JP4295182B2 - Color toner, color toner set, and image forming method and image forming apparatus using the same - Google Patents

Description

  The present invention relates to a color toner set suitably used for electrophotography, electrostatic recording method, electrostatic printing method, and the like, and a developer, a process cartridge, an image forming apparatus, and an image forming method using the color toner set. .

  Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image with a developer to form a visible image (toner image), The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Document 1). On the other hand, toner remaining on the photoreceptor without being transferred to the recording medium is cleaned by a cleaning member such as a blade disposed in pressure contact with the surface of the photoreceptor.

In recent years, copying machines and printers are rapidly expanding from black and white to full color, and the full color market is particularly expanding.
The color toner is a colored particle containing a colorant, a charge control agent, etc. in a binder (binder resin). As a method for producing the toner, for example, a pulverization method, an emulsion dispersion method, and the like are known. Yes.

  The pulverization method is a method for producing a toner by pulverizing and classifying a toner composition obtained by melt-mixing a colorant, a charge control agent, and the like in a binder resin and uniformly dispersing them. The pulverization method has the following problems. That is, a pulverizer or the like for pulverizing the toner composition is required, which increases costs and is not efficient. In addition, toner particles having a wide particle size distribution are easily formed during the pulverization, and in order to obtain a high resolution / high gradation image, for example, fine powder having a particle size of 5 μm or less and coarse powder having a particle size of 20 μm or more are classified. There is a problem that the yield is greatly reduced.

The emulsification dispersion method is a method for producing a toner by mixing a toner material containing a polymer and the like with an aqueous medium and emulsifying or dispersing to form oil droplets (see Patent Documents 2 to 3).
In the case of the emulsification dispersion method, various problems in the pulverization method are solved, and a spherical toner having a small particle size (hereinafter referred to as a chemical toner) can be obtained. Although the chemical toner has good fluidity even with a small particle size, it is advantageous for the design of the developing device such as the design of the hopper and the torque for rotating the developing roll. There is a problem that it is difficult to be done. That is, the surface of the photosensitive layer after the toner image has been transferred is cleaned by means such as a blade, a fur brush, or a magnetic brush, for example. Generally used extensively. In the case of this method, spherical toner rotates between the cleaning blade and the photosensitive member and enters into the gap, which causes a big problem that it is difficult to clean.

  Since the full-color image is colored by mixing two or more color toners that are superimposed, it is necessary to obtain a balanced hue. For example, each pigment in each color toner of yellow, magenta, and cyan And a color toner kit in which the content thereof is appropriately selected has been proposed (see Patent Document 4). However, when this color toner kit is used, an image having a good image quality density can be obtained, but there is a problem that the toner stacking thickness tends to increase and the toner consumption increases, and the color toner in the color toner kit is Since it is a chemical toner, there is a problem that it is inferior to the aforementioned cleaning property.

  Therefore, in order to adapt the chemical toner to the blade cleaning method, for example, there is a method of obtaining a deformed toner using a deforming agent. According to this method, a deformed toner having irregularities on the surface can be easily obtained, but there is a problem that the low-temperature fixability is inferior when the content of the deforming agent is large. In addition, since the deforming agent is present on the surface of the toner particles, when a toner image is formed using the toner, the fixed image is transferred to the conveying roller when the transfer paper is fed inside the image forming apparatus. The fixed image discharged from the image forming apparatus is rubbed with a user's clothes, etc., and the smearing property is deteriorated. is there. Among the color toners of each color, in the color toner having a large pigment content, the pigment is easily exposed on the surface of the toner particles, and together with the deforming agent, it adversely affects the toner fixing property and is particularly inferior in smearing property. There was a problem.

  Therefore, a color toner set including a deformed color toner, which has excellent cleaning properties, good low-temperature fixability, further excellent smearing properties, and can obtain high image quality with a small amount of use, and the color toner set are used. The related technology that has been provided has not yet been provided.

US Pat. No. 2,297,691 JP-A-5-66600 JP-A-8-21655 JP 2004-126248 A

  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 is a color toner set including a deformed color toner that has excellent cleaning properties, good low-temperature fixability, further excellent smearing properties, and can obtain high image quality with a small amount of use, and An object of the present invention is to provide a developer, a process cartridge, an image forming apparatus, and an image forming method capable of improving image quality using a color toner set.

As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, at least two color toners are included, and when the toner adhesion amount of each color toner is 0.4 mg / cm ² , the image density is 1.2 to 1.8. With respect to at least one color toner having a high pigment content of ˜20% by mass, by making the content of the deforming agent less than 3% by mass, the cleaning property is excellent, the low-temperature fixability is good, and the smear is further improved. It has been found that a color toner set including an irregularly shaped color toner can be obtained which is excellent in properties and can obtain high image quality with a small amount of use.
In addition, even when the content of the deforming agent is extremely small (for example, 0.01% by mass or less), a color toner set containing the deformed color toner can be obtained. The inventors have found that the smear property is particularly excellent, and have completed the present invention.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner solution in which a toner material containing an adhesive substrate, a bisacetoacetolide pigment or a quinacridone pigment, and an organosilica sol is dissolved or dispersed in an organic solvent is emulsified or dispersed in an aqueous medium, and then the organic solvent is used. A color toner obtained by removing
The image density when the toner adhesion amount is 0.4 mg / cm ² is 1.2 to 1.8,
A color toner comprising 6 to 20% by mass of the bisacetoacetalilide pigment or quinacridone pigment and less than 3% by mass of organosilica as a deforming agent .
<2> A bisacetoacetalilide pigment is C.I. I. The color toner according to <1>, which is CI Pigment Yellow 155 .
<3> The quinacridone pigment is C.I. I. The color toner according to <1>, which is CI Pigment Red 122.
<4> The color toner according to any one of <1> to <3>, wherein the organosilica is present on at least a surface of the color toner .
<5> The color toner according to any one of <1> to <4>, wherein the average circularity of the color toner is 0.900 to 0.975 .
<6> The color toner according to any one of <1> to <5>, wherein the content of the organosilica is 1% by mass or less .
<7> The color toner according to any one of <1> to <2> and <4> to <6>, wherein an average particle diameter of the bisacetoacetalilide pigment is 80 to 100 nm .
<8> A color toner comprising an organic solvent as a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a bisacetoacetalilide pigment or a quinacridone pigment, and an organosilica sol A toner solution is prepared by dissolving or dispersing in an aqueous medium, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion liquid. The color toner according to any one of <1> to <7>, which is obtained by reacting a polymer capable of reacting with the polymer to form an adhesive substrate in a particle form and removing the organic solvent .
<9> The color toner according to any one of <1> to <8>, wherein the volume average particle diameter (Dv) is 3 to 8 μm .
<10> The color toner according to any one of <1> to <9>, wherein the volume average particle diameter (Dv) / number average particle diameter (Dn) is 1.00 to 1.15 .
<11> The color toner according to any one of <1> to <10>, wherein the color toner includes a polyester resin as an adhesive substrate.
<12> The color toner according to any one of <1> to <11>, wherein the color toner includes a crystalline polyester resin.
<13> A color toner set including at least two color toners,
A color toner set comprising at least one color toner according to any one of <1> to <12> .
<14> A toner solution in which a toner material containing an adhesive substrate, a bisacetoacetolide pigment or a quinacridone pigment, and an organosilica sol is dissolved or dispersed in an organic solvent is emulsified or dispersed in an aqueous medium. A color toner set including a color toner obtained by removing
Including at least two color toners,
The image density when the toner adhesion amount of each color toner is 0.4 mg / cm 2 is 1.2 to 1.8,
Among the color toners, at least one of the pigment high-content color toners containing 6 to 20% by mass of the bisacetoacetalilide pigment or the quinacridone pigment contains less than 3% by mass of organosilica as a deforming agent. A color toner set characterized by the above .
<15> A two-component development comprising the color toner according to any one of <1> to <12> or the color toner set according to any one of <13> or <14> and a carrier. It is an agent .
<16> a step of emulsifying or dispersing a toner solution obtained by dissolving or dispersing a toner material containing an adhesive substrate, a bisacetoacetalilide pigment or a quinacridone pigment, and an organosilica sol in an organic solvent; A method of producing a color toner having at least a step of removing
The pigment and the organosilica sol are blended in such amounts that the pigment concentration in the obtained toner is 6 to 20% by mass and the organosilica concentration is less than 3% by mass.
<17> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, the color toner according to any one of <1> to <12>, <13> or <14> The color toner set according to any one of the above, or the two-component developer according to the above <15> to develop the visible image, An image forming method comprising at least a transfer step of transferring to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium.
<18> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image as defined in <1> to <12> Development is performed using the color toner according to any one of the above, the color toner set according to any one of <13> or <14>, or the two-component developer according to <15> to form a visible image. An image forming apparatus comprising at least developing means, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium.

The color toner set of the present invention includes at least two color toners, and an image density when the toner adhesion amount of each color toner is 0.4 mg / cm ² is 1.2 to 1.8. Among the toners, at least one color of the high-pigment color toner containing 6 to 20% by mass of the pigment contains less than 3% by mass of the deforming agent. The color toner set has a high image density when the toner adhesion amount of each color toner is 0.4 mg / cm ² , and the content of the deforming agent is contained in at least one color of the high pigment content color toner. Since it is deformed even if it is small, it has excellent cleaning properties, good low-temperature fixability, and excellent smearing properties, and high image quality can be obtained with a small amount of use. Further, when the color toner includes an adhesive substrate obtained by reacting a polymer capable of reacting with the active hydrogen group-containing compound to form particles, aggregation resistance, chargeability, fluidity, Excellent properties such as transferability and fixability. When an image is formed using a color toner set containing the color toner, high image quality can be obtained under low-temperature fixing conditions.
In the color toner set of the present invention, the color pigment-containing color toner includes an embodiment containing a bisacetoacetalilide pigment, and the bisacetoacetalilide pigment is C.I. I. Pigment Yellow 155, an embodiment in which the deforming agent is selected from organosilica, an embodiment in which the deforming agent is present on at least the surface of the color toner, and the content of the deforming agent is 1% by mass or less. An embodiment, an embodiment including a yellow toner, a magenta toner, a cyan toner, and a black toner are preferable.

  The developer of the present invention includes the color toner set of the present invention. For this reason, when an image is formed by electrophotography using the developer, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  The process cartridge of the present invention develops an electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier using the color toner set of the present invention to form a visible image. And at least means. The process cartridge is attachable to and detachable from the image forming apparatus, is excellent in convenience, and uses the color toner set of the present invention, so that it is excellent in smearing even under a low temperature fixing condition, and has a high image density with a small amount of use. A sharp and high quality image is formed.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. At least development means for forming a visible image by developing using a color toner set, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium . In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the color toner set of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, it is excellent in smearing even under low temperature fixing conditions, and a high quality image with high image density and high sharpness can be formed with a small amount of use.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image using the color toner set of the present invention. It includes at least a developing step for forming a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the color toner set of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, it is excellent in smearing even under low temperature fixing conditions, and a high quality image with high image density and high sharpness can be formed with a small amount of use.

  According to the present invention, various conventional problems can be solved, excellent cleaning properties, low-temperature fixability, further excellent smearing properties, high quality can be obtained with a small amount of use, and a deformed color. There can be provided a color toner set including toner, and a process cartridge, an image forming apparatus, and an image forming method capable of improving image quality using the color toner set.

(Color toner set)
The color toner set of the present invention includes at least two color toners,
The image density when the toner adhesion amount of each color toner is 0.4 mg / cm ² is 1.2 to 1.8,
Among the color toners, at least one color of the pigment high-content color toner containing 6 to 20% by mass of the pigment contains less than 3% by mass of the deforming agent.
The color toner set of the present invention needs to include at least two color toners, and preferably includes, for example, yellow toner, magenta toner, cyan toner, and black toner.

[Color toner]
As the color toner, the image density when the toner adhesion amount of the color toner of each color in the color toner set of the present invention is 0.4 mg / cm ² is, for example, a spectrometer (938 Spectroscopy, manufactured by X-Light Corporation). It is necessary to be 1.2 to 1.8 in terms of concentration measured using a tomometer), preferably 1.3 to 1.7, and more preferably 1.4 to 1.6. When the image density is less than 1.2, the image density is low and high image quality may not be obtained. When the image density exceeds 1.8, an image lacking gradation is formed in a halftone image. There is.

The image density when the toner adhesion amount of the color toner is 0.4 mg / cm ² is, for example, a copy paper (TYPE 6200; Ricoh Co., Ltd.) using a color copying machine (“Pretail 550”; manufactured by Ricoh Co., Ltd.). A solid image having a color toner adhesion amount of 0.4 ± 0.05 mg / cm ² is formed at a surface temperature of the fixing roller of 160 ± 2 ° C., and any three colors in the obtained solid image are formed. A density | concentration can be measured by measuring using a spectrometer (the X-light company make, 938 spectrodensitometer), and calculating the average value.

The pigment high-content color toner has a high content of the pigment among the color toners of at least two colors included in the color toner set of the present invention, that is, as long as the pigment contains 6 to 20% by mass. Although there is no restriction | limiting in particular about coloring, It is preferable to contain 8-18 mass% of the said pigment, and it is more preferable to contain 10-15 mass%.
When the content of the pigment is less than 6% by mass, the color toner is reduced in coloring power. When the content exceeds 20% by mass, the pigment is poorly dispersed in the color toner, and the coloring power is reduced. Deterioration, low-temperature fixability, smearability, and electrical characteristics of the color toner may be reduced.
.

The pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon black, iron black, bisacetoacetalilide pigment (CI Pigment Yellow), naphthol yellow S, and 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), benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, Parare , Phi Sae Red, Parachlor Ortho Nitroaniline Red, Resol 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 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, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Examples include lean lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable that the color toner having a high pigment content contains the bisacetoacetoarylide pigment (CI pigment yellow). When the pigment-rich color toner contains the bisacetoacetalilide pigment (CI Pigment Yellow), a modified color toner can be obtained even if the content of the deforming agent is small.

The bisacetoacetalilide pigment (CI Pigment Yellow) is a yellow pigment having a function as a colorant, and the bisacetoacetalilide pigment (CI Pigment Yellow) is particularly limited. However, it may be appropriately selected according to the purpose, may be synthesized as appropriate, or may be a commercially available product. I. Pigment Yellow (C.I.PY) 155, C.I. I. PY16, C.I. I. PY98 etc. are mentioned. Among these, C.I. I. PY155 is preferred.
The average particle diameter of the bisacetoacetalilide pigment (CI Pigment Yellow) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 80 to 100 nm, and preferably 85 to 95 nm. Is more preferable. When the average particle size is less than 80 nm, a toner having a desired particle size and particle size distribution may not be obtained. Sometimes.
In the method for producing toner to be granulated in the aqueous medium, an oil phase obtained by dissolving or dispersing a toner material in an organic solvent is emulsified or dispersed in an aqueous phase to granulate the toner. At this time, when the bisacetoacetalilide pigment (CI Pigment Yellow) is contained in the oil phase, the viscosity of the oil phase becomes high and the emulsification becomes difficult. There is a problem that it is difficult to obtain and inferior in productivity. However, the viscosity of the oil phase can be controlled by appropriately selecting the average particle size of the bisacetoacetarylide pigment (CI Pigment Yellow). In particular, the larger the average particle size, the lower the viscosity of the oil phase and the easier the emulsification.
The viscosity of the oil phase is, for example, preferably 500 to 2,000 Pa, more preferably 500 to 1,500 Pa in an oil phase having a solid content concentration of 50 mass% and containing 5 mass% of wax.

  The content of the deforming agent in the color toner having a high pigment content is preferably as small as possible. When there are a plurality of color toners having a high pigment content, the content of the deforming agent in at least one color thereof. However, it is necessary to be less than 3% by mass, for example, preferably 1% by mass or less, and more preferably 0.01% by mass or less. In the color toner having a high pigment content, a deformed color toner can be obtained even if the content of the deforming agent is small. When the content is 3% by mass or more, the smear property is inferior, and when an image is formed using the obtained color toner, the paper on which the image is formed is fed in the image forming apparatus. In addition, the image may be rubbed with a conveyance roller or a paper feed roller to cause deterioration of image quality such as dirt, and low-temperature fixability may be deteriorated. The clothes may be soiled by rubbing with other clothes.

-Profiler-
The deforming agent is not particularly limited as long as it can change the shape of the color toner, and can be appropriately selected according to the purpose. For example, it is selected from organosilica Is preferred.
The shape of the deformed color toner is not particularly limited as long as it is not a true sphere, and can be appropriately selected depending on the purpose. It is preferable to satisfy the average circularity shown in FIG.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the color toner by the circumference of the actual particles. For example, 0.900 to 0.975 is preferable, and 0.950 to 0.975 is more preferable. The particles having an average circularity of less than 0.940 are preferably 15% or less.
If the average circularity is less than 0.900, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.975, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and transfer belt, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. As a result, the accumulated toner may become a transfer residual toner on the photoconductor, which may cause background smearing of the image, or may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is determined by, for example, an optical detection band method in which a suspension containing the color toner is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

The deforming agent is preferably present on at least the surface of the color toner.
By removing the organic solvent from an oil droplet obtained by emulsifying or dispersing an oil phase in which a toner material is dissolved or dispersed in an organic solvent, toner particles can be formed. Removal of the organic solvent causes the toner particle volume to shrink. When the deforming agent is present on the surface or inside of the toner particles, the surface area of the particles does not change, so that the contraction cannot be followed, and deformed toner particles having irregularities on the surface can be obtained.

The color toner is not particularly limited, and may be appropriately selected from, for example, toners that contain at least a binder resin and are produced by a granulation method in an aqueous medium such as a known emulsion dispersion method. However, after preparing a toner solution by dissolving or dispersing a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an organic solvent, the toner solution is dispersed in an aqueous medium. A dispersion liquid is prepared by dispersing in an aqueous medium, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form an adhesive substrate in the form of particles. And a color toner obtained by removing the organic solvent.
The color toner may contain a crystalline polyester resin and, if necessary, further contain other components such as a release agent and a charge control agent.

-Adhesive substrate-
The adhesive base material is adhesive to a recording medium such as paper, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form particles. It contains at least an adhesive polymer obtained by the formation, and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 are particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner of the present invention, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature can be measured by, for example, 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.

The storage elastic modulus of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² , Usually, it is 100 ° C. or higher, and preferably 110 to 200 ° C. When the (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.
The viscosity of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (Tη) at which a measurement frequency of 20 Hz is 1,000 poise is usually 180 ° C. or lower. Yes, 90-160 degreeC is preferable. When the (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated.
Therefore, from the viewpoint of achieving both hot offset resistance and low-temperature fixability, the (TG ′) is preferably higher than the (Tη). That is, the difference (TG′−Tη) between (TG ′) and (Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. The larger the difference, the better.
Further, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, the (TG′−Tη) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 20 to 80 ° C.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred are polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophoronediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol Polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene Mixture of oxide 2 mol adduct and terephthalic acid polycondensate, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A Polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and ureaated with hexamethylenediamine, a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate with urea and hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (9) bisphenol A ethylene Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer urea-modified with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and isophthalic acid with toluene diisocyanate with urea methylenediamine, a 2-mole adduct of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (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 block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a heating medium for fixing. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and the like are preferable. Mixtures are particularly preferred.

As the trivalent or higher polyol (TO), those having 3 to 8 or higher valences are preferable. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, sebacic acid, and the like. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
As said aromatic polycarboxylic acid, a C9-C20 thing is preferable, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

The polyisocyanate (PIC) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, and isocyanurates. And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing group are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 1,000 to 30,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 1,500-15,000 are more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or Toyo Soda Kogyo Co., Ltd. having a molecular weight of ^{6 × 10 2, 2.1 × 10} 2, 4 × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

--- Aqueous medium--
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with this water, a mixture thereof, etc. are mentioned.
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 cell solves include methyl cell solve. 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.

--Binder resin--
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Undenatured polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
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 weight average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferred. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, as described above, the content of the component having the weight average molecular weight (Mw) of less than 1,000. Is required to be 8 to 28% by mass. On the other hand, when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 35 to 70 ° C, still more preferably 35 to 50 ° C, and particularly preferably 35 to 45 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, more preferably 1.0 to 30.0, and still more preferably 5.0 to 20.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Glossiness may deteriorate.
As content of the said non-modified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, 70-95 mass% is more preferable, 80-90 mass% is still more preferable. When the content is less than 50% by mass, the low-temperature fixability and the glossiness of the image may be deteriorated.

-Crystalline polyester resin-
The crystalline polyester resin has crystallinity and exhibits a heat-melting characteristic that causes a sudden decrease in viscosity near the fixing start temperature. In other words, until the melting start temperature, the heat resistant storage stability is good due to crystallinity, and at the melting starting temperature, a sharp viscosity drop (sharp melt property) occurs and fixing is performed. A compatible toner can be produced. In addition, the mold release width (the difference between the low temperature fixing lower limit temperature and the hot offset occurrence temperature) is also excellent.

  The crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diol compounds having 2 to 6 carbon atoms as alcohol components, particularly 1,4-butanediol, 1, Using 6-hexanediol and those derivatives containing 80 mol% or more, preferably 85 to 100 mol%, and at least maleic acid, fumaric acid, succinic acid, and derivatives thereof as acidic components A crystalline polyester resin represented by the following general formula (1) is preferably exemplified.

In the general formula (1), n and m represent the number of repeating units, L represents an integer of 1 to 3, and R ¹ and R ² may be the same as or different from each other. Often represents a hydrogen atom or a hydrocarbon group.

In order to control the crystallinity and softening point of the crystalline polyester resin, when synthesizing the crystalline polyester, a trihydric or higher polyhydric alcohol such as glycerin as an alcohol component, trimellitic anhydride as an acid component, etc. A non-linear polyester obtained by condensation polymerization by adding a trivalent or higher polyvalent carboxylic acid may be used. The molecular structure of the crystalline polyester can be confirmed by solid NMR.
The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 1,000 to 30,000, more preferably 1,000 to 6,500 in terms of molecular weight distribution by GPC of the soluble portion of orthodichlorobenzene. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
The number average molecular weight (Mn) of the crystalline polyester resin is preferably 500 to 6,000, more preferably 500 to 2,000 in terms of molecular weight distribution by GPC of the soluble part of orthodichlorobenzene. Moreover, as (Mw / Mn), 2-8 are preferable and 2-5 are more preferable.
In the molecular weight distribution by GPC, the peak position of the molecular weight distribution diagram in which the horizontal axis represents log (M) and the vertical axis represents mass% is in the range of 3.5 to 4.0, and the peak half width is 1. .5 or less is preferable.

The melting temperature and F1 _{/ 2} temperature of the crystalline polyester resin are preferably low as long as the heat resistant storage stability is not deteriorated. For example, the DSC endothermic peak temperature is preferably 50 to 150 ° C. When the melting temperature and the F _1/2 temperature are less than 50 ° C., the heat-resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device. Therefore, the low temperature fixability may be deteriorated.

The crystalline polyester resin preferably has an absorption based on at least the olefin to any of the infrared absorption spectrum at 965 ± 10 cm ^-1 and 990 ± 10cm ^-1 δCH (out-of-plane bending vibration). When absorption based on δCH of the olefin is present at the position, the low-temperature fixability is improved.

The acid value of the crystalline polyester resin is preferably 8 mgKOH / g or more and more preferably 20 mgKOH / g or more in order to achieve low-temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, in order to improve hot offset property, 45 mgKOH / g or less is preferable.
The hydroxyl value of the crystalline polyester resin is preferably from 0 to 50 mgKOH / g, more preferably from 5 to 50 mgKOH / g, from the viewpoint of improving low-temperature fixability and charging characteristics.

  When the non-modified polyester resin (b) and the crystalline polyester resin (c) are contained in the toner, the urea bond-forming group-containing polyester resin (a), the unmodified polyester resin (b), and the crystalline The mixing mass ratio with the polyester resin (c) is usually (a) / (b) + (c) of 5/95 to 25/75, preferably 10/90 to 25/75, and 12/88 to 25/75 is more preferable, 12/88 to 22/78 is still more preferable, and the mass ratio of (b) to (c) is 99/1 to 50/50, and 95/5 to 60/40. Is preferable, and 90/10 to 65/35 is more preferable. When the mass ratio is out of the numerical range, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat resistant storage stability and low temperature fixability.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a release agent, a charge control agent, resin fine particles, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic property Examples include materials, metal soaps, and the like.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, long chain hydrocarbons, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Among these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferable.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1,000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known materials according to the purpose. However, since a color tone may change when a colored material is used, a material that is colorless to nearly white is used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigments, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded together with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts 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 attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

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 resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin 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 acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, 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”). "; Manufactured by 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.

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

As an example of the method for producing the toner of the present invention, a method for granulating the toner by producing the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive base material in the form of particles, for example, preparation of an aqueous medium phase, preparation of a toner solution, preparation of a dispersion, formation of the adhesive base material, formation of an organic solvent Removal and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.) are performed.

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin microparticles | fine-particles, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by mixing the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the pigment, the deforming agent, the release agent, and the charge control agent in the organic solvent. The toner material such as the unmodified polyester resin can be dissolved or dispersed.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. It may be added and mixed in the aqueous medium, or when the toner solution is added to the aqueous medium phase, it may be added to the aqueous medium phase together with the toner solution.

  Here, the pigment may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the pigment with high shearing force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the pigment and the resin. Also, the so-called flushing method is preferable in that the wet cake of pigment can be used as it is, and there is no need to dry it. This flushing method is a method in which an aqueous paste containing pigment water is mixed or kneaded together with a resin and an organic solvent, and the pigment is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are 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, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

The dispersion liquid can be prepared by emulsifying or dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. When the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an elongation reaction or a crosslinking reaction during the emulsification or dispersion, the adhesive base material is generated.
At this time, it is preferable that the deforming agent is present on at least the surface of the dispersed toner solution. When the toner solution is dispersed in the aqueous medium, oil droplets composed of the toner solution are formed. When the deforming agent is present on at least the surface of the oil droplet, the toner particles can be deformed in the removal of the organic solvent described later.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). A toner solution is emulsified or dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are subjected to an extension reaction or the like in the aqueous medium phase. (2) The toner solution is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and in the aqueous medium phase Or (3) the active hydrogen group after the toner solution is added and mixed in the aqueous medium. The organic compound is added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the pigment, the deforming agent, the release agent, and the charge control agent And a method in which the toner solution prepared by dissolving or dispersing the toner material such as the unmodified polyester resin in the organic solvent is added and dispersed by shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch system, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

In the preparation of the dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material.
If the amount used is less than 50 parts by mass, the toner material may be poorly dispersed and toner particles having a predetermined particle size may not be obtained. If the amount used exceeds 2,000 parts by mass, the production cost will be high. May be.

In the preparation of the dispersion, it is preferable to use a dispersant from the viewpoint of sharpening the particle size distribution and performing stable dispersion as necessary.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In preparing the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

When the organic solvent is removed, toner particles are formed. At this time, the removal of the organic solvent causes the volume of the toner particles to shrink, while the deforming agent is present on the surface of the toner particles and cannot follow the shrinkage. Toner particles are obtained.
The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the pigment, the release agent, the charge control agent, and the like, or further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented 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 for 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, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  The color toner in the color toner set of the present invention has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), penetration, smear, and low temperature fixability. It preferably has an offset non-occurrence temperature, thermal characteristics, glass transition temperature, BET specific surface area, and the like.

The volume average particle diameter (Dv) of the color toner is, for example, preferably 3 to 8 μm, more preferably 4 to 7, and still more preferably 5 to 6.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, filming of color toner on the developing roller and thinning of the color toner are likely to cause color toner fusion to a member such as a blade. It becomes difficult to obtain a high-quality image as an image, and when the balance of the color toner in the developer is performed, the variation in the particle diameter of the color toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the color toner is preferably 1.15 or less, more preferably 1.00 to 1.15, More preferred is 1.10 to 1.15.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.00, with a two-component developer, the color toner is fused to the surface of the carrier during long-term stirring in the developing device. The chargeability of the carrier may be deteriorated or the cleaning property may be deteriorated. In the case of a one-component developer, the color toner is filmed on the developing roller or the color toner is thinned. Color toner fusion to the member is likely to occur, and if it exceeds 1.15, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the color toner in the developer was performed. In some cases, the variation in the particle size of the color toner may become large.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

As said penetration, the penetration measured by the penetration test (JIS K2235-1991) needs to be 15 mm or more, for example, and 20-30 mm is more preferable.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with color toner and left in a constant temperature bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the color toner to room temperature and performing a penetration test. In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.

As the smearing property, for example, a spectrometer (X-Light, 938 Spectrodensitometer) of an image attached after rubbing using a smear tester (friction tester type I, JIS L0823) is used. For example, the measured density value (smear ID) is evaluated based on the fixing temperature when it is 0.4 or less, and the lower the fixing temperature, the better.
The smear ID is such that, for example, a color copying machine ("Pretail 550"; manufactured by Ricoh Co., Ltd.) is used, and the amount of developer adhered to the copy paper (TYPE 6200; manufactured by Ricoh Co., Ltd.) is 0.75 ± 0.1 mg. A halftone image is formed so as to be / cm ^2, and a white cotton cloth (JIS L0803 cotton 3) of about 25 × 25 mm is applied to a friction element of a smear tester (friction tester type I, JIS L0823, friction element diameter: φ15). No.) is attached with double-sided tape so that the fiber direction is parallel to the moving direction of the friction element, and the halftone image is rubbed in 5 reciprocations and continuously, then the white cotton cloth is peeled off and the image is adhered. The smear ID is measured by measuring the image density at any three positions on the friction trace using a spectrometer (938 Spectrodensimeter, manufactured by X-Light Corporation) and calculating the average value. Door can be.

As the low-temperature fixability, from the viewpoint of achieving both a reduction in fixing temperature and no occurrence of offset, the lower fixing minimum temperature is preferably lower, and the higher the offset non-reaction temperature is, the lower the fixing temperature and no occurrence of offset. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the non-offset temperature is 200 ° C. or more.
The fixing minimum temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The fixing roll temperature is the lower limit fixing temperature.
The offset non-occurrence temperature is set, for example, by using an image forming apparatus and setting a transfer sheet, and developing single colors of yellow, magenta, cyan, and black, and solid images of red, blue, and green as intermediate colors in a single color. The temperature of the fixing belt can be adjusted to be variable, and the temperature at which no offset occurs can be determined.

The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 30 degreeC or more is preferable and 50-120 degreeC is more preferable. When the softening temperature (Ts) is less than 30 ° C., at least one of heat resistant storage stability and low temperature storage stability may be deteriorated.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 60-150 degreeC is more preferable. When the outflow start temperature (Tfb) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 ° C. or higher is preferable, and 80 to 170 ° C. is more preferable. If the 1/2 method softening point (T1 / 2) is less than 60 ° C., at least one of heat-resistant storage stability and low-temperature storage stability may deteriorate.

There is no restriction | limiting in particular as said glass transition temperature, Although it can select suitably according to the objective, For example, 40-70 degreeC is preferable and 45-65 degreeC is more preferable. When the glass transition temperature (Tg) is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.
The glass transition temperature can be measured using, for example, a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation).

The BET specific surface area in the color toner, for example, preferably ^{0.5~8.0m 2 / g, 0.5~7.5m 2 /} g is more preferable.
When the BET specific surface area is less than 0.5 m ² / g, the resin fine particles remaining on the color toner surface become a film or cover the entire toner surface, and the resin fine particles are in a binder resin inside the color toner. In some cases, the adhesiveness between the components and the fixing paper is inhibited, and the minimum fixing temperature may be increased. On the other hand, if it exceeds 8.0 m ² / g, the resin fine particles inhibit the exudation of the wax, and the release of the wax. In some cases, the sexual effect cannot be obtained and the occurrence of an offset is observed.
The specific surface area of the color toner can be measured according to the BET method. For example, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device Tristar 3000 (manufactured by Shimadzu Corporation), and the BET multipoint method is used. Can be measured.

  The acid value of the color toner is preferably, for example, 0.5 to 40.0 (KOH mg / g), more preferably 1.0 to 30.0, and still more preferably 5.0 to 20.0. By giving the toner an acid value, it becomes easy to be negatively charged.

  The color toner set of the present invention has an image density of 1.2 to 1.8 per color toner adhesion amount of each color toner, and a high pigment content color containing 6 to 20% by mass of pigment among the color toners. Since at least one color of the toner contains at least two color-modifying agent-containing color toners containing less than 3% by weight of the deforming agent, the toner has excellent cleaning properties, good low-temperature fixability, and smear. High quality and high quality images can be formed with a small amount of use. Further, the color toner of the present invention comprises the adhesive base obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium to form particles. When it is included, it is excellent in various properties such as aggregation resistance, chargeability, fluidity, transferability, and fixability. For this reason, the color toner set of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following developer, process cartridge, It can be particularly suitably used for an image forming apparatus and an image forming method.

(Developer)
The developer of the present invention contains at least the color toner set of the present invention, and can be suitably used as a developer containing other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the color toner set of the present invention, even if the balance of the color toner is performed, the variation in the particle diameter of the color toner is small, and the color toner filming on the developing roller, The color toner is not fused to a member such as a blade for thinning the toner, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the color toner of the present invention, even if the balance of the color toner for a long time is performed, the variation in the particle diameter of the color toner in the developer is small, and the long-term in the developing device. Even with stirring, good and stable developability can be obtained.

  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 this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, weak magnetization such as copper-zinc (Cu-Zn) (30 to 80 emu / g) is advantageous in that the color toner can weaken the contact with the photoconductor which is in a flashing state and is advantageous in improving the image quality. Material is preferred. These may be used alone or in combination of two or more.

The core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and the color toner may scatter, and in the case of full color having a large solid portion, the reproduction of the solid portion may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like, if necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the color toner set of the present invention, it is excellent in cleaning properties, low-temperature fixability, smear properties, etc., and can stably form high-quality images.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. The image forming apparatus and the image forming method can be particularly preferably used.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. At least a developing means for forming the film, and other means appropriately selected as necessary.
As the developing means, the color toner set of the present invention or a developer container that accommodates the developer, and the developer that carries and conveys the color toner set or developer accommodated in the developer container. It may have at least a carrier, and may further include a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably detachably provided in the electrophotographic apparatus of the present invention described later.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
The image forming apparatus of 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 appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon and the like are preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back surface side of the electrostatic latent image carrier may be adopted.

-Development process and development means-
The development step is a step of developing the electrostatic latent image using the color toner set or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the color toner set or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the color toner set or the developer of the present invention, and can be appropriately selected from known ones. Preferred examples include at least a developing unit that accommodates the color toner set or developer and can apply the color toner set or developer to the electrostatic latent image in a contact or non-contact manner.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multicolor developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing unit, for example, the color toner and the carrier are mixed and stirred, and the color 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. Is done. Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the color toner constituting the magnetic brush formed on the surface of the magnet roller is electrically It moves to the surface of the electrostatic latent image bearing member (photosensitive member) by an attractive force. As a result, the electrostatic latent image is developed with the color toner, and a visible image is formed with the color toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer including the color toner set of the present invention, and the developer may be a one-component developer or a two-component developer. . The color toner contained in the developer is the color toner in the color toner set of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably a full color toner, as the color toner, A mode including a secondary transfer step of transferring the composite transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means, the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
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 and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be performed each time the color toner of each color is transferred to the recording medium, or the color toner of each color. On the other hand, it may be carried out at the same time in a state of being laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the color toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited and may be selected from known cleaners as long as it can remove the color toner remaining on the electrostatic latent image carrier. For example, a magnetic brush Suitable examples include cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying color toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 1, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 3 is a tandem color image forming apparatus. The tandem image forming apparatus 100 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 be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. 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. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. 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 pressed against the fixing belt 26.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, 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 the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  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 set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 4), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image of each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the surface, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta image) based on image information of each color. And cyan images) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, 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 sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, the color toner set of the present invention including the color toner that is excellent in cleaning property, low-temperature fixing property, smear property and the like is used. Obtained efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
A color toner set composed of yellow toner, magenta toner, cyan toner, and black toner was manufactured as follows.

[Manufacture of yellow toner]
<Adhesive substrate production process>
First, a yellow toner was manufactured as follows.

-Preparation of toner solution-
--- Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 220 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 561 parts by mass of bisphenol A propion oxide 3 mol adduct, 218 parts by mass of terephthalic acid, 48 masses of adipic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 45 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. A modified polyester was synthesized.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

-Preparation of master batch (MB)-
Bisacetoacetarylide pigment (CI Pigment Yellow) (“Novoperm Yellow 4G”; manufactured by Clariant, average particle size = 90 nm) as a pigment, 50 parts by mass, polyester resin (“RS801”; manufactured by Sanyo Chemical Industries, Ltd.) 50 parts by mass of acid value = 10, weight average molecular weight (Mw) = 20,000, glass transition temperature (Tg) = 64 ° C.) and 30 parts by mass of water were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded for 45 minutes at 130 ° C. with two rolls, rolled and cooled, and pulverized to a size of 1 mm in diameter with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

-Preparation of organic solvent phase-
In a reaction vessel in which a stir bar and a thermometer were set, 378 parts by mass of the unmodified polyester, 110 parts by mass of carnauba wax, 22 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and ethyl acetate 947 parts by mass were charged, and the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of the master batch (the content of the bisacetoacetalilide pigment in the toner of 11% by mass) and 500 parts by mass of ethyl acetate are charged in a reaction vessel and mixed for 1 hour to obtain a raw material solution. It was.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. The bisacetoacetalilide pigment and carnauba wax were dispersed in 3 passes under the condition of 80% by volume of beads. Next, 630 parts by mass of a 65% by mass ethyl acetate solution of the unmodified polyester was added to the wax dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an organic solvent phase.
The solid content concentration (130 ° C., 30 minutes) of the obtained organic solvent phase was 50% by mass.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass 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. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.53% by mass.

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

  In a reaction vessel, 648 parts by mass of the organic solvent phase, 44 parts by mass of the prepolymer, 0.05 part by mass (0.01% by mass) of organosilica as the deforming agent, and 6.6 parts by mass of the ketimine compound. The toner solution was prepared by mixing and mixing at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika).

-Preparation of dispersion-
--Preparation of fine particle dispersion--
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts by weight of water, 11 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries), 83 parts by weight of styrene , 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, so that vinyl resin particles (copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion of polymer) (fine particle dispersion) was prepared.
The volume average particle size of the fine particles contained in the obtained fine particle dispersion was measured with a particle size distribution measuring apparatus (“LA-920”; manufactured by Horiba, Ltd.) using a laser light scattering method, and found to be 105 nm. . Further, a part of the fine particle dispersion was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured. As a result, it was 59 ° C. and the weight average molecular weight (Mw) was measured. 000.

-Preparation of aqueous medium-
990 parts by weight of water, 83 parts by weight of the fine particle dispersion, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and 90 parts by weight of ethyl acetate, Mixing and stirring were performed to obtain a milky white liquid (aqueous medium).

--Emulsification / Dispersion--
809 parts by mass of the toner solution was added to 1200 parts by mass of the aqueous medium, and the mixture was mixed with the TK homomixer at a rotation speed of 13,000 rpm for 20 minutes to prepare a dispersion (emulsion slurry).

Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersion slurry had a volume average particle size of 5.7 μm and a number average particle size of 5.0 μm as measured by Multisizer II (manufactured by Beckman Coulter, Inc.).

--- Washing and drying--
After filtering 100 parts by mass of the dispersion slurry under reduced pressure, adding 300 parts by mass of ion-exchanged water to the filter cake, mixing with a TK homomixer (rotating at 12,000 rpm for 10 minutes), and then filtering three times. And a final filter cake was obtained.
Here, the obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to obtain yellow toner base particles.

[Manufacture of magenta toner]
-Preparation of toner base particles-
In the production of the yellow toner, a bisacetoacetalilide pigment as the pigment is replaced with a naphthol pigment C.I. I. Pigment Red 269 (“Toshiki Red 1022”; manufactured by Dainippon Ink) was added so that the content in the toner was 6.5% by mass, and the content of organosilica as the deforming agent was 3. Magenta toner base particles were prepared in the same manner as in the production of the yellow toner except that the amount was changed to 5% by mass.

[Manufacture of cyan toner]
-Preparation of toner base particles-
In the production of the yellow toner, the bisacetoacetalilide pigment as the pigment was changed to copper phthalocyanine C.I. I. Pigment Blue 15: 3 (“ECB-301”; manufactured by Dainichi Seika) was added so that the content in the toner was 5.5% by mass, Cyan toner base particles were prepared in the same manner as in the production of the yellow toner except that the amount was changed to 3.5% by mass.

[Manufacture of black toner]
-Preparation of toner base particles-
In the production of the yellow toner, a bisacetoacetolide pigment as the pigment is added so that the content in the toner is 5.9% by mass instead of carbon black (“NIPEX 60”; manufactured by Degussa). Black toner base particles were prepared in the same manner as in the production of the yellow toner except that the content of organosilica as the deforming agent was changed to 3.5% by mass.

--External additive treatment--
The obtained yellow toner base particles, magenta toner base particles, cyan toner base particles, and black toner base particles are each 100 parts by mass with respect to 0.7 parts by mass of hydrophobic silica as an external additive and hydrophobized titanium oxide. 0.3 part by mass was mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to produce a yellow toner, a magenta toner, a cyan toner, and a black toner (a color toner set consisting of the toner).

Table 1 shows the image density, the pigment content, and the deforming agent content when the toner adhesion amount is 0.4 mg / cm ² for each color toner of the obtained color toner set. In addition, the average circularity, volume average particle diameter (Dv), number average particle diameter (Dn), and particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)) were measured by the following methods. Table 1 shows.

<Image density>
Using the image forming apparatus provided with the belt fixing device shown in FIG. 6, the image is transferred to a transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a color copying machine (“Pretail 550” manufactured by Ricoh Co., Ltd.). ), A solid image having a color toner adhesion amount of 0.4 ± 0.05 mg / cm ² was formed at a fixing roller surface temperature of 160 ± 2 ° C. The image density of arbitrary three places in the obtained solid image was measured using a spectrometer (“938 Spectrodensitometer”, manufactured by X-Rite). The image density value is shown as an average value of image densities at three locations. Note that the higher the obtained image density value, the higher the image density and the higher the density image can be formed.

<Average circularity>
The average circularity of the toner was measured using a flow particle image analyzer (“FPIA-1000”; manufactured by Toa Medical Electronics Co., Ltd.). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of water from which impure solids have been removed in advance, and each toner is further added. 0.1 to 0.5 g was added and dispersed. The obtained dispersion is dispersed for about 1 to 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), so that the concentration and the distribution of the toner are 3,000 to 10,000 / μl. It was measured. The average circularity was calculated from these measurement results.

<Toner particle size>
The volume average particle diameter (Dv) and number average particle diameter (Dn) of the toner were measured using a particle size measuring device (“Multisizer II”; manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm. From these results, the particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)) was calculated.

  The yellow toner corresponding to the pigment-rich color toner was observed with a scanning electron microscope (SEM) FE-SEM (“S-4200”; manufactured by Hitachi, Ltd.). The SEM photograph at this time is shown in FIG. 5a. From the SEM photograph, it was confirmed that the yellow toner having a high pigment content was deformed even if the content of the deforming agent was small.

(Example 2)
In Example 1, the naphthol pigment C.I. I. Pigment Red 269 (“Toshiki Red 1022”; manufactured by Dainippon Ink) was added to quinacridone pigment C.I. I. Pigment Red 122 (“Hostaperm pin-E02”; manufactured by Clariant) was added so that the content in the toner was 11% by mass, and the content of organosilica as the deforming agent was 0.01% by mass A color toner set of Example 2 was produced in the same manner as in Example 1 except that the color toner set was changed.
Table 2 shows the image density, the pigment content, and the deforming agent content when the toner adhesion amount is 0.4 mg / cm ² for each color toner of the obtained color toner set. In addition, the average circularity, volume average particle size (Dv), number average particle size (Dn), and particle size distribution (volume average particle size (Dv) / number average particle size (Dn)) were measured by the following methods. Table 2 shows.

  A magenta toner corresponding to the color toner having a high pigment content was observed with a scanning electron microscope (SEM). The SEM photograph at this time is shown in FIG. From these SEM photographs, it was recognized that the magenta toner having a high pigment content was deformed even if the content of the deforming agent was small.

(Comparative Examples 1-2)
In Example 1, the colors of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the pigment content and the deforming agent content of each color toner were changed as shown in Table 3. A toner set was manufactured.
Table 3 shows the image density, the pigment content, and the deforming agent content when the toner adhesion amount is 0.4 mg / cm ² for each color toner of the obtained color toner set. In addition, the average circularity, volume average particle size (Dv), number average particle size (Dn), and particle size distribution (volume average particle size (Dv) / number average particle size (Dn)) were measured by the following methods. Table 3 shows.

  Next, in each of the color toner sets of Examples 1 to 2 and Comparative Examples 1 and 2 that have been subjected to the external additive treatment, 5% by mass of each color yellow toner, magenta toner, and cyan toner, and an average particle diameter coated with a silicone resin Developers of Examples 1 to 4 and Comparative Examples 1 to 2 were produced from 95% by mass of 40 μm copper-zinc ferrite carrier by a conventional method.

  Using each developer thus obtained, (a) fixability (smearing property and minimum fixing temperature), (b) cleaning property, (c) toner consumption, and (d) saturation are as follows. evaluated. The results are shown in Table 4.

(A) Fixability (smear property and fixing lower limit temperature)
Using an image forming apparatus provided with the belt fixing device 110 shown in FIG.
The belt-type fixing device 110 includes a heating roller 121, a fixing roller 122, a pressure roller 124, and a fixing belt 123.
The fixing belt 123 is stretched by a heating roller 121 and a fixing roller 122 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 121. The heating roller 121 has a built-in heating source 125 and is designed such that the temperature can be adjusted by a temperature sensor 127 attached in the vicinity of the heating roller 121. The fixing roller 122 is rotatably disposed inside the fixing belt 123 and in contact with the inner surface of the fixing belt 123. The pressure roller 124 is in contact with the outer side of the fixing belt 123 and the outer surface of the fixing belt 123 so as to press the fixing roller 122 so as to be rotatable.
In fixing belt device 110, first, recording medium (sheet) P on which a toner image to be fixed is formed is conveyed to heating roller 121. Then, the toner T on the sheet P is heated and melted by the heating roller 121 and the fixing belt 123 heated to a predetermined temperature by the action of the built-in heating source 125. In this state, the sheet P is inserted into a nip portion formed between the fixing roller 122 and the pressure roller 124. The sheet P inserted into the nip is brought into contact with the surface of the fixing belt 123 that rotates in conjunction with the rotation of the fixing roller 122 and the pressure roller 124, and passes through the nip by the pressing force of the pressure roller 124. When pressed, the toner T is fixed on the sheet P. Next, the sheet P on which the toner T is fixed passes between the fixing roller 122 and the pressure roller 124, is peeled off from the fixing belt 123, and is conveyed to a tray (not shown) through a guide G. The fixing belt 123 is cleaned by the cleaning roller 126.

In the belt-type fixing device shown in FIG. 6, fixing conditions of a belt tension of 1.5 kg / piece, a belt speed of 170 mm / sec, and a nip width of 10 mm are obtained by the fixing roller 122, the pressure roller 124, the heating roller 121, and the fixing belt 123. Fixing was done at
The fixing roller 122 is a roller made of silicone foam having a diameter of 38 mm and an Asker C hardness of about 30 degrees. The pressure roller 124 has a diameter of 50 mm and a Asker C hardness of about 48 mm in diameter. It is a 75 degree roller. The heating roller 121 is an aluminum roller having a diameter of 30 mm and a wall thickness of 2 mm. The fixing belt 123 has a belt diameter of 60 mm and a belt width of 310 mm, and has a release layer made of silicone rubber having a thickness of about 150 μm on the surface of a nickel belt base having a thickness of about 40 μm. It is built.

<Smear properties>
A toner image was formed and fixed on a recording medium using an image forming apparatus including the belt-type image fixing device 110 shown in FIG. That is, for image formation, a color copier (“Pretail 550”; manufactured by Ricoh Co., Ltd.) is used to transfer yellow toner, magenta toner, and cyan toner onto transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.). The mixed color halftone image was adjusted so that 0.75 ± 0.1 mg / cm ² of color toner was developed. The obtained image was fixed using a belt-type image fixing device shown in FIG.
A smear tester (friction tester I type, JIS L0823, friction piece diameter: 15φ), and a white cotton cloth (JIS L0803 cotton No. 3) of about 25 x 25 mm in the fiber direction is parallel to the moving direction of the friction piece. Attached with double-sided tape. The fixed image was rubbed in 5 reciprocating continuous operations.
Peel off the white cotton cloth and measure the image density at any three locations on the friction mark where the color toner is adhered using a spectrometer ("X-Rite, 938 Spectrodensitometer"), and average the values. The smear property was evaluated at a fixing temperature at which the smear ID was 0.4 or less, and the lower the fixing temperature, the better the smear property.

<Fixing temperature limit>
The image forming apparatus provided with the belt fixing device shown in FIG. 6, that is, the image is transferred onto a transfer paper (“Type 6200”; Ricoh Co., Ltd.) was set, and a copy test of a mixed color image of yellow toner, magenta toner, and cyan toner was performed. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with sand eraser (LION GAZA) was 70% or more was defined as the minimum fixing temperature. A fixing lower limit temperature higher than 150 ° C. was judged as defective.

(B) Cleanability An image was formed using an image forming apparatus equipped with a belt fixing device shown in FIG. 6, that is, using a color copying machine ("Pretail 550"; manufactured by Ricoh Co., Ltd.). Transfer residual toner present on the photoreceptor after the cleaning process is transferred to white paper using a scotch tape (manufactured by Sumitomo 3M Limited), and this is transferred to a spectrometer (“938 Spectrodensitometer”, manufactured by X-Rite). ) And the cleaning properties were evaluated based on the following criteria.
〔Evaluation criteria〕
○ (Good): The difference from the blank is 0.01 or less. X (Bad): The difference from the blank exceeds 0.01.

(C) Toner consumption amount 100 g of each toner is set in a color copying machine (“Pretail 550”; manufactured by Ricoh Co., Ltd.), and a solid image of a mixed color of yellow toner, magenta toner, and cyan toner is transferred onto a transfer paper (“Type 6200”). "; Manufactured by Ricoh Co., Ltd.). The number of sheets that can be output before the toner was consumed was measured.

(D) Saturation Using the image forming apparatus provided with the belt fixing device shown in FIG. 6, the image is transferred onto a transfer paper (“Type 6200”) using a color copying machine (“Pretail 550”; manufactured by Ricoh Co., Ltd.). A solid image having an adhesion amount of each color toner of 0.4 ± 0.05 mg / cm ² was formed at a fixing roller surface temperature of 160 ± 2 ° C .; The saturation C * of the obtained solid image was measured using a spectrometer (“938 Spectrodensitometer”, manufactured by X-Rite) and evaluated based on the following criteria. The higher the saturation, the brighter the color is without turbidity.
〔Evaluation criteria〕
○: Cyan: 60 or more, magenta; 71 or more, yellow; 89 or more Δ: Cyan: 56 or more and less than 60, magenta; 67 or more but less than 71, yellow: 85 or more but less than 89 ×: Cyan; less than 56, magenta; Yellow; less than 85

  From the results in Table 4, the following is clear. That is, it was found that the color toner containing a high amount of pigment contained in the color toner sets of Examples 1 and 2 was deformed even when the content of the deforming agent was small. In addition, it was found that a color toner set including the color toner has excellent cleaning properties, good low-temperature fixability, excellent smearing properties, low toner consumption, good chroma, and high image quality. .

  The color toner set of the present invention is excellent in cleaning properties, good low-temperature fixability, and further excellent in smearing properties and contains a deformed color toner, and is therefore suitably used for high-quality image formation. The developer, process cartridge, image forming apparatus and image forming method of the present invention using the color toner set of the present invention are suitably used for high quality image formation.

FIG. 1 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 2 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. 4 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. FIG. 5 a is an SEM photograph of the yellow toner of Example 1. FIG. 5 b is an SEM photograph of the magenta toner of Example 2. FIG. 6 is a schematic explanatory view showing an example of a belt-type fixing device in the image forming apparatus of the present invention.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer 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 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 110 Belt type fixing device 120 Tandem type developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Pressure roller 125 Heat source 126 Cleaning roller 127 Temperature sensor 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 14 Separation roller 146 feed path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)

Claims (18)

A toner solution in which a toner material containing an adhesive substrate, a bisacetoacetolide pigment or a quinacridone pigment, and an organosilica sol is dissolved or dispersed in an organic solvent is emulsified or dispersed in an aqueous medium, and then the organic solvent is removed. A color toner obtained by
The image density when the toner adhesion amount is 0.4 mg / cm ² is 1.2 to 1.8,
A color toner comprising 6 to 20% by mass of the bisacetoacetalilide pigment or quinacridone pigment and less than 3% by mass of organosilica as a deforming agent. The bisacetoacetalilide pigment is C.I. I. The color toner according to claim 1, which is CI Pigment Yellow 155. Quinacridone pigments are C.I. I. The color toner according to claim 1, which is CI Pigment Red 122. The color toner according to claim 1, wherein the organosilica is present on at least a surface of the color toner . The color toner according to claim 1, wherein the average circularity of the color toner is 0.900 to 0.975 . The color toner according to claim 1, wherein the content of the organosilica is 1% by mass or less . The color toner according to any one of claims 1 to 2 and 4 to 6, wherein the average particle size of the bisacetoacetalilide pigment is 80 to 100 nm . A color toner is obtained by dissolving a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, a bisacetoacetoarylide pigment or a quinacridone pigment, and an organosilica sol in an organic solvent. After preparing a toner solution by dispersing, the toner solution is dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and the active hydrogen group-containing compound can react in the aqueous medium. The color toner according to claim 1, wherein the color toner is obtained by reacting with a polymer to form an adhesive substrate in the form of particles and removing the organic solvent . The color toner according to claim 1, wherein the volume average particle diameter (Dv) is 3 to 8 μm . The color toner according to claim 1, wherein the volume average particle diameter (Dv) / number average particle diameter (Dn) is 1.00 to 1.15 . The color toner according to claim 1, comprising a polyester resin as an adhesive substrate. The color toner according to claim 1, comprising a crystalline polyester resin. A color toner set including at least two color toners,
A color toner set comprising at least one color toner according to claim 1 . A toner solution in which a toner material containing an adhesive substrate, a bisacetoacetolide pigment or a quinacridone pigment, and an organosilica sol is dissolved or dispersed in an organic solvent is emulsified or dispersed in an aqueous medium, and then the organic solvent is removed. A color toner set containing the color toner obtained by
Including at least two color toners,
The image density when the toner adhesion amount of each color toner is 0.4 mg / cm 2 is 1.2 to 1.8,
Among the color toners, at least one of the pigment high-content color toners containing 6 to 20% by mass of the bisacetoacetalilide pigment or the quinacridone pigment contains less than 3% by mass of organosilica as a deforming agent. A color toner set characterized by A two-component developer comprising the color toner according to any one of claims 1 to 12 or the color toner set according to any one of claims 13 and 14 and a carrier . A step of emulsifying or dispersing a toner solution obtained by dissolving or dispersing a toner material containing an adhesive substrate, a bisacetoacetarylide pigment or a quinacridone pigment, and an organosilica sol in an organic solvent in an aqueous medium; and removing the organic solvent. A process for producing a color toner having at least a step,
The method for producing a color toner, wherein the pigment and the organosilica sol are blended in such amounts that the pigment concentration in the obtained toner is 6 to 20% by mass and the organosilica concentration is less than 3% by mass. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image is the color toner according to any one of claims 1 to 12, and any one of claims 13 or 14. A development process for forming a visible image by developing using the color toner set according to claim 15 or the two-component developer according to claim 15, a transfer process for transferring the visible image to a recording medium, and a recording An image forming method comprising at least a fixing step of fixing a transferred image transferred to a medium. An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the color according to any one of claims 1 to 12. A developing means for forming a visible image by developing with toner, the color toner set according to claim 13 or 14, or the two-component developer according to claim 15, and recording the visible image An image forming apparatus comprising: a transfer unit that transfers to a medium; and a fixing unit that fixes a transfer image transferred to a recording medium.