JP7395992B2 - Toner, toner manufacturing method, toner storage unit, image forming apparatus, and image forming method - Google Patents

Description

The present invention relates to a toner, a toner manufacturing method, a toner storage unit, an image forming apparatus, and an image forming method.

2. Description of the Related Art As electrophotographic color image forming apparatuses have become widespread, their uses have expanded to a wide variety of uses, and in addition to conventional color images, images with metallic-like glitter are also desired.
Therefore, for the purpose of forming an image having a metallic-like luster, a glitter toner containing a metal pigment as a glitter pigment in a binder resin is used.

In order to obtain an image with a metallic-like shine, it is important that the material has strong light reflectivity when viewed from a certain angle. Therefore, it is necessary to incorporate a highly reflective glitter pigment having a scale-like plane into an electrostatic image developing toner (hereinafter referred to as toner).
A metallic pigment or a pigment whose matrix surface is coated with a metal is suitable as such a highly reflective glittering pigment. Furthermore, in order to ensure high reflective performance, it is necessary that each pigment particle has a flat surface with a certain area, and that the pigments are arranged in a planar manner in the toner-fixed image.

Therefore, in the development and transfer steps, in order to arrange the glitter pigments in a planar manner in the image formed with the toner, a binder resin and a plurality of flat glitter pigments of 3.5 or more are included. A glitter toner containing toner particles in which a plurality of flat glitter pigments are arranged in the same direction is disclosed (for example, see Patent Document 1).

Furthermore, in recent years, image forming apparatuses have become increasingly low in power consumption and high in speed, and there is a demand for toners that have both low-temperature fixability and long-term durability. For a toner with excellent low-temperature fixing properties, it is effective to contain a crystalline polyester resin, and in order to ensure long-term durability, a toner with a predetermined dispersion diameter of crystalline polyester and a dispersion diameter of a release agent is used. It has been disclosed (for example, see Patent Document 2).

An object of the present invention is to provide a glitter toner that has excellent low-temperature fixing properties while ensuring the glitter properties of images.

The glitter toner of the present invention, which is a means for solving the above problems, includes:
Contains bright pigment, mold release agent, and crystalline polyester,
The release agent has a number dispersion average diameter of 30 nm or more and 200 nm or less,
The crystalline polyester has a number dispersion average diameter of 20 nm or more and 40 nm or less,
The crystalline polyester present within a distance of 0.3 μm from the glitter pigment accounts for 50% or more and 80% or less of the total crystalline polyester.

According to the present invention, it is possible to provide a glitter toner that has excellent low-temperature fixing properties while ensuring the glitter properties of images.

FIG. 1A is an image diagram showing an example of an image observed when a cross section of a toner is observed using a field emission scanning electron microscope (FE-SEM). FIG. 1B is an image showing an example of a cross section of a toner observed by FE-SEM. FIG. 2 is an overall configuration diagram of an image forming apparatus showing an embodiment of the present invention.

(Glitter toner)
The glitter toner of the present invention contains at least a glitter pigment, a release agent, and a crystalline polyester, and further contains other components as necessary.

<Number distribution average diameter of mold release agent>
The number dispersion average diameter of the release agent in the glitter toner is from 30 nm to 200 nm, preferably from 100 nm to 200 nm.
When the number dispersion average diameter of the release agent exceeds 200 nm, the amount of release agent on the toner surface increases, contamination of the photoreceptor due to bleed-out and carrier contamination occur, resulting in white spots and charging defects, resulting in high image quality. can no longer be maintained. In addition, there is a large amount of release agent on the surface of the image after fixation, making it difficult to produce a glittering effect due to the glittering pigment. Furthermore, charging characteristics are not stable over time.
If the number-dispersion average diameter of the release agent is less than 30 nm, the release agent will be difficult to seep out during fixing, resulting in poor low-temperature fixability.
When the number-dispersion average diameter of the release agent is within a preferable range, it is advantageous in achieving both fixing properties and stain resistance.

In glitter toners, the proportion of glitter pigments in the toner may be large. In that case, the amount of release agent present on the surface of the toner increases compared to a toner that does not contain a glitter pigment. Therefore, the release agent bleeds out due to stress during development, which tends to cause photoreceptor contamination and carrier contamination, making it difficult to maintain high image quality.
In the glitter toner of the present invention, the above problem can be solved by setting the number dispersion average diameter of the release agent in the glitter toner to 30 nm or more and 200 nm or less.

The number-dispersion average diameter of the mold release agent is determined, for example, as follows.
A cross section of an ultrathin section of the toner is observed using a transmission electron microscope (TEM), and the number distribution average diameter of the release agent is measured based on the observed image. Specifically, the measurement is performed as follows.

[Observation and measurement by TEM]
The produced toner is embedded in epoxy resin and cured.
An ultrathin section (approximately 100 nm thick) of the toner is prepared using an ultramicrotome (ULTRACUT UCT manufactured by Leica, using a diamond knife).
The sample is exposed to gas with ruthenium tetroxide, osmium tetroxide, or another staining agent to distinguish between the release agent phase and other parts. The exposure time is adjusted as appropriate depending on the contrast during observation. Thereafter, it is observed using a transmission electron microscope (JEM-2100 manufactured by JEOL) at an acceleration voltage of 100 kV and a magnification of 3,000 times.
By measuring at this accelerating voltage and magnification, it is possible to observe 3 to 15 mold release agents per field of view. Then, observation is performed in a plurality of visual fields under these conditions so that the total number of mold release agents is about 50. Here, for example, if the total number of mold release agents is 48 in four fields of view, and 15 mold release agents are observed in the fifth field of view, the total number of mold release agents is 48 and 7, which is 53. The equivalent circular diameter of the mold release agent is determined as follows.
When a dye is used, the release agent phase is not stained by the dye, so when a cross section is observed, the release agent is observed as a white domain. Note that there are cases where it can be identified without staining, and in that case, it is evaluated without staining. It is also possible to impart a compositional contrast by other means such as selective etching, and after such pretreatment, the release agent portion may be evaluated by observing with a transmission microscope.
The observed cross-sectional image is binarized using commercially available image processing software (eg, Image-Pro Plus, etc.) to calculate the equivalent circular diameter of the release agent. That is, the equivalent circular diameter of each of the approximately 50 release agent domains observed in the plurality of fields of view is determined. By taking the number average value, the number dispersion average diameter of the mold release agent can be determined.

<Number % of crystalline polyester adjacent to bright pigment>
Conventionally, in order to realize a glitter image, it has been thought that planes of glitter pigments are arranged side by side on the surface of the image formed by toner, and it is necessary to efficiently reflect light. Therefore, it has been thought that it is good for the flat pigment to be oriented in one direction inside the toner.
However, if the glitter pigments are arranged in a certain direction and are present in the toner, a plurality of flat pigments will exist in a state where they are overlapped with narrow intervals.
Bright pigments are often metallic pigments or pigments whose matrix surface is coated with metal. Therefore, if the glitter pigments are present in the toner in a state where they are overlapped at narrow intervals, the electrical resistance of the toner decreases, making it difficult for the toner surface to retain electric charge, and the charging property of the toner decreases. Further, if the toner does not contain crystalline polyester, there is a problem that low-temperature fixability is poor.

Therefore, in the glitter toner, it is important that the crystalline polyester present within a distance of 0.3 μm from the glitter pigment accounts for 50% to 80% by number of the entire crystalline polyester.
It is clear that by adjusting the crystalline polyester present near the glitter pigment, rather than simply dispersing the crystalline polyester in the glitter toner, it is possible to achieve both excellent low-temperature fixability and excellent glitter. became. During fixation and melting, the crystalline polyester present near the glitter pigment effectively causes a rapid viscosity reduction, allowing the glitter pigment to move more easily in the toner, causing the glitter pigment to move parallel to the toner layer during fixing. It is thought that it becomes easier to orient. As a result of the study, it was found that the glitter properties of the toner can be significantly improved by specifying the number ratio of crystalline polyester present within a distance of 0.3 μm from the glitter pigment.
Here, the reason why the thickness is within 0.3 μm is that the crystalline polyester has a high effect of facilitating orientation of the glittering pigment in parallel to the toner layer.
If the crystalline polyester present within a distance of 0.3 μm from the glitter pigment accounts for less than 50% by number of the total crystalline polyester, the orientation of the glitter pigment during fixing will be restricted, making it difficult to obtain good glitter. do not have. If the amount exceeds 80% by number, the amount of crystalline polyester present on the surface of the toner decreases, resulting in insufficient plasticization during heating for fixing, resulting in poor low-temperature fixability.
The crystalline polyester present within a distance of 0.3 μm from the glitter pigment is preferably 50% by number or more and 70% by number or less, and 55% by number or more and 60% by number, from the viewpoint of further improving glitter and charging stability. It is more preferable that it is less than % by number.

The percentage of the number of crystalline polyesters present within a distance of 0.3 μm from the glitter pigment based on the total crystalline polyesters can be determined as follows.
Observe the cross section of an ultra-thin section of the toner using a transmission electron microscope (TEM), identify the glitter pigment and crystalline polyester from the observed image, and identify the crystals present within a distance of 0.3 μm from the glitter pigment. The number % of the crystalline polyester based on the total crystalline polyester is measured. Specifically, it is performed as follows.

[Observation and measurement by TEM]
The produced toner is embedded in epoxy resin and cured.
An ultrathin section (approximately 100 nm thick) of the toner is prepared using an ultramicrotome (ULTRACUT UCT manufactured by Leica, using a diamond knife).
The sample is exposed to gas with ruthenium tetroxide, osmium tetroxide, or another staining agent to distinguish between the bright pigment and crystalline polyester phase and the rest. The exposure time is adjusted as appropriate depending on the contrast during observation. Thereafter, it is observed using a transmission electron microscope (JEM-2100 manufactured by JEOL) at an accelerating voltage of 100 kV. Note that there are cases where it can be identified without staining, and in that case, it is evaluated without staining. It is also possible to impart a compositional contrast by other means such as selective etching, and after such pretreatment, observation with a transmission microscope may be used to evaluate the bright pigment and the crystalline polyester phase.
The crystalline polyester existing within a distance of 0.3 μm from the glitter pigment refers to the crystalline polyester phase existing within the range connecting the points at a distance of 0.3 μm from the outer periphery of the glitter pigment. Crystalline polyester phases that exist across the range are excluded. The number of all crystalline polyester phases dispersed in the cross section of the toner is counted, and the ratio of the number of crystalline polyester phases existing within a range of 0.3 μm from the outer periphery is calculated.
By observing the cross sections of 20 pieces of toner and taking the average value, the crystalline polyester present within a distance of 0.3 μm from the glitter pigment is determined.

Examples of methods for controlling the release agent and the number distribution average diameter of the crystalline polyester in the toner and for controlling the arrangement of the crystalline polyester include the following methods.
In manufacturing toner by the dissolution/suspension method, the release agent and crystalline polyester are dissolved in an organic solvent separately, and then cooled and precipitated to prevent crystal growth of the release agent and crystalline polyester. make me wake up At that time, the size of the crystals can be adjusted by adjusting the concentration of the liquid, precipitation rate, stirring conditions, cooling rate, etc. If the crystals are too large, they can be further adjusted to an appropriate size using a homogenizer, high-pressure emulsifier, bead mill, etc. By doing so, it is possible to control the release agent and the number distribution average diameter of the crystalline polyester in the toner.
In addition, as a method for controlling the number of crystalline polyesters present within a distance of 0.3 μm from the glitter pigment, in the production of toner, the oil phase and the aqueous phase are heated at a temperature higher than room temperature and below the melting point of the crystalline polyester. After emulsification, the temperature is slowly lowered to allow crystal growth. Depending on the temperature reached at this time, the internal dispersion of the crystalline polyester in the toner can be controlled, and the number of crystalline polyesters present at a predetermined distance from the glitter pigment can be adjusted.

<Glitter pigment>
The glitter pigment preferably has a flat plate shape in order to enhance the glitter of the image after fixing.
The glitter pigment is preferably a metal pigment.
Examples of the material of the metal pigment include metals such as aluminum, brass, bronze, nickel, stainless steel, zinc, copper, silver, gold, and platinum, and flaky glass coated with metal.
It is preferable that the surface of the bright pigment be surface-treated in terms of dispersibility and stain resistance.
The bright pigment may be coated with various surface treatment agents, silane coupling agents, titanate coupling agents, fatty acids, silica particles, acrylic resins, polyester resins, and the like.
The glittering pigment is preferably scale-like (plate-like) or flat so as to have a light-reflecting surface. Thereby, glittering properties can be exhibited. In order for one particle to have a small volume and a constant plane, it needs to be a thin piece.
The glitter pigments may be contained alone or in combination of two or more. Further, for color tone adjustment, various coloring materials such as dyes and pigments may be used in combination.

The content of the glitter pigment is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less, based on the total mass of the glitter toner. When the content is within a more preferable range, it is advantageous in that uniform and stable glitter can be obtained.

Further, the average thickness D of the glitter pigment is preferably 0.3 μm or more and 1.5 μm or less, more preferably 0.5 μm or more and 1.0 μm or less. When the average thickness is 0.3 μm or more, it is difficult for light to pass through, and the shine is more excellent. When the average thickness is 1.0 μm or less, the metals are less likely to come into contact with each other, so the electrical resistance value of the toner is less likely to decrease, and as a result, the charging characteristics are excellent.

<<Average thickness D>>
The average thickness D of the glitter pigment is determined as follows.
A cross section of the toner is observed using a scanning electron microscope (FE-SEM). The average thickness D is measured based on the observed image.
An image of the observed glitter pigment is shown in FIG. 1A.
Furthermore, an image actually observed is shown in FIG. 1B.
As shown in FIG. 1A, for a cross section of a toner containing a glitter pigment, the arithmetic mean value D of the maximum thicknesses d1, d2, and d3 of the glitter pigment contained in the toner particles is determined. Arithmetic mean value D is obtained for other toner particles in the same manner. The arithmetic mean of the 20 arithmetic mean values D obtained for a total of 20 toner cross sections is taken, and the value is defined as the average thickness D.

<<Declination angle θ>>
When a cross-sectional image of toner particles of the glitter toner is observed, among the plurality of glitter pigments included in the toner particles, the glitter pigment has the longest length and the glitter pigment has the largest deviation angle with respect to this glitter pigment. The proportion of toner particles whose polarization angle θ with the glitter pigment is 20° or more is preferably 20% by number or more, and more preferably 30% by number or more. The upper limit of the ratio is not particularly limited and can be selected as appropriate depending on the purpose, for example, the ratio may be 60% by number or less or 50% by number or less. .
When toner is fixed on a flat surface such as paper or film, the toner melts and the glitter pigments tend to line up with parallel surfaces. Therefore, the glitter pigments do not necessarily have to be arranged in the same direction inside the toner particles. When the glitter pigment is present with misaligned orientation, the circularity of the toner tends to be higher. In this case, the toner can be cleaned without damaging the photoreceptor or the transfer belt while ensuring good toner transfer performance.
If the proportion of toner particles having an angle of deviation θ of 20° or more is 20% or more, it is possible to effectively prevent the problem of a decrease in the electrical resistance value of the toner due to excessive alignment of the glitter pigments. .

The proportion of toner particles having an angle of deviation θ of 20° or more can be determined as follows.
As shown in FIG. 1A, with respect to a cross section of a toner particle of a glitter toner containing a glitter pigment, the longest glitter pigment among the glitter pigments contained in the toner particle is identified. For example, in FIG. 1A, the length of the pigment is L3. Next, with respect to the longest glitter pigment, a glitter pigment having the maximum angle of deviation is identified. Then, the polarization angle θ between the longest glittering pigment and the glittering pigment having the largest polarization angle with respect to this glittering pigment is determined. The deflection angle θ is determined in the same manner for the cross sections of other toner particles, and the deflection angle θ is determined for the cross sections of a total of 20 toner particles.
It is preferable that the proportion of toner particles having an angle of deviation θ of 20° or more is 20% or more by number in the observed toner.

The cross-sectional observation of the glitter toner is performed, for example, by FE-SEM cross-sectional observation. The cross-sectional observation conditions of FE-SEM are shown below.
[Sample preparation and observation conditions in FE-SEM]
-Measuring method-
1: The sample is dyed in a 5% _Ru04 aqueous solution vapor atmosphere.
2: After embedding the dyed sample in a curable epoxy resin for 30 minutes, it is sandwiched between two parallel Teflon (registered trademark) plates and cured.
3: Cut the center of the cured oval sample with a razor.
4: Use Ag paste on a sample boulder for ion milling to fix the cut surface of the sample so that it can be processed.
5: Using an ion milling device, process the cross section while cooling at -100 degrees.
6: Observe the state of processing of the prepared cross section using a field emission scanning electron microscope (cold FE-SEM).

The processing conditions and observation conditions are shown below.
-Ion milling processing conditions-
ACCELERATION V. /3.8kV (acceleration voltage setting)
DISCHAGE V. /2.0V (discharge voltage setting)
DISCHAGE CURR. Display/386μA (discharge current)
ION BEAM CURR. Display/126μA (beam current)
Stage control/C4 swing angle ±30° Speed/30 reciprocation/min Ar GAS FLOW/0.08cm/min
Cooling temperature/-100 degrees Setting time/2.5 hours SEM observation conditions Acceleration voltage 1.0kV WD3.8mm X3K, X3.5K
SEM image: SE (∪), backscattered electron image: HA (T)
-Device-
Observation: Cold cathode field emission scanning microscope (cold FE-SEM) SU8230 manufactured by Hitachi Processing: Ion milling device IM4000 manufactured by Hitachi High-Technologies

In order to have the glitter pigment present in the glitter toner in a desired ratio of toner particles having a desired average thickness and angle of deviation θ of 20° or more, it is effective to make the following adjustments during toner production. It is.
As a preferred method for producing a toner, an organic liquid containing the bright pigment, the release agent, and the crystalline polyester is dispersed in an aqueous medium to prepare an oil-in-water (O/W type) emulsion. For example, the process may include the step of: When oil droplets are formed in an aqueous medium, the glitter pigments can move freely within the oil droplets, and it is possible to prevent the glitter pigments from lining up in the same direction. Since the oil droplets then become toner particles, the bright pigment, release agent, crystalline polyester, etc. are fixed as they are to form the toner.
Specific methods for manufacturing toner that achieve the above method include the dissolution suspension method in which toner resin and coloring material are dissolved and dispersed in an organic solvent to create oil droplets, and the suspension polymerization method using radically polymerizable monomers. Legal is suitable.

<Release agent>
The mold release agent is not particularly limited and can be appropriately selected depending on the purpose, but waxes, waxes, etc. are preferable.
Examples of the waxes and waxes include natural waxes and synthetic waxes.
Examples of the natural wax include animal wax, mineral wax, and petroleum wax. Examples of the animal wax include carnauba wax, cotton wax, wood wax, and rice wax. Examples of the petroleum wax include paraffin wax, microcrystalline, petrolatum, and the like.
Examples of the synthetic wax include synthetic hydrocarbon waxes, esters, ketones, and ethers. Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax and polyethylene wax.
Furthermore, fatty acid amides such as 12-hydroxystearamide, stearamide, phthalic anhydride, and chlorinated hydrocarbons; low molecular weight crystalline polymer resins such as poly-n-stearyl methacrylate and poly-n-lauryl; Homopolymers or copolymers of polyacrylate such as methacrylate (for example, n-stearylacrylate-ethyl methacrylate copolymers, etc.); crystalline polymers having long alkyl groups in side chains, etc. may also be used.
These waxes may be used alone or in combination of two or more, but paraffin wax is more preferable because it has sharp melt properties and is less likely to contaminate the photoreceptor or carrier.

The melting point of the mold release agent is not particularly limited and can be appropriately selected depending on the purpose, but preferably 50°C or more and 120°C or less, more preferably 60°C or more and 90°C or less. When the melting point is 50° C. or higher, it is possible to prevent the release agent from having an adverse effect on heat-resistant storage stability. When the melting point is 120° C. or lower, the problem of cold offset occurring during fixing at low temperatures can be effectively prevented.

The melting point of the mold release agent can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). That is, first, 5.0 mg of a mold release agent is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature was raised from 0 °C to 150 °C at a temperature increase rate of 10 °C/min, and then the temperature was lowered from 150 °C to 0 °C at a temperature decrease rate of 10 °C/min, and then further heated at a temperature increase rate of 10 °C/min. The temperature is raised to 150° C. at min and the DSC curve is measured. From the obtained DSC curve, the maximum peak temperature of the heat of fusion during the second temperature increase can be determined as the melting point using the analysis program in the DSC-60 system.

The melt viscosity of the mold release agent is preferably 5 cps or more and 1,000 cps or less, more preferably 10 cps or more and 100 cps or less, as measured at a temperature 20° C. higher than the melting point of the mold release agent. If the melt viscosity is 5 cps or more, deterioration in mold releasability can be prevented, and if it is 1,000 cps or less, the effects of hot offset resistance and low-temperature fixing properties can be sufficiently exhibited.

The content of the release agent in the glitter toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3% by mass or more and 40% by mass or less, and 3% by mass or more and 30% by mass. The following is more preferable, and 5% by mass or more and 20% by mass or less is particularly preferable. When the content is within a particularly preferable range, it is advantageous in achieving both hot offset resistance and stain resistance.

<Crystalline polyester>
Preferred examples of the crystalline polyester include a polyester resin synthesized from a diol component and a dicarboxylic acid component, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid polymer. Further, examples include urethane-modified polyester resins and urea-modified polyester resins having urethane bonds and/or urea bonds. Among these, a polyester resin (unmodified crystalline polyester) obtained by polycondensation of a diol component and a dicarboxylic acid component is preferred from the viewpoint of crystallinity expression.

<<Unmodified crystalline polyester>>
The unmodified crystalline polyester is obtained by polycondensation of a diol component and a dicarboxylic acid component.

[Diol component]
The diol component is preferably an aliphatic diol, and preferably has a chain carbon number of 2 or more and 36 or less. The aliphatic diol includes linear and branched diols, but linear aliphatic diols are preferred, and linear aliphatic diols having 4 or more and 6 or less carbon atoms are more preferred. Although a plurality of diol components may be used, the content of the linear aliphatic diol is preferably 80 mol% or more, more preferably 90 mol% or more, based on the total amount of diol components. be. When the amount is 80 mol % or more, the crystallinity of the resin is improved, low-temperature fixability and heat-resistant storage stability are compatible, and resin hardness tends to be improved, which is preferable.

Specifically, the linear aliphatic diol includes, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1, Examples include, but are not limited to, 14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,20-eicosandiol, etc. It is not something that will be done. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferred in terms of availability. 1,4-butanediol and 1,6-hexanediol are more preferred.

Other diols that may be used as necessary include aliphatic diols other than those mentioned above having 2 to 36 carbon atoms (1,2-propylene glycol, 1,3-butanediol, hexanediol, octanediol, decanediol, dodecane diol, tetradecane diol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol) , polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene oxides of the above alicyclic diols (hereinafter abbreviated as AO) ) [Ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] Adducts (additional mole number 1 to 30); Bisphenols (bisphenol A , bisphenol F, bisphenol S, etc.) and AO (EO, PO, BO, etc.) adducts (number of added moles of 2 to 30); polylactone diols (polyε-caprolactone diol, etc.); and polybutadiene diol.

In addition, as the trihydric to octavalent or higher alcohol component used as necessary in the synthesis of the crystalline polyester, the trivalent to octavalent or higher polyhydric aliphatic alcohol having 3 to 36 carbon atoms (Alkane polyols and their intramolecular or intermolecular dehydrates, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; sugars and their derivatives, such as sucrose, and methyl glucoside); Tris AO adducts (number of added moles of 2 to 30) of phenols (trisphenol PA, etc.); AO adducts of novolac resins (phenol novolak, cresol novolak, etc.) (number of added moles of 2 to 30); acrylic polyol [hydroxy copolymers of ethyl (meth)acrylate and other vinyl monomers]; and the like. Among these, preferred are AO adducts of polyhydric aliphatic alcohols having a valence of 3 to 8 or more and novolak resins, and more preferred are AO adducts of novolac resins.

[Dicarboxylic acid component]
As the carboxylic acid component, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable. The aliphatic dicarboxylic acids include linear and branched dicarboxylic acids, with linear dicarboxylic acids being more preferred. Furthermore, among the linear dicarboxylic acids, saturated aliphatic dicarboxylic acids having 6 or more and 12 or less carbon atoms are particularly preferred.

The dicarboxylic acids include alkanedicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, etc.); carbon number 6 Alicyclic dicarboxylic acids with a carbon number of 4 to 36 (such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.) (Alkenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, etc.); Aromatic dicarboxylic acids with 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butyl isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.).

Further, as polycarboxylic acids having a valence of 3 or more and 6 or less or more which are used as necessary in the synthesis of the crystalline polyester, aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc. ), etc.
In addition, as the dicarboxylic acid or the polycarboxylic acid having a valence of 3 or more and 6 or less or more, acid anhydrides or lower alkyl esters having 1 or more and 4 or less carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned ones can be used. May be used.

Among these dicarboxylic acids, it is preferable to use the aforementioned aliphatic dicarboxylic acids (preferably adipic acid, sebacic acid, dodecanedioic acid, etc.) alone or in combination of two or more types. Copolymerized dicarboxylic acids (preferably terephthalic acid, isophthalic acid, t-butyl isophthalic acid, lower alkyl esters thereof, etc.) are also preferred. The amount of copolymerized aromatic dicarboxylic acid is preferably 20 mol% or less.

<<Lactone ring-opening polymer>>
The lactone ring-opening polymer as the crystalline polyester is, for example, a monolactone having 3 to 12 carbon atoms (the number of ester groups in the ring is It can be obtained by ring-opening polymerization of lactones such as 1) using a catalyst such as a metal oxide or an organometallic compound. Among these, the preferred lactone is ε-caprolactone from the viewpoint of crystallinity.

It may also be a lactone ring-opening polymer having a hydroxyl group at the terminal, which is obtained by ring-opening polymerizing the above lactones using a glycol (e.g., ethylene glycol, diethylene glycol, etc.) as an initiator. For example, it may be modified to become a carboxyl group. Furthermore, commercially available products may be used, such as highly crystalline polycaprolactones such as H1P, H4, H5, and H7 of the PLACCEL series manufactured by Daicel Corporation.

<<Polyhydroxycarboxylic acid>>
The polyhydroxycarboxylic acid as the crystalline polyester can be obtained by direct dehydration condensation of hydroxycarboxylic acids such as glycolic acid and lactic acid (L-form, D-form, racemic form), A cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) corresponding to a bimolecular or trimolecular dehydration condensate of hydroxycarboxylic acid such as Ring-opening polymerization using a catalyst such as an organometallic compound is preferable from the viewpoint of controlling the molecular weight. Among these, preferred cyclic esters are L-lactide and D-lactide from the viewpoint of crystallinity. Further, these polyhydroxycarboxylic acids may be modified so that the terminal thereof becomes a hydroxyl group or a carboxyl group.

<<Urethane modified polyester resin>>
The urethane-modified polyester resin can be obtained, for example, by a reaction between a polyester resin and an isocyanate compound having a valence of at least two or more, or a reaction between a polyester resin having an isocyanate group at the terminal and a polyol component.

[Isocyanate component with valence of 2 or more]
Examples of the isocyanate component include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and aromatic aliphatic isocyanates, and among them, aromatic isocyanates having 6 to 20 carbon atoms excluding carbon in the NCO group. group diisocyanates, aliphatic diisocyanates of 2 to 18, alicyclic diisocyanates of 4 to 15, aromatic aliphatic diisocyanates of 8 to 15, and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups) , biuret group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified products, etc.) and mixtures of two or more of these. Further, if necessary, a trivalent or higher valent isocyanate may be used in combination.

<<<Urea-modified polyester resin>>>
The urea-modified polyester resin can be obtained, for example, by reacting a polyester resin having an isocyanate group at its terminal with an amine compound.

[Divalent or higher amine component]
Examples of the amine component include aliphatic amines and aromatic amines, including aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms. Furthermore, if necessary, amines having a valence of 3 or more may be used.

The crystalline polyester may be a block resin having a crystalline part and an amorphous part, and the above crystalline polyester can be used for the crystalline part. Examples of the resin used to form the amorphous portion include, but are not limited to, polyester resin, polyurethane resin, polyurea resin, and the like. The composition of these amorphous parts is the same as that of the crystalline part, and specific examples of the monomers used include the diol component, the dicarboxylic acid component, the diisocyanate component, and the diamine component. , any combination may be used as long as it results in an amorphous resin.

The crystalline polyester is a crystalline resin precursor having a functional group at the end that can react with an active hydrogen group, and is processed into a resin having an active hydrogen group, a crosslinking agent, an extender, etc. having an active hydrogen group in the toner manufacturing process. It can also be obtained by increasing the molecular weight by reacting with a compound. The crystalline resin precursor includes the above-mentioned crystalline polyester resin, urethane-modified crystalline polyester resin, urea-modified crystalline polyester resin, crystalline polyurethane resin, crystalline polyurea resin, etc., which has a functional group that can react with an active hydrogen group. It can be obtained by reacting with a compound that has

There are no particular restrictions on the functional groups that can react with the active hydrogen group, but examples include functional groups such as isocyanate groups, epoxy groups, carboxylic acids, and acid chloride groups. From this point of view, isocyanate groups are preferred. Examples of the compound having an isocyanate group include the diisocyanate component described above.

In order to obtain the crystalline resin precursor, for example, when the crystalline polyester resin and the diisocyanate component are reacted, the crystalline polyester resin is a hydroxyl group-containing crystalline polyester resin containing a hydroxyl group at the terminal. It is preferable to use

In the hydroxyl group-containing crystalline polyester resin, the ratio of the diol component to the dicarboxylic acid component is preferably 2/1 to 1/1 as an equivalent ratio [OH]/[COOH] of hydroxyl group [OH] and carboxyl group [COOH]. , more preferably 1.5/1 to 1/1, particularly preferably 1.3/1 to 1.02/1.

The resin having active hydrogen groups and the crosslinking agent, extender, and other compounds having active hydrogen groups are not particularly limited as long as they have active hydrogen groups, and can be appropriately selected depending on the purpose. For example, when the functional group capable of reacting with the active hydrogen group is an isocyanate group, examples thereof include resins and compounds having hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, etc. From the viewpoint of reaction rate, water and amines are particularly suitable.

<Number dispersion average diameter of crystalline polyester>
The number dispersion average diameter of the crystalline polyester in the glitter toner is preferably 10 nm or more and 200 nm or less, more preferably 15 nm or more and 100 nm or less, and more preferably 30 nm or more and 40 nm or less.
When the number-dispersion average diameter of the crystalline polyester is 10 nm or more, it is advantageous in achieving rapid viscosity reduction.
It is advantageous in terms of charging stability that the number dispersion average diameter of the crystalline polyester is 200 nm or less.

The number-dispersion average diameter of the crystalline polyester is determined, for example, as follows.
A cross section of an ultrathin section of the toner is observed using a transmission electron microscope (TEM), and the number distribution average diameter of the crystalline polyester is measured based on the observed image. Specifically, the measurement is performed as follows.
[Observation and measurement by TEM]
The produced toner is embedded in epoxy resin and cured.
An ultrathin section (approximately 100 nm thick) of the toner is prepared using an ultramicrotome (ULTRACUT UCT manufactured by Leica, using a diamond knife).
The sample is exposed to gas with ruthenium tetroxide, osmium tetroxide, or another staining agent to distinguish between the crystalline polyester phase and the rest. The exposure time is adjusted as appropriate depending on the contrast during observation. Thereafter, it is observed using a transmission electron microscope (JEM-2100 manufactured by JEOL) at an accelerating voltage of 100 kV. Note that there are cases where it can be identified without staining, and in that case, it is evaluated without staining. It is also possible to impart a compositional contrast by other means such as selective etching, and after such pretreatment, the release agent portion may be evaluated by observing with a transmission microscope.
The observed cross-sectional image is binarized using commercially available image processing software (eg, Image-Pro Plus, etc.) to calculate the equivalent circular diameter of the crystalline polyester. Observe 50 toner cross sections and determine the equivalent circular diameter of each part of the release agent. By taking the number average value, the number dispersion average diameter of the mold release agent can be determined.

<<<Melting point of crystalline polyester>>>
The maximum peak temperature (melting point) of the heat of fusion of the crystalline polyester is preferably 55°C or more and 80°C or less, more preferably 60°C or more and 75°C or less, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability. , 65°C or higher and 70°C are particularly preferred. When the melting point is 55° C. or higher, the low-temperature fixability and heat-resistant storage stability of the toner can be maintained well, and the generation of aggregates of toner and carrier due to stirring stress in the developing device can be effectively prevented. I can do it. On the other hand, if the melting point is 80° C. or lower, the toner can maintain good low-temperature fixability and good heat-resistant storage stability.

The ratio of the softening temperature of the crystalline polyester to the maximum peak temperature of heat of fusion (softening temperature/maximum peak temperature of heat of fusion) is preferably 0.80 or more and 1.55 or less, and 0.85 or more and 1.55 or less. It is more preferably 25 or less, even more preferably 0.90 or more and 1.20 or less, particularly preferably 0.90 or more and 1.19 or less. The closer this value is to 1.00, the more rapidly the resin softens, and the better it is from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability.

<<<Weight average molecular weight (Mw) of crystalline polyester>>>
The weight average molecular weight (Mw) of the crystalline polyester is preferably 10,000 or more and 40,000 or less, more preferably 15,000 or more and 35,000 or less, from the viewpoint of compatibility between low-temperature fixability and heat-resistant storage stability. ,000 or more and 30,000 or less is particularly preferable. When it is 10,000 or more, it is possible to effectively prevent the deterioration of the heat-resistant storage stability of the toner, and when it is 40,000 or less, it is possible to effectively prevent the deterioration of the low-temperature fixability of the toner.

The weight average molecular weight (Mw) of the resin can be measured using a gel permeation chromatography (GPC) measuring device (eg, GPC-8220GPC (manufactured by Tosoh Corporation)).
The column used is TSKgel SuperHZM-H 15cm triple column (manufactured by Tosoh Corporation). The resin to be measured is made into a 0.15% by mass solution in tetrahydrofuran (THF) (contains stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.), filtered through a 0.2 μm filter, and the filtrate is used as a sample. 100 μL of the THF sample solution is injected into the measuring device and measured at a flow rate of 0.35 mL/min in an environment at a temperature of 40° C. When measuring the molecular weight of a sample, it is calculated from the relationship between the logarithm value of a calibration curve prepared using several types of monodisperse polystyrene standard samples and the count number. As the standard polystyrene sample, ShowdexSTANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, toluene is used. An RI (refractive index) detector is used as the detector.

The content of the crystalline polyester in the glitter toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3% by mass or more and 30% by mass or less, and 3% by mass or more and 20% by mass. The following is more preferable, and 3% by mass or more and 15% by mass or less is particularly preferable. When the content is within a particularly preferable range, it is advantageous in achieving both low-temperature fixability and charging stability.

The molecular structure of the crystalline polyester can be confirmed by solution or solid NMR, X-ray diffraction, GC/MS, LC/MS, IR, etc. For example, in the IR spectrum, those having olefin δCH (out-of-plane bending vibration) absorption at 965±10 cm ⁻¹ or 990±10 cm ⁻¹ can be detected as the crystalline polyester.

<Other ingredients>
The glitter toner of the present invention may also contain other components such as an amorphous polyester, a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material.

<<Amorphous polyester>>
Examples of the amorphous polyester include unmodified polyester resin (unmodified polyester), modified polyester, and the like.
The unmodified polyester is a polyester obtained using a polyhydric alcohol and a polyhydric carboxylic acid or a derivative thereof such as a polyhydric carboxylic acid, a polycarboxylic acid anhydride, or a polyhydric carboxylic acid ester, and is an isocyanate. Polyester that has not been modified with compounds.

Examples of the polyhydric alcohol include diols.
Examples of the diol include polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane. Alkylene (carbon number 2 to 3) oxide (average added mole number 1 to 10) adducts of bisphenol A such as; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (carbon number 2 to 3) ) oxide (average number of moles added is 1 or more and 10 or less) adducts, and the like.
These may be used alone or in combination of two or more.

Examples of the polyhydric carboxylic acid include dicarboxylic acids.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; an alkyl group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms, such as dodecenylsuccinic acid and octylsuccinic acid; Examples include succinic acid substituted with an alkenyl group.
These may be used alone or in combination of two or more.

The content of the amorphous polyester in the glitter toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60% by mass or more and 95% by mass or less, and 60% by mass or more and 80% by mass. % or less, and particularly preferably 65% by mass or more and 80% by mass or less.

The molecular structure of the amorphous polyester can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc. in addition to NMR measurement using a solution or solid. A convenient method is to detect, as an amorphous polyester, a polyester that does not have absorption based on δCH (out-of-plane bending vibration) of an olefin at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in an infrared absorption spectrum.

<<Colorant>>
The coloring agent that can be used in combination with the glitter pigment is not particularly limited, and can be appropriately selected from known coloring agents depending on the purpose.
Examples of black materials include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (C.I. Pigment Black 11), titanium oxide, etc. metals, organic pigments such as aniline black (C.I. Pigment Black 1), and the like.
As a coloring pigment for magenta, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48:1, 49, 50, 51, 52, 53, 53:1, 54, 55, 57, 57:1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; C. I. Pigment Violet 19; C. I. Examples include Butt Red 1, 2, 10, 13, 15, 23, 29, 35, and the like.
Examples of cyan coloring pigments include C.I. I. Pigment Blue 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 60; C.I. I. Bat Blue 6;C. I. Examples include Acid Blue 45, copper phthalocyanine pigments in which the phthalocyanine skeleton is substituted with 1 to 5 phthalimidomethyl groups, Green 7, Green 36, and the like.
As the coloring pigment for yellow, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; C. I. Examples include Bat Yellow 1, 3, 20, Orange 36, etc.

The content of the colorant in the glitter toner is preferably 1% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less. If the content is 1% by mass or more, it is possible to prevent a decrease in the coloring power of the toner, and if the content is 15% by mass or less, poor dispersion of the pigment in the toner can be prevented, and a decrease in the coloring power and a decrease in the toner can be prevented. The problem of deterioration of electrical characteristics can be effectively prevented.

The colorant may be used as a masterbatch complexed with a resin. Although there are no particular limitations on such resin, from the viewpoint of compatibility with the binder resin, it is preferable to use the binder resin or a resin having a structure similar to the binder resin.
The masterbatch can be manufactured by mixing or kneading a resin and a colorant while applying high shear force. At this time, it is preferable to add an organic solvent to enhance the interaction between the colorant and the resin. The so-called flushing method is also suitable because the wet cake of the coloring agent can be used as it is and there is no need to dry it. The flushing method is a method in which an aqueous paste containing colorant water is mixed or kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and organic solvent are removed. For mixing or kneading, a high shear dispersion device such as a three-roll mill can be used, for example.

<<Charge control agent>>
Furthermore, in order to impart appropriate charging ability to the glitter toner, it is also possible to include a charge control agent in the glitter toner, if necessary.
As the charge control agent, any known charge control agent can be used. If colored materials are used, the color tone may change, so materials that are colorless or close to white are preferable.For example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine (including modified quaternary ammonium salts), alkylamides, phosphorus alone or its compounds, tungsten alone or its compounds, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used alone or in combination of two or more.

The content of the charge control agent is determined by the toner manufacturing method including the type of binder resin and the dispersion method, and is not uniquely limited to 0.01% of the binder resin. It is preferably from 0.02% by mass to 2% by mass, more preferably from 0.02% by mass to 2% by mass. If the content is 5% by mass or less, the effect of the charge control agent can be exerted without the toner's chargeability becoming too large, suppressing the electrostatic attraction force with the developing roller, and reducing the fluidity of the developer. It is possible to effectively prevent the problems of image density reduction and reduction of image density. When the content is 0.01% by mass or more, the charge rise property and charge amount are sufficient.

<<External additives>>
Various external additives can be added to the glitter toner for purposes such as improving fluidity, adjusting the amount of charge, and adjusting electrical properties. The external additive is not particularly limited and can be appropriately selected from known ones depending on the purpose, but examples include silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (e.g. zinc stearate, stearin metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.) or hydrophobized products thereof, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferably mentioned.

Examples of the hydrophobized silica fine particles include HDK H2000, HDK H2000/4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all manufactured by Hoechst); (manufactured by Nippon Aerosil Co., Ltd.).
Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65CS (both manufactured by Titanium Kogyo Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Kogyo Co., Ltd.); MT- 150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.).
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Kogyo Co., Ltd.); TAF-500T, TAF-1500T. (both manufactured by Fuji Titanium Industries Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); and IT-S (manufactured by Ishihara Sangyo Co., Ltd.).

The hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles are obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. It can be obtained by treatment with a hydrophobizing agent.

Examples of the hydrophobizing agent include silane coupling agents such as dialkyldihalogenated silanes, trialkylhalogenated silanes, alkyltrihalogenated silanes, and hexaalkyldisilazane, silylating agents, and silane coupling agents having a fluorinated alkyl group. agent, organic titanate coupling agent, aluminum coupling agent, silicone oil, silicone varnish, etc.

The average particle diameter of the primary particles of the external additive is preferably 1 nm or more and 100 nm or less, more preferably 3 nm or more and 70 nm or less. When the average particle size is 1 nm or more, it is possible to effectively prevent the problem that the external additive is buried in the toner and is difficult to effectively exert its function. If the thickness is 100 nm or less, the problem of uneven damage to the surface of the photoreceptor can be effectively prevented.
As the external additive, inorganic fine particles or hydrophobized inorganic fine particles can be used in combination, but it is preferable that the external additive contains at least two types of inorganic fine particles whose average particle diameter of hydrophobized primary particles is 20 nm or less, and whose average particle size is 30 nm or more. It is more preferable that at least one kind of inorganic fine particles is included. Further, the specific surface area of the inorganic fine particles measured by the BET method is preferably 20 m ² /g or more and 500 m ² /g or less.

The amount of the external additive added is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 3% by mass or less, based on the toner.

Resin fine particles can also be added as the external additive. Examples include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization; copolymers of methacrylic esters and acrylic esters; polycondensation systems such as silicone, benzoguanamine, and nylon; and polymer particles made of thermosetting resins. It will be done. By using such fine resin particles in combination, it is possible to enhance the chargeability of the toner, reduce the amount of toner with an opposite charge, and reduce background stains.

The amount of the resin fine particles added is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less, based on the toner.

<Method for producing glitter toner>
Known methods for producing the glitter toner and materials used can be used as appropriate. Examples of the method for producing the glitter toner of the present invention include a kneading and pulverizing method and a so-called chemical method in which toner particles are granulated in an aqueous medium.
Methods for producing the glitter toner of the present invention include a dissolution suspension method in which toner resins and coloring materials are dissolved and dispersed in an organic solvent to form oil droplets, and a suspension polymerization method using radically polymerizable monomers. Are suitable.
A more preferable manufacturing method is to disperse an organic liquid containing the bright pigment, the mold release agent, and the crystalline polyester in an aqueous medium to prepare an oil-in-water (O/W type) emulsion. A method for producing a glitter toner includes a step of: When oil droplets are formed in an aqueous medium, the glitter pigment, the release agent, and the crystalline polyester can move freely within the oil droplets, preventing the glitter pigments from lining up in the same direction. be able to. Since the oil droplets then become toner particles, the glitter pigment, the release agent, and the crystalline polyester are immobilized as they are. Such a method is a type of dissolution suspension method.

<<Dissolution suspension method and suspension polymerization method>>
In the dissolution/suspension method, for example, an oil phase composition in which a toner composition containing a crystalline polyester, a glitter pigment, and a release agent is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium. This is a method of manufacturing toner base particles by emulsifying the particles.

The organic solvent used for dissolving or dispersing the toner composition is preferably a volatile one with a boiling point of less than 100° C. from the standpoint of facilitating subsequent solvent removal.

Examples of the organic solvent include ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl. Ether solvents such as ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcoholic solvents such as ethylhexyl alcohol and benzyl alcohol, and mixed solvents of two or more of these solvents are included.

In the dissolution/suspension method, an emulsifier or a dispersant may be used as necessary when dispersing or emulsifying the oil phase composition in an aqueous medium.

As the emulsifier or dispersant, known surfactants, water-soluble polymers, etc. can be used.
The surfactant is not particularly limited, and includes anionic surfactants (alkylbenzenesulfonic acids, phosphoric acid esters, etc.), cationic surfactants (quaternary ammonium salt type, amine salt type, etc.), amphoteric surfactants (carboxylic acid, etc.) Examples include acid salt type, sulfate ester salt type, sulfonate salt type, phosphate ester salt type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.), and the like. One type of surfactant may be used alone or two or more types of surfactants may be used in combination.
Examples of the water-soluble polymer include cellulose compounds (for example, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, saponified products thereof, etc.), gelatin, starch, dextrin, gum arabic, chitin, and chitosan. , polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, polymers containing acrylic acid (salts) (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid) , sodium acrylate-acrylic ester copolymer), sodium hydroxide (partial) neutralization of styrene-maleic anhydride copolymer, water-soluble polyurethane (reaction product of polyethylene glycol, polycaprolactone diol, etc. and polyisocyanate) etc.).
Moreover, the above-mentioned organic solvents, plasticizers, etc. can also be used in combination as emulsifying or dispersing aids.

Glittering toner is produced by dispersing or emulsifying an oil phase composition containing at least a glittering pigment, a mold release agent, and a crystalline polyester in an aqueous medium containing fine resin particles in a dissolution/suspension method. It is preferable to obtain it by granulation.

The fine resin particles can be formed using a known polymerization method, but are preferably obtained as an aqueous dispersion of fine resin particles.
Examples of methods for preparing an aqueous dispersion of fine resin particles include the following methods (a) to (h).
(a) A method of directly preparing an aqueous dispersion of resin particles using a vinyl monomer as a starting material through a polymerization reaction of suspension polymerization, emulsion polymerization, seed polymerization, or dispersion polymerization.
(b) After dispersing precursors (monomers, oligomers, etc.) of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins or their solvent solutions in an aqueous medium in the presence of an appropriate dispersant, A method of preparing an aqueous dispersion of fine resin particles by curing by heating or by adding a curing agent.
(c) Precursors (monomers, oligomers, etc.) of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, or their solvent solutions (preferably liquid, and may be liquefied by heating). A method of preparing an aqueous dispersion of fine resin particles by dissolving a suitable emulsifier in and then adding water for phase inversion emulsification.
(d) A resin synthesized in advance through a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized using a mechanical rotary type or jet type pulverizer, and then classified. A method in which fine resin particles are obtained by this method, and then dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of fine resin particles.
(e) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (e.g., addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. After that, the resin particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of the resin particles.
(f) Adding a poor solvent to a resin solution prepared by dissolving a resin synthesized in advance through a polymerization reaction (e.g., addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heating the solvent in advance Fine resin particles are precipitated by cooling the dissolved resin solution, and after removing the solvent to form fine resin particles, the fine resin particles are dispersed in water in the presence of an appropriate dispersant to form an aqueous dispersion of the fine resin particles. How to prepare the liquid.
(g) A resin solution prepared by dissolving a resin synthesized in advance through a polymerization reaction (e.g., addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is added to an aqueous medium in the presence of a suitable dispersant. A method of preparing an aqueous dispersion of fine resin particles by removing the solvent by heating, reducing pressure, etc.
(h) After dissolving a suitable emulsifier in a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent, A method of preparing an aqueous dispersion of fine resin particles by adding and performing phase inversion emulsification.

The volume average particle size of the resin fine particles is preferably 10 nm or more and 300 nm or less, more preferably 30 nm or more and 120 nm or less. If the volume average particle diameter of the resin fine particles is 10 nm or more and 300 nm or less, the problem of deterioration of the particle size distribution of the toner can be effectively prevented.

The solid content concentration of the oil phase composition is preferably 40% by mass or more and 80% by mass or less. If the concentration is too high, it will be difficult to dissolve or disperse the toner, and the viscosity will become high, making it difficult to handle. If the concentration is too low, the productivity of the toner will decrease.

It is preferable to prepare dispersions of the crystalline polyester and the mold release agent. It is preferable to mix these dispersions together with other components to obtain an oil phase composition.

The aqueous medium may be water alone, but a water-miscible solvent may also be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

The method of dispersion or emulsification in the aqueous medium is not particularly limited, but known equipment such as a low-speed shearing method, a high-speed shearing method, a friction method, a high-pressure jet method, and an ultrasonic method can be used. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shear type disperser is used, the rotation speed is not particularly limited, but is usually 1,000 rpm or more and 30,000 rpm or less, preferably 5,000 rpm or more and 20,000 rpm or less. The temperature during dispersion is usually 0°C or more and 150°C or less (under pressure), preferably 20°C or more and 80°C or less.

In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular restriction, and a known method can be used. A method can be adopted in which the organic solvent in the droplets is completely evaporated and removed by heating.

Known techniques are used to wash and dry the toner base particles dispersed in the aqueous medium. That is, after solid-liquid separation using a centrifuge, filter press, etc., the obtained toner cake is redispersed in ion-exchanged water at room temperature to about 40°C, and the pH is adjusted with acid or alkali as necessary. Separate solid and liquid again. After repeating this process several times to remove impurities, surfactants, etc., toner powder is obtained by drying using a flash dryer, circulation dryer, vacuum dryer, vibrating fluidized dryer, or the like. At this time, fine particle components of the toner may be removed by centrifugation or the like, and after drying, a known classifier may be used if necessary to obtain a desired particle size distribution.

If an oil phase is prepared using a radically polymerizable monomer and a polymerization initiator instead of an organic solvent, and oil droplets are formed by emulsification in the same manner, a polymerization reaction is performed using heat or the like, resulting in a suspension polymerization method.
The radically polymerizable monomer is preferably a styrene, acrylic ester, or methacrylic ester monomer, and the polymerization initiator is an azo-based or peroxide-based initiator.
In the case of suspension polymerization, there is no need for a step to remove the organic solvent.
Furthermore, in order to improve the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be added to and mixed with the toner base particles produced as described above.
A general powder mixer is used to mix the additives, but it is preferably equipped with a jacket or the like so that the internal temperature can be adjusted. Note that in order to change the history of the load applied to the additive, the additive may be added midway or gradually. In this case, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. Also, a strong load may be applied first and then a relatively weak load, or vice versa. Examples of mixing equipment that can be used include a V-type mixer, a rocking mixer, a Loedige mixer, a Nauta mixer, a Henschel mixer, and the like. Next, the toner is passed through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles.

(Developer)
The developer of the present invention contains at least the above-mentioned toner and, if necessary, other appropriately selected components such as a carrier.
Therefore, while ensuring the brightness of the image, the charging characteristics over time are stable, the toner has excellent low-temperature fixability, and high image quality can be maintained. Note that the developer may be a one-component developer or a two-component developer.
When the toner is used in a two-component developer, it may be mixed with a carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 90% by mass or more and 98% by mass or less, and 93% by mass or more and 97% by mass. The following are more preferred.

<Career>
The carrier is not particularly limited and can be appropriately selected depending on the purpose, but preferably has a core material and a resin layer covering the core material.

-Core material-
The core material is not particularly limited as long as it is a magnetic particle, and suitable examples include ferrite, magnetite, iron, nickel, and the like. In addition, when considering the adaptability to the environment, which has progressed significantly in recent years, ferrites, for example, manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese-magnesium ferrite, rather than conventional copper-zinc ferrite, It is preferable to use magnesium-strontium ferrite, lithium-based ferrite, or the like.

(toner storage unit)
The toner storage unit in the present invention refers to a unit that has a function of storing toner and stores toner therein. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
The toner storage container refers to a container that stores toner.
A developing device has means for storing and developing toner.
A process cartridge is a cartridge that integrates at least an electrostatic latent image carrier (also referred to as an image carrier) and a developing means, stores toner, and is removably attached to an image forming apparatus. The process cartridge may further include at least one selected from charging means, exposure means, and cleaning means.
By attaching the toner storage unit of the present invention to an image forming apparatus and forming an image, it is possible to form an image that takes advantage of the toner's characteristics of having excellent low-temperature fixability while ensuring the brightness of the image. I can do it.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further includes other means as necessary.
The image forming method of the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be suitably performed by the electrostatic latent image forming means, and the developing step can be suitably performed by the developing means. The above-mentioned other steps can be suitably carried out by the above-mentioned other means.
The image forming apparatus of the present invention more preferably includes an electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and an electrostatic latent image carrier. a developing means comprising a glitter toner for developing the electrostatic latent image formed on the body using a glitter toner to form a toner image; and a toner formed on the electrostatic latent image carrier. It includes a transfer device that transfers an image onto the surface of a recording medium, and a fixing device that fixes the toner image transferred to the surface of the recording medium.
Further, the image forming method of the present invention more preferably includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image using a glitter toner to form a toner image; a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium; and a fixing step of fixing the toner image transferred to the surface of the recording medium.
The glitter toner is used in the developing means and the developing step. Preferably, the toner image is formed by using a developer containing the glitter toner and, if necessary, other components such as a carrier.

In the image forming apparatus and the image forming method, since the glitter toner of the present invention is used, it is possible to form an image by taking advantage of the toner's characteristics of having excellent low-temperature fixability while ensuring the glitter of the image. It can be carried out.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. , polysilane, phthalopolymethine, and other organic photoreceptors. Among these, amorphous silicon is preferred in terms of long life.

<Electrostatic latent image forming means and electrostatic latent image forming process>
The electrostatic latent image forming means is not particularly limited as long as it forms an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected depending on the purpose. Examples include means having at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that imagewise exposes the surface of the electrostatic latent image carrier.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected depending on the purpose. This can be done by charging the surface of the electrostatic latent image carrier and then exposing it imagewise, and can be done using the electrostatic latent image forming means.

<<Charging member and charging>>
The charging member is not particularly limited and can be appropriately selected depending on the purpose, for example, a contact charger that is known per se and equipped with a conductive or semiconductive roller, brush, film, rubber blade, etc. , corotron, scorotron, and other non-contact chargers that utilize corona discharge.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

<<Exposure member and exposure>>
The exposure member is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charging member in the form of an image to be formed, and is appropriately selected depending on the purpose. Examples thereof include various exposure members such as copying optical systems, rod lens array systems, laser optical systems, and liquid crystal shutter optical systems.

<Developing means and developing process>
The developing means is not particularly limited as long as it is equipped with toner and is capable of developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. It can be selected as appropriate.
The developing step is not particularly limited as long as it is a step in which the electrostatic latent image formed on the electrostatic latent image carrier is developed with toner to form a visible image, and it can be used depending on the purpose. It can be selected as appropriate depending on the situation, and for example, it can be carried out using the above-mentioned developing means.

The developing means may be of a dry type development type or may be of a wet type development type. Further, it may be a single color developing means or a multicolor developing means. The developing means includes a stirrer that frictionally stirs the toner to charge it and a magnetic field generating means fixed therein, and a rotatable developer carrier that carries the developer containing the toner on its surface. A developing device having a body is preferred.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static eliminating means, a recycling means, a control means, and the like.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, a control process, and the like.

Image formation using the toner of the present invention will be described below.
FIG. 2 is an overall configuration diagram of an image forming apparatus showing an embodiment of the present invention.
The image forming apparatus 1 shown in FIG. 2 is a color image forming apparatus that forms a color image by a tandem image forming section (hereinafter referred to as an image forming section), and includes an image reading section 10, an image forming section 11, and a paper feeding section. 12, a transfer section 13, a fixing section 14, and a paper discharge section 15.

The image reading unit 10 is for reading an image of a document and generating image information. The image reading unit 10 includes a contact glass 101 and a reading sensor 102. In the image reading unit 10, light is irradiated onto the original, and the reflected light is received by a sensor such as a CCD (charge-coupled device) or CIS (contact image sensor). Load color separation signals.

The image forming section 11 forms and outputs toner images of the glitter toner (S) of the present invention in addition to four colors of yellow (Y), magenta (M), cyan (C), and black (K). It is composed of three image forming units 110S, 110Y, 110M, 110C, and 110K.

The five image forming units 110S, 110Y, 110M, 110C, and 110K each use S toner, Y toner, M toner, C toner, and K toner of different colors as image forming materials, respectively. , otherwise have the same configuration, and are replaced when the service life is reached. The image forming units 110S, 110Y, 110M, 110C, and 110K are configured to be removably attached to the apparatus main body 2, and constitute a so-called process cartridge. Hereinafter, the common configuration will be explained using the image forming unit 110K for forming a K toner image as an example.

The image forming unit 110K includes a charging device 111K (charging member), a photoreceptor 112K (electrostatic latent image carrier) serving as a K color toner image carrier that carries a K color toner image on its surface, and a developing device 114K (developing means). ), a static eliminator 115K, a photoreceptor cleaning device 116K (cleaning means), and the like. These devices are held in a common holder and can be replaced at the same time by being integrally attached to and detached from the device body 2.

The photoreceptor 112K has a drum shape with an outer diameter of 60 mm and has an organic photosensitive layer formed on the surface of a substrate, and is rotated counterclockwise by a driving means. The charging device 111K applies a charging bias to the charging wire, which is the charging electrode of the charging charger, to generate a discharge between the charging wire and the outer peripheral surface of the photoreceptor 112K, and the surface of the photoreceptor 112K is is uniformly charged. In this embodiment, the toner is charged to the same negative polarity as the toner. As the charging bias, a voltage obtained by superimposing an alternating current voltage on a direct current voltage is used. Note that instead of the charging charger, a method using a charging roller provided in contact with or close to the photoreceptor 112K may be adopted.

The surface of the uniformly charged photoreceptor 112K is optically scanned by a laser beam irradiated from an exposure device 113 (exposure member), which will be described later, to form an electrostatic latent image for K. Of the entire area of the uniformly charged surface of the photoreceptor 112K, the potential of the area irradiated with the laser beam is attenuated, and the potential of the laser irradiation area is smaller than the potential of the other area (background area) due to the electrostatic potential. Become a statue. This electrostatic latent image for K is developed into a K toner image by a developing device 114K using K toner, which will be described later. The image is then primarily transferred onto an intermediate transfer belt 131, which will be described later.

The developing device 114K has a container in which a two-component developer containing K toner and carrier is stored, and the developer is supported on the surface of the developing sleeve by the magnetic force of a magnet roller inside the developing sleeve provided in the container. A developing bias having the same polarity as the toner, larger than the electrostatic latent image on the photoreceptor 112K, and smaller than the charging potential of the photoreceptor 112K is applied to the development sleeve. A developing potential from the developing sleeve toward the electrostatic latent image acts between the developing sleeve and the electrostatic latent image on the photoreceptor 112K. Further, a non-development potential that moves the toner on the development sleeve toward the sleeve surface acts between the development sleeve and the background portion of the photoreceptor 112K. Due to the action of the developing potential and non-developing potential, the K toner on the developing sleeve is selectively attached to the electrostatic latent image on the photoreceptor 112K and developed, thereby forming a K color toner image on the photoreceptor 112K. be done.

The static eliminator 115K removes static from the surface of the photoreceptor 112K after the toner image has been primarily transferred to the intermediate transfer belt 131. The photoreceptor cleaning device 116K includes a cleaning blade and a cleaning brush, and removes transfer residual toner and the like remaining on the surface of the photoreceptor 112K, which has been neutralized by the static eliminator 115K.

In FIG. 2, the image forming unit 110S includes a charging device 111S, a photoreceptor 112S as a special color toner image carrier that carries a special color toner image on its surface, a developing device 114S, a static eliminator 115S, a photoreceptor cleaning device 116S, and the like. ing. The same applies to the other image forming units 110C, 110M, and 110Y. Therefore, in the image forming units 110C, 110M, 110Y, and 110S, S toner images and Y toner images are formed on the respective photoreceptors 112S, 112Y, 112M, and 112C in the same manner as in the image forming unit 110K. A toner image, an M toner image, and a C toner image are respectively formed.

An exposure device 113 serving as a latent image writing member or an exposure member is arranged above the image forming units 110S, 110Y, 110M, 110C, and 110K. The exposure device 113 optically scans the photoreceptors 112S, 112Y, 112M, 112C, and 112K with laser light emitted from a laser diode based on image information sent from the image reading unit 10 or external equipment such as a personal computer. do.

The exposure device 113 polarizes the laser beam emitted from the light source in the main scanning direction by a polygon mirror rotationally driven by a polygon motor, and passes it through a plurality of optical lenses and mirrors to the photoreceptors 112S, 112Y, 112M, 112C, and 112K. It irradiates the area. Instead of laser light, a configuration may be adopted in which optical writing and irradiation are performed using LED light emitted from a plurality of LEDs.

The paper feed section 12 supplies paper, which is an example of paper, to the transfer section 13, and includes a paper storage section 121, a paper feed pickup roller 122, a paper feed belt 123, and a registration roller 124. The paper feed pickup roller 122 is provided to rotate in order to move the paper stored in the paper storage section 121 toward the paper feed belt 123. The paper feed pickup roller 122 provided in this manner picks out the uppermost paper sheets one by one from among the stored paper sheets and places them on the paper feed belt 123. The paper feed belt 123 conveys the paper picked up by the paper feed pickup roller 122 to the transfer section 13 . The registration rollers 124 feed the paper at the timing when the portion of the intermediate transfer belt 131 on which the toner image is formed reaches the secondary transfer nip 139 as a transfer nip of the transfer section 13.

The transfer section 13 is arranged below the image forming units 110S, 110Y, 110M, 110C, and 110K. The transfer unit 13 includes a drive roller 132, a driven roller 133, an intermediate transfer belt 131, primary transfer rollers 134S, 134Y, 134M, 134C, 134K, a secondary transfer roller 135, a secondary transfer opposing roller 136, and a toner adhesion amount sensor 137. , and a belt cleaning device 138.

The intermediate transfer belt 131 functions as an endless intermediate transfer body, and includes a drive roller 132, a driven roller 133, a secondary transfer opposing roller 136, primary transfer rollers 134S, 134Y, 134M, and It is strung with 134C, 134K, etc. Note that "arrangement" means to arrange and provide or to provide at a determined position, and "stretch" means to stretch something under tension.

The intermediate transfer belt 131 endlessly moves and runs in the same direction by a drive roller 132 that is rotationally driven clockwise in the figure by a drive means, and moves while contacting the photoreceptors 112S, 112Y, 112M, 112C, and 112K.

The intermediate transfer belt 131 used has a thickness of 20 to 200 [μm], preferably about 60 [μm]. In addition, the volume resistivity is about 1×10 ⁶ to 1×10 ¹² [Ω・cm], preferably about 1×10 ⁹ [Ω・cm] (using Mitsubishi Chemical's Hirester UP MCP HT45 at an applied voltage of 100 V). carbon-dispersed polyimide resin (measured under the following conditions) is desirable.

A toner adhesion amount sensor 137 is arranged near the intermediate transfer belt 131 wrapped around the drive roller 132 . The toner adhesion amount sensor 137 functions as a toner amount detection means for detecting the amount of toner image transferred onto the intermediate transfer belt 131. The toner adhesion amount sensor 137 is composed of a light reflection type photosensor. The toner adhesion amount sensor 137 measures the amount of toner adhesion by detecting the amount of reflected light from the toner image (including special color toner) attached and formed on the intermediate transfer belt 131. Note that the toner adhesion amount sensor 137 may also be used as a toner concentration sensor as toner concentration detection means for detecting and measuring toner concentration that has been commonly used in the past due to the above function. In this case, it is possible to avoid providing a new toner amount detection means, thereby reducing the number of parts and contributing to cost reduction. Note that instead of the position facing the intermediate transfer belt 131, the toner adhesion amount sensor 137 may be placed at a position where the toner image on the photoreceptor 112 is detected.

The primary transfer rollers 134S, 134Y, 134M, 134C, and 134K are arranged to face the photoreceptors 112S, 112Y, 112M, 112C, and 112K, respectively, with the intermediate transfer belt 131 in between, and move the intermediate transfer belt 131. Rotate as follows. As a result, a primary transfer nip is formed in which the front surface of the intermediate transfer belt 131 and the photoreceptors 112S, 112Y, 112M, 112C, and 112K are in contact (meaning that they are in contact with each other). . A primary transfer bias is applied to each of the primary transfer rollers 134S, 134Y, 134M, 134C, and 134K by a primary transfer bias power source. As a result, each of the S toner image, Y toner image, M toner image, C toner image, and K toner image on each of the photoreceptors 112S, 112Y, 112M, 112C, and 112K, and the primary transfer roller 134S, A primary transfer bias is formed between each of 134Y, 134M, 134C, and 134K. Then, the toner images of each color are sequentially transferred onto the intermediate transfer belt 131.

The S toner image formed on the surface of the S photoconductor 112S enters the S primary transfer nip as the photoconductor 112S rotates. Then, the image is primarily transferred from the photoreceptor 112S onto the intermediate transfer belt 131 by the action of the transfer bias and nip pressure. The intermediate transfer belt 131 to which the S toner image has been primarily transferred in this manner then passes through Y, M, C, and K primary transfer nips in sequence. Then, each of the Y toner image, M toner image, C toner image, and K toner image on each of the photoreceptors 112Y, 112M, 112C, and 112K is primarily transferred onto the S toner image by being superimposed on the image. Ru. By this primary transfer of superposition, a superimposed toner image including a color toner image and a special color toner image such as clear toner is formed on the intermediate transfer belt 131. That is, toner images carried on the surfaces of the color toner image carrier and the special color toner image carrier are superimposed and transferred onto the intermediate transfer belt 131 .

The primary transfer rollers 134S, 134Y, 134M, 134C, and 134K are elastic rollers having a metal core and a conductive sponge layer fixed on the surface thereof, and have an outer diameter of 16 mm. , with a core metal diameter of 10 [mm]. In addition, while pressing a grounded metal roller with an outer diameter of 30 [mm] against the sponge layer with a force of 10 [N], the core metal of the primary transfer rollers 134S, 134Y, 134M, 134C, and 134K was The resistance value R of the sponge layer was calculated from the current I flowing when a voltage of [V] was applied. Specifically, the resistance value R of the sponge layer calculated based on Ohm's law (R=V/I) from the current I flowing when a voltage of 1000 [V] is applied to the core metal is approximately 3. ×10 ⁷ [Ω]. A primary transfer bias output from a primary transfer bias power source under constant current control is applied to such primary transfer rollers 134S, 134Y, 134M, 134C, and 134K. Note that a transfer charger, a transfer brush, or the like may be used instead of the primary transfer rollers 134S, 134Y, 134M, 134C, and 134K.

The secondary transfer roller 135 sandwiches the intermediate transfer belt 131 and the paper between it and the secondary transfer opposing roller 136, and is rotationally driven by a driving means. The secondary transfer roller 135 contacts the front surface of the intermediate transfer belt 131 to form a secondary transfer nip 139 as a transfer nip, and also transfers the toner image of the intermediate transfer belt onto the recording medium sandwiched by the secondary transfer nip. It functions as a nip forming member and a transfer member for transferring. The secondary transfer opposing roller 136 functions as a nip forming member and an opposing member. While the secondary transfer roller 135 is grounded, a secondary transfer bias is applied to the secondary transfer opposing roller 136 by the secondary transfer bias power source 130.

The secondary transfer bias power supply 130 has a DC power supply and an AC power supply, and can output a DC voltage superimposed with an AC voltage as the secondary transfer bias. The output terminal of the secondary transfer bias power supply 130 is connected to the core of the secondary transfer opposing roller 136. The potential of the core metal of the secondary transfer opposing roller 136 becomes approximately the same value as the output voltage value from the secondary transfer bias power supply 130.

By applying a secondary transfer bias to the secondary transfer counter roller 136, toner of negative polarity is transferred between the secondary transfer counter roller 136 and the secondary transfer roller 135 from the secondary transfer counter roller 136 side. A secondary transfer bias for electrostatic movement toward the roller 135 side is formed. Thereby, the negative polarity toner on the intermediate transfer belt 131 can be moved from the secondary transfer opposing roller 136 side to the secondary transfer roller 135 side.

For the secondary transfer bias power supply 130, a DC component having the same negative polarity as the toner is used, and the time-average potential of the superimposed bias is made to have the same negative polarity as the toner. Note that instead of applying a superimposed bias to the secondary transfer roller 136 and grounding the secondary transfer roller 135, applying a superimposition bias to the secondary transfer roller 135 and grounding the core metal of the secondary transfer counter roller 136. It may be grounded, in which case the polarity of the DC voltage and DC component will be different.

When using paper with large surface irregularities, such as embossed paper, by applying the above-mentioned superimposed bias, the toner is moved back and forth and relatively moved from the intermediate transfer belt 131 side to the paper side. and transfer it onto the paper. Thereby, it is possible to improve the transferability to the recessed portions of the paper, improve the transfer rate, and improve abnormal images such as hollow spots. On the other hand, when using paper with small irregularities such as ordinary transfer paper, a shading pattern that follows the uneven pattern does not appear, so sufficient transferability can be obtained by applying a secondary transfer bias using only a DC component. I can do it.

The secondary transfer opposing roller 136 is made of a metal core made of stainless steel, aluminum, or the like and a resistance layer laminated thereon. The secondary transfer opposing roller 136 has the following characteristics. That is, the outer diameter is approximately 24 [mm]. Further, the diameter of the core metal is approximately 16 [mm]. The resistance layer is made of polycarbonate, fluorine rubber, or silicone rubber in which conductive particles such as carbon or metal complexes are dispersed, or rubber such as NBR or EPDM, NBR/ECO copolymer rubber, or semiconductive polyurethane. Made of rubber, etc. Its volume resistivity is 10 ⁶ to 10 ¹² [Ω], preferably 10 ⁷ to 10 ⁹ [Ω]. Further, the rubber hardness (ASKER-C) may be a foam type with a rubber hardness of 20 to 50 degrees or a rubber type with a rubber hardness of 30 to 60 degrees, but since it contacts the secondary transfer roller 135 via the intermediate transfer belt 131, the contact pressure is small. However, a sponge type that does not create non-contact parts is preferable. Transfer residual toner that was not transferred to the paper remains on the intermediate transfer belt 131 after the secondary transfer that has passed through the secondary transfer nip. This is removed and cleaned from the surface of the intermediate transfer belt 131 by a belt cleaning device 138 equipped with a cleaning blade that is in contact with the surface of the intermediate transfer belt 131.

The fixing unit 14 is of a belt fixing type, and is configured by pressing a pressure roller 142 against a fixing belt 141 that is an endless belt. The fixing belt 141 is wound around a fixing roller 143 and a heating roller 144, and at least one of the rollers is provided with a heat source/heating means (heater, lamp, electromagnetic induction heating device, etc.). The fixing belt 141 is sandwiched and pressed between the fixing roller 143 and the pressure roller 142, forming a fixing nip between the fixing belt 141 and the pressure roller 142.

The paper fed into the fixing unit 14 is held in the fixing nip in such a manner that its unfixed toner image bearing surface is brought into close contact with the fixing belt 141 . Then, since the toner in the toner image is softened by heating and pressure, the toner image is fixed, and the paper is discharged outside the machine. Furthermore, when an image is to be formed on the opposite side of the paper to which the toner image has been transferred, after the toner image is fixed, the paper is conveyed to a paper reversing mechanism, and the paper is reversed by the paper reversing mechanism. Thereafter, a toner image is formed on the opposite side in the same manner as in the image forming process described above.

The paper to which the toner has been fixed in the fixing section 14 is ejected from the image forming apparatus main body 2 to the outside of the image forming apparatus via a paper ejection roller that constitutes a paper ejection section 15, and is stored in a paper storage section 151 such as a paper ejection tray. Ru.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. In addition, "part" represents "part by mass" unless otherwise specified. "%" represents "mass %" unless otherwise specified.

<Preparation of aqueous phase>
In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, 16 parts of sodium salt Eleminol RS-30 (manufactured by Sanyo Chemical Industries, Ltd.) of the sulfuric ester of the ethylene oxide adduct of methacrylic acid, 83 parts of styrene, and 83 parts of methacrylic acid. 1 part, 110 parts of n-butyl acrylate, and 1 part of ammonium persulfate. Thereafter, the mixture was stirred at 400 rpm for 15 minutes. Next, the temperature was raised to 75°C, and the mixture was reacted for 5 hours. Furthermore, after adding 30 parts of a 1% by mass ammonium persulfate aqueous solution, the mixture was aged at 75° C. for 5 hours to obtain a vinyl resin dispersion.
The volume average particle diameter of the vinyl resin dispersion was measured using a laser diffraction/scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) and found to be 14 nm.
Further, the vinyl resin had an acid value of 45 mgKOH/g, a weight average molecular weight of 300,000, and a glass transition point of 60°C.
455 parts of water, 7 parts of vinyl resin dispersion, 17 parts of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate Eleminol MON-7 (manufactured by Sanyo Chemical Industries, Ltd.), and 41 parts of ethyl acetate were mixed and stirred. (total of 520 parts).

<Synthesis of wax dispersant 1>
480 parts of xylene and 100 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.) were placed in a reaction tank equipped with a stirring rod and a thermometer and heated until dissolved, then replaced with nitrogen and heated to 170°C. It was warm. Next, a mixed solution of 740 parts of styrene, 100 parts of acrylonitrile, 60 parts of butyl acrylate, 36 parts of di-t-butylperoxyhexahydroterephthalate, and 100 parts of xylene was added dropwise over 3 hours, and then heated at 170°C for 30 minutes. held. Furthermore, the wax dispersant 1 was obtained by removing the solvent.

<Preparation of wax dispersion W1>
In a container equipped with a stirring rod and a thermometer, 150 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 15 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed. Thereafter, the temperature was raised to 80°C while stirring and maintained at 80°C for 5 hours. Next, after cooling to 30°C in 1 hour, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 1 kg/h, the circumferential speed of the disk was 10 m/s, and the diameter of the disk was 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed under three pass conditions to obtain a wax dispersion W1.
The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 180 nm.

<Synthesis of crystalline polyester resin (C)>
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1,6-hexanediol was used as the diol component, sebacic acid was used as the dicarboxylic acid component, and the molar ratio of hydroxyl group to carboxylic acid (OH/COOH) was 1. I put it in so that it would be 2.
Next, titanium tetraisopropoxide was added in an amount of 500 ppm based on the total amount of monomers, the temperature was raised to 180° C. over 2 hours, and the reaction was carried out for 8 hours while distilling off the water produced. Next, while gradually raising the temperature to 200°C, the reaction was carried out for 3 hours while distilling off the generated water under a nitrogen stream, and further under reduced pressure of 5 mmHg to 20 mmHg, the melting point was 67°C, the weight average molecular weight was 20, 000 [crystalline polyester resin (C)] was obtained.

<Preparation of crystalline polyester resin (C1) dispersion>
After putting 10 parts of [crystalline polyester resin (C)] and 90 parts of ethyl acetate into a reaction vessel equipped with a cooling tube, a thermometer, and a stirrer, the temperature was raised to 80°C with stirring, and the mixture was sufficiently dissolved. .
Thereafter, after cooling to 30°C, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 1 kg/h, the circumferential speed of the disk was 6 m/s, and 80 volumes of zirconia beads with a diameter of 0.5 mm were added. % filling, wet pulverization under 3-pass conditions, and ethyl acetate was added to prepare a [crystalline polyester resin (C1) dispersion] with a solid content concentration of 10%.

<Synthesis of amorphous polyester resin R2>
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen insertion tube, 222 parts of an adduct of bisphenol A with 2 mol of ethylene oxide, 129 parts of an adduct of bisphenol A with 2 mol of propylene oxide, 166 parts of isophthalic acid, and 0.0 parts of tetrabutoxy titanate were added. I included 5 parts. Thereafter, the reaction was carried out at 230° C. for 8 hours under a nitrogen stream while distilling off the produced water. Next, the reaction was carried out under reduced pressure of 5 mmHg to 20 mmHg, and when the acid value reached 2 mgKOH/g, it was cooled to 180°C (normal pressure), and 35 parts of trimellitic anhydride was added and reacted for 3 hours. A crystalline polyester resin R2 was obtained.
The amorphous polyester resin R2 had a weight average molecular weight of 8,000 and a glass transition point of 62°C.

<Preparation of oil phase 1>
In a container equipped with a thermometer and a stirrer,
- 100 parts of amorphous polyester resin R2, and - 105 parts of ethyl acetate were added and stirred to dissolve.
Here,
・Crystalline polyester resin (C1) dispersion 15 parts ・Wax dispersion W1 20 parts, and ・Large particle diameter aluminum paste pigment 20 parts (BPB180PA manufactured by Toyo Aluminum Co., Ltd. (propyl acetate dispersion solid content 50%))
After adding, using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), the mixture was mixed at 5,000 rpm for 1 hour while keeping the internal temperature at 20°C in an ice bath, and the liquid was stirred at room temperature with air. The oil phase 1 having a solid content concentration of 50% by mass was obtained by spraying onto the surface.

(Example 1)
After 550 parts of the aqueous phase was placed in a container equipped with a stirrer and a thermometer, the mixture was maintained at 60° C. on a water bath. Next, 450 parts of oil phase 1 kept at 60°C was added and mixed for 1 minute at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while keeping it at 60°C. An emulsified slurry was obtained. The obtained emulsified slurry was stirred for 1 hour until the temperature reached 50°C. The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed under reduced pressure at 50° C. to obtain a slurry with a solid content of 80% in oil droplets.
Next, the obtained slurry was cooled to room temperature and then filtered under reduced pressure. 200 parts of ion-exchanged water was added to the filter cake, mixed for 5 minutes at 800 rpm using a Three-One Motor (manufactured by Shinto Kagakusha), and after reslurry, it was filtered. Furthermore, 10 parts of a 1% by mass aqueous sodium hydroxide solution and 190 parts of ion-exchanged water were added to the filter cake, and the mixture was reslurried in the same manner, followed by filtration. Next, 10 parts of 1% by mass hydrochloric acid and 190 parts of ion-exchanged water were added to the filter cake to reslurry it in the same manner, followed by filtration. Furthermore, 300 parts of ion-exchanged water was added to the filter cake to reslurry it, and then filtering was repeated twice.
The filter cake was dried at 45° C. for 48 hours using a circulating air dryer, and then sieved using a mesh having an opening of 75 μm to obtain toner base particles.
100 parts of toner base particles and 1 part of hydrophobized silica HDK-2000 (manufactured by Wacker Chemie) were mixed for 30 seconds at a circumferential speed of 30 m/s using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The operation of pausing for a minute was repeated five times. Next, the toner 1 of Example 1 was obtained by sieving using a mesh having an opening of 35 μm.

(Example 2)
In Example 1, the large particle size aluminum paste pigment used in the preparation of oil phase 1 was changed to the following medium particle size aluminum pigment paste, and the wax dispersion W1 was replaced with the following wax dispersion W2. Toner 2 was obtained in the same manner as in Example 1.
・Medium particle diameter aluminum pigment paste 20 parts (manufactured by Toyo Aluminum Co., Ltd. 2172EAYC (propyl acetate dispersion, solid content 50%)

<Preparation of wax dispersion W2>
In a container equipped with a stirring rod and a thermometer, 150 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 15 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed. Thereafter, the temperature was raised to 80°C while stirring and maintained at 80°C for 5 hours. Next, after cooling to 30°C for 3 hours, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 1 kg/h, the circumferential speed of the disk was 15 m/s, and the diameter of the disk was 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed under six passes to obtain a wax dispersion W2.
The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 105 nm.

(Example 3)
Oil phase 2 was obtained by changing the large particle size aluminum paste pigment used in the preparation of oil phase 1 to the following small particle size aluminum pigment paste. Furthermore, the following operations were performed to obtain a toner.
・20 parts of small particle size aluminum pigment paste (manufactured by Toyo Aluminum Co., Ltd. 2173EAYC (propyl acetate dispersion, solid content 50%)

After 550 parts of the aqueous phase was placed in a container equipped with a stirrer and a thermometer, the mixture was maintained at 60° C. on a water bath. Next, 450 parts of oil phase 2 kept at 60°C was added and mixed for 1 minute at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while keeping it at 60°C. An emulsified slurry was obtained. The resulting emulsified slurry was stirred for 1 hour until the temperature reached 25°C. The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed under reduced pressure at 25° C. to obtain a slurry with a solid content of 80% in oil droplets.
Next, the obtained slurry was cooled to room temperature and then filtered under reduced pressure. 200 parts of ion-exchanged water was added to the filter cake, mixed for 5 minutes at 800 rpm using a Three-One Motor (manufactured by Shinto Kagakusha), and after reslurry, it was filtered. Furthermore, 10 parts of a 1% by mass aqueous sodium hydroxide solution and 190 parts of ion-exchanged water were added to the filter cake, and the mixture was reslurried in the same manner, followed by filtration. Next, 10 parts of 1% by mass hydrochloric acid and 190 parts of ion-exchanged water were added to the filter cake to reslurry it in the same manner, followed by filtration. Furthermore, 300 parts of ion-exchanged water was added to the filter cake to reslurry it, and then filtering was repeated twice.
The subsequent processing was the same as in Example 1 to obtain Toner 3.

(Example 4)
After 550 parts of the aqueous phase was placed in a container equipped with a stirrer and a thermometer, the mixture was maintained at 60° C. on a water bath. Next, 450 parts of oil phase 2 kept at 60°C was added and mixed for 1 minute at 8,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while keeping it at 60°C. An emulsified slurry was obtained. The obtained emulsified slurry was stirred for 1 hour until the temperature reached 40°C. The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed under reduced pressure at 40° C. to obtain a slurry with a solid content of 80% in terms of solid content in oil droplets.
Next, the obtained slurry was cooled to room temperature and then filtered under reduced pressure. 200 parts of ion-exchanged water was added to the filter cake, mixed for 5 minutes at 800 rpm using a Three-One Motor (manufactured by Shinto Kagakusha), and after reslurry, it was filtered. Furthermore, 10 parts of a 1% by mass aqueous sodium hydroxide solution and 190 parts of ion-exchanged water were added to the filter cake, and the mixture was reslurried in the same manner, followed by filtration. Next, 10 parts of 1% by mass hydrochloric acid and 190 parts of ion-exchanged water were added to the filter cake to reslurry it in the same manner, followed by filtration. Furthermore, 300 parts of ion-exchanged water was added to the filter cake to reslurry it, and then filtering was repeated twice.
The subsequent processing was the same as in Example 3 to obtain Toner 4.

(Example 5)
Toner 5 was obtained by processing in the same manner as in Example 3, except that wax dispersion W1 was replaced with wax dispersion W3.

<Preparation of wax dispersion W3>
In a container equipped with a stirring rod and a thermometer, 200 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 20 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed, and the mixture was heated to 80°C while stirring. The temperature was raised to 80° C. and maintained at 80° C. for 5 hours. Next, after cooling to 30°C for 3 hours, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 1 kg/h, the circumferential speed of the disk was 15 m/s, and the diameter of the disk was 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed under three pass conditions to obtain a wax dispersion W3.
The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 200 nm.

(Example 6)
Toner 6 was obtained in the same manner as in Example 3, except that the [crystalline polyester resin (C1) dispersion] was replaced with the following [crystalline polyester resin (C2) dispersion]. .

<Preparation of crystalline polyester resin (C2) dispersion>
After putting 10 parts of [crystalline polyester resin (C)] and 90 parts of ethyl acetate into a reaction vessel equipped with a cooling tube, a thermometer, and a stirrer, the temperature was raised to 80 ° C. with stirring, and the mixture was sufficiently dissolved. .
Thereafter, after cooling to 30°C, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 5 kg/h, the circumferential speed of the disk was 3 m/s, and 80 volumes of zirconia beads with a diameter of 0.5 mm were added. % filling, wet pulverization under one pass conditions, and ethyl acetate was added to prepare a [crystalline polyester resin (C2) dispersion] with a solid content concentration of 10%.

(Example 7)
Toner 10 was obtained in the same manner as in Example 1 except that wax dispersion W1 was replaced with wax dispersion W4.

<Preparation of wax dispersion W4>
In a container equipped with a stirring rod and a thermometer, 150 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 15 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed. Thereafter, the temperature was raised to 80°C while stirring and maintained at 80°C for 5 hours. Next, after cooling to 30°C for 3 hours, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding speed was 10 kg/h, the circumferential speed of the disk was 30 m/s, and the diameter of the disk was 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed under six pass conditions to obtain a wax dispersion W4.
The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 50 nm.

(Example 8)
Toner 11 was obtained in the same manner as in Example 1 except that wax dispersion W1 was replaced with wax dispersion W5.

<Preparation of wax dispersion W5>
In a container equipped with a stirring rod and a thermometer, 150 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 15 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed. Thereafter, the temperature was raised to 80°C while stirring and maintained at 80°C for 5 hours. Next, after cooling to 30°C for 1 hour, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 1 kg/h, the circumferential speed of the disk was 5 m/s, and the diameter of the disk was 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed in one pass to obtain wax dispersion W21.
The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 350 nm.

(Example 9)
After 550 parts of the aqueous phase was placed in a container equipped with a stirrer and a thermometer, the mixture was maintained at 60° C. on a water bath. Next, 450 parts of oil phase 1 kept at 60°C was added and mixed for 1 minute at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while keeping it at 60°C. An emulsified slurry was obtained. The resulting emulsified slurry was stirred for 1 hour until the temperature reached 55°C. The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed under reduced pressure at 55° C. to obtain a slurry with a solid content of 80% in terms of solid content in oil droplets.
Next, the obtained slurry was cooled to room temperature and then filtered under reduced pressure. 200 parts of ion-exchanged water was added to the filter cake, mixed for 3 minutes at 800 rpm using a Three-One Motor (manufactured by Shinto Kagakusha Co., Ltd.), and after reslurry, it was filtered. Furthermore, 10 parts of a 1% by mass aqueous sodium hydroxide solution and 190 parts of ion-exchanged water were added to the filter cake, and the mixture was reslurried in the same manner, followed by filtration. Next, 10 parts of 1% by mass hydrochloric acid and 190 parts of ion-exchanged water were added to the filter cake to reslurry it in the same manner, followed by filtration. Further, 300 parts of ion-exchanged water was added to the filter cake to reslurry it, and then filtering was repeated twice.
The subsequent processing was carried out in the same manner as in Example 1 to obtain toner 12.

(Comparative example 1)
Toner 7 was obtained by processing in the same manner as in Example 1, except that wax dispersion W1 was replaced with wax dispersion W6 below.

<Preparation of wax dispersion W6>
In a container equipped with a stirring rod and a thermometer, 200 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 20 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed, and the mixture was heated to 80°C while stirring. The temperature was raised to 80° C. and maintained at 80° C. for 5 hours. Next, after cooling to 30°C in 15 minutes, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 1 kg/h, the circumferential speed of the disk was 3 m/s, and the diameter of the disk was 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed in one pass to obtain a wax dispersion W6. The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 350 nm.

(Comparative example 2)
After 550 parts of the aqueous phase was placed in a container equipped with a stirrer and a thermometer, the mixture was maintained at 20° C. on a water bath. Next, 450 parts of oil phase 1 kept at 20°C was added and mixed for 1 minute at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while keeping it at 20°C. An emulsified slurry was obtained. The obtained emulsified slurry was stirred for 1 hour until the temperature reached 40°C. The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed under reduced pressure at 40° C. to obtain a slurry with a solid content of 80% in terms of solid content in oil droplets.
Next, the obtained slurry was cooled to room temperature and then filtered under reduced pressure. 200 parts of ion-exchanged water was added to the filter cake, mixed for 5 minutes at 800 rpm using a Three-One Motor (manufactured by Shinto Kagakusha), and after reslurry, it was filtered. Furthermore, 10 parts of a 1% by mass aqueous sodium hydroxide solution and 190 parts of ion-exchanged water were added to the filter cake, and the mixture was reslurried in the same manner, followed by filtration. Next, 10 parts of 1% by mass hydrochloric acid and 190 parts of ion-exchanged water were added to the filter cake to reslurry it in the same manner, followed by filtration. Furthermore, 300 parts of ion-exchanged water was added to the filter cake to reslurry it, and then filtering was repeated twice.
The subsequent processing was the same as in Example 1 to obtain Toner 8.

(Comparative example 3)
Toner 9 was obtained in the same manner as in Example 1, except that oil phase 1 was changed to oil phase 3 below.

<Preparation of oil phase 3>
In a container equipped with a thermometer and a stirrer,
- 100 parts of amorphous polyester resin R2, and - 105 parts of ethyl acetate were added and stirred to dissolve. Here,
- 20 parts of wax dispersion W1, and - 20 parts of small particle size aluminum paste pigment (manufactured by Toyo Aluminum Co., Ltd. 2173YC (propyl acetate dispersion solid content 50%))
After adding the mixture, mix at 5,000 rpm for 1 hour while keeping the internal temperature at 20°C using a TK type homomixer (manufactured by Tokushu Kika Co., Ltd.), and blow air onto the liquid surface while stirring at room temperature. As a result, an oil phase 3 having a solid content concentration of 50% by mass was obtained.

(Comparative example 4)
Toner 13 was obtained in the same manner as in Example 1 except that wax dispersion W1 was replaced with wax dispersion W7.

<Preparation of wax dispersion W7>
In a container equipped with a stirring rod and a thermometer, 150 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 30 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed. Thereafter, the temperature was raised to 80°C while stirring and maintained at 80°C for 5 hours. Next, after cooling to 30°C for 3 hours, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 5 kg/h, the circumferential speed of the disk was 60 m/s, and a diameter of 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed under six pass conditions to obtain a wax dispersion W7.
The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 40 nm.

(Comparative example 5)
Toner 14 was obtained by processing in the same manner as in Example 1, except that wax dispersion W1 in Example 1 was replaced with wax dispersion W8.

<Preparation of wax dispersion W8>
In a container equipped with a stirring rod and a thermometer, 150 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.), 15 parts of wax dispersant 1, and 335 parts of ethyl acetate were placed. Thereafter, the temperature was raised to 80°C while stirring and maintained at 80°C for 5 hours. Next, after cooling to 30°C for 1 hour, using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding rate was 1 kg/h, the circumferential speed of the disk was 5 m/s, and the diameter of the disk was 0.5 mm. Zirconia beads were filled at 80% by volume and dispersed in one pass to obtain wax dispersion W8.
The particle size of the obtained wax dispersion was measured with LA-920 (manufactured by Horiba, Ltd.) and was 450 nm.

(Comparative example 6)
After 550 parts of the aqueous phase was placed in a container equipped with a stirrer and a thermometer, the mixture was maintained at 60° C. on a water bath. Next, 450 parts of oil phase 1 kept at 60°C was added and mixed for 1 minute at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while keeping it at 60°C. An emulsified slurry was obtained. The obtained emulsified slurry was stirred for 3 hours until the temperature reached 20°C. The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed under reduced pressure at 20° C. to obtain a slurry with a solid content of 80% in oil droplets.
Next, the obtained slurry was cooled to room temperature and then filtered under reduced pressure. 200 parts of ion-exchanged water was added to the filter cake, mixed for 3 minutes at 800 rpm using a Three-One Motor (manufactured by Shinto Kagaku Co., Ltd.), and after reslurry, it was filtered. Furthermore, 10 parts of a 1% by mass aqueous sodium hydroxide solution and 190 parts of ion-exchanged water were added to the filter cake, and the mixture was reslurried in the same manner, followed by filtration. Next, 10 parts of 1% by mass hydrochloric acid and 190 parts of ion-exchanged water were added to the filter cake to reslurry it in the same manner, followed by filtration. Furthermore, 300 parts of ion-exchanged water was added to the filter cake to reslurry it, and then filtering was repeated twice.
The subsequent processing was carried out in the same manner as in Example 1 to obtain Toner 15.

<Evaluation method of obtained toner>
<<Glitter evaluation>>
Using an image forming apparatus using a developer containing toner, the metallicity of the image was evaluated by the evaluation method described below. The results are shown in Table 1.
Using a commercially available copying machine Imageo Neo C600 (manufactured by Ricoh Co., Ltd.), a solid image was created on the entire surface of the paper with a toner adhesion amount of 0.50 ± 0.02 mg/cm ² after transfer onto POD gloss paper manufactured by Oji Paper Co., Ltd. (image size 3 cm x 8 cm) was created. Further, a solid image was created on the transfer paper at a position 3.0 cm from the leading edge in the paper passing direction. Note that the speed of passing through the nip portion of the fixing device was 146 rpm, and the fixing temperature was 180°C.
The flop index value (color change depending on the viewing angle) was used as an evaluation index for the metallicity of the obtained toner-fixed image.
The flop index value is calculated using the following formula. The lightness (L*) value required for calculation was measured with a multi-angle colorimeter (BYK-mac i). Note that "L*15°" is the brightness measured from an angle of 15° with respect to the image, and "L*45°" is the brightness measured from an angle of 45° with respect to the image. "L*110°" is the brightness measured from an angle of 110° with respect to the image. Furthermore, the higher the flop index value, the greater the color change depending on the viewing angle, and the higher the metallicity.
(Formula) [2.69×(L*15°-L*110°) ^1.11 ]/[(L*45°) ^0.86 ]
Based on the obtained flop index value, metallicity was evaluated based on the following evaluation criteria.
[Evaluation criteria]
Rank 5: Flop index value is 7.5 or more Rank 4: Flop index value is 6.5 or more and less than 7.5 Rank 3: Flop index value is 5.5 or more and less than 6.5 Rank 2: Flop index value is 4.5 or more and less than 5.5 Rank 1: Flop index value is less than 4.5

<<Low temperature fixability>>
Using an imagio MP C4300 (manufactured by Ricoh Co., Ltd.) unit, a 2 cm x 15 cm rectangular solid image was printed on PPC paper type 6000 <70W> A4 T (manufactured by Ricoh Co., Ltd.) with a toner adhesion amount of 0. It was formed to have a concentration of 40 mg/cm ² .
At this time, change the surface temperature of the fixing roller, observe whether an offset occurs in which the undeveloped image of the solid image is fixed to a location other than the desired location, and set the lowest surface temperature at which no offset occurs as the lower fixing limit. Temperature. As for a toner having low-temperature fixability, if it is 0 or higher, there is no problem in use.
[Low temperature fixability evaluation criteria]
◎: Less than 110℃ ○: 110℃ or more, less than 120℃ △: 120℃ or more, less than 130℃ ×: 130℃ or more

<<Charging stability over time>>
Using an evaluation machine that was a modified Ricoh digital full-color copying machine imagioColor 2800 and tuned to allow adjustment of linear speed and transfer time, a solid pattern of A4 size and toner adhesion amount of 0.6 mg/cm ² was created for each developer. A paper passing test was conducted using 100,000 sheets as test images.
As a substitute index for durability, we sampled some of the developer at the initial stage (at the time of 0K sheets) and after the running test of 100,000 sheets (after 100K sheets), and measured the amount of charge using the method shown below. Charge stability over time was evaluated by comparing the amount of charge of the toner after the paper test.

- Initial charge amount, after 100K sheets (charge amount of developer in actual machine) -
The amount of charge of the toner was measured using a blow-off device (manufactured by Ricoh Sozo Kaihatsu Co., Ltd.).
A sample of 1 g of developer from a copying machine is used to measure the toner charge amount distribution using a single mode method using a blow-off device (manufactured by Ricoh Sozo Kaihatsu Co., Ltd.). When blowing, use a 635 mesh opening. The measurement conditions are height 5mm, suction 100, and blow twice.
[Durability evaluation criteria]
◎: Difference between initial charging and charging after 100K is less than 5μC/g ○: Difference between initial charging and charging after 100K is 5μC/g or more and less than 8μC/g △: Difference between initial charging and charging after 100K is 8μC/g or more and 10μC Less than /g ×: Difference between initial charging and charging after 100K is 10μC/g or more

<<Image stability>>
Using each toner, a continuous output durability test of 300,000 sheets of a chart with an image area ratio of 10% was carried out, and unevenness in image density after output was visually evaluated. ◎ indicates that there is no unevenness on the image, ○ indicates that slight density unevenness is observed but is not a problem, △ indicates that density unevenness is slightly noticeable and is on the edge of the allowable range, × indicates that the density is outside the allowable range The unevenness becomes very noticeable.

Table 1 shows the physical properties of the produced toner and the evaluation results. Note that various physical properties were determined by the methods described in this specification.

Physical properties using abbreviations in Table 1 are as follows.
・“Ratio of crystalline PE”: Number of crystalline polyesters existing within a distance of 0.3 μm from the glitter pigment, relative to the total crystalline polyesters
・"Percentage of toner with an angle of deviation θ of 20° or more": Among the plurality of glitter pigments contained in the toner particles of a glitter toner, the longest glitter pigment and the maximum angle of deflection for this glitter pigment. Percentage of toner particles whose polar angle θ is 20° or more with the bright pigment having

Aspects of the present invention are, for example, as follows.
<1> Contains a bright pigment, a mold release agent, and a crystalline polyester,
The release agent has a number dispersion average diameter of 30 nm or more and 200 nm or less,
The glitter toner is characterized in that the crystalline polyester present within a distance of 0.3 μm from the glitter pigment accounts for 50% by number or more and 80% by number or less of the entire crystalline polyester.
<2> An angle of deviation between the longest glittering pigment among the plurality of glittering pigments contained in the toner particles of the glittering toner and the glittering pigment having the largest polarization angle with respect to this glittering pigment. The glitter toner according to <1> above, wherein the proportion of toner particles having θ of 20° or more is 20% by number or more.
<3> The glitter toner according to any one of <1> to <2>, wherein the crystalline polyester has a number-dispersion average diameter of 20 nm or more and 40 nm or less.
<4> The glitter toner according to any one of <1> to <3>, wherein the glitter pigment has an average thickness of 0.3 μm or more and 1.0 μm or less.
<5> The glitter toner according to any one of <1> to <4>, wherein the release agent is paraffin wax.
<6> A method for producing a glitter toner, comprising producing the glitter toner according to any one of <1> to <5> above.
A glitter toner comprising the step of dispersing an organic liquid containing the glitter pigment, the release agent, and the crystalline polyester in an aqueous medium to prepare an oil-in-water emulsion. This is a manufacturing method.
<7> A toner storage unit containing the glitter toner according to any one of <1> to <5>.
<8> Electrostatic latent image carrier;
an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
a developing means equipped with the glitter toner, which develops the electrostatic latent image formed on the electrostatic latent image carrier using a glitter toner to form a toner image;
The image forming apparatus is characterized in that the glitter toner is the glitter toner according to any one of <1> to <5>.
<9> An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier using a glitter toner to form a toner image,
The image forming method is characterized in that the glitter toner is the glitter toner described in any one of <1> to <5> above.

The glitter toner according to the above <1> to <5>, the method for producing the glitter toner according to the above <6>, the toner storage unit according to the above <7>, the image forming apparatus according to the above <8> , and the image forming method described in <9> above can solve the above-mentioned conventional problems and achieve the object of the present invention.

1 Image forming device 112Y Photoconductor 112M Photoconductor 112C Photoconductor 112K Photoconductor 112S Photoconductor 131 Intermediate transfer belt 135 Secondary transfer roller 137 Toner adhesion amount sensor 139 Secondary transfer nip

Japanese Patent Application Publication No. 2016-139053 Japanese Patent Application Publication No. 2017-003990

Claims (8)

Contains bright pigment, mold release agent, and crystalline polyester,
The release agent has a number dispersion average diameter of 30 nm or more and 200 nm or less,
The crystalline polyester has a number dispersion average diameter of 20 nm or more and 40 nm or less,
A glitter toner characterized in that the crystalline polyester present within a distance of 0.3 μm from the glitter pigment accounts for 50% by number or more and 80% by number or less of the entire crystalline polyester. Among the plurality of glitter pigments contained in the toner particles of the glitter toner, the polar angle θ between the longest glitter pigment and the glitter pigment having the largest polar angle with respect to the glitter pigment is: The glitter toner according to claim 1, wherein the proportion of toner particles having an angle of 20° or more is 20% or more by number. 3. The glitter toner according to claim 1, wherein the glitter pigment has an average thickness of 0.3 μm or more and 1.0 μm or less. 4. The glitter toner according to claim 1, wherein the release agent is paraffin wax. 5. A method for producing a glitter toner, comprising: producing the glitter toner according to any one of claims 1 to 4 .
A glitter toner comprising the step of dispersing an organic liquid containing the glitter pigment, the release agent, and the crystalline polyester in an aqueous medium to prepare an oil-in-water emulsion. manufacturing method. A toner storage unit containing the glitter toner according to any one of claims 1 to 4 . an electrostatic latent image carrier;
an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
a developing means equipped with the glitter toner, which develops the electrostatic latent image formed on the electrostatic latent image carrier using a glitter toner to form a toner image;
An image forming apparatus, wherein the glitter toner is the glitter toner according to any one of claims 1 to 4 . an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier using a glitter toner to form a toner image,
An image forming method, wherein the glitter toner is the glitter toner according to any one of claims 1 to 4 .

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