JP2006084836A - Electrostatic charge image developing toner, electrostatic charge image developing developer, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner or the like improved in releasing property and having excellent fixing characteristics. <P>SOLUTION: The electrostatic charge image developing toner contains a binder resin copolymerized with a crosslinking agent having IR absorption peak spectra at the absorption positions of at least 2,920 to 2,940 cm<SP>-1</SP>, 2,840 to 2,860 cm<SP>-1</SP>, 3,100 to 3,000 cm-1 and 1,750 to 1,735 cm<SP>-1</SP>, and having a fragment ion showing at least one mass charge ratio peak at 280 to 420 by mass spectrometry. The binder resin constituting the electrostatic charge image developing toner has 50 to 65°C glass transition temperature. As the other way, the toner contains a binder resin copolymerized with a crosslinking agent expressed by the formula. In the formula, X represents CH<SB>2</SB>or CH<SB>2</SB>CH<SB>2</SB>O; n is an integer 20 to 30 and R represents a hydrogen atom or CH<SB>3</SB>. An image forming method is carried out by using an electrostatic charge image developing developer containing the above electrostatic charge image developing toner, wherein the process speed in a fixing step is specified to 200 to 370 mm/s. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developing developer, and an image forming method used when developing an electrostatic latent image formed by an electrophotographic method, an electrostatic recording method or the like.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process.

  As the developer used here, a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a nonmagnetic toner alone are known. For the production of these toners, a kneading and pulverizing method is generally used in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent and a wax, and after cooling, is finely pulverized and classified. In these toners, inorganic and organic fine particles may be added to the surface of the toner particles as necessary for the purpose of improving fluidity and cleaning properties. Although these methods can produce a considerably excellent toner, they have the following problems.

  In the ordinary kneading and pulverizing method, the toner shape and the surface structure of the toner are indeterminate, and change slightly depending on the pulverization properties of the materials used and the conditions of the pulverization process, making it difficult to actively control the toner shape and surface structure. It is. In the kneading and pulverizing method, there are restrictions on the selection range of materials. Specifically, the resin / colorant dispersion must be sufficiently brittle and finely pulverized by an economically possible manufacturing apparatus.

  However, if the resin / colorant dispersion is made brittle, it may generate a fine powder or change the toner shape due to mechanical shearing force in the developing machine. As a result, in the case of a two-component developer, fine powder adheres to the carrier surface to accelerate the deterioration of the charging property of the developer, and in the case of a one-component developer, the particle size distribution increases to cause toner scattering, or due to a change in toner shape Deterioration in developability tends to cause image quality degradation.

  In addition, a toner in which a large amount of a release agent such as wax is internally added often affects the exposure of the release agent to the toner surface depending on the combination with a thermoplastic resin. In particular, in the case of a combination of a resin having increased elasticity due to a high molecular weight component and slightly pulverized, and a brittle wax such as polyethylene, polyethylene is often exposed on the toner surface. Although this is advantageous for releasability during 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 reduced reliability.

  Furthermore, if the toner shape becomes indeterminate, sufficient fluidity cannot be ensured even if a flow aid is added, and the fine particles on the toner surface move to the toner recesses due to mechanical shearing force during use. As a result, the fluidity is lowered over time, or the fluidity aid is buried in the toner to deteriorate the developing property, transfer property, and cleaning property. In addition, when the toner collected by cleaning is returned to the developing machine and used again, the image quality is further deteriorated. In order to prevent these problems, if the flow aid is further increased, problems such as generation of black spots on the photoreceptor or scattering of the aid particles occur.

  In recent years, as a method for positively controlling the toner shape and the surface structure, Patent Documents 1 and 2 propose a toner production method using an emulsion polymerization aggregation method. These are generally prepared by dispersing resin fine particles by emulsion polymerization or the like, while preparing a colorant dispersion in which a colorant is dispersed in a solvent and mixing both to form aggregated particles corresponding to the toner particle size, This is a method for producing a toner by fusing and uniting them by heating. This method can control the toner shape to some extent and improve the chargeability and durability, but it is difficult to control the particle size and position of the release agent and colorant in the toner. As a result, problems may remain in the peelability of the sheet to be fixed at the time of fixing and the transparency of the OHP output image.

  As described above, in the electrophotographic process, since the toner stably maintains its characteristics even under various mechanical stresses, the exposure of the release agent to the toner surface is suppressed and the fixing property is not impaired. It is necessary to improve the mechanical strength of the toner itself by increasing the surface hardness and to achieve both sufficient charging property and fixing property.

  Recently, there has been an increasing demand for higher image quality, and particularly in the formation of color images, there is a significant tendency to reduce the diameter of toner in order to realize high-definition images. However, with the simple size reduction with the conventional particle size distribution, problems such as carrier and photoconductor contamination and toner scattering become noticeable due to the presence of the fine powder side toner, 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.

  In digital full-color copiers and printers, a color image original is color-separated 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 is used. The image is developed by using a subtractive color mixing action using Y (yellow), M (magenta), C (cyan), and Bk (black) developers. Compared to conventional black-and-white copiers, digital full-color copiers, etc. need to transfer a large amount of developer and need to cope with a small dot diameter, so that uniform chargeability, durability, toner strength, The sharpness of the particle size distribution becomes increasingly important. Further, in order to meet the high speed and energy saving performance of these machines, a further low temperature fixing property is required. Considering these points, a toner produced by an aggregation / fusion coalescence method having a sharp particle size distribution and suitable for producing a small particle diameter has excellent characteristics.

  In a full-color machine, it is necessary to sufficiently mix a large amount of toner, and improvement in color reproducibility and OHP transparency are essential. Generally, a polyolefin wax is internally added to the toner in the release agent component for the purpose of preventing low temperature offset during fixing. At the same time, a small amount of silicone oil is uniformly applied to the fixing roller to improve the high temperature offset property. For this reason, there is a problem that silicone oil adheres to the transfer material to cause sticky discomfort.

  Therefore, Patent Document 3 proposes an oilless fixing toner in which a large amount of a release agent component is included in the toner and no oil is applied to the fixing roll. However, when a large amount of release agent is added, the peelability can be improved to some extent, but the binder resin component and the release agent are compatible, the exudation of the release agent becomes uneven, and the release stability is stable. Sex is difficult to obtain. In addition, the free component of the release agent may cause charging inhibition. In addition, the dispersibility of the colorant in the toner causes an interaction with the release agent, and an aggregate of the colorant is formed, causing problems such as OHP transparency inhibition and color development inhibition.

  Therefore, in order to solve these problems, Patent Document 4 proposes that a resin having a polar group be positively introduced to improve the encapsulating property and the bleeding property of the release agent. However, this method can improve the bleeding property of the release agent to some extent and improve its inclusion, but it improves the control of the position of the release agent in the toner and the dispersibility of the pigment in the toner. There is almost no effect, and it is impossible to improve the overall fixability such as peelability, adhesion of a fixed image, transparency of OHP, and resistance to bending of the fixed image. Further, insufficient dispersibility of these colorants and the like has a great influence on the charging performance.

  Patent Document 5 proposes to use a colorant that has been surface-treated with a monomer component, a wax component, or the like of a binder resin in advance in order to improve the dispersibility of the colorant. Although this method improves the colorant dispersibility to some extent, the wax embraces the colorant particles, and the dispersibility of the pigment inside the toner cannot be controlled, causing the colorant particles to agglomerate and peel off the fixing sheet. It is difficult to satisfy both stability and OHP transparency at the same time.

  Patent Documents 6 and 7 propose a method of adding a crosslinking agent component to the binder resin in order to improve the cohesive force of the binder resin for the purpose of improving the peelability of the fixing sheet. However, simply adding a cross-linking agent component to the binder resin improves the cohesive strength of the binder resin and improves the peelability, but the rigidity of the binder resin itself increases, so that the fixing image is resistant to bending. Becomes scarce. Folding resistance of a fixed image is important as a practical physical property because an image defect occurs when the fixed image on a sheet is bent and the quality of an output image is remarkably deteriorated. Further, when the melt viscosity of the binder resin is increased, the smoothness of the fixed image surface is impaired, the glossiness of the fixed image and the OHP transparency are lowered, and sufficient color mixing properties are hardly obtained in a full color image.

  Further, Patent Documents 8 and 9 propose a method of improving the apparent cohesive force of the binder resin by adding a high molecular weight component. In these methods, although the flexibility of the fixed image itself is slightly improved, it is difficult to control the cross-linking (entanglement) density of the binder resin and the molecular weight between cross-links, and the releasability is maintained while maintaining the bending resistance of the fixed image. It has been difficult to achieve both OHP transparency and transparency stably. Japanese Patent Application Laid-Open No. 11-133776 proposes a high-speed and low-pressure energy-saving type fixing device. However, in this fixing machine, the above problem is remarkable.

  Japanese Patent Laid-Open No. 2000-250266 discloses a method of controlling the density of a crosslinked structure of a binder resin, the density between crosslinks representing the degree and strength, and the molecular weight between crosslinks. Proposed toner for electrostatic image development that has excellent fixing characteristics such as fixability, peelability, OHP transparency, offset resistance, fixed image adhesion, and fixed image folding resistance, and high charging uniformity and stability. ing. However, even with the above toner, particularly when the process speed in the fixing step is 200 to 370 mm / s, the releasability is not always sufficient, and image defects may occur in the bending resistance.

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP-A-5-061239 Japanese Patent Laid-Open No. 2-105163 JP-A-4-188156 JP 59-218459 A JP 59-218460 A JP-A-4-69666 Japanese Patent Laid-Open No. 9-258481 Japanese Patent Application Laid-Open No. 11-133776 JP 2000-250266 A

  Therefore, in the present invention, in the image forming apparatus in which the process speed in the fixing step is 200 to 370 mm / s, the above-mentioned problems are solved, and particularly, the releasability is improved, the releasability of the fixing sheet, and the OHP transparency. The present invention intends to provide a toner for developing an electrostatic image having excellent fixing characteristics such as hot offset resistance, adhesion of a fixed image, and bending resistance of a fixed image, and excellent image quality.

  The present invention has the following features.

(1) and at least 2920～2940Cm ^-1 and 2840～2860Cm ^-1, and 3100～3000Cm ^-1, has an infrared absorption peak spectrum in the absorption position of the 1750～1735Cm ^-1, in mass spectrometry, 280-420 An electrostatic charge image developing toner comprising a binder resin copolymerized with a crosslinking agent having a fragment ion in which at least one mass-to-charge ratio peak appears, and the binding toner constituting the electrostatic charge image developing toner The toner for developing an electrostatic charge image has a glass transition temperature of 50 to 60 ° C. of the resin.

(2) In the electrostatic image developing toner according to (1), the cross-linking agent further includes at least one absorption position of 2950 to 2970 cm ⁻¹ and 2860 to 2880 cm ⁻¹ or 1250 to 1100 cm ^−1. And an electrostatic charge image developing toner having an infrared absorption spectrum.

（式中、ＸはＣＨ_２又はＣＨ_２ＣＨ_２Ｏ、ｎは２０〜３０の整数、Ｒは水素又はＣＨ_３を表す。） (3) An electrostatic charge image developing toner containing a binder resin obtained by copolymerizing a crosslinking agent represented by the following general formula.

(Wherein, X is CH ₂ or _CH 2 _CH 2 O, n is 20 to 30 integer, R represents hydrogen or CH _3.)

  (4) The electrostatic image developing toner according to (3), wherein n is 20 to 30 in the formula of the crosslinking agent represented by the general formula.

  (5) The addition amount of the crosslinking agent is in the range of 0.1 to 1.5% by weight with respect to the resin fine particles, as described in any one of (1) to (4) above This is a toner for developing an electrostatic image.

  (6) The toner for developing an electrostatic charge image according to (3) or (4), wherein the toner for developing an electrostatic charge image has a glass transition temperature (Tg) in the range of 50 to 65 ° C. .

  (7) The volume average particle size distribution index GSDv of the electrostatic image developing toner is 1.30 or less, and the ratio of the GSDv to the number average particle size distribution index GSDp is 0.95 or more. The toner for developing an electrostatic charge image according to any one of (1) to (6).

  (8) Any of (1) to (7) above, wherein the content of the release agent dispersed in the electrostatic image developing toner is in the range of 5 to 25% by weight in terms of solid content. The toner for developing an electrostatic charge image according to one of the above.

  (9) From the above (1), wherein the center diameter of the release agent particles dispersed in the electrostatic image developing toner is in the range of 150 to 1500 nm as measured with a transmission electron microscope (TEM). (8) The electrostatic image developing toner according to any one of (8).

  (10) Any one of (1) to (8) above, wherein the content of the colorant dispersed in the electrostatic image developing toner is in the range of 4 to 16% by weight in terms of solid content. The toner for developing an electrostatic image described in 1.

  (11) From the above (1) to (1), wherein the center diameter of the colorant particles dispersed in the toner for developing an electrostatic charge image is in the range of 100 to 330 nm as measured with a transmission electron microscope (TEM). 9) The toner for developing an electrostatic charge image according to any one of 9).

  (12) The electrostatic charge image developing toner according to any one of (1) to (11) above, wherein the electrostatic charge image developing toner has a shape factor SF1 in the range of 110 to 145. is there.

  (13) The electrostatic image developing toner according to any one of (1) to (12) above, wherein the cumulative volume average particle diameter D50 of the toner is in the range of 3 to 9 μm.

  (14) A step of preparing a dispersion of aggregated particles containing resin fine particles and a colorant by mixing a resin fine particle dispersion in which resin fine particles having a particle size of 1 μm or less, a colorant dispersion, and a release agent dispersion are mixed. And a step of fusing and coalescing the aggregated particles by heating to a temperature equal to or higher than the glass transition point of the resin fine particles, and in the step of preparing the aggregated particles, a polymer of at least one metal salt A manufacturing method for manufacturing a toner for developing an electrostatic charge image according to any one of (1) to (3), wherein the toner is used.

  (15) Following the step of preparing the aggregated particle dispersion, an adhesion step is provided in which resin fine particle dispersion is added to and mixed with the aggregated particle dispersion and the resin fine particles are adhered to the aggregated particles to form adhered particles. Then, the method for producing a toner for developing an electrostatic charge image according to the above (14), comprising a step of fusing and coalescing the adhered particles.

  (16) In the method for producing a toner for developing an electrostatic charge image according to the above (14) or (15), wherein at least one kind of metal salt polymer is used in the step of preparing the aggregated particle dispersion. is there.

  (17) The method for producing a toner for developing an electrostatic charge image according to (16), wherein a polymer of a tetravalent aluminum inorganic metal salt is used as the metal salt polymer.

  (18) An electrostatic charge image developer containing a carrier and a toner, wherein the toner is the electrostatic charge image developing toner according to any one of (1) to (13). Charge image developer.

  (19) The electrostatic charge image developer according to (18), wherein the carrier has a resin coating layer.

  (20) forming an electrostatic latent image on the electrostatic charge image carrier, developing the electrostatic latent image with a developer on the developer carrier to form a toner image, and transferring the toner image (18) as the developer in an image forming method comprising a step of transferring onto a body, a step of transferring a toner image on a transfer member onto a transfer sheet, and a step of thermally fixing the toner image on the thermal transfer sheet. Or an image forming method using the electrostatic charge image developer described in (19).

  (21) The above (17), characterized by comprising a step of recovering excess toner when forming the toner image, and a recycling step of returning the toner recovered in the recovery step onto the developer carrying member. The image forming method described.

  In particular, in the image forming apparatus in which the process speed in the fixing process is 200 to 370 mm / s, the present invention adopts the above-described configuration, so that the oilless fixing property like a PFA tube roller is high and the hot offset resistance is high. Therefore, it is possible to provide an excellent electrostatic charge image developer toner.

  The present inventors diligently studied the above problem, and by adopting the above-described configuration, the fixing sheet peelability, OHP transparency, hot offset resistance, fixed image adhesion, and fixed image folding resistance. This makes it possible to provide fixed images with excellent fixing characteristics.

  By controlling the density and molecular weight between crosslinks that express the degree and strength of the crosslink structure, this is a method that simultaneously satisfies the fixability between the fixing sheet and the fixed image and the hot offset property when the image is folded. However, it is known that the hydrophilicity / hydrophobicity of the polymerizable monomer greatly affects the binder resin (hereinafter also referred to as “binder resin”) in an aqueous medium. Since the polymerizable monomer enters the inside, in the subsequent polymerization, the hydrophobic polymerizable monomer is polymerized inside the binder resin.

  When trying to achieve both bending resistance and image glossiness, the use of a cross-linking agent having a long-chain alkylene group suppresses the decrease in glossiness despite having a cross-linked structure, and obtains some bending resistance. However, since the long-chain alkylene group is generally highly hydrophobic, it is difficult to control the degree of crosslinking of the binder resin molecular chain inside the binder resin and the degree of crosslinking on the surface of the binder resin. Not enough. Further, this tendency becomes remarkable in a high-speed type fixing machine having a process speed of 200 to 370 mm / s.

  When the binder resin is prepared by the emulsion polymerization method as in the present invention, the polymerization is started from solubilized micelles, and the polymerization proceeds by supplying a polymerizable monomer into the micelles. Here, when the hydrophobic polymerizable monomer as described above is used, the supply to the micelle is delayed. Therefore, by using a highly hydrophobic crosslinking agent such as an aliphatic crosslinking agent having a long-chain alkyl group, the polymerization of the crosslinking component is delayed, and as a result, the degree of crosslinking inside and outside the binder is changed, and the outside is more A binder resin having a high degree of crosslinking can be obtained.

  However, a compound having an extremely long part of the long-chain alkyl group as in the present invention has a slower transfer to the micelle, and thus does not react even at the stage where the stability of the micelle becomes insufficient at the end of polymerization. In some cases, micelles are destroyed, resulting in substances with extremely low molecular weights relative to the target.

  In view of this point, the present invention uses the cross-linking agent having a long part of the long-chain alkyl group to remove the aforementioned extremely low molecular weight substance while having the above-mentioned properties of the binder resin. This makes it possible to obtain a toner that does not affect the characteristics of the subsequent toner.

  Hereinafter, the electrostatic image developing toner of the present embodiment and the manufacturing method thereof will be described in detail.

  The toner of the present embodiment uses resin particles produced by emulsion polymerization. After using a resin particle dispersion in which resin particles are dispersed in an ionic surfactant, mixing an ionic material having the opposite polarity to this, causing heteroaggregation, and forming aggregated particles corresponding to the toner particle size Then, the aggregated particles are fused and united by heating above the glass transition temperature of the resin particles, washed and dried to obtain a toner. According to this method, toner having a desired shape from an indeterminate shape to a spherical shape can be produced.

  In addition, the toner components can be mixed together, aggregated, fused and united to produce, but the balance of the amount of the polar ionic dispersant is shifted in advance at the initial stage of the aggregation process, For example, by using an inorganic metal salt such as calcium nitrate or a polymer of inorganic metal salt such as polyaluminum chloride, the ionic potential shift is alleviated, and the first-stage base aggregated particles are formed at a temperature lower than the glass transition temperature. After that, as a second step, an additional particle dispersion treated with a dispersing agent of a polarity and quantity that compensates for the above-mentioned balance deviation is added, and further included in the base aggregated particles and additional particles as necessary Slightly heated below the glass transition temperature of the resin to adhere additional particles to the surface of the base aggregated particles, stabilize at a higher temperature, then heat above the glass transition temperature to fuse and coalesce It may be. Further, this stepwise operation of aggregation may be repeated a plurality of times.

  The cumulative volume average particle diameter D50 of the toner of the present invention is in the range of 3 to 9 μm, preferably 3 to 8 μm. When the particle size is less than 3 μm, the chargeability becomes insufficient and the developability is deteriorated, and when it exceeds 9 μm, the resolution of the image is deteriorated. The volume average particle size distribution index GSDv of the toner of the present invention is preferably 1.30 or less, and the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp is preferably 0.95 or more. When the volume average particle size distribution index GSDv exceeds 1.30, the resolution decreases, and when the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp is less than 0.95, the chargeability decreases. It causes image defects such as scattering and fogging.

  The particle size and average particle size distribution index of the toner of the present invention are, for example, a particle size distribution measured using a measuring machine such as Coulter Counter TA II (manufactured by Beckman-Coulter), Multisizer II (manufactured by Beckman-Coulter). Based on the above, a cumulative distribution is drawn from the small diameter side for each of the divided particle size ranges (channels) from the small diameter side, and the volume particle size at which accumulation is 16% is defined as volume D16V, and the number particle size is defined as number D16P. The volume particle size at which accumulation is 50% is defined as volume D50V, the number particle size is defined as number D50P, the volume particle size at accumulation 84% is defined as volume D84V, and the number particle size is defined as number D84P. Using these, the volume average particle size distribution index (GSDv) is obtained from D84V / D16V, and the number average particle size index (GSDp) is calculated from D84P / D16P.

  The polymer used for the resin particles of the present invention is preferably a copolymer of a monofunctional monomer and a crosslinking agent (bifunctional) monomer. The monofunctional monomer that can be used in the present invention is not particularly limited. For example, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, and acrylic acid n- Esters having a vinyl group such as propyl, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; Vinyl nitriles such as acrylonitrile and methacrylonitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Ethylene, propylene, butadiene, etc. Alone such as Li olefins, or may be used in combination of two or more.

Crosslinking agent used in this embodiment has at least 2920～2940Cm ^-1 and 2840～2860Cm ^-1, and 3100～3000Cm ^-1, the infrared absorption spectrum to the absorption position of the 1750～1735Cm ^-1, mass In the analysis, it has a fragment ion in which at least one peak at 280 to 420 or at least one mass to charge ratio peak at 880 to 1320 appears. Furthermore, the crosslinking agent used in the present embodiment may further have an infrared absorption spectrum at at least one absorption position of 2950 to 2970 cm ⁻¹ and 2860 to 2880 cm ⁻¹ or 1250 to 1100 cm ⁻¹ .

The infrared absorption spectrum was measured by the following KBr method using an infrared absorption analyzer (“FT / IR-410”, manufactured by JASCO Corporation). First, a small amount of toner particles and potassium bromide were mixed in a mortar, and then pressed to form a tablet. This was set in a cell of an infrared absorption analyzer, and an absorption spectrum was measured in a range of 1000 to 3200 cm ⁻¹ .

  The mass-to-charge ratio was measured using a mass spectrometer (“SX102A”, manufactured by JEOL Ltd.) under the following conditions. Mass spectrometry method: FD-MS analysis, ionization method: field desorption, measurement range: m / z = 150-1500, pressurization voltage: 8 Kv, ion multi: 1.2 Kv, emitter current: 0 → 30 mA.

（式中、ＸはＣＨ_２又はＣＨ_２ＣＨ_２Ｏ、ｎは２０〜３０の整数、Ｒは水素又はＣＨ_３を表す。） The crosslinking agent used in the present embodiment has the following general formula in order to impart flexibility.

(Wherein, X is CH ₂ or _CH 2 _CH 2 O, n is 20 to 30 integer, R represents hydrogen or CH _3.)

The bifunctional monomer represented by is preferably used. The addition amount of the crosslinking agent to the resin fine particles is suitably in the range of 0.1 to 1.5% by weight. If the amount is less than 0.1% by weight, the chargeability is improved, but a crosslinked structure is hardly obtained and the durability of the image is hardly improved. On the other hand, if the amount exceeds 1.5% by weight, fixing with a high-speed machine may increase MFT and cause image defects, which is not preferable.

  The cross-linking agent (bifunctional monomer) used in the present embodiment is not particularly limited as long as it is represented by the above general formula, but specifically, eicosene diacrylate and eicosene dimethacrylate. , Docosaethylene glycol dimethacrylate, tetracosaethylene glycol diacrylate, docosaethylene glycol dimethacrylate, tetracosaethylene glycol diacrylate, tetracosaethylene glycol dimethacrylate, tricosanediol diacrylate, tricosanediol dimethacrylate can do.

  When a vinyl monomer is used as the binder resin component of the present embodiment, an ionic surfactant or the like can be used to carry out emulsion polymerization to create a resin particle dispersion. Other resins If the oil is soluble in a solvent that is oily and has a relatively low solubility in water, the resin is dissolved in those solvents and a disperser such as a homogenizer is added to the water together with an ionic surfactant or polymer electrolyte. The resin dispersion can be prepared by dispersing into fine particles in water and then evaporating the solvent by heating or decompressing. The particle diameter of the obtained resin fine particle dispersion is measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The center particle diameter of the resin fine particles used in the present invention is 50 to 400 nm, preferably 70 to 350 nm. If the thickness is less than 50 nm, the cohesiveness is slightly inferior, and the productivity tends to decrease.

  The toner in this embodiment has a glass transition temperature (Tg) of 50 to 65 ° C., preferably 52 to 60 ° C. If the temperature is less than 50 ° C., the cohesive force of the binder resin itself in a high temperature range is reduced, so that hot offset is likely to occur during fixing. If the temperature exceeds 65 ° C., sufficient melting cannot be obtained, and the fixing sheet is bent. Resistance may deteriorate.

  The release agent that can be used in the present embodiment is preferably a substance having a main maximum endothermic peak measured in accordance with ASTM D3418-8 in the range of 50 to 140 ° C. Below 50 ° C., offset tends to occur during fixing. On the other hand, if the temperature exceeds 140 ° C., the fixing temperature becomes high, and the smoothness of the surface of the fixed image cannot be obtained and the glossiness is impaired. For the measurement of the main maximum endothermic peak of the present invention, for example, a differential thermal analyzer DSC-7 manufactured by PerkinElmer is used. The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the heating rate was 10 ° C./min. Measure with.

  The content of the release agent dispersed in the toner of the present embodiment is 5 to 25% by weight, preferably 7 to 15% by weight in terms of solid content. It is preferable from the viewpoint of chargeability and durability that the release agent is added before the additional particles adhere. The center diameter (median diameter) of the release agent particles dispersed in the toner of the present invention is preferably in the range of 150 to 1500 nm as measured with a transmission electron microscope (TEM).

  The mold release agent used in the present embodiment includes low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point by heating; oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, and the like Fatty acid amides such as; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, etc .; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline Minerals such as waxes, microcrystalline waxes, Fischer-Tropsch waxes, petroleum-based waxes; and their modified products can be used.

  These release agents (waxes) are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, and above the melting point using a homogenizer or pressure discharge type disperser. It is possible to produce a fine particle dispersion of 1 μm or less by applying strong shearing while heating. The particle size of the obtained release agent particle dispersion is measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The center particle diameter of the release agent particles used in the present invention is 50 to 400 nm, preferably 70 to 350 nm. If it is less than 50 nm, the leaching property of the release agent at the time of fixing tends to be lowered, and a peeling failure may occur. On the other hand, if it exceeds 400 nm, it is easy to form release agent particles having a size of 1500 nm or more during aggregation, which may impair OHP transparency.

  The colorant of the present embodiment is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the 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, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG.

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK. Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C , Rose bengal, oxin red, alizarin lake and the like. Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on.

  Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake. Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide. Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

  And these can be used individually or in mixture, and also in the state of a solid solution. These colorants are dispersed in the dispersion by a known method. For example, a rotary-type homogenizer, a ball mill, a sand mill, an attritor, or other media type disperser, a high-pressure counter-collision type disperser, or the like is preferably used. It is done. Moreover, the particle diameter of the obtained colorant particle dispersion is measured by, for example, a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The center diameter (median diameter) of the colorant particles in the toner of the present invention is preferably in the range of 100 to 330 nm as measured with a transmission electron microscope (TEM).

  The content of the colorant in the toner in the present embodiment is suitably in the range of 1 to 20 parts by weight in terms of solid content with respect to 100 parts by weight of the resin. When a magnetic material is used for the black colorant, it is preferably contained in the range of 30 to 100 parts by weight, unlike other colorants.

  When the toner is used as a magnetic toner, magnetic powder may be included. As such magnetic powder, a substance magnetized in a magnetic field is used, and ferromagnetic powder such as iron, cobalt, nickel, or a compound such as ferrite, magnetite, or the like is used. In the present invention, since the toner is produced in the aqueous phase, it is necessary to pay attention to the transferability of the magnetic material to the aqueous phase, and the surface of the magnetic material is modified by subjecting it to a hydrophobic treatment or the like. Is preferred.

The toner shape factor SF1 in the present embodiment is preferably in the range of 110 to 145 from the viewpoint of image formability. If it is less than 110, it is very difficult to produce stably, and the yield is lowered, which is disadvantageous in cost. On the other hand, if it exceeds 145, transferability in the electrophotographic process is lowered, which is not preferable. The shape factor SF1 is a value obtained by dividing (the square of the maximum toner length) by (projected area), and is calculated by the following method. That is, the optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, and the [maximum length square (ML ² ) / projection area (A)] of 50 or more toners is calculated. Obtain the average value.

  In the toner of the present embodiment, a charge control agent can be used in order to further improve and stabilize the chargeability. As the charge control agent, commonly used charge control agents such as quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments can be used. In view of controlling the ionic strength that affects the stability of the mixture and temporary contamination and reducing wastewater contamination, a material that is difficult to dissolve in water is preferable.

  In this embodiment mode, inorganic fine particles can be added in a wet manner in order to stabilize the chargeability. Examples of inorganic fine particles to be added include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, which are usually used by adding them externally to the toner surface. It can be used dispersed in a molecular base.

  Also, for the purpose of imparting fluidity to the toner and improving cleaning properties, after drying the toner in the same manner as normal toner, inorganic particles such as silica, alumina, titania, calcium carbonate, vinyl resin fine particles, polyester, silicone It is also possible to add resin fine particles such as those to the toner surface by applying shearing in a dry state.

  Examples of the surfactant used for emulsion polymerization, colorant dispersion, resin fine particle dispersion, mold release agent dispersion, aggregation, or stabilization thereof in the toner production method of the present embodiment include sulfate ester salts and sulfonic acids. Anionic surfactants such as salt, phosphate ester and soap, cationic surfactants such as amine salts and quaternary ammonium salts, polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols It is also effective to use a nonionic surfactant or the like such as a system. As the dispersing means, a rotary shear type homogenizer, a ball mill having a media, a sand mill, a dyno mill, or the like can be used.

  In the case of using a composite consisting of a resin and a colorant, the resin and the colorant are dissolved and dispersed in a solvent, then dispersed in water together with the appropriate dispersant, and the solvent is removed by heating and decompression. Alternatively, it can be prepared and prepared by a method of imparting to the surface of resin fine particles prepared by emulsion polymerization with a mechanical shear force or a method of electrically adsorbing and fixing. These methods are effective in suppressing the liberation of the colorant as additional particles and improving the chargeable colorant dependency.

  After completion of the polymerization, a desired toner is obtained through any washing step, solid-liquid separation step, and drying step. In the washing step, it is preferable to sufficiently perform substitution 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 preferable from the viewpoint of productivity. The drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  The method for producing the resin of the present embodiment (hereinafter also referred to as “latex polymer”) is as follows: (i) A small amount of monomer emulsion in the emulsification tank is added to the aqueous phase in the polymerization tank, and seed polymerization is started to produce a polymer. And (ii) adding a monomer emulsion to the composition produced in the step (i) to carry out emulsion polymerization, and in the step of producing a latex polymer, the monomer emulsion from the emulsion tank is passed through a pipe provided with a strainer. It is a manufacturing method of the latex polymer supplied to a polymerization tank, Comprising: It is preferable that the opening of the strainer installed in the monomer emulsion supply piping shall be 5-200 mesh.

  Thereby, the coarse particle of the latex polymer obtained by the emulsion polymerization method can be removed.

  If the mesh of the strainer is less than 5 mesh, the resistance will be high and it will be difficult to obtain the desired emulsion flow rate. If it is 200 mesh or more, the deposit will come off and the emulsion flow control valve or flow meter will be used. This makes it difficult to produce latex polymers with stable strainers.

  The installation position of the strainer is preferably between the emulsification tank bottom valve, the flow meter and the flow control valve. Strainers can be placed in multiple stages in order of increasing mesh size to reduce the strainer load. There are no particular restrictions on the shape, size, and material of the strainer, but stainless steel is desirable for durability.

  The clogging of the deposits captured by the strainer can be grasped by a pressure gauge installed on the pipe, and has a mechanism that can be cleaned as needed. In addition, a bypass line having the same strainer can be installed so that it can be closed even during production.

  Moreover, since the crosslinking agent used in the present embodiment may cause the micelle to become unstable at the end of the polymerization, which may result in formation of a polymer having an extremely small molecular weight relative to the desired molecular weight. It is desirable to use this preparation method.

  Other latex polymer preparation methods in the present embodiment include (i) a step of preparing an aqueous phase containing an anionic surfactant, and (ii) adjusting an aqueous emulsion of monomers using the anionic surfactant. (Iii) adding a part of the monomer emulsion to the aqueous phase, starting seed polymerization to produce a seed polymer, and (iv) adding the monomer to the composition produced in the step (iii) In the preparation method including the steps of adding an emulsion to complete emulsion polymerization and forming a latex polymer, in the process of stirring in the step (ii) of preparing the aqueous emulsion, 0.1 min. 90 min. This adjustment method provides the following stirring rest time.

  In the stirring process, by providing a standing time, the oil phase and the aqueous phase that have not formed the emulsion are separated, but the O / W type emulsion formed by the stirring exists in the intermediate layer. Take. In this O / W type emulsion, since the continuous phase is an aqueous phase, it functions as an aqueous phase during emulsification, and apparently the volume of the aqueous phase increases and the volume of the oil phase decreases. Therefore, when re-stirring is performed after standing, the formation of a W / O type emulsion due to the volume ratio is suppressed, and a stable emulsion can be produced. At this time, the standing time was 0.1 min. 90 min. It is necessary that:

  In the process of stirring when producing the emulsion, when the standing time is not provided, or the standing time is 0.1 min. If the oil phase, water phase, and intermediate layer are not sufficiently separated, the emulsion liquid becomes unstable due to the mixed system of W / O type emulsion for the above reasons, and the latex particle size and molecular weight As a result, the desired latex characteristics cannot be obtained. Also, due to the causes of coarse particles in the latex, such as emulsion breakage during emulsion addition and frequent occurrence of sediment, and large deposits on the tank, baffle plates, stirring blades, etc., this may hinder stable production. There are problems such as.

  On the other hand, the stationary time is 90 min. When longer, the emulsion phase formed at the interface between the water phase and the oil phase breaks down and separates into the original water phase and the oil phase, so the effect of setting the standing time is lost and the mixture is stirred again. Since the re-volume ratio is not improved and mixing of the W / O type emulsion is not suppressed, the emulsion liquid becomes unstable, resulting in variations in latex particle diameter and molecular weight, and the desired latex characteristics cannot be obtained. In addition, there are obstacles to stable production due to coarse particles in the latex, such as destruction of the emulsion during emulsion addition and frequent occurrence of sediment, and large deposits on the tank, baffle plates, stirring blades, etc. There are problems such as becoming.

  In the present embodiment, by adopting the above-described configuration, fixing having excellent fixing characteristics such as peelability of a fixing sheet, OHP transparency, hot offset property, adhesion of a fixed image, bending resistance of a fixed image, and the like. Made it possible to provide images.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all. For the toner of the present invention, the following resin fine particle dispersion, colorant dispersion, and release agent dispersion are prepared, and a polymer of an inorganic metal salt is added thereto while mixing and stirring at a predetermined ratio. And then ionically neutralized to form aggregated particles. The pH of the system is adjusted from weakly acidic to neutral with an inorganic hydroxide, and then heated to the glass transition temperature or higher of the resin fine particles to raise the temperature to the coalescence / unification temperature. After reaching the fusion / unification temperature, the pH in the system is adjusted from weakly acidic to acidic and heating is continued. After completion of the reaction, a desired toner is obtained through sufficient washing, solid-liquid separation, and drying processes. Hereinafter, each preparation method is demonstrated.

を２．６７重量部
ドデカンチオール ８重量部
四臭化炭素 ４重量部 (Preparation of resin fine particle dispersion 1)
Styrene 335 parts by weight n-butyl acrylate 65 parts by weight Acrylic acid 6 parts by weight or less of the crosslinking agent (I) shown in Chemical Formula 3 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester)

2.67 parts by weight Dodecanethiol 8 parts by weight Carbon tetrabromide 4 parts by weight

  A solution was prepared by mixing and dissolving the above components (412.6 parts by weight in total), while 6 parts by weight of a nonionic surfactant (Sanyo Kasei Co., Ltd., Nonipol 400) and an anionic surfactant (first 10 parts by weight of Kogyo Seiyaku Co., Ltd., Neogen SC) are dissolved in 550 parts by weight of ion-exchanged water, and the above solution is added to the flask, mixed at 750 rpm for 10 minutes at room temperature, allowed to stand for 10 minutes, and then again at room temperature. A monomer emulsion is prepared by mixing at 1300 rpm for 60 minutes, and the dispersed and emulsified monomer emulsion is polymerized through a flowmeter and a stainless steel 20 mesh mesh strainer installed in front of a control valve for controlling the flow rate. Then, while slowly stirring and mixing for 10 minutes, 50 weight of ion-exchanged water in which 4 weight of ammonium persulfate was dissolved was added. Next, after the system was sufficiently replaced with nitrogen, the flask was heated to 75 ° C. in an oil bath while stirring, and emulsion polymerization was continued for 5 hours, followed by volume average diameter 175 nm, glass transition temperature 57 ° C., Mw 55 Anionic resin fine particle dispersion 1 containing 700 resin fine particles was obtained.

を用いた以外は樹脂微粒子分散液１の調製と同様にして、中心径１６８ｎｍ、ガラス転移温度５６℃、Ｍｗ３９,２００の樹脂微粒子を含有するカチオン性樹脂微粒子分散液２を得た。 (Preparation of resin fine particle dispersion 2)
Instead of the crosslinking agent (I) in the preparation of the resin fine particle dispersion 1, the crosslinking agent (II) shown in the following chemical formula 4 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester)

A cationic resin particle dispersion 2 containing resin particles having a center diameter of 168 nm, a glass transition temperature of 56 ° C., and a Mw of 39,200 was obtained in the same manner as in the preparation of the resin particle dispersion 1 except that was used.

を用いた以外は樹脂微粒子分散液１の調製と同様にして、中心径１６２ｎｍ、ガラス転移温度５４℃、Ｍｗ６２,４００の樹脂微粒子を含有するカチオン性樹脂微粒子分散液３を得た。 (Preparation of resin fine particle dispersion 3)
In place of the crosslinking agent (I) in the preparation of the resin fine particle dispersion 1, the crosslinking agent (III) shown in the following chemical formula 5 (NK ester manufactured by Shin-Nakamura Chemical Co., Ltd.)

A cationic resin particle dispersion 3 containing resin particles having a center diameter of 162 nm, a glass transition temperature of 54 ° C., and a Mw of 62,400 was obtained in the same manner as in the preparation of the resin particle dispersion 1 except that was used.

を用い、１０分間混合し、８０分間静置した後、再度室温で１３００ｒｐｍ、６０分間混合し、モノマーエマルションを調製した以外は樹脂微粒子分散液１の調製と同様にして、中心径１７５ｎｍ、ガラス転移温度５８℃、Ｍｗ６１,３００の樹脂微粒子を含有するカチオン性樹脂微粒子分散液４を得た。 (Preparation of resin fine particle dispersion 4)
In place of the crosslinking agent (I) in the preparation of the resin fine particle dispersion 1, the crosslinking agent (IV) shown in the following chemical formula 6 (made by Shin-Nakamura Chemical Co., Ltd., NK ester)

The mixture was mixed for 10 minutes, allowed to stand for 80 minutes, and then mixed again at room temperature at 1300 rpm for 60 minutes to prepare a monomer emulsion. A cationic resin fine particle dispersion 4 containing resin fine particles having a temperature of 58 ° C. and Mw of 61,300 was obtained.

を８．９重量部とし、１０分間混合し、０．０５分間静置した後、再度室温で１３００ｒｐｍ、６０分間混合し、モノマーエマルションを調製した以外は樹脂微粒子分散液１の調製と同様にして、中心径１６６ｎｍ、ガラス転移温度５０℃、Ｍｗ７２,３００の樹脂微粒子を含有するカチオン性樹脂微粒子分散液５を得た。 (Preparation of resin fine particle dispersion 5)
In the preparation of the resin fine particle dispersion 1, 300 parts by weight of styrene and 100 parts by weight of n-butyl acrylate, a cross-linking agent (V) represented by the following chemical formula 7 (NK ester manufactured by Shin-Nakamura Chemical Co., Ltd.)

8.9 parts by weight, mixed for 10 minutes, allowed to stand for 0.05 minutes, then mixed again at room temperature at 1300 rpm for 60 minutes to prepare a monomer emulsion, and the same procedure as in the preparation of resin fine particle dispersion 1 A cationic resin fine particle dispersion 5 containing resin fine particles having a center diameter of 166 nm, a glass transition temperature of 50 ° C., and a Mw of 72,300 was obtained.

(Preparation of resin fine particle dispersion 6)
In the preparation of the resin fine particle dispersion 5, the crosslinking agent (V) (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester) is 6.8 parts by weight, mixed for 10 minutes, allowed to stand for 100 minutes, and again at room temperature at 1300 rpm, 60 A cationic resin fine particle dispersion 6 containing resin fine particles having a center diameter of 162 nm, a glass transition temperature of 53 ° C., and a Mw of 85,600 was obtained in the same manner as the resin fine particle dispersion 5 except that the monomer emulsion was prepared by mixing for a minute. .

を用い、１０分間混合し、０．０５分間静置した後、再度室温で１３００ｒｐｍ、６０分間混合し、モノマーエマルションを調製し、この分散し乳化したモノマーエマルションを、ストレーナーを設置しない配管ラインを通じて重合槽に供給した以外は樹脂微粒子分散液１の調製と同様にして、中心径１７５ｎｍ、ガラス転移温度５２℃、Ｍｗ６１,３００の樹脂微粒子を含有するカチオン性樹脂微粒子分散液７を得た。 (Preparation of resin fine particle dispersion 7)
Instead of the crosslinking agent (I) in the preparation of the resin fine particle dispersion 1, the crosslinking agent (VI) shown in the following chemical formula 8 (made by Shin-Nakamura Chemical Co., Ltd., NK ester)

The mixture is mixed for 10 minutes and allowed to stand for 0.05 minute, and then mixed again at room temperature at 1300 rpm for 60 minutes to prepare a monomer emulsion, and this dispersed and emulsified monomer emulsion is polymerized through a piping line without a strainer. A cationic resin fine particle dispersion 7 containing resin fine particles having a center diameter of 175 nm, a glass transition temperature of 52 ° C., and a Mw of 61,300 was obtained in the same manner as in the preparation of the resin fine particle dispersion 1 except that it was supplied to the tank.

(Preparation of colorant dispersion 1)
Cyan pigment (Daiichi Seika Co., Ltd., CIPigment Blue 15: 3) 50 parts by weight Nonionic surfactant (Sanyo Kasei Co., Ltd., Nonipol 400) 5 parts by weight Ion-exchanged water 210 parts by weight

  The above components were mixed and dissolved, and dispersed for 10 minutes with a homogenizer (manufactured by IKA, Ultra Turrax) to obtain a colorant dispersion 1 having a volume average particle size of 170 nm.

(Preparation of colorant dispersion 2)
A colorant dispersion containing colorant particles having a volume average particle diameter of 180 nm in the same manner as in the preparation of colorant dispersion 1 except that the same amount of yellow pigment (CIPigment Yellow 180 manufactured by Clariant Japan Co., Ltd.) was used as the colorant. 2 was obtained.

(Preparation of colorant dispersion 3)
A colorant dispersion containing colorant particles having a center diameter of 188 nm, in the same manner as in the preparation of colorant dispersion 1, except that the same amount of magenta pigment (manufactured by Dainippon Ink & Chemicals, CIPment Red122) was used as the colorant. 3 was obtained.

(Preparation of colorant dispersion 4)
A colorant dispersion 4 containing colorant particles having a center diameter of 155 nm is obtained in the same manner as in the preparation of the colorant dispersion 1, except that the same amount of black pigment (carbon black, manufactured by Cabot) is used as the colorant. It was.

(Preparation of mold release agent dispersion 1)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP0190, melting point 85 ° C.) 50 parts by weight Cationic surfactant (manufactured by Kao Corporation, Sanizol B50) 5 parts by weight

  200 parts by weight of ion-exchanged water The above components are heated to 95 ° C. and sufficiently dispersed with IKA Ultra Turrax T50, then subjected to dispersion treatment with a pressure discharge type homogenizer, and contain release agent particles having a center diameter of 185 nm A release agent dispersion 1 was obtained.

(Manufacture of toner 1)
Resin fine particle dispersion 2 200 parts by weight Colorant dispersion 2 30 parts by weight Release agent dispersion 1 37 parts by weight Polyaluminum chloride 1.21 parts by weight

  The components were thoroughly mixed and dispersed in a round stainless steel flask using a homogenizer (IKA, Ultra Turrax T50), and then heated to an aggregation temperature of 52 ° C. while stirring the flask in a heating oil bath. Then, after maintaining at 53 ° C. for 60 minutes, 35 parts by weight 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 sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 97 ° C. while stirring was continued using a magnetic seal. Thereafter, the pH was lowered to 4.0 and held for 6 hours. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, it was dispersed again in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  After this washing operation was repeated 5 times, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner 1. The toner volume average D50 was 5.1 μm, and the volume average particle size distribution index GSDv was 1.2. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.09. Furthermore, it was observed that the shape factor SF1 of the particles obtained from the shape observation by Luzex was 116 and spherical. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles, the volume average particle size (median diameter) of the release agent was 315 nm, and the volume average of the colorant. The particle size was 176 nm.

Infrared absorption peak ^{2930cm -1, 2850cm -1, 3060cm -1} , confirmed respectively 1741cm ^-1, The mass-to-charge ratio peaks 338,354,370 in mass spectrometry has emerged.

(Manufacture of toner 2)
In the production of the toner 1, the addition amount of the release agent dispersion 1 is changed to 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 3 is changed to 16.0% by weight in terms of solid content. The toner 2 was obtained in the same manner as in the production of the toner 1 except that the pH in the system when the temperature reached 97 ° C. after the stop of aggregation was set to 4.0. This toner had a volume average particle size D50 of 5.3 μm and a volume average particle size distribution index GSDv of 1.21. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.03. In addition, it was observed that the shape factor SF1 was 128, which was a rounded potato shape. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles. The release agent had a volume average particle size of 400 nm and the colorant had a volume average particle size of 300 nm. Met.

Infrared absorption peak ^{2930cm -1, 2850cm -1, 3060cm -1} , confirmed respectively 1741cm ^-1, The mass-to-charge ratio peaks 338,354,370 in mass spectrometry has emerged.

(Manufacture of toner 3)
In the production of the toner 1, the addition amount of the release agent dispersion liquid 1 is changed to 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion liquid 1 is changed to 9.0% by weight in terms of solid content. The toner 3 was obtained in the same manner as in the production of the toner 1 except that the system pH was 53 ° C. and the system pH when the temperature reached 97 ° C. after the stop of aggregation was 5.0. The toner had a volume average particle diameter D50 of 5.4 μm and a volume average particle size distribution index GSDv of 1.19. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.00. Further, it was observed that the shape factor SF1 was 137 and it was a potato shape. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles. The release agent had a volume average particle size of 200 nm and the colorant had a volume average particle size of 220 nm. Met.

Infrared absorption peak ^{2930cm -1, 2850cm -1, 3060cm -1} , confirmed respectively 1741cm ^-1, The mass-to-charge ratio peaks 338,354,370 in mass spectrometry has emerged.

(Manufacture of toner 4)
In the production of the toner 1, the resin fine particle dispersion 2 is used, the addition amount of the release agent dispersion 1 is 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 4 is 15.0 in terms of solid content. The procedure is the same as in the production of toner 1 except that the weight is changed to 50%, the aggregation temperature is 53 ° C., the system pH is 3.8 when 97 ° C. is reached after the aggregation is stopped, and the fusion and coalescence time is 10 hours. Thus, toner 4 was obtained. The toner had a volume average particle diameter D50 of 4.9 μm and a volume average particle size distribution index GSDv of 1.23. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.15. Further, it was observed that the shape factor SF1 was 120 and it was spherical. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles, the volume average particle size of the release agent was 1000 nm, and the volume average particle size of the colorant was 105 nm. Met.

Infrared absorption peak ^{2930cm -1, 2850cm -1, 3060cm -1} , confirmed respectively 1741cm ^-1, The mass-to-charge ratio peaks 338,354,370 in mass spectrometry has emerged.

(Manufacture of toner 5)
In the production of the toner 1, the resin fine particle dispersion 1 is used, the addition amount of the release agent dispersion 1 is 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 1 is 9.0 in terms of solid content. The procedure is the same as that of toner 1 except that the weight is changed to wt%, the aggregation temperature is 55 ° C., the pH in the system when the temperature reaches 97 ° C. after the aggregation is stopped is 5.5, and the fusion and coalescence time is 10 hours. Thus, toner 5 was obtained. The toner had a volume average particle diameter D50 of 5.9 μm and a volume average particle size distribution index GSDv of 1.2. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.2. Further, it was observed that the shape factor SF1 was 125, which was a rounded potato shape. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles. The release agent had a volume average particle size of 1200 nm and the colorant had a volume average particle size of 150 nm. Met.

Infrared absorption peak ^{2931cm -1, 2851cm -1, 3060cm -1} , confirmed respectively 1740 cm ^-1, The mass-to-charge ratio peaks 352,368 in mass spectrometry has emerged.

(Manufacture of toner 6)
In the production of the toner 1, the resin fine particle dispersion 3 is used, the addition amount of the release agent dispersion 1 is 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 1 is 9.0 in terms of solid content. The procedure was the same as in the production of toner 1 except that the weight was changed to 51%, the aggregation temperature was 51 ° C, the system pH when the temperature reached 97 ° C after stopping aggregation was 6.5, and the coalescence and coalescence time was 10 hours. Thus, toner 6 was obtained. The toner had a volume average particle diameter D50 of 6.0 μm and a volume average particle size distribution index GSDv of 1.24. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.04. Further, it was observed that the shape factor SF1 was 135, which was a rounded potato shape. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles. The release agent had a volume average particle size of 1320 nm and the colorant had a volume average particle size of 302 nm. Met.

Infrared absorption peak ^{2933cm -1, 2852cm -1, 3061cm -1} , confirmed respectively 1748cm ^-1, The mass-to-charge ratio peaks 392,408 in mass spectrometry has emerged.

(Manufacture of toner 7)
In the production of the toner 1, the resin fine particle dispersion 4 is used, the addition amount of the release agent dispersion 1 is 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 1 is 9.0 in terms of solid content. The procedure is the same as that of toner 1 except that the weight is changed to wt%, the aggregation temperature is 56 ° C., the pH in the system when the temperature reaches 97 ° C. after the aggregation is stopped is 6.5, and the fusion and coalescence time is 5 hours. Thus, toner 7 was obtained. This toner had a volume average particle size D50 of 4.7 μm and a volume average particle size distribution index GSDv of 1.2. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 0.99. Further, it was observed that the shape factor SF1 was 134 and the potato shape was rounded. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles. The release agent had a volume average particle size of 270 nm and the colorant had a volume average particle size of 200 nm. Met.

Infrared absorption peak ^{2930cm -1, 2851cm -1, 3061cm -1} , confirmed respectively 1738 cm ^-1, The mass-to-charge ratio peaks 338,354,370 in mass spectrometry has emerged.

(Manufacture of toner 8)
In the production of the toner 1, the resin fine particle dispersion 5 is used, the addition amount of the release agent dispersion 1 is 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 1 is 9.0 in terms of solid content. The toner 8 was obtained in the same manner as in the production of the toner 1 except that the aggregation temperature was changed to 48%, and the pH in the system when reaching 97 ° C. after the aggregation was stopped was set to 4.5. The toner had a volume average particle diameter D50 of 5.2 μm and a volume average particle size distribution index GSDv of 1.21. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.15. In addition, it was observed that the shape factor SF1 was 128, which was a rounded potato shape. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles. The release agent had a volume average particle size of 300 nm and the colorant had a volume average particle size of 110 nm. Met.

Infrared absorption peak ^{2930cm -1, 2850cm -1, 3060cm -1} , confirmed respectively 1741cm ^-1, The mass-to-charge ratio peaks 338,354,370 in mass spectrometry has emerged.

(Manufacture of toner 9)
In the production of the toner 1, the resin fine particle dispersion 6 is used, the addition amount of the release agent dispersion 1 is 7.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 1 is 9.0 in terms of solid content. The toner 8 was obtained in the same manner as in the production of the toner 1 except that the aggregation temperature was changed to 51%, the aggregation temperature was 51 ° C., and the pH in the system when reaching 97 ° C. after the aggregation was stopped was 4.5. The toner had a volume average particle diameter D50 of 5.1 μm and a volume average particle size distribution index GSDv of 1.23. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.14. In addition, it was observed that the shape factor SF1 was 128, which was a rounded potato shape. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles. The release agent had a volume average particle size of 320 nm and the colorant had a volume average particle size of 120 nm. Met.

Infrared absorption peak ^{2942cm -1, 2860cm -1, 3000cm -1} , confirmed respectively 1742 cm ^-1, The mass-to-charge ratio peaks 140,156,172 in mass spectrometry has emerged.

(Manufacture of toner 10)
In the production of the toner 1, the resin fine particle dispersion 7 is used, the addition amount of the release agent dispersion 1 is 30.0% by weight in terms of solid content, and the addition amount of the colorant dispersion 1 is 9.0 in terms of solid content. The toner 10 was obtained in the same manner as in the production of the toner 1 except that the aggregation temperature was changed to 51%, the aggregation temperature was 51 ° C., and the pH in the system when reaching 97 ° C. after the aggregation was stopped was 4.5. The toner had a volume average particle diameter D50 of 5.2 μm and a volume average particle size distribution index GSDv of 1.20. The ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp was 1.18. Further, it was observed that the shape factor SF1 was 126, which was a rounded potato shape. When a cross-sectional image of the toner was observed with a transmission electron microscope (TEM), the release agent was dispersed in the toner particles, the volume average particle size (median diameter) of the release agent was 310 nm, and the volume average of the colorant. The particle size (median diameter) was 130 nm.

Infrared absorption peak ^{2920cm -1, 2841cm -1, 3110cm -1} , confirmed respectively 1731 cm ^-1, The mass-to-charge ratio peaks 588,574,590 in mass spectrometry has emerged.

(Preparation of developer)
50 parts of each of toners 1 to 10 were weighed, 1.8 parts by weight of hydrophobic silica (manufactured by Cabot, TS 720) was added and mixed by a sample mill. The externally added toner was weighed so that the toner concentration would be 5% by weight with respect to a ferrite carrier having an average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd.), and stirred for 5 minutes with a ball mill. -A developer was obtained by mixing.

Example 1
The toner 1 was fixed at PS: 300 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd., but the peelability and offset property by the PFA tube roller were slightly good, and it was peeled off without any resistance. It was confirmed that Further, the surface gloss of this fixing sheet was also good. The transparency of the OHP sheet was also good, and a transmission image without turbidity was confirmed. In addition, when the fixed image is folded in half and strongly squeezed with the nail and the fixing sheet is opened again, the fixing image has a good fixability to the fixing sheet, and no image defect is observed at the bent portion. It was.

(Example 2)
The toner 2 was fixed at PS: 320 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd .. Both the oil-less peelability and the offset property by the PFA tube roller were good, and no resistance. It was confirmed that there was no peeling. Further, the surface gloss of this fixing sheet was also good. The transparency of the OHP sheet was also good, and a transmission image without turbidity was confirmed. In addition, when the fixed image was folded in half and squeezed firmly with the nail, and the fixing sheet was re-opened, the fixing property of the fixed image to the fixing sheet was examined. No image defects were observed.

(Example 3)
The toner 3 was fixed at PS: 280 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd. As a result, the oilless releasability and the offset property by the PFA tube roller were both good and no resistance. It was confirmed that there was no peeling. Further, the surface gloss of this fixing sheet was also good. The transparency of the OHP sheet was also good, and a transmission image without turbidity was confirmed. In addition, when the fixed image was folded in half and squeezed firmly with the nail, and the fixing sheet was re-opened, the fixing property of the fixed image to the fixing sheet was examined. No image defects were observed.

Example 4
The toner 4 was fixed at PS: 340 mm / s using a DocuCenter Color400 remodeled machine manufactured by Fuji Xerox Co., Ltd., and both the oilless peelability and the offset property by the PFA tube roller were both good and no resistance. It was confirmed that there was no peeling. Further, the surface gloss of this fixing sheet was also good. The transparency of the OHP sheet was also good, and a transmission image without turbidity was confirmed. In addition, when the fixed image was folded in half and squeezed firmly with the nail, and the fixing sheet was re-opened, the fixing property of the fixed image to the fixing sheet was examined. No image defects were observed.

(Example 5)
The toner 5 was fixed at PS: 350 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd. As a result, the oil-less peelability and offset property by the PFA tube roller were both good and no resistance. It was confirmed that there was no peeling. Further, the surface gloss of this fixing sheet was also good. The transparency of the OHP sheet was also good, and a transmission image without turbidity was confirmed. In addition, when the fixed image was folded in half and squeezed firmly with the nail, and the fixing sheet was re-opened, the fixing property of the fixed image to the fixing sheet was examined. No image defects were observed.

(Example 6)
The toner 6 was fixed at PS: 230 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd., and both the oil-less peelability and offset property by the PFA tube roller were good, and no resistance. It was confirmed that there was no peeling. Further, the surface gloss of this fixing sheet was also good. The transparency of the OHP sheet was also good, and a transmission image without turbidity was confirmed. In addition, when the fixed image was folded in half and squeezed firmly with the nail, and the fixing sheet was re-opened, the fixing property of the fixed image to the fixing sheet was examined. No image defects were observed.

(Example 7)
The toner 7 was fixed at PS: 310 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd., and both the oil-less peelability and offset property by the PFA tube roller were good, and no resistance. It was confirmed that there was no peeling. Further, the surface gloss of this fixing sheet was also good. The transparency of the OHP sheet was also good, and a transmission image without turbidity was confirmed. In addition, when the fixed image was folded in half and squeezed firmly with the nail, and the fixing sheet was re-opened, the fixing property of the fixed image to the fixing sheet was examined. No image defects were observed.

[Evaluation methods and standards]
(Image density)
After adjusting the development toner amount of each single-color solid image on the paper to 4.0 g / m ² , an amount of solid image corresponding to the tertiary color was output as a solid image having a size of 5 cm × 5 cm. As the paper, the product name “C2r paper” manufactured by Fuji Xerox Office Supply Co., Ltd. was used. Image density uniformity was measured visually. In the evaluation, “◯” indicates that the entire surface was uniform and had no problem, “Δ” indicates that density unevenness is observed, and “x” indicates that the overall density is lowered.

(Offset property)
Also, the development toner amount for a single color was changed from 4.0 g / m ² to 4.5 g / m ² to evaluate whether hot offset occurred (when the development toner amount increased and the image thickness increased, Offset is likely to occur). The product name “C2r paper” manufactured by Fuji Xerox Office Supply Co. was used. As the output image, an image corresponding to a tertiary color was used on the side of the A4 sheet, 5 mm from the leading end of the sheet, and 20 mm × the entire sheet width in the sheet conveyance direction. The case where no hot offset occurred was marked with ◎, and the case where it occurred was marked with ×.

(Fixing sheet peelability)
The peel strength was measured by changing the developing toner amount for a single color from 4.0 g / m ² to 4.5 g / m ² . The product name “C2r paper” manufactured by Fuji Xerox Office Supply Co. was used. Evaluation is that the fixing object is peeled off from the fixing roll without any problem, and peeling is possible, but if the peeling stress causes image unevenness and other defects, ○, peeling becomes unstable, partly A case where winding on the fixing roll occurred was indicated by Δ, and a member to be fixed cannot be peeled, and all cases where the fixing roll was wound were indicated by ×.

(Surface gloss of the fixing sheet)
After adjusting the development toner amount of each single-color solid image on the paper to 4.0 mg / m ² , an amount of solid image corresponding to the tertiary color was output as a solid image having a size of 5 cm × 5 cm. As the paper, the product name “C2r paper” manufactured by Fuji Xerox Office Supply Co., Ltd. was used. The gloss of the fixed image was measured. For the gloss measurement, a gloss meter GM-26D (manufactured by Murakami Color Research Laboratory Co., Ltd.) was used, and measurement was performed under the condition that the incident light angle to the sample was 75 degrees. In the evaluation, 47 or more was evaluated as ◎, 43 or more and less than 47 as ◯, 40 or more and less than 43 as Δ, and less than 40 as ×.

(Transparency of OHP sheet)
At the same time, a monochrome image was formed on an OHP sheet (black and white OHP sheet manufactured by Fuji Xerox Co., Ltd.) in the OHP mode, and the light transmittance (PE value) was measured. A match scan (manufactured by DIANO) was used for measuring the light transmittance. In the evaluation, 70 or more was evaluated as ◎, 67 or more and less than 70 as ◯, 64 or more and less than 67 as Δ, and less than 64 as ×.

(Foldability of fixed image)
The fixed image was folded in half, strongly squeezed there, and when the fixing sheet was opened again, the fixing property of the fixing image to the fixing sheet was examined. The evaluation criteria were ○ where there was no image loss, and x where image loss occurred.

(Comparative Example 1)
The toner 8 was fixed at PS: 330 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd., but the oilless peelability and hot offset property with the PFA tube roller were slightly poor, and 180 ° C. The occurrence of HOT (hot offset) was observed at the fixing temperature of. Further, the peelability of the fixing sheet became unstable, and a part of the fixing sheet was wound around the fixing roll. The surface gloss was slightly lowered. Regarding the transparency of the OHP sheet, it was observed that the transmission image was blackish. Also, when the fixed image was folded in half and strongly squeezed with the nail and the fixing sheet was opened again, the fixing property of the fixed image to the fixing sheet was examined. A defect was observed.

(Comparative Example 2)
The toner 9 was fixed at PS: 350 mm / s using a DocuCenter Color400 remodeling machine manufactured by Fuji Xerox Co., Ltd., and it was found that oil-less peelability and offset property with a PFA tube roller were HOT and poorly peeled. I couldn't. However, the surface gloss of the fixing sheet was low, and white turbidity was observed in the OHP sheet. Also, when the fixed image was folded in half and squeezed firmly with the nail, the fixing property of the fixed image to the fixing sheet when the fixing sheet was opened again was examined. An image defect was observed.

(Comparative Example 3)
The toner 10 was fixed at PS: 330 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd. As a result, HOT and peeling failure were recognized even in oil-less peelability and offset property with a PFA tube roller. It was. However, the surface gloss of the fixing sheet is high, and there is no problem with the transparency of the OHP sheet. Also, when the fixed image was folded in half and squeezed firmly with the nail, the fixing property of the fixed image to the fixing sheet was examined when the fixing sheet was opened again. No image defect was observed.

  This is presumed that the molecular weight of the cross-linking agent was large, and it was difficult for cross-linking to occur during the polymerization, so that the behavior was substantially the same as that of an uncross-linked resin.

(Comparative Example 4)
When the toner 8 was fixed at PS: 180 mm / s using a DocuCentre Color 400 modified machine manufactured by Fuji Xerox Co., Ltd., no HOT (hot offset) was observed. However, in the oilless releasability by the PFA tube roller, the occurrence of image unevenness was observed at the fixing temperature of 180 ° C. due to the peeling stress. The surface gloss was slightly lowered. Regarding the transparency of the OHP sheet, it was observed that the transmission image was blackish. Also, when the fixed image was folded in half and strongly squeezed with the nail and the fixing sheet was opened again, the fixing property of the fixed image to the fixing sheet was examined. A defect was observed.

(Comparative Example 5)
The toner 8 was fixed at PS: 400 mm / s using a DocuCentre Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd., and the oilless releasability and hot offset property with the PFA tube roller were inferior. Generation of HOT (hot offset) was observed at the fixing temperature. Also, the fixing sheet could not be peeled off, and all of the sheets were wrapped around the fixing sheet. The surface gloss was remarkably lowered. Regarding the transparency of the OHP sheet, it was observed that the transmission image was blackish. Also, when the fixed image was folded in half and strongly squeezed with the nail and the fixing sheet was opened again, the fixing property of the fixed image to the fixing sheet was examined. A defect was observed.

  The toner for developing an electrostatic charge image, the developer for developing an electrostatic charge image, and the image forming method of the present invention are useful for applications such as electrophotography and electrostatic recording.

Claims (5)

Having at least 2920～2940Cm ^-1 and 2840~2860cm ^-1, and 3100~3000cm ^-1, the infrared absorption peak spectrum in the absorption position of the 1750~1735cm ^-1,
An electrostatic charge image developing toner comprising a binder resin obtained by copolymerizing a crosslinking agent having a fragment ion in which at least one mass to charge ratio peak appears at 280 to 420 in mass spectrometry,
A toner for developing an electrostatic charge image, wherein the binder resin constituting the toner for developing an electrostatic charge image has a glass transition temperature of 50 to 65 ° C. The electrostatic image developing toner according to claim 1,
The toner for developing an electrostatic charge image, wherein the cross-linking agent further has an infrared absorption spectrum at at least one absorption position of 2950 to 2970 cm ⁻¹ and 2860 to 2880 cm ⁻¹ or 1250 to 1100 cm ⁻¹ . An electrostatic image developing toner comprising a binder resin obtained by copolymerizing a crosslinking agent represented by the following general formula.

(Wherein, X is CH ₂ or _CH 2 _CH 2 O, n is 20 to 30 integer, R represents hydrogen or CH _3.)   An electrostatic charge image developer containing a carrier and a toner, wherein the toner is the electrostatic charge image developing toner according to any one of claims 1 to 3. Developer. A step of forming an electrostatic latent image on the electrostatic charge image carrier, a step of developing the electrostatic latent image with a developer on the developer carrier to form a toner image, and the toner image on the transfer member. An image forming method comprising: a step of transferring a toner image on a transfer member to a transfer sheet; and a fixing step of thermally fixing the toner image on the transfer sheet.
The developer for developing an electrostatic charge image according to claim 4 is used as the developer.
An image forming method, wherein a process speed in the fixing step is 200 to 370 mm / s.