styrene: 300 parts by mass
n-butyl acrylate: 100 parts by mass
Acrylic acid: 8 parts by mass
Dodecanethiol: 30 parts by mass
Carbon tetrabromide: 4 parts by mass
The above components were mixed and dissolved, while 4 g of nonionic surfactant Nonipol 400 (manufactured by Kao Corporation) and 8 g of anionic surfactant Neogen SC (manufactured by Daiichi Kogyo Seiyaku) were dissolved in 500 g of ion-exchanged water. Was placed in a flask, and the above-mentioned mixed solution was added to disperse and emulsify. While slowly stirring and mixing for 10 minutes, 50 g of an ion exchange aqueous solution in which 4 g of ammonium persulfate was dissolved was added. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated to 70 ° C. in an oil bath while stirring, and the emulsion polymerization was continued for 5 hours. Thus, an anionic resin particle dispersion liquid 5 having a center particle diameter of the resin particles of 250 nm, a glass transition point of 45 ° C., and a weight average molecular weight Mw of 19,500 was obtained.
[0058]
(Preparation of Colorant Dispersion 1 (Cyan))
Cyan pigment (copper phthalocyanine CI Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.): 50 parts by mass
Nonionic surfactant (Niopol 400, manufactured by Kao Corporation): 5 parts by mass
Ion exchange water: 200 parts by mass
The above components were mixed and dissolved, and dispersed with a homogenizer (Ultra Turrax, manufactured by IKA) for 10 minutes to obtain Colorant Dispersion Liquid 1 having a center particle size of 168 nm.
The central particle size of the colorant particles was measured by a laser diffraction type particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The same measurement was performed for the following colorant dispersions.
[0059]
(Preparation of Colorant Dispersion 2 (Yellow))
A colorant except that the same amount of a yellow pigment (CI Pigment Yellow 180, Clariant Japan Co., Ltd.) was used instead of the cyan pigment (Dainichi Seika Co., Ltd., copper phthalocyanine CI Pigment Blue 15: 3). In the same manner as in the preparation of the dispersion 1, a colorant dispersion 2 containing a colorant particle having a center particle diameter of 177 nm was obtained.
[0060]
(Preparation of Colorant Dispersion 3 (Magenta))
Instead of using a cyan pigment (manufactured by Dainichi Seika, copper phthalocyanine CI Pigment Blue 15: 3), an equal amount of a magenta pigment (manufactured by Dainichi Ink Chemical Company, CI Pigment Red 122) was used. In the same manner as in the preparation of the colorant dispersion 1, a colorant dispersion 3 containing colorant particles having a center diameter of 186 nm was obtained.
[0061]
(Preparation of Colorant Dispersion 4 (Black))
Preparation of Colorant Dispersion Liquid 1 except that the same amount of a black pigment (manufactured by Cabot Corporation, carbon black) was used in place of the cyan pigment (manufactured by Dainichi Seika, copper phthalocyanine CI Pigment Blue 15: 3). Similarly, a colorant dispersion liquid 4 containing colorant particles having a center diameter of 159 nm was obtained.
[0062]
(Preparation of Colorant Dispersion 5 (Cyan))
Cyan pigment (copper phthalocyanine CI Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.): 50 parts by mass
Nonionic surfactant (Niopol 400, manufactured by Kao Corporation): 5 parts by mass
Ion exchange water: 200 parts by mass
The above components were mixed and dissolved, and dispersed with a homogenizer (Ultra Turrax, manufactured by IKA) for 5 minutes to obtain a colorant dispersion liquid 5 having a central particle diameter of 420 nm.
[0063]
(Preparation of Colorant Dispersion 6 (Yellow))
A colorant except that the same amount of a yellow pigment (CI Pigment Yellow 180, Clariant Japan Co., Ltd.) was used instead of the cyan pigment (Dainichi Seika Co., Ltd., copper phthalocyanine CI Pigment Blue 15: 3). A colorant dispersion 6 containing colorant particles having a center diameter of 320 nm was obtained in the same manner as in the preparation of the dispersion 5.
[0064]
(Preparation of Colorant Dispersion 7 (Magenta))
Instead of using a cyan pigment (manufactured by Dainichi Seika, copper phthalocyanine CI Pigment Blue 15: 3), an equal amount of a magenta pigment (manufactured by Dainichi Ink Chemical Company, CI Pigment Red 122) was used. In the same manner as in the preparation of the colorant dispersion 5, a colorant dispersion 7 containing colorant particles having a center diameter of 350 nm was obtained.
[0065]
(Preparation of Colorant Dispersion 8 (Black))
Preparation of Colorant Dispersion Liquid 5 except that the same amount of a black pigment (Cabot, carbon black) was used in place of the cyan pigment (Dainichi Seika Co., copper phthalocyanine CI Pigment Blue 15: 3). Similarly, a colorant dispersion 8 containing colorant particles having a center diameter of 380 nm was obtained.
[0066]
(Preparation of release agent dispersion liquid 1)
Paraffin wax (manufactured by Nippon Seiro, HNP09, melting point 77 ° C): 50 parts by mass
Cationic surfactant (Sanisol B50, manufactured by Kao Corporation): 5 parts by mass
Ion exchange water: 200 parts by mass
After heating the above components to 95 ° C. and sufficiently dispersing with an Ultra Turrax T50 manufactured by IKA, the dispersion was subjected to a dispersion treatment using a pressure discharge type homogenizer, and a release agent dispersion containing release agent particles having a center diameter of 160 nm was dispersed. Liquid 1 was obtained.
The center particle size of the release agent particles was measured by a laser diffraction type particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The same measurement was performed for the following release agent dispersions.
[0067]
(Preparation of release agent dispersion liquid 2)
Polyethylene wax (Toyo Petrolite, polywax 1000, melting point 113 ° C): 50 parts by mass
Cationic surfactant (Sanisol B50, manufactured by Kao Corporation): 5 parts by mass
Ion exchange water: 200 parts by mass
After the above components were heated and stirred at 120 ° C. in a pressurized container, they were subjected to dispersion treatment with a pressure discharge type homogenizer to obtain a release agent dispersion liquid 2 containing release agent particles having a center diameter of 20 nm.
[0068]
(Preparation of release agent dispersion 3)
Paraffin wax (HNP11, melting point 66 ° C, manufactured by Nippon Seiro): 50 parts by mass
Cationic surfactant (Sanisol B50, manufactured by Kao Corporation): 5 parts by mass
Ion exchange water: 200 parts by mass
After heating the above components to 95 ° C. and sufficiently dispersing with an Ultra Turrax T50 manufactured by IKA, the dispersion was subjected to a dispersion treatment using a pressure discharge homogenizer, and a release agent containing release agent particles having a center diameter of 180 nm. Dispersion 3 was obtained.
[0069]
(Preparation of release agent dispersion liquid 4)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP0190, melting point: 88 ° C.): 50 parts by mass
Cationic surfactant (Sanisol B50, manufactured by Kao Corporation): 5 parts by mass
Ion exchange water: 200 parts by mass
After heating the above components to 98 ° C. and sufficiently dispersing them in Ultra Turrax T50 manufactured by IKA, the components were subjected to dispersion treatment with a pressure discharge type homogenizer, and release agents containing release agent particles having a center diameter of 350 nm were used. Dispersion 4 was obtained.
[0070]
(Preparation of release agent dispersion liquid 5)
Paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP05, melting point 64 ° C.): 50 parts by mass
5 parts by mass of a cationic surfactant (Sanisol B50, manufactured by Kao Corporation)
200 parts by mass of ion-exchanged water
The above-mentioned components were heated to 85 ° C. and sufficiently dispersed in Ultra Turrax T50 manufactured by IKA Co., Ltd., and then subjected to dispersion treatment using a pressure discharge type homogenizer to obtain a center diameter of 150 nm.
The release agent dispersion liquid 5 containing the release agent particles of the above was obtained.
[0071]
(Production of Toner 1 (Yellow))
Resin fine particle dispersion 1: 200 parts by mass
Colorant dispersion 2: 28 parts by mass
Release agent dispersion 1: 37 parts by mass (in terms of solid content)
Polyaluminum chloride: 1.23 parts by mass
After the above components were sufficiently mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKE), the mixture was heated to a coagulation temperature of 50 ° C. while stirring the flask in a heating oil bath. Thereafter, the mixture was kept at 50 ° C. for 60 minutes, and then 30 parts by mass of the resin fine particle dispersion 1 was further added and gently stirred. Thereafter, the pH in the system was adjusted to 7.0 with a 0.5 Mol / L aqueous sodium hydroxide solution, and then the stainless steel flask was sealed and heated to 90 ° C. while continuing to stir using a magnetic seal. Thereafter, the pH was lowered to 3.8 and maintained for 6 hours. After completion of the reaction, the reaction solution was cooled, filtered, and sufficiently washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the resultant was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. After repeating this washing operation five times, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Then, vacuum drying was continued for 12 hours to obtain a yellow toner 1.
[0072]
(Production of Toner 2 (Magenta))
In the production of the toner 1, the amount of the release agent dispersion 1 added to 8.0 parts by mass, the colorant dispersion 228 parts by mass to the colorant dispersion 3 7.5 parts by mass, and 90 ° C. Toner 2 was obtained in the same manner as in the production of Toner 1 except that the pH in the system at the time of arrival was set to 4.1, and the coalescence / coalescence time was changed to 5 hours.
[0073]
(Production of Toner 3 (Cyan))
In the production of the toner 1, the addition amount of the release agent dispersion liquid 1 was changed to 9.0 parts by mass, and the colorant dispersion liquid 228 parts by mass was changed to 5.0 parts by mass of the colorant dispersion liquid 1. Toner 3 was obtained in the same manner as in the production of Toner 1 except that the in-system pH at 90 ° C. was changed to 4.0.
[0074]
(Manufacture of Toner 4 (Black))
In the production of the toner 1, the addition amount of the release agent dispersion liquid 1 was set to 7.0 parts by mass, the colorant dispersion liquid 228 parts by mass was added to the colorant dispersion liquid 45.0 parts by mass, and 90 ° C. after stopping the aggregation. Toner 4 was obtained in the same manner as in the production of Toner 1 except that the pH in the system at the time of arrival was changed to 4.0.
[0075]
(Production of Toner 5 (Yellow))
Resin fine particle dispersion 2: 200 parts by mass
Colorant dispersion 2: 28 parts by mass
Release agent dispersion 1: 42 parts by mass
Polyaluminum chloride: 1.23 parts by mass
After the above components were sufficiently mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKE), the flask was heated to a coagulation temperature of 48 ° C. while stirring the flask in a heating oil bath. Thereafter, the mixture was kept at 48 ° C. for 60 minutes, and then 30 parts by mass of the resin fine particle dispersion liquid 2 was further added, followed by gentle stirring. Thereafter, the pH in the system was adjusted to 7.0 with a 0.5 Mol / L aqueous sodium hydroxide solution, and then the stainless steel flask was sealed and heated to 90 ° C. while continuing to stir using a magnetic seal. Thereafter, the pH was lowered to 3.8 and maintained for 6 hours. After completion of the reaction, the reaction solution was cooled, filtered, and sufficiently washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the resultant was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. After repeating this washing operation five times, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Then, vacuum drying was continued for 12 hours to obtain a yellow toner 5.
[0076]
(Production of Toner 6 (Magenta))
In the production of the toner 5, the amount of the release agent dispersion 1 added to 9.0 parts by mass, the colorant dispersion 228 parts by mass to the colorant dispersion 3 7.5 parts by mass, and 90 ° C. Toner 6 was obtained in the same manner as in the production of toner 5, except that the pH in the system at the time of arrival was 4.1, and the coalescence / coalescence time was changed to 5 hours.
[0077]
(Production of Toner 7 (Cyan))
In the production of the toner 5, the amount of the release agent dispersion liquid 1 added to 10.0 parts by mass, the colorant dispersion liquid 228 parts by mass to the colorant dispersion liquid 1 5.0 parts by mass, and 90 ° C. Toner 7 was obtained in the same manner as in the production of Toner 5, except that the pH in the system at the time of arrival was changed to 4.0.
[0078]
(Production of Toner 8 (Black))
In the production of the toner 5, the amount of the release agent dispersion 1 added to 9.0 parts by mass, the colorant dispersion 228 parts by mass to the colorant dispersion 4 5.0 parts by mass, and 90 ° C. Toner 8 was obtained in the same manner as in the production of toner 5, except that the pH in the system at the time of arrival was changed to 4.0.
[0079]
(Production of Toner 9 (Yellow))
Resin fine particle dispersion 3: 200 parts by mass
Colorant dispersion 2: 28 parts by mass
Release agent dispersion 2: 85 parts by mass
Polyaluminum chloride: 1.5 parts by mass
After the above components were sufficiently mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKE), the flask was heated to a coagulation temperature of 61 ° C. while stirring the flask in a heating oil bath. Thereafter, the mixture was kept at 54 ° C. for 60 minutes, and then 30 parts by mass of the resin fine particle dispersion 1 was further added and gently stirred. Thereafter, the pH in the system was adjusted to 7.0 with a 0.5 Mol / L aqueous sodium hydroxide solution, and then the stainless steel flask was sealed and heated to 97 ° C. while continuing to stir using a magnetic seal. Thereafter, the pH was lowered to 6.0 and maintained for 2 hours. After completion of the reaction, the reaction solution was cooled, filtered, and sufficiently washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the resultant was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. After repeating this washing operation five times, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Then, vacuum drying was continued for 12 hours to obtain a yellow toner 9.
[0080]
(Production of Toner 10 (Magenta))
In the production of the toner 9, when the addition amount of the release agent dispersion liquid 2 is 18 parts by mass, the colorant dispersion liquid 2 28 parts by mass is the colorant dispersion liquid 3 7.5 parts by mass, and the temperature reaches 97 ° C. after stopping the aggregation. The toner 10 was obtained in the same manner as in the production of the toner 9 except that the in-system pH was changed to 6.2.
[0081]
(Production of Toner 11 (Cyan))
In the production of the toner 9, when the addition amount of the release agent dispersion liquid 2 is 17 parts by mass, and the colorant dispersion liquid 2 is 28 parts by mass and the colorant dispersion liquid 1 is 5.0 parts by mass. The toner 11 was obtained in the same manner as in the production of the toner 9 except that the pH in the system was changed.
[0082]
(Manufacture of Toner 12 (Black))
In the production of the toner 9, when the amount of the release agent dispersion liquid 2 added to 18 parts by mass and the colorant dispersion liquid 228 parts by mass to the colorant dispersion liquid 4 5.0 parts by mass reach 90 ° C. after stopping the aggregation. The toner 12 was obtained in the same manner as in the production of the toner 9 except that the in-system pH was changed to 6.8.
[0083]
(Production of Toner 13 (Yellow))
Resin fine particle dispersion 4: 200 parts by mass
Colorant dispersion 2: 28 parts by mass
Release agent dispersion 3: 25 parts by mass
Polyaluminum chloride: 1.5 parts by mass
After the above components were sufficiently mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKE), the flask was heated to a coagulation temperature of 51 ° C. while stirring the flask in a heating oil bath. Then, after maintaining at 51 ° C. for 60 minutes, 30 parts by mass of the resin fine particle dispersion 4 was further added and gently stirred. Thereafter, the pH of the system was adjusted to 7.0 with a 0.5 Mol / L aqueous sodium hydroxide solution, and then the stainless steel flask was sealed and heated to 90 ° C. while continuing to stir using a magnetic seal. Thereafter, the pH was lowered to 4.3 and maintained for 5 hours. After completion of the reaction, the reaction solution was cooled, filtered, and sufficiently washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the resultant was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. After repeating this washing operation five times, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Then, vacuum drying was continued for 12 hours to obtain a yellow toner 13.
[0084]
(Manufacture of Toner 14 (Magenta))
In the production of the toner 9, the amount of the release agent dispersion 3 added to 6.5 parts by mass, the colorant dispersion 228 to 28 parts by mass, the colorant dispersion 3 to 7.5 parts by mass, and 90 ° C. Toner 14 was obtained in the same manner as in the production of toner 13 except that the pH in the system at the time of arrival was 4.4 and the fusing / union time was changed to 5 hours.
[0085]
(Production of Toner 15 (Cyan))
In the production of the toner 9, the addition amount of the release agent dispersion 3 was changed to 6 parts by mass and the colorant dispersion 228 was changed to 15.0 parts by mass of the colorant dispersion 1. The toner 15 was obtained in the same manner as in the production of the toner 13 except that the pH in the system at the time of arrival was changed to 4.5.
[0086]
(Manufacture of Toner 16 (Black))
In the production of the toner 9, when the addition amount of the release agent dispersion 3 is 7 parts by mass and the colorant dispersion 228 is 28 parts by mass and the colorant dispersion 4 is 5.0 parts by mass, the temperature reaches 90 ° C. after the aggregation is stopped. The toner 16 was obtained in the same manner as in the production of the toner 13 except that the in-system pH was changed to 4.2.
[0087]
(Production of Toner 17 (Yellow))
Resin fine particle dispersion 1: 200 parts by mass
Colorant dispersion 6: 28 parts by mass
Release agent dispersion 1: 70 parts by mass
Polyaluminum chloride: 1.5 parts by mass
After the above components were sufficiently mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKE), the flask was heated to an aggregation temperature of 53 ° C. while stirring the flask in a heating oil bath. Then, after maintaining at 53 ° C. for 60 minutes, 30 parts by mass of the resin fine particle dispersion 4 was further added and gently stirred. Thereafter, the pH in the system was adjusted to 7.0 with a 0.5 Mol / L aqueous sodium hydroxide solution, and then the stainless steel flask was sealed and heated to 90 ° C. while continuing to stir using a magnetic seal. Thereafter, the pH was lowered to 4.2 and maintained for 5 hours. After completion of the reaction, the reaction solution was cooled, filtered, and sufficiently washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the resultant was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. After repeating this washing operation five times, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Then, vacuum drying was continued for 12 hours to obtain a yellow toner 17.
[0088]
(Production of Toner 18 (Magenta))
In the production of the toner 17, when the addition amount of the release agent dispersion liquid 1 is 15 parts by mass, the colorant dispersion liquid 628 parts by mass is added to the colorant dispersion liquid 7 7.5 parts by mass, and the temperature reaches 90 ° C. after stopping the aggregation. Was adjusted to 4.4 and the coalescence / coalescing time was changed to 5 hours, and a toner 18 was obtained in the same manner as in the production of the toner 17.
[0089]
(Production of Toner 19 (Cyan))
In the production of the toner 17, when the addition amount of the release agent dispersion 1 is 11 parts by mass, the colorant dispersion 628 parts by mass is added to the colorant dispersion 5 5.0 parts by mass, and the temperature reaches 90 ° C. after the aggregation is stopped. Toner 19 was obtained in the same manner as in the production of Toner 17, except that the in-system pH was changed to 4.5.
[0090]
(Production of Toner 20 (Black))
In the production of the toner 17, the addition amount of the release agent dispersion liquid 1 was set to 7 parts by mass, the colorant dispersion liquid 628 parts by mass was added to the colorant dispersion liquid 8 5.0 parts by mass, and the temperature reached 90 ° C. after the aggregation was stopped. The toner 20 was obtained in the same manner as in the production of the toner 17 except that the pH in the system was changed to 4.2.
[0091]
(Production of Toner 21 (Yellow))
Resin fine particle dispersion 1: 200 parts by mass
Colorant dispersion 2: 28 parts by mass
Release agent dispersion liquid 4:45 parts by mass
Polyaluminum chloride: 1.5 parts by mass
After the above components were sufficiently mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKE), the flask was heated to a coagulation temperature of 48 ° C. while stirring the flask in a heating oil bath. Thereafter, the mixture was kept at 48 ° C. for 60 minutes, and then 30 parts by mass of the resin fine particle dispersion liquid 1 was further added, followed by gentle stirring. Thereafter, the pH in the system was adjusted to 7.0 with an aqueous 0.5 Mol / L sodium hydroxide solution, and then the stainless steel flask was sealed, and heated to 95 ° C. while continuing to stir using a magnetic seal. Thereafter, the pH was lowered to 4.2 and maintained for 5 hours. After completion of the reaction, the reaction solution was cooled, filtered, and sufficiently washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the resultant was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. After repeating this washing operation five times, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain a yellow toner 21.
[0092]
(Production of Toner 22 (Magenta))
In the production of the toner 21, when the addition amount of the release agent dispersion 4 is 7 parts by mass, the colorant dispersion 228 is 28 parts by mass, and the colorant dispersion 3 is 7.5 parts by mass. Was adjusted to 4.4 and the fusing / union time was changed to 5 hours, except that the operation was the same as in the production of toner 21. Thus, a toner 22 was obtained.
[0093]
(Production of Toner 23 (Cyan))
In the production of the toner 21, the addition amount of the release agent dispersion 4 was changed to 8 parts by mass, and the colorant dispersion 228 was changed to 5.0 parts by mass of the colorant dispersion 1, and 95 ° C. after stopping the aggregation. The toner 23 was obtained in the same manner as in the production of the toner 21 except that the pH in the system at the time of arrival was changed to 4.5.
[0094]
(Production of Toner 24 (Black))
In the production of the toner 21, when the addition amount of the release agent dispersion 4 is 8 parts by mass and the colorant dispersion 228 is 28 parts by mass and the colorant dispersion 4 is 5.0 parts by mass, the temperature reaches 95 ° C. after the aggregation is stopped. The toner 24 was obtained in the same manner as in the production of the toner 21 except that the in-system pH was changed to 4.3.
[0095]
(Production of Toner 25 (Yellow))
Resin fine particle dispersion 5: 200 parts by mass
Colorant dispersion 2: 28 parts by mass
Release agent dispersion 5: 15 parts by mass
Polyaluminum chloride: 1.5 parts by mass
After the above components were sufficiently mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKE), the mixture was heated to a coagulation temperature of 43 ° C. while stirring the flask in a heating oil bath. Thereafter, the mixture was kept at 43 ° C. for 60 minutes, and then 30 parts by mass of the resin fine particle dispersion 1 was further added and gently stirred. Thereafter, the pH in the system was adjusted to 7.0 with an aqueous 0.5 Mol / L sodium hydroxide solution, and then the stainless steel flask was sealed, and heated to 85 ° C. while continuing to stir using a magnetic seal. Thereafter, the pH was lowered to 3.7 and maintained for 5 hours. After completion of the reaction, the reaction solution was cooled, filtered, and sufficiently washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the resultant was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. After repeating this washing operation five times, solid-liquid separation was performed by Nutsche suction filtration using No. 5A filter paper. Then, vacuum drying was continued for 12 hours to obtain a yellow toner 25.
[0096]
(Production of Toner 26 (Magenta))
In the production of the toner 25, when the addition amount of the release agent dispersion 5 is 4 parts by mass, the colorant dispersion 228 is 28 parts by mass, and the colorant dispersion 3 is 7.5 parts by mass. Was adjusted to 4.0 and the coalescence / coalescence time was changed to 5 hours, except that the operation was the same as in the production of the toner 21 to obtain a toner 26.
[0097]
(Production of Toner 27 (Cyan))
In the production of the toner 25, when the addition amount of the release agent dispersion 5 is 4 parts by mass, and the colorant dispersion 228 is 28 parts by mass and the colorant dispersion 1 is 5.0 parts by mass. The toner 27 was obtained in the same manner as in the production of the toner 21 except that the in-system pH was changed to 3.6.
[0098]
(Manufacture of Toner 28 (Black))
In the production of the toner 25, when the addition amount of the release agent dispersion liquid 5 is 5 parts by mass, the colorant dispersion liquid 228 parts by mass is added to the colorant dispersion liquid 45.0 parts by mass, and the temperature reaches 85 ° C. after stopping the aggregation. The toner 28 was obtained in the same manner as in the production of the toner 21 except that the pH in the system was changed to 3.8.
[0099]
The Tg, endothermic peak, peak endothermic amount, melt viscosity at 100 ° C., toner volume average particle diameter, volume particle size distribution index (GSDv), number particle size distribution index (GSDp), and average circularity of the obtained toners 1 to 28 are shown below. It was measured. Table 1 shows the results.
In addition, Tg, endothermic peak, and peak endothermic amount were measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50) at a heating rate of 3 ° C./min. The melt viscosity at 100 ° C. was determined by measuring the temperature dependence of the melt viscosity with a flow tester (manufactured by Shimadzu Corporation, nozzle 1 × 1 mm, load 10 kg) and interpolating the same. Volume average particle diameter D of toner ₅₀ The volume particle size distribution index and the number particle size distribution index were measured using a Coulter counter (TA2, manufactured by Coulter Co., Ltd.). Here, the volume particle size distribution index GSDv and the number particle size distribution index GSDp (D _84p / D _16p ) Is the (volume D) using the particle size (D16%) that becomes 16% cumulative from the smaller diameter side of the cumulative particle size distribution and the particle size D84% that becomes 84% cumulative, respectively. _84% / Volume D _16% ) ^0.5 , (Number D _84% / Number D _16% ) ^0.5 , Represented by The average circularity was determined by taking an optical microscopic image of the toner scattered on a slide glass into a Luzex image analyzer through a video camera, and measuring [(4 × projected area / π) of 50 or more toners. ^0.5 / Perimeter] was calculated and the average value was obtained.
[0100]
[Table 1]

[0101]
(Adjustment of developer)
To each of the obtained toners 1 to 28, 1.5 parts by mass of hydrophobic silica (TS720) was mixed with a Henschel mixer with respect to 100 parts by mass of the toner. This externally added toner is weighed to a ferrite carrier coated with 1% by mass of methacrylate (manufactured by Soken Chemical Co., Ltd.) and having an average particle size of 50 μm so that the toner concentration becomes 5% by mass, and stirred and mixed in a ball mill for 5 minutes. Thus, Developers 1 to 28 were obtained.
[0102]
(Fusing unit 1)
The DPC 2200 fixing unit was modified and the average pressure at the fixing nip was 1.6 kg / cm. ² The pressure applied to the heating roll of the endless belt was adjusted so that The pressure pad, which is located inside the endless belt, is divided into two parts. The height of the pressure pad is adjusted by using silicone rubber for the pad on the entrance side and aluminum for the pad on the exit side. The pressure on the outlet side was set to be 2.5 times the pressure on the inlet side. The heating roll was prepared by providing a 0.3 mm thick silicone rubber elastic layer on a 0.5 mm iron core, and covering the PFA tube (20 μm thick) thereon. As the pressure belt, an endless belt provided with a surface layer having a thickness of 40 μm was formed by applying a powder coating of PFA on a polyimide substrate having a thickness of 100 μm and baking it.
[0103]
(Fusing unit 2)
The DPC 2200 fixing unit was modified and the average pressure at the fixing nip was 0.7 kg / cm. ² The pressure applied to the heating roll of the endless belt was adjusted so that The pressure pad arranged inside the endless belt was made of silicone rubber, and was set so that the pressures on the outlet side and the inlet side were equal. The heating roll was formed by covering a 0.5 mm iron core with a PFA tube (thickness: 20 μm). As the pressure belt, a polyimide endless belt having a thickness of 100 μm was used, and the fixing device 2 was used.
[0104]
(Fusing unit 3)
The average pressure of the fixing nip is 2.4 kg / cm ² The fixing unit 3 was set in the same manner as the fixing unit 1 except that the pressure applied to the heating roll by the endless belt was adjusted so that
[0105]
(Fusing unit 4)
The average pressure of the fixing nip is 1.8 kg / cm ² The same settings as in the fixing device 1 were adopted except that the pressure applied to the heating roll of the endless belt was adjusted so that the pressure on the outlet side was set to be four times the pressure on the inlet side. The container 4 was used.
[0106]
(Fusing unit 5)
The average pressure of the fixing nip is 1.0 kg / cm ² The same setting as that of the fixing device 1 was adopted except that the pressure applied to the heating roll of the endless belt was adjusted so that the pressure on the outlet side was set to 1.5 times the pressure on the inlet side. And a fixing device 5.
The ratio of the pressure on the exit side to the pressure on the entrance side is determined by measuring the relative value of the pressure distribution in the fixing nip portion using a tactile sensor (manufactured by Nitta), and measuring the relative value from the center position of the fixing nip to the entrance side nip start position. It is expressed as Pout / Pin using an average value (Pin) and an average value (Pout) from the center position of the fixing nip to the exit nip end position.
[0107]
<Example 1>
Using the obtained developers 1 to 4, a minimum fixing test, a hot offset start temperature, a durability test of a fixing device, a winding property test on a fixing roll, and an image output test were performed by the fixing device 1. Further, from the obtained developers 1 to 4, secondary colors (Red), secondary colors (Green), secondary colors (Blue) and tertiary colors (Black) were similarly evaluated.
For the secondary color (Red), an image was created by overlaying a 100% image density Magenta toner image on a 100% image density Yellow toner image. An image was created by overlaying a 100% image density Cyan toner image on a secondary color (Green) image density 100% Yellow toner image. For the secondary color (Blue), an image was created by superimposing a cyan toner image having an image density of 100% on a magenta toner image having an image density of 100%. For the tertiary color (Black), an image was created by superimposing a 100% image density Magenta toner image on a 100% image density Yellow toner image, and further superimposing a 100% image density Cyan toner image.
[0108]
The minimum fixing temperature and the hot offset start temperature were adjusted in steps of 5 ° C. in a temperature range of 110 ° C. to 200 ° C., and measured by a fixing property test on Fuji Xerox P paper. The minimum fixing temperature was determined to be the lowest temperature at which the obtained fixed image was rubbed with P paper and there was no toner transfer on the rubbed P paper side. The hot offset start temperature was determined by observing the occurrence of an afterimage of a fixed image.
In the durability test of the fixing device, the test of winding property around the fixing roll, and the image output test, the surface temperature of the heating roll of the fixing device is measured by a temperature sensor placed at the center position in the roll axis direction, and the information is fed back. The temperature was controlled to 145 ° C., and an unfixed image sequentially formed on P paper was continuously output from a fixing device using a DPC 2200 modified machine manufactured by Fuji Xerox. Table 2 shows the results.
[0109]
In addition, as the above-mentioned image forming test, tests of color development, OHP transparency, image defects, reproducibility of fine lines, and image quality of the back surface during double-sided printing were performed on the following criteria.
(Color development)
A: The desired color is reproduced vividly on paper.
：: A desired color is reproduced on paper.
Δ: The color is slightly turbid, and the desired color is hardly reproduced on paper.
X: The color is turbid and the desired color is not reproduced on paper.
[0110]
(OHP transparency)
A: OHP transmission image is vividly reproduced in a desired color.
：: OHP transmission image is reproduced in a desired color.
X: OHP transmission image has turbidity and desired color is not reproduced.
[0111]
(Reproducibility of fine lines)
：: One dot thin line of 600 dpi resolution is clearly reproduced.
：: A one-dot thin line with a resolution of 600 dpi is reproduced.
×: One dot thin line with a resolution of 600 dpi is not reproduced faintly.
[0112]
(Image quality of the back side when printing on both sides)
：: No offset was generated, and there was almost no difference in gloss between the front and back images.
Δ: Difference in gloss between front and rear images occurs.
X: Offset occurred.
[0113]
[Table 2]

[0114]
<Example 2>
Evaluation was performed in the same manner as in Example 1 except that developers 1 to 4 were changed to developers 5 to 8.
Table 3 shows the results.
[0115]
[Table 3]

[0116]
<Example 3>
Evaluation was performed in the same manner as in Example 1 except that developers 1 to 4 were changed to developers 13 to 16. Table 4 shows the results.
[0117]
[Table 4]

[0118]
<Example 4>
Evaluation was performed in the same manner as in Example 1 except that developers 1 to 4 were changed to developers 17 to 20. Table 5 shows the results.
[0119]
[Table 5]

[0120]
<Example 5>
Evaluation was performed in the same manner as in Example 1 except that developers 1 to 4 were changed to developers 21 to 24. Table 6 shows the results.
[0121]
[Table 6]

[0122]
<Example 6>
Evaluation was performed in the same manner as in Example 1 except that the fixing device 1 was changed to the fixing device 4. Table 7 shows the results.
[0123]
[Table 7]

[0124]
<Example 7>
Evaluation was performed in the same manner as in Example 1 except that the fixing device 1 was changed to the fixing device 5. Table 8 shows the results.
[0125]
[Table 8]

[0126]
Example 8
Evaluation was performed in the same manner as in Example 1 except that the developers 1 to 4 were changed to the developers 5 to 8 and the fixing device 1 was changed to the fixing device 5. Table 9 shows the results.
[0127]
[Table 9]

[0128]
<Comparative Example 1>
Evaluation was performed in the same manner as in Example 1 except that the developers 1 to 4 were changed to the developers 9 to 12 and the fixing device 1 was changed to the fixing device 2. Table 10 shows the results.
[0129]
[Table 10]

[0130]
<Comparative Example 2>
Evaluation was performed in the same manner as in Example 1 except that the fixing device 1 was changed to the fixing device 3. Table 11 shows the results.
[0131]
[Table 11]

[0132]
<Comparative Example 3>
Evaluation was performed in the same manner as in Example 1 except that developers 1 to 4 were changed to developers 25 to 28. Table 12 shows the results.
[0133]
[Table 12]

[0134]
<Comparative Example 4>
Evaluation was performed in the same manner as in Example 1 except that developers 1 to 4 were changed to developers 9 to 12. Table 13 shows the results.
[0135]
[Table 13]

[0136]
From Tables 2 to 13, the average value of the pressure applied to the fixing nip is 0.8 kg / cm. ² ~ 2.0kg / cm ² Where the toner Tg is 45 ° C. to 55 ° C., the endothermic peak temperature of the release agent is 65 ° C. to 90 ° C., and the endothermic amount of the endothermic peak of the release agent is 8 J / g to 30 J / g. In the image forming method of the present invention using the toner that satisfies, all of the minimum fixing test, the hot offset start temperature, the durability test of the fixing device, the winding property test on the fixing roll, and the image output test are good. Understand.
[0137]
【The invention's effect】
The present invention is excellent in low-temperature fixing property, wrap resistance and reliability of a fixing device, excellent in color development of a full-color image, transparency of an OHP image, high-definition image reproduction, excellent in blocking resistance, and excellent in a developing device. It is possible to provide an image forming method in which an image defect does not occur due to a change in toner properties due to stress or the like.

Claims (1)

A heat-fixing roll having a surface layer made of fluororesin and having a rubber elastic layer between the surface layer and the core, and a fixing nip for fixing the toner on the image carrier by pressing the heat-fixing roll against the heat-fixing roll. Pressure member, using an image fixing device having, at least, a binder resin, an image forming method for forming an image using a toner containing a colorant and a release agent,
The average value of pressure applied to the fixing nip portion is ^{0.8kg / cm 2 ~2.0kg / cm 2} ,
Further, the toner has a toner Tg of 45 ° C. to 55 ° C., an endothermic peak temperature of the release agent of 65 ° C. to 90 ° C., and an endothermic amount of an endothermic peak of the release agent of 8 J / g to 30 J / g. An image forming method, wherein the toner satisfies each condition.