JP4501742B2 - Toner for developing electrostatic image and method for producing the same, developer for electrostatic image, and image forming method - Google Patents

Description

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

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic image is formed on a photoreceptor by charging and exposure processes, the electrostatic 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 non-magnetic toner alone are known. As a method for producing the toner, 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 are 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 good toner, they have several problems as follows.

  In a normal 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, so it is difficult to control the toner shape and the surface structure. . In the kneading and pulverizing method, the range of material selection is limited. Specifically, the resin colorant dispersion is sufficiently brittle and can be finely pulverized by an ordinary pulverizer. However, when the resin colorant dispersion is fragile, the toner is subjected to mechanical shearing force in the developing machine. May generate fine powder or change the toner shape. In the two-component developer, the generated fine powder adheres to the carrier surface and accelerates the deterioration of the chargeability of the developer. In the one-component developer, toner scattering occurs due to the expansion of the particle size distribution, and development occurs due to a change in the toner shape. The image quality is likely to be deteriorated.

  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 in combination with a thermoplastic resin. In particular, in the case of a combination of a resin that has increased elasticity due to a high molecular weight component and is slightly pulverized, and a brittle wax such as polyethylene, a large amount of polyethylene is exposed on the toner surface. Although this toner 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 to the developing roll, photoreceptor, carrier, etc. by mechanical force. Contamination reduces reliability.

  Furthermore, if the toner shape is indefinite, the fluidity of the toner cannot be sufficiently ensured even if a flow aid is added, and the fine powder moves to the toner recesses due to mechanical shearing force during use. The fluidity decreases with time, or the fluidity aid is buried in the toner, and the developability, transferability, and cleaning properties are deteriorated. In addition, when the toner collected by the cleaning is returned to the developing machine and used again, the image quality is liable to deteriorate. In order to prevent these problems, if the flow aid is further increased, black spots are generated on the photoconductor and the aid particles are scattered.

  As described above, in the electrophotographic process, the toner remains stable even under various mechanical stresses, so that the exposure of the release agent to the toner surface is suppressed and the fixing property is not impaired. It is important to increase the surface hardness, and at the same time, improve both the mechanical strength of the toner itself and sufficient charging and fixing properties.

  Further, in recent years, there has been a growing demand for higher image quality, and in particular 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, if the particle size distribution is simply reduced while maintaining the conventional particle size distribution, the presence of the toner on the fine powder side causes significant contamination of the carrier and photoconductor, and toner scattering, so that high image quality and high reliability can be realized at the same time. difficult. In order to solve this problem, it is important to sharpen the particle size distribution of the toner and to make it possible to reduce the particle size.

  In recent years, in digital full-color copiers and printers, color image originals are separated by B (blue), R (red), and G (green) filters, and then the dot diameter is in the range of 20 to 70 μm corresponding to the original original. The latent image is developed using Y (yellow), M (magenta), C (cyan), and Bk (black) developers and utilizing a subtractive color mixing effect, but digital full color compared to conventional black and white machines. In copiers and the like, it is necessary to transfer a large amount of developer, and further, it is necessary to cope with a small dot diameter. Therefore, uniform chargeability, durability, toner strength, and sharpness of particle size distribution are increasingly important. From these points of view, an agglomeration and fusion method suitable for the production of a toner having a sharp particle size distribution and a small particle size is excellent.

It is important for a toner mounted on a full-color copying machine or the like that a large amount of toner is mixed with certainty, and improvement of color reproducibility and OHP transparency at that time are essential. Further, as a means for controlling the toner shape and its surface structure, a toner production method by an emulsion polymerization aggregation method has been proposed (for example, see Patent Document 1 or 2).
In these methods, a resin particle dispersion is generally prepared by emulsion polymerization or the like, while a colorant dispersion in which a colorant is dispersed in a solvent is prepared and mixed to form aggregated particles corresponding to the toner particle size. Then, the toner is manufactured by heating and fusing and coalescing. When this method is used, not only the toner having a sharp particle size distribution and a small particle diameter can be produced, but also the toner shape can be controlled and the exposure of the release agent to the toner surface can be suppressed.

  Generally, a thermoplastic resin is used in these electrophotographic toners, and the rheology of the binder resin used for the toner and the glass transition temperature (Tg) in order to achieve both low energy fixing and powder blocking properties. It has been proposed to optimize the control (see, for example, Patent Documents 3 to 5). In recent electrophotographic processes, a binder resin having a lower glass transition temperature has been used in order to cope with an increase in fixing speed in response to the demand for the advancement of digitization and high speed as described above. Yes.

  However, when a toner image containing this type of binder resin is heated to a temperature near or above the glass transition temperature, the resin component of the image portion melts and adheres to the back side of the printed matter or other printed matter. However, a problem that an image is lost, that is, a document offset problem occurs. In recent years, double-sided printing has been increasing. However, in double-sided output, image portions are inevitably brought into contact with each other, and thus image loss is more likely to occur than in single-sided output.

  In order to improve the offset problem of the fixed output image, that is, the document offset, the thermosetting resin is externally added to the toner to cause the polyester binder resin to undergo a curing reaction, so that the document offset and the low temperature fixability are achieved. (See, for example, Patent Document 6).

However, there is a demand for low energy fixing due to the recent movement toward strong environmental conservation, demand for double-sided printing, use of coated paper with poor toner penetration at the time of fixing, and half-fixed image as a response to high image quality. There are various stress requirements, such as a request for fixing with tones, etc., and with such technology alone, it is becoming difficult to acquire document offset (image loss) at low temperature fixing and achieve both characteristics. Is the current situation.
JP 63-282275 A JP-A-6-250439 JP-B-2-37586, JP-A-1-225967, Japanese Patent Laid-Open No. 2-235069 JP-A-4-186368

  The present invention has been made in view of the above-described conventional problems, and is an electrostatic image developing toner capable of forming an image excellent in low-temperature fixability and excellent in document offset property, a method for producing the same, and electrostatic image development. The present invention relates to an agent and an image forming method.

That is, the present invention
<1> binder resin and a colorant and a volume average particle size of 0.1~0.5μm inorganic fine particles and a volume average particle diameter a specific gravity of 1.0 to 2.0 is 0.1~1.0μm The toner for developing an electrostatic charge image is obtained by coating the surface of core particles having a glass transition temperature of 20 to 40 ° C. containing fine terpene-modified novolak resin fine particles with a coating layer having a glass transition temperature of 50 to 100 ° C.

<3> The coating layer includes at least two resin layers having different glass transition temperatures, and the difference between the glass transition temperature of the core particles and the glass transition temperature of the outermost layer of the at least two resin layers is The electrostatic charge image developing toner according to <1 >, which is 30 ° C. or higher.

  <4> The electrostatic image developing toner according to <3>, wherein the difference in acid value between adjacent resin layers is 2.0 mgKOH / g or less.

<5> The electrostatic image developing toner according to any one of <1> , <3>, and <4>, wherein the coating layer has a thickness of 0.1 to 0.9 μm.

<6> The electrostatic image developing toner according to any one of <1> , <3>, <4>, or <5>, having a volume average particle diameter of 3 to 9 μm.

<7> binder resin and a colorant and a volume average particle size of 0.1~0.5μm inorganic fine particles and a volume average particle diameter a specific gravity of 1.0 to 2.0 is 0.1~1.0μm For producing electrostatic charge image developing toner comprising coating the surface of core particles having a glass transition temperature of 20 to 40 ° C. containing fine terpene-modified novolak resin fine particles with a coating layer having a glass transition temperature of 50 to 100 ° C. A binder resin fine particle dispersion in which binder resin fine particles having a volume average particle size of 1.0 μm or less are dispersed, a colorant dispersion , a volume average particle size of 0.1 to 0.5 μm, and a specific gravity of 1 An inorganic fine particle dispersion in which inorganic fine particles of 0.0 to 2.0 are dispersed and a terpene-modified novolak resin fine particle dispersion in which a terpene-modified novolak resin fine particle having a volume average particle size of 0.1 to 1.0 μm is mixed. Agglomeration step to form agglomerated particles and before A deposition step of depositing the coating resin particles to the surface of the agglomerated particles, wherein the coating resin particles are fused by heating the aggregated particles adhering fusion step, at least has the production method of the toner for electrostatic image development of.

<8> binder resin and a colorant and a volume average particle size of 0.1~0.5μm inorganic fine particles and a volume average particle diameter a specific gravity of 1.0 to 2.0 is 0.1~1.0μm At least a toner for developing an electrostatic image formed by coating the surface of a core particle having a glass transition temperature of 20 to 40 ° C. containing fine terpene-modified novolak resin fine particles with a coating layer having a glass transition temperature of 50 to 100 ° C. An electrostatic charge image developer.

  <9> The electrostatic charge image developer according to <8>, further including a carrier having a resin coating layer.

<10> A latent image forming step of forming an electrostatic charge image on the surface of the latent image carrier, and developing the electrostatic charge image formed on the surface of the latent image carrier using a developer carried on the developer carrier. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing for thermally fixing the toner image transferred on the surface of the transfer target. An image forming method having at least a step, wherein the developer has a binder resin, a colorant, a volume average particle size of 0.1 to 0.5 μm, and a specific gravity of 1.0 to 2.0. Coating the surface of core particles having a glass transition temperature of 20 to 40 ° C. containing inorganic fine particles and terpene-modified novolak resin fine particles having a volume average particle size of 0.1 to 1.0 μm and a glass transition temperature of 50 to 100 ° C. A small amount of toner for developing an electrostatic charge image coated with a layer. Both contained an image forming method.

  According to the present invention, it is possible to provide an electrostatic image developing toner capable of forming an image excellent in low-temperature fixability and excellent in document offset property, a manufacturing method thereof, an electrostatic image developer, and an image forming method.

Hereinafter, the toner for developing an electrostatic image of the present invention, a production method thereof, an electrostatic image developer, and an image forming method will be described in detail.
<Electrostatic image developing toner and method for producing the same>
The toner for developing an electrostatic charge image of the present invention (hereinafter sometimes referred to as “the toner of the present invention”) has a binder resin, a colorant, a volume average particle size of 0.1 to 0.5 μm, and a specific gravity. The surface of the core particle having a glass transition temperature of 20 to 40 ° C. containing inorganic fine particles of 1.0 to 2.0 is coated with a coating layer having a glass transition temperature of 50 to 100 ° C.

The toner of the present invention has a core (core particle) -shell (coating layer) type double structure. The core part has a low-temperature fixability function at a low glass transition temperature, the shell part has a document offset resistance function at a high glass transition temperature, and the core part and shell part functions are well balanced at the time of fixing and images. Toner.
The glass transition temperature of the core particles is 20 to 40 ° C, and preferably 20 to 30 ° C. When the glass transition temperature of the core particles is lower than 20 ° C., the probability that the binder resin component having a low glass transition temperature contained in the core particles is exposed on the surface of the fixed image is increased, and the document offset property of the fixed image is lowered. On the other hand, when the temperature exceeds 40 ° C., the low glass transition temperature component of the core particles hardly contributes at the time of fixing, and the low-temperature fixability is impaired. The coating layer has a glass transition temperature of 50 to 100 ° C, preferably 60 to 80 ° C. When the glass transition temperature of the coating layer is lower than 50 ° C., the resin component having a high glass transition temperature does not exist on the image surface after fixing, and the document offset property of the fixed image is lowered.

For the measurement of the glass transition temperature (Tg) of the toner of the present invention, for example, DSC-7 (differential thermal analyzer) manufactured by Perkin Elmer 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, and an empty pan was set as a control, and measurement was performed at a heating rate of 10 ° C./min.
The calculation of the molecular weight peak area was performed by gel permeation chromatography (using GPC under the following conditions. GPC was “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation))” Two columns, “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” were used, and THF (tetrahydrofuran) was used as an eluent. The experiment was conducted using a flow rate of 0.6 ml / min, a sample injection volume of 10 μl, a measurement temperature of 40 ° C., an IR detector, and the calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”. , “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”, “F-4”, “F-40”, “F 128 ", was made from 10" F-700 ".
The peak area was sliced for each retention time range, and the distribution ratio was obtained from the area ratio.

In the toner of the present invention, the glass transition temperature of the core particle and the glass transition temperature of the coating layer are different. However, due to the constitution of the toner of the present invention, the toner particles have two different temperature ranges of 20 to 40 ° C. Since the peak can be easily observed, the glass transition temperature of the core particle and the glass transition temperature of the coating layer can be distinguished from the data obtained from the differential thermal analyzer.
When the coating layer is composed of a plurality of resin layers, a plurality of different peaks are observed in the range of 50 to 100 ° C. due to the constitution of the toner of the present invention. If separation by peak observation is not easy, peak observation can be performed by adjusting the magnification of the measurement axis as necessary.

The core particles according to the present invention include inorganic fine particles having a volume average particle size of 0.1 to 0.5 μm and a specific gravity of 1.0 to 2.0. By adding inorganic fine particles with a relatively small particle size and a small specific gravity to the core particles, these inorganic fine particles are likely to be present on the image surface during fixing, and it is established that the binder resin component is present on the surface. Can be lowered. As a result, it is possible to suppress the presence of a core resin component having a low glass transition temperature and a shell resin component having a high glass transition temperature on the image surface as compared with a core-shell type toner that does not contain the inorganic fine particles in the core particles. Further, it is better to keep the movement of the toner material for forming an image when a plurality of fixed images after fixing overlap, that is, the so-called document offset property.
Accordingly, both high-speed printing, low-energy fixing, and halftone of a fixed image can be achieved even under stressful conditions for compatibility between low-temperature fixing and document offset.

  The inorganic fine particles can be added by a wet method. As the inorganic fine particles to be added, all of those usually used as external additives on the toner surface such as silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate can be used. It is preferable to use by dispersing with a molecular acid or a polymer base. The volume average particle diameter of the inorganic fine particles in the obtained inorganic fine particle dispersion is measured, for example, with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.). The volume average particle size of the inorganic fine particles is required to be 0.1 to 1.0 μm, and preferably 0.1 to 0.5 μm. If the volume average particle size of the inorganic fine particles is not within the above range, internal addition to the core particles is difficult, and exposure to the toner surface may occur.

  The specific gravity of the inorganic fine particles needs to be 1.0 to 2.0, preferably 1.0 to 1.5. If it is less than 1.0, it becomes difficult to form an inorganic fine particle dispersion, or exposure to the toner surface may occur. On the other hand, if it exceeds 2.0, it becomes difficult to exist on the image surface at the time of fixing due to an increase in specific gravity.

The method for measuring the specific gravity of inorganic fine particles will be described below.
<Specific gravity measurement of inorganic fine particles>
The specific gravity was measured according to JIS-K-0061 5-2-1 using a Le Chatelier specific gravity bottle. The operation is as follows.
(1) About 250 ml of ethyl alcohol is put into a Lechatelier specific gravity bottle and adjusted so that the meniscus is at the position of the scale.
(2) The Lechatelier specific gravity bottle is immersed in a constant temperature water bath, and when the liquid temperature reaches 20.0 ± 0.2 ° C., the position of the meniscus is accurately read with the scale of the specific gravity bottle. (Accuracy 0.025ml)
(3) About 100 g of the sample is accurately weighed and its mass is designated W.
(4) Place the weighed sample in a Le Chatelier specific gravity bottle and remove the foam.
(5) The Lechatelier specific gravity bottle is immersed in a constant temperature water bath, and when the liquid temperature reaches 20.0 ± 0.2 ° C., the position of the meniscus is accurately read with the scale of the specific gravity bottle. (Accuracy 0.025ml)
(6) The specific gravity S is calculated by the following equation.

D = W / (L2−L1)
S = D / 0.9982

In the formula, D is the density of the sample (20 ° C) (g / cm ³ ), S is the specific gravity of the sample (20 ° C), W is the apparent mass of the sample (g), L1 is the sample in a Le Chatelier specific gravity bottle Meniscus reading (20 ° C) (ml) before loading, L2 is the meniscus reading (20 ° C) (ml) after placing the sample in a Le Chatelier specific gravity bottle, 0.9982 is the density of water at 20 ° C (G / cm ³ ).

The thickness of the coating layer of the toner of the present invention is preferably from 0.1 to 0.9 μm, more preferably from 0.2 to 0.8 μm. When the thickness of the coating layer is less than 0.1 μm, the probability that the low glass transition temperature component of the core portion is exposed on the image surface after fixing is increased, and the document offset property becomes insufficient. On the other hand, when the thickness of the coating layer exceeds 0.9 μm, the low glass transition temperature component of the core part hardly contributes at the time of fixing, and the low temperature fixing property is lowered.
The thickness of the coating layer was also stopped by the following method.
(1) Using a transmission electron microscope, photograph a cross-sectional view of the toner at a magnification of 10,000 times for a toner having a particle diameter of 80 to 120% of the volume average particle diameter measured by the following method.
(2) The photographed photograph is observed to measure the film thickness of the coating layer of each toner.
(3) The thickness of the coating layer for 100 toners was measured, and the average value was taken as the thickness of the coating layer.

The toner of the present invention preferably has a volume average particle size of 3 to 9 μm, more preferably 3 to 8 μm. When the volume average particle size is less than 3 μm, the chargeability becomes insufficient and the developability may be lowered, and when it exceeds 9 μm, the resolution of the image is lowered.
The particle size of the toner can be determined, for example, by measuring with an aperture diameter of 50 μm using a measuring instrument such as Coulter Counter TA II (manufactured by Beckman-Coulter) or Multisizer II (manufactured by Beckman-Coulter). . In this case, the measurement is performed after the toner is dispersed in an electrolyte aqueous solution (isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds or more.
Based on the measured particle size distribution, the cumulative distribution is drawn from the small diameter side to the divided particle size range (channel) from the small diameter side, and the particle size that becomes 50% cumulative is the volume average particle size (D50V), It is defined as the number average particle size (D50P).

  The core particles according to the present invention preferably contain terpene-modified novolak resin fine particles having a volume average particle size of 0.1 to 1.0 μm. The terpene-modified novolak resin fine particles do not have Tg and have a melting point in a high temperature range of 100 ° C. or higher. Therefore, by adding terpene-modified novolak resin fine particles to the core particles, the binder resin of the core particles melts at the time of fixing, and phase separation easily occurs between these resin fine particles. It tends to exist on the image surface. Further, the probability that the binder resin component is present on the image surface can be reduced. Thereby, it is possible to suppress the presence of a core resin component having a low glass transition temperature and a shell resin component having a high glass transition temperature on the image surface as compared with a core-shell type toner not containing the terpene-modified novolak resin fine particles, In addition, since a resin having a high melting point component can be present on the image surface, it is better to maintain document offset at the time of low-temperature fixing. Accordingly, both high-speed printing, low-energy fixing, and halftone of a fixed image can be achieved even under stressful conditions for compatibility between low-temperature fixing and document offset.

  The terpene-modified novolac resin fine particles can be added by a wet method. The terpene-modified novolak resin used in the present invention is obtained by modifying and modifying a normal novolak resin with terpenes. The novolak resin includes a novolak dinuclear, trinuclear or higher polynuclear body, and may include an ortho-ortho bond or an isomer thereof. Specific examples include phenol novolac resins and cresol novolac resins.

  Examples of terpenes include hemiterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes and compounds derived from these (alcohols, aldehydes, ketones, oxides, esters, etc.), and specific examples include Pinene, dipentene, limonene, paramentan, pinane, terpene dimer, paramentadiene, terpenol, dihydroterpineol, camphor, myrtenol, cineol, borneol, carveol, carboxoxide, carbyl acetate, citronellal, citronellol, cymen, dihydrocarbeo, Dihydrocarbon, dihydrocarbyl acetate, dihydroterpineol, dihydroterpinyl acetate, isobornyl acetate, linalool, menthol Le, myrtenol, terpinene, abietic acid, neoabietic acid, levopimaric acid and palustric acid. These may be used alone or in combination of two or more.

  From the viewpoint of the strength of the fixed image, it is preferable to use terpenes having a cyclic structure. As the terpene-modified novolak resin, fine powder, lump, flake, rod or marble can be used. These are pulverized and powdered as necessary, dispersed in water with polymer electrolytes such as ionic surfactants, polymer acids, and polymer bases, heated above the melting point, and homogenizers or pressure discharge type dispersers A fine shear is applied to make fine particles to create a dispersion of resin fine particles.

  The volume average particle diameter of the terpene-modified novolak resin fine particles is measured by, for example, a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.). The volume average particle size is preferably from 0.1 to 1.0 μm, more preferably from 0.1 to 0.5 μm. When the volume average particle size is less than 0.1 μm, even if it is contained in the core particles, a sufficient effect on the document offset property cannot be exhibited. If the volume average particle size exceeds 1.0 μm, internal addition to the core particles becomes difficult, and the effect of the present invention due to internal addition to the core particles cannot be exhibited.

  In the present invention, the terpene-modified novolak resin is preferably contained in an amount of 3 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on the toner. When the content of the terpene-modified novolak resin is less than 3 parts by mass, the image surface cannot be sufficiently covered at the time of low-temperature fixing, and the effect thereof becomes insufficient. On the other hand, when the content of the terpene-modified novolak resin is larger than 30 parts by mass, the low-temperature fixability is adversely affected.

The coating layer according to the present invention comprises at least two resin layers having different glass transition temperatures, and the difference between the glass transition temperature of the core particles and the glass transition temperature of the outermost layer of the at least two resin layers is 30 ° C. The above is preferable. By providing at least two coating layers, the low glass transition temperature resin can be prevented from coming out on the toner surface, and document offset can be prevented. Moreover, when the difference between the glass transition temperature of the core particles and the glass transition temperature of the outermost layer of at least two resin layers is 30 ° C. or less, it is difficult to realize both low-temperature fixability and document offset prevention. Sometimes.
When a coating layer consists of at least two resin layers, the glass transition temperature of one layer should just be 50-100 degreeC. Moreover, it is preferable that a glass transition temperature becomes high toward an outer resin layer from an inner resin layer.

  When the coating layer according to the present invention is composed of at least two resin layers having different glass transition temperatures, the total thickness of the coating layer is preferably 0.3 to 0.9 μm. When the thickness of the coating layer is less than 0.3 μm, it is difficult to realize a multilayer structure, and the effect of the coating layer is not sufficiently exhibited, so that document offset is not suppressed. When the thickness of the coating layer is larger than 0.9 μm, the coating layer is too thick, and the core particles having a low glass transition temperature do not function and it is difficult to realize low-temperature fixability.

When the coating layer according to the present invention is composed of at least two resin layers having different glass transition temperatures, the difference in acid value between adjacent resin layers is preferably 2.0 mgKOH / g or less. Here, the acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. By setting the difference in acid value to 2.0 mgKOH / g or less, the electric repulsion between the resin layers is reduced, the coating layer can be easily formed, and the core particles and the coating layer are more compatible.
In the present invention, the acid value of the resin layer refers to the acid value of the coating resin.

  The toner of the present invention preferably has an acid value in the range of 3 to 20 mgKOH / g. When the acid value is less than 3 mgKOH / g, sufficient charging characteristics cannot be obtained. When the acid value is more than 20 mgKOH / g, the moisture absorption characteristics of the toner are deteriorated, causing problems in charging characteristics such as poor charging and lowering of environmental dependency.

  The toner of the present invention may be produced by any method such as a kneading pulverization method, a polymerization method, a heteroaggregation method, etc., but generally a dispersion of resin fine particles produced by emulsion polymerization or the like is used. The colorant dispersion dispersed in the ionic surfactant having the opposite polarity and the inorganic fine particle dispersion are mixed to form heteroaggregation to form aggregated particles corresponding to the toner diameter, and then the glass transition of the resin. The toner shape can be appropriately manufactured from an indeterminate shape to a spherical shape by a method in which the aggregated particles are fused and united by heating to a temperature higher than that, washed and dried to obtain a toner.

  The electrostatic charge image developing toner of the present invention has a binder resin fine particle dispersion in which binder resin fine particles having a volume average particle size of 1.0 μm or less are dispersed, a colorant dispersion, and a volume average particle size of 0.1 to 0. An agglomeration step in which an inorganic fine particle dispersion in which inorganic fine particles having a specific gravity of 1.0 to 2.0 are dispersed is mixed to form agglomerated particles, and adhesion for attaching the coated resin fine particles to the surface of the agglomerated particles It is preferable to produce at least a process and a fusion process in which the aggregated particles to which the coating resin fine particles are adhered are heated and fused.

The above method is a method in which the raw material dispersion is mixed and agglomerated in a lump, but the balance of the amount of polar ionic dispersant is shifted in advance in the initial stage of the agglomeration process, and an inorganic metal such as calcium nitrate is used. This is ionically neutralized using a salt or a polymer of an inorganic metal salt such as polyaluminum chloride to form aggregated particles that become core particles of the first stage below the glass transition temperature. The coating resin fine particles are adhered to the surface of the agglomerated particles to be the core particles by adding a coating resin fine particle dispersion of polarity and quantity that compensates for the above-mentioned balance deviation in two steps (adhesion step), and further required The glass transition temperature is then stabilized by slightly heating at a high temperature below the glass transition temperature of the resin contained in the aggregated particles to be core particles or added coating resin fine particles. By heating to above (fusion step) particles may remain by coalescence was attached to the surface of the agglomerated particles as the core particles was added in the second stage.
Furthermore, this stepwise operation of aggregation may be repeated a plurality of times. The surface of the core particle can be coated with at least two resin layers by repeating the stepping operation of aggregation a plurality of times. Further, a release agent may be contained in the aggregated particles in an amount of 5 to 25% by mass in terms of solid content per toner weight. The release agent is preferably added before adhering the coating resin fine particles from the viewpoint of chargeability and durability.

  In order to contain the terpene-modified novolak resin fine particles having a volume average particle size of 0.1 to 1.0 μm in the core particles, the terpene-modified novolak resin fine particle dispersion may be further mixed in the aggregation step.

  The polymer used for the resin fine particles such as the binder resin fine particles and the coated resin fine particles is not particularly limited. For example, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, acrylic Has vinyl groups such as n-propyl acid, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate Esters; 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; Polymers of monomers such as polyolefins such as len and butadiene, copolymers obtained by combining two or more of these, or mixtures thereof, as well as epoxy resins, polyester resins, polyurethane resins, polyamide resins, and cellulose resins And non-vinyl condensation resins such as polyether resins, mixtures of these with the vinyl resins, and graft polymers obtained by polymerizing vinyl monomers in the presence of these.

  The particle size of the fine particles in the resin fine particle dispersion can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The volume average particle size of the resin fine particles used in the present invention is preferably 50 to 400 nm, more preferably 70 to 350 nm. If it is less than 50 nm, the aggregation rate tends to decrease, and the productivity tends to decrease and the particle size distribution tends to expand. If it exceeds 400 nm, the cohesiveness is good, but the aggregate tends to contain voids, making it difficult to form a sphere and making shape control difficult.

  The vinyl monomer can be emulsion-polymerized using an ionic surfactant or the like to prepare a resin fine particle dispersion. Other resins are those that are oily and soluble in solvents with relatively low solubility in water. Dissolve the resin in these solvents and disperse in water with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte. Then, the resin fine particle dispersion can be prepared by evaporating the solvent by heating or depressurization.

  The release agent used in the present invention 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. If it is less than 50 ° C., an offset tends to occur during fixing. On the other hand, if it 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, DSC-7 (differential thermal analyzer) manufactured by Perkin Elmer can be 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. For the sample, an aluminum pan is used, an empty pan is set for control, and the measurement is performed at a heating rate of 10 ° C./min.

  Release agents used in the present invention include, for example, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point upon heating; fatty acids such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide Amides; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, fishertro Minerals such as schwax and the like, petroleum-based waxes; and their modified products can be used.

These waxes are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, heated above their melting point, and subjected to strong shearing with a homogenizer or pressure discharge type disperser. Then, a dispersion of release agent fine particles of 1 μm or less is prepared. In the present invention, the addition amount of the release agent dispersed in the toner is suitably in the range of 5 to 25% by mass with respect to the toner mass part.
The volume average particle size of the release agent fine particles in the obtained release agent dispersion is measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). The volume average particle size of the release agent fine particles is preferably 50 to 400 nm, and more preferably 70 to 350 nm. If the thickness is less than 50 nm, the required amount of the release agent at the time of fixing tends to increase, and if it exceeds 400 nm, aggregation may be unstable.

  The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, 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 yellow pigments 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. Is mentioned.

  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, indanthrene brilliant orange GK and the like. 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, indanthrene 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. These pigments and dyes can be used alone or in combination, and further in a solid solution state.

  These colorants can be dispersed in the dispersion by a known method. For example, a rotary shear type homogenizer, a media mill such as a ball mill, a sand mill, or an attritor, a high-pressure counter collision type disperser, or the like is preferable. Used. In the present invention, the addition amount of the colorant dispersed in the toner is suitably in the range of 4 to 15% by mass in the toner. In addition, when using a magnetic body as a black coloring agent, the range of 30-100 mass% is suitable unlike other coloring agents.

  Moreover, when using a toner as a magnetic toner, you may contain a magnetic powder. As the magnetic powder, a material that is magnetized in a magnetic field is used, and a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used. In the present invention, since the toner is produced in the aqueous phase, attention must be paid to the aqueous phase migration of the magnetic material. The surface is preferably modified and used, for example, after being subjected to a hydrophobic treatment.

The shape factor SF1 of the toner of the present invention is preferably in the range of 110 to 145 from the viewpoint of image formability. The shape factor SF1 is calculated as an average value of (the square of the perimeter / projection area), for example, by the following method. That is, an optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, and the square of the circumference of 50 or more toners / projection area (ML ² / A) is calculated and averaged. Find the value.

  In the toner of the present invention, a charge control agent can be used in order to further improve and stabilize the chargeability. As the charge control agent, various 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. A material that is difficult to dissolve in water is preferable from the viewpoint of controlling the ionic strength that affects the stability of aggregation, fusion, and temporary combination and reducing wastewater contamination.

  To the toner of the present invention, inorganic fine particles can be added in a wet manner in order to stabilize the chargeability. As the inorganic fine particles to be added, all of those usually used as external additives on the toner surface such as silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate can be used. It is preferable to use by dispersing with a molecular acid or a polymer base.

  In the present invention, for the purpose of imparting fluidity and improving cleaning properties, after drying the toner, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin fine particles such as vinyl resin, polyester and silicone are removed. The additive is preferably added to the toner surface while being sheared.

  In the toner production method of the present invention, as a surfactant used for emulsion polymerization, resin fine particle dispersion, colorant dispersion, release agent dispersion, aggregation, or stabilization thereof, for example, sulfate ester salt type, sulfonate salt type Anionic surfactants such as phosphate esters and soaps, cationic surfactants such as amine salts and quaternary ammonium salts, polyethylene glycols, alkylphenol ethylene oxide adducts, polyhydric alcohols, etc. It is also effective to use a nonionic surfactant in combination. 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 composed of a resin and a colorant, the composite is dissolved and dispersed in a solvent after the resin and the colorant are dissolved, and then dispersed in water together with the appropriate dispersant. It can be prepared and prepared by a method for removing the surface, a method for imparting to the surface of resin fine particles prepared by emulsion polymerization with a mechanical shear force, or a method for electrically adsorbing and fixing. These methods are effective in suppressing the liberation of the colorant as additional particles and improving the dependency of the chargeable colorant.

  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.

  In the present invention, it is possible to provide an image excellent in low-temperature fixability and excellent in document offset by adopting the above configuration.

<Electrostatic image developer>
The electrostatic charge image developer of the present invention includes a glass transition containing a binder resin, a colorant, and inorganic fine particles having a volume average particle size of 0.1 to 0.5 μm and a specific gravity of 1.0 to 2.0. It contains at least an electrostatic image developing toner obtained by coating the surface of core particles having a temperature of 20 to 40 ° C. with a coating layer having a glass transition temperature of 50 to 100 ° C.

When the electrostatic image developing toner of the present invention is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer. .
The carrier that can be used in the two-component electrostatic image developer is not particularly limited, and a known carrier can be used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin dispersion type carrier in which a conductive material or the like is dispersed in a matrix resin may be used. In the present invention, it is possible to obtain a developer having a narrow charge distribution because the charge characteristics can be controlled well, so a developer using a carrier having a resin coating layer provided on the surface is used. It is preferable.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples thereof include, but are not limited to, acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins and the like.

  Examples of the conductive material include metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black. It is not limited.

  Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, it is a magnetic material. It is preferable. The volume average particle size of the core material of the carrier is generally 10 to 500 μm, preferably 30 to 100 μm.

  In order to coat the surface of the core material of the carrier with a resin, a method of coating the surface with a coating solution for forming the surface layer in which the coating resin and, if necessary, various additives are dissolved in an appropriate solvent may be mentioned. The solvent is not particularly limited and may be appropriately selected in consideration of the coating resin to be used, coating suitability, and the like.

  Specific resin coating methods include a dipping method in which the carrier core material is immersed in the surface layer forming solution, a spray method in which the surface layer forming solution is sprayed on the surface of the carrier core material, and the carrier core material is fluidized air. And a kneader coater method in which the core material of the carrier and the surface layer forming solution are mixed in a kneader coater to remove the solvent.

  The mixing ratio (mass ratio) of the electrostatic image developing toner of the present invention and the carrier in a two-component electrostatic image developer is in the range of toner: carrier = 1: 100 to 30: 100, The range of about 3: 100 to 20: 100 is more preferable.

<Image forming method>
The image forming method of the present invention comprises a latent image forming step for forming an electrostatic charge image on the surface of the latent image carrier and a developer formed on the surface of the latent image carrier using a developer carried on the developer carrier. A developing step of developing a charge image to form a toner image, a transferring step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a toner image transferred to the surface of the transfer target And a fixing step for heat-fixing the toner. The electrostatic image developer of the present invention is used as the developer.

  The developer may be either a one-component system or a two-component system. As each of the above steps, a known step in the image forming method can be used. The image forming method of the present invention may include steps other than the steps described above.

As the latent image holding member, for example, an electrophotographic photosensitive member and a dielectric recording member can be used.
In the case of an electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic charge image (latent image forming step). Next, the toner is attached to the electrostatic image by bringing it into contact with or in proximity to a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member (developing step). The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like (transfer process). Further, the toner image transferred to the surface of the transfer target is heat-fixed by a fixing device, and a final toner image is formed.
In the heat fixing by the fixing machine, a release agent is usually supplied to a fixing member in the fixing machine in order to prevent an offset or the like.

  In the electrostatic image developing toner of the present invention (including those contained in a two-component developer; the same applies hereinafter), if the binder resin has a crosslinked structure, it is excellent in releasability due to its effect. Fixing can be performed without using a mold release agent or without using a mold release agent.

The release agent is preferably not used from the viewpoint of eliminating oil adhesion to the transfer target and image after fixing. However, when the supply amount of the release agent is 0 mg / cm ² , the fixing agent is fixed during fixing. When the member and the transfer medium such as paper come into contact with each other, the amount of wear of the fixing member may increase and the durability of the fixing member may decrease. It is preferable that the amount used is supplied to the fixing member in a small amount within a range of 8.0 × 10 ⁻³ mg / cm ² or less.

When the supply amount of the release agent exceeds 8.0 × 10 ⁻³ mg / cm ² , the image quality deteriorates due to the release agent adhering to the image surface after fixing, and in particular, transmitted light such as OHP is transmitted. When used, such a phenomenon may be prominent. Further, the adhesion of the release agent to the transfer target becomes remarkable, and stickiness may occur. Furthermore, the larger the supply amount of the release agent, the larger the capacity of the tank for storing the release agent, which causes an increase in the size of the fixing device itself.

  Although there is no restriction | limiting in particular as said mold release agent, For example, liquid mold release agents, such as modified oils, such as dimethyl silicone oil, fluorine oil, fluoro silicone oil, and amino modified silicone oil, are mentioned. Among these, modified oils such as amino-modified silicone oil are preferable because they are adsorbed on the surface of the fixing member and can form a homogeneous release agent layer, because they have excellent wettability to the fixing member. Further, from the viewpoint of forming a homogeneous release agent layer, fluorine oil and fluorosilicone oil are preferable.

  The method for supplying the release agent to the surface of the roller or belt, which is a fixing member used for the thermocompression bonding, is not particularly limited. For example, a pad method using a pad impregnated with a liquid release agent, a web method, Examples thereof include a roller method and a non-contact type shower method (spray method). Among these, a web method and a roller method are preferable. These methods are advantageous in that the release agent can be supplied uniformly and it is easy to control the supply amount. In order to supply the release agent uniformly to the entire fixing member by the shower method, it is necessary to use a separate blade or the like.

The supply amount of the release agent can be measured as follows. That is, when a normal paper (typically a copy paper manufactured by Fuji Xerox Co., Ltd., trade name J paper) used in a general copying machine is passed through a fixing member supplied with a release agent on its surface. The release agent adheres to the plain paper. The attached release agent is extracted using a Soxhlet extractor. Here, hexane is used as the solvent.
By quantifying the amount of the release agent contained in the hexane with an atomic absorption analyzer, the amount of the release agent adhering to the plain paper can be quantified. This amount is defined as the amount of release agent supplied to the fixing member.

Examples of the transfer target (recording material) to which the toner image is transferred include plain paper, OHP sheet, and the like used in electrophotographic copying machines and printers.
In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer object is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin or the like, art paper for printing Etc. can be used suitably.

  The image forming method of the present invention uses the electrostatic charge image developer of the present invention (the toner for developing an electrostatic charge image of the present invention), and therefore can form an image having excellent low-temperature fixability and excellent document offset property. is there.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by the following Example.
The following resin fine particle dispersion, colorant dispersion, inorganic fine particle dispersion, release agent dispersion, and terpene-modified novolak resin fine particle dispersion were prepared, mixed at a predetermined ratio, and stirred, A metal salt polymer is added and ionically neutralized to form aggregated particles. After adjusting the pH of the system from weakly acidic to neutral with an inorganic hydroxide, the mixture is heated to a temperature higher than the glass transition temperature of the resin fine particles to be fused and united. Then, the desired toner was obtained through sufficient steps of washing, solid-liquid separation, and drying. Hereinafter, each preparation method is demonstrated.

(Preparation of resin fine particle dispersion 1A)
Styrene (manufactured by Wako Pure Chemical Industries) 200 parts by mass n-butyl acrylate (manufactured by Wako Pure Chemical Industries) 200 parts by mass β-carboxyethyl acrylate (manufactured by Rhodia Nikka) 9 parts by mass 1, 10 decanediol diacrylate (manufactured by Shin-Nakamura Chemical) 5 parts by mass dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) 2.7 parts by mass The above is mixed and dissolved, and this is added to 550 parts by mass of ion-exchanged water containing 4 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical). Dissolved, further dispersed and emulsified in a flask, and slowly stirred and mixed for 10 minutes, and then charged with 50 parts by mass of ion-exchanged water in which 6 parts by mass of ammonium persulfate was dissolved. Next, after sufficiently replacing the nitrogen in the system, the system was heated in an oil bath while stirring the flask until it reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, an anionic resin fine particle dispersion 1A having a volume average particle size of 196 nm and a glass transition temperature of 28.3 ° C. was obtained.

(Preparation of resin fine particle dispersion 2A)
In the adjustment of the resin fine particle dispersion 1A, a resin fine particle dispersion 2A was obtained in the same manner as the adjustment of the resin fine particle dispersion 1A except that 210 parts by mass of styrene and 190 parts by mass of n-butyl acrylate were used. The volume average particle size was 195 nm and the glass transition temperature was 32.1 ° C.

(Preparation of resin fine particle dispersion 3A)
In the adjustment of the resin fine particle dispersion 1A, a resin fine particle dispersion 3A was obtained in the same manner as the adjustment of the resin fine particle dispersion 1A except that 230 parts by mass of styrene and 170 parts by mass of n-butyl acrylate were used. The volume average particle diameter was 199 nm and the glass transition temperature was 35.5 ° C.

(Preparation of resin fine particle dispersion 4A)
A resin fine particle dispersion 4A was obtained in the same manner as the adjustment of the resin fine particle dispersion 1A except that the resin fine particle dispersion 1A was adjusted to 250 parts by mass of styrene and 150 parts by mass of n-butyl acrylate. The volume average particle size was 200 nm and the glass transition temperature was 38.9 ° C.

(Preparation of resin fine particle dispersion 5A)
A resin fine particle dispersion 5A was obtained in the same manner as the adjustment of the resin fine particle dispersion 1A except that the resin fine particle dispersion 1A was adjusted to 315 parts by mass of styrene and 75 parts by mass of n-butyl acrylate. The volume average particle size was 201 nm, and the glass transition temperature was 54.2 ° C.

(Preparation of resin fine particle dispersion 6A)
Resin fine particle dispersion liquid 1A was prepared in the same manner as the resin fine particle dispersion liquid 1A except that 330 parts by mass of styrene, 70 parts by mass of n-butyl acrylate, and 9.5 parts by mass of β-carboxyethyl acrylate were used. 6A was obtained. The volume average particle size was 198 nm and the glass transition temperature was 58.7 ° C.

(Preparation of resin fine particle dispersion 7A)
Resin fine particle dispersion 7A was obtained in the same manner as the adjustment of resin fine particle dispersion 1A, except that in the adjustment of resin fine particle dispersion 1A, 360 parts by mass of styrene and 40 parts by mass of n-butyl acrylate were used. The volume average particle size was 202 nm, and the glass transition temperature was 62.4 ° C.

(Preparation of resin fine particle dispersion 8A)
A resin fine particle dispersion 8A was obtained in the same manner as the adjustment of the resin fine particle dispersion 1A, except that the adjustment of the resin fine particle dispersion 1A was changed to 375 parts by mass of styrene and 25 parts by mass of n-butyl acrylate. The volume average particle diameter was 199 nm and the glass transition temperature was 68.2 ° C.

(Preparation of colorant dispersion 1A)
Phthalocyanine pigment (manufactured by Dainichi Seika Co., Ltd., PVFASTBLUE) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass or more, and homogenizer (manufactured by IKA, After dispersing for 10 minutes using an ultra turrax T50), a colorant dispersion 1A was prepared by applying to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP). The number average particle diameter of the colorant in the colorant dispersion 1A was 150 nm.

(Preparation of colorant dispersion 2A)
Carbon black (manufactured by CABOT, R330) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass or more are mixed and the same as the colorant dispersion 1A Colorant dispersion 2A was prepared under the conditions. The number average particle diameter of the colorant in the colorant dispersion 2A was 155 nm.

(Preparation of colorant dispersion 3A)
C. I Pigment Red 122 (manufactured by Dainichi Chemical Co., Ltd., ECR-185) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass Colorant dispersion 3A was prepared under the same conditions as colorant dispersion 1A. The number average particle diameter of the colorant in the colorant dispersion 3A was 165 nm.

(Preparation of colorant dispersion 4A)
C. I Pigment Yellow 74 (manufactured by Clariant) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass or more and the same as the colorant dispersion 1A A colorant dispersion 4A was prepared under the conditions. The number average particle diameter of the colorant in the colorant dispersion 4A was 175 nm.

(Preparation of inorganic fine particle dispersion 1A)
Silica sol (specific gravity 1.6) 50 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by mass Ion-exchanged water 200 parts by mass The above was mixed and homogenizer (IKA, Ultra Turrax T50). ) For 10 minutes, and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain an inorganic fine particle dispersion 1A containing silica fine particles having a volume average particle size of 0.4 μm.

(Preparation of inorganic fine particle dispersion 2A)
Silica sol (specific gravity 3.0) 50 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by mass Ion-exchanged water 200 parts by mass The above was mixed and a homogenizer (IKA, Ultra Turrax T50). ) Was applied for 10 minutes, and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain an inorganic fine particle dispersion 2A containing fine particles having a volume average particle diameter of 0.4 μm.

(Preparation of inorganic fine particle dispersion 3A)
Silica sol (specific gravity 1.8) 50 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by mass Ion-exchanged water 200 parts by mass The above is mixed, and a homogenizer (IKA, Ultra Turrax T50) is mixed. ) For 10 minutes, and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain an inorganic fine particle dispersion 3A containing silica fine particles having a volume average particle size of 1.1 μm.

(Preparation of release agent dispersion 1A)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP0190, melting point 85 ° C.) 50 parts by mass Cationic surfactant (manufactured by Kao Corporation, Sanizol B50) 5 parts by mass Ion-exchanged water 200 parts by mass The above components are heated to 95 ° C., After sufficiently dispersing with a homogenizer (manufactured by IKA, Ultra Turrax T50), it was dispersed with a pressure discharge type homogenizer to obtain a release agent dispersion 1A containing release agent particles having a volume average particle diameter of 200 nm.

(Manufacture of toner 1A)
(Aggregation process)
Ion-exchanged water 500 parts by weight Resin fine particle dispersion 1A 200 parts by weight Resin fine particle dispersion 5A 25 parts by weight Colorant dispersion 1A 36 parts by weight Inorganic fine particle dispersion 1A 10 parts by weight Release agent dispersion 1A 35 parts by weight Flocculant [ Asada Chemical Co., Ltd., polyaluminum chloride] 0.5 parts by mass The above mixed components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the agglomeration temperature was heated to 30 ° C. while stirring the flask in a heating oil bath. Thereafter, it was kept at 32 ° C. for 1.5 hours.
(Adhesion process)
25 parts by mass of resin fine particle dispersion 5A was slowly added to the dispersion containing the aggregated particles prepared above, and the temperature of the heating oil bath was raised and maintained at 35 ° C. for 1 hour.
(Fusion process)
Next, after adding a 1 mol / L sodium hydroxide aqueous solution so that the pH becomes 6.0, the stainless steel flask was sealed, and gently heated to 85 ° C. while continuing stirring using a magnetic seal, Thereafter, the mixture was heated to 96 ° C., a 1 mol / L aqueous nitric acid solution was added until pH 5.0, and the mixture was held for 5 hours. Thereafter, the toner 1A was produced by cooling, filtering, thoroughly washing with ion-exchanged water, and drying using a vacuum dryer. The volume average particle diameter was 5.3 μm, and the coating layer thickness was 0.41 μm.

(Manufacture of toner 2A)
Instead of resin fine particle dispersion 1A, 175 parts by mass of resin fine particle dispersion 2A was used, and 25 parts by mass of resin fine particle dispersion 6A was added in the adhering step. A toner 2A was obtained in the same manner as in the production of the toner 1A, except that the heating temperature when the resin fine particle dispersion was added in the adhesion step was changed to 35 ° C. The volume average particle diameter was 5.4 μm, and the coating layer thickness was 0.50 μm.

(Manufacture of toner 3A)
In place of the resin fine particle dispersion 1A, 150 parts by mass of the resin fine particle dispersion 3A was used, and 20 parts by mass of the resin fine particle dispersion 7A was added in the attaching step. A toner 3A was obtained in the same manner as in the production of the toner 1A except that the heating temperature when the resin fine particle dispersion was added in the attaching step was changed to 37 ° C. The volume average particle diameter was 6.3 μm, and the coating layer thickness was 0.74 μm.

(Manufacture of toner 4A)
In place of the resin fine particle dispersion 1A, 160 parts by mass of the resin fine particle dispersion 4A was aggregated at 32 ° C., and 15 parts by mass of the resin fine particle dispersion 8A was added in the attaching step. A toner 4A was obtained in the same manner as in the production of the toner 1A except that the heating temperature when the resin fine particle dispersion was added in the attaching step was changed to 37 ° C. The volume average particle diameter was 6.5 μm, and the coating layer thickness was 0.62 μm.

(Manufacture of toner 5A)
A toner 5A was obtained in the same manner as in the production of the toner 1A except that the inorganic fine particle dispersion 2A was used instead of the inorganic fine particle dispersion 1A. The volume average particle diameter was 5.3 μm, and the coating layer thickness was 0.41 μm.

(Manufacture of toner 6A)
A toner 6A was obtained in the same manner as in the production of the toner 1A except that the inorganic fine particle dispersion 3A was used instead of the inorganic fine particle dispersion 1A. The volume average particle diameter was 5.3 μm, and the coating layer thickness was 0.41 μm.

(Manufacture of toner 7A)
A toner 7A was obtained in the same manner as in the production of the toner 1A except that the inorganic fine particle dispersion 1A was not added. The volume average particle size was 5.3 μm, and the coating layer thickness was 0.40 μm.

(Manufacture of toner 8A)
The resin fine particle dispersion 5A was used instead of the resin fine particle dispersion 1A, the aggregation temperature was 55 ° C., the resin fine particle dispersion 6A was used instead of the resin fine particle dispersion 5A in the adhesion step, and the heating temperature was 59 ° C. Except for the above, Toner 8A was obtained in the same manner as in the manufacture of Toner 1A. The volume average particle diameter was 5.3 μm, and the coating layer thickness was 0.53 μm.

(Manufacture of toner 9A)
Production of toner 1A except that resin fine particle dispersion 2A is used instead of resin fine particle dispersion 1A, resin fine particle dispersion 4A is used instead of resin fine particle dispersion 5A, and the heating temperature is 40 ° C. in the attaching step. In the same manner as described above, a toner 9A was obtained. The volume average particle diameter was 5.8 μm, and the coating layer thickness was 0.63 μm.

(Manufacture of toner 10A)
The resin fine particle dispersion 5A was used in place of the resin fine particle dispersion 1A, the aggregation temperature was 55 ° C., and the resin fine particle dispersion 4A was used in place of the resin fine particle dispersion 5A in the attaching step, and the heating temperature was 55 ° C. Except for the above, a toner 10A was obtained in the same manner as in the production of the toner 1A. The volume average particle diameter was 5.9 μm, and the coating layer thickness was 0.76 μm.

(Preparation of external toner)
0.70 parts by mass of hydrophobic silica (Cabot, TS720) was added to 100 parts by mass of each of the toners 1A to 10A, and mixed with a sample mill to obtain externally added toners 1A to 10A.

(Image output)
8 parts by mass of externally added toners 1A to 10A and 100 parts by mass of carrier are stirred and mixed in a ball mill for 5 minutes to adjust developers 1A to 10A, and image output for evaluation of fixing performance and the like is performed according to the following procedure. went. The carrier was a resin-coated carrier, and a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by mass of methyl methacrylate (Mw 78000, manufactured by Soken Chemical Co., Ltd.) was used. The adjusted developer was set in a developing unit of a color copying machine Doccolor 1250 manufactured by Fuji Xerox Co., Ltd., from which the fixing unit was removed, and an unfixed image was output. The output image was a halftone image having a size of 40 × 40 mm, and the image toner amount was adjusted to 0.20 mg / cm ² . As the paper, the product name “J Coated Paper” manufactured by Fuji Xerox Office Supply Co., Ltd. was used.

(Fixing method)
For fixing, the fixing device taken out from the Doccolor 1250 copier was remodeled so that the roll temperature of the fixing device could be changed, and the fixing roll was replaced with a Teflon (registered trademark) tube. The sheet conveying speed of the fixing device was 160 mm per second. Unfixed images of toners 1A to 10A were fixed by appropriately changing the temperature of the fixing device from 90 ° C. to 180 ° C. to obtain a fixed image.

(Minimum fixing temperature evaluation method)
The minimum fixing temperature of the toners 1A to 10A was set to a temperature at which fixing is started without causing a low temperature offset.

(Document offset evaluation method)
The images of fixed images formed at 120 ° C. using developers 1A to 10A are superposed on each other and left in a 60 ° C. atmosphere under a load of 80 g / cm ² for 7 days. The presence or absence was visually confirmed and evaluated. The evaluation criteria were ○ that the image was not deteriorated even if the force was applied to peel it, and △ that there was slight image deterioration, and marked image deterioration occurred. The thing was made into x.

( Reference Examples 1A to 4A, Comparative Examples 1A to 6A)
The performance evaluations for the toners of Reference Examples 1A to 4A and Comparative Examples 1A to 6A are shown in Table 1 together with the glass transition temperatures of the core particles and the coating layer, and the volume average particle diameter and specific gravity of the inorganic fine particles.

For the toners of Reference Examples 1A to 4A, the minimum fixing temperature was 120 ° C. or lower, and no document offset occurred.
In Comparative Examples 1A to 2A, if the specific gravity of the inorganic fine particles to be added is large or the particle diameter is large, the document offset property is slightly poor even though low temperature fixing can be obtained by controlling the glass transition temperature of the desired core-shell structure.
In Comparative Example 3A, if the desired inorganic fine particles are not added, low-temperature fixing can be obtained by controlling the glass transition temperature of the desired core-shell structure, but the document offset property is poor.
In Comparative Examples 4A to 6A, when the glass transition temperatures of the core particles and the coating layer are both too high, the document offset property is good but the low-temperature fixability is bad. On the other hand, if the glass transition temperatures of the core particles and the coating layer are both too low, the document offset property cannot be obtained even if the low-temperature fixability is good. If the glass transition temperature of the core particles is high and the glass transition temperature of the coating layer is low, both the low-temperature fixability and the document offset property are poor.

(Preparation of resin fine particle dispersion 1B)
Styrene (manufactured by Wako Pure Chemical Industries) 160 parts by mass n-butyl acrylate (manufactured by Wako Pure Chemical Industries) 230 parts by mass β-carboxyethyl acrylate (manufactured by Rhodia Nikka) 9 parts by mass 1, 10 decanediol diacrylate (manufactured by Shin-Nakamura Chemical) 5 parts by mass dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) 2.7 parts by mass The above is mixed and dissolved, and this is added to 550 parts by mass of ion-exchanged water containing 4 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical). Dissolved, further dispersed and emulsified in a flask, and slowly stirred and mixed for 10 minutes, and then charged with 50 parts by mass of ion-exchanged water in which 6 parts by mass of ammonium persulfate was dissolved. Next, after sufficiently replacing the nitrogen in the system, the system was heated in an oil bath while stirring the flask until it reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, an anionic fine resin particle dispersion 1B having a volume average particle size of 196 nm and a glass transition temperature of 20.1 ° C. was obtained.

(Preparation of resin fine particle dispersion 2B)
Resin fine particle dispersion 2B was obtained in the same manner as in the preparation of resin fine particle dispersion 1B except that in the adjustment of resin fine particle dispersion 1B, 2,000 parts by mass of styrene and 200 parts by mass of n-butyl acrylate were used. The volume average particle size was 195 nm and the glass transition temperature was 28.3 ° C.

(Preparation of resin fine particle dispersion 3B)
A resin fine particle dispersion 3B was obtained in the same manner as the adjustment of the resin fine particle dispersion 1B except that the resin fine particle dispersion 1B was adjusted to 250 parts by mass of styrene and 150 parts by mass of n-butyl acrylate. The volume average particle size was 199 nm and the glass transition temperature was 38.9 ° C.

(Preparation of resin fine particle dispersion 4B)
Resin fine particle dispersion 4B was obtained in the same manner as in the preparation of resin fine particle dispersion 1B except that 300 parts by mass of styrene and 100 parts by mass of n-butyl acrylate were used in the adjustment of resin fine particle dispersion 1B. The volume average particle size was 200 nm and the glass transition temperature was 51.0 ° C.

(Preparation of resin fine particle dispersion 5B)
In the adjustment of the resin fine particle dispersion 1B, a resin fine particle dispersion 5B was obtained in the same manner as the adjustment of the resin fine particle dispersion 1B except that 360 parts by mass of styrene and 40 parts by mass of n-butyl acrylate were used. The volume average particle size was 201 nm, and the glass transition temperature was 62.4 ° C.

(Preparation of resin fine particle dispersion 6B)
Resin fine particle dispersion 1B was prepared in the same manner as the resin fine particle dispersion 1B except that 390 parts by mass of styrene, 10 parts by mass of n-butyl acrylate, and 9.5 parts by mass of β-carboxyethyl acrylate were prepared. 6B was obtained. The volume average particle size was 198 nm, and the glass transition temperature was 75.8 ° C.

(Preparation of colorant dispersion 1B)
Phthalocyanine pigment (manufactured by Dainichi Seika Co., Ltd., PVFASTBLUE) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass or more, and homogenizer (manufactured by IKA, After dispersing for 10 minutes using an ultra turrax T50), a colorant dispersion 1B was prepared by applying to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP). The number average particle diameter of the colorant in the colorant dispersion 1B was 150 nm.

(Preparation of terpene-modified novolak resin fine particle dispersion 1B)
PR-12603 (Sumitomo Durez) 50 parts by weight anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by weight ion-exchanged water 200 parts by weight or more, homogenizer (IKA, Ultrata) Terpene-modified novolac resin fine particles containing resin fine particles having a volume average particle size of 0.11 μm after being dispersed at 5500 rpm for 10 minutes using Lux T50) and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) Dispersion 1B was obtained.

(Preparation of terpene-modified novolak resin fine particle dispersion 2B)
PR-12603 (Sumitomo Durez) 50 parts by weight anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by weight ion-exchanged water 200 parts by weight or more, homogenizer (IKA, Ultrata) Terpene-modified novolak resin fine particles containing resin fine particles having a volume average particle diameter of 0.52 μm after being dispersed at 4500 rpm for 10 minutes using Lux T50) and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) Dispersion 2B was obtained.

(Preparation of terpene-modified novolak resin fine particle dispersion 3B)
PR-12603 (Sumitomo Durez) 50 parts by weight anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by weight ion-exchanged water 200 parts by weight or more, homogenizer (IKA, Ultrata) Terpene-modified novolac resin fine particles containing resin fine particles having a volume average particle size of 0.98 μm after being dispersed at 3000 rpm for 10 minutes using Lux T50) and then subjected to a circulating ultrasonic disperser (RUS-600TCVP, manufactured by Nippon Seiki Seisakusho) Dispersion 3B was obtained.

(Preparation of terpene-modified novolak resin fine particle dispersion 4B)
PR-12603 (Sumitomo Durez) 50 parts by weight anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by weight ion-exchanged water 200 parts by weight or more, homogenizer (IKA, Ultrata) Terpene-modified novolak resin fine particles containing resin fine particles having a volume average particle size of 1.3 μm after being dispersed at 1500 rpm for 10 minutes using a Lux T50) and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) Dispersion 4B was obtained.

(Preparation of terpene-modified novolak resin fine particle dispersion 5B)
PR-12603 (Sumitomo Durez) 50 parts by weight anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by weight ion-exchanged water 200 parts by weight or more, homogenizer (IKA, Ultrata) Terpene-modified novolac resin fine particles containing resin fine particles having a volume average particle size of 0.06 μm after being dispersed at 7000 rpm for 10 minutes using Lux T50) and then subjected to a circulating ultrasonic disperser (RUS-600TCVP, manufactured by Nippon Seiki Seisakusho) Dispersion 5B was obtained.

(Preparation of release agent dispersion 1B)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP0190, melting point 85 ° C.) 50 parts by mass Cationic surfactant (manufactured by Kao Corporation, SANISOL B50) 5 parts by mass Ion-exchanged water 200 parts by mass After sufficiently dispersing with a homogenizer (manufactured by IKA, Ultra Turrax T50), it was dispersed with a pressure discharge type homogenizer to obtain a release agent dispersion 1B containing release agent particles having a volume average particle diameter of 200 nm.

(Manufacture of toner 1B)
(Aggregation process)
Ion-exchanged water 500 parts by weight Resin fine particle dispersion 1B 200 parts by weight Colorant dispersion 1B 36 parts by weight Terpene-modified novolak resin fine particle dispersion 2B 80 parts by weight Release agent dispersion 1B 35 parts by weight Inorganic fine particle dispersion 1A 10 parts by weight Flocculant [manufactured by Asada Chemical Co., Ltd., polyaluminum chloride] 0.5 parts by mass The above mixed components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the agglomeration temperature was heated to 25 ° C. while stirring the flask in a heating oil bath and held for 1.5 hours.
(Adhesion process)
25 parts by mass of resin fine particle dispersion 5B was slowly added to the dispersion containing the aggregated particles prepared above, and the temperature of the heating oil bath was raised and maintained at 30 ° C. for 1 hour.
(Fusion process)
Next, after adding a 1 mol / L sodium hydroxide aqueous solution so that the pH becomes 6.0, the stainless steel flask was sealed, and gently heated to 85 ° C. while continuing stirring using a magnetic seal, Thereafter, the mixture was heated to 96 ° C., a 1 mol / L nitric acid aqueous solution was added until pH 5.0, and the mixture was held for 5 hours. Thereafter, the mixture was cooled, filtered, sufficiently washed with ion-exchanged water, and then dried using a vacuum drier to produce toner 1B. The volume average particle diameter was 5.3 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 2B)
Toner 2B was obtained in the same manner as in the production of toner 1B except that resin particle dispersion 2B was used instead of resin particle dispersion 1B and the aggregation temperature was 30 ° C. The volume average particle diameter was 5.4 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 3B)
The resin fine particle dispersion 3B was used in place of the resin fine particle dispersion 1B, the aggregation temperature was 40 ° C., and the heating temperature was 45 ° C. in the attaching step. Otherwise, the toner 3B was obtained in the same manner as in the production of the toner 1B. The volume average particle diameter was 6.3 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 4B)
The resin fine particle dispersion 2B is used in place of the resin fine particle dispersion 1B and is aggregated at 30 ° C., and 25 parts by mass of the resin fine particle dispersion 4B is added instead of the resin fine particle dispersion 5B in the adhesion step, and the heating temperature is 55 ° C. It was. Otherwise, the toner 4B was obtained in the same manner as in the production of the toner 1B. The volume average particle diameter was 6.5 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 5B)
The resin fine particle dispersion 2B is used in place of the resin fine particle dispersion 1B and is aggregated at 30 ° C., and 25 parts by mass of the resin fine particle dispersion 6B is added instead of the resin fine particle dispersion 5B in the attaching step, and the heating temperature is 50 ° C. It was. Otherwise, the toner 5B was obtained in the same manner as in the production of the toner 1B. The volume average particle diameter was 6.3 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 6B)
210 parts by mass of resin fine particle dispersion 2B was used in place of resin fine particle dispersion 1B and agglomerated at 30 ° C., and 15 parts by mass of resin fine particle dispersion 5B was added in the adhering step, and the heating temperature was set to 33 ° C. Otherwise, the toner 6B was obtained in the same manner as in the production of the toner 1B. The volume average particle diameter was 6.0 μm, and the coating layer thickness was 0.12 μm.

(Manufacture of toner 7B)
In place of resin fine particle dispersion 1B, 160 parts by mass of resin fine particle dispersion 2B was aggregated at 30 ° C., and 65 parts by mass of resin fine particle dispersion 5B was added in the adhering step, and the heating temperature was set to 40 ° C. Otherwise, the toner 7B was obtained in the same manner as in the production of the toner 1B. The volume average particle diameter was 5.9 μm, and the coating layer thickness was 0.89 μm.

(Manufacture of toner 8B)
The resin fine particle dispersion 2B is used in place of the resin fine particle dispersion 1B, the aggregation temperature is 30 ° C., and the terpene modified novolak resin fine particle dispersion 1B is used in place of the terpene modified novolak resin fine particle dispersion 2B. The temperature was set to 35 ° C., and otherwise, toner 8B was obtained in the same manner as in the production of toner 1B. The volume average particle diameter was 5.3 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 9B)
The resin fine particle dispersion 2B is used instead of the resin fine particle dispersion 1B, the aggregation temperature is set to 30 ° C., and the terpene modified novolak resin fine particle dispersion 2B is used instead of the terpene modified novolak resin fine particle dispersion 2B. A toner 9B was obtained in the same manner as in the production of the toner 1B except that the temperature was 35 ° C. The volume average particle diameter was 5.5 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 10B)
The toner 10B was obtained in the same manner as in the production of the toner 1B except that the terpene-modified novolak resin fine particle dispersion and the inorganic fine particle dispersion 1A were not added in the aggregation step. The volume average particle diameter was 5.9 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 11B)
A toner 11B was obtained in the same manner as in the production of the toner 1B except that the terpene-modified novolak resin fine particle dispersion 5B was used instead of the terpene-modified novolak resin fine particle dispersion 2B in the aggregation step, and the inorganic fine particle dispersion 1A was not added. . The volume average particle diameter was 5.8 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 12B)
A toner 12B was obtained in the same manner as in the production of the toner 1B, except that the terpene-modified novolak resin fine particle dispersion 4B was used instead of the terpene-modified novolak resin fine particle dispersion 2B in the aggregation step, and the inorganic fine particle dispersion 1A was not added. . The volume average particle diameter was 6.0 μm, and the coating layer thickness was 0.89 μm.

(Manufacture of toner 13B)
The resin fine particle dispersion 4B is used in place of the resin fine particle dispersion 1B and is aggregated at 50 ° C., and 25 parts by mass of the resin fine particle dispersion 6B is added instead of the resin fine particle dispersion 5B in the adhesion step, and the heating temperature is 55 ° C. A toner 13B was obtained in the same manner as in the production of the toner 1B except that the inorganic fine particle dispersion 1A was not added. The volume average particle diameter was 6.3 μm, and the coating layer thickness was 0.4 μm.

(Manufacture of toner 14B)
Toner 14B is manufactured in the same manner as in the production of toner 1B except that 25 parts by mass of resin fine particle dispersion 3B is added instead of resin fine particle dispersion 5B in the attaching step, the heating temperature is 40 ° C., and no inorganic fine particle dispersion 1A is added. Got. The volume average particle diameter was 6.2 μm, and the coating layer thickness was 0.4 μm.

(Preparation of external toner)
0.70 parts by mass of hydrophobic silica (manufactured by Cabot, TS720) was added to 100 parts by mass of each of toners 1B to 14B, and mixed with a sample mill to obtain externally added toners 1B to 14B.

(Image output)
8 parts by mass of externally added toners 1B to 14B and 100 parts by mass of carrier are stirred and mixed in a ball mill for 5 minutes to adjust developers 1B to 14B, and image output for evaluation of fixing performance and the like is performed by the following procedure. went. The carrier used in Reference Example 1A was used as it was. The adjusted developer was set in a developing unit of a color copying machine Doccolor 1250 manufactured by Fuji Xerox Co., Ltd., from which the fixing unit was removed, and an unfixed image was output. The output image was a halftone image having a size of 40 × 40 mm, and the image toner amount was adjusted to 0.20 mg / cm ² . The paper used was a trade name “J Coated Paper” manufactured by Fuji Xerox Office Supply.

(Fixing method)
For fixing, the fixing device taken out from the Doccolor 1250 copier was remodeled so that the roll temperature of the fixing device could be changed, and the fixing roll was replaced with a Teflon (registered trademark) tube. The sheet conveying speed of the fixing device was 160 mm per second. Unfixed images of toners 1B to 14B were fixed by appropriately changing the temperature of the fixing device from 90 ° C. to 180 ° C. to obtain a fixed image.

(Minimum fixing temperature evaluation method)
The minimum fixing temperature of the toners 1B to 14B is set to a temperature at which fixing is started without causing a low temperature offset.

(Document offset evaluation method)
Developers 1B to 14B were evaluated in the same manner as in Reference Example 1A.

(Examples 1B-9B, Comparative Examples 1B-5B)
The performance evaluation for the toners of Examples 1B to 9B and Comparative Examples 1B to 5B are shown in Table 2 together with the glass transition temperatures of the core particles and the coating layer, the volume average particle diameter of the terpene-modified novolak resin fine particles, and the thickness of the coating layer.

For the toners of Examples 1B to 9B, the minimum fixing temperature was 120 ° C. or less, and no document offset occurred.
In Comparative Example 1B, if the desired terpene-modified novolak resin fine particles are not added, low-temperature fixing can be obtained by controlling the glass transition temperature of the desired core-shell structure, but the document offset property is poor.
In Comparative Example 2B, if the particle size of the terpene-modified novolak resin fine particles to be added is small, the low-temperature fixing can be obtained by controlling the glass transition temperature of the desired core-shell structure, but the document offset property is poor.
In Comparative Example 3B, when the particle size of the terpene-modified novolak resin fine particles to be added is large, the document offset property becomes better, but the core portion has a low glass transition temperature component by controlling the glass transition temperature of the desired core-shell structure. Even if it is, it will adversely affect the low-temperature fixing.
In Comparative Examples 4B to 5B, when both the core particles and the glass transition temperature of the coating layer are high, the document offset property is good but the low-temperature fixability is bad. On the contrary, if the glass transition temperature of the core particle and the coating layer is low, even if the desired terpene-modified novolak resin particles of the present invention are contained, the low-temperature fixing property is good but the document offset property cannot be achieved.

(Preparation of resin fine particle dispersion 1C)
Styrene (manufactured by Wako Pure Chemical Industries) 160 parts by mass n-butyl acrylate (manufactured by Wako Pure Chemical Industries) 240 parts by mass β-carboxyethyl acrylate (manufactured by Rhodia Nikka) 9 parts by mass 1, 10 decanediol diacrylate (manufactured by Shin-Nakamura Chemical) 5 parts by mass Dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) 2.7 parts by mass The above is mixed and dissolved, and this is dissolved in 550 parts by mass of ion-exchanged water containing 4 parts by mass of the anionic surfactant Daupax (manufactured by Rhodia). Further, 50 parts by mass of ion-exchanged water in which 6 parts by mass of ammonium persulfate was dissolved was added while being dispersed and emulsified in the flask and slowly stirred and mixed for 10 minutes. Next, after sufficiently replacing the nitrogen in the system, the system was heated in an oil bath while stirring the flask until it reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thus, an anionic resin fine particle dispersion 1C having a volume average particle size of 198 nm, a glass transition temperature of 18.5 ° C., a weight average molecular weight (Mw) of 32300, and an acid value of 12.0 mgKOH / g was obtained.

(Preparation of resin fine particle dispersion 2C)
A resin fine particle dispersion 2C was obtained in the same manner as the resin fine particle dispersion 1C except that 180 parts by mass of styrene and 220 parts by mass of n-butyl acrylate were used in the adjustment of the resin fine particle dispersion 1C. The volume average particle size was 190 nm, the glass transition temperature was 21.3 ° C., the Mw was 31200, and the acid value was 12.4 mgKOH / g.

(Preparation of resin fine particle dispersion 3C)
In the adjustment of the resin fine particle dispersion 1C, a resin fine particle dispersion 3C was obtained in the same manner as the adjustment of the resin fine particle dispersion 1C, except that 200 parts by mass of styrene and 200 parts by mass of n-butyl acrylate were used. The volume average particle size was 196 nm, the glass transition temperature was 30.6 ° C., the Mw was 31000, and the acid value was 12.2 mg KOH / g.

(Preparation of resin fine particle dispersion 4C)
A resin fine particle dispersion 4C was obtained in the same manner as the adjustment of the resin fine particle dispersion 1C except that the resin fine particle dispersion 1C was adjusted to 250 parts by mass of styrene and 150 parts by mass of n-butyl acrylate. The volume average particle size was 200 nm, the glass transition temperature was 38.9 ° C., the Mw was 32000, and the acid value was 11.8 mgKOH / g.

(Preparation of resin fine particle dispersion 5C)
A resin fine particle dispersion 5C was obtained in the same manner as in the preparation of the resin fine particle dispersion 1C except that the adjustment of the resin fine particle dispersion 1C was changed to 270 parts by mass of styrene and 130 parts by mass of n-butyl acrylate. The volume average particle size was 198 nm, the glass transition temperature was 45.2 ° C., the Mw was 31800, and the acid value was 12.4 mgKOH / g.

(Preparation of resin fine particle dispersion 6C)
Resin fine particle dispersion 6C was obtained in the same manner as the adjustment of resin fine particle dispersion 1C except that 280 parts by mass of styrene and 120 parts by mass of n-butyl acrylate were used in the adjustment of resin fine particle dispersion 1C. The volume average particle size was 201 nm, the glass transition temperature was 48.3 ° C., the Mw was 32000, and the acid value was 11.9 mgKOH / g.

(Preparation of resin fine particle dispersion 7C)
A resin fine particle dispersion 7C was obtained in the same manner as the adjustment of the resin fine particle dispersion 1C except that 300 parts by mass of styrene and 100 parts by mass of n-butyl acrylate were used in the adjustment of the resin fine particle dispersion 1C. The volume average particle diameter was 197 nm, the glass transition temperature was 51.0 ° C., the Mw was 33200, and the acid value was 12.5 mgKOH / g.

(Preparation of resin fine particle dispersion 8C)
A resin fine particle dispersion 8C was obtained in the same manner as the adjustment of the resin fine particle dispersion 1C, except that the adjustment of the resin fine particle dispersion 1C was changed to 315 parts by mass of styrene and 75 parts by mass of n-butyl acrylate. The volume average particle size was 201 nm, the glass transition temperature was 54.2 ° C., the Mw was 34100, and the acid value was 12.4 mgKOH / g.

(Preparation of resin fine particle dispersion 9C)
Resin fine particle dispersion 1C was prepared in the same manner as in the fine resin particle dispersion 1C except that 330 parts by mass of styrene, 70 parts by mass of n-butyl acrylate, and 9.5 parts by mass of β-carboxyethyl acrylate were used. 9C was obtained. The volume average particle size was 198 nm, the glass transition temperature was 58.7 ° C., the Mw was 32100, and the acid value was 13.6 mgKOH / g.

(Preparation of resin fine particle dispersion 10C)
A resin fine particle dispersion 10C was obtained in the same manner as the adjustment of the resin fine particle dispersion 1C except that in the adjustment of the resin fine particle dispersion 1C, 360 parts by mass of styrene and 40 parts by mass of n-butyl acrylate were used. The volume average particle size was 202 nm, the glass transition temperature was 62.4 ° C., the Mw was 31300, and the acid value was 12.2 mgKOH / g.

(Preparation of resin fine particle dispersion 11C)
In the adjustment of the resin fine particle dispersion 1C, a resin fine particle dispersion 11C was obtained in the same manner as the adjustment of the resin fine particle dispersion 1C except that 375 parts by mass of styrene and 25 parts by mass of n-butyl acrylate were used. The volume average particle diameter was 199 nm, the glass transition temperature was 68.2 ° C., the Mw was 33600, and the acid value was 12.5 mgKOH / g.

(Preparation of resin fine particle dispersion 12C)
A resin fine particle dispersion 12C was obtained in the same manner as in the preparation of the resin fine particle dispersion 1C except that 390 parts by mass of styrene and 10 parts by mass of n-butyl acrylate were used in the adjustment of the resin fine particle dispersion 1C. The volume average particle diameter was 197 nm, the glass transition temperature was 75.8 ° C., the Mw was 32500, and the acid value was 12.8 mgKOH / g.

(Preparation of resin fine particle dispersion 13C)
A resin fine particle dispersion 13C was obtained in the same manner as the adjustment of the resin fine particle dispersion 1C, except that the resin fine particle dispersion 1C was adjusted to 395 parts by mass of styrene and 5 parts by mass of n-butyl acrylate. The volume average particle size was 193 nm, the glass transition temperature was 80.3 ° C., the Mw was 34500, and the acid value was 12.5 mgKOH / g.

(Preparation of resin fine particle dispersion 14C)
A resin fine particle dispersion 14C was obtained in the same manner as in the preparation of the resin fine particle dispersion 1C except that the resin fine particle dispersion 1C was adjusted to 12 parts by mass of β-carboxyethyl acrylate. The volume average particle diameter was 195 nm, the glass transition temperature was 51.2 ° C., the Mw was 34,000, and the acid value was 16.8 mgKOH / g.

(Preparation of colorant dispersion 1C)
Phthalocyanine pigment (manufactured by Dainichi Seika Co., Ltd., PVFASTBLUE) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass or more, and homogenizer (manufactured by IKA, After dispersing for 10 minutes using an ultra turrax T50), a colorant dispersion 1C was prepared by applying to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP). The number average particle diameter of the colorant in the colorant dispersion 1C was 150 nm, particles having a particle diameter of 0.03 μm or less were 4.0% by number, and particles having a particle diameter of 0.5 μm or more were 0.5% by number.

(Preparation of colorant dispersion 2C)
Carbon black (manufactured by CABOT, R330) 90 parts by weight anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by weight ion-exchanged water 240 parts by weight The above is mixed and the same as colorant dispersion 1C Colorant dispersion 2C was prepared under the conditions. In the colorant dispersion 2C, the number average particle diameter of the colorant was 155 nm, particles having a particle diameter of 0.03 μm or less were 5.0 number%, and particles having a particle diameter of 0.5 μm or more were 0.5 number%.

(Preparation of colorant dispersion 3C)
C. I Pigment Red 122 (manufactured by Dainichi Chemical Co., Ltd., ECR-185) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass A colorant dispersion 3C was prepared under the same conditions as the colorant dispersion 1C. In the colorant dispersion 3C, the number average particle diameter of the colorant was 165 nm, particles having a particle diameter of 0.03 μm or less were 6.0 number%, and particles having a particle diameter of 0.5 μm or more were 0.5 number%.

(Preparation of colorant dispersion 4C)
C. I Pigment Red 185 (manufactured by Clariant) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass or more A colorant dispersion 4C was prepared under the following conditions. The number average particle diameter of the colorant in the colorant dispersion 4C was 170 nm, particles having a particle diameter of 0.03 μm or less were 7% by number, and particles having a particle diameter of 0.5 μm or more were 0.5% by number.

(Preparation of colorant dispersion 5C)
C. I Pigment Yellow 74 (manufactured by Clariant) 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass ion-exchanged water 240 parts by mass or more A colorant dispersion 5C was prepared under the conditions. The number average particle diameter of the colorant in the colorant dispersion 5C was 175 nm, the number of particles having a particle size of 0.03 μm or less was 6% by number, and the number of particles having a particle size of 0.5 μm or more was 0.3% by number.

(Preparation of mold release agent dispersion 1C)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP0190, melting point 85 ° C.) 50 parts by mass Cationic surfactant (manufactured by Kao Corporation, SANISOL B50) 5 parts by mass Ion-exchanged water 200 parts by mass After sufficiently dispersing with a homogenizer (manufactured by IKA, Ultra Turrax T50), it was dispersed with a pressure discharge type homogenizer to obtain a release agent dispersion 1C containing release agent particles having a volume average particle diameter of 200 nm.

(Manufacture of toner 1C)
(Aggregation process)
Ion-exchanged water 500 parts by weight Resin fine particle dispersion 3C 175 parts by weight Colorant dispersion 1C 36 parts by weight Release agent dispersion 1C 35 parts by weight Inorganic fine particle dispersion 1A 10 parts by weight flocculant [manufactured by Asada Chemical Co., polyaluminum chloride 0.5 parts by mass The above mixed components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the agglomeration temperature was heated to 30 ° C. while stirring the flask in a heating oil bath. Thereafter, it was kept at 30 ° C. for 1.5 hours.
(Adhesion process)
25 parts by mass of resin fine particle dispersion 9C is slowly added to the prepared dispersion containing aggregated particles, and the temperature of the heating oil bath is raised and maintained at 56 ° C. for 1 hour. Add part by weight, raise the temperature of the heating oil bath and hold at 60 ° C. for 1 hour, add 25 parts by weight of resin fine particle dispersion 12C, raise the temperature of the heating oil bath and hold at 73 ° C. for 1 hour. .
(Fusion process)
Next, after adding a 1 mol / L sodium hydroxide aqueous solution so that the pH becomes 6.0, the stainless steel flask was sealed, and gently heated to 85 ° C. while continuing stirring using a magnetic seal, Thereafter, the mixture was heated to 96 ° C., a 1 mol / L aqueous nitric acid solution was added until pH 5.0, and the mixture was held for 5 hours. Thereafter, the mixture was cooled, filtered, sufficiently washed with ion-exchanged water, and then dried using a vacuum dryer, thereby producing toner particles 1C having a three-layer coating layer. The volume average particle diameter was 5.2 μm, the total coating layer thickness was 0.61 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 75 ° C.

(Manufacture of toner 2C)
The resin fine particle dispersion 2C was used in place of the resin fine particle dispersion 3C to be agglomerated at 20 ° C., and 25 parts by mass of the resin fine particle dispersion 8C, the resin fine particle dispersion 10C, and the resin fine particle dispersion 12C were added in the attaching step. A toner 2C having a three-layer coating layer is obtained in the same manner as in the production of the toner 1C except that the heating temperature when the resin fine particle dispersion is added in the adhesion step is changed to 52 ° C., 60 ° C., and 72 ° C. in the order of addition. It was. The volume average particle size was 5.5 μm, the total coating layer thickness was 0.68 μm, the glass transition temperature of the core particles was 21 ° C., and the glass transition temperature of the outermost resin layer was 75 ° C.

(Manufacture of toner 3C)
The resin fine particle dispersion 4C was used instead of the resin fine particle dispersion 3C to be aggregated at 36 ° C., and 25 parts by mass of each of the resin fine particle dispersion 9C, the resin fine particle dispersion 11C, and the resin fine particle dispersion 12C were added in the attaching step. A toner 3C having a three-layer coating layer is obtained in the same manner as in the production of the toner 1C except that the heating temperature when the resin fine particle dispersion is added in the attaching step is changed to 56 ° C., 65 ° C., and 72 ° C. in the order of addition. It was. The volume average particle size was 5.6 μm, the total coating layer thickness was 0.64 μm, the glass transition temperature of the core particles was 39 ° C., and the glass transition temperature of the outermost resin layer was 76 ° C.

(Manufacture of toner 4C)
25 mass parts of resin fine particle dispersion 7C, resin fine particle dispersion 8C, and resin fine particle dispersion 10C are added in the adhesion step, and the heating temperature when the resin fine particle dispersion is added is 50 ° C., 52 ° C. in the order of addition. A toner 4C having a three-layer coating layer was obtained in the same manner as in the production of the toner 1C except that the temperature was changed to 60 ° C. The volume average particle diameter was 5.7 μm, the total coating layer thickness was 0.65 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 62 ° C.

(Manufacture of toner 5C)
25 parts by mass of each of the resin fine particle dispersion 11C, the resin fine particle dispersion 12C, and the resin fine particle dispersion 13C are added in the attaching step, and the heating temperature when the resin fine particle dispersion is added is 65 ° C., 72 ° C. in order of addition. A toner 5C having a three-layer coating layer was obtained in the same manner as in the production of the toner 1C except that the temperature was changed to 78 ° C. The volume average particle size was 5.0 μm, the total coating layer thickness was 0.63 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 80 ° C.

(Manufacture of toner 6C)
Using 200 parts by mass of resin fine particle dispersion 3C, 25 parts by mass of resin fine particle dispersion 8C and resin fine particle dispersion 10C were added in the adhering step, and the heating temperature when adding the resin fine particle dispersion was 52 in the order of addition. A toner 6C having a coating layer consisting of two layers was obtained in the same manner as in the production of the toner 1C except that the temperature was changed to ° C and 65 ° C. The volume average particle size was 5.4 μm, the total coating layer thickness was 0.41 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 62 ° C.

(Manufacture of toner 7C)
Using 150 parts by mass of resin fine particle dispersion 3C, 25 parts by mass of resin fine particle dispersion 7C, resin fine particle dispersion 9C, resin fine particle dispersion 10C, and resin fine particle dispersion 12C were added in the adhering step. A toner 7C having a coating layer consisting of four layers was obtained in the same manner as in the production of the toner 1C except that the heating temperature at the time of adding was changed to 50 ° C., 56 ° C., 60 ° C., and 72 ° C. in the order of addition. The volume average particle size was 5.5 μm, the total coating layer thickness was 0.84 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 76 ° C.

(Manufacture of toner 8C)
200 parts by mass of resin fine particle dispersion 1C is used instead of resin fine particle dispersion 3C, and 25 parts by mass of resin fine particle dispersion 7C and resin fine particle dispersion 9C are added in the adhering step without adding inorganic fine particle dispersion 1A. did. A toner 8C having a coating layer consisting of two layers was obtained in the same manner as in the production of the toner 1C except that the heating temperature when the resin fine particle dispersion was added in the adhesion step was changed to 50 ° C. and 56 ° C. in the order of addition. The volume average particle size was 5.8 μm, the total coating layer thickness was 0.48 μm, the glass transition temperature of the core particles was 18 ° C., and the glass transition temperature of the outermost resin layer was 59 ° C.

(Manufacture of toner 9C)
200 parts by mass of resin fine particle dispersion 5C is used instead of resin fine particle dispersion 3C, and 25 parts by mass of resin fine particle dispersion 8C and resin fine particle dispersion 10C are added in the adhering step without adding inorganic fine particle dispersion 1A. did. A toner 9C having a two-layer coating layer was obtained in the same manner as in the production of the toner 1C except that the heating temperature when the resin fine particle dispersion was added in the attaching step was changed to 52 ° C. and 60 ° C. in the order of addition. The volume average particle size was 5.6 μm, the total coating layer thickness was 0.43 μm, the glass transition temperature of the core particles was 45 ° C., and the glass transition temperature of the outermost resin layer was 62 ° C.

(Manufacture of toner 10C)
Without adding the inorganic fine particle dispersion 1A, 25 parts by mass of the resin fine particle dispersion 6C and the resin fine particle dispersion 8C were added in the adhering step, and the heating temperature when the resin fine particle dispersion was added was 45 ° C. in the order of addition, A toner 10C having a two-layer coating layer was obtained in the same manner as in the production of the toner 1C except that the temperature was changed to 52 ° C. The volume average particle size was 5.4 μm, the total coating layer thickness was 0.45 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 54 ° C.

(Manufacture of toner 11C)
200 parts by mass of the resin fine particle dispersion 3C was used, and 50 parts by mass of the resin fine particle dispersion 9C was added in the adhering step without adding the inorganic fine particle dispersion 1A. A toner 11C having a single coating layer was obtained in the same manner as in the production of the toner 1C, except that the heating temperature when the resin fine particle dispersion was added in the adhesion step was changed to 56 ° C. The volume average particle size was 5.7 μm, the coating layer thickness was 0.42 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 59 ° C.

(Manufacture of toner 12C)
The resin fine particle dispersion 4C is used in place of the resin fine particle dispersion 3C, the inorganic fine particle dispersion 1A is not added, and aggregated at 35 ° C., and the resin fine particle dispersion 8C, the resin fine particle dispersion 9C, and the resin fine particle dispersion are adhered in the attaching step 25 parts by mass of each 10C of liquid 10C was added. A toner 13C having a three-layer coating layer is obtained in the same manner as in the production of the toner 1C except that the heating temperature when the resin fine particle dispersion is added in the adhesion step is changed to 52 ° C., 56 ° C., and 60 ° C. in the order of addition. It was. The volume average particle size was 5.4 μm, the total coating layer thickness was 0.63 μm, the glass transition temperature of the core particles was 39 ° C., and the glass transition temperature of the outermost resin layer was 62 ° C.

(Manufacture of toner 13C)
Without adding the inorganic fine particle dispersion 1A, 25 parts by mass of the resin fine particle dispersion 14C, the resin fine particle dispersion 10C, and the resin fine particle dispersion 12C were added in the attaching step. A toner 14C having a three-layer coating layer is obtained in the same manner as in the production of the toner 1C except that the heating temperature when the resin fine particle dispersion is added in the adhesion step is changed to 50 ° C., 60 ° C., and 72 ° C. in the order of addition. It was. The volume average particle size was 5.5 μm, the total coating layer thickness was 0.68 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 76 ° C.

(Manufacture of toner 14C)
Three layers as in the production of the toner 1C except that 220 parts by mass of the resin fine particle dispersion 3C is used, the inorganic fine particle dispersion 1A is not added, and each resin fine particle dispersion is changed to 10 parts by mass in the attaching step. Toner 15C having a coating layer made of The volume average particle size was 5.7 μm, the total coating layer thickness was 0.28 μm, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 75 ° C.

(Manufacture of toner 15C)
Three layers as in the production of the toner 1C, except that 100 parts by mass of the resin fine particle dispersion 3C is used, the inorganic fine particle dispersion 1A is not added, and each resin fine particle dispersion is changed to 50 parts by mass in the attaching step. Toner 16C having a coating layer made of The volume average particle size was 5.8 μm, the total coating layer thickness was 1.06 m, the glass transition temperature of the core particles was 31 ° C., and the glass transition temperature of the outermost resin layer was 75 ° C.

(Preparation of external toner)
0.70 parts by mass of hydrophobic silica (manufactured by Cabot, TS720) was added to 100 parts by mass of each of toners 1C to 15C, and mixed with a sample mill to obtain externally added toners 1C to 15C.

(Image output)
8 parts by mass of externally added toners 1C to 15C and 100 parts by mass of carrier are stirred and mixed for 5 minutes by a ball mill to adjust developers 1C to 15C, and image output for evaluation of fixing performance and the like is performed by the following procedure. went. The carrier was a resin-coated carrier, and a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by mass of methacrylate (manufactured by Soken Chemical Co., Ltd.) was used. The adjusted developer was set in a developing unit of a color copying machine Doccolor 1250 manufactured by Fuji Xerox Co., Ltd., from which the fixing unit was removed, and an unfixed image was output. The output image was a solid image having a size of 40 × 40 mm, and the amount of image toner was adjusted to 0.50 mg / cm ² . As the paper, the product name “J paper” manufactured by Fuji Xerox Office Supply Co., Ltd. was used.

(Fixing method)
For fixing, the fixing device taken out from the Doccolor 1250 copier was remodeled so that the roll temperature of the fixing device could be changed, and the fixing roll was replaced with a Teflon (registered trademark) tube. The sheet conveying speed of the fixing device was 160 mm per second. Unfixed images of toners 1C to 15C were fixed by appropriately changing the temperature of the fixing device from 90 ° C. to 180 ° C. to obtain a fixed image.

(Minimum fixing temperature evaluation method)
The minimum fixing temperature of toners 1C to 15C was set to a temperature at which fixing is started without causing a low temperature offset. The evaluation criteria were ◯ for those that did not cause a low temperature offset even at a fixing temperature of 110 ° C., Δ at a minimum fixing temperature of 120 ° C. or lower, and × when higher than 120 ° C.

(Document offset evaluation method)
Developers 1C to 15C were evaluated in the same manner as in Reference Example 1A.

( Reference Examples 1C-7C, Comparative Examples 1C-8C)
The performance evaluation of the toners of Reference Examples 1C to 7C and Comparative Examples 1C to 8C is shown in Table 3 together with the total coating layer thickness and the volume average particle diameter of the toner.

For the toners of Reference Examples 1C to 7C, the minimum fixing temperature was 110 ° C. or lower, and no document offset occurred.
In Comparative Examples 1C to 3C, when the glass transition temperature of the core particle or the coating layer was too low, the low temperature fixability was obtained but the document offset occurred. If the glass transition temperature of the core resin is too high, document offset does not occur but low temperature fixability cannot be achieved. Since Comparative Example 4C does not have a multilayer structure, the compatibility between the resins is not uniform, and the core resin having a low glass transition temperature is likely to appear on the toner surface. As a result, significant image degradation was observed partially. The minimum fixing temperature was 115 ° C. In Comparative Example 5C, since the glass transition temperature difference between the core particles and the coating layer is not sufficient, it is difficult to achieve both low-temperature fixing and document offset resistance. The minimum fixing temperature was 120 ° C. and slight image deterioration was observed. In Comparative Example 6C, since the difference in acid value between the resin layers was large, the electrical repulsion between the resins was large, and the core particles and the coating layer were not uniformly mixed, resulting in slight image deterioration. The minimum fixing temperature was 115 ° C. In Comparative Example 7C, the coating layer was not sufficiently thick, and the binder resin in the core particles having a low glass transition temperature appeared on the surface, resulting in document offset. In Comparative Example 8C, the coating resin in the core particles having a low glass transition temperature did not function because the coating layer was too thick, and the low-temperature fixability could not be obtained.

Claims (4)

Binder resin, colorant, inorganic fine particles having a volume average particle size of 0.1 to 0.5 μm and specific gravity of 1.0 to 2.0, and terpene modification having a volume average particle size of 0.1 to 1.0 μm A toner for developing an electrostatic charge image, wherein the surface of core particles having a glass transition temperature of 20 to 40 ° C. containing novolac resin fine particles is coated with a coating layer having a glass transition temperature of 50 to 100 ° C. Binder resin, colorant, inorganic fine particles having a volume average particle size of 0.1 to 0.5 μm and specific gravity of 1.0 to 2.0, and terpene modification having a volume average particle size of 0.1 to 1.0 μm A method for producing a toner for developing an electrostatic charge image, comprising coating the surfaces of core particles having a glass transition temperature of 20 to 40 ° C. containing novolac resin fine particles with a coating layer having a glass transition temperature of 50 to 100 ° C. ,
Binder resin fine particle dispersion in which binder resin fine particles having a volume average particle size of 1.0 μm or less are dispersed, a colorant dispersion , a volume average particle size of 0.1 to 0.5 μm and a specific gravity of 1.0 to 2 Aggregate particles are formed by mixing an inorganic fine particle dispersion in which inorganic fine particles of 0.0 are dispersed and a terpene-modified novolac resin fine particle dispersion in which a terpene-modified novolak resin fine particle having a volume average particle size of 0.1 to 1.0 μm is dispersed. An electrostatic charge image developing toner having at least a coagulation step, an adhesion step of attaching coated resin fine particles to the surface of the aggregated particles, and a fusion step of heating and coalescing the aggregated particles to which the coated resin fine particles adhere Production method. Binder resin, colorant, inorganic fine particles having a volume average particle size of 0.1 to 0.5 μm and specific gravity of 1.0 to 2.0, and terpene modification having a volume average particle size of 0.1 to 1.0 μm An electrostatic charge containing at least an electrostatic charge image developing toner obtained by coating the surface of core particles having a glass transition temperature of 20 to 40 ° C. containing novolac resin fine particles with a coating layer having a glass transition temperature of 50 to 100 ° C. Image developer. A latent image forming step for forming an electrostatic charge image on the surface of the latent image holding member, and a toner image obtained by developing the electrostatic charge image formed on the surface of the latent image holding member using a developer carried on the developer carrying member. A developing step for forming the toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step for thermally fixing the toner image transferred to the surface of the transfer target; An image forming method having at least
The developer is a binder resin, a colorant, an inorganic fine particle having a volume average particle size of 0.1 to 0.5 μm and a specific gravity of 1.0 to 2.0, and a volume average particle size of 0.1 to 1. A toner for developing an electrostatic charge image obtained by coating the surface of a core particle having a glass transition temperature of 20 to 40 ° C. containing 0.0 μm terpene-modified novolak resin fine particles with a coating layer having a glass transition temperature of 50 to 100 ° C. An image forming method containing at least.