JP2014186128A - Glittering toner, developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glittering toner with which glittering images having a high excellent glittering property and image intensity.SOLUTION: There is provided a glittering toner including glittering pigment having a volume average particle diameter of 1 μm or more and 15 μm or less, a maximum particle diameter of 30 μm or more and 50 μm or less, and a ratio of particles having a particle diameter of 20 μm or more accounting for the entire particles of 5% or more and 20% or less, which are measured by a coulter counter method.

Description

  The present invention relates to a glitter toner, a developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  For the purpose of forming an image having a brightness such as a metallic luster, glittering toner is used.

In order to provide a toner for developing an electrostatic image capable of outputting a silver color, in the toner for developing an electrostatic image containing at least a colorant and a resin, the colorant contains silver, zinc and aluminum as main components, An electrostatic charge image developing toner is disclosed in which the average particle diameter of the colorant is 0.5 to 25 μm and the apparent density is 0.7 to 3.0 g / cm ³ (for example, Patent Documents). 1).

  In addition, in order to provide a toner capable of forming an image having excellent glitter, when a solid image is formed, the image is measured when incident light with an incident angle of −45 ° is irradiated by a goniophotometer. A toner is disclosed in which the ratio (A / B) of the reflectance A at a light reception angle + 30 ° and the reflectance B at a light reception angle −30 ° is 2 or more and 100 or less (see, for example, Patent Document 2). ).

  In order to provide a developer that maintains the brightness of the formed image even when the environmental humidity varies, when a solid image is formed, the incident angle is −45 by a goniophotometer. A toner having a ratio (A / B) of a reflectance A at a light receiving angle of + 30 ° and a reflectance B at a light receiving angle of −30 ° (A / B) of 2 or more and 100 or less measured when irradiated with incident light of A core particle having an internal porosity of 8% or less, and a (meth) acrylic acid ester having a cycloalkyl group in the side chain provided on the surface of the core particle and a (meth) acrylic acid ester having a nitrogen atom in the side chain A developer containing a carrier having a resin layer containing a copolymer is disclosed (for example, see Patent Document 3).

JP 2006-039475 A JP 2012-032765 A JP 2012-022156 A

  An object of the present invention is to provide a glittering toner on which a glittering image having excellent glitter and image strength is formed.

Specific means for achieving the above object are as follows.
That is, the invention according to claim 1
The volume average particle diameter measured by the Coulter counter method is 1 μm or more and 15 μm or less, the maximum particle diameter is 30 μm or more and 50 μm or less, and the ratio of particles having a particle diameter of 20 μm or more in the whole particle is 5% on a volume basis. It is a glittering toner containing a glittering pigment that is 20% or less.

The invention according to claim 2
A developer comprising at least the glittering toner according to claim 1.

The invention according to claim 3
A toner cartridge containing the glitter toner according to claim 1.

The invention according to claim 4
A process cartridge comprising: a toner holder that accommodates and conveys the glitter toner according to claim 1.

The invention according to claim 5
An image carrier,
A charging device for charging the surface of the image carrier;
A latent image forming apparatus for forming an electrostatic latent image on the surface of the image carrier;
A developing device that develops the electrostatic latent image as a toner image with the glitter toner according to claim 1;
A transfer device for transferring the toner image formed on the surface of the image carrier onto a recording medium;
An image forming apparatus having

The invention according to claim 6
A charging step for charging the surface of the image carrier;
A latent image forming step of forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image as a toner image with the glitter toner according to claim 1;
A transfer step of transferring the toner image formed on the surface of the image carrier onto a recording medium;
Is an image forming method.

The invention according to claim 7 provides:
The image forming method according to claim 6, wherein the smoothness measured based on JIS P8119: 1998 on the surface of the recording medium on which the toner image is transferred is 20 seconds or more and 20000 seconds or less.

According to the first aspect of the present invention, there is provided a glitter toner capable of forming a glitter image having excellent glitter and image strength as compared with a case where a specific glitter pigment is not included.
According to the second aspect of the present invention, there is provided a developer capable of forming a glitter image having excellent glitter and image strength as compared with a case where a specific glitter pigment is not included.
According to the third aspect of the present invention, there is provided a toner cartridge containing glitter toner that forms a glitter image having excellent glitter and image strength as compared with the case where a specific glitter pigment is not included. .
According to the fourth aspect of the present invention, there is provided a process cartridge that accommodates a glitter toner that forms a glitter image having excellent glitter and image intensity as compared with a case where a specific glitter pigment is not included. .
According to the fifth aspect of the present invention, there is provided an image forming apparatus using a glitter toner that forms a glitter image having excellent glitter and image intensity as compared with a case where a specific glitter pigment is not included. The
According to the sixth aspect of the present invention, there is provided an image forming method using a glitter toner that forms a glitter image having excellent glitter and image strength as compared with a case where a specific glitter pigment is not included. The
According to the invention of claim 7, even if the smoothness measured based on JIS P8119: 1998 on the surface of the recording medium on which the toner image is transferred is in the range of 20 seconds to 20000 seconds, A glitter image having excellent glitter and image intensity is formed.

It is a figure for demonstrating the relationship between the smoothness of the surface of a recording medium, and the magnitude | size of a luster pigment. FIG. 3 is a cross-sectional view schematically illustrating a toner according to an exemplary embodiment. 1 is a schematic configuration diagram illustrating an image forming apparatus to which the exemplary embodiment is applied. It is a schematic block diagram which shows an example of the process cartridge of this embodiment.

  Hereinafter, embodiments of the glitter toner, developer, toner cartridge, process cartridge, image forming apparatus, and image forming method of the present invention will be described.

<Brightness toner>
The glittering toner of the present embodiment (hereinafter sometimes referred to as the toner of the present embodiment) has a volume average particle size of 1 μm or more and 15 μm or less and a maximum particle size of 30 μm or more and 50 μm as measured by a Coulter counter method. The composition contains a glittering pigment having a ratio of particles having a particle diameter of 20 μm or more to the whole particles of 5% to 20% on a volume basis.

  As the glitter pigment contained in the glitter toner, a flat pigment may be used conventionally. When forming a brilliant image using a brilliant toner containing a flat-shaped brilliant pigment, in order to obtain a highly brilliant image that is one of the indicators of brilliant feeling, the brilliant pigment is used as the lowest layer of the image. It is important that the flat surface of the flat glittering pigment is oriented with respect to the paper (recording medium). In the prior art, when glossy paper with excellent smoothness on the surface of the recording medium is used, an image with high glossiness can be obtained, but when using paper with poor surface smoothness such as plain paper or rough paper, In some cases, glitter was not obtained.

FIG. 1 is a diagram for explaining the relationship between the smoothness of the surface of a recording medium and the size of the glitter pigment. FIG. 1A shows the case where a glitter pigment having a relatively large particle diameter is used. FIG. 1B shows a case where a bright pigment having a relatively small particle diameter is used. In FIGS. 1A and 1B, the surface of the paper 10 having inferior surface smoothness has a glitter pigment 12 (a pigment having a relatively large particle diameter, FIG. 1A) or a glitter pigment. A toner image 16 or a toner image 18 including 14 (a pigment having a relatively small particle diameter, FIG. 1B) is formed.
Comparing FIG. 1A and FIG. 1B, the bright pigment 12 having a relatively large particle size is more effective on the surface of the paper 10 than the bright pigment 14 having a relatively small particle size. It is difficult to be affected by the unevenness, and the bright pigment 12 is difficult to follow the unevenness on the surface of the paper 10. As a result, the toner image 16 containing the glitter pigment 12 is less likely to cause irregular reflection of light, and the toner image 16 is an image having excellent glitter.
On the other hand, the bright pigment 14 having a relatively small particle size is more susceptible to the unevenness of the surface of the paper 10 than the bright pigment 12 having a relatively large particle size. It is easy to follow the surface irregularities. As a result, the toner image 18 containing the glitter pigment 14 is likely to cause irregular reflection of light, and the toner image 18 is an image having inferior glitter.

From the above, it is presumed that if the particle size of the glitter pigment is large, the toner image is less affected by the unevenness of the paper surface, and as a result, the glitter is improved.
On the other hand, if the particle diameter of the glitter pigment is too large, the glitter pigment is likely to protrude from the surface of the toner image, so that a portion where the glitter pigment is not covered with the binder resin occurs, and the strength of the spot may be reduced. . Therefore, there is a limit to increase the particle size of the glitter pigment for the purpose of improving the glitter. In addition, as the particle size of the glitter pigment increases, the particle size of the toner containing the glitter pigment may also increase. If the particle size of the toner is too large, it may be difficult to use the toner. From the viewpoint of mastering, there is a limit to the upper limit of the particle size of the glitter pigment.
As a result of intensive studies, the present inventors have found that by using a glitter pigment having a specific particle diameter, it is possible to obtain a glitter toner that forms a glitter image having excellent glitter and image strength. Was completed.
The toner of the present exemplary embodiment is particularly effective when a paper having poor surface smoothness such as plain paper or rough paper is used.

-Evaluation of glitter-
Using a modified device (apparatus) of Apeos Port-II4300 manufactured by Fuji Xerox Co., Ltd., in a high temperature and high humidity environment (30 ° C./85% RH) and in a low temperature and low humidity environment (10 ° C., 15% RH) Under each environment, a writing test was performed in which 100,000 solid images were continuously written on a recording medium (P paper manufactured by Fuji Xerox). Then, after the writing test on the 100,000th sheet, the amount of applied toner on a recording paper (OK topcoat + paper, manufactured by Oji Paper Co., Ltd.) at a fixing temperature of 180 ° C. and a fixing pressure of 4.0 kg / cm ² . A solid image of 5 cm × 5 cm having a weight of 4.5 g / cm ² was formed. A direction in which the solid image is tilted by −45 ° with respect to the vertical direction of the surface of the solid image using a three-dimensional spectral change colorimeter DDS5000 spectrocolorimeter three-dimensional goniophotometer (manufactured by Nippon Denshoku Industries Co., Ltd.) The lightness index L * 45 ° obtained by irradiating light from the surface and receiving light in the vertical direction of the surface of the solid image and the lightness index obtained by receiving light in a direction inclined by 30 ° with respect to the vertical direction of the surface of the solid image L * 15 ° and the lightness index L * 110 ° obtained by receiving light in a direction inclined by −65 ° with respect to the vertical direction of the surface of the solid image are measured. Then, each lightness index was substituted into the following equation to measure a flop index value (Flop Index value; FI).

FI = 2.69 × (L * 15 ° −L * 110 °) ^1.11 / (L * 45 °) ^0.86

The evaluation criteria are as follows.
◎: Flop index value is 12.5 or more ○: Flop index value is 10.0 or more and less than 12.5 △: Flop index value is 5.0 or more and less than 10.0, actual usable level ×: Flop index value is 0 More than 5.0

A flop index value of 5 or more indicates that there is more reflection on the side opposite to the incident side (angle + side) than on the side on which incident light enters (angle-side). This shows that the irregular reflection of light is suppressed. When irregular reflection occurs in which incident light is reflected in various directions, the color looks dull when the reflected light is visually confirmed. Therefore, when the flop index value is less than 5, the gloss cannot be confirmed even when the reflected light is viewed, and the glossiness may be inferior.
On the other hand, if the flop index value exceeds 50, the viewing angle at which the reflected light can be visually recognized becomes too narrow, and the specularly reflected light component is large, so that it may appear black depending on the viewing angle. In addition, it is difficult to manufacture a toner having a flop index value exceeding 50.

  The flop index value is preferably 5 or more and 50 or less, more preferably 10 or more and 40 or less, and particularly preferably 15 or more and 30 or less.

<Configuration of toner>
The toner of the present exemplary embodiment preferably satisfies the following requirements (1) to (2) from the viewpoint of satisfying the above-described flop index value.
(1) The average equivalent circle diameter D is longer than the average maximum thickness C of the toner. (2) When the cross section in the thickness direction of the toner is observed, the long axis direction of the toner and the long axis of the pigment particles The number of pigment particles whose angle to the direction is in the range of −30 ° to + 30 ° is 60% or more of all the observed pigment particles.

Here, FIG. 2 is a cross-sectional view schematically showing a toner that satisfies the requirements (1) to (2). The schematic diagram shown in FIG. 2 is a cross-sectional view in the thickness direction of the toner.
The toner 2 shown in FIG. 2 is a flat toner having an equivalent circle diameter longer than the thickness L, and contains scale-like pigment particles 4 (corresponding to a bright pigment).

As shown in FIG. 2, when the toner 2 has a flat shape having a circle-equivalent diameter longer than the thickness L, the toner moves to an image carrier, an intermediate transfer member, a recording medium, etc. At this time, since the toner tends to move so as to cancel the charge to the maximum, it is considered that the toners are arranged so that the area to be adhered becomes the maximum. That is, on the recording medium to which the toner is finally transferred, it is considered that the flat toner is arranged so that the flat surface side faces the recording medium surface. Also in the fixing step of image formation, it is considered that the flat toner is aligned so that the flat surface side faces the recording medium surface due to the pressure during fixing.
Therefore, among the scale-like pigment particles contained in the toner, “the angle between the major axis direction in the cross section of the toner and the major axis direction of the pigment particles is −30 ° to + 30 ° shown in the above (2). It is considered that the pigment particles satisfying the requirement “in the range” are arranged so that the surface side having the largest area faces the recording medium surface. When the image formed in this way is irradiated with light, the ratio of the pigment particles that diffusely reflect the incident light is suppressed, so that the above-described flop index value range is considered to be achieved. In addition, when the ratio of pigment particles that diffusely reflect incident light is suppressed, the reflected light intensity varies greatly depending on the viewing angle, so that more ideal glitter can be obtained.

  Next, components constituting the toner of the exemplary embodiment will be described.

-Bright pigment-
In the present embodiment, the volume average particle diameter is 1 μm or more and 15 μm or less, the maximum particle diameter is 30 μm or more and 50 μm or less, and the particle diameter occupying the whole particle is measured by a Coulter counter method (electric detection zone method). A bright pigment having a ratio of particles having a particle diameter of 20 μm or more of 5% or more and 20% or less is used.
When the volume average particle diameter of the glitter pigment is less than 1 μm, there may be a problem that the glitter is lowered. On the other hand, if the volume average particle diameter of the glitter pigment exceeds 15 μm, problems such as transfer failure may occur. The volume average particle size of the glitter pigment is preferably 3 μm or more and 12 μm or less, more preferably 5 μm or more and 10 μm or less.
If the maximum particle size of the glitter pigment is less than 30 μm, the glitter of the toner image may be lowered. On the other hand, when the maximum particle diameter of the glitter pigment exceeds 50 μm, the glitter of the toner image is improved, but the image strength may be deteriorated. The maximum particle size of the glitter pigment is preferably 20 μm or more and 45 μm or less, and more preferably 30 μm or more and 40 μm or less.
When the ratio of particles having a particle diameter of 20 μm or more in the entire particles in the glitter pigment is less than 5%, the glitter of the toner image may be lowered. On the other hand, when the proportion of particles having a particle diameter of 20 μm or more in the entire particles in the glitter pigment exceeds 20%, the image strength may be deteriorated. The ratio of particles having a particle diameter of 20 μm or more to the entire particles in the glitter pigment is preferably 7.5% or more and 17.5% or less, and more preferably 10% or more and 15% or less.

In this embodiment, when measuring the particle diameter by the Coulter counter method, a dispersion prepared as follows is used.
Wet the sample to be measured in ion-exchanged water using a surfactant, etc., and disperse the aqueous solution that has been subjected to dispersion treatment with an ultrasonic disperser if necessary using an electrolytic solution (Iston II-PC) The liquid was adjusted.
In this embodiment, the particle diameter is measured under the following conditions using the dispersion prepared as described above.
The measurement was performed using Multisizer II (manufactured by Coulter) using an aperture tube of 100 μm.

In the present embodiment, the maximum particle size of the glitter pigment means a particle size of 1% of the cumulative distribution (on the sieve).
In the present embodiment, “the ratio of particles having a particle diameter of 20 μm or more in the whole particle is 5% or more and 20% or less on a volume basis” means that the particle diameter in the particle size distribution on the volume basis of the glitter pigment. Means that the cumulative distribution (on the sieve) of particles of 20 μm or more is 5% or more and 20% or less.

  The components of the glitter pigment used in the present embodiment include metal powders such as aluminum, brass, bronze, nickel, stainless steel and zinc, mica coated with titanium oxide and yellow iron oxide, barium sulfate, layered silicate, layered Brightness such as coated flaky inorganic crystal substrate such as aluminum silicate, single crystal plate titanium oxide, basic carbonate, bismuth acid oxychloride, natural guanine, flaky glass powder, flaky glass powder with metal vapor deposition, etc. There is no particular limitation as long as it has properties.

  The content of the glitter pigment in the toner of the exemplary embodiment is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the binder resin described later. desirable.

-Binder resin-
Examples of the binder resin used in the present embodiment include ethylene resins such as polyester, polyethylene, and polypropylene; styrene resins such as polystyrene and α-polymethylstyrene; and (meth) acrylic resins such as polymethyl methacrylate and polyacrylonitrile. Resin; Polyamide resin, polycarbonate resin, polyether resin and copolymer resins thereof may be used. Among these, it is desirable to use a polyester resin that has a high smoothness on the surface of a fixed image and realizes further glitter.
In the following, polyester resins that are particularly desirably used will be described.

The polyester resin of this embodiment is obtained mainly by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols, for example.
Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and other aromatic carboxylic acids; maleic anhydride, fumaric acid, succinic acid, Examples thereof include aliphatic carboxylic acids such as alkenyl succinic anhydride and adipic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and one or more of these polycarboxylic acids are used.
Among these polyvalent carboxylic acids, it is desirable to use an aromatic carboxylic acid, and in order to secure a good fixing property, a trivalent or higher carboxylic acid (trimellitic acid) is used together with a dicarboxylic acid to form a crosslinked structure or a branched structure. And acid anhydrides thereof) are preferably used in combination.

Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentylglycol, and glycerin; cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol And alicyclic diols such as A; aromatic diols such as ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A. One or more of these polyhydric alcohols are used.
Among these polyhydric alcohols, aromatic diols and alicyclic diols are desirable, and among these, aromatic diols are more desirable. In order to secure better fixability, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol in order to take a crosslinked structure or a branched structure.

(Production method of polyester resin)
There is no restriction | limiting in particular as a manufacturing method of a polyester resin, It manufactures with the general polyester polymerization method which makes an acid component and an alcohol component react. For example, direct polycondensation, transesterification, and the like are used depending on the type of monomer. The molar ratio (acid component / alcohol component) at the time of reacting the acid component with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated. Degree is desirable.

  Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compound; phosphorous acid compound; phosphoric acid compound; and amine compound.

-Release agent-
Examples of the release agent used in the present embodiment include paraffin waxes such as low molecular weight polypropylene and low molecular weight polyethylene; silicone resins; rosins; rice wax; carnauba wax; The melting temperature of these release agents is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 95 ° C. or lower.
The content of the release agent in the toner is desirably 0.5% by mass or more and 15% by mass or less, and more desirably 1.0% by mass or more and 12% by mass or less.

-Other additives-
In the present embodiment, in addition to the components described above, various components such as an internal additive, a charge control agent, inorganic powder (inorganic particles), and organic particles may be used as necessary.

  Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes containing complexes of aluminum, iron, chromium, and triphenylmethane pigments.

  As the inorganic particles, for example, known inorganic particles such as silica particles, titanium oxide particles, alumina particles, cerium oxide particles, or those obtained by hydrophobizing the surface thereof may be used alone or in combination of two or more kinds. Good. Among these, silica particles having a refractive index smaller than that of the binder resin are desirably used. Further, the silica particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like are desirably used.

-Toner characteristics-
・ Average maximum thickness C and average equivalent circle diameter D
As shown in (1) above, it is desirable that the toner of this embodiment has an average equivalent circle diameter D longer than the average maximum thickness C. The ratio (C / D) of the average maximum thickness C to the average equivalent circle diameter D is preferably in the range of 0.001 to 0.500, more preferably in the range of 0.010 to 0.200. Desirably, the range from 0.050 to 0.100 is particularly desirable.
When the ratio (C / D) is 0.001 or more, the strength of the toner is ensured, breakage due to stress during image formation is suppressed, charging is reduced due to exposure of the pigment, and fog is generated as a result. Is suppressed. On the other hand, when it is 0.500 or less, excellent glitter can be obtained.

The average maximum thickness C and the average equivalent circle diameter D are measured by the following methods.
The toner is placed on a smooth surface, and is vibrated and dispersed so that there is no unevenness. For 1000 toners, the color laser microscope “VK-9700” (manufactured by Keyence Corporation) was magnified 1000 times to measure the maximum thickness C and the equivalent circle diameter D of the surface viewed from above, and the arithmetic average of them. Calculate by finding the value.

The angle between the major axis direction in the cross section of the toner and the major axis direction of the pigment particles As shown in (2) above, when the cross section in the thickness direction of the toner is observed, the major axis direction in the cross section of the toner and the pigment The number of pigment particles whose angle with the major axis direction of the particles is in the range of −30 ° to + 30 ° is desirably 60% or more of the total pigment particles observed. Furthermore, the number is more preferably 70% or more and 95% or more, and particularly preferably 80% or more and 90% or less.
When the number is 60% or more, excellent glitter can be obtained.

Here, a method for observing the cross section of the toner will be described.
After embedding the toner with a bisphenol A liquid epoxy resin and a curing agent, a cutting sample is prepared. Next, the cutting sample is cut at −100 ° C. using a cutting machine using a diamond knife (in this embodiment, a LEICA ultramicrotome (manufactured by Hitachi Technologies)) to prepare an observation sample. A cross section of the toner particles is observed with a transmission electron microscope (TEM) at a magnification of about 5000 times. Using the image analysis software, the number of pigment particles in which the angle between the major axis direction of the toner cross section and the major axis direction of the pigment particles is in the range of −30 ° to + 30 ° is counted for the 1000 toners observed. Calculate the percentage.

  The “major axis direction in the cross section of the toner” means a direction perpendicular to the thickness direction of the toner having an average equivalent circle diameter D longer than the above average maximum thickness C, and “the major axis direction of the pigment particles”. "Represents the length direction of the pigment particles.

  The volume average particle size of the toner of the exemplary embodiment is preferably 1 μm or more and 30 μm or less, more preferably 3 μm or more and 20 μm or less, and further preferably 5 μm or more and 10 μm or less.

The volume average particle size D _50v is _smaller than the particle size range (channel) divided based on the particle size distribution measured by a measuring instrument such as Multisizer II (manufactured by Coulter Inc.). Drawing the cumulative distribution from the side, the particle diameter to be accumulated 16% is the volume D _16v , the number D _16p , the particle diameter to be accumulated 50% is the volume D _50v , the number D _50p , the particle diameter to be accumulated 84% is the volume D _84v , number D _84p . Using these, the volume average particle size distribution index (GSDv) is calculated as ( _D84v / _D16v ) ^1/2 .

<Toner production method>
The toner according to the exemplary embodiment may be manufactured by adding an external additive to the toner particles after the toner particles are manufactured.
The method for producing the toner particles is not particularly limited, and the toner particles are produced by a known dry method such as a kneading / pulverizing method or a wet method such as an emulsion aggregation method or a suspension polymerization method.
The kneading and pulverization method involves mixing materials such as a colorant, then melt-kneading the above materials using a kneader, an extruder, etc., and roughly pulverizing the resulting melt-kneaded product, followed by a jet mill In this method, toner particles having a target particle size are obtained using an air classifier.
Among these methods, the emulsion aggregation method is preferable because the shape of the toner particles and the particle diameter of the toner particles can be easily controlled, and the control range of the toner particle structure such as the core-shell structure is wide. Hereinafter, a method for producing toner particles by the emulsion aggregation method will be described in detail.

  In the emulsification aggregation method of the present embodiment, the raw material constituting the toner particles is emulsified to form resin particles (emulsion particles) and the like, the aggregation step of forming aggregates of the resin particles, and the aggregates are fused. Fusion process.

(Emulsification process)
The resin particle dispersion can be prepared by using a general polymerization method, such as emulsion polymerization, suspension polymerization, dispersion polymerization, or the like. In addition, a solution in which an aqueous medium and a binder resin are mixed is used. Alternatively, emulsification may be performed by applying a shearing force with a disperser. At that time, particles may be formed by heating to lower the viscosity of the resin component. A dispersant may be used for stabilizing the dispersed resin particles. Furthermore, if the resin is oily and dissolves in a solvent with a relatively low solubility in water, the resin is dissolved in those solvents and dispersed in water together with a dispersant and a polymer electrolyte, and then heated or decompressed. By evaporating the solvent, a resin particle dispersion is produced.

Examples of the aqueous medium include water such as distilled water and ion-exchanged water; alcohols; and the like. Water is preferable.
Examples of the dispersant used in the emulsification step include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, Anionic surfactants such as sodium octadecyl sulfate, sodium oleate, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, amphoteric such as lauryldimethylamine oxide Ionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Surfactants such as nonionic surfactants such as alkyl amines; and the like are; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, inorganic salts such as barium carbonate.

  Examples of the disperser used for preparing the emulsion include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. As the size of the resin particles, the average particle diameter (volume average particle diameter) is desirably 1.0 μm or less, more desirably 60 nm or more and 300 nm or less, and further desirably 150 nm or more and 250 nm or less. . When the thickness is 60 nm or more, the resin particles tend to be unstable particles in the dispersion, and thus the resin particles may be easily aggregated. If the particle size is 1.0 μm or less, the particle size distribution of the toner may become narrow.

  In preparing the release agent dispersion, the release agent is dispersed in water together with an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base, and then heated to a temperature equal to or higher than the melting temperature of the release agent. Dispersion treatment is performed using a homogenizer or a pressure discharge type disperser to which a strong shearing force is applied while heating. By undergoing such treatment, a release agent dispersion is obtained. During the dispersion treatment, an inorganic compound such as polyaluminum chloride may be added to the dispersion. Examples of desirable inorganic compounds include polyaluminum chloride, aluminum sulfate, highly basic polyaluminum chloride (BAC), polyaluminum hydroxide, and aluminum chloride. Among these, polyaluminum chloride and aluminum sulfate are desirable. The release agent dispersion is used in the emulsion aggregation method, but the release agent dispersion may also be used when the toner is produced by suspension polymerization.

By the dispersion treatment, a release agent dispersion liquid containing release agent particles having a volume average particle diameter of 1 μm or less is obtained. In addition, the more preferable volume average particle diameter of the release agent particles is 100 nm or more and 500 nm or less.
When the volume average particle diameter is 100 nm or more, the properties of the binder resin to be used are affected, but in general, the release agent component is easily taken into the toner. In the case of 500 nm or less, the state of dispersion of the release agent in the toner is good.

A known dispersion method can be used for the preparation of the colorant (brilliant pigment) dispersion. For example, a general dispersion means such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or an optimizer can be employed. It can be done and is not limited at all. The colorant is dispersed in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid, or a polymer base. The volume average particle diameter of the dispersed colorant particles may be 20 μm or less, but if it is in the range of 3 μm or more and 16 μm or less, the dispersion of the colorant in the toner is preferable without impairing the cohesiveness.
Also, a dispersion of the glitter pigment coated with the binder resin is prepared by dispersing and dissolving the glitter pigment and the binder resin in a solvent, mixing, and dispersing in water by phase inversion emulsification or shear emulsification. May be.

(Aggregation process)
In the agglomeration step, a resin particle dispersion, a colorant dispersion, a release agent dispersion, etc. are mixed to form a mixed liquid, which is heated to agglomerate at a temperature lower than the glass transition temperature of the resin particles to form aggregated particles. To do. Aggregated particles are often formed by making the pH of the mixed solution acidic under stirring. It becomes possible to make ratio (C / D) into a preferable range with the said stirring conditions. More specifically, the ratio (C / D) can be reduced by heating at a high speed and heating at the stage of forming aggregated particles, and the ratio can be reduced by heating at a lower speed and at a lower temperature. (C / D) can be increased. In addition, as pH, the range of 2-7 is desirable, and it is also effective in this case to use a flocculant.
Further, in the aggregation step, the release agent dispersion may be added and mixed at once with various dispersions such as a resin particle dispersion, or may be added in multiple portions.

  As the aggregating agent, a surfactant having a polarity opposite to that of the surfactant used for the dispersant, an inorganic metal salt, and a divalent or higher-valent metal complex are preferably used. In particular, the use of a metal complex is particularly desirable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

As the inorganic metal salt, an aluminum salt and a polymer thereof are particularly suitable. In order to obtain a narrower particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. Inorganic metal salt polymers are more suitable.
In this embodiment, it is desirable to use a polymer of a tetravalent inorganic metal salt containing aluminum in order to obtain a narrow particle size distribution.

  Further, a toner having a configuration in which the surface of the core aggregated particles is coated with a resin may be prepared by additionally adding a resin particle dispersion when the aggregated particles have a desired particle size (coating step). In this case, the release agent and the colorant are not easily exposed on the toner surface, which is desirable from the viewpoint of chargeability and developability. In the case of additional addition, a flocculant may be added or pH adjustment may be performed before additional addition.

(Fusion process)
In the fusion step, the agglomeration is stopped by raising the pH of the suspension of aggregated particles to a range of 3 to 9 under stirring conditions in accordance with the aggregation step, and the glass transition temperature of the resin is higher than the glass transition temperature. The aggregated particles are fused by heating at a temperature. Moreover, when it coat | covers with the said resin, this resin is also united and a core aggregated particle is coat | covered. The heating time may be performed to the extent that fusion is performed, and may be performed for about 0.5 hour to 10 hours.

Cool after fusion to obtain fused particles. Further, in the cooling step, crystallization may be promoted by reducing the cooling rate in the vicinity of the glass transition temperature (range of glass transition temperature ± 10 ° C.) of the resin, so-called slow cooling.
The fused particles obtained by fusing are made into toner particles through a solid-liquid separation process such as filtration and, if necessary, a washing process and a drying process.

To the obtained toner particles, inorganic oxides such as silica, titania, and aluminum oxide are added and adhered as external additives for the purpose of charge adjustment, fluidity provision, charge exchangeability and the like. These can be performed by, for example, a V-type blender, a Henschel mixer, a Redige mixer, or the like, and may be attached in stages. The addition amount of the external additive is preferably in the range of 0.1 to 5 parts by mass, more preferably in the range of 0.3 to 2 parts by mass with respect to 100 parts by mass of the toner particles.
Further, if necessary, coarse particles of toner may be removed after external addition using an ultrasonic sieving machine, a vibration sieving machine, a wind sieving machine, or the like.

  In addition to the inorganic oxides described above, other components (particles) such as a charge control agent, organic particles, a lubricant, and an abrasive may be added as external additives.

  The charge control agent is not particularly limited, but a colorless or light-colored agent is desirably used. For example, quaternary ammonium salt compounds, nigrosine compounds, complexes of aluminum, iron, chromium, and triphenylmethane pigments can be used.

Examples of the organic particles include particles usually used as an external additive on the toner surface, such as vinyl resins, polyester resins, and silicone resins. These inorganic particles and organic particles are used as fluidity aids, cleaning aids, and the like.
Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.
As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

<Developer>
The toner according to the exemplary embodiment may be used as it is as a one-component developer, or may be mixed with a carrier and used as a two-component developer.

  The carrier that can be used in the two-component developer is not particularly limited, and a known carrier is used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples include, but are not limited to, an acid copolymer, a straight silicone resin composed of an organosiloxane bond or a modified product thereof, a fluororesin, a polyester resin, a polycarbonate resin, a phenol resin, and an epoxy resin.

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

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

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

  Specific resin coating methods include an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. A fluidized bed method in which the coating layer forming solution is sprayed in a state of being suspended by the above, a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (mass ratio) of the toner of the exemplary embodiment and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100, and 3: 100 to 20: 100. The range of is more desirable.

<Image Forming Apparatus and Image Forming Method>
The image forming apparatus of the present embodiment includes an image carrier, a charging device that charges the surface of the image carrier, a latent image forming device that forms an electrostatic latent image on the surface of the image carrier, and the electrostatic latent image. And a transfer device for transferring the toner image formed on the surface of the image carrier onto a recording medium.
A charging process for charging the surface of the image carrier by the image forming apparatus according to the present embodiment, a latent image forming process for forming an electrostatic latent image on the surface of the image carrier, and the toner of the present embodiment. Thus, the image forming method according to this embodiment including a developing step of developing as a toner image and a transfer step of transferring the toner image formed on the surface of the image carrier onto a recording medium is performed.

FIG. 3 is a schematic configuration diagram showing an embodiment of an image forming apparatus including a developing device to which the toner of the present embodiment is applied.
In FIG. 1, the image forming apparatus of the present embodiment has a photosensitive drum 20 as an image holding member that rotates in a predetermined direction, and the photosensitive drum 20 is charged around the photosensitive drum 20. A charging device 21, for example, an exposure device 22 as a latent image forming device for forming an electrostatic latent image Z on the photosensitive drum 20, and a visible image of the electrostatic latent image Z formed on the photosensitive drum 20. Developing device 30, transfer device 24 for transferring a toner image visualized on photosensitive drum 20 to recording paper 28 as a recording medium, and cleaning device for cleaning residual toner on photosensitive drum 20 25 are sequentially arranged.

In the present embodiment, as shown in FIG. 3, the developing device 30 has a developing housing 31 in which a developer G containing toner 40 is accommodated, and the developing housing 31 is developed to face the photosensitive drum 20. A developing roll (developing electrode) 33 serving as a toner holding member facing the developing opening 32 and applying a predetermined developing bias to the developing roll 33. A developing electric field is formed in a region (developing region) sandwiched between the photosensitive drum 20 and the developing roll 33. Further, a charge injection roll (injection electrode) 34 as a charge injection member is provided in the development housing 31 so as to face the development roll 33. In particular, in the present embodiment, the charge injection roll 34 also serves as a toner supply roll for supplying the toner 40 to the developing roll 33.
Here, the rotation direction of the charge injection roll 34 may be selected. However, in consideration of the toner supply property and the charge injection characteristic, the charge injection roll 34 has the same direction at the portion facing the developing roll 33. Further, it is desirable that the rotation is performed with a peripheral speed difference (for example, 1.5 times or more), the toner 40 is sandwiched between the regions sandwiched between the charge injection roll 34 and the developing roll 33, and the charges are injected while being rubbed.

Next, the operation of the image forming apparatus of this embodiment will be described.
When the image forming process is started, first, the surface of the photosensitive drum 20 is charged by the charging device 21, and the exposure device 22 writes the electrostatic latent image Z on the charged photosensitive drum 20, and the developing device 30 then The electrostatic latent image Z is visualized as a toner image. Thereafter, the toner image on the photoconductive drum 20 is conveyed to a transfer site, and the transfer device 24 electrostatically transfers the toner image on the photoconductive drum 20 to a recording paper 28 as a recording medium. The residual toner on the photosensitive drum 20 is cleaned by the cleaning device 25. Thereafter, the toner image on the recording paper 28 is fixed by a fixing device (not shown) to obtain an image.

  Examples of the recording paper 28 include plain paper used for electrophotographic copying machines, printers, and OHP sheets. In the present embodiment, a recording medium having a smoothness measured in accordance with JIS P8119: 1998 of the surface on which the toner image is transferred may be 20 seconds or more and 20000 seconds or less. By using the toner of the present exemplary embodiment, a glitter image having excellent glitter and image strength can be formed even on a recording medium having a smoothness in the above range and a small smoothness.

<Process cartridge, toner cartridge>
FIG. 4 is a schematic configuration diagram illustrating an example of a process cartridge according to the present embodiment. The process cartridge according to the present embodiment is characterized in that the toner according to the present embodiment is accommodated and a toner holder that holds and conveys the toner is provided.

  A process cartridge 200 shown in FIG. 4 includes a photosensitive roller 107 as an image holding member, a charging roller 108, a developing device 111 that accommodates the toner of the above-described embodiment, a photosensitive member cleaning device 113, and an opening 118 for exposure. , And the opening 117 for static elimination exposure is combined and integrated using a mounting rail 116. The process cartridge 200 is detachable from an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components not shown. It constitutes. In FIG. 4, reference numeral 300 denotes a recording medium.

  The process cartridge 200 shown in FIG. 4 includes a charging device 108, a developing device 111, a cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. May be combined. In the process cartridge of this embodiment, in addition to the developing device 111, the photosensitive member 107, the charging device 108, the cleaning device 113, the opening 118 for exposure, and the opening 117 for static elimination exposure are configured. It comprises at least one selected from the group.

  Next, the toner cartridge of this embodiment will be described. The toner cartridge according to this embodiment is detachably attached to the image forming apparatus, and at least the toner cartridge that stores toner to be supplied to the developing device provided in the image forming apparatus. The toner according to the exemplary embodiment. It should be noted that at least the toner may be stored in the toner cartridge of the present embodiment, and for example, a developer may be stored depending on the mechanism of the image forming apparatus.

  The image forming apparatus shown in FIG. 3 is an image forming apparatus having a configuration in which a toner cartridge (not shown) can be freely attached and detached, and the developing device 30 is connected to the toner cartridge by a toner supply pipe (not shown). . Further, when the amount of toner stored in the toner cartridge is low, this toner cartridge may be replaced.

  Hereinafter, although an example and a comparative example are given and this embodiment is described more concretely, this embodiment is not limited to the following examples. Unless otherwise specified, “part” and “%” are based on mass.

(Preparation of glitter pigment 1)
Aluminum pigment (Asahi Kasei Chemicals Co., Ltd., TR-5060): 100 parts isopropyl alcohol (Kanto Chemical Co., Ltd.): 400 parts dispersed, 131 filter paper (Advantech) solid-liquid separation work Repeated 5 times and dried to obtain 7.5 μm aluminum pigment A.
Next, 100 parts of aluminum pigment (Showa Aluminum Powder Co., Ltd., 574EA): 100 parts are dispersed in 400 parts of isopropyl alcohol (Kanto Chemical Co., Ltd.): solid-liquid separation is performed with 131 filter paper (manufactured by Advantech). After repeating the operation 5 times and drying, classification is performed with an elbow jet classifier (Matsubo Co., Ltd., EJ-L3) with a fine powder cut point of 25 μm and a coarse powder cut point of 40 μm. As a result of collecting the coarse powder, an aluminum pigment B having a volume average particle size of 44 μm was obtained.
Luminous pigment 1 having a volume average particle size of 9.3 μm, a maximum particle size of 50 μm, and a particle size of 20 μm or more of 5% was prepared by mixing 95% of aluminum pigment A and 5% of aluminum pigment B.

(Preparation of glitter pigment 2)
Aluminum pigment (produced by Showa Aluminum Powder Co., Ltd., 574EA): 100 parts of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.): 400 parts are dispersed, and solid-liquid separation is performed using 131 filter paper (manufactured by Advantech). After repeated drying, the powder was classified with an elbow jet classifier (Matsubo Co., Ltd., EJ-L3) with a fine particle cut point of 25 μm and a coarse powder cut point of 40 μm. As a result of collecting the powder, an aluminum pigment C having a volume average particle diameter of 29 μm was obtained.
Luminous pigment 2 was prepared by mixing aluminum pigment A at a ratio of 96% and aluminum pigment C at a ratio of 4%.
In addition, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 3)
Luminous pigment 3 was prepared by mixing 90% of aluminum pigment A and 10% of aluminum pigment C.
Further, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 4)
Luminous pigment 4 was prepared by mixing aluminum pigment A at a ratio of 80% and aluminum pigment B at a ratio of 20%.
Further, as described above, the volume average particle diameter, the maximum particle diameter, and the ratio of particles having a particle diameter of 20 μm or more in the entire particles were determined.

(Preparation of glitter pigment 5)
Aluminum pigment (produced by Showa Aluminum Powder Co., Ltd., 574EA): 100 parts of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.): 400 parts are dispersed, and solid-liquid separation is performed using 131 filter paper (manufactured by Advantech). After repeated drying, an elbow jet classifier (Matsubo Co., Ltd., EJ-L3) performs a classification operation with a fine powder cut point of 25 μm and a coarse powder cut point of 30 μm. As a result of collecting the powder, an aluminum pigment D having a volume average particle diameter of 26 μm was obtained.
Luminous pigment 5 was prepared by mixing 80% of aluminum pigment A and 20% of aluminum pigment D.
Further, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 6)
Luminous pigment 6 was prepared by mixing aluminum pigment A at a ratio of 97% and aluminum pigment B at a ratio of 3%.
In addition, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 7)
Luminous pigment 7 was prepared by mixing aluminum pigment A at a ratio of 98% and aluminum pigment C at a ratio of 2%.
Further, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 8)
Aluminum pigment (produced by Showa Aluminum Powder Co., Ltd., 574EA): 100 parts of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.): 400 parts are dispersed, and solid-liquid separation is performed using 131 filter paper (manufactured by Advantech). After repeated drying and drying, an elbow jet classifier (Matsubo Co., Ltd., EJ-L3) performs a classification operation by setting the fine powder cut point to a particle size of 35 μm and the coarse powder cut point to a particle size of 50 μm. As a result of collecting the powder, an aluminum pigment E having a volume average particle diameter of 49 μm was obtained.
Luminous pigment 8 was prepared by mixing 95% of aluminum pigment A and 5% of aluminum pigment E.
In addition, as described above, the volume average particle diameter, the maximum particle diameter, and the ratio of particles having a particle diameter of 20 μm or more in the entire particle were obtained.

(Preparation of luster pigment 9)
Aluminum pigment (produced by Showa Aluminum Powder Co., Ltd., 574EA): 100 parts of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.): 400 parts are dispersed, and solid-liquid separation is performed using 131 filter paper (manufactured by Advantech). After repeated drying, the powder was classified with an elbow jet classifier (Matsubo Co., Ltd., EJ-L3) with a fine powder cut point of 15 μm and a coarse powder cut point of 25 μm. As a result of collecting the powder, an aluminum pigment F having a volume average particle diameter of 19 μm was obtained.
Luminous pigment 9 was prepared by mixing 92% of aluminum pigment A and 8% of aluminum pigment F.
In addition, as described above, the volume average particle diameter, the maximum particle diameter, and the ratio of particles having a particle diameter of 20 μm or more in the entire particles were obtained.

(Preparation of glitter pigment 10)
Luminous pigment 10 was prepared by mixing aluminum pigment A at a ratio of 80% and aluminum pigment E at a ratio of 20%.
Further, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 11)
Luminous pigment 11 was prepared by mixing 60% of aluminum pigment A and 40% of aluminum pigment F.
In addition, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 12)
Luminous pigment 12 was prepared by mixing 75% of aluminum pigment A and 25% of aluminum pigment B.
In addition, as described above, the volume average particle diameter, the maximum particle diameter, and the ratio of particles having a particle diameter of 20 μm or more in the entire particle were obtained.

(Preparation of glitter pigment 13)
Luminous pigment 13 was prepared by mixing 75% of aluminum pigment A and 25% of aluminum pigment D.
Further, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.

<Preparation of glitter pigment particle dispersion 1>
-Glittering pigment 1: 100 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts-Ion exchange water: 900 parts A bright pigment particle dispersion 1 (solid content concentration: 10%) obtained by dispersing the bright pigment 1 was prepared by dispersing for 1 hour using CR1010).

(Synthesis of binder resin)
Dimethyl adipate: 74 parts Dimethyl terephthalate: 192 parts Bisphenol A ethylene oxide adduct: 216 parts Ethylene glycol: 38 parts Tetrabutoxy titanate (catalyst): 0.037 parts
The above components are placed in a heat-dried two-necked flask, and nitrogen gas is introduced into the container and heated while stirring in an inert atmosphere, and then subjected to a copolycondensation reaction at 160 ° C. for 7 hours, and then gradually up to 10 Torr. The temperature was raised to 220 ° C. while reducing the pressure to 4 hours. Once the pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced to 10 Torr, and maintained at 220 ° C. for 1 hour to synthesize a binder resin.
The glass transition temperature (Tg) of the binder resin is 10 ° C. from a room temperature (25 ° C.) to 150 ° C. using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-50) in accordance with ASTM D3418-8. It was determined by measuring under the conditions of / min. The glass transition temperature was the temperature at the intersection of the extended line of the base line and the rising line in the endothermic part. The glass transition temperature of the binder resin was 63.5 ° C.

<Preparation of resin particle dispersion>
・ Binder resin: 160 parts ・ Ethyl acetate: 233 parts ・ Sodium hydroxide aqueous solution (0.3N): 0.1 part The above ingredients were placed in a 1000 ml separable flask and heated at 70 ° C. A resin mixed solution was prepared by stirring with Science Co., Ltd. While this resin mixture was further stirred at 90 rpm, 373 parts of ion-exchanged water was gradually added to cause phase inversion emulsification, and the solvent was removed to obtain a resin particle dispersion (solid content concentration: 30%). The volume average particle diameter of the resin particle dispersion is 162 nm.

<Preparation of release agent dispersion>
Carnauba wax (Toa Kasei Co., Ltd., RC-160): 50 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1.0 parts Ion-exchanged water: 200 parts After mixing the above and heating to 95 ° C. and dispersing using a homogenizer (IQA, Ultra Tarrax T50), the dispersion was treated with a Manton Gorin high-pressure homogenizer (Gorin) for 360 minutes to obtain a volume average particle. A release agent dispersion (solid content concentration: 20%) prepared by dispersing release agent particles having a diameter of 0.23 μm was prepared.

[Example 1]
<Production of toner>
-Resin particle dispersion: 375 parts-Release agent dispersion: 50 parts-Bright pigment particle dispersion 1 400 parts

The above-mentioned glitter pigment particle dispersion 1, resin particle dispersion, and release agent dispersion are placed in a 2 L cylindrical stainless steel container, and a shear force is applied at 4000 rpm by a homogenizer (IKA, Ultra Lalux T50). Dispersed and mixed for minutes. Next, 1.75 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5000 rpm for 15 minutes and mixed to obtain a raw material dispersion.
Thereafter, the raw material dispersion was transferred to a polymerization vessel equipped with a stirring device using two paddle stirring blades for forming a laminar flow, and a thermometer, and started to be heated with a mantle heater at a stirring speed of 810 rpm. The growth of aggregated particles was promoted at 54 ° C. At this time, the pH of the raw material dispersion was controlled in the range of 2.2 to 3.5 with 0.3N nitric acid or 1N sodium hydroxide aqueous solution. The agglomerated particles were formed by maintaining the above pH range for 2 hours.
Next, 125 parts of a resin particle dispersion was additionally added, and the resin particles of the binder resin were adhered to the surface of the aggregated particles. The temperature was further raised to 56 ° C., and aggregated particles were prepared while confirming the size and form of the particles with an optical microscope and Multisizer II. Thereafter, the pH was raised to 8.0 in order to fuse the aggregated particles, and then the temperature was raised to 67.5 ° C. After confirming that the aggregated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining the temperature at 67.5 ° C., and the heating was stopped after 1 hour, followed by cooling at a rate of temperature decrease of 0.1 ° C./min. Thereafter, it was sieved with a 106 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain toner particles.
Further, the toner particles were heat-treated with a hot air dryer at 45 ° C. for 1 hour.
Sample mill of 1.5 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0 part of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) with respect to 100 parts of toner particles after heat treatment Was mixed for 30 seconds at 10,000 rpm. Thereafter, the toner was prepared by sieving with a vibrating sieve having an aperture of 106 μm.

The volume average particle diameter of the toner is 12.2 μm.
Further, it is observed when a “flop index”, “ratio of average maximum thickness C of toner to average equivalent circle diameter D (C / D)”, and “cross section in the thickness direction of toner” are observed. Among all the pigment particles, the number of pigment particles in which the angle between the major axis direction of the cross section of the toner and the major axis direction of the pigment particles is in the range of −30 ° to + 30 ° (hereinafter, simply “pigment particles in the range of ± 30 °”). ”)” Was measured by the method described above. The results are shown in Table 1 below.

<Creation of carrier>
Ferrite particles (volume average particle diameter: 35 μm): 100 parts Toluene: 14 parts Perfluoroacrylate copolymer (critical surface tension: 24 dyn / cm): 1.6 parts Carbon black (trade name: VXC-72 Manufactured by Cabot Corporation, volume resistivity: 100 Ωcm or less): 0.12 parts Cross-linked melamine resin particles (average particle size: 0.3 μm, toluene insoluble): 0.3 parts

  First, carbon black was diluted in toluene and added to a perfluoroacrylate copolymer and dispersed with a sand mill. Next, the above components other than ferrite particles were added thereto and dispersed with a stirrer for 10 minutes to prepare a coating layer forming solution. Next, this coating layer forming solution and ferrite particles are put in a vacuum degassing type kneader and stirred at a temperature of 60 ° C. for 30 minutes, and then the pressure is reduced to distill off toluene to form a resin coating layer to obtain a carrier. It was.

<Production of developer>
36 parts of the toner and 414 parts of the carrier were put in a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare a developer.

〔Evaluation test〕
An evaluation image was formed by the following method.
The developer used as a sample is filled in a developing device of DocuCentre-III C7600 manufactured by Fuji Xerox Co., Ltd., and the smoothness measured based on recording paper (C2 paper, manufactured by Fuji Xerox Interfield, JIS P8119: 1998). 90 seconds), a solid image with a toner loading of 4.5 g / m ² was formed at a fixing temperature of 190 ° C. and a fixing pressure of 4.0 kg / cm ² .

-Image strength evaluation-
The obtained solid image was lightly folded so that the solid image was directed inward, and a roll having a weight of 860 g and a diameter of 76 mm was rolled on the horizontal desk at 150 mm / s to make a crease. When the solid image was expanded as it was, the level where the maximum width of the image defect in the bent portion was 0.30 mm or less (scale loupe, observed at a magnification of 10 times) was regarded as a level that does not cause any problem. The evaluation criteria are shown below. The obtained results are shown in Table 1.

◎: Level where there is no image cracking and no problem ○: Level where there is little image cracking and no problem △: Level where there is some image cracking, but there is no problem ×: There are many image cracking and there is a problem

-Brightness evaluation-
With respect to the obtained solid image, color observation illumination (natural daylighting) according to JIS K5600-4-3: 1999 “Paint General Test Method—Part 4: Visual Characteristics of Coating Film—Section 3: Visual Comparison of Colors” The brightness was visually evaluated under (light illumination). The evaluation was based on the following criteria for particle feeling (effect of glittering glitter) and optical effect (change in hue depending on viewing angle). Two or more are actually usable levels. The obtained results are shown in Table 1.

5: Particle feeling and optical effect are harmonized.
4: Slight particle feeling and optical effects.
3: Ordinary sensation 2: Slightly blurred 1: No particle feeling or optical effect.

[Example 2]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 2.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Example 3]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 3.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Example 4]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 4.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Example 5]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 5.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Example 6]
Using the toner and developer obtained in Example 3, GR100 paper (manufactured by Fuji Xerox Interfield, smoothness measured based on JIS P8119: 1998) was used instead of C2 paper as the recording medium. The evaluation was the same as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 1]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 6.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 2]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 7.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 3]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 8.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 4]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 9.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 5]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 10.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 6]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 11.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 7]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 12.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 8]
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 13.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

[Comparative Example 9]
(Preparation of glitter pigment particle dispersion 14)
Aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA): 100 parts Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R): 1.5 parts Ion-exchanged water: 900 parts From aluminum pigment paste After removing the solvent, the above are mixed, dissolved, and dispersed for about 1 hour using an emulsifier-dispersing machine Cavitron (manufactured by Taiheiyo Kiko Co., Ltd., CR1010). A particle dispersion 14 (solid content concentration: 10%) was prepared.
Further, as described above, the volume average particle size, the maximum particle size, and the ratio of particles having a particle size of 20 μm or more in the entire particle were obtained.
A toner and a developer were prepared in the same manner as in Example 1 except that the glitter pigment particle dispersion 1 was replaced with the glitter pigment particle dispersion 14.
Evaluation was conducted in the same manner as in Example 1 using the obtained toner and developer. The evaluation results are shown in Table 1.

2 Toner 4 Pigment particle 10 Paper 12, 14 Luminous pigment 16, 18 Toner image 20 Photosensitive drum 21 Charging device 22 Exposure device 24 Transfer device 25 Cleaning device 28 Recording paper 30 Developing device 31 Developing housing 32 Developing opening 33 Developing roll 34 Charge injection roll 40 Toner 107 Photoconductor (image carrier)
108 Charging roller 111 Developing device 112 Transfer device 113 Photoconductor cleaning device 115 Fixing device 116 Mounting rail 117 Opening portion 118 for static elimination exposure Opening portion 200 for exposure Process cartridge 300 Recording paper (recording medium)

Claims (7)

  The volume average particle diameter measured by the Coulter counter method is 1 μm or more and 15 μm or less, the maximum particle diameter is 30 μm or more and 50 μm or less, and the ratio of particles having a particle diameter of 20 μm or more in the whole particle is 5% on a volume basis. A glittering toner comprising a glittering pigment that is 20% or less.   A developer comprising at least the glittering toner according to claim 1.   A toner cartridge containing the glitter toner according to claim 1.   A process cartridge comprising: a toner holder that contains the glitter toner according to claim 1 and that holds and conveys the glitter toner. An image carrier,
A charging device for charging the surface of the image carrier;
A latent image forming apparatus for forming an electrostatic latent image on the surface of the image carrier;
A developing device that develops the electrostatic latent image as a toner image with the glitter toner according to claim 1;
A transfer device for transferring the toner image formed on the surface of the image carrier onto a recording medium;
An image forming apparatus. A charging step for charging the surface of the image carrier;
A latent image forming step of forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image as a toner image with the glitter toner according to claim 1;
A transfer step of transferring the toner image formed on the surface of the image carrier onto a recording medium;
An image forming method comprising:   The image forming method according to claim 6, wherein the smoothness measured based on JIS P8119: 1998 on the surface of the recording medium on which the toner image is transferred is 20 seconds or more and 20000 seconds or less.