JP5696583B2 - Image forming method - Google Patents

Description

  The present invention relates to an electrophotographic image forming method.

  In an electrophotographic image forming method using a toner for developing an electrostatic charge image (hereinafter also simply referred to as “toner”), the toner used for heat-fixing a toner image on an image support such as paper is used. The separability of the image support with respect to the fixing roller is determined in accordance with the leaching temperature and leaching speed of the contained wax.

In particular, in the commercial printing area, being able to handle a wide range of paper types from thin paper to thick paper greatly increases the commercial value of the image forming apparatus.
In recent years, there has been a growing demand for image forming apparatuses capable of handling paper that is thinner than conventional specifications from the viewpoints of paper cost and energy saving due to weight reduction. However, in color image forming apparatuses, toner images are superimposed. In addition, since the toner adhesion amount per image area is high, it has been a difficult task to deal with thin paper (see, for example, Patent Document 1).
Specifically, if there is unevenness in the leaching speed of the wax, the wax is not sufficiently supplied at the time of heat-fixing the toner image. Therefore, the separation property of the thin paper with respect to the fixing roller (hereinafter also referred to as “thin paper separation property”). )) Cannot be obtained sufficiently.

In particular, in a toner using an oil-soluble dye used as a colorant for improving saturation, the wax contained therein is crystallized at a temperature lower than the original crystallization temperature, that is, a freezing point. Therefore, it has been confirmed that the dispersion of the wax becomes non-uniform and unevenness occurs in the leaching speed of the wax when the toner image is heated and fixed.
Therefore, when image formation is performed using such a toner in combination with a toner using an organic pigment as a colorant, the crystallization temperature of the wax contained in the toner based on the organic pigment and the toner based on the oil-soluble dye is low. Due to the difference, a difference in the leaching speed of the wax occurs at the time of heat fixing of the toner image. Therefore, a difference in the fixing separation characteristic occurs, and a good thin paper separation property cannot be obtained.

Japanese Patent Laid-Open No. 2005-208201

  The present invention has been made based on the above circumstances, and an object of the present invention is to provide an image forming method in which a toner using an organic pigment as a colorant and a toner using an oil-soluble dye as a colorant are used. Another object of the present invention is to provide an image forming method capable of obtaining good thin paper separation.

The image forming method of the present invention includes at least
Forming a toner image (A) using an electrostatic image developing toner (A) containing a binder resin, a colorant comprising an organic pigment, and a wax;
A toner image (B) is produced using a binder resin, a colorant comprising an oil-soluble dye, and an electrostatic image developing toner (B) containing the same wax as the electrostatic image developing toner (A). And forming a process,
In an image forming method of forming an image by performing a step of heat-fixing the toner image (A) and the toner image (B) collectively,
The electrostatic image developing toner (B) contains a high melting point wax of at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2):
The high melting point wax has a melting point higher by 20 ° C. or more than the wax,
The high melting point wax is contained in a proportion of 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the binder resin contained in the toner (B) for developing an electrostatic charge image. And

Formula (1): R ¹ —COO—R ²
[In the general formula (1), R ¹ and R ² are linear hydrocarbon groups having 20 to 30 carbon atoms, and may be the same or different from each other. ]

General formula (2): R < ³ > -COO-M
[In the general formula (2), R ³ represents a linear hydrocarbon group having 20 to 30 carbon atoms, and M represents an alkaline earth metal of Ca, Li, or Na, or an alkali metal. ]

  In the image forming method of the present invention, the electrostatic image developing toner (B) contains a high melting point wax of any one of the compound represented by the general formula (1) and the compound represented by the general formula (2). It is preferable that

  According to the present invention, in the image forming method using the toner (A) in which an organic pigment is used as a colorant and the toner (B) in which an oil-soluble dye is used as a colorant, the toner (B) has a specific melting point. When the toner image is heat-fixed, the main wax contained in the toner (A) and the toner (B) (hereinafter referred to as “main wax”) is included. )), The difference in the leaching rate is small, and good thin paper separation is obtained.

1 is a schematic diagram illustrating an example of a configuration of an image forming apparatus used in an image forming method of the present invention.

  Hereinafter, the present invention will be described in detail.

(Image forming method)
The image forming method of the present invention includes a step of forming a toner image (A) using a toner (A) containing at least a binder resin, a colorant composed of an organic pigment and a main wax, a binder resin, and an oil-soluble property. Forming a toner image (B) using a colorant comprising a dye, a toner (B) containing the same main wax as the toner (A), and a high melting point wax, and a toner image (A) And a toner image (B) are collectively heat-fixed to form an image.
It has been confirmed that when the main wax and the oil-soluble dye are contained in the toner, the endothermic peak is lowered by about 20 to 30 ° C. from the melting point of the original main wax. Therefore, in the present invention, by adding the high melting point wax to the toner (B), the endothermic peak position of the main wax returns to the original endothermic peak position, and this toner (B) is used for image formation. It is thought that thin paper separability is improved. In addition, it has not been confirmed that the same effect is expressed in the toner (A) in which an organic pigment is used as a colorant.
Therefore, in the present invention, by aligning the endothermic peak positions of the toner (A) containing the organic pigment and the toner (B) containing the oil-soluble dye, the wax leaching rate and the leaching amount can be reduced. It is considered that the thin paper separation can be improved evenly.

Specific examples of the image forming method of the present invention include the following methods (1) and (2).
(1) a step of directly transferring a toner image (A) formed by developing the electrostatic latent image formed on the electrostatic latent image carrier with toner (A) to an image support; A step of directly transferring a toner image (B) formed by developing the electrostatic latent image formed on the image carrier with toner (B) to the image support; and a toner carried on the image support A so-called direct transfer type image forming method in which the image (A) and the toner image (B) are collectively heated and fixed.
(2) a step of transferring the toner image (A) formed by developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner (A) to an intermediate transfer member; A step of transferring the toner image (B) formed by developing the electrostatic latent image formed on the carrier with the toner (B) to an intermediate transfer member, and a toner image transferred on the intermediate transfer member ( A so-called intermediate transfer type image forming method in which an image is formed by going through a step of A) and a toner image (B) that are collectively heated and fixed.

[Toner (A)]
The toner (A) used in the image forming method of the present invention is not particularly limited as long as it contains an organic pigment as a colorant. For example, black toner, magenta toner, red toner, yellow toner, orange toner , Cyan toner, green toner and the like, and two or more kinds of toners (A) having different colors can be used in combination.
The toner (A) contains at least a binder resin and a main wax together with a colorant made of an organic pigment.
The toner (A) may contain an internal additive such as a charge control agent.

(Binder resin)
The binder resin contained in the toner (A) is, for example, a styrene resin, a (meth) acrylic resin, a styrene- (meth) acrylic copolymer resin, a polyester resin, a polyether / polyol resin, or polyacetic acid. Various known resins such as vinyl resins can be used. In order to uniformly disperse the main wax and obtain sufficient thin paper separability, styrene- (meth) acrylic copolymer resins, polyester resins Is preferred. Particularly preferred is a styrene- (meth) acrylic copolymer resin.

  When the binder resin contained in the toner (A) is a styrene resin, a (meth) acrylic resin, or a styrene- (meth) acrylic copolymer resin, a polymerizable monomer for obtaining the binder resin is used. Examples of the monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, p-tert-butyl styrene. Styrene or styrene derivatives such as pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene; methyl methacrylate, ethyl methacrylate, N-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate , Methacrylate derivatives such as n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, Acrylate derivatives such as isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and phenyl acrylate; olefins such as ethylene, propylene and isobutylene And vinyl monomers such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These vinyl monomers can be used alone or in combination of two or more.

Further, as the polymerizable monomer for obtaining the binder resin, it is preferable to use a combination of the polymerizable monomer having an ionic dissociation group. The polymerizable monomer having an ionic dissociation group has, for example, a substituent such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group as a constituent group, and specifically includes acrylic acid, methacrylic acid, maleic acid. Examples include acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
Furthermore, as a polymerizable monomer, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl A binder resin having a crosslinked structure can also be obtained using a polyfunctional vinyl such as glycol diacrylate.

The glass transition point (Tg) of the binder resin is preferably 30 to 50 ° C.
The glass transition point (Tg) of the binder resin is measured using a differential scanning calorimeter “DSC8500” (manufactured by PerkinElmer). Specifically, 4.5 mg of a sample (binder resin) is precisely weighed to two digits after the decimal point, sealed in an aluminum pan, and set in a DSC-7 sample holder. For the reference, an empty aluminum pan was used, and heat-cool-heat temperature control was performed at a measurement temperature of 0 to 200 ° C., a temperature increase rate of 10 ° C./min, and a temperature decrease rate of 10 ° C./min. Analysis is performed based on the data in Heat. The glass transition point is defined as the value of the intersection of the extension line of the base line before the rise of the first endothermic peak and the tangent line indicating the maximum slope between the rising portion of the first endothermic peak and the peak apex.

(Coloring agent)
The colorant contained in the toner (A) is composed of an organic pigment, and known organic pigments can be used. For example, as a colorant for black, furnace black, channel black, acetylene. As a colorant for carbon black such as black, thermal black and lamp black, magenta or red, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48; 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment Red 222, as a coloring agent for orange or yellow, C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 100, C.I. I. Pigment Yellow 104; as a colorant for green or cyan, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15; 2, C.I. I. Pigment blue 15; 3, C.I. I. Pigment blue 15; 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue 66, C.I. I. And CI Pigment Green 7. These organic pigments can be used alone or in combination of two or more.

  The content of the colorant composed of the organic pigment is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

(Main wax)
As the main wax contained in the toner (A), known waxes can be used. For example, polyolefin waxes such as polyethylene wax and polypropylene wax, branched hydrocarbon waxes such as microcrystalline wax, paraffin wax, sacrificial wax. Long chain hydrocarbon waxes such as sol wax, dialkyl ketone waxes such as distearyl ketone, carnauba wax, montan wax, behenate behenate, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate Ester wax such as dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid, distearyl maleate, ethyl Diamine behenyl amides, amide-based waxes such as trimellitic acid tristearyl amide. Among these, branched hydrocarbon waxes such as microcrystalline wax are particularly preferable from the viewpoint of suppressing gloss unevenness.

The melting point of the main wax contained in the toner (A) is preferably 80 to 110 ° C, more preferably 80 to 90 ° C.
The melting point of the main wax indicates the temperature at the top of the endothermic peak, and is differentially scanned using a differential scanning calorimeter “DSC-7” (manufactured by PerkinElmer) and a thermal analyzer controller “TAC7 / DX” (manufactured by PerkinElmer). DSC measurements are made by calorimetric analysis.
Specifically, 4.5 mg of a sample (main wax) was enclosed in an aluminum pan (KITNO.0219-0041), and this was set in a sample holder of “DSC-7”. Heating-cooling-heating temperature control is performed under measurement conditions of a temperature rising rate of 10 ° C./min and a temperature decreasing rate of 10 ° C./min, and analysis is performed based on the data in the second heating. However, an empty aluminum pan is used for the reference measurement.

  The content of the main wax is preferably 0.1 to 30 parts by mass, more preferably 1 to 16 parts by mass with respect to 100 parts by mass of the binder resin.

(Charge control agent)
When the toner (A) contains a charge control agent, a known positive charge control agent or negative charge control agent can be used.
Specifically, as the positive charge control agent, for example, a nigrosine dye such as “Nigrosine Base EX” (manufactured by Orient Chemical Industries), “quaternary ammonium salt P-51” (manufactured by Orient Chemical Industries), “ Examples include quaternary ammonium salts such as “Copy Charge PX VP435” (manufactured by Hoechst Japan), alkoxylated amines, alkylamides, molybdate chelate pigments, and imidazole compounds such as “PLZ1001” (manufactured by Shikoku Kasei Kogyo). .
Examples of the negative charge control agent include “Bontron S-22” (manufactured by Orient Chemical Industries), “Bontron S-34” (manufactured by Orient Chemical Industries), and “Bontron E-81” (Orient Chemical Industries, Ltd.). ), “Bontron E-84” (manufactured by Orient Chemical Co., Ltd.), “Spiron Black TRH” (manufactured by Hodogaya Chemical Co., Ltd.), thioindigo pigments, “Copy Charge NX VP434” (Hoechst Japan) Quaternary ammonium salts such as “Bontron E-89” (manufactured by Orient Chemical Industries), boron compounds such as “LR147” (manufactured by Nippon Carlit), magnesium fluoride, fluorinated carbon Fluorine compounds such as In addition to the metal complexes used as negative charge control agents, oxycarboxylic acid metal complexes, dicarboxylic acid metal complexes, amino acid metal complexes, diketone metal complexes, diamine metal complexes, azo group-containing benzene-benzene derivatives Examples thereof include those having various structures such as skeletal metal bodies and azo group-containing benzene-naphthalene derivative skeleton metal complexes.

  The content of the charge control agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

(External additive)
The toner (A) can be used as it is in the image forming method of the present invention, but may be added with an external additive in order to improve fluidity, chargeability, cleaning properties, and the like. .
Examples of the external additive include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titanium oxide fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, strontium titanate, and zinc titanate. And inorganic fine particles such as inorganic titanic acid compound fine particles.
These inorganic fine particles are preferably those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil, or the like from the viewpoint of heat-resistant storage stability and environmental stability.
The inorganic fine particles constituting the external additive preferably have an average primary particle size of 30 nm or less.
When the external additive made of inorganic fine particles has the above particle diameter, the toner (A) is less likely to be liberated during the image formation.

  The additive amount of the external additive is 0.05 to 5% by mass, preferably 0.1 to 3% by mass in the toner (A).

(Developer)
The toner (A) used in the image forming method of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.
In the case where the toner (A) is used as a two-component developer, the carrier is conventionally a ferromagnetic metal such as iron, an alloy such as ferromagnetic metal and aluminum and lead, or a compound of a ferromagnetic metal such as ferrite and magnetite. Magnetic particles made of known materials can be used, and ferrite particles are particularly preferable. As the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a binder type carrier in which magnetic fine powder is dispersed in a binder resin, and the like can also be used. The coating resin constituting the coat carrier is not particularly limited, and examples thereof include olefin resins, styrene resins, styrene-acrylic resins, silicone resins, ester resins, and fluorine resins. Moreover, it does not specifically limit as resin which comprises a resin dispersion type carrier, A well-known thing can be used, For example, a styrene-acrylic-type resin, a polyester resin, a fluororesin, a phenol resin etc. can be used.

(Particle size)
The particle size of the toner particles constituting the toner (A) is preferably 4 to 10 μm, and more preferably 5 to 9 μm, for example, in terms of volume-based median diameter.
When the volume-based median diameter is in the above range, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.
The volume-based median diameter of the toner particles is measured and calculated using a measuring apparatus in which a computer system for data processing (manufactured by Beckman Coulter) is connected to “Coulter Multisizer 3” (manufactured by Beckman Coulter). Is.
Specifically, 0.02 g of a sample (toner (A)) was added to 20 mL of a surfactant solution (for the purpose of dispersing toner particles, for example, an interface obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water. After adding to the activator solution and acclimatizing, ultrasonic dispersion treatment is performed for 1 minute to prepare a toner particle dispersion, and this toner particle dispersion is added to “ISOTONII” (Beckman Coulter) in the sample stand. Pipette into a beaker containing (made by the company) until the displayed concentration of the measuring device is 5% to 10%. Here, a reproducible measurement value can be obtained by setting the concentration range. In the measurement apparatus, the measurement particle count is 25000, the aperture diameter is 50 μm, the frequency value is calculated by dividing the measurement range of 1 to 30 μm into 256, and the volume integrated fraction is 50 % Is the volume-based median diameter.

(Softening point)
The softening point (Tsp) of the toner (A) is preferably 90 to 110 ° C.
When the softening point (Tsp) is in the above range, the influence of heat applied to the toner (A) during fixing can be further reduced. Therefore, since image formation can be performed without imposing a burden on the colorant, it is expected that a wider and more stable color reproducibility is expressed.

The softening point (Tsp) of the toner (A) can be controlled by, for example, the following methods alone or in combination. That is,
(1) The kind and composition ratio of the polymerizable monomer for forming the binder resin are adjusted.
(2) The molecular weight of the binder resin is adjusted according to the type and addition amount of the chain transfer agent.
(3) Adjust the type and amount of main wax.

As for the softening point (Tsp) of the toner (A), “Flow Tester CFT-500” (manufactured by Shimadzu Corporation) is used to form a cylindrical shape having a height of 10 mm and is heated while heating at a heating rate of 6 ° C./min. A pressure of 1.96 × 10 ⁶ Pa is applied from the jar and pushed out from a nozzle having a diameter of 1 mm and a length of 1 mm, thereby drawing a curve (softening flow curve) between the plunger drop amount of the flow tester and the temperature, It is measured by a method in which the temperature that flows out first is the melting start temperature, and the temperature with respect to the drop amount of 5 mm is the softening point temperature.

(Average circularity)
The average circularity of the toner particles constituting the toner (A) is preferably 0.930 to 1.000, more preferably 0.950 to 0.995.

The average circularity of the toner particles is measured using “FPIA-2100” (manufactured by Sysmex). Specifically, the sample (toner (A)) was blended with an aqueous solution containing a surfactant, dispersed by performing ultrasonic dispersion for 1 minute, and then measured by “FPIA-2100” (manufactured by Sysmex). In the condition HPF (high magnification imaging) mode, photographing is performed at an appropriate density of 3,000 to 10,000 HPF detections, and the circularity of each toner particle is calculated according to the following formula (T). Are added to each other and divided by the total number of toner particles.
Formula (T): Circularity = (perimeter of a circle having the same projection area as the particle image) / (perimeter of the particle projection image)

(Manufacturing method of toner (A))
The toner (A) can be produced by a kneading / pulverization method, an emulsion dispersion method, a suspension polymerization method, a dispersion polymerization method, an emulsion polymerization method, an emulsion polymerization aggregation method, a miniemulsion polymerization aggregation method, an encapsulation method, Known methods and the like can be mentioned. From the viewpoint of production cost and production stability, emulsification is necessary in view of the necessity of obtaining a toner having a reduced particle size in order to achieve high image quality. It is preferable to use a polymerization aggregation method. In the emulsion polymerization aggregation method, a dispersion of fine particles made of a binder resin (hereinafter also referred to as “binder resin fine particles”) produced by the emulsion polymerization method is used to form a dispersion of fine particles made of a colorant (hereinafter referred to as “colorant fine particles”). )), And slowly agglomerates while balancing the repulsive force on the surface of the fine particles by adjusting the pH and the agglomeration force by adding an aggregating agent made of an electrolyte to control the average particle size and particle size distribution. At the same time, the toner is manufactured by performing the shape control by fusing the fine particles by heating and stirring at the same time as the association.

  In the method for producing a toner, the binder resin fine particles formed when using the emulsion polymerization aggregation method can be constituted by two or more layers composed of binder resins having different compositions. A method in which a polymerization initiator and a polymerizable monomer are added to a dispersion of first binder resin fine particles prepared by emulsion polymerization treatment (first stage polymerization), and this system is polymerized (second stage polymerization). Can be adopted.

  Further, the toner (A) may have a core-shell structure, and the production method of the toner (A) having the core-shell structure associates and aggregates the binder resin fine particles and the colorant fine particles for the core. Then, the core particles are prepared by fusing, and then the binder resin particles for shell for forming the shell layer are added to the dispersion of the core particles, and the binder resin particles for shell are added to the surface of the core particles. It can be obtained by agglomerating and fusing to form a shell layer covering the core particle surface.

[Toner (B)]
The toner (B) used in the image forming method of the present invention contains an oil-soluble dye as a colorant, contains the same main wax as that of the toner (A), and has the above general formula as a high melting point wax. It contains at least one of the compound shown in (1) and the compound shown in the general formula (2). Examples of such toner (B) include magenta toner, red toner, yellow toner, orange toner, cyan toner, green toner, and the like, and two or more kinds of toners (B) having different colors are used in combination. Can do.
The toner (B) may contain an internal additive such as a charge control agent.

(Coloring agent)
The colorant contained in the toner (B) is made of an oil-soluble dye. Here, in the present invention, the oil-soluble dye refers to a dye that is soluble in an organic solvent and insoluble in water, and a dye that exhibits oil solubility by salting a water-soluble dye with a long-chain base, for example, Also included are acid dyes, direct dyes, and salt-forming dyes of reactive dyes and long chain amines. Specifically, the solubility in water is 1% by mass or less, and the solubility in toluene is 0.01 g / 100 mL or more. It means what is.
The solubility of the oil-soluble dye in toluene was determined by adding the dye to 100 mL of toluene at room temperature (25 ° C.), stirring the mixture, leaving it to stand for 24 hours, and then filtering the mass of the dye contained in this solution. It can be measured by distilling off and obtaining. The solubility of the dye in water can also be measured in the same manner except that toluene is replaced with water.
However, in this invention, since the same effect is acquired, the coloring agent which made the oil-soluble dye lake with respect to a metal salt shall also be included in an oil-soluble dye.

  As the oil-soluble dye, known dyes can be used. For example, as a colorant for magenta or red, C.I. I. Solvent Red 111, C.I. I. Solvent Red 135, C.I. I. Solvent Red 179, C.I. I. Solvent Red 195, C.I. I. Pigment red 181, C.I. I. Pigment red 81: 4, C.I. I. Basic Red 1, C.I. I. 45160, C.I. I. Basic Red 1; As a colorant for orange or yellow, C.I. I. Solvent Yellow 93, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 114, C.I. I. Solvent Yellow 133, C.I. I. Solvent Yellow 145, C.I. I. Solvent Yellow 147, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163, C.I. I. Solvent Yellow 192, C.I. I. Solvent Yellow 196, C.I. I. Solvent Orange 63, Solvent Orange 114; as a colorant for green or cyan, C.I. I. Solvent Blue 45, C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 86, C.I. I. Solvent Blue 97, C.I. I. Solvent Blue 104, C.I. I. Solvent Blue 122, C.I. I. Solvent Blue 199, C.I. I. Solvent Green 3, C.I. I. Solvent Green 5, C.I. I. Solvent green 28 etc. are mentioned.

  The content of the colorant composed of the oil-soluble dye is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the binder resin. In the present invention, the content of the oil-soluble dye may be 70% by mass or more of the total colorant contained in the toner (B), and even if an organic pigment of less than 30% by mass is used in combination, The effect is obtained.

(Main wax)
The main wax contained in the toner (B) is the same as the main wax contained in the toner (A).
Moreover, it is preferable that content of the main wax is 0.1-30 mass parts with respect to 100 mass parts of binder resin, More preferably, it is 1-16 mass parts.

(High melting point wax)
The toner (B) contains at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2) as a high melting point wax.
This high melting point wax has a function of promoting crystallization of the main wax contained in the toner (B).
In the present invention, the toner (B) contains either one of the compound represented by the general formula (1) and the compound represented by the general formula (2) as a high melting point wax without being used in combination. It is preferable that the crystallization promoting function is enhanced and the thin paper separability can be further improved.

  This high melting point wax has a melting point that is 20 ° C. or more higher than the melting point of the main wax contained in toner (A) and toner (B), more preferably 25 ° C. or more.

The melting point of the high melting point wax indicates the temperature at the peak top of the endothermic peak, and is differentially detected using a differential scanning calorimeter “DSC-7” (Perkin Elmer) and a thermal analyzer controller “TAC7 / DX” (Perkin Elmer). DSC measurements are made by scanning calorimetry.
Specifically, 4.5 mg of a sample (high melting point wax) was sealed in an aluminum pan (KITNO.0219-0041), and this was set in a sample holder of “DSC-7” at a measurement temperature of 0 to 200 ° C. The temperature control of heating-cooling-heating is performed under the measurement conditions of a heating rate of 10 ° C./min and a cooling rate of 10 ° C./min, and the analysis is performed based on the second heating data. However, an empty aluminum pan is used for the reference measurement.

The content of the high melting point wax is 0.1 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the binder resin. Further, the content of the high melting point wax is 1 to 10 parts by mass, more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the main wax.
When the content of the high melting point wax is within the above range, the crystallization temperature of the main wax contained in the toner (B) is increased (the speed is increased), and the crystallization temperature of the main wax with the toner (A) is increased. Therefore, the difference in the leaching speed of the main wax at the time of heat fixing of the toner image can be reduced.

In the high melting point wax, in the general formula (1), R ¹ and R ² are linear hydrocarbon groups having 20 to 30 carbon atoms, and they may be the same or different from each other. Also good. In particular, R ¹ and R ² are each preferably a linear hydrocarbon group having 22 to 28 carbon atoms.

Specific examples of the high melting point wax composed of the compound represented by the general formula (1) include a crystalline organic compound composed of a montanic acid ester (a linear compound in which R ¹ and R ² in the general formula (1) are 28 carbon atoms) Hydrocarbon group) and the like. The high melting point wax composed of the compound represented by the general formula (1) can be used alone or in combination of two or more.

In the high melting point wax, in the general formula (2), R ³ represents a linear hydrocarbon group having 20 to 30 carbon atoms, and M is an alkaline earth metal of Ca, Li or Na, or an alkali metal Indicates. In particular, R ³ is preferably a linear hydrocarbon group having 22 to 28 carbon atoms. M is preferably Ca.

Specific examples of the high-melting-point wax composed of the compound represented by the general formula (2) include a carboxylic acid calcium salt composed of a montanic acid ester (a linear hydrocarbon group in which R ³ in the general formula (2) has 28 carbon atoms. ) And the like. The high melting point wax composed of the compound represented by the general formula (2) can be used alone or in combination of two or more.

Specific examples of the binder resin and the charge control agent contained in the toner (B) are the same as those shown in the toner (A).
Specific examples of the external additive added to the toner (B) and the carrier in the case where the toner (B) is configured as a two-component developer are the same as those shown in the toner (A). Can be mentioned.

(Particle size)
The particle diameter of the toner particles constituting the toner (B) is preferably 4 to 10 μm, and more preferably 5 to 9 μm, for example, in terms of volume-based median diameter.
When the volume-based median diameter is in the above range, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.
The volume-based median diameter of the toner particles is measured and calculated by the same measurement method as that of the toner (A) described above.

(Softening point)
The softening point (Tsp) of the toner (B) is preferably 90 to 120 ° C.
When the softening point (Tsp) is in the above range, the influence of heat applied to the toner (B) during fixing can be further reduced. Therefore, since image formation can be performed without imposing a burden on the colorant, it is expected that a wider and more stable color reproducibility is expressed.

  The softening point (Tsp) of the toner (B) is measured by the same measurement method as that of the toner (A) described above.

(Average circularity)
The average circularity of the toner particles constituting the toner (B) is preferably 0.930 to 1.000, more preferably 0.950 to 0.995.

  The average circularity of the toner particles is measured and calculated by the same measurement method as that for the toner (A) described above.

(Manufacturing method of toner (B))
The method for producing the toner (B) is the same as the method for producing the toner (A), such as kneading / pulverization method, suspension polymerization method, emulsion polymerization method, emulsion polymerization aggregation method, miniemulsion polymerization aggregation method, encapsulation. Method, other known methods, etc., but considering that it is necessary to obtain a toner with a reduced particle size in order to achieve high image quality, the production cost and production stability From the viewpoint, it is preferable to use an emulsion polymerization aggregation method.

  In the method for producing the toner (B), the binder resin fine particles formed when the emulsion polymerization aggregation method is used may have a constitution of two or more layers made of binder resins having different compositions. A polymerization initiator and a polymerizable monomer are added to the dispersion of the first binder resin fine particles prepared by emulsion polymerization treatment (first-stage polymerization) according to the above, and this system is polymerized (second-stage polymerization). ) Method can be adopted.

  Further, the toner (B) may have a core-shell structure, and the production method of the toner (B) having the core-shell structure associates and aggregates the binder resin fine particles and the colorant fine particles for the core. Then, the core particles are prepared by fusing, and then the binder resin particles for shell for forming the shell layer are added to the dispersion of the core particles, and the binder resin particles for shell are added to the surface of the core particles. It can be obtained by agglomerating and fusing to form a shell layer covering the core particle surface.

In the case where the toner (B) has a core-shell structure, the production method will be specifically described below.
(1) a colorant fine particle dispersion preparing step for preparing a dispersion of colorant fine particles in which a colorant is dispersed in the form of fine particles;
(2-1) A core binder resin fine particle polymerization step for obtaining a core binder resin fine particle comprising a core binder resin containing a main wax and an internal additive, and preparing this dispersion;
(2-2) A shell binder resin fine particle polymerization step of obtaining a binder resin fine particle for shell made of a binder resin for shell and preparing this dispersion;
(3) Aggregation / fusion process for aggregating and fusing core binder resin fine particles and colorant fine particles in an aqueous medium to form associated particles to be core particles,
(4) a first aging step of aging associated particles with thermal energy to control the shape and obtaining core particles;
(5) A core-shell structure is obtained by adding binder resin fine particles for shell to form a shell layer to a dispersion of core particles, and aggregating and fusing the binder fine resin particles for shell on the surface of the core particles. A shell layer forming step for forming particles of
(6) a second aging step in which core-shell structured particles are aged by thermal energy to control the shape to obtain core-shell structured toner particles;
(7) a filtration and washing step for solid-liquid separation of the toner particles from the cooled dispersion (aqueous medium) of the toner particles and removing the surfactant from the toner particles;
(8) Consists of a drying step for drying the washed toner particles, and if necessary, after the drying step,
(9) An external additive treatment step of adding an external additive to the dried toner particles may be added.

(1) Colorant fine particle dispersion preparation step In this step, a colorant in which the colorant is dispersed in the form of fine particles by adding an oil-soluble dye as a colorant to an aqueous medium and dispersing it with a disperser. A process for preparing a dispersion of fine particles is performed. Specifically, the colorant dispersion treatment is performed in an aqueous medium in which the surfactant concentration is set to a critical micelle concentration (CMC) or more as described later. The disperser used for the dispersion treatment is not particularly limited, but preferably, an ultrasonic disperser, a mechanical homogenizer, a manton gourin, a pressure disperser such as a pressure homogenizer, a media type such as a sand grinder, a Getzman mill, or a diamond fine mill. Examples include a disperser.
The dispersion diameter of the colorant fine particles in the colorant fine particle dispersion is preferably 40 to 200 nm in terms of volume-based median diameter.

The volume-based median diameter of the colorant fine particles is measured using “MICROTRAC UPA-150 (manufactured by HONEYWELL)” under the following measurement conditions.
Sample refractive index 1.59
・ Sample specific gravity 1.05 (in terms of spherical particles)
Solvent refractive index 1.33
・ Solvent viscosity 0.797 (30 ° C), 1.002 (20 ° C)
・ 0 point adjustment Ion-exchanged water was added to the measurement cell for adjustment.

(2-1) Core Binder Resin Fine Particle Polymerization Step In this step, a dispersion of core binder resin fine particles comprising a core binder resin containing a main wax, an internal additive and the like after being subjected to a polymerization treatment. The process of preparing is performed.
In a preferred example of the polymerization treatment in this step, a polymerizable monomer containing a main wax and an internal additive as necessary in an aqueous medium containing a surfactant having a critical micelle concentration (CMC) or less. A body solution is added, mechanical energy is applied to form droplets, then a water-soluble polymerization initiator is added, and the polymerization reaction proceeds in the droplets. Note that an oil-soluble polymerization initiator may be contained in the droplet. In such a process, it is essential to perform mechanical emulsification (formation of droplets) by applying mechanical energy. Examples of the mechanical energy applying means include strong stirring such as homomixer, ultrasonic wave, and manton gorin, or ultrasonic vibration energy applying means.

[Surfactant]
Here, the surfactant used in the aqueous medium used at the time of polymerization of the colorant fine particle dispersion and the core binder resin fine particles will be described.
The surfactant is not particularly limited, but sulfonate (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate), sulfate ester salt (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, Suitable ionic surfactants such as sodium octyl sulfate), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.) It can be illustrated. Also, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, sorbitan ester, etc. Nonionic surfactants can also be used.

  Hereinafter, the polymerization initiator and chain transfer agent used in the core binder resin fine particle polymerization step will be described.

(Polymerization initiator)
Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.
Examples of the oil-soluble polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy Carbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,4 -T-butylperoxycyclohexyl) propane, tri - such as (t-butylperoxy) polymeric initiator having a side chain a peroxide-based polymerization initiator or a peroxide such as triazine.

[Chain transfer agent]
Generally used chain transfer agents can be used for the purpose of adjusting the molecular weight of the obtained binder resin for the core. The chain transfer agent is not particularly limited, for example, mercaptan such as n-octyl mercaptan, n-decyl mercaptan, tert-dodecyl mercaptan, mercaptopropionate such as n-octyl-3-mercaptopropionate, Turpinolene, α-methylstyrene dimer and the like are used.

(2-2) Shell Binder Resin Fine Particle Polymerization Step In this step, the polymer is treated in the same manner as the core binder resin fine particle polymerization step (2-1) above, and is made of a shell binder resin. A treatment for preparing a dispersion of binder resin fine particles for shell is performed.

(3) Aggregation / fusion process In this process, the core binder resin fine particles and the colorant fine particles are aggregated and fused in an aqueous medium to form associated particles to be core particles. As a method of aggregation and fusion in this step, the colorant fine particles obtained by the colorant fine particle dispersion preparation step (1) and the core binder resin fine particle polymerization step (2-1) are obtained. The salting out / fusion method using the core binder resin fine particles is preferable. In the agglomeration / fusion step, fine particles of internal additives such as wax fine particles and charge control agents can be agglomerated and fused together with the binder resin fine particles for the core and the colorant fine particles.
Here, “salting out / fusing” means that agglomeration and fusing are carried out in parallel, and when the particles grow to a desired particle diameter, an agglomeration terminator is added to stop the particle growth, and further if necessary. This means that heating for controlling the particle shape is continued.

  In the salting-out / fusion method, a salting-out agent comprising an alkali metal salt, an alkaline earth metal salt, a trivalent salt, or the like is added to an aqueous medium in which the binder resin fine particles for the core and the colorant fine particles are present. Add as a coagulant with a critical coagulation concentration or higher, then heat to a temperature above the glass transition point of the core binder resin microparticles and above the melting peak temperature of the core binder resin microparticles and colorant microparticles. In this way, salting-out is advanced, and at the same time, aggregation and fusion are performed. Here, the alkali metal salt and the alkaline earth metal salt which are salting-out agents include lithium, potassium, sodium and the like as the alkali metal, and examples of the alkaline earth metal include magnesium, calcium, strontium and barium. Preferably, potassium, sodium, magnesium, calcium, and barium are used.

(3) When the coagulation / fusion process is performed by salting out / fusion, it is preferable to shorten the time allowed to stand after adding the salting-out agent as much as possible. The reason for this is not clear, but the aggregation state of the particles fluctuates depending on the standing time after salting out, and the particle size distribution becomes unstable and the surface property of the fused toner fluctuates. Occur. The temperature for adding the salting-out agent needs to be at least the glass transition point of the binder resin fine particles for core. The reason for this is that if the temperature at which the salting-out agent is added is equal to or higher than the glass transition point of the core binder resin fine particles, the salting out / fusion of the core binder resin fine particles proceeds rapidly, but the particle size There is a problem that control cannot be performed and particles having a large particle size are generated. The range of the addition temperature may be not more than the glass transition point of the binder resin, but is generally 5 to 55 ° C, preferably 10 to 45 ° C.
In addition, the salting-out agent is added below the glass transition point of the core binder resin fine particles, and then the temperature is raised as quickly as possible. Heat to a temperature equal to or higher than the melting peak temperature (° C.) of the resin fine particles and the colorant fine particles. The time until this temperature rise is preferably less than 1 hour. Further, although it is necessary to quickly raise the temperature, the rate of temperature rise is preferably 0.25 ° C./min or more. The upper limit is not particularly clear, but if the temperature is increased instantaneously, salting out proceeds rapidly, so there is a problem that particle size control is difficult, and 5 ° C./min or less is preferable. By the salting-out / fusion method described above, a dispersion of associated particles (core particles) obtained by salting-out / fusion of the core binder resin fine particles and arbitrary fine particles is obtained.

  The “aqueous medium” refers to a medium composed of 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Of these, alcohol-based organic solvents that do not dissolve the produced resin are preferred.

(4) First aging step In this step, a process of aging associated particles with thermal energy is performed. And by controlling the heating temperature and time of (3) the aggregation / fusion process and especially the heating temperature and time of (4) the first aging process, the surface of the core particles formed with a uniform particle size and a narrow distribution is smoothed. However, it can be controlled to have a uniform shape. Specifically, (3) the heating temperature is lowered in the agglomeration / fusion process to suppress the progress of fusion between the core binder resin fine particles to promote homogenization, and the heating temperature in the first aging process. The surface of the core particle is controlled to have a uniform shape by lowering the time and increasing the time.

(5) Shell layer forming step In this step, a dispersion of the binder resin particles for shells is added to the dispersion of the core particles to aggregate and fuse the binder resin particles for shells on the surface of the core particles, Shelling treatment is performed in which the surface of the core particles is coated with the binder resin particles for shell to form the core-shell structure particles.
This step is a preferable production condition for imparting both low temperature fixability and heat resistant storage stability. Further, when forming a color image, it is preferable to form this shell layer in order to obtain high color reproducibility for the secondary color.
Specifically, the dispersion of the core particles is added to the dispersion of the core particles while maintaining the heating temperature in the (3) agglomeration / fusion step and (4) the first aging step. While the stirring is continued, the binder resin particles for shell are slowly coated on the surface of the core particles over several hours to form core-shell structured particles. The heating and stirring time is preferably 1 to 7 hours, particularly preferably 3 to 5 hours.

(6) Second aging step In this step, (5) the growth of particles is performed by adding a stopper such as sodium chloride when the core-shell structured particles have reached a predetermined particle size in the shell layer forming step. The heating and stirring are continued for several hours in order to melt the binder resin particles for the shell adhered to the core particles. And the thickness of the layer by the binder resin particle for shells which coat | covers the surface of a core particle shall be 100-300 nm. In this way, the shell binder resin fine particles are fixed to the surface of the core particles to form a shell layer, and toner particles having a rounded core-shell structure are formed.

(7) Filtration and Washing Step In this step, first, a treatment for cooling the dispersion of toner particles is performed. As a cooling treatment condition, it is preferable to cool at a cooling rate of 1 to 20 ° C./min. The cooling treatment method is not particularly limited, and examples thereof include a method of cooling by introducing a refrigerant from the outside of the reaction vessel, and a method of cooling by directly introducing cold water into the reaction system.
Next, the toner particles are solid-liquid separated from the dispersion of the toner particles cooled to a predetermined temperature, and then the solid-liquid separated toner cake (aggregate of toner particles in a wet state is aggregated in a cake shape) to the interface. A cleaning process is performed to remove deposits such as activators and salting-out agents. Here, the filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a filtration method using a filter press or the like.

(8) Drying step In this step, a process of drying the washed toner cake is performed. Examples of dryers used in this process include spray dryers, vacuum freeze dryers, vacuum dryers, etc., stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers It is preferable to use a stirring dryer or the like. The moisture of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less. In addition, when the toner particles that have been dried are aggregated due to weak interparticle attraction, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

(9) External Addition Processing Step In this step, a process of adding an external additive to the toner particles dried in the (8) drying step is performed. As a method for adding the external additive, for example, it can be added using a mechanical mixing device such as a Henschel mixer or a coffee mill.

  In the method for producing the toner (B), the high melting point wax is added when the core binder resin is polymerized in the (2-1) core binder resin fine particle polymerization step, (3) In the aggregation / fusion step, when forming the associated particles to be the core particles, the toner is obtained by adding a dispersion liquid in which the first auxiliary wax and the second auxiliary wax are dispersed in the form of fine particles. It can be contained in (B).

[Image forming apparatus]
FIG. 1 is a schematic diagram showing an example of the configuration of an image forming apparatus used in the image forming method of the present invention.
The image forming apparatus 40 is a tandem full-color image forming apparatus, and includes a plurality of image forming units 50Y, 50M, 50C, and 50K provided along a belt-like intermediate transfer member 46, a paper feed cassette 42, and the like. And a fixing device 49. In FIG. 1, reference numeral 41 denotes an operation unit, and reference numerals 47Y, 47M, 47C, and 47K denote toner cartridges for respective colors.

  The image forming unit 50Y forms a yellow toner image, and includes a photoreceptor 51Y. Around the photoreceptor 51Y, a charging unit 52Y, an exposure unit 53Y, a developing device 54Y, a primary transfer unit 57Y, and a cleaning unit are provided. The means 58Y is arranged and configured.

The image forming units 50M, 50C, and 50K have the same configuration as that of the image forming unit 50Y, except that magenta, cyan, and black toner images are formed instead of forming yellow toner images.
Here, a yellow toner image is formed by the image forming unit 50Y, a magenta toner image is formed by the image forming unit 50M, and a cyan toner image is formed by the image forming unit 50C. According to the image forming unit 50K, a black toner image is formed.

  The intermediate transfer member 46 is stretched around a plurality of support rollers 46A, 46B, and 46C, and is supported so as to be able to circulate.

The fixing device 49 is provided in a state in which the toner images of the respective colors on the image support P are collectively brought into pressure contact with, for example, a heating roller having a heating source therein and a fixing nip portion. And a pressure roller.
In the present invention, the fixing device is not particularly limited as long as it can heat and fix the toner images of the respective colors collectively.
Further, as an example of fixing conditions in the fixing device 49, the fixing temperature (surface temperature of the heating roller) is preferably 150 to 190 ° C., and the nip width of the fixing nip portion formed by the heating roller and the pressure roller is It is preferable that it is 3-5 mm. Here, the fixing nip portion refers to a contact width between the toner image transferred onto the image support P and the surface of the heating roller.

In this image forming apparatus 40, the toner images of the respective colors formed by the image forming units 50Y, 50M, 50C, and 50K are sequentially transferred onto the intermediate transfer body 46 that circulates by the primary transfer units 57Y, 57M, 57C, and 57K. Primary transfer is performed and superimposed to form a color toner image.
On the other hand, the image support P accommodated in the paper feed cassette 42 is fed one by one by the paper feed roller 43, conveyed to the secondary transfer means 57A by the registration roller 44, and the color support on the image support P. The toner image is secondarily transferred.
Next, the image support P is conveyed to the fixing device 49 and subjected to a fixing process. Thereafter, the image support P is sandwiched between the discharge rollers 45 and discharged onto the discharge tray 48 outside the apparatus.

  Further, after the color toner image is transferred to the image support P by the secondary transfer means 57A, the residual toner is removed by the cleaning means 59 from the intermediate transfer body 46 from which the image support P has been separated by curvature.

  According to the image forming method using the image forming apparatus, for example, a yellow toner, a cyan toner and a black toner are used as a toner (A) containing an organic pigment as a colorant, and an oil-soluble dye is contained as a colorant. In the case of using, for example, magenta toner as (B), the toner (B) contains a high melting point wax having a specific melting point at a specific ratio. When the toner image is collectively heat-fixed on the image support P, the main wax of the toner (A) relating to the yellow toner image, the cyan toner image and the black toner image and the toner (B) relating to the magenta toner image The difference in the leaching speed of the sheet becomes small, and good thin paper separability is obtained.

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

<Production example of toner (A)>
The following yellow toner [A-1], magenta toner [A-1] and cyan toner [A-1] were produced as toner (A) containing an organic pigment as a colorant.

[Production Example A-1 of Yellow Toner]
(1) Preparation of Colorant Fine Particle Dispersion [Y1] 11.5 parts by mass of sodium n-dodecyl sulfate was added to 160 parts by mass of ion-exchanged water, dissolved and stirred to prepare an aqueous surfactant solution. In this surfactant aqueous solution, 2 parts by weight of organic pigment “CI Pigment Yellow 74” is gradually added as a colorant, and “Clearmix W Motion CLM-0.8” (manufactured by M Technique Co., Ltd.) is used. Dispersion treatment was performed to prepare a colorant fine particle dispersion [Y1] in which colorant fine particles are dispersed. The colorant fine particles had a volume-based median diameter of 98 nm.

(2) Preparation of binder resin fine particles [Y1] for core (a) First stage polymerization An anionic interface represented by the following structural formula (1) in a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device 4 parts by mass of an activator was added together with 3040 parts by mass of ion-exchanged water to prepare an aqueous surfactant solution.
Structural formula (1): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na
A polymerization initiator solution in which 10 parts by mass of potassium persulfate is dissolved in 400 parts by mass of ion-exchanged water is added to the surfactant aqueous solution, and the temperature is raised to 75 ° C. The body mixture was dropped into the reaction vessel over 1 hour.
Styrene 532 parts by mass n-butyl acrylate 200 parts by mass Methacrylic acid 68 parts by mass n-octyl mercaptan 16.4 parts by mass After the above monomer mixture is added dropwise, the system is heated and stirred at 75 ° C. for 2 hours. Polymerization (first stage polymerization) was carried out to prepare a dispersion of resin fine particles [X1]. The resin fine particles [X1] had a weight average molecular weight of 16,400.

(B) Second-stage polymerization A monomer mixed solution composed of the following compounds was introduced into a flask equipped with a stirrer, and subsequently, microcrystalline wax “HNP-0190” (manufactured by Nippon Wax Co., Ltd.) as the main wax. (Melting point 85 ° C.) 93.8 parts by mass was added, and the mixture was heated to 85 ° C. and dissolved to prepare a monomer solution.
Styrene 101.1 parts by mass n-butyl acrylate 62.2 parts by mass Methacrylic acid 12.3 parts by mass n-octyl mercaptan 1.75 parts by mass On the other hand, 3 parts by mass of the anionic surfactant is added to 1560 parts by mass of ion-exchanged water. A dissolved aqueous surfactant solution was prepared and heated to 98 ° C. After adding 32.8 parts by mass (in terms of solid content) of the dispersion of resin fine particles [X1] to this surfactant aqueous solution, and further adding the monomer solution containing the microcrystalline wax, the circulation route is It was mixed and dispersed for 8 hours with a mechanical disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.). An emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm was prepared.
Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to this emulsified particle dispersion, and this system was polymerized by heating and stirring at 98 ° C. for 12 hours. (Second-stage polymerization) was performed to prepare a dispersion of resin fine particles [Z1]. The resin fine particles [Z1] had a weight average molecular weight of 23,000.

(C) Third-stage polymerization A polymerization initiator solution in which 5.45 parts by mass of potassium persulfate is dissolved in 220 parts by mass of ion-exchanged water is added to the resin fine particles [Z1]. A monomer mixture composed of the compound was added dropwise over 1 hour.
Styrene 293.8 parts by mass n-butyl acrylate 154.1 parts by mass n-octyl mercaptan 7.08 parts by mass After completion of the dropwise addition, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization). By cooling to 28 ° C., binder resin fine particles [Y1] for core were produced. The weight average molecular weight of the core binder resin fine particles [Y1] was 26,800.

(3) Preparation of binder resin fine particles [Y1] for shells The monomer mixture used in the first stage polymerization in the preparation of the above (2) binder resin fine particles [Y1] for cores was changed to the following. Except for the above, the polymerization reaction and the post-reaction treatment were carried out to produce binder resin particles for shell [Y1].
Styrene 624 parts by mass 2-ethylhexyl acrylate 120 parts by mass Methacrylic acid 56 parts by mass n-octyl mercaptan 16.4 parts by mass

(4) Preparation of toner particles [1] (a) Formation of core particles In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device,
420.7 parts by mass of dispersion of core binder resin fine particles [Y1] (solid content conversion)
900 parts by mass of ion-exchanged water 200 parts by mass of the colorant fine particle dispersion [Y1] was added and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 8-11.
Next, an aqueous solution obtained by dissolving 2 parts by mass of magnesium chloride hexahydrate in 1000 parts by mass of ion-exchanged water was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, the heating was started, and the system was heated to 65 ° C. over 60 minutes to associate the particles. In this state, the particle size of the associated particles was measured using “Multisizer 3” (manufactured by Coulter), and when the volume-based median diameter of the associated particles reached 5.5 μm, 40.2 parts by mass of sodium chloride was ion-exchanged. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass of water.
After termination of the association, the core temperature [Y1] was prepared by continuing the fusion by heating and stirring for 1 hour at a liquid temperature of 70 ° C. as an aging treatment.

(B) Formation of Shell Layer Next, the dispersion liquid in which the core particles [Y1] are dispersed is brought to 65 ° C., and 96 parts by mass of binder resin fine particles for shell [Y1] are added. An aqueous solution in which 2 parts by mass of the product was dissolved in 1000 parts by mass of ion-exchanged water was added over 10 minutes, and then the temperature was raised to 70 ° C. and stirring was performed for 1 hour. In this manner, the binder resin fine particles for shell [Y1] were fused on the surface of the core particles [Y1], and then aged at 75 ° C. for 20 minutes to form a shell layer.
Thereafter, an aqueous solution in which 40.2 parts by mass of sodium chloride was dissolved in 1000 parts by mass of ion-exchanged water was added to stop shell formation. Further, the colored particles produced by cooling to 30 ° C. at a rate of 8 ° C./min are filtered, washed repeatedly with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. Toner particles [Y1] having a shell layer formed thereon were produced.

(5) Addition of external additive To toner particles [Y1], 0.6 parts by mass of hexamethylsilazane-treated silica particles (average primary particle size: 12 nm) and n-octylsilane-treated titanium dioxide particles (average primary) (Particle size: 24 nm) 0.8 parts by mass was added, and a Henschel mixer was used to add external additives by mixing under conditions of a stirring blade peripheral speed of 40 m / sec and a processing temperature of 25 ° C. -1] was obtained. The toner particles [Y1] constituting the yellow toner [A-1] had a volume-based median diameter of 6.6 μm and an average circularity of 0.940.

[Magenta Toner Production Example A-1]
In the same manner as in Production Example A-1 of Yellow Toner, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y1] was changed to “CI Pigment Red 122”. [A-1] was obtained.

[Cyan Toner Production Example A-1]
In the same manner as in the production example A-1 of yellow toner, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y1] was changed to “CI Pigment Blue 15: 3”. Cyan toner [A-1] was obtained.

<Production example of toner (B)>
As the toner (B) containing an oil-soluble dye as a colorant, the following yellow toners [B-1] to [B-7], magenta toners [B-1] to [B-6], and cyan toner [B] -1] to [B-7] were produced.

[Yellow Toner Production Example B-1]
(1) Preparation of Colorant Fine Particle Dispersion [Y2] 11.5 parts by mass of sodium n-dodecyl sulfate was added to 160 parts by mass of ion-exchanged water, and dissolved and stirred to prepare an aqueous surfactant solution. In this surfactant aqueous solution, 2 parts by weight of oil-soluble dye “CI Solvent Yellow 162” is gradually added as a colorant, and “Clearmix W Motion CLM-0.8” (manufactured by M Technique Co., Ltd.) is added. Dispersion treatment was performed to prepare a colorant fine particle dispersion [Y2] in which colorant fine particles are dispersed. The colorant fine particles had a volume-based median diameter of 98 nm.

(2) Preparation of binder resin fine particles [Y2] for core (a) First stage polymerization An anionic interface represented by the following structural formula (1) in a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device 4 parts by mass of an activator was added together with 3040 parts by mass of ion-exchanged water to prepare an aqueous surfactant solution.
Structural formula (1): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na
A polymerization initiator solution in which 10 parts by mass of potassium persulfate is dissolved in 400 parts by mass of ion-exchanged water is added to the surfactant aqueous solution, and the temperature is raised to 75 ° C. The body mixture was dropped into the reaction vessel over 1 hour.
Styrene 532 parts by mass n-butyl acrylate 200 parts by mass Methacrylic acid 68 parts by mass n-octyl mercaptan 16.4 parts by mass After the above monomer mixture is added dropwise, the system is heated and stirred at 75 ° C. for 2 hours. Polymerization (first stage polymerization) was carried out to prepare a dispersion of resin fine particles [X2]. The resin fine particles [X2] had a weight average molecular weight of 16,400.

(B) Second-stage polymerization A monomer mixed solution composed of the following compounds was introduced into a flask equipped with a stirrer, and subsequently, microcrystalline wax “HNP-0190” (manufactured by Nippon Wax Co., Ltd.) as the main wax. (Melting point 85 ° C.) 93.8 parts by mass was added, and the mixture was heated to 85 ° C. and dissolved to prepare a monomer solution. The “high melting point wax [1]” shown in the following compounds is shown in Table 1 below.
Styrene 101.1 parts by weight n-butyl acrylate 62.2 parts by weight Methacrylic acid 12.3 parts by weight n-octyl mercaptan 1.75 parts by weight High melting point wax [1] 0.53 parts by weight On the other hand, the anionic surfactant A surfactant aqueous solution having 3 parts by mass dissolved in 1560 parts by mass of ion-exchanged water was prepared and heated to 98 ° C. After adding 32.8 parts by mass (in terms of solid content) of the dispersion of resin fine particles [X2] to this surfactant aqueous solution, and further adding the monomer solution containing the microcrystalline wax, the circulation route is changed. It was mixed and dispersed for 8 hours with a mechanical disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.). An emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm was prepared.
Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to this emulsified particle dispersion, and this system was polymerized by heating and stirring at 98 ° C. for 12 hours. (Second-stage polymerization) was performed to prepare a dispersion of resin fine particles [Z2]. The resin fine particles [Z2] had a weight average molecular weight of 23,000.

(C) Third stage polymerization A polymerization initiator solution in which 5.45 parts by mass of potassium persulfate was dissolved in 220 parts by mass of ion-exchanged water was added to the resin fine particles [Z2], A monomer mixture composed of the compound was added dropwise over 1 hour.
Styrene 293.8 parts by mass n-butyl acrylate 154.1 parts by mass n-octyl mercaptan 7.08 parts by mass After completion of the dropwise addition, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization). By cooling to 28 ° C., binder resin fine particles for core [Y2] were produced. The weight average molecular weight of the core binder resin fine particles [Y2] was 26,800.

(3) Preparation of binder resin fine particles [Y2] for shells The monomer mixed solution used in the first stage polymerization in the preparation of the above (2) binder resin fine particles [Y2] for cores was changed to the following. In the same manner as above, the polymerization reaction and the post-reaction treatment were performed to produce binder resin particles for shell [Y2].
Styrene 624 parts by mass 2-ethylhexyl acrylate 120 parts by mass Methacrylic acid 56 parts by mass n-octyl mercaptan 16.4 parts by mass

(4) Preparation of toner particles [Y2] (a) Formation of core particles In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device,
420.7 parts by mass of a dispersion of core binder resin fine particles [Y2] (solid content conversion)
900 parts by mass of ion-exchanged water Colorant fine particle dispersion [Y2] 200 parts by mass were charged and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 8-11.
Next, an aqueous solution obtained by dissolving 2 parts by mass of magnesium chloride hexahydrate in 1000 parts by mass of ion-exchanged water was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, the heating was started, and the system was heated to 65 ° C. over 60 minutes to associate the particles. In this state, the particle size of the associated particles was measured using “Multisizer 3” (manufactured by Coulter), and when the volume-based median diameter of the associated particles reached 5.5 μm, 40.2 parts by mass of sodium chloride was ion-exchanged. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass of water.
After termination of the association, the core temperature [Y2] was produced by continuing the fusion by heating and stirring for 1 hour at a liquid temperature of 70 ° C. as an aging treatment.

(B) Formation of Shell Layer Next, the dispersion liquid in which the core particles [Y2] are dispersed is brought to 65 ° C., and 96 parts by mass of binder resin fine particles for shell [Y2] are added. An aqueous solution in which 2 parts by mass of the product was dissolved in 1000 parts by mass of ion-exchanged water was added over 10 minutes, and then the temperature was raised to 70 ° C. and stirring was performed for 1 hour. In this manner, the binder resin particles for shell [Y2] were fused to the surface of the core particle [Y2], and then aged at 75 ° C. for 20 minutes to form a shell layer.
Thereafter, an aqueous solution in which 40.2 parts by mass of sodium chloride was dissolved in 1000 parts by mass of ion-exchanged water was added to stop shell formation. Further, the colored particles produced by cooling to 30 ° C. at a rate of 8 ° C./min are filtered, washed repeatedly with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. Toner particles [Y2] having a shell layer formed thereon were produced.

(5) Addition of external additive To toner particles [Y2], hexamethylsilazane-treated silica particles (average primary particle size: 12 nm) 0.6 parts by mass and n-octylsilane-treated titanium dioxide particles (average primary) (Particle size: 24 nm) was added 0.8 part by mass, and a Henschel mixer was used to add an external additive by mixing under a stirring blade peripheral speed of 40 m / sec and a processing temperature of 25 ° C. -1] was obtained. The toner particles [Y2] constituting the yellow toner [B-1] had a volume-based median diameter of 6.6 μm and an average circularity of 0.940. The content of the high melting point wax in the yellow toner [B-1] is 0.3 part by mass with respect to 100 parts by mass of the binder resin.

[Production Example B-2 of Yellow Toner]
In the same manner as in Yellow toner production example B-1, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y2] was changed to “CI Solvent Yellow 93” [B-2] was obtained.

[Production Example B-3 of Yellow Toner]
In the production example B-1 for yellow toner, (2) high melting point wax [1] to be introduced in the second stage polymerization in (2) preparation of core binder resin fine particles [Y2] is used. A yellow toner [B-3] was obtained in the same manner except that

[Production Example B-4 of Yellow Toner]
(1) Preparation of Colorant Fine Particle Dispersion [Y5] 11.5 parts by mass of sodium n-dodecyl sulfate was added to 160 parts by mass of ion-exchanged water, and dissolved and stirred to prepare an aqueous surfactant solution. In this surfactant aqueous solution, 2 parts by weight of oil-soluble dye “CI Solvent Yellow 93” is gradually added as a colorant, and “Clearmix W Motion CLM-0.8” (manufactured by M Technique Co., Ltd.) is added. Dispersion treatment was used to prepare a colorant fine particle dispersion [Y5] in which colorant fine particles are dispersed. The colorant fine particles had a volume-based median diameter of 98 nm.

(2) Preparation of High Melting Point Wax Particle Dispersion [1] After dissolving 20 parts by mass of high melting point wax [2] in 450 parts by mass of ethyl acetate, “AQUALON KH-05” (Daiichi Kogyo Seiyaku Co., Ltd.) 8 After dropping into 750 parts by mass of an aqueous solution containing part by mass (active agent) and stirring, the mixture was emulsified for 300 seconds using “Clearmix W Motion CLM-0.8W” (manufactured by M Technique Co., Ltd.). Thereafter, ethyl acetate was removed under reduced pressure to prepare a high melting point wax particle dispersion [1] in which high melting point wax particles having a volume-based median diameter of 45 nm were dispersed.

(3) Preparation of binder resin fine particles [Y5] for core (a) First stage polymerization An anionic interface represented by the following structural formula (1) in a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device 4 parts by mass of an activator was added together with 3040 parts by mass of ion-exchanged water to prepare an aqueous surfactant solution.
Structural formula (1): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na
A polymerization initiator solution in which 10 parts by mass of potassium persulfate is dissolved in 400 parts by mass of ion-exchanged water is added to the surfactant aqueous solution, and the temperature is raised to 75 ° C. The body mixture was dropped into the reaction vessel over 1 hour.
Styrene 532 parts by mass n-butyl acrylate 200 parts by mass Methacrylic acid 68 parts by mass n-octyl mercaptan 16.4 parts by mass After the above monomer mixture is added dropwise, the system is heated and stirred at 75 ° C. for 2 hours. Polymerization (first stage polymerization) was carried out to prepare a dispersion of resin fine particles [X5]. The resin fine particles [X5] had a weight average molecular weight of 16,400.

(B) Second-stage polymerization A monomer mixed solution composed of the following compounds was introduced into a flask equipped with a stirrer, and subsequently, microcrystalline wax “HNP-0190” (manufactured by Nippon Wax Co., Ltd.) as the main wax. (Melting point 85 ° C.) 93.8 parts by mass was added, and the mixture was heated to 85 ° C. and dissolved to prepare a monomer solution.
Styrene 101.1 parts by mass n-butyl acrylate 62.2 parts by mass Methacrylic acid 12.3 parts by mass n-octyl mercaptan 1.75 parts by mass On the other hand, 3 parts by mass of the anionic surfactant is added to 1560 parts by mass of ion-exchanged water. A dissolved aqueous surfactant solution was prepared and heated to 98 ° C. After adding 32.8 parts by mass (in terms of solid content) of the dispersion of resin fine particles [X5] to this surfactant aqueous solution, and further adding the monomer solution containing the microcrystalline wax, the circulation route is It was mixed and dispersed for 8 hours with a mechanical disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.). An emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm was prepared.
Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to this emulsified particle dispersion, and this system was polymerized by heating and stirring at 98 ° C. for 12 hours. (Second-stage polymerization) was performed to prepare a dispersion of resin fine particles [Z5]. The resin fine particles [Z5] had a weight average molecular weight of 23,000.

(C) Third-stage polymerization A polymerization initiator solution in which 5.45 parts by mass of potassium persulfate was dissolved in 220 parts by mass of ion-exchanged water was added to the resin fine particles [Z5]. A monomer mixture composed of the compound was added dropwise over 1 hour.
Styrene 293.8 parts by mass n-butyl acrylate 154.1 parts by mass n-octyl mercaptan 7.08 parts by mass After completion of the dropwise addition, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization). By cooling to 28 ° C., binder resin fine particles [Y5] for core were produced. The weight average molecular weight of the core binder resin fine particles [Y5] was 26,800.

(4) Preparation of binder resin fine particles [Y5] for shells The monomer mixture used in the first stage polymerization in the preparation of the above (2) binder resin fine particles [Y5] for cores was changed to the following. The binder resin fine particles [Y5] for shells were produced in the same manner except that the polymerization reaction and the treatment after the reaction were performed.
Styrene 624 parts by mass 2-ethylhexyl acrylate 120 parts by mass Methacrylic acid 56 parts by mass n-octyl mercaptan 16.4 parts by mass

(5) Preparation of toner particles [Y5] (a) Formation of core particles In a reaction vessel equipped with a stirring device, a temperature sensor, a cooling pipe, and a nitrogen introducing device,
420.7 parts by mass of a dispersion of core binder resin fine particles [Y5] (solid content conversion)
900 parts by weight of ion-exchanged water 200 parts by weight of the fine colorant dispersion [Y5] 4.5 parts by weight of the high melting point wax particle dispersion [1] was added and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 8-11.
Next, an aqueous solution obtained by dissolving 2 parts by mass of magnesium chloride hexahydrate in 1000 parts by mass of ion-exchanged water was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, the heating was started, and the system was heated to 65 ° C. over 60 minutes to associate the particles. In this state, the particle size of the associated particles was measured using “Multisizer 3” (manufactured by Coulter), and when the volume-based median diameter of the associated particles reached 5.5 μm, 40.2 parts by mass of sodium chloride was ion-exchanged. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass of water.
After the association was stopped, the liquid temperature was set to 70 ° C. as a ripening treatment, and the mixture was heated and stirred for 1 hour to continue the fusion, thereby producing core particles [Y5].

(B) Formation of Shell Layer Next, the dispersion liquid in which the core particles [Y5] are dispersed is brought to 65 ° C., and 96 parts by mass of binder resin fine particles for shell [Y5] are added. An aqueous solution in which 2 parts by mass of the product was dissolved in 1000 parts by mass of ion-exchanged water was added over 10 minutes, and then the temperature was raised to 70 ° C. and stirring was performed for 1 hour. In this manner, the binder resin fine particles for shell [Y5] were fused to the surface of the core particles [Y5], and then aged at 75 ° C. for 20 minutes to form a shell layer.
Thereafter, an aqueous solution in which 40.2 parts by mass of sodium chloride was dissolved in 1000 parts by mass of ion-exchanged water was added to stop shell formation. Further, the colored particles produced by cooling to 30 ° C. at a rate of 8 ° C./min are filtered, washed repeatedly with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. Toner particles [Y5] having a shell layer formed thereon were produced.

(6) Addition of external additive To toner particles [Y5], 0.6 parts by mass of hexamethylsilazane-treated silica particles (average primary particle size: 12 nm) and n-octylsilane-treated titanium dioxide particles (average primary) (Particle size: 24 nm) was added 0.8 part by mass, and a Henschel mixer was used to add an external additive by mixing under a stirring blade peripheral speed of 40 m / sec and a processing temperature of 25 ° C. -4]. The toner particles [Y5] constituting the yellow toner [B-4] had a volume-based median diameter of 6.5 μm and an average circularity of 0.940. In addition, the content of the high melting point wax in the yellow toner [B-4] is 0.3 part by mass with respect to 100 parts by mass of the binder resin.

[Yellow Toner Production Example B-5]
In the production example B-4 of yellow toner, (2) the high melting point wax particle dispersion is obtained by changing the high melting point wax [2] added in the preparation of the high melting point wax particle dispersion [1] to the high melting point wax [4]. A yellow toner [B-5] was obtained in the same manner except that was prepared.

[Yellow Toner Production Example B-6]
In the production example B-4 of yellow toner, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Solvent Yellow 162”, and (5) toner particles [ In the formation of (a) core particles in the preparation of Y5], a yellow toner [B-6] was obtained in the same manner except that the high melting point wax particle dispersion [1] was not added.

[Yellow Toner Production Example B-7]
In the production example B-4 of yellow toner, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Solvent Yellow 162”, and (2) a high melting point wax. A yellow toner [B-7] was obtained in the same manner except that the high melting point wax [2] added in the preparation of the particle dispersion [1] was changed to the high melting point wax [6].

[Magenta Toner Production Example B-1]
In the same manner as in the production example B-1 of yellow toner, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y2] was changed to “CI Pigment Red 81: 4”. Magenta toner [B-1] was obtained.

[Magenta Toner Production Example B-2]
In the production example B-1 of yellow toner, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y2] is changed to “CI Solvent Red 111”, and (B) Magenta toner [B-2] in the same manner except that (b) the high melting point wax [1] introduced in the second stage polymerization is changed to the high melting point wax [3] in the preparation of the resin fine particles [Y2]. ] Was obtained.

[Magenta Toner Production Example B-3]
In the yellow toner production example B-4, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Pigment Red 81: 4”, and (2 ) A magenta toner [B-3] was obtained in the same manner except that the high melting point wax [2] added in the preparation of the high melting point wax particle dispersion [1] was changed to the high melting point wax [4].

[Magenta Toner Production Example B-4]
In the same manner as in yellow toner production example B-4, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Pigment Red 81: 4”. Magenta toner [B-4] was obtained.

[Magenta Toner Production Example B-5]
In the production example B-4 of yellow toner, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Solvent Red 111”, and (5) toner particles [ (5) Magenta toner [B-5] was obtained in the same manner except that the high melting point wax particle dispersion [1] was not added in the formation of the core particles in the preparation of Y5].

[Magenta Toner Production Example B-6]
In the yellow toner production example B-4, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Pigment Red 81: 4”, and (2) high Magenta toner [B-6] was obtained in the same manner except that the high melting point wax [2] added in the preparation of the melting point wax particle dispersion [1] was changed to the high melting point wax [5].

[Cyan Toner Production Example B-1]
In the same manner as in yellow toner production example B-1, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y2] was changed to “CI Solvent Blue 86” [B-1] was obtained.

[Cyan Toner Production Example B-2]
In Production Example B-1 for yellow toner, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y2] was changed to “CI Solvent Blue 199”, and (2) (B) Cyan toner [B-2] except that (b) high melting point wax [1] introduced in the second stage polymerization was changed to high melting point wax [3] ] Was obtained.

[Cyan Toner Production Example B-3]
In the same manner as in yellow toner production example B-4, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Solvent Blue 86” [B-3] was obtained.

[Cyan Toner Production Example B-4]
In the same manner as in yellow toner production example B-4, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Solvent Blue 199” [B-4] was obtained.

[Cyan Toner Production Example B-5]
In the same manner as in yellow toner production example B-4, except that (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] was changed to “CI Solvent Blue 86” [B-5] was obtained.

[Cyan Toner Production Example B-6]
In the production example B-4 of yellow toner, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] is changed to “CI Solvent Blue 199”, and (2) a high melting point wax. A cyan toner [B-6] was obtained in the same manner except that the high melting point wax [2] added in the preparation of the particle dispersion [1] was changed to the high melting point wax [5].

[Cyan Toner Production Example B-7]
In the production example B-4 of yellow toner, (1) the colorant added in the preparation of the colorant fine particle dispersion [Y5] is changed to “CI Solvent Blue 199”, and (2) a high melting point wax. Cyan toner [B-7] was obtained in the same manner except that the high melting point wax [2] added in the preparation of the particle dispersion [1] was changed to the high melting point wax [6].

[Examples of developer preparation]
Yellow toner [A-1] and [B-1] to [B-7], magenta toner [A-1] and [B-1] to [B-6], and cyan toner [A-1] and Each of [B-1] to [B-7] is mixed with a ferrite carrier coated with a silicone resin so that the toner concentration is 8% by mass, whereby yellow developers [A-1] and [B-1] and [B-7] are mixed. B-1] to [B-7], magenta developers [A-1] and [B-1] to [B-6], and cyan developers [A-1] and [B-1] to [B-1] to [B-1] to [B-1] B-7] was prepared.

[Examples 1-9, Comparative Examples 1-3]
Yellow developers [A-1] and [B-1] to [B-7], magenta developers [A-1] and [B-1] to [B-6], and cyan developers [A- 1] and [B-1] to [B-7] are filled into a color image forming apparatus “bizhub C500” (manufactured by Konica Minolta Business Technologies, Inc.) according to the combinations shown in Table 2, and red (R), green A secondary color image of (G) and blue (B) and a black image of process black (PBk) were formed and evaluated for “thin paper separability”.

[Evaluation: Thin paper separability]
Using a commercially available digital copier “bizhub C500” (manufactured by Konica Minolta Business Technologies) as an evaluation machine, remodeling the equipped fixing device, setting the surface temperature of the fixing heat roller to 180 ° C., and an image support A4 image having a belt-like secondary color image and a black image having a width of 5 cm in the conveying direction and 3 mm of the leading edge of the paper with respect to “A4 Kimmari Y (basis weight 52.3 g)” (made by Hokuetsu Paper Co., Ltd.) The separation between the fixing roller on the image side and the image support when transported by the above was determined according to the following evaluation criteria.
○: The image support is separated from the fixing roller without curling.
Δ: The image support is separated from the fixing roller by the separation claw, but the trace of the separation claw is hardly noticeable on the image.
X: The image support is separated from the fixing roller by the separation claw, and a separation claw mark remains on the image or is wound around the fixing roller and cannot be separated from the fixing roller.

40 Image forming apparatus 41 Operation unit 42 Paper feed cassette 43 Paper feed roller 44 Registration roller 45 Paper discharge roller 46 Intermediate transfer members 46A, 46B, 46C Support rollers 47Y, 47M, 47C, 47K Toner cartridge 48 Paper discharge tray 49 Fixing device 50Y , 50M, 50C, 50K Image forming unit 51Y Photoconductor 52Y Charging means 53Y Exposure means 54Y Developing device 57Y Primary transfer means 57A Secondary transfer means 58Y Cleaning means 59 Cleaning means P Image support

Claims (2)

at least,
Forming a toner image (A) using an electrostatic image developing toner (A) containing a binder resin, a colorant comprising an organic pigment, and a wax;
A toner image (B) is produced using a binder resin, a colorant comprising an oil-soluble dye, and an electrostatic image developing toner (B) containing the same wax as the electrostatic image developing toner (A). And forming a process,
In an image forming method of forming an image by performing a step of heat-fixing the toner image (A) and the toner image (B) collectively,
The electrostatic image developing toner (B) contains a high melting point wax of at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2):
The high melting point wax has a melting point higher by 20 ° C. or more than the wax,
The high melting point wax is contained in a proportion of 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the binder resin contained in the toner (B) for developing an electrostatic charge image. An image forming method.
Formula (1): R ¹ —COO—R ²
[In the general formula (1), R ¹ and R ² are linear hydrocarbon groups having 20 to 30 carbon atoms, and may be the same or different from each other. ]
General formula (2): R < ³ > -COO-M
[In the general formula (2), R ³ represents a linear hydrocarbon group having 20 to 30 carbon atoms, and M represents an alkaline earth metal of Ca, Li, or Na, or an alkali metal. ]   The toner for developing an electrostatic charge image (B) contains a high melting point wax of any one of the compound represented by the general formula (1) and the compound represented by the general formula (2). The image forming method according to claim 1.