JP2011075702A - Toner, developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner, improved in low temperature fixability without deteriorating shelf life, and having favorable coloring degree and color reproduction region even with a low adhesion amount, and provide a developer and an image forming method using the toner. <P>SOLUTION: This toner at least contains a binder resin, a coloring agent, a mold releasing agent, and aliphatic amide compound, and is granulated in an aqueous medium. Granulation in the aqueous medium is performed as follows. In an organic solvent, at least a compound containing an active hydrogen group as the binder resin, denatured polyester resin containing prepolymer at least having an isocyanate group as a reactive part with the compound containing an active hydrogen group, native polyester resin, the coloring agent, the mold releasing agent, and the aliphatic amide compound are dissolved and dispersed, and the dissolved and dispersed material is dispersed in the aqueous medium including resin fine particles to prepare a dispersed liquid. In the aqueous medium, the compound containing the active hydrogen group and the natured polyester resin are crosslinked and elongation-interacted with each other, and the organic solvent is removed from the obtained dispersed liquid. A difference ΔT between the flow tester softening temperature (Ts) of the toner and the flow-out starting temperature (Tfb) (wherein ΔT indicates Tfb-Ts) is 40°C or lower, and the glass transition temperature (Tg) of the toner is 50°C or higher. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a toner used for image formation using an electrophotographic process, a developer using the toner, and an image forming method.

  In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then transferred to a transfer process. After being transferred from the photoconductor to a transfer medium such as transfer paper, the toner is fixed on the medium in a fixing step. At that time, as a developer for developing an electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, or a one-component developer that does not require a carrier (magnetic toner, non-toner). Magnetic toner) is known.

Conventionally, dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are obtained by melt-kneading and finely pulverizing a toner binder (binder resin) such as styrene resin and polyester together with a colorant. It has been.
These dry toners are developed and transferred onto paper or the like, and then fixed by heating and melting using a hot roll. At that time, if the hot roll temperature is too high, the toner is excessively melted and a problem (hot offset) of fusing to the hot roll occurs. On the other hand, if the heat roll temperature is too low, there is a problem that the toner is not sufficiently melted and fixing is insufficient.
As energy savings and miniaturization of copiers, etc. are being studied, toners with higher hot offset generation temperature (good hot offset resistance) and low fixing temperature (good low temperature fixability) are required. ing.

In addition, recently, the area where the printed matter of the simple printing system such as the electrophotographic method and the inkjet method is used is being expanded to the area of the printed matter by offset printing. In that case, high image quality equivalent to offset printing is required. With regard to the high image quality of offset printing, (1) smoothness of the image and (2) wide color reproducibility are particularly emphasized. Further, in the commercial printing field, from the low cost printing with low toner consumption, (3) the need to achieve a desired high image quality with a low adhesion amount has newly arisen.
The current trend of the above three points in the electrophotographic method is that, for (1) and (3), a highly colored color material is selected mainly for the reduction of the toner particle size, and low pile height image formation is achieved. A method is considered. The above (2) has been repeatedly improved in the direction of improving the selection of the color material and the dispersibility in the toner.

  Here, particularly in full-color copying machines and full-color printers, the gloss and color mixing of the image are required, so the toner needs to have a lower melt viscosity, and a sharp-melt polyester-based toner binder. Is used. However, with such toner, solidification or the like during toner storage is likely to occur, and conventionally, in a full-color device, silicone oil or the like is applied to a heat roll. However, the method of applying silicone oil to the hot roll requires an oil tank and an oil application device, and the device is complicated and large. Moreover, it causes deterioration of the heat roll and requires maintenance every certain period.

In order to improve the hot offset property with toner, a method in which a part of a high molecular polyester resin containing a gel component is used as a binder resin and an appropriate release agent is used in combination is well known. However, in the case of color toners, as described above, it is difficult to use the method particularly from the viewpoint of image gloss after fixing.
Even if the fixing device side is provided with a function to impart gloss, the colorant is uniformly contained in the polymer polyester when the polymer polyester resin containing the gel component is kneaded with other toner materials. It is difficult to disperse, and the high-molecular polyester resin itself is present in the toner in a shape like a sea-island structure, and it is difficult for the colorant to be uniformly present in the toner particles. Therefore, it is difficult to obtain a wide color reproducibility only by selecting an appropriate color material as a colorant.
In addition, in order to prevent the high-molecular polyester resin and other polyester resins from being present in the sea-island state, it is conceivable to use a structure with good compatibility with each other. Is difficult to obtain, and the desired hot offset property cannot be obtained.

Further, proposals have been made regarding a toner having excellent low-temperature fixing and hot offset properties in a styrene-acrylic copolymer (see, for example, Patent Document 1). However, when a styrene-acrylic copolymer is used as a starting material, the styrene monomer remaining in the toner has recently been a concern in terms of safety in the commercial high-speed printing field where a large amount of printing is performed.
Furthermore, the desired low-temperature fixability and hot-offset properties can be obtained by finely controlling the molecular weight distribution of the toner in this way, but in the case of trying to achieve only the molecular weight distribution for the purpose of recent low-temperature fixing. It is clear that the toner storage stability deteriorates. Further, since the binder resin is produced by finely defining the molecular weight distribution, it is difficult to produce the binder resin at a low cost.

  Therefore, development of a toner that improves low-temperature fixability without deteriorating storage stability and has good coloration degree and color reproduction range even with a low adhesion amount, a developer using the toner, and an image forming method Is strongly desired.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention improves the low-temperature fixability without deteriorating the storage stability, and has a good coloring degree and color reproduction range even with a low adhesion amount, a developer using the toner, and an image. An object is to provide a forming method.

Means for solving the problems are as follows. That is,
<1> A toner comprising at least a binder resin, a colorant, a release agent, and an aliphatic amide compound, and granulated in an aqueous medium,
Modification in which the granulation in the aqueous medium includes, in an organic solvent, at least an active hydrogen group-containing compound as the binder resin, and a prepolymer having at least an isocyanate group as a site capable of reacting with the active hydrogen group-containing compound. Dissolving or dispersing a polyester resin and an unmodified polyester resin, the colorant, the release agent, and the aliphatic amide compound,
Dispersing the solution or dispersion in an aqueous medium containing resin fine particles to prepare a dispersion,
In the aqueous medium, the active hydrogen group-containing compound and the modified polyester resin are subjected to a crosslinking or extension reaction,
It is performed by removing the organic solvent from the obtained dispersion,
The difference ΔT (where ΔT represents Tfb−Ts) between the flow tester softening temperature (Ts) and the outflow start temperature (Tfb) of the toner is 40 ° C. or less,
The toner has a glass transition temperature (Tg) of 50 ° C. or higher.
<2> The toner according to <1>, wherein a THF insoluble content in the toner is 1% by mass to 10% by mass.
<3> A developer containing the toner according to any one of <1> to <2>.
<4> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium,
The toner is the toner according to any one of <1> to <2>,
The fixing step is a fixing belt method;
Gloss of the image on the recording medium after the fixing step is, when the toner adhesion amount of ^{0.25mg / cm 2 ~0.35mg / cm 2} , an image forming method, wherein a is 15 or more.
<5> The electrostatic latent image forming step is a step of forming an electrostatic latent image on each of the plurality of electrostatic latent image carriers.
The developing step is a step of developing each electrostatic latent image using a toner of a different color for each electrostatic latent image carrier to form a visible image,
The image forming method according to <4>, wherein the transfer step is a step of transferring the visible image to a recording medium via an intermediate transfer member.

  According to the present invention, the conventional problems can be solved, the object can be achieved, the low-temperature fixability can be improved without deteriorating the storage stability, and good coloration and color can be achieved even with a low adhesion amount. A toner having a reproduction area, a developer using the toner, and an image forming method can be provided.

FIG. 1 is a diagram illustrating an example of an image forming apparatus according to the present invention. FIG. 2 is a diagram showing another example of the image forming apparatus of the present invention. FIG. 3 is a diagram showing the tandem developing device of FIG. FIG. 4 is a graph showing an example of a flow curve of the flow tester.

(toner)
The toner of the present invention is granulated in an aqueous medium and contains at least a binder resin, a colorant, a release agent, and an aliphatic amide compound, and further contains other components as necessary.
The granulation in the aqueous medium includes a modification containing an active hydrogen group-containing compound as the binder resin and a prepolymer having at least an isocyanate group as a site capable of reacting with the active hydrogen group-containing compound in an organic solvent. A polyester resin, an unmodified polyester resin, the colorant, the release agent, and the aliphatic amide compound are dissolved or dispersed, and the dissolved or dispersed material is dispersed in an aqueous medium containing resin fine particles. A dispersion is prepared, the active hydrogen group-containing compound and the modified polyester resin are crosslinked or extended in the aqueous medium, and the organic solvent is removed from the obtained dispersion.
The difference ΔT between the flow tester softening temperature (Ts) of the toner and the outflow start temperature (Tfb) (where ΔT represents Tfb−Ts) is 40 ° C. or less, and the glass transition temperature (Tg) of the toner is 50 ° C. or higher.

<Aliphatic amide compound>
By using the aliphatic amide compound, the softening action of the binder resin granulated in an aqueous medium necessary for obtaining the thermal characteristics of the toner of the present invention can be obtained.
The aliphatic amide compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include palmitic acid amide, stearic acid amide, behenic acid amide and mixtures thereof, and n-stearyl-stearic acid amide. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as content of the said aliphatic amide compound in a toner, Although it can select suitably according to the objective, 1 mass part-10 mass parts are preferable with respect to 100 mass parts of toner, 3 Mass parts to 10 parts by mass are more preferable, and 3 parts to 6 parts by mass are particularly preferable. When the content is less than 3 parts by mass, the effect of softening the resin is small, and the desired low-temperature fixing may not be obtained. Inhibition may be manifested, or in the case of aqueous granulation, granulation stability may be reduced, making it difficult to obtain a desired particle size distribution.

The aliphatic amide compound is present in the toner as a crystalline domain independent of the binder resin before the toner is heated from the fixing portion. It becomes compatible and promotes softening of the binder resin.
Since the aliphatic amide compound does not cause softening of the binder resin before fixing, the toner of the present invention is excellent in heat-resistant storage stability. Furthermore, since the aliphatic amide compound has a function of softening the binder resin at the time of fixing, the toner of the present invention is excellent in low-temperature fixability.

Examples of the method for confirming that the aliphatic amide compound has crystallinity before toner fixing include a method for measuring a crystalline retention state (compatible or incompatible) from an X-ray diffraction chart.
Specifically, it can be confirmed that the aliphatic amide compound has crystallinity in the toner by using a crystal analysis X-ray diffractometer (manufactured by X'Pert MRDX'Pert MRD Phillips). First, a sample powder is prepared by grinding a single aliphatic amide compound using a mortar, and the obtained sample powder is uniformly applied to a sample holder. Thereafter, a sample holder is set in the diffractometer and measurement is performed to obtain a diffraction spectrum of the aliphatic amide compound. Next, toner powder is applied to the holder, and measurement is performed in the same manner. The aliphatic amide compound contained in the toner can be identified from the diffraction spectrum of the aliphatic amide compound obtained in advance. Moreover, in the said diffraction apparatus, the change of the diffraction spectrum at the time of changing temperature can be measured by using an attached heating unit. Using the heating unit, by measuring the change in the peak area of the X-ray diffraction spectrum derived from the aliphatic amide compound at room temperature and 150 ° C., the proportion of the compatible and incompatible components in the resin before and after heating the aliphatic amide compound Can be requested. The larger the rate of change of the peak area derived from the aliphatic amide compound before and after the heating, the more the compatibilization with the toner resin proceeds by heating at the time of fixing. Since the toner contains the aliphatic amide compound, the rate of change of the peak area derived from the aliphatic amide compound before and after heating increases, and thus the toner has an excellent low-temperature fixing effect.

  There is no restriction | limiting in particular as a dispersion diameter of the said aliphatic amide compound, Although it can select suitably according to the objective, For example, as a particle size of a maximum direction, 10 nm-3 micrometers are preferable, and 50 nm-1 micrometer are more preferable. When the dispersion diameter is less than 10 nm, the heat-resistant storage stability of the toner may be inferior due to an increase in the contact surface area between the aliphatic amide compound and the binder resin. At this time, the compatibility with the binder resin is not sufficiently performed, and the low-temperature fixability of the toner may be inferior.

  As a method for measuring the dispersion diameter of the aliphatic amide compound, for example, the toner is embedded in an epoxy resin, cut into an ultrathin section of about 100 nm, stained with ruthenium tetroxide, and then magnified with a transmission electron microscope (TEM). By observing at 10,000 times, taking a photograph, and evaluating the photograph, the dispersion state of the aliphatic amide compound can be observed and the dispersion diameter can be measured. In order to distinguish between the aliphatic amide compound and the release agent in the toner, each of the aliphatic amide compound and the release agent is previously dyed with ruthenium tetroxide in the same manner as described above, so that the transmission type By observing with an electron microscope and confirming the difference in contrast between the aliphatic amide compound and the release agent, based on the contrast difference when observing the aliphatic amide compound and the release agent in the toner, It is possible to distinguish between the aliphatic amide compound and the release agent.

<Binder resin>
The binder resin includes at least an active hydrogen group-containing compound, a modified polyester resin, and an unmodified polyester resin, and further includes a polyester resin, a monomer, a polymer, and the like as necessary.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably.
The polyester resin can be obtained by dehydration condensation of a polyhydric alcohol and a polycarboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, , 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, divalent alcohols obtained by adding cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.
In order to crosslink the polyester resin, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. It is preferable to use a trivalent or higher alcohol together.

  Examples of the polyvalent carboxylic acid include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or anhydrides thereof. Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, etc., unsaturated maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Dibasic acid anhydride, trimet acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid Acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicar Xyl-2-methyl-2-methylenecarboxypropane, tetrakis (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, emporic trimer acid, anhydrides thereof, partial lower alkyl esters, etc. It is done.

  There is no restriction | limiting in particular as an acid value of the said polyester resin, Although it can select suitably according to the objective, 5 mgKOH / g-40 mgKOH / g are preferable, and 10 mgKOH / g-30 mgKOH / g are still more preferable. When the acid value is less than 5 mgKOH / g, the affinity with paper as a main recording medium is lowered, so that the low-temperature fixability of the toner may be lowered, and it is difficult to obtain a negative chargeability. The image may deteriorate. Further, when the acid value is less than 5 mgKOH / g, the compatibility with the aliphatic amide compound may be inferior, so that the low-temperature fixability of the toner may not be sufficiently obtained. On the other hand, when the acid value exceeds 40 mgKOH / g, the image is likely to be deteriorated under an environment such as high temperature and high humidity, low temperature and low humidity, and the like.

  There is no restriction | limiting in particular as a hydroxyl value of the said polyester resin, Although it can select suitably according to the objective, 5 mgKOH / g-100 mgKOH / g are preferable, and 20 mgKOH / g-60 mgKOH / g are still more preferable. When the hydroxyl value is less than 5 mgKOH / g, the affinity with paper as the main recording medium is lowered, so that the low-temperature fixability of the toner may be lowered, and the negative chargeability is hardly obtained. The image may be deteriorated. Further, if the hydroxyl value is less than 5 mgKOH / g, the compatibility with the aliphatic amide compound may be inferior, so that the low-temperature fixability of the toner may not be sufficiently obtained. On the other hand, when the hydroxyl value exceeds 100 mgKOH / g, the image may be deteriorated because it is easily affected by the environment in an environment such as high temperature and high humidity or low temperature and low humidity.

In addition, the polyester resin has at least one peak in a molecular weight range of 3,000 to 50,000 in the molecular weight distribution of components soluble in THF from the viewpoint of toner fixing property and offset resistance. Preferably, it has at least one peak in a region having a molecular weight of 5,000 to 20,000. Furthermore, the content of the component having a molecular weight of 100,000 or less is preferably 60% by mass to 100% by mass in the polyester resin soluble in THF.
Here, the molecular weight distribution of the polyester resin can be measured, for example, by gel permeation chromatography (GPC) using THF as a solvent.

  The glass transition temperature (Tg) of the polyester resin is preferably 55 ° C. to 80 ° C., more preferably 60 ° C. to 75 ° C., from the viewpoint of toner storage stability. When the Tg is 55 ° C. to 80 ° C., the toner has excellent stability during high-temperature storage, and the effect of softening the binder resin by the aliphatic amide compound can be obtained sufficiently. Excellent fixability.

<Release agent>
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably, For example, the following are mentioned including petroleum waxes, such as paraffin wax, microcrystalline, and petrolatum.
Examples of mold release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; And natural waxes. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers; Among these, hydrocarbon waxes such as paraffin, polyethylene, and polypropylene are preferable in that sufficient low-temperature fixability of the toner can be obtained.
The said mold release agent may be used individually by 1 type, and may use 2 or more types together.
There is no restriction | limiting in particular as content of the said mold release agent in a toner, Although it can select suitably according to the objective, It is preferable that it is 1 mass part or more and less than 30 mass parts. Depending on the type of release agent used, the heat loss characteristics of the toner change, so it is not uniquely determined, but if it is 1 part by mass or less, it may be inferior in hot offset resistance, and if it is 30 parts by mass or more If there is, deterioration of filming property and fogging of the image may occur.

<Colorant>
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), Cadmium yellow, Yellow iron oxide, Ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR) , Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Parallel , Faise red, parachloroortho nitroaniline red, risor fast scarlet G, brilliant fast scarlet, brilliant carmine BS, permanent red (F2R, F4R, FRL, FRLL, F4RH), fast scarlet VD, Belkan Fast Rubin B, brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil le Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Glee Nlake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litobon and the like.
The said colorant may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said coloring agent in a toner, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 5 mass%-12 mass% are more preferable. When a low adhesion amount image is formed with toner having a particle diameter of 3 μm to 6 μm, the colorant adhesion amount needs to be a certain amount or more. On the other hand, when the content of the colorant in the toner is less than 3% by mass, the coloring power of the toner is lowered, and when it exceeds 15% by mass, the pigment is not well dispersed in the toner and the toner is fixed due to the filler effect. Insufficient spreadability may occur, and conversely, the concealment rate may be lowered and the electrical characteristics of the toner may be lowered.

The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited and can be appropriately selected depending on the purpose. For example, a polyester resin, a polymer of styrene or a substituted product thereof can be applied, and the same kind as the resin constituting the toner particles. The polyester resin is particularly preferable.
Examples of the polymer of styrene or a substituted product thereof include polystyrene, poly (p-chlorostyrene), and polyvinyl toluene.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. A so-called flushing method is also preferable in that the wet cake of the colorant can be used as it is, and it does not need to be dried. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organically modified layered inorganic minerals, charge control agents, inorganic fine particles, cleaning improvers, and magnetic materials. .

-Organically modified layered inorganic minerals-
The organically modified layered inorganic mineral is preferably a layered inorganic mineral having a smectite-based basic crystal structure in which at least some of the ions of the layered inorganic mineral are modified with organic ions. Examples of layered inorganic minerals modified with such organic ions include montmorillonite, bentonite, beidellite, nontronite, saponite, hectorite, and the like.
Examples of the organic ions include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like, and quaternary alkyl ammonium salts are preferable. Examples of the quaternary alkyl ammonium include trimethyl stearyl ammonium, dimethyl stearyl benzyl ammonium, dimethyl octadecyl ammonium, oleyl bis (2-hydroxyethyl) methyl ammonium, and the like.

  The organically modified layered inorganic mineral is not particularly limited and may be appropriately selected depending on the purpose. Commercially available products may be used. , BENTONE27, BENTONE57, BENTONE SD1, BENTONE SD2, BENTONE SD3 etc. Esben NZ, Esben NZ70, Esven W, Esben N400, Esben NX, Esben NX80, Esbe NO12S, S-BEN NEZ, S-BEN NO12, S-BEN WX, S-BEN NE, and the like; Kunimine Industries Co., Ltd. of Kunibisu 110, Kunibisu 120, Kunibisu 127, and the like.

  The content of the organically modified layered inorganic mineral in the toner is preferably 0.1% by mass to 5% by mass. When the content is less than 0.1% by mass, the effect of toner shape and toner chargeability may be reduced, and when it exceeds 5% by mass, fixing performance may be deteriorated.

-Charge control agent-
Examples of the charge control agent include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary ammonium salts). ), Alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based surfactant, salicylic acid metal salt, salicylic acid derivative metal salt, and the like.
Commercially available products may be used as the charge control agent, for example, Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid type E-82 of metal complex, E-84 of salicylic acid metal complex, E-89 of phenol condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above , Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, Hoechst) LRA-901, LR-147 which is a boron complex (manufactured by Nippon Carlit) Copper phthalocyanine, perylene, quinacridone, azo pigments, a sulfonic acid group, a carboxyl group, such as polymer compounds having a functional group such as quaternary ammonium bases.
The charge control agent may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content of the said charge control agent in a toner, Although it can select suitably according to the objective, 0.1 mass%-10 mass% are preferable with respect to binder resin, 0 More preferably, the content is 2% by mass to 5% by mass. When the content is less than 0.1% by mass, the charge controllability may not be obtained. When the content exceeds 10% by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attraction force with the developing roller increases, which may lead to a decrease in toner fluidity and a decrease in image density.

-Inorganic fine particles-
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.
The inorganic fine particles may be used alone or in combination of two or more.

The primary particle size of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm.
The content of inorganic fine particles in the toner is preferably 0.01% by mass to 5.0% by mass and more preferably 0.01% by mass to 2.0% by mass with respect to the total amount of the toner.

The inorganic fine particles are preferably surface-treated with a fluidity improver. As a result, the hydrophobicity of the inorganic fine particles is improved, and a decrease in fluidity and chargeability can be suppressed even under high humidity.
Examples of the fluidity improver include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Etc. Silica and titanium oxide are preferably surface-treated with a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

-Cleaning improver-
The cleaning property improver is used to facilitate removal of toner remaining on the photoreceptor and the primary transfer medium after transfer.
Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate and calcium stearate, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle size of 0.01 μm to 1 μm.

-Magnetic material-
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably, For example, iron powder, a magnetite, a ferrite etc. are mentioned. The magnetic material is preferably white from the viewpoint of the color tone of the toner.

  The toner has the following difference ΔT between the flow tester softening temperature (Ts) and the outflow start temperature (Tfb), the glass transition temperature (Tg), and the following THF insoluble content. Preferably it is.

<Difference ΔT between toner flow tester softening temperature (Ts) and outflow start temperature (Tfb)>
The difference ΔT between the flow tester softening temperature (Ts) and the outflow start temperature (Tfb) of the toner is not particularly limited as long as it is 40 ° C. or less, depending on the purpose. However, it is particularly preferably 30 ° C. or lower. When the ΔT exceeds 40 ° C., low-temperature fixing is difficult to occur or storage stability may be lowered.

The flow tester softening temperature (Ts) of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C. to 70 ° C. or higher.
The toner flow tester outflow start temperature (Tfb) is not particularly limited and may be appropriately selected depending on the intended purpose. However, 90 ° C. to 100 ° C. is preferable in that desired low-temperature fixability can be obtained. .
By setting the flow tester softening temperature (Ts) and the low tester outflow start temperature (Tfb) in the preferred ranges, it is advantageous in that both low-temperature fixability and storage stability can be achieved.

Here, the flow tester softening temperature (Ts) and the outflow start temperature (Tfb) of the toner can be measured as follows.
The flow tester softening temperature (Ts) and the outflow start temperature (Tfb) can be obtained from a flow curve (see FIG. 4) measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation). Here, in FIG. 4, Ts represents the softening temperature, and Tfb represents the outflow start temperature.
Measurement conditions can be as follows: a load of 10 kg / cm ² , a temperature increase rate of 3.0 ° C./min, a die diameter of 0.50 mm, and a die length of 10.0 mm.

<Glass transition temperature (Tg) of toner>
The glass transition temperature (Tg) of the toner is not particularly limited as long as it is 50 ° C. or higher, and can be appropriately selected according to the purpose, but 55 ° C. or higher is particularly preferable. If the glass transition temperature (Tg) is less than 50 ° C., the toner fluidity may be lowered due to heat in the copying machine, in addition to the normal storability.

Here, the glass transition temperature (Tg) of the toner can be measured as follows.
The glass transition temperature can be measured by the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.

<THF insoluble content in toner>
The amount of THF-insoluble matter in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1% by mass to 10% by mass, and more preferably 5% by mass to 10% by mass. When the amount of THF-insoluble matter in the toner is less than 5% by mass, the high-temperature offset property may be deteriorated. Sometimes.

Here, the amount of insoluble THF in the toner can be measured as follows.
1 g of toner is weighed, 100 g of tetrahydrofuran (THF) is added thereto, and the mixture is allowed to stand at 10 ° C. for 20 to 30 hours. After 20 to 30 hours, the gel component which is insoluble in THF absorbs THF as the solvent, swells and settles, and is separated by filter paper. The separated gel content is heated at 120 ° C. for 3 hours to volatilize the absorbed THF, and then the mass is weighed to measure the amount of THF insoluble matter (gel content).

  The toner of the present invention is excellent in low-temperature fixability and storage stability and can form a high-quality image. Therefore, the toner of the present invention can be used in various fields, and is particularly preferably used for image formation by electrophotography.

<Toner production method (polymerization method)>
The toner of the present invention is granulated in an aqueous medium.
The granulation in the aqueous medium includes a modification containing an active hydrogen group-containing compound as the binder resin and a prepolymer having at least an isocyanate group as a site capable of reacting with the active hydrogen group-containing compound in an organic solvent. A polyester resin, an unmodified polyester resin, the colorant, the release agent, and the aliphatic amide compound are dissolved or dispersed, and the dissolved or dispersed material is dispersed in an aqueous medium containing resin fine particles. A dispersion is prepared, the active hydrogen group-containing compound and the modified polyester resin are crosslinked or extended in the aqueous medium, and the organic solvent is removed from the obtained dispersion.
According to the method for producing a toner by the polymerization method, a toner having a small particle size and a spherical shape can be produced at low cost with little environmental load.

-Organic solvent-
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, Since removal is easy, the organic solvent whose boiling point is less than 150 degreeC is preferable. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, And methyl isobutyl ketone. Of these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, Although it can select suitably according to the objective, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of toner materials, and 60 mass parts-140 mass parts. Mass parts are more preferred, with 80 to 120 parts by weight being particularly preferred.
The toner material includes at least a binder resin, a colorant, a release agent, and an aliphatic amide compound, and further includes other components as necessary.

-Modified polyester resin-
The modified polyester resin contains at least a prepolymer having an isocyanate group as a site capable of reacting with the active hydrogen group-containing compound, and optionally contains other modified polyester resins.

The prepolymer having at least an isocyanate group as a site capable of reacting with the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a modified polyester capable of bonding with urea or urethane Based resins.
Examples of the modified polyester resin capable of being bonded with urea or urethane include, for example, a polyester prepolymer having an isocyanate group (A) obtained by reacting a terminal carboxyl group or hydroxyl group of a polyester with a polyvalent isocyanate compound (PIC) (A). ) And the like. The modified polyester resin obtained by crosslinking and / or extending the molecular chain by the reaction of the polyester prepolymer with amines (B) as the active hydrogen group-containing compound maintains the low-temperature fixability of the toner. Hot offset property can be improved.

Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane). Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; And those blocked with oxime, caprolactam, and the like. These may be used individually by 1 type and may use 2 or more types together.
The ratio of the polyvalent isocyanate compound (PIC) is preferably 5/1 to 1/1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group, 4/1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable.

  As an isocyanate group contained per molecule in the polyester prepolymer (A) having the isocyanate group, one or more is preferable, an average of 1.5 to 3 is more preferable, and an average of 1.8 to 2 .5 is more preferable.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound is used as an elongation agent, a crosslinking agent, etc. when a prepolymer having at least an isocyanate group as a site capable of reacting with the active hydrogen group-containing compound undergoes an extension reaction, a crosslinking reaction, or the like in the aqueous medium. Works.
There is no restriction | limiting in particular as said active hydrogen group containing compound, According to the objective, it can select suitably.
For example, as the active hydrogen group-containing compound (amines (B)) to be reacted with the polyester prepolymer, a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), Examples include amino mercaptan (B4), amino acid (B5), and amino acid block of B1 to B5 (B6).

Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-). Dimethyl dicyclohexyl methane, diamine cyclohexane, isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the blocked B1-B5 amino group (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). . Among these amines (B), B1 and a mixture of B1 and a small amount of B2 are particularly preferable.

  The ratio of the amines (B) is equivalent to the equivalent ratio [NCO] / [NHx of the isocyanate group [NCO] in the polyester prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). ] Is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and still more preferably 1.2 / 1 to 1 / 1.2.

-Unmodified polyester resin-
The unmodified polyester is used for securing low-temperature fixability and storage stability.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to hot offset.

  The mass average molecular weight of the unmodified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, the molecular weight distribution obtained by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF) is 1 It is preferable that it is 3,000-30,000, and 1,500-15,000 are more preferable. When the mass average molecular weight is less than 1,000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose mass mean molecular weight is less than 1,000 is 8 mass%-28 mass%. On the other hand, if the mass average molecular weight exceeds 30,000, the low-temperature fixability may deteriorate.

  There is no restriction | limiting in particular as a glass transition temperature of the said unmodified polyester resin, Although it can select suitably according to the objective, 30 to 70 degreeC is preferable, 35 to 60 degreeC is more preferable, and 35 to 55 degreeC. More preferred is ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.

  The hydroxyl value of the unmodified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and 20 mgKOH / g to 80 mg KOH / g is more preferable. When the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.

  There is no restriction | limiting in particular as an acid value of the said unmodified polyester resin, Although it can select suitably according to the objective, 1.0 mgKOH / g-50.0 mgKOH / g is preferable, 1.0 mgKOH / g-30. 0 mg KOH / g is more preferable. Thereby, the toner is easily negatively charged.

Here, the acid value and the hydroxyl value are specifically determined by the following procedure.
・ Measuring device: potentiometric automatic titrator DL-53 Titoror (manufactured by METTLER TOLEDO)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
・ Measurement temperature: 23 ℃
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potentialial 2 No
Stop for revaluation No

-Method of measuring acid value-
The acid value can be measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, and specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and obtain the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)

-Measurement method of hydroxyl value-
The hydroxyl value can be measured under the following conditions based on the measurement method described in JIS K0070-1966.
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the hydroxyl value.

  The mass ratio of the polyester prepolymer having an isocyanate group to the unmodified polyester resin is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. When the mass ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

-Aqueous medium-
The aqueous medium preferably contains at least resin fine particles and, if necessary, further contains a polymer dispersant.
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

--Resin fine particles--
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples of the resin include vinyl resins. Among these, vinyl resins are particularly preferable.
These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin in that an aqueous dispersion of fine spherical resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Further, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate, and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

--Polymer dispersant--
There is no restriction | limiting in particular as said polymer dispersing agent, Although it can select suitably according to the objective, A water-soluble polymer is preferable. The water-soluble polymer can be appropriately selected from known ones, and examples thereof include sodium carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol. These may be used individually by 1 type and may use 2 or more types together.

As an example of the toner production method, a method for forming toner base particles while producing an adhesive substrate will be described below.
In the method, preparation of an aqueous medium phase, preparation of a solution or dispersion containing the toner material, preparation of the dispersion, formation of the adhesive substrate, removal of the organic solvent, and others (of the modified polyester resin) Synthesis, synthesis of active hydrogen group-containing compounds, etc.).

  The aqueous medium phase can be prepared by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount of the said resin fine particle in an aqueous medium, Although it can select suitably according to the objective, 0.5 mass%-10 mass% are preferable.

  In the organic solvent, the active hydrogen group-containing compound, the modified polyester resin, the unmodified polyester resin, the colorant, the release agent, the aliphatic are prepared in the organic solvent. It can be carried out by dissolving or dispersing a toner material such as an amide compound or the charge control agent.

The dispersion can be prepared by dispersing a solution or dispersion containing the toner material in an aqueous medium containing resin fine particles.
When the dissolved or dispersed material containing the toner material is dispersed in the aqueous medium, the dissolved or dispersed material containing the toner material is preferably dispersed in the aqueous medium while stirring.
A known disperser or the like can be appropriately used for the dispersion. Specific examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Especially, since the particle diameter of a dispersion (oil drop) can be controlled to 2 micrometers-20 micrometers, a high-speed shearing disperser is preferable.

  When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The number of rotations is preferably 1,000 rpm to 30,000 rpm, and more preferably 5,000 rpm to 20,000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 ° C. to 150 ° C. and more preferably 40 ° C. to 98 ° C. under pressure. . In general, the dispersion is easier when the dispersion temperature is higher.

The adhesive base is produced by crosslinking or extending the active hydrogen group-containing compound and the modified polyester resin.
Crosslinking or elongation reaction between the active hydrogen group-containing compound and the modified polyester resin proceeds when the dissolved or dispersed material containing the toner material is dispersed in an aqueous medium.
The reaction conditions for the crosslinking or extension reaction are not particularly limited and may be appropriately selected depending on the combination of the active hydrogen group-containing compound and the modified polyester resin, but preferably 10 minutes to 40 hours. Time to 24 hours are more preferable.

The removal of the organic solvent removes the organic solvent from the dispersion (dispersion slurry).
The method for removing the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) the temperature of the entire reaction system is gradually raised, and the organic solvent in the oil droplets (2) Spraying the emulsified dispersion into a dry atmosphere to completely remove the water-insoluble organic solvent in the oil droplets to form toner fine particles. And a method of evaporating and removing.

When the organic solvent is removed, toner base particles are formed.
The toner base particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, and the classification operation may be performed after obtaining a powder after drying.

In this way, the obtained toner base particles are mixed with particles of the colorant, the release agent, the charge control agent, etc., and further applied with a mechanical impact force from the surface of the toner base particles. It is possible to prevent particles such as a release agent from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, a hybridization system (Nara Machinery) Manufactured by Seisakusho), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

(Developer)
The developer includes at least the toner of the present invention, and includes other configurations as necessary.
The developer may be used as a one-component magnetic developer and a non-magnetic developer that do not use a carrier, or may be used as a two-component developer that uses a carrier.
When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. More preferred.

-Career-
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.

--- Core material--
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, a manganese-strontium type material, a manganese-magnesium type material, etc. of 50emu / g-90emu / g etc. are mentioned. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. When the volume average particle diameter is more than 150 μm, the specific surface area is decreased, and the toner In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

--- Resin layer--
The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, Examples thereof include fluoroterpolymers such as copolymers of tetrafluoroethylene, vinylidene fluoride, and monomers having no fluoro group, silicone resins, and the like.
These may be used individually by 1 type and may use 2 or more types together.

Specific examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin.
Specific examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral.
Specific examples of the polystyrene-based resin include polystyrene and styrene-acrylic copolymer.
Specific examples of the polyhalogenated olefin include polyvinyl chloride.
Specific examples of the polyester-based resin include polyethylene terephthalate and polybutylene terephthalate.

  The resin layer may contain conductive powder or the like as necessary. Specific examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.

The resin layer is formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then coating and drying the coating solution on the surface of the core using a known coating method, followed by baking. Can do.
As the coating method, for example, a dip coating method, a spray method, a brush coating method, or the like can be used.
The solvent can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl cellosolve and the like.
The baking may be an external heating method or an internal heating method, a method using a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, or a method using a microwave. Etc.

  There is no restriction | limiting in particular as content of the resin layer in the said carrier, Although it can select suitably according to the objective, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer is thick and the carrier Fusion may occur between them, and the uniformity of the carrier may decrease.

(Image forming method, image forming apparatus)
The image forming method of the present invention preferably includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further includes a cleaning step. The process includes, for example, a static elimination process, a recycling process, a control process, and the like.
The image forming apparatus used in the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further includes a cleaning unit. And other means appropriately selected as necessary, for example, a static elimination means, a recycling means, a control means and the like.
The image forming method of the present invention can be carried out by the image forming apparatus used in the present invention. The electrostatic latent image forming step uses an electrostatic latent image forming unit, and the developing step uses a developing unit. The transfer step can be performed using a transfer unit, the fixing step can be performed using a belt fixing unit, and the other steps can be performed using other units.

  In the image forming method, the electrostatic latent image forming step is a step of forming an electrostatic latent image on each of a plurality of electrostatic latent image carriers, and the developing step is a step of forming each electrostatic latent image. Development of a different color toner for each electrostatic latent image carrier to form a visible image, and the transfer step transfers the visible image to a recording medium via an intermediate transfer member It is preferable that it is a process.

-Glossy-
In the image forming method, the gloss of the image on the recording medium after the fixing step is, when the toner adhesion amount of ^{0.25mg / cm 2 ~0.35mg / cm 2} , is 15 or more. In the image forming method of the present invention, the gloss of the image on the recording medium after the fixing step is, when the toner adhesion amount of ^{0.25mg / cm 2 ~0.35mg / cm 2} , because it is 15 or more, a small amount It is advantageous in that a desired image can be obtained with this toner, and it can be printed at low cost, and since the toner layer thickness is thin, it is possible to form an image with a natural feeling and a paper type (such as uneven paper). is there.
There is no restriction | limiting in particular as the measuring method of the glossiness of the said image, According to the objective, it can select suitably, For example, it can measure with a glossiness meter (Nippon Denshoku Industries Co., Ltd. VGS-1D).

-Electrostatic latent image formation process-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier such as a photoconductive insulator or a photoconductor. The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, an amorphous silicon photoconductor is preferable because of its long life.

The electrostatic latent image is formed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and can be formed using electrostatic latent image forming means. . The electrostatic latent image forming means includes, for example, a charger that applies a voltage to the surface of the electrostatic latent image carrier and uniformly charges it, and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise At least.
The charger is not particularly limited. For example, a known contact charger provided with a conductive or semiconductive roll, brush, film, rubber blade, etc., non-contact using corona discharge such as corotron, scorotron, etc. Examples include a charger.
The exposure device is not particularly limited as long as it can be exposed like an image to be formed on the surface of the electrostatic latent image carrier charged by the charger. For example, a copying optical system, a rod lens array system, a laser Various exposure devices such as an optical system and a liquid crystal shutter optical system may be mentioned. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of an electrostatic latent image carrier.

-Development process-
The developing step is a step of developing an electrostatic latent image with the toner of the present invention to form a visible image, and the visible image can be formed using a developing unit. The developing unit is not particularly limited as long as it can be developed with the toner of the present invention. For example, a developing device that stores the developer of the present invention and can apply toner to a latent electrostatic image in a contact or non-contact manner. A developing device equipped with the developer container of the present invention is preferable. Examples of the developing device include a stirrer that charges the developer of the present invention by friction stirring and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier, and a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted by the electrostatic latent image carrier. Move to the surface. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the electrostatic latent image carrier.

-Transfer process-
The transfer step is a step of transferring the toner image to a recording medium by charging the electrostatic latent image carrier on which the toner image is formed using, for example, a transfer charger. can do. At this time, the transfer step preferably includes a primary transfer step of transferring the toner image onto the intermediate transfer member, and a secondary transfer step of transferring the toner image transferred onto the intermediate transfer member onto the recording medium. Further, the transfer step includes a primary transfer step in which a toner image of two or more colors, preferably a full color toner, is used to transfer a toner image of each color onto an intermediate transfer member to form a composite toner image; It is more preferable to have a secondary transfer step of transferring the composite toner image formed on the recording medium.

The transfer means includes a primary transfer means for transferring a toner image onto an intermediate transfer member to form a composite toner image, and a secondary transfer means for transferring the composite toner image formed on the intermediate transfer member onto a recording medium. It is preferable to have. The intermediate transfer member is not particularly limited, and examples thereof include an endless transfer belt. The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer device that charges and separates the toner image formed on the electrostatic latent image carrier on the recording medium side. The transfer means can have one or more transfer devices.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited, and can be appropriately selected from known recording media (recording paper).

-Fixing process-
The fixing step is a step of fixing the toner image transferred to the recording medium, and is fixed by a fixing belt method. The fixing unit used in the fixing belt method is not particularly limited and may be appropriately selected depending on the intended purpose. However, a combination of a heating roller, a pressure roller, and an endless belt is preferable. At this time, heating temperature is 80 degreeC-200 degreeC normally.
In the present invention, since the fixing step is a belt fixing method, a long nip time can be taken, so that a plurality of color toners can be sufficiently melted and fixed as an image, so that a desired color and image quality can be obtained. It is advantageous.

-Static elimination process-
The neutralization step is a step of neutralizing by applying a neutralization bias to the electrostatic latent image carrier, and can be neutralized using a neutralization unit. The neutralization means is not particularly limited as long as a neutralization bias can be applied to the electrostatic latent image carrier. For example, a neutralization lamp can be used.

-Cleaning process-
The cleaning step is a step of removing toner remaining on the electrostatic latent image carrier and can be cleaned using a cleaning unit. The cleaning means is not particularly limited as long as the toner remaining on the electrostatic latent image carrier can be removed. For example, a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, A web cleaner or the like can be used.

-Recycling process-
The recycling step is a step of recycling the toner removed in the cleaning step to the developing means, and can be recycled using the recycling means. The recycling unit is not particularly limited, and a known conveyance unit or the like can be used.

-Control process-
The said control process is a process of controlling each process, and can be controlled using a control means. The control unit is not particularly limited as long as the operation of each unit can be controlled. For example, a sequencer, a computer, or the like can be used.

FIG. 1 shows an example of an image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, an exposure device (not shown) as an exposure unit, and a developing device (for black) as a developing unit. Developing unit 45K, yellow developing unit 45Y, magenta developing unit 45M, cyan developing unit 45C), intermediate transfer member 50, cleaning device 60 having a cleaning blade as a cleaning unit, and neutralizing lamp 70 as a neutralizing unit. Have
The intermediate transfer member 50 is an endless belt, is stretched by three rollers 51 arranged on the inner side thereof, and can move in the arrow direction. A part of the three rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.
Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Further, a transfer roller 80 as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) the toner image to the recording medium 95 is disposed to face the intermediate transfer member 50.
Further, around the intermediate transfer member 50, a corona charger 52 for applying a charge to the toner image on the intermediate transfer member 50, a contact portion between the photosensitive drum 10 and the intermediate transfer member 50, and the intermediate transfer member 50 are provided. And the contact portion of the recording medium 95.
Black (K), yellow (Y), magenta (M) and cyan (C) developing devices (black developing device 45K, yellow developing device 45Y, magenta developing device 45M, cyan developing device 45C) , A developer container (42K, 42Y, 42M, 42C), a developer supply roller (43K, 43Y, 43M, 43C), and a developing roller (44K, 44Y, 44M, 44C).
In the image forming apparatus 100A, the photosensitive drum 10 is uniformly charged by the charging roller 20, and then the exposure light 30 is exposed imagewise on the photosensitive drum 10 by an exposure device (not shown) to form an electrostatic latent image. Form. Next, a developer is supplied to the electrostatic latent image formed on the photosensitive drum 10 from a developing device (black developing device 45K, yellow developing device 45Y, magenta developing device 45M, cyan developing device 45C). Then, after developing and forming a toner image, the toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the transfer bias applied from the roller 51. Further, the toner image on the intermediate transfer member 50 is given a charge by the corona charger 52 and then transferred (secondary transfer) onto the recording medium 95. The toner remaining on the photosensitive drum 10 is removed by the cleaning device 60, and the photosensitive drum 10 is once discharged by the discharging lamp 70.

FIG. 2 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100B is a tandem color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can rotate in the direction of the arrow.

  A cleaning device 17 for removing the toner remaining on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. Further, four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other on the intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 along the conveyance direction. A tandem developing device 120 is disposed. As shown in FIG. 3, the image forming means 18 for each color includes a photosensitive drum 10, a charging roller 20 that uniformly charges the photosensitive drum 10, and a black electrostatic latent image formed on the photosensitive drum 10. (K), yellow (Y), magenta (M), and cyan (C) are developed with each color developer to form a toner image, and each color toner image is transferred onto the intermediate transfer member 50. A transfer roller 62, a cleaning device 63, and a static elimination lamp 64.

An exposure device 21 is disposed in the vicinity of the tandem developing device 120. The exposure device 21 exposes the exposure light L on the photoconductor drum 10 (black photoconductor 10K, yellow photoconductor 10Y, magenta photoconductor 10M, cyan photoconductor 10C) to form an electrostatic latent image. .
Further, a secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. The secondary transfer device 22 includes a secondary transfer belt 24 that is an endless belt stretched between a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It has become.
A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26.

Further, in the vicinity of the secondary transfer device 22 and the fixing device 25, a reversing device 28 for reversing the recording paper in order to form images on both sides of the recording paper is disposed.
Next, full color image formation (color copy) in the image forming apparatus 100B will be described. First, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300. close. Next, when a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is placed on the contact glass 32. When set, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is emitted from the first traveling body 33, and reflected light from the document surface is reflected by a mirror in the second traveling body 34 and received by the reading sensor 36 through the imaging lens 35. . Thus, a color original (color image) is read, and image information of each color of black, yellow, magenta, and cyan is obtained.

  Further, after an electrostatic latent image of each color is formed on the photosensitive drum 10 based on the obtained image information of each color by the exposure device 21, the electrostatic latent image of each color is supplied from the developing device 61 of each color. The developed developer is used to form a toner image of each color. The formed toner images of the respective colors are sequentially transferred (primary transfer) on the intermediate transfer member 50 that is rotated and moved by the support rollers 14, 15, and 16, thereby forming a composite toner image on the intermediate transfer member 50. .

  In the paper feed table 200, one of the paper feed rollers 142 is selectively rotated, the recording paper is fed out from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and separated one by one by the separation roller 145. Then, the sheet is fed to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the recording paper on the manual feed tray 151 is fed out, separated one by one by the separation roller 58, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording paper.

Then, the registration roller 49 is rotated in synchronization with the composite toner image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the composite toner image is transferred onto the recording paper. Transfer to (secondary transfer).
The recording sheet on which the composite toner image has been transferred is conveyed by the secondary transfer device 22 and sent out to the fixing device 25. In the fixing device 25, the composite toner image is fixed on the recording paper by being heated and pressed by the fixing belt 26 and the pressure roller 27. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55, reversed by the reversing device 28, guided again to the transfer position, formed on the back surface, then discharged by the discharge roller 56, and stacked on the discharge tray 57.
The toner remaining on the intermediate transfer member 50 after the composite toner image is transferred is removed by the cleaning device 17.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. Further, unless otherwise specified, “part” indicates mass part, and “%” indicates mass%.

-Synthesis of unmodified polyester resin A-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 2 parts adduct of bisphenol A ethylene oxide, 3 parts adduct of bisphenol A propion oxide, 2 parts of terephthalic acid, adipic acid, trimellitic acid, and dibutyltin oxide Was allowed to react at 230 ° C. for 10 hours under normal pressure. Next, the unmodified polyester resin A was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 6 hours.
The resulting unmodified polyester resin A has a number average molecular weight (Mn) of 2,300, a mass average molecular weight (Mw) of 7,000, a glass transition temperature (Tg) of 50 ° C., an acid value of 22 mgKOH / g, a hydroxyl group The value was 40 mg KOH / g.

-Synthesis of unmodified polyester resin B-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 2 parts adduct of bisphenol A ethylene oxide, 3 parts adduct of bisphenol A propion oxide, 2 parts of terephthalic acid, adipic acid, trimellitic acid, and dibutyltin oxide Then, the mixture was reacted at 230 ° C. for 10 hours under normal pressure. Next, the unmodified polyester resin B was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 6 hours.
The obtained unmodified polyester resin B has a number average molecular weight (Mn) of 2,300, a mass average molecular weight (Mw) of 5,000, a glass transition temperature (Tg) of 54 ° C., an acid value of 22 mgKOH / g, and a hydroxyl group. The value was 40 mg KOH / g.

-Synthesis of unmodified polyester resin C-
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 2 parts of bisphenol A ethylene oxide adduct, 3 parts of bisphenol A propion oxide adduct, terephthalic acid, adipic acid, trimellitic acid, and dibutyltin oxide 2 parts The unmodified polyester resin C was synthesized by adjusting the ratio and reaction conditions.
The resulting unmodified polyester resin C has a number average molecular weight (Mn) of 2,300, a mass average molecular weight (Mw) of 7,000, a glass transition temperature (Tg) of 46 ° C., an acid value of 22 mgKOH / g, and a hydroxyl group. The value was 35 mg KOH / g.

-Synthesis of prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10 mmHg-15 mmHg for 5 hours, and the intermediate polyester resin was synthesize | combined.
The obtained intermediate polyester resin had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. .
Next, 410 parts of the intermediate polyester resin, 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. A polymer was synthesized.
The resulting prepolymer had a free isocyanate content of 1.53% by mass.

-Synthesis of ketimine compounds (active hydrogen group-containing compounds)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound.
The amine value of the obtained ketimine compound was 418 mgKOH / g.

-Preparation of master batch-
1,000 parts of water, DBP oil absorption 42 mL / 100 g, pH 9.5 carbon black Printex 35 (manufactured by Degussa) 540 parts, and 1,200 parts of the unmodified polyester resin B were added to a Henschel mixer (Mitsui Mine). Mixed). Next, the obtained mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then cooled by rolling and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

Example 1 Preparation of Toner A
-Preparation of wax dispersion-
In a reaction vessel in which a stir bar and a thermometer were set, 240 parts of the unmodified polyester resin A, 121 parts of microcrystalline wax (BSQ-180 manufactured by Toyo Adre Co., Ltd.), and 672 parts of ethyl acetate were charged and stirred at 80 ° C. The temperature was raised to 80 ° C. and maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour to obtain wax dispersion A.

-Preparation of aliphatic amide compound dispersion-
In a reaction vessel equipped with a stirrer and a thermometer, 241 parts of the unmodified polyester resin A, 121 parts of n-stearyl stearamide (Nippon Kasei) and 672 parts of ethyl acetate were charged, and the mixture was stirred up to 80 ° C. The temperature was raised and maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour to obtain an aliphatic amide compound dispersion A.

-Preparation of organic solvent phase-
Into a reaction vessel in which 517 parts of the wax dispersion liquid and 1,035 parts of the aliphatic amide compound dispersion liquid A were mixed and stirred, 250 parts of the master batch were charged and mixed for 1 hour to obtain a raw material solution A.
The obtained raw material solution A was transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). Three passes were performed under the condition of a peripheral speed of 6 m / sec to obtain a raw material dissolved or dispersed liquid A.
Next, 585 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin A is added to 1,802 parts of the raw material dissolution or dispersion A, and then a bead mill ("Ultra Visco Mill", manufactured by Imex Corporation). The dispersion A was obtained by filling 80% by volume of 0.5 mm zirconia beads, 1 pass under the conditions of a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the obtained dispersion A, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) is added as an organically modified layered inorganic mineral. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a dispersion A of toner material.
Next, 749 parts of the toner material dispersion A, 7.25 parts of the prepolymer and 2.9 parts of the ketimine compound were charged into a reaction container, and a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) was used. The mixture was mixed at 5,000 rpm for 1 minute to obtain an oil phase mixture A (dissolved or dispersed A).

-Preparation of resin fine particle dispersion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of reactive emulsifier (sodium salt of methacrylic acid ethylene oxide adduct) Eleminol RS-30 (manufactured by Sanyo Chemical Industries), styrene 83 Parts, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain an emulsion. The emulsion was heated, heated to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by mass aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to prepare a resin fine particle dispersion A.
The volume average particle size of the resin fine particles contained in the obtained resin fine particle dispersion A is measured using a particle size distribution measuring device Microtrac Ultra Fine Particle Size Distribution Meter UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method. As a result, it was 45 nm. Further, a part of the resin particle dispersion A was dried to isolate the resin, and the glass transition temperature of the resin was measured. As a result, it was 59 ° C., and the mass average molecular weight was measured. .

-Preparation of aqueous medium-
990 parts of water, 83 parts of resin fine particle dispersion A, 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate 37 parts of Eleminol MON-7 (manufactured by Sanyo Chemical Industries), 1% by weight aqueous solution of polymer dispersant sodium carboxymethylcellulose (Serogen BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.)) 135 parts and ethyl acetate 90 parts were mixed and stirred to obtain an aqueous medium A.

-Preparation of toner base particles-
To 1,200 parts of the aqueous medium, 867 parts of oil phase mixture A (dissolved or dispersed A) is added, and mixed for 20 minutes at 13,000 rpm using a TK homomixer to obtain a dispersion (emulsified slurry). Was prepared.
Next, the emulsified slurry was charged into a reaction vessel in which a stirrer and a thermometer were set, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersion slurry was measured using Multisizer III (manufactured by Beckman Coulter, Inc.). The volume average particle size was 5.1 μm, and the number average particle size was 4.9 μm.
After filtering 100 parts of the dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration. 10% by mass phosphoric acid was added to the obtained filter cake to adjust the pH to 3.7, and the mixture was mixed at 12,000 rpm for 10 minutes using a TK homomixer, followed by filtration. Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain toner base particles A.

-External additive treatment-
To 100 parts of the obtained toner base particles A, 1.5 parts of hydrophobic silica as an external additive and 0.7 parts of hydrophobic titanium oxide are added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The toner A of Example 1 was obtained.

(Example 2: Preparation of toner B)
-Preparation of wax dispersion-
A wax dispersion A was prepared in the same manner as in Example 1.

-Preparation of aliphatic amide compound dispersion-
In the same manner as in Example 1, an aliphatic amide compound dispersion A was prepared.

-Preparation of organic solvent phase-
In the raw material solution A in the preparation of the organic solvent phase of Example 1, 250 parts of the master batch were mixed in a reaction vessel in which 517 parts of the wax dispersion A and 1,035 parts of the aliphatic amide compound dispersion A were mixed and stirred. In Example, except that 517 parts of the wax dispersion A and 518 parts of the aliphatic amide compound dispersion A were stirred, 250 parts of the master batch and 200 parts of ethyl acetate were charged. In the same manner as in Example 1, a raw material solution B was obtained.
The obtained raw material solution B was transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). Three passes were performed under the condition of a peripheral speed of 6 m / sec to obtain a raw material solution or dispersion B.
Next, after adding 732 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin A to 1,485 parts of the raw material dissolution or dispersion B, a bead mill ("Ultra Visco Mill", manufactured by Imex Corporation) The dispersion B was obtained by filling 80% by volume of 0.5 mm zirconia beads, and making one pass under the conditions of a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the resulting dispersion B, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) as an organically modified layered inorganic mineral is added. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a dispersion B of toner material.
Next, 749 parts of the toner material dispersion B, 15.3 parts of the prepolymer and 2.9 parts of the ketimine compound were charged into a reaction vessel, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. The mixture was mixed at 5,000 rpm for 1 minute to obtain an oil phase mixture B (dissolved or dispersed B).

-Preparation of resin fine particle dispersion-
In the same manner as in Example 1, resin fine particle dispersion A was prepared.

-Preparation of aqueous medium-
In the same manner as in Example 1, an aqueous medium A was prepared.

-Preparation of toner base particles-
In Example 1, the oil phase mixed liquid A (dissolved or dispersed A) was replaced with the oil phase mixed liquid B (dissolved or dispersed B), and the volume average particle diameter of the dispersed slurry was 5.1 μm as in Example 1. Toner base particles B were obtained in the same manner as in Example 1 except that the emulsification conditions were adjusted so that the number average particle diameter was 4.9 μm.

-External additive treatment-
In Example 1, except that the toner base particles A were replaced with the toner base particles B, the external additive treatment was performed in the same manner as in Example 1 to obtain the toner B of Example 2.

(Example 3: Preparation of toner C)
-Preparation of wax dispersion-
A wax dispersion A was prepared in the same manner as in Example 1.

-Preparation of aliphatic amide compound dispersion-
An aliphatic amide compound dispersion C was obtained in the same manner as in Example 1 except that the unmodified polyester resin A was replaced with the unmodified polyester resin B in Example 1.

-Preparation of organic solvent phase-
In the raw material solution A in the preparation of the organic solvent phase of Example 1, 250 parts of the master batch were mixed in a reaction vessel in which 517 parts of the wax dispersion A and 1,035 parts of the aliphatic amide compound dispersion A were mixed and stirred. In the reaction vessel in which 517 parts of the wax dispersion A and 724.5 parts of the aliphatic amide compound dispersion C were stirred, 250 parts of the master batch and 135 parts of ethyl acetate were charged. In the same manner as in Example 1, a raw material solution C was obtained.
The obtained raw material solution C was transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). The raw material dissolution thru | or the dispersion liquid C were obtained by carrying out 3 passes on the conditions whose peripheral speed is 6 m / sec.
Next, after adding 703 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin B to 1,626.5 parts of the raw material dissolution or dispersion C, a bead mill (“Ultra Visco Mill”, Imex Corporation) was added. The dispersion liquid C was obtained by filling 80% by volume of 0.5 mm zirconia beads with a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the obtained dispersion C, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) as an organically modified layered inorganic mineral was added. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a toner material dispersion C.
Next, 749 parts of the toner material dispersion C, 7.25 parts of the prepolymer, and 2.9 parts of the ketimine compound were charged into a reaction container, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. The mixture was mixed at 5,000 rpm for 1 minute to obtain an oil phase mixture C (dissolved or dispersed C).

-Preparation of resin fine particle dispersion-
In the same manner as in Example 1, resin fine particle dispersion A was prepared.

-Preparation of aqueous medium-
In the same manner as in Example 1, an aqueous medium A was prepared.

-Preparation of toner base particles-
In Example 1, the oil phase mixed liquid A (dissolved or dispersed A) was replaced with the oil phase mixed liquid C (dissolved or dispersed C), and the volume average particle diameter of the dispersed slurry was 5.1 μm as in Example 1. Toner base particles C were obtained in the same manner as in Example 1 except that the emulsification conditions were adjusted so that the number average particle size was 4.9 μm.

-External additive treatment-
In Example 1, except that the toner base particles A were replaced with the toner base particles C, the external additive treatment was performed in the same manner as in Example 1 to obtain the toner C of Example 3.

(Example 4: Preparation of toner D)
-Preparation of wax dispersion-
A wax dispersion A was prepared in the same manner as in Example 1.

-Preparation of aliphatic amide compound dispersion-
In the same manner as in Example 3, an aliphatic amide compound dispersion C was obtained.

-Preparation of organic solvent phase-
In the raw material solution A in the preparation of the organic solvent phase of Example 1, 250 parts of the master batch were mixed in a reaction vessel in which 517 parts of the wax dispersion A and 1,035 parts of the aliphatic amide compound dispersion A were mixed and stirred. In the reaction vessel in which 517 parts of the wax dispersion A and 724.5 parts of the aliphatic amide compound dispersion C were stirred, 1,000 parts of the master batch and 100 parts of ethyl acetate were charged. Except for the above, a raw material solution D was obtained in the same manner as in Example 1.
The obtained raw material solution D was transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). The raw material dissolution thru | or the dispersion liquid D were obtained by carrying out 3 passes on the conditions whose peripheral speed is 6 m / sec.
Next, after adding 630 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin B to 1,591.5 parts of the raw material dissolution or dispersion D, a bead mill ("Ultra Visco Mill", Imex Corporation) was added. The dispersion liquid D was obtained by filling 80% by volume of 0.5 mm zirconia beads and making one pass under the conditions of a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the resulting dispersion D, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) as an organically modified layered inorganic mineral is added. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a dispersion D of toner material.
Next, 749 parts of the toner material dispersion D, 15.3 parts of the prepolymer, and 2.9 parts of the ketimine compound were charged into a reaction container, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. By mixing at 5,000 rpm for 1 minute, an oil phase mixture D (dissolved or dispersed D) was obtained.

-Preparation of resin fine particle dispersion-
In the same manner as in Example 1, resin fine particle dispersion A was prepared.

-Preparation of aqueous medium-
In the same manner as in Example 1, an aqueous medium A was prepared.

-Preparation of toner base particles-
In Example 1, the oil phase mixed solution A (dissolved or dispersed A) was replaced with the oil phase mixed solution D (dissolved or dispersed D), and the volume average particle size of the dispersed slurry was 5.1 μm as in Example 1. Toner base particles D were obtained in the same manner as in Example 1 except that the emulsification conditions were adjusted so that the number average particle size was 4.9 μm.

-External additive treatment-
In Example 1, except that the toner base particles A were replaced with the toner base particles D, the external additive treatment was performed in the same manner as in Example 1 to obtain the toner D of Example 4.

(Comparative Example 1: Preparation of Toner E)
-Preparation of wax dispersion-
A wax dispersion A was prepared in the same manner as in Example 1.

-Preparation of aliphatic amide compound dispersion-
In the same manner as in Example 3, an aliphatic amide compound dispersion C was obtained.

-Preparation of organic solvent phase-
In the raw material solution A in the preparation of the organic solvent phase of Example 1, 250 parts of the master batch were mixed in a reaction vessel in which 517 parts of the wax dispersion A and 1,035 parts of the aliphatic amide compound dispersion A were mixed and stirred. In Example, except that 517 parts of the wax dispersion A and 207 parts of the aliphatic amide compound dispersion C were stirred, 250 parts of the master batch and 390 parts of ethyl acetate were charged. In the same manner as in Example 1, a raw material solution E was obtained.
The obtained raw material solution E was transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). The raw material dissolution thru | or dispersion liquid E were obtained by carrying out 3 passes on the conditions whose peripheral speed is 6 m / sec.
Next, 981 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin A is added to 1,364 parts of the raw material dissolution or dispersion E, and then a bead mill ("Ultra Visco Mill", manufactured by Imex Corporation). The dispersion E was obtained by filling 80% by volume of 0.5 mm zirconia beads and performing one pass under the conditions of a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the resulting dispersion E, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) as an organically modified layered inorganic mineral is added. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a dispersion E of toner material.
Next, 749 parts of the toner material dispersion E, 7.25 parts of the prepolymer and 2.9 parts of the ketimine compound were charged into a reaction vessel, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. The mixture was mixed at 5,000 rpm for 1 minute to obtain an oil phase mixture E (dissolved or dispersed E).

-Preparation of resin fine particle dispersion-
In the same manner as in Example 1, resin fine particle dispersion A was prepared.

-Preparation of aqueous medium-
In the same manner as in Example 1, an aqueous medium A was prepared.

-Preparation of toner base particles-
In Example 1, the oil phase mixed solution A (dissolved or dispersed A) was replaced with the oil phase mixed solution E (dissolved or dispersed E), and the volume average particle size of the dispersed slurry was 5.1 μm as in Example 1. Toner base particles E were obtained in the same manner as in Example 1 except that the emulsification conditions were adjusted so that the number average particle size was 4.9 μm.

-External additive treatment-
In Example 1, except that the toner base particles A were replaced with the toner base particles E, the external additive treatment was performed in the same manner as in Example 1 to obtain the toner E of Comparative Example 1.

(Comparative Example 2: Preparation of Toner F)
-Preparation of wax dispersion-
A wax dispersion A was prepared in the same manner as in Example 1.

-Preparation of aliphatic amide compound dispersion-
An aliphatic amide compound dispersion F was obtained in the same manner as in Example 1 except that the unmodified polyester resin A was replaced with the unmodified polyester resin C in Example 1.

-Preparation of organic solvent phase-
In the raw material solution A in the preparation of the organic solvent phase of Example 1, 250 parts of the master batch were mixed in a reaction vessel in which 517 parts of the wax dispersion A and 1,035 parts of the aliphatic amide compound dispersion A were mixed and stirred. Except that 517 parts of the wax dispersion A and 724.5 parts of the aliphatic amide compound dispersion F were stirred in a reaction vessel except that 250 parts of the master batch and 100 parts of ethyl acetate were charged. In the same manner as in Example 1, a raw material solution F was obtained.
The obtained raw material solution F was transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). Three passes were performed under the condition of a peripheral speed of 6 m / sec.
Next, after adding 630 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin C to 1,591.5 parts of the raw material dissolution or dispersion F, a bead mill (“Ultra Visco Mill”, Imex Corporation) was added. The dispersion liquid F was obtained by filling 80% by volume of 0.5 mm zirconia beads and making one pass under the conditions of a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the resulting dispersion F, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) as an organically modified layered inorganic mineral is added. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a dispersion F of toner material.
Next, 749 parts of the toner material dispersion F, 15.3 parts of the prepolymer, and 2.9 parts of the ketimine compound were charged into a reaction container, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. The mixture was mixed at 5,000 rpm for 1 minute to obtain an oil phase mixed solution F (dissolved or dispersed F).

-Preparation of resin fine particle dispersion-
In the same manner as in Example 1, resin fine particle dispersion A was prepared.

-Preparation of aqueous medium-
In the same manner as in Example 1, an aqueous medium A was prepared.

-Preparation of toner base particles-
In Example 1, the oil phase mixed liquid A (dissolved or dispersed A) was replaced with the oil phase mixed liquid F (dissolved or dispersed F), and the volume average particle diameter of the dispersed slurry was 5.1 μm as in Example 1. Toner base particles F were obtained in the same manner as in Example 1 except that the emulsification conditions were adjusted so that the number average particle diameter was 4.9 μm.

-External additive treatment-
In Example 1, except that the toner base particles A were replaced with the toner base particles F, the external additive treatment was performed in the same manner as in Example 1 to obtain the toner F of Comparative Example 2.

(Comparative Example 3: Preparation of Toner G)
In Comparative Example 3, no aliphatic amide compound dispersion was prepared.
-Preparation of wax dispersion-
A wax dispersion A was obtained in the same manner as in Example 1.

-Preparation of organic solvent phase-
In the raw material solution A in the preparation of the organic solvent phase of Example 1, 250 parts of the master batch were mixed in a reaction vessel in which 517 parts of the wax dispersion A and 1,035 parts of the aliphatic amide compound dispersion A were mixed and stirred. In the same manner as in Example 1 except that 250 parts of the master batch and 455 parts of ethyl acetate were charged into a reaction vessel in which 517 parts of the wax dispersion A were stirred, the raw material solution G was prepared. Obtained.
The obtained raw material solution G was transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). The raw material dissolution thru | or the dispersion liquid G were obtained by carrying out 3 passes on the conditions whose peripheral speed is 6 m / sec.
Next, after adding 996 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin A to 1,222 parts of the raw material dissolution or dispersion G, a bead mill ("Ultra Visco Mill", manufactured by Imex Corporation) The dispersion G was obtained by filling 80% by volume of 0.5 mm zirconia beads and performing one pass under the conditions of a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the resulting dispersion G, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) as an organically modified layered inorganic mineral is added. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a dispersion G of toner material.
Next, 749 parts of the toner material dispersion G, 15.3 parts of the prepolymer, and 2.9 parts of the ketimine compound were charged into a reaction container, and a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) was used. The mixture was mixed at 5,000 rpm for 1 minute to obtain an oil phase mixture G (dissolved or dispersed G).

-Preparation of resin fine particle dispersion-
In the same manner as in Example 1, resin fine particle dispersion A was prepared.

-Preparation of aqueous medium-
In the same manner as in Example 1, an aqueous medium A was prepared.

-Preparation of toner base particles-
In Example 1, the oil phase mixed solution A (dissolved or dispersed A) was replaced with the oil phase mixed solution G (dissolved or dispersed G), and the volume average particle size of the dispersed slurry was 5.1 μm as in Example 1. Toner base particles G were obtained in the same manner as in Example 1 except that the emulsification conditions were adjusted so that the number average particle diameter was 4.9 μm.

-External additive treatment-
In Example 1, except that the toner base particles A were replaced with the toner base particles G, the external additive treatment was performed in the same manner as in Example 1 to obtain the toner G of Comparative Example 3.

(Comparative Example 4: Preparation of Toner H)
-Preparation of wax dispersion-
A wax dispersion A was prepared in the same manner as in Example 1.

-Preparation of aliphatic amide compound dispersion-
In the same manner as in Example 1, an aliphatic amide compound dispersion A was prepared.

-Preparation of organic solvent phase-
In the raw material solution A in the preparation of the organic solvent phase of Example 1, 250 parts of the master batch were mixed in a reaction vessel in which 517 parts of the wax dispersion A and 1,035 parts of the aliphatic amide compound dispersion A were mixed and stirred. Except for charging 250 parts of the master batch and 80 parts of ethyl acetate into a reaction vessel in which 517 parts of the wax dispersion A and 724.5 parts of the aliphatic amide compound dispersion A were stirred. In the same manner as in Example 1, a raw material solution H was obtained.
The obtained raw material solution H is transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.). Three passes were performed under the condition of a peripheral speed of 6 m / sec.
Next, 556 parts of a 68.3 mass% ethyl acetate solution of the unmodified polyester resin A is added to 1,571.5 parts of the raw material dissolution or dispersion H, and then a bead mill (“Ultra Visco Mill”, Imex Corporation) is added. The dispersion liquid H was obtained by filling 80% by volume of 0.5 mm zirconia beads and making one pass under the conditions of a liquid feeding speed of 1 kg / hour and a disk peripheral speed of 6 m / second.
To 200 parts of the resulting dispersion H, 1.5 parts of Clayton APA (manufactured by Southern Clay Products) as an organically modified layered inorganic mineral was added. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7,000 rpm for 60 minutes to obtain a dispersion H of toner material.
Next, 749 parts of the toner material dispersion H, 22.95 parts of the prepolymer, and 2.9 parts of the ketimine compound were charged into a reaction vessel, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used. The mixture was mixed at 5,000 rpm for 1 minute to obtain an oil phase mixed solution H (dissolved or dispersed H).

-Preparation of resin fine particle dispersion-
In the same manner as in Example 1, resin fine particle dispersion A was prepared.

-Preparation of aqueous medium-
In the same manner as in Example 1, an aqueous medium A was prepared.

-Preparation of toner base particles-
In Example 1, the oil phase mixed solution A (dissolved or dispersed A) was replaced with the oil phase mixed solution H (dissolved or dispersed H), and the volume average particle diameter of the dispersed slurry was 5.1 μm as in Example 1. Toner base particles H were obtained in the same manner as in Example 1 except that the emulsification conditions were adjusted so that the number average particle size was 4.9 μm.

-External additive treatment-
A toner H of Comparative Example 4 was obtained in the same manner as in Example 1 except that the toner base particles A were replaced with the toner base particles H in Example 1.

-Measurement of softening temperature of flow tester (Ts) and outflow start temperature (Tfb)-
The flow tester softening temperature (Ts) and outflow start temperature (Tfb) of the toners A to H obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured as follows.
The flow tester softening temperature (Ts) and the outflow start temperature (Tfb) were determined from a flow curve (see FIG. 4) measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation). Here, in FIG. 4, Ts represents the softening temperature, and Tfb represents the outflow start temperature.
The measurement conditions were a load of 10 kg / cm ² , a temperature increase rate of 3.0 ° C./min, a die diameter of 0.50 mm, and a die length of 10.0 mm.
Moreover, (DELTA) T (Tfb-Ts) was calculated | required from the measurement result. The results are shown in Table 1.

-Measurement of THF insoluble content in toner-
The amount of THF-insoluble matter in the toners A to H obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was measured as follows.
1 g of toner was weighed, 100 g of tetrahydrofuran (THF) was added thereto, and the mixture was allowed to stand at 10 ° C. for 20 to 30 hours. After 20 to 30 hours, the gel component which is insoluble in THF absorbs THF as the solvent, swells and settles, and this was separated by filter paper. The separated gel was heated at 120 ° C. for 3 hours to volatilize the absorbed THF, and then the mass was weighed to measure the amount of THF insoluble matter (gel content). The results are shown in Table 1.

-Measurement of glass transition temperature (Tg) of toner-
The glass transition temperatures (Tg) of the toners A to H obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured as follows.
The glass transition temperature was measured by the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner was put in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, and the sample was cooled to room temperature and left for 10 min. Then, the DSC curve was measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. did. The results are shown in Table 1.

The content (mass%) of the aliphatic amide compound in the toners A to H obtained in Examples 1 to 4 and Comparative Examples 1 to 4, the flow tester softening temperature (Ts), and the outflow start temperature of each toner. Table 1 shows (Tfb), ΔT, glass transition temperature (Tg), and the amount of THF-insoluble matter in the toner.

(Example 5: Production of developer A)
-Carrier manufacturing-
The raw materials shown below were dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of acrylic resin and silicon resin containing alumina particles.
A fired ferrite powder [(MgO) 1.8 (MnO) 49.5 (Fe ₂ O ₃ ) 48.0: average particle size; 50 μm] was used as the core material, and the coating film forming solution was formed on the surface of the core material. It was applied with a Spira coater (manufactured by Okada Seiko Co., Ltd.) to a thickness of 0.15 μm and dried.
The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour.
After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier.
--Raw materials--
Acrylic resin solution (solid content 50% by mass) 21.0 parts Guanamin solution (solid content 70% by mass) 6.4 parts Alumina particles [0.3 μm, specific resistance 1,014 (Ω · cm) 7.6 parts Silicone resin solution [solid content 23% by mass, (SR2410: manufactured by Toray Dow Corning Silicone)] 65.0 parts Aminosilane [solid content 100% by mass, (SH6020: Toray)・ Dow Corning Silicone Co., Ltd.]] 0.3 parts Toluene 60 parts Butyl cellosolve 60 parts

-Production of developer-
6 parts by mass of the toner A and 94 parts by mass of the carrier were stirred for 5 minutes with a tumbler mixer (Willy A. Bachofen AG Machinenfabrik T2F) to prepare Developer A.

(Example 6: Production of developer B)
A developer B was produced in the same manner as in Example 5 except that the toner A was replaced with the toner B in Example 5.

(Example 7: Production of developer C)
A developer C was produced in the same manner as in Example 5 except that the toner A was replaced with the toner C in Example 5.

(Example 8: Production of developer D)
A developer D was prepared in the same manner as in Example 5 except that the toner A was replaced with the toner D in Example 5.

(Comparative Example 5: Production of developer E)
A developer E was produced in the same manner as in Example 5 except that the toner A was replaced with the toner E in Example 5.

(Comparative Example 6: Production of developer F)
A developer F was produced in the same manner as in Example 5 except that the toner A was replaced with the toner F in Example 5.

(Comparative Example 7: Production of developer G)
A developer G was produced in the same manner as in Example 5 except that the toner A was replaced with the toner G in Example 5.

(Comparative Example 8: Production of developer H)
A developer H was produced in the same manner as in Example 5 except that the toner A was replaced with the toner H in Example 5.

<Evaluation>
The developers A to H produced in Examples 5 to 8 and Comparative Examples 5 to 8 were evaluated as follows. The results are shown in Table 2.

-Fixability (low temperature fixability, hot offset resistance)-
With respect to the fixability, a Ricoh digital color imagioNeoC285 remodeling machine was used to fix a solid image with a toner adhesion amount of 0.25 ± 0.1 mg / cm ² , and the fixability was evaluated.
-Low temperature fixability-
A copy test was performed while changing the fixing set temperature from 110 ° C. in increments of 5 ° C. The fixing temperature at which the smear ID of the fixed image was 0.4 or less was defined as the minimum fixing temperature.
--- Hot offset resistance ---
A copy test was performed while changing the fixing set temperature from 110 ° C. in increments of 5 ° C. The fixing temperature when the hot offset occurred was defined as the hot offset occurrence temperature.

-Preservability-
In the evaluation of storability, evaluation was performed using toner instead of developer.
The toner was filled in a 50 ml glass container, and the solidified state of the toner after being left in a constant temperature bath at 50 ° C. for 24 hours was observed and evaluated.

-Glossy-
As an evaluation machine, the fixing process is a belt fixing system, Ricoh's digital color imagioNeoC285 remodeling machine (hereinafter sometimes referred to as “evaluation machine A”), and imagioNeo351 remodeling machine (hereinafter referred to as “evaluation machine B”). Glossiness meter (Nippon Denshoku Industries Co., Ltd. VGS-1D) is used to fix the gloss of an image fixed at a fixing temperature of 150 ° C. and a solid image with a toner adhesion amount of 0.25 ± 0.1 mg / cm ^2. It was evaluated with.

  From the results shown in Tables 1 and 2, the toner of the above-described example, the developer using the toner, and the image forming method improve the low-temperature fixability without deteriorating the storage stability and are high even with a low adhesion amount. It has been found that a glossy image can be provided. Thus, since gloss was high, it was shown that the color reproduction range is wide (high saturation) and highly colored.

  The toner of the present invention and the developer containing the toner improve the low-temperature fixability without deteriorating the storage stability, and have a good coloring degree and color reproduction range even with a low adhesion amount. It can be widely used in printers, direct digital machines, full-color copiers using direct or indirect electrophotographic multicolor image development systems, full-color laser printers, full-color plain paper fax machines, and the like.

DESCRIPTION OF SYMBOLS 10 Photosensitive drum 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 Cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Reversing device 30 Exposure light 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 42K, 42Y, 42M, 42C Development Agent container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Developing roller 45K Black developer 45Y Yellow developer 45M Magenta developer 45C Cyan developer 49 Registration roller 5 Intermediate transfer member 51 Roller 52 Corona charger 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separation roller 60 Cleaning device 61 Developer 62 Transfer roller 63 Cleaning device 64 Static discharge lamp 70 Static discharge lamp 80 Transfer roller 90 Cleaning Device 95 Recording medium 100A, 100B Image forming device 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying apparatus main body 151 Manual tray 200 Paper feeding table 300 Scanner 400 Automatic document feeder L Exposure

Japanese Patent No. 3168351

Claims (5)

A toner comprising at least a binder resin, a colorant, a release agent, and an aliphatic amide compound, and granulated in an aqueous medium,
Modification in which the granulation in the aqueous medium includes, in an organic solvent, at least an active hydrogen group-containing compound as the binder resin, and a prepolymer having at least an isocyanate group as a site capable of reacting with the active hydrogen group-containing compound. Dissolving or dispersing a polyester resin and an unmodified polyester resin, the colorant, the release agent, and the aliphatic amide compound,
Dispersing the solution or dispersion in an aqueous medium containing resin fine particles to prepare a dispersion,
In the aqueous medium, the active hydrogen group-containing compound and the modified polyester resin are subjected to a crosslinking or extension reaction,
It is performed by removing the organic solvent from the obtained dispersion,
The difference ΔT (where ΔT represents Tfb−Ts) between the flow tester softening temperature (Ts) and the outflow start temperature (Tfb) of the toner is 40 ° C. or less,
A toner having a glass transition temperature (Tg) of 50 ° C. or higher.   The toner according to claim 1, wherein the THF insoluble content in the toner is 1% by mass to 10% by mass.   A developer comprising the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
The toner is the toner according to claim 1,
The fixing step is a fixing belt method;
Gloss of the image on the recording medium after the fixing step is, when the toner adhesion amount of ^{0.25mg / cm 2 ~0.35mg / cm 2} , an image forming method, wherein a is 15 or more. The electrostatic latent image forming step is a step of forming an electrostatic latent image on each of the plurality of electrostatic latent image carriers,
The developing step is a step of developing each electrostatic latent image using a toner of a different color for each electrostatic latent image carrier to form a visible image,
The image forming method according to claim 4, wherein the transfer step is a step of transferring the visible image to a recording medium via an intermediate transfer member.