JP2005249848A - Release agent for manufacture of toner, colorant for manufacture of toner, and electrostatic charge image developing toner obtained by using them and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge developing toner excellent in fixing property, release property, charging property, color developing property, color reproducibility, and transparency for an OHP sheet. <P>SOLUTION: The electrostatic charge image developing toner is manufactured by using: a release agent for the manufacture of toner, the release agent containing a core release agent and a coating resin covering the core release agent; and/or a colorant for the manufacture of toner, the colorant containing a core colorant and a coating resin covering the core colorant, wherein the acid value of the coating resin is in the range of 3.0 to 6.0 meq/mg-KOH, and the coating resin contains a SO<SB>3</SB><SP>-</SP>group and a COO<SP>-</SP>group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner producing release agent and a toner producing colorant used for producing a toner used in electrophotography, an electrostatic charge developing toner using the same, and a method for producing the same.

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

  As the developer used here, a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a nonmagnetic toner alone are known. The toner used in these developers is usually produced by a kneading and pulverizing method in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent and a wax, cooled, and then finely pulverized and classified. Further, if necessary, inorganic and organic fine particles may be added to the toner particle surface to improve fluidity and cleaning properties. Although these methods can produce very good toners, they have several problems as described below.

  In the ordinary kneading and pulverizing method, the toner shape and the surface structure of the toner are indeterminate, and although it varies slightly depending on the pulverization properties of the materials used and the conditions of the pulverization process, it is difficult to control the intentional toner shape and surface structure. . In the kneading and pulverizing method, the range of material selection is limited. Specifically, the resin colorant dispersion must be sufficiently brittle and capable of being finely pulverized by an economically possible production apparatus.

  However, if the resin colorant dispersion is made brittle to satisfy these requirements, finer powder may be generated or the toner shape may be changed due to mechanical shearing force applied in the developing machine. Due to these effects, in the two-component developer, the charging deterioration of the developer due to adhesion of fine powder to the carrier surface is accelerated, and in the one-component developer, toner scattering occurs due to the expansion of the particle size distribution. Deterioration in developability due to changes in image quality tends to cause image quality degradation. In addition, when a toner is formed by adding a large amount of a release agent such as wax, the exposure of the release agent to the toner surface is often remarkable due to the combination with a thermoplastic resin.

  In particular, in a toner prepared by combining a resin having increased elasticity due to a high molecular weight component and slightly pulverized, and a brittle wax such as polyethylene or polypropylene, exposure of these wax components is often observed on the surface thereof. This is advantageous for releasability at the time of fixing and cleaning of untransferred toner from the photoreceptor, but because the wax component present on the toner surface layer is easily transferred by mechanical force, the developing roll, photoreceptor, carrier Contamination is likely to occur, leading to a decrease in reliability.

  Furthermore, since the shape of the toner is irregular, there may be cases where sufficient fluidity cannot be obtained even if a flow aid is added to the toner. In this case, since mechanical shearing force is applied to the toner during image formation, the fluidity is decreased over time due to the movement of fine particles externally added to the toner surface to the toner concave portion, and the flow aid is introduced into the toner. Since the embedding occurs, developability, transfer property, and cleaning property are deteriorated. Further, when the toner collected by cleaning is returned to the developing machine and used again, the image quality is likely to further deteriorate. If the flow aid is further increased to prevent the occurrence of these problems, black spots are generated on the photoreceptor and the flow aid particles are scattered.

  On the other hand, in recent years, a toner production method using an emulsion polymerization aggregation method has been proposed as means for intentionally enabling control of the toner shape and surface structure (see, for example, Patent Documents 1 and 2). In general, a resin dispersion prepared by emulsion polymerization or a colorant dispersion in which a colorant is dispersed in a solvent is prepared, and then mixed to form an aggregate corresponding to the toner particle size. In this method, toner is obtained by fusing and coalescing the aggregates.

  By this method, the shape of the toner can be controlled to some extent, and the chargeability and durability of the toner can be improved. However, since the internal structure of the toner is almost uniform, there are problems in the oilless peelability of the fixing sheet at the time of fixing, the transparency when the OHP sheet is output, the environment-dependent stability of charging, and the like.

  In order to stabilize the peeling, it is necessary to make it easy to elute a release agent component such as wax during fixing. Ensuring such elution is conventionally achieved by lowering the melting point of the release agent component, narrowing the molecular weight distribution, or reducing the molecular weight. However, although the elution property can be improved to some extent by the above-described method, the ratio of the release agent component and the binder resin component is inevitably increased as the ratio of the low molecular weight component of the release agent increases. In some cases, it melts and deteriorates the spinnability at the time of melting of the toner itself, and the hot offset property in a high temperature range may deteriorate.

  On the other hand, a mold release agent synthesized using a metallocene catalyst has been proposed as a method for increasing the melting point of the mold release agent and lowering the viscosity (see Patent Document 3). Since the viscosity of the acid anhydride itself generally used as a copolymer is relatively high, this release agent is certainly preferable for a high pressure and low speed fixing system such as two-roll fixing. However, when the above release agent is used on the premise of an energy saving type fixing system (see, for example, Patent Document 4), the required amount of the release agent cannot be eluted from the toner at the time of fixing. As a result, a fixed image with good quality cannot be obtained.

  Furthermore, in order to improve the transparency of the OHP image, application of an ester release agent having low crystallinity has been proposed (see Patent Document 5). However, in this case, since compatibility between the release agent and the binder resin component of the toner occurs, it is necessary to prevent the compatibility by introducing a crosslinked structure into the binder resin. Such suppression of the plasticity of the binder resin can surely improve the transparency problem of the OHP image caused by the release agent to some extent. However, since the melt fluidity of the toner itself at the time of toner fixing is lowered, it is difficult to form an image having high glossiness.

  As described above, in the electrophotographic process, in order to stably maintain the performance of the toner even under various mechanical stresses, it is necessary to suppress the exposure of the release agent to the surface or to prevent the fixing property from being impaired. It is necessary to increase the hardness, improve the mechanical strength of the toner itself, and achieve both sufficient charging and fixing properties.

  In recent years, there has been an increasing demand for higher image quality, and particularly in the formation of color images, the toner particle size has been remarkably reduced in order to realize high-definition images. However, in the conventional simple particle size reduction while maintaining the particle size distribution, the presence of the fine powder side toner in the particle size distribution causes significant problems of carrier and photoconductor contamination and toner scattering, resulting in high image quality and high reliability. It is difficult to realize at the same time. For this purpose, it is necessary that the particle size distribution can be sharpened and the particle size can be reduced.

  In recent years, in digital full-color copiers and printers, a color image original is color-separated with B (blue), R (red), and G (green) filters, and then has a dot diameter 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 using the subtractive color mixing action. Therefore, it is necessary to transfer a larger amount of developer than conventional black-and-white machines, and since it is necessary to cope with a small dot diameter, uniform chargeability, durability, toner strength, and sharpness of particle size distribution are increasing. It is becoming important.

  In view of speeding up and energy saving of these machines, further low-temperature fixability of toner is required. In view of these points, wet-process toners such as agglomerated toner, which is sharp in particle size distribution and suitable for the production of small particle diameters, suspension polymerization toner, suspension granulation toner, and dissolved suspension emulsion aggregation toner are excellent. It has the characteristics.

On the other hand, with respect to the toner mounted on the full-color machine, it is necessary to mix a large amount of toner sufficiently, and improvement of color reproducibility and OHP transparency at this time are essential.
In order to obtain excellent color reproducibility and OHP transparency, the colorant contained in the toner particles needs to be uniformly dispersed in the binder resin without forming secondary aggregates. . However, it is known that the dispersibility of the colorant added to the toner is inferior in the wet process toner as compared with the kneading and pulverizing toner. In the suspension polymerization method, polymerization is performed after a pigment, which is a colorant, is dispersed in a monomer. However, as the polymerization proceeds, the viscosity of the monomer droplets increases and the colorant aggregates. In the aggregation / fusion coalescence method, the influence of pH and the like in the aggregation process causes aggregation of the colorant.
As described above, the wet-process toner has a problem that the dispersibility is deteriorated because the aggregation of the colorant is likely to occur in the production process. Therefore, a technical improvement for improving the dispersibility of the colorant is also studied. However, the problem of aggregation of the colorant has not been sufficiently solved.

  In general, a release wax component is internally added with a polyolefin wax for the purpose of preventing a low temperature offset during fixing. At the same time, a small amount of silicone oil is uniformly applied to the fixing roller to improve the high temperature offset property. For this reason, silicone oil adheres to the output transfer material that is output, and there is an unpleasant feeling of stickiness when handling this, which is not preferable.

Therefore, an oilless fixing toner in which a large amount of a release agent component is included in the toner has been proposed (for example, Patent Document 6). However, in this case, the releasability can be improved to some extent by adding a large amount of the release agent, but the compatibility between the binder resin component and the release agent occurs, and the release agent from the toner is stable. Since exudation is not uniform, it is difficult to obtain stability of peeling. Furthermore, since the means for controlling the cohesive strength of the binder resin of the toner depends on the weight average molecular weight Mw of the binder resin and the glass transition temperature Tg, the spinnability and cohesiveness during toner fixing are directly controlled. It is difficult to do. Furthermore, the free component of the release agent may cause charging inhibition.
Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 Japanese Patent Laid-Open No. 08-248671 JP 2001-75392 A JP-A-6-337541 JP-A-5-61239

An object of the present invention is to solve the above problems. That is, the first object of the present invention is to provide a release agent for producing a toner excellent in dispersibility in a toner necessary for obtaining good fixability, releasability and chargeability, and using the same. It is an object of the present invention to provide an electrostatic charge developing toner and a method for producing the same.
In addition, the second object of the present invention is to provide a colorant for producing a toner having excellent color developability, color reproducibility, dispersibility in a toner necessary for obtaining transparency of an OHP sheet, and It is an object of the present invention to provide an electrostatic charge developing toner using the toner and a method for producing the same.

The above-mentioned subject is achieved by the following present invention. That is, the present invention
<1>
In a mold release agent for toner production comprising a core mold release agent and a coating resin for coating the core mold release agent,
A release agent for toner production, which comprises a group ^- the acid value of the coating resin is in the range of 3.0~6.0meq / mg-KOH, the coating resin is SO ₃ ^- group and COO is there.

<2>
The release agent for toner production according to <1>, wherein the glass transition temperature of the coating resin is in the range of 50 to 80 ° C.

<3>
The release agent for toner production according to <1> or <2>, wherein the coating resin has a polystyrene-equivalent molecular weight in the range of 3000 to 50000.

<4>
The mold release for toner production according to any one of <1> to <3>, wherein a weight ratio of the core release agent to the coating resin is in a range of 100: 10 to 100: 120. It is an agent.

<5>
The core mold release agent is polyalkylene, the endothermic maximum value obtained from the differential thermal analysis of the polyalkylene is in the range of 85 to 95 ° C., and the endothermic peak area obtained by the differential thermal analysis is <1> characterized in that the ratio of the endothermic amount based (the endothermic amount of 85 ° C. or less based on the endothermic peak area / the total endothermic amount based on the endothermic peak area) is in the range of 5 to 15%. -The release agent for toner production according to any one of <4>.

<6>
The viscosity ηs140 of the core release agent at 140 ° C. measured with an E-type viscometer equipped with a cone plate with a cone angle of 1.34 ° is in the range of 1.5 to 5.0 mPa · s. The release agent for toner production according to any one of <1> to <5>.

<7>
In a colorant for toner production comprising a core colorant and a coating resin for coating the core colorant,
When the acid value of the coating resin is in the range of 3.0~6.0meq / mg-KOH, the coating resin is SO ₃ ^- is a toner producing colorant which comprises a group ^- group and COO .

<8>
<7> The colorant for toner production according to <7>, wherein the glass transition temperature of the coating resin is in the range of 50 to 80 ° C.

<9>
<7> or <8>, wherein the coating resin has a polystyrene-reduced molecular weight in the range of 3000 to 50000.

<10>
<7> to <9> The colorant for producing a toner according to any one of <7> to <9>, wherein a weight ratio of the core colorant to the coating resin is in a range of 100: 10 to 100: 120. It is.

<11>
In the electrostatic charge developing toner produced using at least a binder resin, a release agent, and a colorant,
The toner for electrostatic charge development, wherein the release agent is a release agent for toner production according to any one of <1> to <6>.

<12>
In the electrostatic charge developing toner produced using at least a binder resin, a release agent, and a colorant,
An electrostatic charge developing toner, wherein the colorant is a release agent for producing a toner according to any one of <7> to <10>.

<13>
The binder resin, a release agent for toner production according to any one of <1> to <6>, and a colorant for toner production according to any one of <7> to <10>. The electrostatic charge developing toner according to <11> or <12>, wherein the toner is produced using at least.

<14>
<11> to <13>, wherein the exposure rate of the core release agent on the surface of the electrostatic charge developing toner obtained by X-ray photoelectron spectroscopy (XPS) is in the range of 11 to 40% atm. The electrostatic charge developing toner according to any one of the above.

<15>
The electrostatic charge developing toner according to any one of <11> to <14>, wherein a shape factor (SF1) is in a range of 110 to 140.

<16>
The electrostatic charge developing toner according to any one of <11> to <15>, wherein a volume average particle size distribution index (GSDv) is 1.3 or less.

<17>
The maximum value of the endotherm determined by differential thermal analysis is in the range of 70 to 120 ° C., and the content of the core release agent determined based on the maximum intensity of the endothermic peak determined by differential thermal analysis is 6-9. The toner for developing an electrostatic charge according to any one of <11> to <16>, wherein the toner is in a range of% by weight.

<18>
In a mixed solution in which a (first) resin fine particle dispersion in which a (first) resin fine particle having a volume average particle size of 1 μm or less is dispersed, a release agent dispersion, and a colorant dispersion is mixed at least. An aggregating step of adding an aggregating agent to form an agglomerate (core agglomerate); a fusing step of fusing and coalescing the agglomerates by heating to a temperature higher than the glass transition temperature of the resin fine particles contained therein; In the method for producing a toner for electrostatic charge development according to any one of <11> to <17>, which is produced through at least
The release agent dispersion liquid contains the release agent for toner production according to any one of <1> to <6>, and / or the colorant dispersion liquid is <7> to <10. A toner for producing electrostatic charge, comprising the colorant for producing toner according to any one of the above.

<19>
An adhesion step is included between the aggregation step and the fusion step,
In the attaching step, a second resin fine particle dispersion in which second resin fine particles are dispersed is added to the mixed solution after the core aggregate is formed, whereby the second aggregate is added to the core aggregate. Forming a core / shell aggregate to which resin fine particles are adhered,
In the fusion step, the core / shell aggregate is heated to a glass transition temperature higher than the glass transition temperature of the first resin fine particles contained therein or the glass transition temperature of the second resin fine particles contained therein. The method for producing a toner for developing electrostatic charge as described in <18>, wherein the toner is a step of fusing and uniting.

<20>
The flocculant is a metal salt polymer, the metal salt polymer is a tetravalent aluminum salt polymer or a mixture of a tetravalent aluminum polymer and trivalent aluminum, and the aggregation step The method for producing a toner for developing an electrostatic charge according to <18> or <19>, wherein the concentration of the mixture contained in the mixed solution is in the range of 0.11 to 0.25% by weight. It is.

<21>
The resin fine particle dispersion used in the aggregating step is added with at least an anionic surfactant in a solution in which a binder resin is dissolved in an organic solvent, and then emulsified by applying mechanical shearing force. <18> to <, wherein the step is performed through steps of obtaining an emulsified resin dispersion and adding a mechanical shearing force after adding an anionic surfactant to the emulsified resin dispersion. 20>. The method for producing a toner for developing an electrostatic charge according to any one of 20>.

<22>
At least a (first) polymerizable monomer, a polymerization initiator, a colorant, and a release agent are mixed to prepare a raw material solution, and an inorganic or organic dispersant is added to the raw material solution. After the addition, at least a suspension step in which a mechanical shearing force is applied to suspend the suspension to prepare a suspension solution, and a polymerization step in which polymerization is performed by heating while adding stirring and shearing to the suspension solution. In the method for producing a toner for electrostatic charge development according to any one of <11> to <17>,
The release agent is the release agent for toner production according to any one of <1> to <6>, and / or the colorant is any of <7> to <10>. A method for producing a toner for developing electrostatic charge, which is a release agent for producing a toner according to any one of the above.

<23>
The raw material solution was obtained by polymerizing the second polymerizable monomer so that the weight average molecular weight Mw measured by gel permeation chromatography (GPC) of the polymer was in the range of 3000 to 15000. <22> characterized by being prepared by mixing at least a prepolymer, the first polymerizable monomer, the polymerization initiator, the colorant, and the release agent. It is a manufacturing method of the toner for electrostatic charge development of description.

As described above, according to the present invention, according to the first aspect of the present invention, the toner is excellent in dispersibility in the toner necessary for obtaining good fixability, peelability and chargeability. A release agent, an electrostatic charge developing toner using the same, and a method for producing the same can be provided.
In addition, according to the second aspect of the present invention, a colorant for producing a toner having excellent color developability, color reproducibility, and dispersibility in the toner necessary for obtaining transparency of the OHP sheet, and And a method for producing the same.

In the following, the present invention is broadly described in terms of a release agent for toner production, a colorant for toner production, a toner for electrostatic charge development, and a method for producing a toner for electrostatic charge development.
In the following description of the present invention, for convenience of explanation, a release agent whose surface is partially or entirely coated with a coating resin is referred to as a “precoat release agent”, and the coating resin of this precoat release agent The net release agent part (including the release agent in the raw material state that can be the core release agent in the production of the precoat release agent) is called “core release agent” and is completely covered with the coating resin. A mold release agent that does not exist is referred to as a “non-coated mold release agent”.
In addition, when described as “release agent”, unless otherwise specifically limited, a broadly defined release agent that basically includes a non-coat release agent, a precoat release agent, and / or a core release agent. Means.

Similarly, a colorant whose surface is partially or entirely coated with a coating resin is referred to as a “precoat colorant”, and the net colorant part excluding the coating resin of this precoat colorant (the core in the production of the precoat colorant). (Including a colorant in a raw material state that can be a colorant) is referred to as a “core colorant”, and a colorant that is not coated with a coating resin is referred to as a “non-coat colorant”.
In addition, the term “colorant” means a broadly defined colorant that basically includes a non-coat release agent, a precoat colorant, and / or a core colorant, unless otherwise specified. And
In addition, the term “core agent” may be used when referring to a core release agent and / or a core colorant.

(Release agent for toner production and colorant for toner production)
The release agent for toner production of the present invention may be abbreviated as a release agent for toner production (hereinafter referred to as “precoat release agent”) including a core release agent and a coating resin that coats the core release agent. ), The acid value of the coating resin is in the range of 3.0 to 6.0 meq / mg-KOH, and the coating resin contains SO ₃ ^— groups and COO 2 ^— groups.
Therefore, when a toner is produced using the toner production release agent of the present invention, the dispersibility of the core release agent in the toner can be improved. For this reason, the toner produced using the release agent for producing the toner of the present invention can improve the fixability, the peelability and the chargeability more than the toner produced using the conventional release agent. .

Further, the colorant for toner production of the present invention is a colorant for toner production comprising a core colorant and a coating resin that coats the core colorant (hereinafter sometimes abbreviated as “precoat colorant”). When the acid value of the coating resin is in the range of 3.0~6.0meq / mg-KOH, the coating resin is SO ₃ ^-, characterized in that it comprises a group ^- group and COO.
Therefore, when a toner is produced using the colorant for toner production of the present invention, the dispersibility of the core colorant in the toner can be improved. For this reason, the toner produced using the release agent for producing the toner of the present invention can improve the fixability, the peelability and the chargeability more than the toner produced using the conventional release agent. .

  When the toner is produced using the release agent for toner production of the present invention or the colorant for toner production of the present invention, the dispersibility of the core agent in the toner is improved as described above. The cause is due to the action of the coating resin that coats each core agent. The coating resin for coating the core agent will be described in detail below.

-Coating resin-
In order to improve the dispersibility of the core agent in the toner, the coating resin for coating the core agent is as described above. [1] The acid value of the coating resin is within the range of 3.0 to 6.0 meq / mg-KOH. It must be at, and, (2) the coating resin is SO ₃ ^- it is necessary to contain both the group ^- group and COO.

When the acid value of the coating resin is less than 3.0 meq / mg-KOH, when the toner is produced, the dispersibility of the core agent is lowered, and as a result, good fixability and color developability cannot be obtained. . Further, if it exceeds 6.0 meq / mg-KOH, the hydrophilicity of the coating resin becomes too large, and when the toner is prepared using an aqueous solvent, the coating resin that coats the core agent dissolves. As a result, the dispersibility of the core agent decreases. Also, while the pre-coat release agent and pre-coat colorant once produced are stored before they are used for toner production, the coating resin absorbs moisture and dissolves, resulting in quality deterioration and variation. I will.
In addition, the more preferable range of the acid value of the coating resin is 3.3 to 5.8 meq / mg-KOH, and the more preferable range is 3.5 to 5.5 meq / mg-KOH.

On the other hand, the coating resin needs to contain SO ₃ ⁻ groups in addition to COO ⁻ groups. The SO3 ⁻ group has high polarity and high dispersibility, and when the SO ₃ ⁻ group is present in the coating resin, the dispersibility of the precoat release agent and precoat colorant in the toner is improved.
The acid value resulting from the SO ₃ ⁻ group in the coating resin is preferably in the range of 0.05 to 0.35 meq / mg-KOH, and in the range of 0.1 to 0.3 meq / mg-KOH. Is more preferable.
When the acid value resulting from the SO ₃ ^- group exceeds 0.35 meq / mg-KOH, the hydrophilicity is partially increased and a part of the coating resin is dissolved, resulting in a decrease in the dispersibility of the core agent. There is. Further, when the acid value attributable to the SO ₃ ^- group is less than 0.05 meq / mg-KOH, the dispersibility of the precoat release agent and the precoat colorant in the toner becomes insufficient, and the toner is fixed on the OHP sheet. There is a case in which the transparency of the obtained image is impaired.

  In addition, it calculates | requires by the acid value of coating resin, or neutralization titration of KOH. Specifically, methyl orange or the like as an indicator is added in advance to a solution in which the coating resin is dissolved in a solvent, and the KOH titration amount when titrated with a 1 mol KOH aqueous solution is obtained. Next, by dividing the KOH titration amount by the molecular weight 56 of KOH, the acid value of the coating resin can be obtained.

On the other hand, the acid value of the SO ₃ ⁻ group contained in the coating resin can be easily obtained by measuring the amount of S element in the coating resin by elemental analysis of the coating resin and converting it to the amount of SO ₃ ⁻ . The equivalent of the COO ⁻ group in the acid value of the coating resin can be obtained by subtracting the acid value attributable to the SO ₃ ⁻ group from the acid value of the coating resin determined from the above KOH titration value.

  In the past, precoat release agents and precoat colorants have been used to improve dispersibility in the production of toner. However, the acid value of the coating resin is low, resulting in toner fixability and color development. In some cases, the properties and the like cannot be sufficiently improved. However, since the coating resin used in the precoat release agent and precoat colorant of the present invention has a higher ability to improve the dispersibility of the core agent than the conventional coating resin, the fixing property and color developability of the toner are further improved. It is possible to make it.

  Further, since the coating resin used in the present invention has a higher ability to improve the dispersibility of the core agent than the conventional coating resin, the amount of the coating resin used for the core agent is suppressed, so that the productivity during toner production Improvement and cost reduction can be achieved. In addition, when the amount of coating resin used for the core agent is reduced, the thickness of the coating resin that coats the core agent becomes thinner, or the coatability decreases, and part of the core agent is exposed. However, it is easy to maintain and secure sufficient dispersibility.

The coating resin used in the precoat release agent and precoat colorant of the present invention is not particularly limited as long as it satisfies the conditions described in [1] and [2], but will be described below. It is preferable to have such characteristics.
That is, the glass transition temperature of the coating resin is preferably in the range of 50 to 80 ° C. When the glass transition temperature is less than 50, the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. When the glass transition temperature exceeds 80 ° C., peeling failure may be caused.

  Moreover, it is preferable that the polystyrene conversion molecular weight of coating resin exists in the range of 3000-50000. When the molecular weight in terms of polystyrene is less than 3000, the coating resin may permeate into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the bending resistance of the fixed image may be reduced. When exceeding, the light transmittance at the time of fixing to an OHP sheet may be impaired.

  The resin material that can be specifically used as the coating resin is not particularly limited as long as it satisfies the conditions described in the above items [1] and [2]. For example, styrene, parachlorostyrene, Styrenes such as α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n methacrylate -Esters having a vinyl group such as propyl, lauryl methacrylate, 2-ethylhexyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl Ketone, vinyl Polymers that are polymerized using monomers such as vinyl ketones such as isopropenyl ketone, polyolefins such as ethylene, propylene, and butadiene, copolymers obtained by combining two or more of the above monomers, or Mention may be made of these mixtures.

  In addition, non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., or vinyl resins that are polymerized using these resin materials and the above-mentioned monomers And a graft polymer obtained when a vinyl monomer is polymerized in the presence of these.

-Core colorant-
Next, the core colorant used for the precoat colorant of the present invention will be described. A known colorant can be used as the core colorant used in the present invention, and is preferably selected in consideration of hue angle, saturation, brightness, weather resistance, and OHP permeability.
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 given.

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, Eoxin 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.
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. These core colorants can be used alone or in combination.

  When the toner to be finally produced is a magnetic toner, magnetic powder that can also function as a colorant can be used as the core colorant. As such magnetic powder, a substance magnetized in a magnetic field is used, and it is a ferromagnetic powder such as iron, cobalt, nickel, or a compound such as magnetite.

In the precoat colorant of the present invention, the weight ratio of the core colorant to the coating resin is preferably in the range of 100: 10 to 100: 120, and in the range of 100: 20 to 100: 100. Is more preferable.
When the weight ratio is less than 100: 10, the dispersibility of the core colorant in the toner is lowered, and thus fogging and scattering occur in an image formed with the toner prepared using the precoat colorant of the present invention. May end up. Also, if the weight ratio is greater than 100: 120, the absolute amount of the core colorant contained in the toner decreases, so the image density of the image formed with the toner prepared using the precoat colorant of the present invention is low. It may become thinner.

-Manufacturing method of toner colorant-
Next, the manufacturing method of the precoat colorant of this invention is demonstrated. As the precoat colorant of the present invention, any known method can be used as long as it is a method of coating particles with a resin. For example, an interfacial polymerization method, an in-site polymerization method, a submerged drying method, a coacervation method, A spray drying method, a dry mixing method, or the like can be used.

For example, the precoat colorant of the present invention can be prepared as follows. First, the coating resin is dissolved in an organic solvent, and the core colorant is dispersed in the obtained solution to obtain a core colorant-dispersed resin solution. Next, an aqueous solution in which a surfactant is dissolved in deionized water is prepared, and the above-described core colorant-dispersed resin solution is added and mixed thereto. By distilling off the organic solvent from this mixed solution, a colorant dispersion in which the precoat colorant of the present invention is dispersed can be obtained.
In the production of the toner, the toner may be used in the state of a colorant dispersion, or the colorant dispersion may be separated into solid and liquid as necessary to extract only the precoat colorant.
Moreover, the particle diameter of the precoat colorant contained in the obtained colorant dispersion can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

-Core release agent-
Next, the core release agent used for the precoat release agent of the present invention will be described.
As the core mold release agent, known mold release agents can be used. For example, minerals such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, petroleum wax, and polyalkylene which is a modified product thereof. Can be used.
Among these materials, a polyalkylene is preferable because the core release agent used in the precoat release agent of the present invention can easily satisfy preferable physical properties as a release agent as described below.

  Next, preferable physical properties of the core release agent will be described below. The main maximum peak measured according to ASTM d3418-8 of the core release agent is preferably in the range of 85 to 95 ° C. If the temperature is less than 85 ° C., offset may easily occur during fixing. On the other hand, if it exceeds 95 ° C., the fixing temperature becomes high, and the smoothness of the fixed image surface cannot be obtained, and the glossiness may be impaired.

  For the measurement of the main maximum peak, for example, DSC-7 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 is used, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

Moreover, 85-95 degreeC is preferable and the maximum value of the endotherm calculated | required from the differential thermal analysis of a core mold release agent, More preferably, it is 86-93 degreeC. If it is less than 85, the melt viscosity will be low and the dissolution property during oilless fixing will be improved, but the core release agent will melt when the toner is produced by the hetero-aggregation method. Not only deteriorates the particle size controllability but also increases the amount of the core release agent exposed on the toner surface, which may impair the powder flowability of the toner.
If the temperature exceeds 95 ° C., the production stability of the toner will be good, but the melt viscosity will rise. Therefore, the oil-less foil properties may be lowered to reduce the elution of the core release agent in oil-less fixing. is there.

Further, the ratio of the endothermic amount based on the endothermic peak area determined by differential thermal analysis (the endothermic amount of 85 ° C. or less based on the endothermic peak area / the total endothermic amount based on the endothermic peak area) is in the range of 5 to 15%. Is preferably within the range of 7 to 13%. The ratio of the endothermic amount based on the area of the endothermic peak means the ratio of the endothermic amount due to the low melting point component in the polyalkylene.
Here, if the ratio of the endothermic amount due to the low melting point component is less than 5%, the compatibility between the core release agent component and the binder resin is poor, and the fixability may be lowered. On the other hand, when the amount exceeds 15%, the binder resin is plasticized when the toner is produced, and the elution property of the core release agent at the time of fixing is lowered, and as a result, the oilless peelability is impaired. There is.

  Note that “endothermic amount of 85 ° C. or less based on endothermic peak area (hereinafter abbreviated as“ low melting point component endothermic amount ”)” and “total endothermic amount based on endothermic peak area (hereinafter“ total endothermic amount ”). "Means a value obtained based on a graph obtained when a differential thermal analysis is performed. Hereinafter, it will be specifically described with reference to the drawings.

FIG. 1 is a schematic diagram for explaining an analysis method of a graph obtained by differential thermal analysis of a core release agent.
In FIG. 1, the horizontal axis represents temperature (° C.), the vertical axis represents the amount of heat, the direction toward the origin means heat absorption, and the direction away from the origin means heat generation. Moreover, the solid line (endothermic peak) which draws a curve with respect to the increase in temperature in the graph shows the endothermic / exothermic change with respect to the temperature when the core release agent is subjected to differential thermal analysis, and is less than 85 ° C. Endotherm begins in the temperature range, exceeds 85 ° C., and the endothermic peak shows a maximum value at temperature Tmax (° C.). When the temperature rises beyond temperature Tmax (° C.), the endotherm decreases, and finally the endotherm ends. It is shown that.

  Here, a state in which no endotherm / exotherm has occurred is defined as a standard (two straight line portions separated by a solid line endothermic peak in the graph, and a dotted line provided on an extension line of the two straight line portions), and a curve and a dotted line The region surrounded by is defined as “total endotherm”, and among the regions surrounded by the curve and dotted line, the region having a temperature of 85 ° C. or lower (the hatched portion in FIG. 1) was determined as “low melting point component endotherm”. . In addition, when obtaining the thermal characteristics of the core release agent as described above by differential thermal analysis, the measurement is performed with the core release agent alone.

  Moreover, it is preferable that the core mold release agent used for this invention has the following viscosity characteristics. That is, the viscosity ηs140 of the core release agent at 140 ° C. measured using an E-type viscometer equipped with a cone plate with a cone angle of 1.34 ° is within a range of 1.5 to 5.0 mPa · s. It is preferable that it is within a range of 2.5 to 4.0 mPa · s.

  When the viscosity ηs140 is lower than 1.5 mPa · s, the elution property at the time of fixing is good, but the core release agent layer formed on the image becomes non-uniform, causing peeling unevenness, and visually It may cause uneven gloss. In addition, since elution is reduced when the viscosity is higher than 5.0 mPa · s, a core release agent sufficient to peel off the image and the fixing roll is not supplied during oilless fixing, resulting in poor peeling. May occur.

The viscosity ηs140 of the core release agent is measured with an E-type viscometer. For the measurement, an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with an oil circulation type thermostat is used. Here, a cone plate having a cone angle of 1.34 ° is used.
Specifically, the measurement is performed as follows. First, the temperature of the circulation device is set to 140 ° C., and an empty sample measurement cup, an empty reference cup, and a cone are set in the measurement device, and kept at a constant temperature while circulating oil. Next, when the temperature is stabilized, 1 g of the sample is put in the sample measuring cup, and the cone is allowed to stand still for 10 minutes. After stabilization, rotate the cone and measure. The rotational speed of the cone is 60 rpm. The measurement is performed three times, and the average value is defined as a viscosity η140.

In the precoat release agent of the present invention, the weight ratio between the core release agent and the coating resin is preferably within the range of 100: 10 to 100: 120, and within the range of 100: 20 to 100: 100. More preferably.
When the weight ratio is less than 100: 10, the dispersibility of the core release agent in the toner is lowered, and the core release agent cannot be eluted uniformly from the inside of the toner at the time of fixing, so that the peeling performance is lowered. There is a case. On the other hand, if the weight ratio is larger than 100: 120, the amount of elution of the core release agent sufficient for peeling cannot be obtained, and the peelability is impaired and surface roughness occurs, so that the image glossiness may be lowered.

-Manufacturing method of release agent for toner production-
Next, the manufacturing method of the precoat mold release agent of this invention is demonstrated. As the precoat release agent of the present invention, any known method can be used as long as it is a method of coating particles with a resin. For example, an interfacial polymerization method, an in-site polymerization method, a submerged drying method, a coacervation method. A spray drying method, a dry mixing method, or the like can be used.

For example, the precoat release agent of the present invention can be prepared as follows. First, after dispersing the core release agent in water with a polymer electrolyte such as an ionic surfactant, polymer acid, or polymer base, the homogenizer can be heated to a temperature higher than the melting point of the core release agent and subjected to strong shearing. After making the core release agent into a finely divided dispersion by a pressure discharge type disperser, a water-soluble polymerization initiator is added to the dispersion.
Next, a monomer for forming a coating resin that is sparingly soluble in this dispersion is added, and the mixture is heated and stirred so that the monomer slightly dissolved in the aqueous phase is polymerized with the core release agent particles as the core. By doing so, a release agent dispersion liquid in which the precoat release agent of the present invention is dispersed can be obtained.

In the production of the toner, the toner may be used in the state of a release agent dispersion, or the release agent dispersion may be separated into solid and liquid as necessary to take out only the precoat release agent. .
Moreover, the particle diameter of the precoat release agent contained in the obtained release agent dispersion can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

(Static image developing toner)
Next, the electrostatic image developing toner of the present invention (hereinafter sometimes abbreviated as “toner”) will be described.
The toner of the present invention is prepared using a binder resin, a release agent, and a colorant. When the toner is prepared, the precoat release agent of the present invention is always used as the release agent. Alternatively, the precoat colorant of the present invention is always used as a colorant.
Therefore, in the former case, good performance can be obtained in any of the fixing property, releasability and charging property of the produced toner. In the latter case, good performance can be obtained in any of the characteristics such as color developability, color reproducibility, and transparency of the OHP sheet.

Of course, it is more preferable to use the precoat release agent of the present invention as a release agent and to use the precoat colorant of the present invention as a colorant in the preparation of toner.
Further, when the precoat release agent of the present invention is used as a release agent in the production of the toner of the present invention, an uncoated release agent may be used together as necessary, or a non-coat colorant or a conventional colorant may be used. The precoat colorant may be used.
Further, when the precoat colorant of the present invention is used as a colorant in the production of the toner of the present invention, a non-coat colorant may be used in combination as necessary, or a non-coat release agent or a conventional release agent may be used. A precoat release agent may be used.

  The volume average particle diameter of the toner of the present invention is preferably in the range of 2 to 10 μm, and more preferably in the range of 3 to 8 μm. When the volume average particle size is less than 2 μm, the chargeability becomes insufficient and the developability may be deteriorated, and when it exceeds 10 μm, the resolution of the image may be deteriorated.

The particle size distribution index of the toner of the present invention is preferably such that the volume average particle size distribution index GSDv is 1.30 or less, and the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp (GSDp / GSDv ) Is preferably 0.95 or more.
If the volume distribution index GSDv exceeds 1.30, the resolution may decrease. In addition, when the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp (GSDp / GSDv) is less than 0.95, it may cause a decrease in chargeability and, at the same time, scatter, image defects such as fogging. It can also be a cause.

  The volume average particle size and the particle size distribution index can be determined using a measuring instrument such as Coulter Counter TA II (manufactured by Nikka Kisha Co., Ltd.), Multisizer II (manufactured by Nikka Kisha Co., Ltd.), or the like. Specifically, from the measured particle size distribution (particle number distribution obtained for each divided particle size range (channel)), based on the volume and number of particles, draw a cumulative distribution from the small diameter side to each, The particle diameter that is cumulative 16% is defined as volume average particle diameter D16v or number average particle diameter D16p, and the particle diameter that is cumulative 50% is defined as volume average particle diameter D50v or number average particle diameter D50p. To do. Further, it is defined as a volume average particle diameter D84v or a number average particle diameter D84p. Here, the volume average particle size distribution index (GSDv) can be defined as D84v / D16v, and the number average particle size index (GSDp) is defined as D84p / D16p.

  The shape factor SF1 of the toner of the present invention is preferably in the range of 110 to 140 from the viewpoint of image formability. The shape factor SF1 is obtained as an average value of the shape factors (square of the perimeter / projected area) of individual toners. Specifically, for example, the shape factor SF1 can be obtained 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 (ML2 / A) is calculated, and the average value thereof Is obtained, the value of the shape factor SF1 can be obtained.

Further, the amount of the release agent present on the toner surface determined by X-ray photoelectron spectroscopy (XPS) (the amount of the release agent due to the core release agent and / or the non-coat release agent) is in the range of 11 to 40 atm%. It is preferable that If it is less than 11%, the oil-less peelability may be impaired, and if it exceeds 40%, the fluidity of the toner may be lowered.
The amount of the release agent present on the toner surface using XPS was determined using an X-ray electron spectrometer (JPS-9000MX: manufactured by JEOL Ltd.). Specifically, the amount of the release agent on the toner surface is quantified by a C _1S spectrum peak separation method. In the peak separation method, the measured C _1S spectrum is separated into components using curve fitting by the least square method. As a component spectrum that is a base for separation, a C _1S spectrum obtained by measuring a release agent and a binder resin alone is used.

  Further, the maximum endothermic value when the toner is subjected to differential thermal analysis is preferably in the range of 70 to 120 ° C. If the maximum value of the endotherm is less than 70 ° C., problems such as an offset being liable to occur at the time of fixing and deterioration of the storage stability of the fixed image may occur. On the other hand, if the temperature exceeds 120 ° C., the toner fixing temperature becomes high, and the smoothness of the fixed image cannot be obtained, and the glossiness may be impaired.

-Binder resin-
As the binder resin used in the present invention, a known binder resin can be used.
For example, styrenes such as styrene, parachlorostyrene, α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate , Ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, esters having vinyl groups such as 2-ethylhexyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether Polymers obtained by polymerizing monomers such as vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, and polyolefins such as ethylene, propylene, butadiene, and the like. Copolymers obtained by combining more species, or a mixture thereof polymers and copolymers thereof.

  Furthermore, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or mixtures of these with vinyl resins obtained by polymerizing the above monomers And a graft polymer obtained when a vinyl monomer is polymerized in the presence of these resin materials.

When a vinyl monomer is used as a raw material for the binder resin, an emulsion polymerization is performed using an ionic surfactant or the like to prepare a resin particle dispersion, which is used for toner preparation. Can do.
In the case of other binder resins, if they are oily and dissolve in a solvent with a relatively low solubility in water, the binder resin is dissolved in those solvents, and together with ionic surfactants and polymer electrolytes in water By dispersing fine particles in water with a disperser such as a homogenizer, and then evaporating the solvent by heating or decompressing, a resin fine particle dispersion can be prepared and used for toner preparation. .
Moreover, the particle diameter of the obtained resin fine particle dispersion is measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

-Colorant-
In the production of the toner of the present invention, the precoat colorant of the present invention is always used when the precoat release agent of the present invention is not used as the mold release agent. In addition, when the precoat release agent of the present invention is used as a release agent, a non-coat colorant, a conventional precoat colorant, and / or a precoat colorant of the present invention can be used.
In addition, as the non-coat colorant and the core colorant of the conventional precoat colorant, the same colorant as the core colorant of the precoat colorant of the present invention can be used.

The amount of the net colorant used in the toner of the present invention is preferably in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. On the other hand, when a magnetic material is used as the black colorant, the net colorant amount is preferably in the range of 30 to 100 parts by weight with respect to 100 parts by weight of the binder resin, unlike other colorants. When a precoat colorant is used in the preparation of the toner, calculation is made so that the amount of the core colorant is included as the net colorant amount.
Furthermore, the larger the proportion of the precoat colorant of the present invention in the net colorant amount, the better, and most preferably 100%.

  When the toner of the present invention is used as a magnetic toner, the precoat colorant of the present invention using a magnetic material as a core colorant as described above can be used. In addition, when a magnetic material that is not covered at all is used regardless of its function as a colorant, the magnetic material dissolves in the aqueous solvent when the toner is prepared using an aqueous solvent as described later, and the toner In order to prevent the particles from being taken into the particles, the surface of the magnetic material is preferably subjected to surface modification, for example, a hydrophobic treatment.

-Release agent-
In the production of the toner of the present invention, if the precoat colorant of the present invention is not used as the colorant, the precoat release agent of the present invention is necessarily used. When the precoat colorant of the present invention is used as the colorant, a non-coat release agent, a conventional precoat release agent, and / or a precoat release agent of the present invention can be used.
In addition, as the non-coat release agent and the core release agent of the conventional precoat release agent, those similar to the core release agent of the precoat release agent of the present invention can be used.

Further, the net release agent amount in the toner determined from the height of the endothermic peak at the endothermic maximum value in the differential thermal analysis of the net release agent is preferably 6 to 9% by weight. More preferably, it is 6.5 to 8.5% by weight (in the case of using a precoat release agent in the preparation of the toner, the amount of the core release agent is included as the net release agent amount).
If the net amount of the release agent is less than 6%, an elution amount sufficient for peeling at the time of oil-less fixing cannot be obtained, the peelability is impaired, and surface roughness may occur, so that the image glossiness may be lowered. On the other hand, if it exceeds 9%, the releasability will be good, but the amount of the release agent on the toner surface and the image will increase, which will not only reduce the powder fluidity of the toner but also when discharging the fixed image. In some cases, a contact mark such as a discharge roll is generated on the sheet, which may impair image quality.
The ratio of the precoat release agent of the present invention in the net release agent amount is preferably as large as possible, and most preferably 100%.

The endothermic peak height at the endothermic maximum value means the endothermic peak height at the temperature Tmax (maximum endothermic value) in FIG. 1, and specifically, a solid line and a dotted line showing a change in the amount of heat at the temperature Tmax. Is the height that connects Here, the amount of the net release agent in the toner can be easily determined from the height of the endothermic peak and a calibration curve prepared in advance using a standard sample.
In the case where the net amount of the release agent in the toner is obtained using differential thermal analysis, it is necessary to use a toner containing the release agent used for the preparation of the toner as a sample.

-Other additives-
In the toner of the present invention, various additives (internal additives and / or external additives) can be used as necessary in addition to the binder resin, the release agent and the colorant.
For example, inorganic fine particles can be used as an internal additive to ensure charging stability, and specific examples include silica, hydrophobized silica, titanium oxide, alumina, calcium carbonate, magnesium carbonate, and phosphoric acid. Examples include tricalcium, colloidal silica, cationic surface-treated colloidal silica, and anionic surface-treated colloidal silica.
These inorganic fine particles are preliminarily dispersed in the presence of an ionic surfactant by using an ultrasonic disperser or the like at the time of preparation of the toner, but it is more preferable to use colloidal silica because this dispersion treatment is not necessary. Moreover, you may use these 1 type or in mixture of 2 or more types. The total amount of these inorganic fine particles added is preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

  To the toner of the present invention, inorganic fine particles can be externally added in a wet manner in order to stabilize chargeability. Examples of inorganic fine particles added to the toner surface include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, all of which are usually used as external additives on the toner surface, such as ionic surfactants and high It can be used by dispersing with molecular acid or polymer base.

  In addition, a charge control agent can be used to 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. When producing toner through the aggregation process and fusion process as described later, a material that is difficult to dissolve in water is charged in terms of controlling ionic strength, which affects the stability in these processes, and reducing wastewater contamination. It is preferable to use it as a control agent.

  In addition, for the purpose of imparting fluidity and improving cleaning properties, as with conventional toners, inorganic particles such as silica, alumina, titania, calcium carbonate, etc. are used on the surface of toner particles as fluidity aids and cleaning aids. It is also possible to externally add resin fine particles such as resin, polyester, and silicone by shearing in a dry state.

(Method for producing toner for developing electrostatic image)
The toner of the present invention can basically be produced using a known wet toner production method. Specifically, the aggregation and coalescence method, the solution suspension emulsion aggregation and aggregation method, and the suspension polymerization method are used. Can be mentioned.
However, when an organic solvent that dissolves the precoat release agent and / or precoat colorant coating resin of the present invention used in the preparation of the toner is used, the precoat release agent of the present invention is used in any step during the toner preparation. It is necessary to prevent the coating resin of the mold and / or the precoat colorant from coming into direct contact with the organic solvent. When such contact occurs, the coating resin is eluted, and the dispersibility of the core release agent and / or core colorant contained in the finally obtained toner is reduced. There is.

When utilizing the aggregation and coalescence method, specifically, it is preferable to produce the toner of the present invention by the method described below.
That is, the toner production method of the present invention using the aggregation and coalescence method includes (first) resin fine particle dispersion in which (first) resin fine particles having a volume average particle diameter of 1 μm or less are dispersed, and a release agent. An aggregating step of adding an aggregating agent to a mixed solution obtained by mixing at least a dispersion and a colorant dispersion to form an agglomerate (core agglomerate); and the agglomeration of the resin fine particles contained therein It preferably includes at least a fusion step of fusing and uniting by heating to a glass transition temperature or higher.
In this case, the release agent dispersion used in the aggregation step includes the precoat release agent of the present invention and / or the precoat colorant of the present invention.
The toner base particles obtained through the fusing process are washed and dried, and the toner of the present invention can be obtained by adding an external additive as necessary.
The shape of the toner produced through such a process is not particularly limited, and can be controlled as necessary from an indeterminate shape to a spherical shape.

Furthermore, other steps can be performed as necessary. For example, an adhesion step can be performed between the aggregation step and the fusion step.
The adhesion step refers to adding a second resin fine particle dispersion in which the second resin fine particles are dispersed to the mixed solution after the core aggregate is formed, so that the second is added to the surface of the core aggregate. This is a step of forming an aggregate (core / shell aggregate) to which the resin fine particles are adhered.
Further, when the adhesion step is performed, the fusion step is performed by either the glass transition temperature of the first resin fine particles or the glass transition temperature of the second resin fine particles contained in the core / shell aggregate. It is carried out by heating above the high glass transition temperature.

  The flocculant used in the aggregation step is not particularly limited, but a metal salt polymer is preferably used. Furthermore, the metal salt polymer used as the flocculant is preferably a tetravalent aluminum salt polymer or a mixture of a tetravalent aluminum polymer and trivalent aluminum. Moreover, it is preferable that the density | concentration of the mixture of the above-mentioned metal salt polymer added in a mixed solution in an aggregation process exists in the range of 0.11-0.25 weight%.

The fine resin particle dispersion used in the aggregation step may be prepared by emulsion polymerization using a monomer capable of forming a binder resin by polymerization as described above. It can also be produced using (binder resin).
In this case, after adding at least an anionic surfactant to a solution in which the binder resin is dissolved in an organic solvent, emulsification is performed by applying mechanical shearing force, and then desolvation is performed to obtain an emulsified resin dispersion. And after adding an anionic surfactant to the emulsified resin dispersion, a resin fine particle dispersion can be prepared through a process of applying a mechanical shearing force.

In the case of the dissolution suspension emulsion aggregation coalescence method, the resin fine particle dispersion is prepared as follows.
First, a solution in which the binder resin component is dissolved in a solvent that is soluble in the binder resin, such as ethyl acetate, is prepared, and this solution is used in the presence of an ionic surfactant, such as a TK homomixer. The emulsified resin fine particles are obtained by the mechanical shearing force by the homogenizer and the surface active force of an ionic surfactant such as sodium alkylbenzene sulfonate. Finally, the resin fine particle dispersion can be obtained by distilling off the remaining solvent from the solution in which the emulsified resin fine particles are formed by distillation under reduced pressure or the like.

Next, each process described above will be described in detail with specific examples.
The agglomeration step is performed by using a resin fine particle dispersion in which the first resin fine particles are dispersed using an ionic surfactant, and an ionic surfactant having the opposite polarity used in the resin fine particle dispersion. In addition, a mixed solution is prepared by mixing various dispersions in which other components (for example, magnetic metal fine particles) to be added as necessary are dispersed. At this time, the balance of the amount of the ionic surfactant (dispersant) of each polarity to be used is shifted in advance.

  Next, for this mixed solution, for example, an inorganic metal salt such as calcium nitrate or a polymer of inorganic metal salt such as polyaluminum chloride is used to correct ionic imbalance due to the imbalance in the amount of dispersant. (Neutralization) and heteroaggregation is generated in a temperature range below the glass transition temperature of the first resin fine particles to form an aggregate (core aggregate). Such agglomeration can be carried out in several stages.

Next, an adhesion process is performed. In the adhering step, the resin particle dispersion in which the second resin fine particles to which a polar and an amount of a dispersant that compensates for the ionic imbalance is added is dispersed into the mixed solution in which the core aggregates are formed. The second resin fine particles are added to the core aggregate to form a core / shell aggregate.
Subsequently, after slightly heating below the glass transition temperature of the resin constituting the core aggregate (resin component of the first resin fine particles) or the resin component of the second resin fine particles and stabilizing at a higher temperature, The core / shell aggregates are fused and united by heating above the glass transition temperature of any resin component to obtain toner mother particles in a moist state.

  When the glass transition temperature of the resin component of the second resin fine particle is different from that of the first resin fine particle, the core aggregate of the core / shell aggregate is selected by selecting the heating temperature using this difference. Only the adhesion layer (shell layer) made of the partial or second resin fine particles may be selectively fused and united. The aggregating operation as described above may be repeated a plurality of times.

After the fusing step, the toner of the present invention can be obtained through a known washing step, solid-liquid separation step, and drying step.
Here, it is preferable that the cleaning step is sufficiently performed with replacement with ion-exchanged water from the viewpoint of charging properties. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, although the drying process is not particularly limited, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

On the other hand, when the toner of the present invention is produced using the suspension polymerization method, the toner production method of the present invention is preferably the following production method.
That is, the toner production method of the present invention using the dissolution suspension emulsion aggregation coalescence method includes at least a (first) polymerizable monomer, a polymerization initiator, a colorant, a release agent, A suspension step of adjusting the suspension solution by adding an inorganic or organic dispersant to the raw material solution and then suspending it by applying mechanical shearing force. It is preferable that the production method includes at least a polymerization step in which polymerization is performed by heating the turbid solution while stirring and shearing.
In this case, the precoat release agent of the present invention and / or the precoat colorant of the present invention is necessarily used as the release agent and / or colorant used in the raw material solution.

  The raw material solution used in the suspending step is a second polymerizable monomer so that the weight average molecular weight Mw measured by gel permeation chromatography (GPC) of the polymer is within the range of 3000 to 15000. It is preferable that it further contains a prepolymer obtained by polymerizing.

Next, each process described above will be described in detail with specific examples.
First, a colorant and a release agent are dispersed in a polymerizable monomer such as styrene, acrylic acid ester or acrylic acid, and this is heated to 60 ° C. in the presence of an inert gas, and then azobisisovaleronitrile is added thereto. A polymerization initiator such as is added.
Next, this is added to an aqueous dispersion of an inorganic dispersant such as calcium phosphate that has been heated to 60 ° C. in advance, and mechanically sheared by a homogenizer such as a TK homomixer to obtain a suspension granulated dispersion. Next, this dispersion is kept at a temperature equal to or higher than the 10-hour half-life temperature of the polymerization initiator and allowed to undergo a polymerization reaction for about 6 hours. The dispersion after completion of the reaction is cooled to room temperature, and then an acid such as hydrochloric acid is added to dissolve and remove the dispersant component. Thereafter, this is washed with sufficient pure water, and when the pH of the filtrate becomes neutral, it is subjected to solid-liquid separation using a filter medium such as No5A filter paper to obtain particles (toner mother particles).

  The surfactant used for the above-mentioned emulsion polymerization, suspension polymerization, suspension emulsification, colorant and release agent, dispersion of resin fine particles, aggregation of toner constituents and stabilization of aggregates obtained by aggregation. For example, anionic surfactants such as sulfate, sulfonate, phosphate, and soap, and cationic surfactants such as amine salts and quaternary ammonium salts can be used. . In addition to these, it is also effective to use nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols in combination. As a means for dispersion, general means such as a rotary shear type homogenizer, a ball mill having a media, a sand mill, and a dyno mill can be used.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited only to the following examples.
The toner of the present invention used in the examples was prepared by using the following method.
In the case of producing a toner by using the aggregation and coalescence method, the following resin fine particles, colorant particle dispersion, release agent particle dispersion, and inorganic fine particle dispersion are prepared. At this time, the inorganic fine particle dispersion may be previously agglomerated by adding a predetermined amount of a part of the inorganic metal salt polymer and stirring.
Next, an inorganic metal salt polymer is added thereto while mixing and stirring a predetermined amount thereof to obtain a toner particle diameter. Next, after adjusting the pH of the system from a weakly acidic to a neutral range with an inorganic hydroxide, it is heated to the glass transition temperature or higher of the resin fine particles to unite and fuse. After completion of the reaction, a desired toner is obtained through sufficient washing, solid-liquid separation, and drying processes.

  In the case of preparing a toner by using the dissolution emulsification aggregation method, after prepolymerizing the polymerizable monomer, it is emulsified with a mechanical shear force in the presence of a surfactant, and then a water-soluble polymerization initiator. Thermal dispersion is performed in the presence to obtain a dispersion containing resin fine particles. In the subsequent steps, a toner is obtained using an agglomeration coalescence method except that this resin fine particle dispersion is used.

  In the case of producing a toner using a suspension polymerization method, a monomer, a release agent, a colorant, etc., which are precursors of a binder resin, are heated and mixed, and this is subjected to shearing with a media-type disperser and dispersed. After the treatment, this was added to a pure water dispersion adjusted with an inorganic dispersant, added together with an oil-soluble polymerization initiator dissolved in a polymerizable monomer, granulated with a homogenizer, heated and then heated. Get coalesced. Next, a desired toner is obtained through washing, solid-liquid separation and drying.

[Acid value of the coating resin, COO ^- group, SO ₃ ^- acid value of quantitative methods due to radical
The acid value of the coating resin of the precoat release agent and the precoat colorant used for the preparation of the toner was obtained by KOH titration as described above. Further, SO ₃ ^- group and COO ^- For an acid value attributable to group each quantified S of the coating resin by the following method, due to the SO ^3- group to by terms of the amount of SO ^3- group The acid value was determined, and the acid value attributed to the COO ⁻ group was determined by subtracting the acid value attributed to the SO ³⁻ group from the acid value of the coating resin determined by KOH titration.

The S atom contained in the coating resin was quantified by first burning the coating resin to convert it into SO ₂ and measuring the IR spectrum absorption with an infrared spectrometer. A commercially available analytical instrument can be used for IR spectrum measurement.

(Preparation of resin fine particle dispersion 1)
-Styrene (Wako Pure Chemical Industries): 295 parts by weight-n-butyl acrylate (Wako Pure Chemical Industries): 68 parts by weight-β-carboxyethyl acrylate (Rhodia Nikka): 8 parts by weight-1'10 decanediol diacrylate (Manufactured by Shin-Nakamura Chemical Co., Ltd.): 1.4 parts by weight / dodecanethiol (manufactured by Wako Pure Chemical Industries): 2.4 parts by weight The above components were mixed and dissolved. Separately from the above-mentioned dissolved product, 3.5 parts by weight of an anionic surfactant Dowfax (manufactured by Dow Chemical Co.) was dissolved in 450 parts by weight of ion-exchanged water to prepare a surfactant solution.
Next, ion-exchanged water 45 in which 5 parts by weight of ammonium persulfate (manufactured by Wako Pure Chemical Industries) was dissolved while slowly stirring and mixing for 10 minutes while the dissolved solution of the above components was dispersed and emulsified in a surfactant solution in a flask. Part by weight was added.

Next, after sufficiently replacing the nitrogen in the flask, the contents were heated in an oil bath while stirring the flask until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours.
As a result, a resin fine particle dispersion 1 in which resin particles having a center diameter of 200 nm, a solid content of 41%, a glass transition temperature of 51.0 ° C., and a weight average molecular weight Mw of 30,000 was obtained.

(Preparation of resin fine particle dispersion 2)
-Styrene (Wako Pure Chemical Industries): 248 parts by weight-n-butyl acrylate (Wako Pure Chemical Industries): 68 parts by weight-β-carboxyethyl acrylate (Rhodia Nikka): 8 parts by weight-1'10 decanediol diacrylate (Manufactured by Shin-Nakamura Chemical Co., Ltd.): 1.4 parts by weight / dodecanethiol (manufactured by Wako Pure Chemical Industries): 2.4 parts by weight The above components were charged into a 1 L flask and heated to 65 ° C. with stirring. To this, 45 parts by weight of styrene and 4.0 parts by weight of azobisvaleronitrile were added and reacted for 8 hours under a nitrogen atmosphere to obtain a prepolymerized liquid having a weight average molecular weight Mw of 29,000.

  This prepolymerized solution is added to an aqueous solution in which 18 parts by weight of a surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved in 2 liters of pure water heated to 65 ° C., and a homogenizer (TK homomixer) is used. Disperse and emulsify for 5 minutes. Next, 4.2 parts by weight of ammonium peroxide was added thereto, and the mixture was further reacted for 6 hours to obtain an emulsion polymerization particle dispersion. The central particle size was 218 nm.

(Adjustment of colorant dispersion 1)
Styrene-acrylic acid copolymer resin 1 (polystyrene equivalent molecular weight 3100, glass transition temperature 65 ° C., acid value: 5.0 meq / mg-KOH [COO ⁻ group: 4.8 meq / mg-KOH, SO ₃ ⁻ group: 0 .2 meq / mg-KOH]) was added to a mixed solution containing 140 parts by weight of methyl ethyl ketone and 60 parts by weight of isopropyl alcohol, and dissolved by stirring. To the obtained solution, 100 parts by weight of a yellow pigment (manufactured by Clariant Japan: PY74) was added and dispersed with a homogenizer (IKA Ultra Tarrax) for 10 minutes to prepare a pigment-dispersed resin solution.

Separately, an aqueous solution in which 10 parts by weight of a surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved in 1100 parts by weight of ion-exchanged water is prepared, and the above-mentioned pigment dispersion resin solution is dropped while stirring. To obtain a dispersion.
Methyl ethyl ketone and isopropyl alcohol were distilled off from the obtained dispersion using a rotary evaporator to obtain a colorant dispersion 1 having a center diameter of 150 nm.

(Adjustment of colorant dispersion 2)
50 parts by weight of a yellow pigment, instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 2 (polystyrene equivalent molecular weight 3100, glass transition temperature 50 ° C., acid value: 4.0 meq / mg) -KOH [COO ^- groups: 3.9meq / mg-KOH, sO 3 - groups: 0.1meq / mg-KOH]) except for using 60 parts by weight, similarly to the adjustment colorant dispersion 1 was operated A colorant dispersion 2 having a central particle size of 170 nm was obtained.

(Adjustment of colorant dispersion 3)
Instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 3 (polystyrene equivalent molecular weight 3100, glass transition temperature 80 ° C., acid value: 3.0 meq / mg-KOH [COO ⁻ group: 2] _{.9meq / mg-KOH, sO 3} - groups: 0.1meq / mg-KOH]) except for using 10 parts by weight, the colorant dispersion 1 of adjustment and operates in the same manner, the center particle size 145nm of the colorant Dispersion 3 was obtained.

(Adjustment of colorant dispersion 4)
Instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 4 (polystyrene equivalent molecular weight 15000, glass transition temperature 70 ° C., acid value: 3.0 meq / mg-KOH [COO ⁻ group: 2 _{.9meq / mg-KOH, sO 3} - groups: 0.1meq / mg-KOH]) except for using 10 parts by weight, the colorant dispersion 1 of adjustment and operates in the same manner, the center particle size 148nm of the colorant Dispersion 4 was obtained.

(Adjustment of colorant dispersion 5)
75 parts by weight of yellow pigment, instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 5 (molecular weight 45,000 in terms of polystyrene, glass transition temperature 60 ° C., acid value: 6.0 meq / mg) -KOH [COO ^- groups: 5.7meq / mg-KOH, sO 3 - groups: 0.3meq / mg-KOH]) except for using 30 parts by weight, operating as adjustment colorant dispersion 1 A colorant dispersion 5 having a central particle size of 160 nm was obtained.

(Adjustment of colorant dispersion 6)
50 parts by weight of a yellow pigment, instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 6 (polystyrene equivalent molecular weight 45000, glass transition temperature 75 ° C., acid value: 6.0 meq / mg) -KOH [COO ^- groups: 5.8meq / mg-KOH, sO 3 - groups: 0.2meq / mg-KOH]) except for using 45 parts by weight, operating as adjustment colorant dispersion 1 A colorant dispersion 6 having a central particle size of 170 nm was obtained.

(Adjustment of colorant dispersion 7)
Instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 7 (polystyrene equivalent molecular weight 2800, glass transition temperature 45 ° C., acid value: 6.4 meq / mg-KOH [COO ⁻ group: 6 _{.4meq / mg-KOH, sO 3} - groups: 0.0meq / mg-KOH (S atom undetected)]) except for using 6 parts by weight, operating as adjustment colorant dispersion 1, the center A colorant dispersion 7 having a particle size of 147 nm was obtained.

(Adjustment of colorant dispersion 8)
50 parts by weight of a yellow pigment, instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 8 (polystyrene equivalent molecular weight 55000, glass transition temperature 90 ° C., acid value: 2.0 meq / mg) -KOH [COO ^- groups: 2.0meq / mg-KOH, SO 3 - groups: 0.0meq / mg-KOH (S atom undetected)]) except for using 70 parts by weight, of colorant dispersion 1 By operating in the same manner as the adjustment, a colorant dispersion 8 having a center particle diameter of 167 nm was obtained.

(Adjustment of colorant dispersion 9)
50 parts by weight of a yellow pigment, instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 9 (polystyrene equivalent molecular weight 60000, glass transition temperature 90 ° C., acid value: 1.3 meq / mg) -KOH [COO ^- groups: 1.3meq / mg-KOH, SO 3 - groups: 0.0meq / mg-KOH (S atom undetected)]) except for using 65 parts by weight, of colorant dispersion 1 By operating in the same manner as the adjustment, a colorant dispersion 9 having a center particle diameter of 171 nm was obtained.

(Adjustment of colorant dispersion 10)
Instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 10 (polystyrene equivalent molecular weight 2800, glass transition temperature 45 ° C., acid value: 6.4 meq / mg-KOH [COO ⁻ group: 6 _{.4meq / mg-KOH, sO 3} - groups: 0.0meq / mg-KOH (S atom undetected)]) 4 except for using the parts by weight, operating as adjustment colorant dispersion 1, the center A colorant dispersion 10 having a particle size of 146 nm was obtained.

(Adjustment of the colorant dispersion 11)
Instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 11 (polystyrene equivalent molecular weight 58000, glass transition temperature 85 ° C., acid value: 2.5 meq / mg-KOH [COO ⁻ group: 2] _{.4meq / mg-KOH, sO 3} - groups: 0.1meq / mg-KOH]) 7 except for using parts, the colorant dispersion liquid 1 of adjustment and operates in the same manner, the center particle size 142nm of the colorant Dispersion 11 was obtained.

(Adjustment of colorant dispersion 12)
50 parts by weight of a yellow pigment, instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 12 (polystyrene equivalent molecular weight 2700, glass transition temperature 46 ° C., acid value: 6.5 meq / mg) -KOH [COO ^- groups: 6.2meq / mg-KOH, sO 3 - groups: 0.3meq / mg-KOH]) except for using 67.5 parts by weight, similarly to the adjustment colorant dispersion 1 By operating, a colorant dispersion 12 having a central particle size of 172 nm was obtained.

(Adjustment of the colorant dispersion 13)
Instead of styrene-acrylic acid copolymer resin 1, styrene-acrylic acid copolymer resin 13 (polystyrene equivalent molecular weight 2900, glass transition temperature 47 ° C., acid value: 5.0 meq / mg-KOH [COO ⁻ group: 5 _{.0meq / mg-KOH, sO 3} - groups: 0.0meq / mg-KOH (S atom undetected)]) 7 except for using the parts by weight, operating as adjustment colorant dispersion 1, the center A colorant dispersion 13 having a particle size of 142 nm was obtained.

(Adjustment of release agent dispersion 1)
・ Polyalkylene wax FNP0090 (melting point 90 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight ・ Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight ・ Ion exchange water: 800 parts by weight or more The component was heated to 110 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 4.8 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 90 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 11%. there were.

The obtained emulsion was heated to 75 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 28.4 parts by weight Styrene: 170 parts by weight n-butyl acrylate: 43 parts by weight Sulfonated styrene: 1.7 parts by weight Acrylic acid: 1.1 parts by weight Trichlorobromo Methane: 0.17 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 1 having a center diameter of 280 nm and a solid content of 33.5%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature 60 ° C., polystyrene equivalent molecular weight 4000, acid value: 3.0 meq / mg-KOH [COO ⁻ group: 2.9 meq / mg-KOH, SO ₃ ^- group: 0.1 meq a / mg-KOH]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 120.

(Adjustment of release agent dispersion 2)
・ Polyalkylene wax FNP0085 (melting point 85 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion-exchanged water: 800 parts by weight or more The component was heated to 100 ° C., sufficiently dispersed with a homogenizer (IKA: Ultra Turrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 1.5 mPa · S. The maximum value of endotherm in the differential thermal analysis is 85 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 5%. there were.

The obtained emulsion was heated to 70 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 2.6 parts by weight Styrene: 11.5 parts by weight n-butyl acrylate: 7.8 parts by weight Sulfonated styrene: 0.5 parts by weight Acrylic acid: 0.2 parts by weight Parts / Trichlorobromomethane: 0.02 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 2 having a center diameter of 240 nm and a solid content of 21.5%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature of 50 ° C., polystyrene equivalent molecular weight of 4000, acid value of 6.0 meq / mg-KOH [COO ⁻ group: 5.7 meq / mg-KOH , SO ₃ ^- group: 0.3 meq a / mg-KOH]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 10.

(Adjustment of release agent dispersion 3)
Polyalkylene wax FNP0100 (melting point: 95 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The component was heated to 110 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 5 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 95 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 15%. there were.

The resulting emulsion was heated to 90 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 7.1 parts by weight Styrene: 34.9 parts by weight n-butyl acrylate: 18.1 parts by weight Sulfonated styrene: 0.43 parts by weight Acrylic acid: 0.48 parts by weight Parts / Trichlorobromomethane: 0.04 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 3 having a center diameter of 250 nm and a solid content of 24.0%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature of 80 ° C., polystyrene equivalent molecular weight of 4000, acid value of 5.0 meq / mg-KOH [COO ⁻ group: 4.9 meq / mg-KOH , SO ₃ ^- group: 0.1 meq a / mg-KOH]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 30.

(Adjustment of release agent dispersion 4)
Polyalkylene wax FNP0090 (melting point: 90 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The above components were heated to 95 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 4.8 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 90 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 11%. there were.

The obtained emulsion was heated to 85 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 26 parts by weight Styrene: 153 parts by weight n-butyl acrylate: 42 parts by weight Sulfonated styrene: 1.6 parts by weight Acrylic acid: 1.1 parts by weight Trichlorobromomethane: 0.3 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 4 having a center diameter of 262 nm and a solid content of 32.5%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature: 78 ° C., polystyrene equivalent molecular weight: 10,000, acid value: 3.2 meq / mg-KOH [COO ⁻ group: 3.1 meq / mg-KOH , SO ₃ ^- group: 0.1 meq a / mg-KOH]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 110.

(Adjustment of release agent dispersion 5)
Polyalkylene wax FNP0100 (melting point: 95 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The component was heated to 112 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 5.0 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 95 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 15%. there were.

The obtained emulsion was heated to 70 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 24 parts by weight Styrene: 105 parts by weight n-butyl acrylate: 69 parts by weight Sulfonated styrene: 2.8 parts by weight Acrylic acid: 3.7 parts by weight Trichlorobromomethane: 0.14 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 5 having a center diameter of 268 nm and a solid content of 31.6%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature: 58 ° C., polystyrene-equivalent molecular weight: 45,000, acid value: 5.8 meq / mg-KOH [COO ⁻ group: 5.6 meq / mg-KOH , SO ₃ ^- group: 0.2 meq a / mg-KOH]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 100.

(Adjustment of release agent dispersion 6)
Polyalkylene wax FNP0080 (melting point: 79.4 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight Part The above components were heated to 100 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 1.3 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 77 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 3%. there were.

The obtained emulsion was heated to 70 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 33 parts by weight Styrene: 218 parts by weight n-butyl acrylate: 32.8 parts by weight Acrylic acid: 0.9 parts by weight Trichlorobromomethane: 0.2 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 6 having a center diameter of 280 nm and a solid content of 35.2%.
The physical properties of the coating resin covering the core release agent are as follows: glass transition temperature: 45 ° C., polystyrene-equivalent molecular weight: 2600, acid value: 2.0 meq / mg-KOH [COO ⁻ group: 2.0 meq / mg-KOH , SO ₃ ^- group: a 0.0meq / mg-KOH (S atom undetected)]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 140.

(Adjustment of release agent dispersion liquid 7)
・ Polyalkylene wax FT100 (melting point: 98 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The above components were heated to 113 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 5.5 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 98 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 18%. there were.

The obtained emulsion was heated to 92 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 1.2 parts by weight Styrene: 4.2 parts by weight n-butyl acrylate: 4.7 parts by weight Acrylic acid: 0.06 parts by weight Trichlorobromomethane: 0.01 parts by weight Part

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 7 having a center diameter of 280 nm and a solid content of 20.7%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature: 86 ° C., polystyrene-equivalent molecular weight: 53000, acid value: 8.0 meq / mg-KOH [COO ⁻ group: 8.0 meq / mg-KOH , SO ₃ ^- group: a 0.0meq / mg-KOH (S atom undetected)]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 5.

(Adjustment of release agent dispersion 8)
・ Polyalkylene wax FT100 (melting point: 98 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The above components were heated to 113 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 5.5 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 98 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 18%. there were.

The obtained emulsion was heated to 92 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 31 parts by weight Styrene: 198 parts by weight n-butyl acrylate: 35 parts by weight Acrylic acid: 0.9 parts by weight Trichlorobromomethane: 0.2 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 8 having a center diameter of 285 nm and a solid content of 34.3%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature: 85 ° C., polystyrene-equivalent molecular weight: 55000, acid value: 2.3 meq / mg-KOH [COO ⁻ group: 2.3 meq / mg-KOH , SO ₃ ^- group: a 0.0meq / mg-KOH (S atom undetected)]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 130.

(Adjustment of release agent dispersion 9)
Polyalkylene wax FNP0080 (melting point: 79.4 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight Part The above components were heated to 100 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 1.3 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 77 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 3%. there were.

The obtained emulsion was heated to 70 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 1.2 parts by weight Styrene: 5.1 parts by weight n-butyl acrylate: 3.8 parts by weight Acrylic acid: 0.1 parts by weight Trichlorobromomethane: 0.01 parts by weight Part

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 9 having a central diameter of 255 nm and a solid content of 20.7%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature is 46 ° C., molecular weight in terms of polystyrene is 2500, and acid value is 6.5 meq / mg-KOH [COO ⁻ group: 6.5 meq / mg-KOH. , SO ₃ ^- group: a 0.0meq / mg-KOH (S atom undetected)]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 5.

(Adjustment of release agent dispersion 10)
Polyalkylene wax FNP0100 (melting point: 95 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The component was heated to 112 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 5.0 mPa · S. In the differential thermal analysis, the maximum endothermic value was 77 ° C., and the ratio of the endothermic area at 95 ° C. or lower was 15%.

The obtained emulsion was heated to 85 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 19 parts by weight Styrene: 87 parts by weight n-butyl acrylate: 53 parts by weight Acrylic acid: 3.7 parts by weight Trichlorobromomethane: 0.1 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 10 having a center diameter of 268 nm and a solid content of 29.6%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature of 79 ° C., polystyrene-equivalent molecular weight of 45,000, acid value of 5.6 meq / mg-KOH [COO ⁻ group: 5.4 meq / mg-KOH , SO ₃ ^- group: 0.2 meq a / mg-KOH]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 80.

(Adjustment of release agent dispersion 11)
・ Polyalkylene wax FT100 (melting point: 98 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The above components were heated to 113 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 5.5 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 98 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 18%. there were.

The resulting emulsion was heated to 95 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 30 parts by weight Styrene: 115 parts by weight n-butyl acrylate: 107 parts by weight Acrylic acid: 2.9 parts by weight Trichlorobromomethane: 0.2 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 11 having a center diameter of 267 nm and a solid content of 33.9%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature 90 ° C., polystyrene equivalent molecular weight 2800, acid value 7.0 meq / mg-KOH [COO ⁻ 7.0 meq / mg-KOH, SO ₃ ^- group: 0.0 meq / mg-KOH (S atom not detected)]), and the ratio (weight ratio) of the core release agent to the coating resin was 100: 125.

(Adjustment of release agent dispersion 12)
Polyalkylene wax FNP0080 (melting point: 79.4 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight Part The above components were heated to 100 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 1.3 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 77 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 3%. there were.

The obtained emulsion was heated to 70 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
-3% hydrogen peroxide solution: 0.9 parts by weight-Styrene: 5.7 parts by weight-n-butyl acrylate: 1.4 parts by weight-Sulfonated styrene: 0.06 parts by weight-Acrylic acid: 0.04 parts by weight Parts / Trichlorobromomethane: 0.005 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 12 having a center diameter of 243 nm and a solid content of 20.5%.
The physical properties of the coating resin to cover the core mold release agent has a glass transition temperature of 92 ° C., a molecular weight in terms of polystyrene is 60000, an acid value of 2.8meq / mg-KOH [COO ^- groups: 2.7meq / mg-KOH , SO ₃ ^- group: 0.1 meq a / mg-KOH], the ratio of the core mold release agent and coating resin (weight ratio) was 100: 4.

(Adjustment of release agent dispersion 13)
・ Polyalkylene wax FT100 (melting point: 98 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight or more The above components were heated to 113 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 5.5 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 98 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 18%. there were.

The resulting emulsion was heated to 95 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
3% hydrogen peroxide solution: 32 parts by weight Styrene: 136 parts by weight n-butyl acrylate: 100 parts by weight Acrylic acid: 2.7 parts by weight Trichlorobromomethane: 0.2 parts by weight

After completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 13 having a center diameter of 252 nm and a solid content of 34.7%.
The physical properties of the coating resin that coats the core release agent are as follows: glass transition temperature of 48 ° C., polystyrene equivalent molecular weight of 2800, acid value of 6.3 meq / mg-KOH [COO ⁻ 6.1 meq / mg-KOH, SO ₃ ^- group: 0.2 meq a / mg-KOH]), the ratio of the core mold release agent and coating resin (weight ratio) was 100: 135.

(Adjustment of release agent dispersion 14)
Polyalkylene wax FNP0080 (melting point: 79.4 ° C., manufactured by Nippon Seiki Co., Ltd.): 180 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 20 parts by weight Ion exchange water: 800 parts by weight Part The above components were heated to 100 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain an emulsion.
The viscosity ηs140 determined using an E-type viscometer of the core release agent was 1.3 mPa · S. In the differential thermal analysis, the maximum value of endotherm is 77 ° C., and the ratio of endothermic amount (endothermic amount of 85 ° C. or less based on the endothermic peak area / total endothermic amount based on the endothermic peak area) is 3%. there were.

The obtained emulsion was heated to 70 ° C. under a nitrogen stream while stirring.
Then, the following components were added and polymerization was performed for 5 hours.
-3% hydrogen peroxide solution: 1.7 parts by weight-Styrene: 9.1 parts by weight-n-butyl acrylate: 3.4 parts by weight-Acrylic acid: 0.09 parts by weight-Trichlorobromomethane: 0.01 parts by weight Part After the completion of the polymerization reaction, the mixture was cooled to obtain a release agent dispersion 14 having a center diameter of 268 nm and a solid content of 21.0%.
The physical properties of the coating resin for coating the core release agent are as follows: glass transition temperature: 48.5 ° C., polystyrene-equivalent molecular weight: 2700, acid value: 4.0 meq / mg-KOH [COO ⁻ group: 4.0 meq / mg -KOH, SO ₃ ^- group: 0.0Meq a / mg-KOH (S atom undetected)], the ratio of the core mold release agent and coating resin (weight ratio) was 100: 7.

(Preparation of inorganic fine particle dispersion)
Hydrophobized silica R972 (manufactured by Nippon Aerosil Co., Ltd.): 24 parts by weight Surfactant Neogen R (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 4 parts by weight Ion-exchanged water: 165 parts by weight The above components are mixed The dissolved solution was dispersed with a homogenizer (IKA Ultra Tarrax) for 10 minutes to obtain an inorganic fine particle dispersion having a center particle size of 18 nm.

<Manufacture of toner>
(Manufacture of toner 1)
-Resin fine particle dispersion 1: 103 parts-Colorant dispersion 1: 93 parts-Release agent dispersion 1: 41 parts-Inorganic fine particle dispersion: 72 parts-Polyaluminum chloride: 0.10 parts by weight The above components were sufficiently mixed and dispersed in a round stainless steel flask using a homogenizer (IKA Ultra Turrax T50).
Next, 0.06 part by weight of polyaluminum chloride was added thereto, and the dispersing operation was continued with a homogenizer (IKA Ultra Tarrax T50).
While stirring the flask, it was heated to 48 ° C. in an oil bath for heating. After maintaining at 48 ° C. for 90 minutes, 61 parts by weight of resin fine particle dispersion 1 was gradually added thereto.
After the pH of the flask was adjusted to 5.3 with a 0.5 M aqueous sodium hydroxide solution, the stainless steel flask was sealed, heated to 96 ° C. with continuous stirring using a magnetic seal, and maintained for 5 hours.

After completion of the reaction, the reaction mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1.5 L of ion exchange water at 40 ° C., and stirred and washed at 280 rpm for 20 minutes.
This operation was repeated five more times. When the pH of the filtrate was 6.95, the electric conductivity was 9.4 μS / cm, and the surface tension was 71.1 Nm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. went. Next, vacuum drying was performed for 12 hours to obtain toner 1.

  The particle diameter of the obtained toner 1 was measured with a Coulter counter. The volume average particle diameter D50 was 5.7 μm, and the volume average particle size distribution index (GSDv) was 1.22. Further, the shape factor (SF1) of the toner 1 obtained from the shape observation by Luzex was 128.9, and it was confirmed to be a potato shape. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 11 atm%.

(Manufacture of toner 2)
The amount of the resin fine particle dispersion 1 is 95 parts by weight, the colorant dispersion 2 is 164 parts by weight instead of the colorant dispersion 1, and the release agent dispersion 2 is 51 parts by weight instead of the release agent dispersion 1. Except for the above, toner 2 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 5.5 μm and a volume average particle size distribution index (GSDv) of 1.29. Further, the shape factor (SF1) of the toner particles obtained from the shape observation by Luzex was 115.8, and it was confirmed to be spherical. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 39 atm%.

(Manufacture of toner 3)
116 parts by weight of the resin fine particle dispersion 1, 85 parts by weight of the colorant dispersion 3 instead of the colorant dispersion 1, and 41 parts by weight of the release agent dispersion 3 instead of the release agent dispersion 1 Except for the above, toner 3 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 5.7 μm and a volume average particle size distribution index (GSDv) of 1.24. Further, the shape factor (SF1) of the toner particles obtained by shape observation with Luzex was 139.8, and it was confirmed to be a potato shape. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 20 atm%.

(Manufacture of toner 4)
95 parts by weight of the resin fine particle dispersion 1, 85 parts by weight of the colorant dispersion 4 instead of the colorant dispersion 1, and 58 parts by weight of the release agent dispersion 4 instead of the release agent dispersion 1 Except for the above, toner 4 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 5.8 μm and a volume average particle size distribution index (GSDv) of 1.21. Further, the shape factor (SF1) of the toner particles obtained from the observation of the shape with Luzex was 118.9, and it was confirmed to be spherical. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 35 atm%.

(Manufacture of toner 5)
The resin fine particle dispersion 2 is used instead of the resin fine particle dispersion 1, and 111 parts by weight of the colorant dispersion 5 is used instead of the colorant dispersion 1, and the release agent dispersion 5 is used instead of the release agent dispersion 1. A toner 5 was obtained in the same manner as in the production of the toner 1 except that the amount was 43 parts by weight.
The obtained toner had a volume average particle size of 5.5 μm and a volume average particle size distribution index (GSDv) of 1.23. Further, the shape factor (SF1) of the toner particles obtained by shape observation with Luzex was 135.8, and it was confirmed to be a potato shape. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 15 atm%.

(Manufacture of toner 6)
From the following components, 77 parts by weight of colorant fine particles obtained by solid-liquid separation of the colorant dispersion 6 using a No5A filter paper and 63 parts by weight of release agent fine particles obtained by solid-liquid separation of the release agent dispersion 10 using a No5A filter paper are used. To the resulting mixture.
-Styrene (made by Wako Pure Chemical Industries): parts by weight-n-butyl acrylate (made by Wako Pure Chemical Industries): 275 parts by weight-β-carboxyethyl acrylate (made by Rhodia Nikka): 9 parts by weight-1'10 decanediol diacrylate (new) Nakamura Chemical Co., Ltd.): 1.5 parts by weight Dodecanethiol (manufactured by Wako Pure Chemical Industries): 2.7 parts by weight Subsequently, the mixture was stirred at 60 ° C. for 15 minutes, and then azobisisobutylnitrile (Japanese 24.5 parts by weight (manufactured by Hikari Pure Chemical) was added and stirred vigorously for 1 minute.

  Next, 35 g of calcium phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) is added to 2000 parts by weight of pure water in a 3 L flask, and the whole amount is added to a dispersion that is dispersed at 58 ° C. for 15 minutes with a homogenizer (IKA Ultra Tarrax T50) for 5 minutes. Granulated. Thereafter, while rapidly purging with nitrogen, the reaction flask was kept at 75 ° C. and reacted for 8 hours to obtain suspended particles having a particle diameter of 6.1 μm.

Then, after cooling to room temperature, 30 mL of 1N HCl solution was added to dissolve and remove calcium phosphate, and solid-liquid separation was performed with No5A filter paper. The rinse with pure water was then repeated until the filtrate was neutral. After solid-liquid separation, the toner 6 was obtained by drying.
This toner had a volume average particle diameter D50 of 6.3 μm and a volume average particle size distribution index (GSDv) of 1.29. In addition, it was observed that the shape factor SF1 of the toner particles obtained from the shape observation by Luzex was 110.5 and was spherical. The amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS) and found to be 13 atm%.

(Manufacture of toner 7)
80 parts by weight of the resin fine particle dispersion 1, 85 parts by weight of the colorant dispersion 7 instead of the colorant dispersion 1, and 71 parts by weight of the release agent dispersion 6 instead of the release agent dispersion 1 Except for the above, toner 7 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 5.3 μm and a volume average particle size distribution index (GSDv) of 1.34. Further, the shape factor (SF1) of the toner particles obtained from the shape observation by Luzex was 142.8, and it was confirmed to be a potato shape. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 45 atm%.

(Manufacture of toner 8)
The amount of the resin fine particle dispersion 1 is 104 parts by weight, the colorant dispersion 8 is 166 parts by weight instead of the colorant dispersion 1, and the release agent dispersion 7 is 28 parts by weight instead of the release agent dispersion 1. Except for the above, toner 8 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 5.9 μm and a volume average particle size distribution index (GSDv) of 1.31. Further, the shape factor (SF1) of the toner particles obtained from the shape observation by Luzex was 105.2, and it was confirmed to be spherical. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 43 atm%.

(Manufacture of toner 9)
97 parts by weight of resin fine particle dispersion 1, 165 parts by weight of colorant dispersion 9 instead of colorant dispersion 1, and 28 parts by weight of release agent dispersion 8 instead of release agent dispersion 1 A toner 9 was obtained in the same manner as in the production of the toner 1 except that.
The obtained toner had a volume average particle size of 5.6 μm and a volume average particle size distribution index (GSDv) of 1.32. Further, the shape factor (SF1) of the toner particles obtained from the shape observation by Luzex was 109.2, and it was confirmed to be spherical. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 5 atm%.

(Manufacture of toner 10)
Instead of resin fine particle dispersion 1, 110 parts by weight of resin fine particle dispersion 2, 85 parts by weight of colorant dispersion 10 instead of colorant dispersion 1, and release agent dispersion instead of release agent dispersion 1 A toner 10 was obtained in the same manner as in the production of the toner 1 except that 9 was changed to 62 parts by weight.
The obtained toner had a volume average diameter of 5.7 μm and a volume average particle size distribution index (GSDv) of 1.31. Further, the shape factor (SF1) of the toner particles obtained from the shape observation by Luzex was 145.1, and it was confirmed to be a potato shape. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 45 atm%.

(Manufacture of toner 11)
Instead of the colorant dispersion 6, 48 parts by weight of the colorant fine particles separated from the colorant dispersion 10 are used, and 141 parts by weight of the release agent fine particles separated from the release agent dispersion 11 instead of the release agent dispersion 10. A toner 11 was obtained in the same manner as in Toner Production 6 except that was used.
The obtained toner had a volume average particle diameter D50 of 6.5 μm and a particle size distribution coefficient of 1.32. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 108.1, and it was spherical. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 8 atm%.

(Manufacture of toner 12)
127 parts by weight of resin fine particle dispersion 1, 85 parts by weight of colorant dispersion 11 instead of colorant dispersion 1, 27 parts by weight of release agent dispersion 12 instead of release agent dispersion 1 Except for the above, toner 12 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 5.9 μm and a volume average particle size distribution index (GSDv) of 1.33. Further, the shape factor (SF1) of the toner particles obtained from the shape observation by Luzex was 105.8, and it was confirmed to be spherical. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 9 atm%.

(Manufacture of toner 13)
59 parts by weight of the resin fine particle dispersion 1, 183 parts by weight of the colorant dispersion 12 instead of the colorant dispersion 1, and 71 parts by weight of the release agent dispersion 13 instead of the release agent dispersion 1 Except for the above, toner 13 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 6.2 μm and a volume average particle size distribution index (GSDv) of 1.34. Further, the shape factor (SF1) of the toner particles obtained from the shape observation by Luzex was 143.5, and it was confirmed to be a potato shape. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 43 atm%.

(Manufacture of toner 14)
The amount of the resin fine particle dispersion 1 is 111 parts by weight, the colorant dispersion 13 is 224 parts by weight instead of the colorant dispersion 1, and the release agent dispersion 14 is 59 parts by weight instead of the release agent dispersion 1. Except for the above, toner 14 was obtained in the same manner as in the production of toner 1.
The obtained toner had a volume average particle size of 5.5 μm and a volume average particle size distribution index (GSDv) of 1.32. Further, the shape factor (SF1) of the toner particles obtained by shape observation with Luzex was 142.3, and it was confirmed to be a potato shape. When the amount of the release agent (exposure rate) on the surface of the toner was measured by X-ray electron spectroscopy (XPS), it was 43 atm%.

(Preparation of external additive toner and adjustment of developer)
To 50 g of the produced toner, 0.21 g of hydrophobic silica (manufactured by Cabot, TS720) was added and blended with a sample mill to prepare an externally added toner.
Next, the above externally added toner is weighed to a ferrite carrier having an average particle diameter of 50 μm coated with 1% by weight of methacrylate (manufactured by Soken Chemical Co., Ltd.) so that the toner concentration becomes 5% by weight and stirred and mixed for 5 minutes by a ball mill. The developer was adjusted.

(Example 1)
The developer fixability adjusted using toner 1 is adjusted to a toner loading of 4.5 g / m ² using a modified Docu Center Color 400 (hereinafter sometimes abbreviated as “DCC400”) manufactured by Fuji Xerox Co., Ltd. After image formation, the image was fixed using a high-speed, low-pressure, low-power type fixing machine at a fixing speed of 200 mm / sec under a nip width of 6.5 mm. As a result, the releasability at the time of fixing was good, and it was confirmed that the film was peeled without any resistance, and no offset was generated. Also, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was good.
Furthermore, when a copy test of 10,000 sheets was performed with a modified copier manufactured by Fuji Xerox Co., Ltd. Docu Center Color 500 (hereinafter sometimes abbreviated as "DCC500"), no toner scattering or fogging was observed, and a good density was obtained. A vivid image was obtained. Further, the color developability of the image was good and fine color reproduction was obtained.

(Example 2)
The developer fixability adjusted using toner 2 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine, and then printed, and then a high speed, low pressure, low power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. As a result, the releasability at the time of fixing was good, and it was confirmed that the film was peeled without any resistance, and no offset was generated. Also, no image defect was observed when the fixed image was folded in two and stretched again.
Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was good.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., no toner scattering or fogging was observed, and a vivid image with a good density was obtained. Further, the color developability of the image was good and fine color reproduction was obtained.

(Example 3)
After adjusting the developer fixability adjusted using toner 3 to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine, and then printing, a high-speed, low-pressure, low-power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. As a result, the releasability at the time of fixing was good, and it was confirmed that the film was peeled without any resistance, and no offset was generated. Also, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was good.
Further, when a copying test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., no toner scattering or fogging was observed, and a vivid image with a good density was obtained. Further, the color developability of the image was good and fine color reproduction was obtained.

Example 4
The developer fixability adjusted using toner 4 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine, and then printed, and then a high speed, low pressure, low power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. As a result, the releasability at the time of fixing was good, and it was confirmed that the film was peeled without any resistance, and no offset was generated. Also, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was good.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., no toner scattering or fogging was observed, and a vivid image with a good density was obtained. Further, the color developability of the image was good and fine color reproduction was obtained.

(Example 5)
Adjust the developer fixability adjusted using toner 5 to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine, and then use a high-speed, low-pressure, low-power type fixing machine. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. As a result, the releasability at the time of fixing was good, and it was confirmed that the film was peeled without any resistance, and no offset was generated. Also, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was good.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., no toner scattering or fogging was observed, and a vivid image with a good density was obtained. Further, the color developability of the image was good and fine color reproduction was obtained.

(Example 6)
The developer fixability adjusted using toner 6 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine and then printed, and then a high-speed, low-pressure, low-power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. As a result, the releasability at the time of fixing was good, and it was confirmed that the film was peeled without any resistance, and no offset was generated. Also, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was good.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., no toner scattering or fogging was observed, and a vivid image with a good density was obtained. Further, the color developability of the image was good and fine color reproduction was obtained.

(Comparative Example 1)
The developer fixability adjusted using toner 7 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine and then printed, and then a high speed, low pressure, low power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The peelability of the fixing machine was poor, and gloss unevenness due to poor peeling of the fixed image occurred. Furthermore, hot offset occurred. However, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The sheet was dull and the transparency was low.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging occurred, and dullness was observed in the image. Further, the color developability of the image was low and the image density was not good.

(Comparative Example 2)
The developer fixability adjusted using toner 8 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine and then printed, and then a high speed, low pressure, low power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The releasability with this fixing machine was poor, and winding around the roll occurred. In addition, a cold offset occurred. Further, an image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was low.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging were not observed, but the applied amount did not appear, and the image density became thin. Further, the color developability of the image was low and the image density was not good.

(Comparative Example 3)
After adjusting the fixing property of the developer adjusted using toner 9 to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine, a high-speed, low-pressure, low-power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The releasability with this fixing machine was poor, and winding around the roll occurred. In addition, a cold offset occurred. Further, an image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The transparency of the sheet was low.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging were not observed, but the applied amount did not appear, and the image density became thin. Furthermore, the color developability of the image was also low.

(Comparative Example 4)
After adjusting the fixability of the developer adjusted using toner 10 to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine, a high-speed, low-pressure, low-power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The peelability of the fixing machine was poor, and gloss unevenness due to poor peeling of the fixed image occurred. Furthermore, hot offset occurred. However, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The sheet was dull and the transparency was low.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging occurred, and dullness was observed in the image. Furthermore, the color developability of the image and the image density were also low.

(Comparative Example 5)
The developer fixability adjusted using toner 11 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine and then printed, and then a high speed, low pressure, low power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The peelability of the fixing machine was poor, and gloss unevenness due to poor peeling of the fixed image occurred. Furthermore, hot offset occurred. However, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The sheet was dull and the transparency was low.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging occurred, and dullness was observed in the image. Furthermore, the color developability and image density of the image were also low.

(Comparative Example 6)
After adjusting the fixing property of the developer adjusted using toner 12 to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine, a high-speed, low-pressure, low-power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The releasability with this fixing machine was poor, and winding around the roll occurred. In addition, a cold offset occurred. Further, an image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The sheet was dull and the transparency was low.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging occurred, and dullness was observed in the image. Furthermore, the color developability and image density of the image were also low.

(Comparative Example 7)
The developer fixability adjusted using toner 13 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine and then printed, and then a high speed, low pressure, low power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The peelability of the fixing machine was poor, and gloss unevenness due to poor peeling of the fixed image occurred. Furthermore, hot offset occurred. However, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The sheet was dull and the transparency was low.
Further, when a copy test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging were not observed, but the applied amount did not appear, and the image density became thin. Furthermore, the color developability of the image was also low.

(Comparative Example 8)
The developer fixability adjusted using toner 14 is adjusted to a toner loading of 4.5 g / m ² using a DCC400 remodeling machine and then printed, and then a high-speed, low-pressure, low-power type fixing machine is used. Fixing was performed at a fixing speed of 200 mm / sec with a nip width of 6.5 mm. The peelability of the fixing machine was poor, and gloss unevenness due to poor peeling of the fixed image occurred. Furthermore, hot offset occurred. However, no image defect was observed when the fixed image was folded in two and stretched again.

Also, after adjusting the toner applied amount to 3.5 g / m ² using a DCC400 remodeling machine and printing out, the OHP fixed at a fixing speed of 50 mm / sec using a high-speed, low-pressure, low-power type fixing machine. The sheet was dull and the transparency was low.
Further, when a copying test of 10,000 sheets was performed with a DCC500 modified copier manufactured by Fuji Xerox Co., Ltd., toner scattering and fogging occurred, and dullness was observed in the image. Furthermore, the color developability and image density of the image were also low.

  Table 1 shows the precoat colorants contained in the colorant dispersion used in the preparation of the toners used in the examples / comparative examples. Table 2 shows the precoat colorants used in the preparation of the toners used in the examples / comparative examples. About the precoat mold release agent contained in a mold release agent dispersion liquid, what summarized each about the result of the Example / comparative example is shown in Table 3, respectively.

It is a schematic diagram for demonstrating the analysis method of the graph obtained by the differential thermal analysis of a core mold release agent.

Claims (6)

In a mold release agent for toner production comprising a core mold release agent and a coating resin for coating the core mold release agent,
When the acid value of the coating resin is in the range of 3.0~6.0meq / mg-KOH, the coating resin is SO ₃ ^- releasing agent for toner production, which comprises a group ^- group and COO. In a colorant for toner production comprising a core colorant and a coating resin for coating the core colorant,
When the acid value of the coating resin is in the range of 3.0~6.0meq / mg-KOH, the coating resin is SO ₃ ^- Toner Production coloring agent characterized in that it comprises a group ^- group and COO. In the electrostatic charge developing toner produced using at least a binder resin, a release agent, and a colorant,
The toner for electrostatic charge development, wherein the release agent is the release agent for toner production according to claim 1. In the electrostatic charge developing toner produced using at least a binder resin, a release agent, and a colorant,
An electrostatic charge developing toner, wherein the colorant is the release agent for toner production according to claim 2.   5. The toner according to claim 3, wherein the binder resin, the release agent for toner production according to claim 1, and the colorant for toner production according to claim 2 are used at least. The toner for developing electrostatic charge according to 1. A flocculant is added to a mixed solution in which a resin fine particle dispersion in which resin fine particles having a volume average particle diameter of 1 μm or less are dispersed, a release agent dispersion, and a colorant dispersion are mixed to form an aggregate. 6. The method according to claim 3, wherein the agglomeration step is performed and at least a fusion step of fusing and coalescing the aggregate by heating to a temperature equal to or higher than a glass transition temperature of the resin fine particles contained therein. In the method for producing the electrostatic charge developing toner according to claim 1,
The release agent dispersion liquid contains the release agent for toner production according to claim 1, and / or the colorant dispersion liquid contains the colorant for toner production according to claim 2. A method for producing a toner for developing electrostatic charge, which is characterized.

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