JP2013130794A - Transparent toner and method for manufacturing the same, toner set, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide transparent toner capable of forming an enlivened print image giving a strong visual impression.SOLUTION: In the transparent toner, a volume average primary particle size is 18 μm or more and 28 μm or less, and a content (composition ratio) of a sulfur element having been measured by fluorescent X rays is 0.01% or more and 0.1% or less. In the toner set containing the transparent toner and colored toner, a number average particle size index GSDPc of the colored toner and a number average particle size index GSDPt of the transparent toner satisfy the relationship of expression (1): 1.03<GSDPt/GSDPc<1.15, and a volume average primary particle size of the transparent toner is three times or more and eight times or less as large as a volume average primary particle size of the colored toner.

Description

  The present invention relates to a transparent toner, a method for producing the same, a toner set, and an image forming method.

In recent years, since the electrophotographic method has started to be used in the printing field, it has been demanded to obtain an image with a special effect that has been conventionally performed in printing by electrophotography. One of them is a technique called enveloping printing in which a transparent resin layer having an image thickness of about 20 to 100 μm is formed on a colored image to give a visually emphasized impression.
The engraving printing requires a thick image and has not been studied so far in electrophotographic printing.
Further, as conventional transparent toners, for example, toners described in Patent Documents 1 to 5 are known, and many of them are for uniformizing the gloss of an image and obtaining a photographic image quality.

JP-A-10-301339 Special table 2010-533318 gazette JP 2002-236396 A JP 2005-99122 A JP 2005-274614 A

  An object of the present invention is to provide a transparent toner capable of forming a raised print image that gives a visually strong impression.

The above-described problems of the present invention have been solved by the means described in <1>, <2>, <4> or <6> below. It is shown below with <3> and <5> which are preferable embodiments.
<1> The volume average primary particle size is 18 μm or more and 28 μm or less, and the content (composition ratio) of sulfur element measured by fluorescent X-ray is 0.01% or more and 0.1% or less. Transparent toner,
<2> The transparent toner according to <1> above and a colored toner, wherein the number average particle size index GSDPc of the color toner and the number average particle size index GSDPt of the transparent toner satisfy the relationship of the following formula (1): A toner set in which the volume average primary particle size of the transparent toner is 3 to 8 times the volume average primary particle size of the colored toner,
1.03 <GSDPt / GSDPc <1.15 (1)
<3> When the content (composition ratio) of sulfur element of the transparent toner measured by fluorescent X-ray is St and the content of sulfur element (composition ratio) of the colored toner measured by fluorescent X-ray is Sc, The toner set according to <2>, wherein the sulfur amount ratio St / Sc satisfies the relationship of the following formula (2):
0.1 ≦ St / Sc ≦ 1.0 (2)
<4> including a step of forming a transparent resin layer derived from the transparent toner according to the above <1> on at least a part of the color image derived from the color toner and performing print-up printing, the number average particle size index GSDPc of the color toner, The number average particle size index GSDPt of the transparent toner satisfies the relationship of the following formula (1), and the volume average primary particle size of the transparent toner is 3 to 8 times the volume average primary particle size of the colored toner. , Image forming method,
1.03 <GSDPt / GSDPc <1.15 (1)
<5> When the content (composition ratio) of the sulfur element of the transparent toner measured by fluorescent X-ray is St and the content (composition ratio) of the sulfur element of the colored toner measured by fluorescent X-ray is Sc, The image forming method according to <4>, wherein the sulfur amount ratio St / Sc satisfies the relationship of the following formula (2).
0.1 ≦ St / Sc ≦ 1.0 (2)
<6> a raw material excluding toner external additives, comprising: an aggregation step of at least aggregating transparent resin particles in an aqueous medium to obtain aggregated particles; and a fusion step of fusing the aggregated particles by heating to obtain a transparent toner. When the glass transition temperature measured by differential scanning calorimetry of the composition mixed at the toner composition ratio is Mg, in the aggregating step, the temperature range is (Mg + 10 ° C.) to (Mg + 30 ° C.) and 45 ° C. to 70 ° C. The method for producing a transparent toner according to <1>, wherein the aggregation is performed in a temperature range of ° C.

According to the invention described in <1>, it is possible to provide a transparent toner capable of forming a raised print image that gives a visually strong impression as compared with the case where the present configuration is not provided.
According to the invention described in <2> above, it is possible to provide a toner set capable of forming a raised print image that gives a visually strong impression as compared with the case where the present configuration is not provided.
According to the invention described in <3> above, it is possible to provide a toner set capable of forming a raised print image that gives a visually stronger impression as compared with the case where the present configuration is not provided.
According to the invention described in <4>, it is possible to provide an image forming method capable of forming a raised print image that gives a visually strong impression as compared with the case where the present configuration is not provided.
According to the invention described in <5> above, it is possible to provide an image forming method capable of forming a raised print image that gives a visually stronger impression as compared with the case where the present configuration is not provided.
According to the invention described in the above <6>, a transparent toner manufacturing method that can easily form a transparent printed image that can form a raised print image that gives a visually strong impression as compared with the case without this configuration. Can be provided.

Hereinafter, the present embodiment will be described.
In the present embodiment, the description “A to B” represents not only a range between A and B but also a range including A and B at both ends thereof. For example, if “A to B” is a numerical value range, “A or more and B or less” or “B or more and A or less” is represented.

(Transparent toner)
The transparent toner of the present embodiment has a volume average primary particle size of 18 μm or more and 28 μm or less, and a sulfur element content (composition ratio) measured by fluorescent X-ray is 0.01% or more and 0.1% or less. It is characterized by being.
The transparent toner of the present exemplary embodiment is preferably used as an electrostatic charge image developing transparent toner, and particularly preferably used as an electrostatic charge image developing transparent toner for raised printing.

The present inventors have found that not only the image gloss but also the sharp image edge is an important factor in the visual impression of the raised image.
As a result of studies by the present inventors, when a raised image is formed with a transparent toner having a large particle diameter, a transparent resin layer is formed on the image. However, since the image is thick, the image structure is affected by the pressure during transfer. The problem that it is easy to collapse was found. Further, it has been found that the image structure is liable to be destroyed even under pressure during heat fixing, and the sharpness of the image edge portion is impaired.
The elemental sulfur (hereinafter also referred to as “S”) contained in the transparent toner is mainly derived from, for example, a surfactant. The present inventors have found that the transparent toner contains an appropriate amount of S, that is, the content (composition ratio) of sulfur element measured by fluorescent X-ray in the transparent toner is 0.01% or more and 0.1% or less. It was also found that due to the hygroscopicity of S, liquid cross-linking force is generated between the toner particles, and the image is not easily collapsed by the transfer pressure and the heat fixing pressure. On the other hand, if the S content is too large, the hygroscopicity increases, the toner transferability deteriorates, and the sharpness of the image edge portion is impaired.

The volume average primary particle size of the transparent toner of the exemplary embodiment is 18 μm or more and 28 μm or less, preferably 18 to 26 μm, and more preferably 18 to 24 μm. Within the above range, the image thickness of the raised image can be easily formed, the deformation of the image can be suppressed, and a raised printed image that gives a visually stronger impression is formed.
As a method for measuring the volume average primary particle size of the transparent toner of the present embodiment and the color toner described later, a known method may be used, but using a Multisizer II (manufactured by Beckman-Coulter) measuring device, A method for measuring the volume average particle diameter of the toner particles is preferable. In the method, it is preferable to use ISOTON-II (manufactured by Beckman Coulter, Inc.) as the electrolytic solution.

In the transparent toner of this embodiment, the content (composition ratio, mol%) of sulfur element measured by fluorescent X-ray is 0.01% or more and 0.1% or less, and 0.02% or more and 0.08. % Or less, more preferably 0.03% or more and 0.06% or less, and further preferably 0.03% or more and 0.04% or less. Within the above range, a sufficient liquid crosslinking force between the toner particles can be obtained, and the collapse of the image due to the transfer pressure and the heat fixing pressure can be suppressed, so that a raised print image that gives a visually stronger impression is formed.
In addition, content of the said sulfur element represents the ratio (mol%) of the composition ratio, ie, the number of sulfur atoms with respect to the number of atoms of all the elements measured.
The sulfur element contained in the transparent toner of this embodiment and the color toner described later is considered to be contained in the toner due to various factors. For example, the case where the binder resin or other component itself contains a sulfur element or the case where the binder resin or other component itself contains a sulfur element is estimated.
Among these, the transparent toner of this embodiment preferably contains a surfactant having a sulfur atom. The surfactant having a sulfur atom is more preferably a sulfonate compound, and further preferably a disulfonate compound. The same applies to the color toner described later.
As a fluorescent X-ray analysis method for measuring the content of elemental sulfur in the toner, for example, XRF-1500 (manufactured by Shimadzu Corporation) is used as a measuring device, and measurement conditions are a tube voltage of 40 kV, a tube current of 70 mA, The measurement time is 15 minutes, and the measurement area is obtained by quantitative analysis with a diameter of 10 mm (sample amount 0.3 g formed into a cylindrical shape with a diameter of 10 mm).

In the transparent toner of the present embodiment, the number average particle size distribution index GSDP is preferably 1.50 or less, more preferably 1.20 to 1.50, and 1.25 to 1.45. More preferably.
In the present embodiment, the value of the number average particle size distribution index GSDP is measured and calculated as follows. First, using the Multisizer II (manufactured by Beckman-Coulter) measurement system, draw the cumulative distribution from the smaller diameter side for the divided particle size range (channel), and the cumulative distribution from the smaller diameter side. cumulative 16% to become the particle diameter D _16v, D _16p the particle diameter at a cumulative 16% for the number, D _50v particle diameter at cumulative 50% for volume, D _50p particle diameter at cumulative 50% for the number , The particle size that is 84% cumulative with respect to volume is defined as D _84v , and the particle size that is cumulative 84% with respect to number is defined as D _84p .
Using these measured values, the volume average particle size distribution index (GSDv) is lower than √ (D _84v / D16 _v ), and the number average particle size distribution index (GSDp) is lower than √ (D _84p / D _16p ). The average particle size distribution index (under GSDp) was calculated from √ (D _50p / D _16p ). In the present embodiment, the particle size is D _50v and GSDP is the lower number average particle size distribution index (below GSDp).

The transparent toner of this embodiment preferably contains a binder resin and does not substantially contain a colorant.
Here, “substantially containing no colorant” means that the content of the colorant in the transparent toner is 1% by weight or less of the whole transparent toner, and is 0.1% by weight or less. Preferably, it contains no colorant. It should be noted that coloring with a small amount of impurities and slight coloring with each component contained in the transparent toner are acceptable. In addition, from the viewpoint of color adjustment, the transparent toner may contain a very small amount of a colorant such as a slight addition of a blue pigment. It can be used, but preferably contains no colorant.
Further, the binder resin in the transparent toner of the present embodiment preferably includes a polyester resin, and more preferably a polyester resin.

<Binder resin>
The transparent toner of this embodiment preferably contains at least a binder resin.
Binder resins include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl acetate, methyl acrylate, acrylic Α-methylene aliphatic monocarboxylic acid ester such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, vinyl methyl ether, Examples thereof include homopolymers or copolymers of vinyl ethers such as vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone.
Particularly typical binder resins include polystyrene resin, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride. Examples include copolymers, polyethylene, and polypropylene. Further examples include polyester resins, polyurethane resins, epoxy resins, silicone resins, polyamide resins, modified rosin resins, paraffins, and waxes. Among these, a polyester resin is particularly preferable.

The polyester resin used in this embodiment is synthesized from a polyol component and a polycarboxylic acid component by polycondensation. In addition, in this embodiment, a commercial item may be used as said polyester resin, and what was synthesize | combined suitably may be used.
Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid And aromatic dicarboxylic acids such as dibasic acids. Furthermore, these anhydrides and these lower alkyl esters are also exemplified, but not limited thereto.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, anhydrides thereof, and the like. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.
Furthermore, it is more preferable to contain a dicarboxylic acid component having an ethylenically unsaturated double bond in addition to the above-mentioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid. A dicarboxylic acid having an ethylenically unsaturated double bond is preferably used to prevent hot offset at the time of fixing in that it can be radically crosslinked through the ethylenically unsaturated double bond. Examples of such dicarboxylic acids include, but are not limited to, maleic acid, fumaric acid, 3-hexenedioic acid, and 3-octenedioic acid. In addition, these lower esters, acid anhydrides and the like are also included. Among these, fumaric acid, maleic acid and the like are mentioned in terms of cost.

Examples of the polyhydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2 -Bisphenol A alkylene (carbon number 2 to 4) oxide adduct (average number of added moles 1.5 to 6) such as bis (4-hydroxyphenyl) propane, ethylene glycol, propylene glycol, neopentyl glycol, 1, 4 -Butanediol, 1,3-butanediol, 1,6-hexanediol and the like.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, pentaerythritol, glycerol, trimethylolpropane and the like.
In the amorphous polyester resin (also referred to as “non-crystalline polyester resin”), among the raw material monomers described above, a dihydric or higher secondary alcohol and / or a divalent or higher aromatic carboxylic acid compound is preferable. Examples of the dihydric or higher secondary alcohol include a propylene oxide adduct of bisphenol A, propylene glycol, 1,3-butanediol, and glycerol. In these, the propylene oxide adduct of bisphenol A is preferable.
As the divalent or higher aromatic carboxylic acid compound, terephthalic acid, isophthalic acid, phthalic acid and trimellitic acid are preferable, and terephthalic acid and trimellitic acid are more preferable.

Further, it is preferable to use a crystalline polyester resin as a part of the binder resin in order to impart low-temperature fixability to the toner.
The crystalline polyester resin is preferably composed of an aliphatic dicarboxylic acid and an aliphatic diol, and more preferably a linear dicarboxylic acid or a linear aliphatic diol having 4 to 20 carbon atoms in the main chain portion. The linear type is excellent in the crystallinity of the polyester resin and has an appropriate crystal melting point, and thus is excellent in toner blocking resistance, image storage stability, and low-temperature fixability. Further, when the carbon number is 4 or more, the ester bond concentration is low, the electric resistance is moderate, and the toner charging property is excellent. Further, when it is 20 or less, it is easy to obtain practical materials. The carbon number is more preferably 14 or less.

Examples of the aliphatic dicarboxylic acid suitably used for the synthesis of the crystalline polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelinic acid, sebacic acid, 1,9-nonane. Dicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid An acid, 1,18-octadecanedicarboxylic acid or the like, or a lower alkyl ester or an acid anhydride thereof may be mentioned, but not limited thereto. Among these, considering availability, sebacic acid and 1,10-decanedicarboxylic acid are preferable.
Specific examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol 1,18-octadecanediol, 1,14-eicosandecanediol and the like, but are not limited thereto. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.
Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

Among the polyvalent carboxylic acid components, the content of the aliphatic dicarboxylic acid is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content of the aliphatic dicarboxylic acid is 80 mol% or more, the polyester resin is excellent in crystallinity and has an appropriate melting point, and therefore toner blocking resistance and image storage stability. And it is excellent in low-temperature fixability.
Among the polyhydric alcohol components, the content of the aliphatic diol component is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content of the aliphatic diol component is 80 mol% or more, the polyester resin is excellent in crystallinity and has an appropriate melting point, and therefore excellent in toner blocking resistance, image storage stability, and low-temperature fixability.

In the present embodiment, the crystalline melting point Tm of the crystalline polyester resin is preferably 50 to 100 ° C, more preferably 50 to 90 ° C, and still more preferably 50 to 80 ° C. The above range is preferable because it is excellent in peelability and low-temperature fixability and can further reduce offset.
Here, for measuring the crystalline melting point of the crystalline polyester resin, a differential scanning calorimeter was used, and JIS K-7121 measured at a temperature rising rate of 10 ° C./min from room temperature (20 ° C.) to 180 ° C. : The melting peak temperature of the input compensated differential scanning calorimetry shown in 87. The crystalline polyester resin may show a plurality of melting peaks, but in this embodiment, the maximum peak is regarded as the crystalline melting point.

On the other hand, the glass transition temperature (Tg) of the amorphous polyester resin is preferably 30 ° C. or higher, more preferably 30 to 100 ° C., and still more preferably 50 to 80 ° C. If it is in the above range, since it is in a glass state in use, toner particles do not aggregate due to heat and pressure received during image formation, and do not adhere and accumulate in the machine, and stable image forming ability over a long period of time. can get.
Here, the glass transition temperature of the non-crystalline polyester resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.
Moreover, the measurement of the glass transition temperature in this embodiment can be measured by, for example, “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to the differential scanning calorimetry, and specifically, about 10 mg of a sample. Is heated at a constant rate of temperature increase (10 ° C./min), and the glass transition temperature is obtained from the intersection of the baseline and the endothermic peak tilt line.

The weight average molecular weight of the crystalline polyester resin is preferably 10,000 to 60,000, more preferably 15,000 to 45,000, and still more preferably 20,000 to 30,000. .
The weight average molecular weight of the amorphous polyester resin is preferably 5,000 to 100,000, more preferably 10,000 to 90,000, and 20,000 to 80,000. Is more preferable.
It is preferable that the weight average molecular weights of the crystalline polyester resin and the non-crystalline polyester resin are within the above ranges because both the image strength and the fixability can be achieved. All of the above weight average molecular weights can be obtained by molecular weight measurement by gel permeation chromatography (GPC) method in which tetrahydrofuran (THF) is soluble. The molecular weight of the resin is calculated by using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample by measuring THF soluble material with THF solvent using TSK-GEL (GMH (manufactured by Tosoh Corporation)) etc. Is done.

The acid value of the crystalline polyester resin and the amorphous polyester resin is preferably 1 to 50 mgKOH / g, more preferably 5 to 50 mgKOH / g, and still more preferably 8 to 50 mgKOH / g. . The above range is preferable because it is excellent in fixing characteristics and charging stability.
If necessary, a monovalent acid such as acetic acid or benzoic acid or a monovalent alcohol such as cyclohexanol benzyl alcohol may be used for the purpose of adjusting the acid value or the hydroxyl value.

The production method of the polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Depending on the type, it will be manufactured separately. Further, it is preferable to use a polycondensation catalyst such as a metal catalyst or a Bronsted acid catalyst.
The polyester resin may be produced by subjecting the polyhydric alcohol and polyhydric carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid, if necessary, a catalyst, and blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heat at 150 ° C to 250 ° C to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant Manufactured by doing.

  Further, the content of the binder resin in the transparent toner of this embodiment is not particularly limited, but is preferably 5 to 99% by weight with respect to the total weight of the electrostatic image developing toner, and 20 to 98% by weight. %, More preferably 40 to 95% by weight. Within the above range, the fixing property, storage property, powder property, charging property and the like are excellent.

<Release agent>
The transparent toner of this embodiment preferably contains at least a release agent.
There is no restriction | limiting in particular in the mold release agent used for this embodiment, A well-known thing is used and what is obtained from the following waxes is preferable. Paraffin wax and derivatives thereof, montan wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, and the like. Derivatives include oxides, polymers with vinyl monomers, and graft modified products. In addition, alcohols, fatty acids, plant waxes, animal waxes, mineral waxes, ester waxes, acid amides and the like are also used.

  The wax used as a release agent is preferably melted at any temperature of 70 ° C. to 140 ° C. and exhibits a melt viscosity of 1 to 200 centipoise, more preferably 1 to 100 centipoise. When the melting temperature is 70 ° C. or higher, the change temperature of the wax is sufficiently high, and the blocking resistance and the developability are excellent when the temperature in the copying machine is increased. When the temperature is 140 ° C. or lower, the change temperature of the wax is sufficiently low, it is not necessary to perform fixing at a high temperature, and the energy saving property is excellent. Further, when the melt viscosity is 200 centipoises or less, the elution from the toner is appropriate and the fixing peelability is excellent.

  The content of the releasing agent is preferably 3 to 60% by weight, more preferably 5 to 40% by weight, and 7 to 20% by weight based on the total weight of the toner. Is more preferable. Within the above range, the toner is more excellent in preventing the toner from being offset to the heating member, and more excellent in preventing the feed roll from being contaminated.

<Other additives>
In addition to the components as described above, various components such as an internal additive, a charge control agent, and an external additive can be added to the toner of the exemplary embodiment as necessary. Moreover, the catalyst, surfactant, those residues, etc. which are mentioned later may be included.
Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, and magnetic materials such as compounds containing these metals.
Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments.
The external additive is added to the toner base particles mainly for the purpose of adjusting the viscoelasticity of the toner. For example, silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide and the like are listed in detail below. In general, all inorganic particles used as an external additive on the toner surface can be used.

In the toner of this embodiment, the shape factor SF1 (= ((absolute maximum length of toner diameter) ² / toner projected area) × (π / 4) × 100) is preferably in the range of 110 to 160, and 125 The range of ~ 140 is more preferable.
Note that the value of the shape factor SF1 indicates the roundness of the toner, which is 100 in the case of a true sphere, and increases as the shape of the toner becomes indefinite. Further, the values required for calculation using the shape factor SF1, that is, the absolute maximum length of the toner diameter and the projected area of the toner are enlarged to 500 times magnification using an optical microscope (Nikon Corporation, Microphoto-FXA). The obtained toner particle image was photographed, and the obtained image information was obtained by introducing the image information into an image analyzer (Luzex III) manufactured by Nireco Co., Ltd. via an interface and performing image analysis. The average value of the shape factor SF1 was calculated based on data obtained by measuring 1,000 toner particles sampled randomly.
When the shape factor SF1 is 110 or more, the generation of residual toner in the transfer process during image formation is suppressed, and the cleaning property when cleaning with a blade or the like is excellent, and as a result image defects are suppressed. On the other hand, when the shape factor SF1 is 160 or less, when the toner is used as a developer, the toner is prevented from being destroyed by the collision with the carrier in the developing device, and as a result, the generation of fine powder is suppressed. As a result, the surface of the photoreceptor is prevented from being contaminated by the release agent component exposed on the toner surface, and not only the charging characteristics are excellent, but also the occurrence of fog caused by fine powder is suppressed.

<Method for producing transparent toner>
The production method of the transparent toner of the present embodiment is not particularly limited as long as the transparent toner of the present embodiment can be obtained. , A kneading and pulverizing method for classifying, a method for changing the shape of particles obtained by the kneading and pulverizing method by mechanical impact force or thermal energy, emulsion polymerization of a polymerizable monomer of a binder resin, and a dispersion formed The emulsion, a release agent, and, if necessary, a dispersion of a charge control agent, etc., and agglomerate and heat-fuse to obtain toner particles, a polymerization monomer for obtaining a binder resin A suspension polymerization method in which a solution of a body, a release agent, and a charge control agent, if necessary, is suspended in an aqueous solvent and polymerized, a binder resin, a release agent, and a charge control agent A solution suspension method in which the solution is suspended in an aqueous solvent and granulated is used. Further, a manufacturing method may be performed in which the toner particles obtained by the above method are used as a core, and further, aggregated particles are attached and heat-fused to have a core-shell structure.
Among these, it is preferable to prepare toner particles by a kneading pulverization method or an emulsion polymerization aggregation method, and it is more preferable to prepare toner particles by an emulsion polymerization aggregation method.

  Further, the method for producing a transparent toner according to the present embodiment includes an aggregation step in which at least the transparent resin particles are aggregated in an aqueous medium to obtain aggregated particles, and a fusion step in which the aggregated particles are fused to obtain transparent toner. When the glass transition temperature measured by differential scanning calorimetry of a composition obtained by mixing raw materials excluding toner external additives at a toner composition ratio is Mg, (Mg + 10 ° C.) to (Mg + 30 ° C.) in the aggregation step. The agglomeration is particularly preferably carried out at a temperature range of 45 ° C to 70 ° C.

<Aggregation process>
The method for producing a transparent toner according to this embodiment preferably includes an aggregating step of aggregating at least the transparent resin particles in an aqueous medium to obtain aggregated particles.
In the agglomeration step, when the glass transition temperature measured by differential scanning calorimetry of a composition obtained by mixing raw materials excluding toner external additives at a toner composition ratio is Mg, (Mg + 10 ° C.) to (Mg + 30 ° C.). It is more preferable to perform aggregation in a temperature range of 45 ° C to 70 ° C.
Further, the aqueous medium in the aggregation step preferably contains a surfactant having a sulfur atom in order to improve the dispersibility of each toner material, and more preferably contains an anionic surfactant having a sulfur atom. preferable.
When agglomerating in an aqueous medium containing a surfactant, the agglomeration is carried out while adsorbing the aqueous medium containing the surfactant, and as a result, a very small amount of the surfactant remains in the toner. The inventors found it. In particular, when a polyester resin is used as the binder resin, the residue of the surfactant is remarkable because the ester group of the polyester resin is highly hydrophilic.
As a result of examining this mechanism in more detail, the present inventors have found that the residual amount of surfactant can be reduced by the following process.
First, in the conventional method, in the aggregation step, aggregated particles are generated while adsorbing water containing a surfactant. In this state, the conventional method increases the pH to stop the particle size growth and shifts to the fusion process. However, the increased pH increases the hydrophilicity of the agglomerated particles, and the adsorption amount of the surfactant is increased. It is presumed that the surfactant remains in the toner due to fusion in an increased state.

On the other hand, when aggregated particles are produced while adsorbing water containing a surfactant in the aggregating step, glass transition measured by DSC of a composition obtained by mixing raw materials excluding toner external additives at a toner composition ratio. When the temperature is Mg, by controlling the aggregation temperature within the range of (Mg + 10 ° C.) to (Mg + 30 ° C.), even in the aggregation process, the fusion of the binder resin exceeding the glass transition temperature starts. Thereafter, it is estimated that the residual amount of the surfactant is reduced even if the pH is increased to stop the particle size growth and the process proceeds to the fusion process.
Moreover, since the temperature at the time of aggregation is high, it is presumed that the adsorption amount of the surfactant is reduced even when the hydrophilicity of the aggregated particles is decreased due to a decrease in surface tension due to an increase in molecular kinetic energy. In order to use the mechanism of lowering the surface tension by increasing the kinetic energy of the molecule, the absolute value of the temperature is preferably 45 ° C. or higher. On the other hand, in view of preventing the destabilization of aggregation by lowering the surface tension, 70 It is preferable that it is below ℃.
That is, the aggregating step is preferably a step of not only aggregating but also fusing part of the binder resin.
The aggregation temperature is more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, and particularly preferably 60 ° C. or higher.
Further, the aggregation temperature is more preferably in a temperature range of (Mg + 15 ° C.) to (Mg + 30 ° C.), and further preferably in a temperature range of (Mg + 20 ° C.) to (Mg + 30 ° C.).

As the aggregating agent used in the aggregating step, an inorganic metal salt or a bivalent or higher-valent metal complex is preferably used. As the aggregating agent used in the aggregating step, a surfactant having a reverse polarity to the surfactant used as a dispersing agent for various dispersions, an inorganic metal salt, and a metal complex having a valence of 2 or more are preferably used.
In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

  Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than divalent, tetravalent than trivalent, and even if the valence is the same, the polymerization type The inorganic metal salt polymer is more suitable.

In the method for producing a transparent toner in this embodiment, it is preferable to add a chelating agent to the aggregated particles immediately before the start of fusion. By adding a chelating agent to the aggregated particles before fusion / unification, the chelating agent coordinates to the metal ions introduced into the aggregated particles for aggregation in the aggregation process, and chelate coordination in the subsequent washing process Metal ions are removed from the toner, and as a result, the content of metal ions in the toner can be reduced.
Moreover, as a chelating agent, it is preferable to use a water-soluble chelating agent.
Examples of chelating agents include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and 3-hydroxy-2,2′-iminodisuccinic acid. (HIDS) and the like.
As an addition amount of a chelating agent, the inside of the range of 0.01 weight part or more and 5.0 weight part or less is mentioned with respect to 100 weight part of binder resin, for example.

<Fusion process>
The method for producing a transparent toner according to this embodiment preferably includes a fusing step of fusing the aggregated particles by heating to obtain a transparent toner.
In the fusing step, the agglomerated particles are preferably fused by heating at a temperature equal to or higher than the agglomeration temperature. Further, in the fusion step, the progress of aggregation is stopped by raising the pH of the suspension of aggregated particles to a range of 4 to 10, more preferably 8 to 10 under stirring conditions in accordance with the aggregation step. It is also preferable. An aqueous NaOH solution is preferred as the alkaline solution used to raise the pH. The aqueous NaOH solution has lower volatility and higher safety than other alkaline solutions such as an ammonia solution. In addition, compared with a divalent alkali solution such as Ca (OH) ₂ , the solubility in water is small, the required amount of addition is small, and the ability to stop aggregation is excellent.
The heating time in the fusing step may be as long as the fusing between particles is performed, and is preferably 0.5 to 10 hours. Cooling is performed after the aggregated particles are fused to obtain fused particles. Also, during cooling, the recrystallization of the release agent and binder resin is suppressed by increasing the cooling rate near the melting temperature of the release agent and binder resin (melting temperature ± 10 ° C range), so-called rapid cooling. Then, the surface exposure may be suppressed.

-Other processes-
After the fusion process, a desired toner may be obtained through an optional washing process, solid-liquid separation process, drying process, external addition process, and the like.
In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used from the viewpoint of productivity.
A method for externally adding the external additive to the toner in the external addition step is not particularly limited, and a known method can be used. For example, a mechanical method or a chemical method is used. Specifically, for example, a method of adhering to the surface of the toner base particles by a dry method using a blender such as a V blender or a Henschel mixer, a surface after dispersing external additives in a liquid, adding to a toner in a slurry state, and drying the surface Examples of the method of adhering to the toner or the wet method include a method of drying while spraying a slurry on a dry toner.

(Toner set)
The toner set of the present embodiment includes the transparent toner of the present embodiment and a colored toner. The number average particle size distribution index GSDPc of the color toner and the number average particle size distribution index GSDPt of the transparent toner are expressed by the following formula (1). And the volume average primary particle size of the transparent toner is 3 to 8 times the volume average primary particle size of the colored toner.
1.03 <GSDPt / GSDPc <1.15 (1)
The volume average primary particle size and number average particle size distribution index of the color toner are also measured in the same manner as the volume average primary particle size and number average particle size distribution index of the transparent toner described above.
In addition, the toner set of the present embodiment is preferably used as an electrostatic charge image developing toner set, and particularly preferably used as an electrostatic charge image developing toner set for raised printing.

In the toner set of this embodiment, the number average particle size distribution index GSDPc of the colored toner and the number average particle size distribution index GSDPt of the transparent toner satisfy 1.03 <GSDPt / GSDPc <1.15, and 1.03 <GSDPt / GSDPc. It is preferable to satisfy <1.10, and it is more preferable to satisfy 1.04 <GSDPt / GSDPc <1.09. Within the above range, the color mixture of the color toner and the transparent toner is suppressed, and a sharp image is obtained particularly in the etched portion of the image having a large influence, and the visual impression of the image is strengthened.
In the toner set of the present embodiment, the volume average primary particle size of the transparent toner is 3 to 8 times the volume average primary particle size of the colored toner, preferably 3 to 6 times, More preferably, it is 3 times or more and 5 times or less. Within the above range, the density of the image formed with the colored toner is moderate, the occurrence of color mixing with the transparent toner is suppressed, and a sharp image is obtained particularly at the edge portion of the image having a large influence, and the image is visually observed. Impression is strengthened.
Further, the volume average primary particle size of the colored toner of the present embodiment is preferably 3 to 8 μm, and more preferably 3 to 6 μm. Within the above range, the cohesive force between particles between chromatic toners increases, and color mixing of the chromatic toner and the transparent toner at the transparent resin layer interface during transfer is suppressed.

The transparent toner in the toner set of the present embodiment is the transparent toner of the present embodiment described above, and a preferable aspect is also the same.
The colored toner in the toner set of this embodiment is the same component as the transparent toner of this embodiment described above except that it contains a colorant, preferably 1% by weight or more, and the preferred aspect is also the same. It is.
In the toner set of this embodiment, when two or more kinds of colored toners are included, the above requirements for GSDPt / GSDPc and volume average primary particle diameter with transparent toners should satisfy at least one kind of colored toner. It is preferable that all colored toners included in the set satisfy the above requirements for GSDPt / GSDPc and volume average primary particle size with transparent toner.
The toner set of this embodiment preferably includes yellow toner, magenta toner, and cyan toner as colored toners, and more preferably includes yellow toner, magenta toner, cyan toner, and black toner.

In the toner set of this embodiment, St is the content (composition ratio) of the sulfur element of the transparent toner measured by fluorescent X-ray, and the content (composition ratio) of the sulfur element of the colored toner is measured by fluorescent X-ray. When it is Sc, the ratio St / Sc of the sulfur amount satisfies the relationship of the following formula (2), that is, preferably 0.1 or more and 1.0 or less, and 0.1 or more and 0.7 or less. Is more preferably 0.2 or more and 0.5 or less, and particularly preferably 0.3 or more and 0.4 or less.
0.1 ≦ St / Sc ≦ 1.0 (2)
Within the above range, the toner image formed from the colored toner has a stronger liquid cross-linking force than the transparent toner layer, serves as a base for supporting the transparent toner layer, and image collapse is suppressed.
Further, in the colored toner of the present embodiment, the content (composition ratio, mol%) of sulfur element measured by fluorescent X-ray is preferably 0.02% or more and 0.30% or less, 0.05 % Or more and 0.20% or less is more preferable, and 0.08% or more and 0.15% or less is still more preferable.

<Colorant>
The colored toner used in this embodiment contains a colorant.
The colorant is not particularly limited, and a known colorant can be used. Specifically, carbon black, nigrosine, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline. Yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 238, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 180, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 is a representative example.
A coloring agent can be used individually by 1 type or in combination of 2 or more types.

  In the colored toner used in the exemplary embodiment, the colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the colored toner. The addition amount of the colorant is not particularly limited, but is preferably in the range of 3 to 60% by weight with respect to the total weight of the colored toner.

(Static charge image developer and electrostatic charge image developer set)
The transparent toner of this embodiment is preferably used as an electrostatic charge image developer.
The electrostatic image developer of this embodiment is not particularly limited except that it contains the transparent toner of this embodiment, and can take an appropriate component composition depending on the purpose. When the electrostatic image developing toner of this embodiment is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development is performed according to an electrostatic latent image is also applied.
Further, the toner set of this embodiment is preferably used as an electrostatic charge image developer set. For example, the transparent toner and the colored toner in the toner set of this embodiment may be used as they are as a one-component developer, or may be used as a two-component developer in combination with a carrier.

  In the present embodiment, the development method is not particularly defined, but the two-component development method is preferable. Further, if the above conditions are satisfied, the carrier is not particularly defined, but as the core material of the carrier, for example, magnetic metals such as iron, steel, nickel, cobalt, alloys of these with manganese, chromium, rare earth, etc., In addition, magnetic oxides such as ferrite and magnetite can be used, and from the viewpoint of core material surface properties and core material resistance, ferrite, particularly alloys with manganese, lithium, strontium, magnesium and the like are preferable.

The carrier used in the present embodiment is preferably formed by coating a resin on the surface of the core material. There is no restriction | limiting in particular as said resin, According to the objective, it selects suitably. For example, polyolefin resins such as polyethylene and polypropylene; polyvinyl resins and polyvinylidene resins such as polystyrene, acrylic resins, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone Vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of organosiloxane bond or modified product thereof; polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. Fluorine resin; Silicone resin; Polyester; Polyurethane; Polycarbonate; Phenol resin; Urea-formaldehyde resin, Melamine tree , Benzoguanamine resins, urea resins, amino resins such as polyamide resins, epoxy resins, per se known resins and the like. These may be used individually by 1 type and may use 2 or more types together. In the present embodiment, among these resins, it is preferable to use at least a fluorine resin and / or a silicone resin. The use of at least a fluorine-based resin and / or a silicone resin as the resin is advantageous in that the effect of preventing carrier contamination (impaction) due to toner and external additives is high.
In the resin coating, it is preferable that resin particles and / or conductive particles are dispersed in the resin. Examples of the resin particles include thermoplastic resin particles and thermosetting resin particles. Among these, thermosetting resins are preferable from the viewpoint of relatively easily increasing the hardness, and resin particles made of nitrogen-containing resin containing N atoms are preferable from the viewpoint of imparting negative chargeability to the toner. In addition, these resin particles may be used individually by 1 type, and may use 2 or more types together. The average particle size of the resin particles is preferably 0.1 to 2 μm, and more preferably 0.2 to 1 μm. When the average particle size of the resin particles is 0.1 μm or more, the resin particles are excellent in dispersibility in the coating, whereas when the average particle size is 2 μm or less, the resin particles are not easily dropped from the coating.

  Examples of the conductive particles include metal particles such as gold, silver, and copper, carbon black particles, and surfaces of titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate powder, tin oxide, carbon black, metal And particles covered with the like. These may be used individually by 1 type and may use 2 or more types together. Among these, carbon black particles are preferable in terms of good production stability, cost, conductivity and the like. The type of carbon black is not particularly limited, but carbon black having a DBP oil absorption of 50 to 250 ml / 100 g is preferable because of excellent production stability. The coating amount of the resin, the resin particles, and the conductive particles on the surface of the core material is preferably 0.5 to 5.0% by weight, and preferably 0.7 to 3.0% by weight. More preferred.

The method for forming the coating is not particularly limited. For example, the resin particles such as crosslinkable resin particles and / or the conductive particles, and a styrene acrylic resin, a fluorine resin, a silicone resin as a matrix resin, etc. And a method of using a film-forming solution containing the above resin in a solvent.
Specifically, the carrier core material is immersed in the film forming liquid, a spray method in which the film forming liquid is sprayed on the surface of the carrier core material, and the carrier core material is floated by flowing air And kneader coater method in which the film forming solution is mixed and the solvent is removed. Among these, the kneader coater method is preferable in the present embodiment.

  The solvent used for the film-forming liquid is not particularly limited as long as it can dissolve only the resin as a matrix resin, and is selected from known solvents such as toluene, Aromatic hydrocarbons such as xylene, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and the like. When the resin particles are dispersed in the coating, since the resin particles and the particles as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface, the carrier is used for a long time. Even when the coating is worn, it is possible to always maintain the same surface formation as when it is not used, and to maintain a good charge imparting ability for the toner over a long period of time. In the case where the conductive particles are dispersed in the coating, the conductive particles and the resin as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface. Even if the coating is worn out over a long period of time, the same surface formation as when not in use can be maintained, and carrier deterioration is prevented for a long period of time. In addition, when the said resin particle and the said electroconductive particle are disperse | distributed to the said film, the above-mentioned effect is exhibited simultaneously.

The electric resistance of the magnetic carrier formed as described above in the state of a magnetic brush under an electric field of 10 ⁴ V / cm is preferably 10 ⁸ to 10 ¹³ Ωcm. When the electric resistance of the magnetic carrier is 10 ⁸ Ωcm or more, the adhesion of the carrier to the image portion on the image carrier is suppressed, and the brush mark is difficult to appear. On the other hand, when the electrical resistance of the magnetic carrier is 10 ¹³ Ωcm or less, the generation of the edge effect is suppressed and a good image quality is obtained.
The volume resistivity is measured as follows.
A measuring jig comprising a pair of 20 cm ² circular electrode plates (made of steel) connected to an electrometer (manufactured by KEITHLEY, trade name: KEITHLEY 610C) and a high-voltage power supply (trade name: FLUKE 415B). The sample is placed on the lower electrode plate so as to form a flat layer having a thickness of about 1 mm to 3 mm. Next, after the upper electrode plate is placed on the sample, a weight of 4 kg is placed on the upper electrode plate in order to eliminate the gap between the samples. In this state, the thickness of the sample layer is measured. Next, the current value is measured by applying a voltage to the bipolar plate, and the volume resistivity is calculated based on the following equation.
Volume resistivity = applied voltage × 20 ÷ (current value−initial current value) ÷ sample thickness In the above formula, the initial current is the current value when the applied voltage is 0, and the current value indicates the measured current value.

  The mixing ratio of the toner and the carrier in the two-component electrostatic image developer is preferably 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method)
The image forming method of the present embodiment is a process of forming a transparent resin layer with the transparent toner of the present embodiment on at least a part of a colored image formed with a colored toner and performing a raised printing (hereinafter, referred to as a “lifting printing process”). The number average particle size distribution index GSDPc of the colored toner and the number average particle size distribution index GSDPt of the transparent toner satisfy the relationship of the following formula (1), and the volume average primary particle size of the transparent toner is The volume average primary particle size of the color toner is 3 to 8 times.
1.03 <GSDPt / GSDPc <1.15 (1)
Further, the transparent toner of the present embodiment and the toner set of the present embodiment are suitably used for an electrostatic charge image developing (electrophotographic) image forming method.
In addition, the image forming method of the present embodiment is particularly preferably used as a raised printing method.
The transparent toner in the image forming method of the present embodiment is the transparent toner of the present embodiment described above, and a preferable aspect is also the same. Further, the color toner in the image forming method of the present embodiment is the color toner in the toner set of the present embodiment described above, and a preferable aspect is also the same.

<Heaping printing process>
The image forming method of the present embodiment includes a step of forming a transparent resin layer with the transparent toner of the present embodiment on at least a part of the colored image formed with the colored toner and performing a raised printing (a raised printing step).
The transparent toner of this embodiment is a toner having a large average particle size of 18 μm or more and 28 μm or less in volume average primary particle size, and easy enlarging printing with a thick transparent resin layer on a colored image.
In the raised printing step, the transparent resin layer formed of the transparent toner may be formed on at least a part of the colored image formed of the colored toner, and of course, it may be formed on the entire colored image. However, if desired, it is preferable to form a transparent resin layer on a portion of the colored image where it is desired to give a visually strong impression.
The thickness of the transparent resin layer in the raised printing step is preferably 18 to 200 μm, and more preferably 20 to 100 μm.
The colored image in the raised printing step may be a colored toner layer before fixing or a colored image after fixing, but the rising printing step is performed at least on the colored toner image formed with colored toner. It is preferable that the transparent toner layer is partially formed with the transparent toner of the present embodiment, fixed, and then subjected to raised printing.
The fixing unit in the rising printing step is not particularly limited, and a known fixing unit can be used. However, the fixing unit is preferably a heating fixing unit, and the unfixed toner between the heating member and the pressure member. More preferably, the toner image is fixed by passing the recording medium on which the image is formed.

Further, in the image forming method of the present embodiment, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and the electrostatic latent image formed on the surface of the image carrier is developed with a developer containing colored toner. It is preferable to include a developing step for forming a toner image and a transfer step for transferring the toner image onto the surface of the transfer target to form a colored image.
Each of the steps in the image forming method of this embodiment is a general step per se, and is described in, for example, Japanese Patent Laid-Open Nos. 56-40868 and 49-91231. Note that the image forming method of the present embodiment is carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.
The charging step is a step of charging the image carrier.
The latent image forming step is a step of forming an electrostatic latent image on the surface of the image carrier.
In the developing step, the electrostatic latent image formed on the surface of the image carrier is developed with the electrostatic image developing toner of the present embodiment or the electrostatic image developer containing the electrostatic image developing toner of the present embodiment. This is a step of forming a toner image.
The transfer step is a step of transferring the toner image onto a transfer target.
The image forming apparatus used in the present embodiment is not particularly limited, and a known image forming apparatus can be used. An image holding body, a charging unit that charges the image holding body, and the charged image holding body. Exposing means for forming an electrostatic latent image on the surface of the image carrier, developing means for developing the electrostatic latent image with a developer containing toner, and forming a toner image; and Preferably, the image forming apparatus includes a transfer unit that transfers the image from the image holding member to the surface of the transfer target, and a fixing unit that fixes the toner image transferred to the surface of the transfer target.

As the image carrier and each of the above-described units, the configurations described in the respective steps of the image forming method are preferably used.
As each of the above-described means, a known means is used in the image forming apparatus. Further, the image forming apparatus used in the present embodiment may include means and devices other than the above-described configuration. Further, the image forming apparatus used in the present embodiment may simultaneously perform a plurality of the above-described means.

(Toner cartridge and process cartridge)
The toner cartridge of this embodiment is a toner cartridge that contains at least the transparent toner of this embodiment. The toner cartridge of this embodiment may contain the transparent toner of this embodiment as an electrostatic charge image developer.
Further, the process cartridge according to the present embodiment includes a developing unit that develops an electrostatic latent image formed on the surface of the image carrier with the transparent toner or the electrostatic charge image developer to form a toner image, and an image carrier. And at least one selected from the group consisting of a charging unit for charging the surface of the image carrier and a cleaning unit for removing the toner remaining on the surface of the image carrier. This is a process cartridge containing at least the electrostatic image developing toner or the electrostatic image developer of this embodiment.

The toner cartridge of this embodiment is preferably detachable from the image forming apparatus. That is, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner cartridge of the present embodiment containing the transparent toner of the present embodiment is preferably used.
Further, the toner cartridge may be a cartridge that stores toner and a carrier, or a cartridge that stores toner alone and a cartridge that stores a carrier independently.

It is preferable that the process cartridge of the present embodiment is attached to and detached from the image forming apparatus.
In addition, the process cartridge according to the present embodiment may include other members such as a static elimination unit as necessary.
As the toner cartridge and the process cartridge, known configurations may be adopted. For example, Japanese Patent Application Laid-Open Nos. 2008-209489 and 2008-233736 are referred to.

  Hereinafter, although this embodiment is described in detail with examples, this embodiment is not limited in any way. In the following description, “parts” and “%” respectively represent “parts by weight” and “% by weight” unless otherwise specified.

<Measuring method of glass transition temperature and melting temperature>
The glass transition temperature and the melting temperature were measured by differential scanning calorimetry (DSC) based on ASTM D3418-8. This measurement was performed as follows.
That is, first, a substance to be measured is set in a differential scanning calorimeter (device name: DSC-50 type) manufactured by Shimadzu Corporation equipped with an automatic tangent processing system, liquid nitrogen is set as a cooling medium, and 10 Heating from 0 ° C. to 150 ° C. at a temperature rising rate of 1 ° C./min (first temperature raising process), determining the relationship between temperature (° C.) and calorie (mW), and then decreasing the temperature by −10 ° C./min The sample was cooled to 0 ° C. at a rate, and again heated to 150 ° C. at a rate of temperature increase of 10 ° C./min (second temperature increase process), and data was collected. In addition, it hold | maintained for 10 minutes each at 0 degreeC and 150 degreeC.
The melting temperature of the mixture of indium and zinc was used for temperature correction of the detection part of the measuring device, and the heat of fusion of indium was used for correction of the amount of heat. The sample was placed in an aluminum pan, and an aluminum pan containing the sample and an empty aluminum pan for control were set.
The glass transition temperature of the toner was defined as the temperature at the intersection of the extension line of the base line and the rising line in the endothermic part of the DSC curve obtained in the first temperature raising process.
The glass transition temperature of the amorphous resin was defined as the glass transition temperature at the intersection of the extension line of the base line and the rising line in the endothermic part of the DSC curve obtained in the second temperature raising process.
Regarding the melting point of the crystalline resin, the maximum peak temperature among the peaks having an endotherm of 25 J / g or more in the DSC curve obtained in the second temperature raising process was taken as the melting point.

<Measurement of weight average molecular weight (Mw), number average molecular weight (Mn), peak molecular weight (Mp)>
The weight average molecular weight (Mw), number average molecular weight (Mn), and peak molecular weight (Mp) (in terms of polystyrene) of the polyester resin are as follows. Used TSKgei, SuperHM-H (6.0 mm ID × 15 cm × 2), and THF (tetrahydrofuran) for chromatograph manufactured by Wako Pure Chemical Industries, Ltd. was used as an eluent. As experimental conditions, the sample concentration was 0.5%, the flow rate was 0.6 ml / min, the sample injection volume was 10 μl, the measurement temperature was 40 ° C., and the calibration curves were A-500, F-1, F-10, F-80, F− It produced from 10 samples of 380, A-2500, F-4, F-40, F-128, F-700. The data collection interval in the sample analysis was set to 300 ms.

<Measurement of acid value>
The acid value A was measured by a neutralization titration method according to JIS K0070. That is, an appropriate amount of a sample is taken, 160 ml of a solvent (acetone / toluene mixture) and a few drops of an indicator (phenolphthalein solution) are added, and the mixture is sufficiently shaken on a water bath until the sample is completely dissolved. This was titrated with a 0.1 mol / l potassium hydroxide ethanol solution, and the end point was when the indicator was light red for 30 seconds.
When the acid value is A, the sample amount is S (g), the 0.1 mol / l potassium hydroxide ethanol solution used for the titration is B (ml), and f is the factor of the 0.1 mol / l potassium hydroxide ethanol solution. , A = (B × f × 5.611) / S.

<Measurement method of flow tester 1/2 drop temperature>
Using a flow tester (manufactured by Shimadzu Corporation: CFT-500C), sample amount: 1.05 g, sample diameter: 1 mm, preheating: 300 ° C. at 65 ° C., load: 10 kg, die size: diameter 0.5 mm, ascending Temperature rate: Measured under the condition of 1.0 ° C./min, and when the amount of plunger drop is plotted, the temperature when half of the sample flows out is defined as the ½ drop temperature.

<Measuring method of particle size / particle size distribution>
The volume average particle diameter of the toner particles was measured using a Multisizer II (manufactured by Beckman-Coulter) measuring device. As the electrolytic solution, ISOTON-II (manufactured by Beckman Coulter, Inc.) was used.
With respect to the measured particle size distribution, a cumulative distribution is drawn from the smaller diameter side with respect to the divided particle size range (channel), the particle size that is 16% cumulative with respect to the volume is D16v, and the cumulative particle size is 16% with respect to the number. The particle size is D _16p , the particle size is 50% cumulative for the volume D _50v , the particle size is 50% cumulative for the number D _50p , the particle size 84% cumulative for the volume is D _84v , and the cumulative 84% for the number Is defined as D84p.
Using these measured values, the volume average particle size distribution index (GSDv) is lower than √ (D _84v / D _16v ), and the number average particle size distribution index (GSDp) is lower than √ (D _84p / D _16p ). The average particle size distribution index (under GSDp) was calculated from √ (D _50p / D _16p ). In the present embodiment, the particle size is D _50v and GSDP is the lower number average particle size distribution index (below GSDp).

<Calculation of shape factor SF1>
The shape factor of the toner was measured using FPIA-3000 (Sysmex Corporation). A toner dispersion for measurement was prepared as follows. First, 30 ml of ion-exchanged water was placed in a 100 ml beaker, and two drops of a surfactant (manufactured by Wako Pure Chemical Industries, Ltd .: Contaminone) were added dropwise thereto as a dispersant. 20 mg of toner was put in this liquid and dispersed for 3 minutes by ultrasonic dispersion to prepare a dispersion.
About the obtained toner dispersion liquid, FPIA-3000 was used and the number of measurement was measured 4,500, and the shape factor was calculated.

<Method for measuring sulfur content>
XRF analysis uses, for example, XRF-1500 (manufactured by Shimadzu Corporation) as a measuring device, measuring conditions are tube voltage 40 kV, tube current 70 mA, measuring time 15 minutes, measuring area is 10 mm in diameter (sample amount) 0.3 g was molded into a cylindrical shape having a diameter of 10 mm) and quantitatively analyzed.

<Method for measuring ion content>
As a method for extracting ammonium ions and Na ions in the toner, a nonionic surfactant corresponding to 20% of the toner solid content is dispersed in water, and the temperature is controlled in a thermostat controlled at 30 ° C. ± 1 ° C. Ultrasonic shaking is performed over 30 minutes.
The amount of Na ions refers to a value obtained by measurement with an ion chromatograph. The ion chromatograph was analyzed under the following conditions using ICS-2000 manufactured by Nippon Dionex Co., Ltd.
Cation separation column: Nippon Dionex Co., Ltd. IonPacCS12A
Cation guard column: Nippon Dionex Co., Ltd. IonPacCG12A
Eluent: Methanesulfonic acid 20 mM
Flow rate: 1 ml / min
Temperature: 35 ° C
Detection method: Electrical conductivity method (suppressor type)

<Measuring method of edge sharpness>
A transparent toner image was formed on the colored image. The image was a 5 × 5 cm solid image.
After fixing, the image was scanned from the non-image area to the image area with a surface roughness meter (Surfcom) to produce a height profile (vertical magnification 500 times, lateral magnification 20 times).
When the height of the non-image part is zero, the point where the image height is 3 μm is X1, and when the point where the image height is 30 μm is X2, the shorter the distance X2-X1, the sharper the edge It was said that. Five images were measured per image, and the average value of three points excluding the maximum and minimum values was taken as the value.

<Preparation of Colorant Dispersion (PDK1)>
Carbon black (Cabot Japan Co., Ltd., REAGAL 330): 200 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 33 parts by weight (active ingredient 60% by weight, colorant) 10% by weight)
-Ion exchange water: 750 parts by weight The above components are put into a stainless steel container whose liquid level is about 1/3 of the height of the container when all of the above ingredients are added. After adding 280 parts by weight and an anionic surfactant and sufficiently dissolving the surfactant, all of the pigment is added and stirred using a stirrer until there is no wet pigment, and the remaining ion exchange Water was added and the mixture was further stirred to sufficiently deaerate.
After defoaming, the mixture was dispersed for 10 minutes at 5000 rpm using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then defoamed by being stirred for one day with a stirrer. After defoaming, the mixture was dispersed again at 6,000 rpm for 10 minutes using a homogenizer, and then stirred for one day with a stirrer for defoaming.
After defoaming, dispersion was performed at a pressure of 240 MPa using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The dispersion was equivalent to 25 passes in terms of the total charge and the processing capacity of the apparatus.
The obtained dispersion was allowed to stand for 72 hours to remove precipitates, and ion exchange water was added to adjust the solid content concentration to 15% by weight to obtain a colorant dispersion. The volume average particle diameter D _50v of the particles in this colorant dispersion was 110 nm. As the volume average particle diameter D _50v , the average value of three measurement values excluding the maximum value and the minimum value out of the five times measured by Microtrack was used.

<Preparation of release agent dispersion (DW1)>
Hydrocarbon wax (Nippon Seiki Co., Ltd., trade name: FNP0090, melting temperature Tw = 90.2 ° C.): 270 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount: 60% by weight): 13.5 parts by weight (as active ingredient, 3.0% by weight with respect to the release agent)
-Ion-exchanged water: 700 parts by weight The above components were mixed, and the release agent was dissolved at a pressure of 120 ° C. in the internal liquid temperature with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin), and then at a dispersion pressure of 5 MPa for 120 minutes. Subsequently, dispersion treatment was performed at 40 MPa for 360 minutes, followed by cooling to obtain a release agent dispersion liquid (W1). The volume average particle diameter D _50v of the particles in the release agent dispersion is 220 nm. Then, ion exchange water was added and it adjusted so that solid content concentration might be 20.0 weight%.

<Synthesis of Amorphous Polyester Resin (PES-A1)>
Into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, a monomer other than dodecenyl succinic acid was charged according to the composition of Table 1, and the inside of the reaction vessel was replaced with dry nitrogen gas. 0.3% by weight was added with respect to the total amount of the monomer components. After stirring and reacting at about 180 ° C. for about 6 hours under a nitrogen gas stream, the temperature is further raised to about 235 ° C. over 1 hour, reacted for about 3 hours, cooled to 220 ° C., The pressure was reduced to 10.0 mmHg, and the reaction was stirred for about 1 hour. After returning to normal pressure, dodecenyl succinic acid shown in Table 1 was added and reacted, and the reaction was terminated when the desired molecular weight was reached. The physical properties of the obtained amorphous polyester resin are shown in Table 1.

<Synthesis of Amorphous Polyester Resin (PES-A2)>
After introducing a monomer other than dodecenyl succinic acid and trimellitic anhydride into a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube according to the composition of Table 1, and replacing the reaction vessel with dry nitrogen gas Then, 0.3% by weight of tin dioctanoate was added to the total amount of the monomer components. After stirring and reacting at about 180 ° C. for about 6 hours under a nitrogen gas stream, the temperature is further raised to about 235 ° C. over 1 hour, reacted for about 3 hours, cooled to 220 ° C., The pressure was reduced to 10.0 mmHg, and the reaction was stirred for about 1 hour. After returning to normal pressure, dodecenyl succinic acid shown in Table 1 was added and reacted for about 2 hours, then trimellitic anhydride was added and further reacted, and the reaction was terminated when the desired molecular weight was reached. The physical properties of the obtained amorphous polyester resin are shown in Table 1.

<Synthesis of Crystalline Polyester Resin (PES-C1)>
Into a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, the monomer was charged according to the composition shown in Table 1, the inside of the reaction vessel was replaced with dry nitrogen gas, and then titanium tetrabutoxide (reagent) was 0.3% by weight was added to 100 parts by weight of the monomer component. After stirring and reacting at 170 ° C for 3 hours under a nitrogen gas stream, the temperature was further increased to 210 ° C over 1 hour, the pressure in the reaction vessel was reduced to 3 kPa, and the reaction was terminated when the desired molecular weight was reached. did. The physical properties of the obtained crystalline polyester resin are shown in Table 1.

<Preparation of amorphous polyester resin particle dispersion (DA-A1)>
While maintaining a jacketed 3 liter reaction tank (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor wing at 40 ° C. in a water circulating thermostat, the reaction tank Into this, a mixed solvent of 180 parts by weight of ethyl acetate and 80 parts by weight of isopropyl alcohol was added, and 300 parts by weight of the amorphous polyester resin (PES-A1) was added thereto, followed by stirring at 150 rpm using a three-one motor. The oil phase was obtained by dissolving. A mixture of 1 part by weight of 10% by weight aqueous ammonia solution and 47 parts by weight of 5% by weight aqueous sodium hydroxide solution was added dropwise to the stirred oil phase over 5 minutes, mixed for 10 minutes, and then ion-exchanged water. 900 parts by weight were added dropwise at a rate of 5 parts by weight per minute to invert the phase to obtain an emulsion.
Immediately, 800 parts by weight of the obtained emulsion and 700 parts by weight of ion-exchanged water were placed in an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, it was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the amount of recovered solvent reached 1,100 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D _50v of the resin particles in this dispersion was 130 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 20% by weight. This was designated as an amorphous polyester resin dispersion (DA-A1).

<Preparation of amorphous polyester resin particle dispersion (DA-A2)>
In the preparation of the amorphous polyester resin particle dispersion (DA-A1),
An amorphous polyester resin dispersion (DA-A2) was obtained in the same manner as described above except that the amorphous polyester resin (PES-A1) was changed to an amorphous polyester resin (PES-A2). The volume average particle diameter D _50v of the resin particles in this dispersion was 100 nm.

<Preparation of crystalline polyester resin dispersion (DA-C1)>
In a jacketed 3 liter reaction tank (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor blade, 300 parts by weight of the crystalline polyester resin (PC1) and methyl ethyl ketone ( Solvent) (160 parts by weight) and isopropyl alcohol (solvent) (100 parts by weight) were added, and the resin was dissolved while stirring and mixing at 100 rpm while maintaining the temperature at 70 ° C. in a water circulating thermostat.
Thereafter, the stirring rotation speed was set to 150 rpm, the water circulation type thermostatic bath was set to 66 ° C., 15 parts by weight of a 10 wt% aqueous ammonia solution was dropped in 5 minutes, mixed for 10 minutes, and then ion-exchanged water 900 kept at 66 ° C. 900 Part by weight was added dropwise at a rate of 5 parts by weight per minute for phase inversion to obtain an emulsion.
Immediately, 800 parts by weight of the obtained emulsion and 700 parts by weight of ion-exchanged water were placed in an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, it was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the amount of recovered solvent reached 1,100 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D _50v of the resin particles in this dispersion was 130 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 20% by weight. This was used as a crystalline polyester resin dispersion (DA-C1).

  Table 1 below shows details of each polyester resin dispersion.

Example 1
<Preparation of transparent toner (TNA1T)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-A1T)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight DOWFAX2A-1 (sodium alkyldiphenyl oxide disulfonate, Dow Chemical Company) Manufactured): 1.25 parts by weight The above ingredients were placed in a beaker, and the pH was adjusted to 4.0 using a 1.0% by weight aqueous nitric acid solution while stirring at a speed not to bite the foam with a magnetic stirrer. Then, an additional amorphous polyester resin particle dispersion (DA-A1T) was obtained.

<Preparation of aqueous aluminum sulfate solution (SA1T)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.2 parts by weight Ion-exchanged water: 20 parts by weight The above components were charged into a container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of transparent toner (TNA1T)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight Release agent dispersion (DW1): 195 parts by weight DOWFAX2A-1 (manufactured by Dow Chemical Co., surfactant): 3.0 parts by weight Ion-exchanged water: 650 parts by weight In a reaction vessel equipped with a stirrer, while stirring to such an extent that vortex does not occur, 1.0 wt% nitric acid was added to adjust the pH to 4.5 at a temperature of 25 ° C, and then a homogenizer (IKA Japan ( The total amount of the prepared aluminum sulfate aqueous solution (SA1T) was added and dispersed for 6 minutes while dispersing at 5,000 rpm with Ultra Tarax T50).

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 47 ° C. at a temperature increase rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and maintained at 47 ° C. The particle size was measured with a multisizer every 10 minutes. When the volume average particle size reached 17.0 μm, all of the additional amorphous polyester resin dispersion (DA-A1T) was added over 60 minutes. did.
After adding an additional amorphous polyester resin dispersion (DA-A1T), 9 parts by weight of ethylenediaminetetraacetic acid (EDTA) tetrasodium salt (manufactured by Kirest Co., Ltd., Kirest 40, 40% by weight of active ingredient) is added for 5 minutes. And the pH was adjusted to 8.5 with a 1% by weight aqueous sodium hydroxide solution.
Thereafter, the temperature was raised to 95 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 95 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 95 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while reducing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 940, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 77 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 0.25 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNA1T).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of resin-coated carrier (C)>
Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts by weight Toluene: 14 parts by weight A cyclohexyl methacrylate / dimethylaminoethyl methacrylate copolymer (copolymerization weight ratio 99: 1, Mw 80,000): 2.0 parts by weight of carbon black (VXC72: manufactured by Cabot Corporation): 0.12 parts by weight Using the sand mill manufactured by Kansai Paint Co., Ltd. The mixture was stirred at 1,200 ppm for 30 minutes to obtain a resin coating layer forming solution. Furthermore, this resin coating layer forming solution and ferrite particles were put into a vacuum degassing kneader, decompressed, distilled off toluene and dried to prepare a resin-coated carrier (C).

<Preparation of developer (DTNA1T)>
After adding 40 parts by weight of the toner (TNA1T) to 500 parts by weight of the resin-coated carrier (C) and blending with a V-type blender for 20 minutes, the aggregates are removed with a vibration sieve having an aperture of 212 μm and developed. An agent (DTNA1T) was prepared.

<Preparation of colored toner (TNA1K)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-A1A)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight DOWFAX2A-1: 1.25 parts by weight The above ingredients in a 500 ml beaker While stirring with a magnetic stirrer at a speed that does not bite the foam, the pH is adjusted to 4.0 using a 1.0 wt% nitric acid aqueous solution, and an additional amorphous polyester resin particle dispersion ( DA-A1A) was obtained.

<Preparation of aqueous aluminum sulfate solution (SA1A)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.2 parts by weight Ion-exchanged water: 20 parts by weight The above components were put into a 30 ml container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of colored toner (TNA1K)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight Release agent dispersion (DW1): 130 parts by weight Colorant dispersion (PDK1): 100 parts by weight DOWFAX2A-1: 3.0 parts by weight Ion-exchanged water: 500 parts by weight In a reaction vessel equipped with a pH meter and a stirrer, with stirring to such an extent that vortex does not occur, at a temperature of 25 ° C., 1.0 wt% nitric acid was added to adjust the pH to 4.0, and then a homogenizer (IKA) The total amount of the prepared aluminum sulfate aqueous solution (SA1A) was added and dispersed for 6 minutes while dispersing at 5,000 rpm with Japan Co., Ltd. product: Ultra Tarax T50.

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 43 ° C. at a temperature increase rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and maintained at 43 ° C. The particle size was measured with a multisizer every 10 minutes. When the volume average particle diameter reached 5.0 μm, all of the additional amorphous polyester resin dispersion (DA-A1A) was added over 60 minutes.
After adding an additional amorphous polyester resin dispersion (DA-A1A), 9 parts by weight of EDTA-Na salt (Cyrest Co., Ltd., Kyrest 40, active ingredient 40% by weight) was added in 5 minutes. The pH was adjusted to 9.0 with a weight% aqueous sodium hydroxide solution.
Thereafter, the temperature was raised to 85 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 85 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 85 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while decreasing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 964, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 20 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 1.0 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNA1K).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of resin-coated carrier (C)>
Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts by weight Toluene: 14 parts by weight A cyclohexyl methacrylate / dimethylaminoethyl methacrylate copolymer (copolymerization weight ratio 99: 1, Mw 80,000): 2.0 parts by weight of carbon black (VXC72: manufactured by Cabot Corporation): 0.12 parts by weight Using the sand mill manufactured by Kansai Paint Co., Ltd. The mixture was stirred at 1,200 ppm for 30 minutes to obtain a resin coating layer forming solution. Furthermore, this resin coating layer forming solution and ferrite particles were put into a vacuum degassing kneader, decompressed, distilled off toluene and dried to prepare a resin-coated carrier (C).

<Preparation of developer (DTNA1K)>
After adding 40 parts by weight of the toner (TNA1K) to 500 parts by weight of the resin-coated carrier (C) and blending with a V-type blender for 20 minutes, the aggregates are removed with a vibrating sieve having an aperture of 212 μm and developed. An agent (DTNA1K) was prepared.

(Examples 2 to 8)
Transparent toners (TNA2T) to (TNA8T) were obtained in the same manner as in the preparation of the transparent toner (TNA1T) in Example 1 except that the conditions were changed according to Table 2 in the preparation of the transparent toner (TNA1T).

Example 9
<Preparation of transparent toner (TNA9T)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-A9T)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight DOWFAX2A-1: 1.25 parts by weight The above ingredients are put in a beaker. While stirring with a magnetic stirrer at a speed that does not entrap bubbles, the pH was adjusted to 4.0 using a 1.0 wt% aqueous nitric acid solution, and an additional amorphous polyester resin particle dispersion (DA -A9T).

<Preparation of aqueous aluminum sulfate solution (SA9T)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.1 parts by weight Ion-exchanged water: 20 parts by weight The above components were charged into a container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of transparent toner (TNA9T)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight -Release agent dispersion (DW1): 195 parts by weight-DOWFAX 2A-1: 15.0 parts by weight-Ion exchange water: 960 parts by weight While stirring to such an extent that vortex does not occur, 1.0% nitric acid nitric acid was added to adjust the pH to 4.5 at a temperature of 25 ° C. All the prepared aqueous solution of aluminum sulfate (SA9T) was added and dispersed for 6 minutes while dispersing at 5,000 rpm.

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 55 ° C. at a heating rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and held at 55 ° C. The particle size was measured with a multisizer every 10 minutes. When the volume average particle size reached 24.0 μm, all of the additional amorphous polyester resin dispersion (DA-A9T) was added over 60 minutes. did.
After adding an additional amorphous polyester resin dispersion (DA-A9T), 9 parts by weight of EDTA-Na salt (Cyrest Co., Ltd., Kyrest 40, active ingredient 40% by weight) was added over 5 minutes. The pH was adjusted to 8.5 with a weight% aqueous sodium hydroxide solution.
Thereafter, the temperature was raised to 95 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 95 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 95 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while reducing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 940, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 77 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 0.25 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNA9T).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of colored toner (TNA9K)>
From the toner obtained by the preparation of the color toner (TNA1K) of Example 1, fine powder was cut with an elbow jet classifier to obtain a color toner (TNA9K). The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of transparent toner (TNA10T)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-A10T)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight DOWFAX2A-1: 1.25 parts by weight The above ingredients are put in a beaker. While stirring with a magnetic stirrer at a speed that does not entrap bubbles, the pH was adjusted to 4.0 using a 1.0 wt% aqueous nitric acid solution, and an additional amorphous polyester resin particle dispersion (DA -A10T).

<Preparation of aqueous aluminum sulfate solution (SA10T)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.2 parts by weight Ion-exchanged water: 20 parts by weight The above components were charged into a container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of transparent toner (TNA10T)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight -Release agent dispersion (DW1): 195 parts by weight-DOWFAX 2A-1: 15.0 parts by weight-Ion exchange water: 650 parts by weight While stirring to such an extent that vortex does not occur, 1.0% nitric acid nitric acid was added to adjust the pH to 4.5 at a temperature of 25 ° C. All the prepared aqueous solution of aluminum sulfate (SA10T) was added and dispersed for 6 minutes while dispersing at 5,000 rpm.

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 47 ° C. at a temperature increase rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and maintained at 47 ° C. The particle size was measured with a multisizer every 10 minutes. When the volume average particle size reached 25.5 μm, all of the additional amorphous polyester resin dispersion (DA-A10T) was added over 60 minutes. did.
After adding an additional amorphous polyester resin dispersion (DA-A10T), 9 parts by weight of an EDTA-Na salt (Cyrest Co., Ltd., Kyrest 40, active ingredient 40% by weight) was added in 5 minutes. The pH was adjusted to 8.5 with a weight% aqueous sodium hydroxide solution.
Thereafter, the temperature was raised to 95 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 95 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 95 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while reducing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 940, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 77 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 0.25 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNA10T).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of colored toner (TNA10K)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-A10K)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight DOWFAX2A-1: 1.55 parts by weight The above ingredients are placed in a beaker. While stirring with a magnetic stirrer at a speed that does not entrap bubbles, the pH was adjusted to 4.0 using a 1.0 wt% aqueous nitric acid solution, and an additional amorphous polyester resin particle dispersion (DA -A10K).

<Preparation of aqueous aluminum sulfate solution (SA10K)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.2 parts by weight Ion-exchanged water: 20 parts by weight The above components were charged into a container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of colored toner (TNA10K)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight -Release agent dispersion (DW1): 130 parts by weight-Colorant dispersion (PDK1): 100 parts by weight-DOWFAX 2A-1: 3.72 parts by weight-Ion exchange water: 240 parts by weight In a reaction vessel equipped with a pH meter and a stirrer, with stirring to such an extent that vortex does not occur, at a temperature of 25 ° C., 1.0 wt% nitric acid was added to adjust the pH to 4.7, and then a homogenizer (IKA) The total amount of the prepared aluminum sulfate aqueous solution (SA10K) was added and dispersed for 6 minutes while dispersing at 6,500 rpm with Japan Co., Ltd. product: Ultra Tarax T50.

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 43 ° C. at a temperature increase rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and maintained at 43 ° C. The particle size was measured with a multisizer every 10 minutes. When the volume average particle diameter reached 3.3 μm, all of the additional amorphous polyester resin dispersion (DA-A10K) was further added over 60 minutes.
After adding an additional amorphous polyester resin dispersion (DA-A10K), 9 parts by weight of EDTA-Na salt (Kyrest Co., Ltd., Kyrest 40, active ingredient 40% by weight) was added in 5 minutes. The pH was adjusted to 9.0 with a weight% aqueous sodium hydroxide solution.
Thereafter, the temperature was raised to 85 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 85 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 85 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while decreasing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 964, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 15 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 1.0 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNA10K).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

(Example 11)
<Preparation of transparent toner (TNA11T)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-A11T)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight Dowfax2A-1: 1.25 parts by weight The above ingredients are placed in a beaker. While stirring with a magnetic stirrer at a speed that does not entrap bubbles, the pH was adjusted to 4.0 using a 1.0 wt% aqueous nitric acid solution, and an additional amorphous polyester resin particle dispersion (DA -A11T).

<Preparation of aqueous aluminum sulfate solution (SA11T)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.1 parts by weight Ion-exchanged water: 20 parts by weight The above components were charged into a container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of transparent toner (TNA11T)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight -Release agent dispersion (DW1): 195 parts by weight-Dowfax2A-1: 15.0 parts by weight-Ion exchange water: 960 parts by weight While stirring to such an extent that vortex does not occur, 1.0% nitric acid nitric acid was added to adjust the pH to 4.5 at a temperature of 25 ° C. All the prepared aqueous solution of aluminum sulfate (SA11T) was added and dispersed for 6 minutes while dispersing at 5,000 rpm.

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 55 ° C. at a heating rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and held at 55 ° C. The particle size was measured with a multisizer every 10 minutes, and when the volume average particle size reached 24.0 μm, all of the additional amorphous polyester resin dispersion (DA-A11T) was added over 60 minutes. did.
After adding an additional amorphous polyester resin dispersion (DA-A11T), 9 parts by weight of EDTA (Cyrest Co., Ltd., Kirest 40, active ingredient 40% by weight) is added over 5 minutes, and 1% by weight water The pH was adjusted to 8.5 with an aqueous sodium oxide solution.
Thereafter, the temperature was raised to 95 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 95 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 95 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while reducing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 940, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 77 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 0.25 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNA11T).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of colored toner (TNA11K)>
From the toner obtained by the preparation of the colored toner (TNA1K) of Example 1, fine powder was cut with an elbow jet classifier to obtain a colored toner (TNA11K). The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

(Example 12)
<Preparation of transparent toner (TNA12T)>
Fine powder of the transparent toner TNA3T obtained in Example 3 was cut with an elbow jet classifier to obtain a transparent toner TNA12T. The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of developer (DTNA12T)>
In the same manner as in Example 1, a developer (DTNA12T) was prepared.

<Preparation of colored toner (TNA12K)>
The color toner (TNA3K) of Example 3 and the color developer DTNA3K were used.

(Comparative Example 1)
<Preparation of Transparent Toner (TNB1T)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-B1T)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight Dowfax2A-1: 1.25 parts by weight The above ingredients are placed in a beaker. While stirring with a magnetic stirrer at a speed that does not entrap bubbles, the pH was adjusted to 4.0 using a 1.0 wt% aqueous nitric acid solution, and an additional amorphous polyester resin particle dispersion (DA -B1T).

<Preparation of aqueous aluminum sulfate solution (SB1T)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.2 parts by weight Ion-exchanged water: 20 parts by weight The above components were charged into a container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of transparent toner (TNB1T)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight -Release agent dispersion (DW1): 195 parts by weight-Dowfax2A-1: 3.0 parts by weight-Ion exchange water: 650 parts by weight 3 liters of the above components equipped with a thermometer, pH meter and stirrer In a container, while stirring to such an extent that vortex does not occur, 1.0 wt% nitric acid is added to adjust the pH to 4.5 at a temperature of 25 ° C. The total amount of the prepared aluminum sulfate aqueous solution (SB1T) was added and dispersed for 6 minutes while dispersing at 5,000 rpm at T50).

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 46 ° C. at a temperature increase rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and maintained at 46 ° C. The particle size was measured with a multisizer every 10 minutes, and when the volume average particle size reached 16.0 μm, all of the additional amorphous polyester resin dispersion (DA-B1T) was added over 60 minutes. did.
After adding an additional amorphous polyester resin dispersion (DA-B1T), 9 parts by weight of EDTA (Cyrest Co., Ltd., Kirest 40, active ingredient 40% by weight) is added over 5 minutes, and 1% by weight water The pH was adjusted to 8.5 with an aqueous sodium oxide solution.
Thereafter, the temperature was raised to 95 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 95 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 95 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while reducing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 940, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 77 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 0.25 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNB1T).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of developer (DTNB1T)>
40 parts by weight of the toner (TNB1T) is added to 500 parts by weight of the resin-coated carrier (C) of Example 1, blended for 20 minutes with a V-type blender, and then aggregates are removed by a vibration sieve having an aperture of 212 μm. A developer (DTNB1T) was prepared.

<Preparation of colored toner (TNB1K)>
The colored toner TNA1K and developer (DTNA1K) of Example 1 were used.

(Comparative Example 2)
<Preparation of Transparent Toner (TNB2T)>
<Preparation of additional amorphous polyester resin particle dispersion (DA-B2T)>
Amorphous polyester resin dispersion (DA-A1): 160 parts by weight Amorphous polyester resin dispersion (DA-A2): 160 parts by weight Dowfax2A-1: 1.25 parts by weight The above ingredients are placed in a beaker. While stirring with a magnetic stirrer at a speed that does not entrap bubbles, the pH was adjusted to 4.0 using a 1.0 wt% aqueous nitric acid solution, and an additional amorphous polyester resin particle dispersion (DA -B2T).

<Preparation of aqueous aluminum sulfate solution (SB2T)>
Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd: Al ₂ O ₃ as a 17 percent containing products, 56.3 to 58.6% equivalent as _{Al 2 (SO 4) 3)} : 1.2 parts by weight Ion-exchanged water: 20 parts by weight The above components were charged into a container and stirred at 30 ° C. until the precipitate disappeared to prepare an aqueous aluminum sulfate solution.

<Preparation of transparent toner (TNB2T)>
Amorphous polyester resin dispersion (DA-A1): 340 parts by weight Amorphous polyester resin dispersion (DA-A2): 340 parts by weight Crystalline polyester resin dispersion (DA-C1): 65 parts by weight -Release agent dispersion (DW1): 195 parts by weight-Dowfax2A-1: 3.0 parts by weight-Ion exchange water: 650 parts by weight The above components are put in a reaction vessel equipped with a thermometer, pH meter, and stirrer. While stirring to such an extent that vortex does not occur, 1.0 wt% nitric acid was added to adjust the pH to 4.5 at a temperature of 25 ° C., and then the homogenizer (manufactured by IKA Japan Ltd .: Ultra Tarax T50) All the prepared aqueous solution of aluminum sulfate (SB2T) was added and dispersed for 6 minutes while dispersing at 5000 rpm.

Thereafter, a mantle heater is installed in the reaction vessel, and the temperature is increased to 68 ° C. at a temperature increase rate of 1.0 ° C./min while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. The temperature was raised and held at 68 ° C. When the particle size was measured with a multisizer every 10 minutes and the volume average particle size reached 27.0 μm, all of the additional amorphous polyester resin dispersion (DA-B2T) was added over 60 minutes. did.
After adding an additional amorphous polyester resin dispersion (DA-B2T), 9 parts by weight of EDTA (Kyrest Co., Ltd., Kyrest 40, active ingredient 40% by weight) is added over 5 minutes, and 1% by weight water The pH was adjusted to 8.5 with an aqueous sodium oxide solution.
Thereafter, the temperature was raised to 95 ° C. at a heating rate of 1 ° C./min while maintaining the pH at 95 ° C. while adjusting the pH to 9.0 with a 1 wt% aqueous sodium hydroxide solution every 5 ° C. After reaching 95 ° C., the shape factor was measured with FPIA-3000 (manufactured by Sysmex Corporation) while reducing the pH by 0.05 using a 1.0 wt% nitric acid aqueous solution every 10 minutes. When the temperature reached 940, the container was cooled to 30 ° C. over 5 minutes with cooling water.

The cooled slurry was passed through a nylon mesh having a mesh size of 77 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator to separate into solid and liquid. The toner remaining on the filter paper was crushed as finely as possible by hand, poured into ion-exchange water 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and solid-liquid separated again with an aspirator. This operation was repeated until the electrical conductivity of the filtrate reached 10 μS / cm or less, and the toner was washed.
The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles. To 100 parts by weight of the obtained toner particles, 0.25 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a toner (TNB2T).
The physical properties of the obtained toner are shown in Table 2. When the SEM image of the toner was observed, it had a smooth surface and no defects such as protrusion of the release agent and peeling of the surface layer were observed.

<Preparation of developer (DTNB2T)>
40 parts by mass of the toner (TNB2T) is added to 500 parts by weight of the resin-coated carrier (C) of Example 1, blended for 20 minutes with a V-type blender, and then aggregates are removed by a vibration sieve having an aperture of 212 μm. A developer (DTNB2T) was prepared.

<Preparation of colored toner (TNB2K)>
The colored toner TNA1K and developer (DTNA1K) of Example 1 were used.

(Comparative Example 3)
<Preparation of transparent toner (TNB3T)>
Amorphous polyester resin (A1): 600 parts by weight Amorphous polyester resin dispersion (A2): 600 parts by weight Crystalline polyester resin dispersion (C1): 75 parts by weight Hydrocarbon wax (Nippon Seiki Made by Sakai Co., Ltd., trade name: FNP0090, melting temperature Tw = 90.2 ° C.): 150 parts by weight, carbon black (manufactured by Cabot Japan Co., Ltd., REALAL 330): 75 parts by weight The above ingredients are mixed with a Henschel mixer After that, the mixture was melt-kneaded for about 15 minutes at a rotation speed of 120 rpm with a BR type Banbury type kneader (manufactured by Kobe Steel). The kneaded product is formed into a plate shape having a thickness of about 1 cm with a rolling roll, coarsely pulverized to a few millimeters with a Fitzmill type pulverizer, finely pulverized with an IDS type pulverizer, and classified with an elbow type classifier in sequence. A transparent toner (TNB3T) was obtained.

<Preparation of developer (DTNB3T)>
40 parts by weight of the toner (TNB3T) is added to 500 parts by weight of the resin-coated carrier (C) of Example 1, blended for 20 minutes with a V-type blender, and then aggregates are removed by a vibration sieve having an aperture of 212 μm. A developer (DTNB3T) was prepared.

<Preparation of colored toner (TNB3K)>
The colored toner TNA1K and developer (DTNA1K) of Example 1 were used.

<Evaluation of image sharpness>
Clean the Fuji Xerox Co., Ltd. DocuCentre Color 400 CP main unit, developer, and toner cartridge by thoroughly removing the developer and toner that have been set so far in an environmental room at a temperature of 25 ° C and a humidity of 60%. After that, the produced transparent toner developer was put in a developing device and set at a position where the yellow developing device of the DocuCenter Color 400 CP main body was originally set. Further, the produced black developer was put in a developing device and set at a position where the magenta developing device was originally set. Replenishment toner was put into the toner cartridge and set at a position corresponding to the developing device.
In order to charge the developer, 10 sheets of A3 paper were passed through without developing anything.
Next, using OK top coat paper, the development amount of transparent toner on paper was adjusted to 25.0 g / m ² , and the development amount of colored toner on paper was adjusted to 4.0 g / m ² .
Next, a transparent toner 100% image is produced on a colored toner single layer 100% image having a size of 5 cm × 5 cm, a process speed is fixed at 60 mm / sec, a stereoscopic image is produced, and the image edge is sharpened. The degree was evaluated.
After fixing, the image was scanned from the non-image area to the image area with a surface roughness meter (Surfcom) to produce a height profile (vertical magnification 500 times, lateral magnification 20 times).
When the height of the non-image part is zero, the point where the image height is 3 μm is X1, and when the point where the image height is 30 μm is X2, the shorter the distance X2-X1, the sharper the edge It was said that. Five images were measured per image, and the average value of three points excluding the maximum and minimum values was taken as the value.
The evaluation results are shown in Table 2.

<Evaluation of transparent toner transfer efficiency>
Using the apparatus prepared for the evaluation of the image sharpness, an image made of only transparent toner having a size of 5 cm × 5 cm is prepared, and the toner amount DVt on the intermediate transfer member and the toner amount DVp on the paper are respectively measured. The transfer efficiency Et was calculated as Et = DVp / DVt. The paper used was OK top coat paper. The evaluation results are shown in Table 2.

Claims (6)

The volume average primary particle size is 18 μm or more and 28 μm or less,
A transparent toner, wherein the content (composition ratio) of sulfur element measured by fluorescent X-ray is 0.01% or more and 0.1% or less. The transparent toner according to claim 1,
Including colored toner,
The number average particle size index GSDPc of the colored toner and the number average particle size index GSDPt of the transparent toner satisfy the relationship of the following formula (1):
The volume average primary particle size of the transparent toner is 3 to 8 times the volume average primary particle size of the colored toner.
Toner set.
1.03 <GSDPt / GSDPc <1.15 (1) When the content (composition ratio) of sulfur in the transparent toner measured by fluorescent X-ray is St and the content (composition ratio) of sulfur in the colored toner measured by fluorescent X-ray is Sc, the amount of sulfur The ratio St / Sc satisfies the relationship of the following formula (2).
The toner set according to claim 2.
0.1 ≦ St / Sc ≦ 1.0 (2) Forming a transparent resin layer derived from the transparent toner according to claim 1 on at least a part of the colored image derived from the colored toner, and performing a raised printing,
The number average particle size index GSDPc of the colored toner and the number average particle size index GSDPt of the transparent toner satisfy the relationship of the following formula (1):
The volume average primary particle size of the transparent toner is 3 to 8 times the volume average primary particle size of the colored toner.
Image forming method.
1.03 <GSDPt / GSDPc <1.15 (1) When the content (composition ratio) of sulfur in the transparent toner measured by fluorescent X-ray is St and the content (composition ratio) of sulfur in the colored toner measured by fluorescent X-ray is Sc, the amount of sulfur The ratio St / Sc satisfies the relationship of the following formula (2).
The image forming method according to claim 4.
0.1 ≦ St / Sc ≦ 1.0 (2) An agglomeration step of obtaining at least aggregated transparent resin particles in an aqueous medium to obtain aggregated particles; and
Fusing the aggregated particles by heating to obtain a transparent toner,
When the glass transition temperature measured by differential scanning calorimetry of a composition obtained by mixing raw materials excluding toner external additives at a toner composition ratio is Mg, (Mg + 10 ° C.) to (Mg + 30 ° C.) in the aggregation step. Agglomeration in a temperature range of 45 ° C. to 70 ° C.,
The method for producing a transparent toner according to claim 1.