Resin particles, toner, developer, developer container, method for manufacturing resin particles, method for manufacturing toner, image forming apparatus, and image forming method

Abstract

To provide a resin particle that is excellent in fixability, storage stability, and durability and is environmentally friendly.SOLUTION: A resin particle includes at least a binder resin. The binder resin includes a resin derived from biomass and a resin derived from recycling. The content (mass%) of the resin derived from biomass and the content (mass%) of the resin derived from recycling in the binder resin satisfies the relational expression (1) [the content of the resin derived from recycling>the content of the resin derived from biomass].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to resin particles, toner, developer, developer container, method for producing resin particles, method for producing toner, image forming apparatus, and image forming method. [Background technology]

[0002] Carbon neutrality is generally used to describe biomass materials composed of organic matter. When such biomass materials are burned, carbon dioxide is emitted, but the carbon contained in this carbon dioxide comes from carbon dioxide absorbed from the atmosphere by the biomass materials through photosynthesis during their growth. Therefore, even if biomass materials are used, it is thought that the amount of carbon dioxide in the atmosphere is not increased overall. This property is called carbon neutrality.

[0003] Conventionally, the constituent materials of toner, particularly binder resins, have been almost entirely dependent on fossil resources, and the carbon dioxide generated when toner and printed images are discarded is released into the atmosphere, contributing to global warming, etc. Furthermore, the shift from finite fossil resources to renewable biomass resources can be seen as a shift to sustainable renewable resources, as living organisms are generated from solar energy, water, and carbon dioxide, and is a technology that is highly desired.

[0004] Examples of constituent materials of toner obtained from such renewable resources include release agents such as carnauba wax and candelilla wax. These are blended into toner to impart release properties during fixing, and the blending amount is generally around several percent by mass, so this alone is far from achieving carbon neutrality.

[0005] Furthermore, in recent years, as the population has grown and energy use has expanded, and resources have become depleted, the need for resource conservation, energy conservation, and resource recycling has become increasingly important. Local governments have begun to recycle PET (polyethylene terephthalate) bottles, which are being used for various clothing and containers, and there is also a strong demand for the development of new applications that allow recycled PET to be reused. From this perspective, toner binder resins are manufactured using recovered polyethylene terephthalate as a raw material, and toner containing this (recycled toner) is becoming known.

[0006] Today, there is a strong demand for toners that use biomass-derived resins to improve their environmental friendliness while also improving their functionality as toners. Patent Documents 1 to 5 propose toners that use biodegradable resins, recycled resins, biomass resins, etc. from the viewpoint of environmental protection. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide resin particles suitable for an environmentally friendly toner that is excellent in all of fixability, storage stability, and durability. [Means for solving the problem]

[0008] The present invention for solving the above problems is as described below. Resin particles containing at least a binder resin, The binder resin includes a biomass-derived resin and a recycled resin, Resin particles characterized in that the content (mass %) of the biomass-derived resin in the binder resin and the content (mass %) of the recycled resin satisfy the following relational expression (1): Recycled resin content > Biomass resin content (1) [Effects of the Invention]

[0009] According to the present invention, it is possible to provide resin particles suitable for an environmentally friendly toner that is excellent in all of fixability, storage stability, and durability. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram showing an example of an image forming apparatus according to an embodiment of the present invention. [Figure 2] FIG. 2 is a schematic view showing an example of a process cartridge. DETAILED DESCRIPTION OF THE INVENTION

[0011] The embodiments of the present invention will be described below. (1) The resin particles according to the present invention are Resin particles containing at least a binder resin, The binder resin includes a biomass-derived resin and a recycled resin, The content (mass%) of the biomass-derived resin in the binder resin and the content (mass%) of the recycled resin are Recycled resin content > Biomass resin content (1) Resin particles that satisfy the following relational expression (1). Polyester resin is preferred as the binder resin. To improve the storage stability and durability of polyester resin, it is preferable to use BPA-PO or BPA-EO as the alcohol component to increase toughness. With biomass, the alcohol component becomes plant-derived, and the amount of BPA used decreases, or even disappears altogether, resulting in a decrease in the toughness of polyester resin, as well as a decrease in storage stability and durability. Therefore, recycled resin > biomass-derived resin aims to achieve both fixation, storage stability, and durability. (2) In the resin particles described in (1) above, the content of the recycled resin and the biomass-derived resin in the binder resin is preferably 80% by mass or more. By ensuring that the content is 80% by mass or more, environmental friendliness is improved, and at the same time, fixability, storage stability, and durability can be achieved at the same time. (3) In the resin particles described in (1) or (2) above, the recycled resin is preferably polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT). (4) The resin particles described in any one of the above items (1) to (3) preferably contain a polyester resin, which provides good fixability. (5) The resin particles described in (4) above preferably contain a crystalline polyester resin as the polyester resin. By including a crystalline polyester resin in the resin particles, it is expected that the low-temperature fixability will be improved. (6) The resin particles according to any one of the above items (1) to (5) preferably further contain a colorant and a release agent. (7) The toner of the present invention is used by adding an external additive to the resin particles described in (6) above. (8) The toner described in (7) above can be used as a developer in an image forming apparatus. (9) The developer described in (8) above is used by being contained in a developer container in an image forming apparatus. (10) The method for producing resin particles of the present invention includes a step of mixing a binder resin and / or a binder resin precursor containing at least a biomass-derived resin and a recycled-derived resin, and is characterized in that the content (mass%) of the biomass-derived resin and the content (mass%) of the recycled-derived resin in the binder resin satisfy the following relational expression (1): Recycled resin content > Biomass resin content (1) (11) The method for producing resin particles of the present invention is a method for producing resin particles as described in (10) above, which comprises the following steps: Step a: A step of preparing a solution by dissolving or dispersing a binder resin and / or a binder resin precursor containing at least a biomass-derived resin and a recycled resin, and a colorant in an organic solvent. Step b: adding water to the solution to invert the phase from a water-in-oil dispersion to an oil-in-water dispersion Step c: removing the organic solvent from the oil-in-water dispersion to obtain a fine particle dispersion. Step d: A step of aggregating the fine particles in the fine particle dispersion to obtain aggregated particles. By carrying out the above-described production method, resin particles having improved fixability, storage stability and durability can be obtained. (12) In the method for producing resin particles described in (10) or (11) above, it is preferable that the precursor of the binder resin contains a prepolymer having a functional group capable of reacting with an active hydrogen group. By using a prepolymer, it is expected that the low-temperature fixing property will be improved due to a low Tg, and the hot offset property, storage stability, and durability will be improved due to elongation with an elongator. (13) A toner manufacturing method according to one embodiment of the present invention is a manufacturing method for obtaining a toner by adding an external additive to resin particles obtained by the resin particle manufacturing method described in any one of (10) to (12) above. (14) The image forming method and apparatus of the present invention comprises: an electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier; a developing means for developing the electrostatic latent image to form a visible image using the toner described in (7) or the developer described in (8); a transfer means for transferring the visible image onto a recording medium; a fixing means for fixing the transferred image on the recording medium; The image forming apparatus is characterized by having: (15) The image forming method of the present invention comprises: an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image to form a visible image using the toner described in (7) or the developer described in (8); a transfer step of transferring the visible image onto a recording medium; a fixing step of fixing the transferred image on the recording medium; The image forming method is characterized by comprising the steps of:

[0012] The resin particles, toner, developer, developer container, resin particle manufacturing method, toner manufacturing method, image forming apparatus, and image forming method according to the present invention will be described below with reference to the drawings. Note that the present invention is not limited to the following embodiments, and can be modified within the scope of what a person skilled in the art can conceive, such as other embodiments, additions, modifications, and deletions, and any embodiment is within the scope of the present invention as long as it exhibits the functions and effects of the present invention.

[0013] As described above, the resin particles of the present invention can be obtained by a production method including the following steps a to d. Step a: A step of preparing a solution by dissolving or dispersing at least a binder resin and / or a precursor of the binder resin and a colorant in an organic solvent. Step b: adding water to the solution to invert the phase from a water-in-oil dispersion to an oil-in-water dispersion Step c: removing the organic solvent from the oil-in-water dispersion to obtain a fine particle dispersion. Step d: A step of aggregating the fine particles in the fine particle dispersion to obtain aggregated particles. The above steps and the materials used in these steps will be described below.

[0014] [Step a] (oil phase preparation step) Step a is a step of preparing a solution by dissolving or dispersing at least a binder resin and / or a precursor of the binder resin and a colorant in an organic solvent. In the production method of the present invention, an oil phase is first prepared by dissolving or dispersing a resin, a colorant, a prepolymer, etc. in an organic solvent. To prepare the oil phase, the resin, the colorant, etc. are gradually added to the organic solvent while stirring, and dissolved or dispersed. Known dissolving or dispersing means can be used, such as a dispersing machine such as a bead mill or a disk mill. The materials used in the oil phase preparation step will be described.

[0015] The resin particles of the present invention are suitable for use as a toner, which can be obtained by adding an external additive to toner base particles made of resin particles. The resin particles of the present invention will be described below by taking toner, which is an embodiment of the resin particles of the present invention, as an example.

[0016] (environmentally friendly resin) In the present invention, biomass-derived resins and recycled resins are sometimes referred to as environmentally friendly resins. -Biomass-derived resin- Biomass-derived resins are resins that contain plant-derived compounds as raw materials. By adjusting the ratio of petroleum-derived and plant-derived alcohol and acid components, it is possible to adjust the environmental friendliness and toner quality.

[0017] The toner contains a radioactive carbon isotope. 14 C concentration (hereinafter referred to as “ 14 The concentration of the soluble fatty acid (sometimes referred to as "C concentration") must be 10.8 pMC or more, and preferably 20 pMC or more. 14 If the C concentration is less than 10.8 pMC, the biomass level is generally low and the object of the present invention may not be achieved. The aforementioned 14 The C concentration is expressed as the biomass degree using the following formula: Biomass ratio (%) = 14 C concentration (pMC)×0.935

[0018] The aforementioned 14 A carbon concentration of 10.8 pMC or more means that the biomass ratio is 10% or more, which is a concentration desired from the standpoint of carbon neutrality. In order to achieve the biomass content of 10% or more, it is necessary to consider biomass not only for the wax in the toner but also for the binder resin, and this is the most important point in constituting the present invention.

[0019] The aforementioned 14 There are no particular limitations on the method for measuring the C concentration, and it can be selected appropriately depending on the purpose, but radiocarbon dating is particularly preferred. The measurement procedure is as follows. First, the toner is burned, and the CO2 (carbon dioxide) is reduced to obtain C (graphite). 14 The carbon concentration is measured by AMS (Accelerator Mass Spectroscopy). Measurement by AMS is disclosed in, for example, Japanese Patent No. 4050051.

[0020] The aforementioned 14 C exists in nature (in the atmosphere), and while plants are active, it is taken up into the plants through photosynthesis and 14 C concentrations exist in the atmosphere 14 However, from the stage when plants cease to function, the carbon dioxide produced by photosynthesis is released. 14 The uptake of C stops, 14 According to the half-life of C, 5730 years 14 The C concentration decreases. Fossil resources derived from living organisms are those that have been around for tens of thousands to hundreds of millions of years since life ceased. 14 C concentration is barely detectable.

[0021] -Recycled resin- Recycled resins include PP (polypropylene), PE (polyethylene), PS (polystyrene), ABS (acrylonitrile butadiene styrene), PET (polyethylene terephthalate), and PBT (polybutylene terephthalate). Among these, PET (polyethylene terephthalate) and PBT (polybutylene terephthalate) are particularly preferable as toner materials. PET (polyethylene terephthalate) and PBT (polybutylene terephthalate) are recycled materials processed into flakes with a weight-average molecular weight (Mw) of approximately 30,000 to 100,000. However, there are no restrictions on the molecular weight distribution, composition, manufacturing method, or form of use of PET and PBT. Furthermore, there is no restriction on recycled materials; off-spec fiber waste or pellets can also be used. By adjusting the ratio of recycled PET used during polyester resin synthesis, it is possible to adjust the environmental friendliness ratio and toner quality.

[0022] In order to adjust the environmentally friendly ratio, it is preferable to use plant-derived alcohol and acid components as the amorphous polyester resin B used in the present invention. At the same time, it is preferable to use a polyester resin synthesized from PET (polyethylene terephthalate) and PBT (polybutylene terephthalate).

[0023] It is preferable to use propylene glycol as the plant-derived alcohol component and terephthalic acid or succinic acid as the acid component, but there is no particular limitation thereto, and any component may be used as long as it is plant-derived.

[0024] The content of recycled resin in the binder resin is preferably 55% to 95% by mass, more preferably 60% to 90% by mass. If the recycled resin content is less than 55% by mass, high-temperature fixability, storage stability, and durability may not be ensured. If a petroleum-based resin is used to ensure these properties, the environmental friendliness ratio cannot be increased. If the recycled resin content exceeds 95% by mass, low-temperature fixability may not be ensured.

[0025] The content of biomass-derived resin in the binder resin is preferably 5% to 45% by mass, more preferably 10% to 40% by mass. If the biomass-derived resin content is less than 5% by mass, petroleum-based resin must be used to ensure low-temperature fixability, but the environmental friendliness ratio cannot be increased. If the content exceeds 45% by mass, high-temperature fixability, storage stability, and durability may not be ensured. If petroleum-based resin is used to ensure these properties, the environmental friendliness ratio cannot be increased.

[0026] The ratio of the content of the recycled resin to the content of the biomass-derived resin in the binder resin is preferably recycled resin:biomass-derived resin=95:5 to 55:45, more preferably 90:10 to 60:40. If the recycled resin content is less than 55%, high-temperature fixability, storage stability, and durability may not be guaranteed. If petroleum-based resin is used to ensure these properties, the environmental friendliness ratio cannot be increased. If it exceeds 95, low-temperature fixability may not be guaranteed. If the biomass-derived resin ratio is less than 5, petroleum-based resin must be used to ensure low-temperature fixability, but the eco-friendliness ratio cannot be increased. If it exceeds 45, high-temperature fixability, storage stability, and durability may not be ensured. If petroleum-based resin is used to ensure these properties, the eco-friendliness ratio cannot be increased.

[0027] (polyester resin) When used as a toner for developing electrostatic latent images in electrophotography, good fixing properties can be obtained by using a resin having a polyester skeleton. Examples of resins having a polyester skeleton include polyester resins and block polymers of polyester resins and resins having other skeletons, but the use of polyester resins is preferred because the resulting colored resin particles are more uniform.

[0028] Examples of polyester resins include ring-opening polymers of lactones, condensation polymers of hydroxycarboxylic acids, and condensation polymers of polyols and polycarboxylic acids, with condensation polymers of polyols and polycarboxylic acids being preferred from the viewpoint of design freedom.

[0029] The weight average molecular weight of the polyester resin is usually 1000 to 30000, preferably 3000 to 15000, and more preferably 5000 to 12000. If it is less than 1000, the heat-resistant storage stability deteriorates, and if it exceeds 30000, the low-temperature fixability of the toner for developing electrostatic latent images deteriorates.

[0030] The glass transition temperature of the polyester resin is preferably in the range of 35°C to 80°C, more preferably 40°C to 70°C, and even more preferably 45°C to 65°C. If the temperature is lower than 35°C, the resulting colored resin particles may deform when placed in a high-temperature environment such as midsummer, or the colored resin particles may stick together and not be able to behave as intended. If the temperature is higher than 80°C, the fixing ability of the colored resin particles may deteriorate when used as a toner for developing electrostatic latent images.

[0031] <Polyol> The polyol (1) includes a diol (1-1) and a trihydric or higher polyol (1-2), and (1-1) alone or a mixture of (1-1) and a small amount of (1-2) is preferred.

[0032] Examples of the diol (1-1) include the following. Alkylene glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.);

[0033] Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols; 4,4'-dihydroxybiphenyls such as 3,3'-difluoro-4,4'-dihydroxybiphenyl; bis(hydroxyphenyl)alkanes such as bis(3-fluoro-4-hydroxyphenyl)methane, 1-phenyl-1,1-bis(3-fluoro-4-hydroxyphenyl)ethane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 2,2-bis(3,5-difluoro-4-hydroxyphenyl)propane (also known as tetrafluorobisphenol A), and 2,2-bis(3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane; bis(4-hydroxyphenyl)ethers such as bis(3-fluoro-4-hydroxyphenyl)ether; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols

[0034] Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferred, and alkylene oxide adducts of bisphenols and their combined use with alkylene glycols having 2 to 12 carbon atoms are particularly preferred.

[0035] Examples of the trihydric or higher polyol (1-2) include trihydric to octahydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.); and alkylene oxide adducts of the above trihydric or higher polyphenols.

[0036] <Polycarboxylic acid> The polycarboxylic acid (2) may be a dicarboxylic acid (2-1) or a tri- or higher carboxylic acid (2-2). A dicarboxylic acid (2-1) alone or a mixture of a dicarboxylic acid (2-1) and a small amount of a tri- or higher carboxylic acid (2-2) is preferred.

[0037] Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5-trifluoroisophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5-trifluoroisophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5-trifluoroisophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroiso ...2,3,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroisophthalic acid, Examples include methylisophthalic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-biphenyldicarboxylic acid, 3,3'-bis(trifluoromethyl)-4,4'-biphenyldicarboxylic acid, 2,2'-bis(trifluoromethyl)-3,3'-biphenyldicarboxylic acid, hexafluoroisopropylidenediphthalic anhydride, etc. Among these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

[0038] Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.). The polycarboxylic acid (2) may be an acid anhydride or a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned compounds, which may be reacted with the polyol (1). The ratio of polyol to polycarboxylic acid, expressed as the equivalent ratio [OH] / [COOH] of hydroxyl groups [OH] to carboxyl groups [COOH], is usually 2 / 1 to 1 / 2, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.3 / 1 to 1 / 1.3.

[0039] (coloring agent)Known dyes and pigments can be used as the colorant in the present invention, for example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ochre, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Balkan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, and isoindolinone. Yellow, red iron oxide, red lead, vermilion lead, cadmium red, cadmium mercury red, antimony vermilion, permanent red 4R, para red, faise red, parachlor orthonitroaniline red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, permanent red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belcan Fast Rubin B, Brilliant Scarlet G, Lithol Rubin GX, permanent red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Prussian Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake,Phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, lithopone, and mixtures thereof can be used.

[0040] (organic solvent) The organic solvent is preferably volatile and has a boiling point of less than 100°C, which facilitates subsequent removal of the organic solvent. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, and isopropyl alcohol, which can be used alone or in combination. When the resin to be dissolved or dispersed in the organic solvent is a resin having a polyester skeleton, it is preferable to use an ester-based solvent such as methyl acetate, ethyl acetate, or butyl acetate, or a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone, as these solvents have high solubility. Among these, methyl acetate, ethyl acetate, and methyl ethyl ketone are particularly preferred, as they are easy to remove from the solvent.

[0041] (prepolymer) Examples of the prepolymer (reactive precursor) include polyesters having a group capable of reacting with an active hydrogen group. Examples of the group capable of reacting with an active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. Among these, an isocyanate group is preferred because it can introduce a urethane bond or a urea bond into the amorphous polyester resin.

[0042] The prepolymer may have a branched structure imparted by at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. Examples of the polyester resin containing an isocyanate group include a reaction product of a polyester resin having an active hydrogen group with a polyisocyanate. The polyester resin having an active hydrogen group can be obtained, for example, by condensation polymerization of a diol, a dicarboxylic acid, and at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin containing an isocyanate group.

[0043] Examples of the diol include aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylolpropanediol; Examples of suitable diols include diols having an oxyalkylene group such as ethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide have been added; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; and alkylene oxide adducts of bisphenols, such as bisphenols to which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide have been added. Among these, from the viewpoint of controlling the glass transition temperature of the polyester resin to 20° C. or lower, it is preferable to use aliphatic diols having 3 to 10 carbon atoms, such as 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, and 3-methyl-1,5-pentanediol, and it is more preferable to use such diols in an amount of 50 mol% or more of the alcohol component in the resin. These diols may be used alone or in combination of two or more.

[0044] The polyester resin is preferably an amorphous resin, and by providing steric hindrance to the resin chain, the melt viscosity during fixing is reduced, making it easier to achieve low-temperature fixability. For this reason, the main chain of the aliphatic diol preferably has a structure represented by the following general formula (1):

[0045] [ka] [In the formula, R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an odd number from 3 to 9. However, in the n repeating units, R1 and R2 may be the same or different.]

[0046] Here, the main chain of the aliphatic diol in the present invention refers to the carbon chain that connects two hydroxyl groups of the aliphatic diol with the shortest number of carbon atoms. The main chain preferably has an odd number of carbon atoms, since the odd-even nature of the main chain reduces crystallinity. Furthermore, the main chain preferably has at least one alkyl group having 1 to 3 carbon atoms in the side chain, since the interaction energy between the main chain molecules is reduced due to the stericity.

[0047] Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid; and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Furthermore, anhydrides, lower (C1 to C3) alkyl esters, and halides of these may also be used. Among these, from the viewpoint of controlling the Tg of the polyester resin to 20°C or less, aliphatic dicarboxylic acids having from 4 to 12 carbon atoms are preferred, and it is more preferred to use them in an amount of 50% by mass or more of the carboxylic acid components in the resin. These dicarboxylic acids may be used alone or in combination of two or more.

[0048] Examples of the trihydric or higher alcohols include trihydric or higher aliphatic alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol; trihydric or higher polyphenols such as trisphenol PA, phenol novolac, and cresol novolac; and alkylene oxide adducts of trihydric or higher polyphenols, such as those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trihydric or higher polyphenols.

[0049] Examples of the trivalent or higher carboxylic acid include trivalent or higher aromatic carboxylic acids, and particularly preferred are trivalent or higher aromatic carboxylic acids having 9 to 20 carbon atoms, such as trimellitic acid and pyromellitic acid. Furthermore, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, and halides of these may also be used.

[0050] Examples of the polyisocyanate include diisocyanates and tri- or higher valent isocyanates. The polyisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or more functional group], Phosgenates of the above polyamines and their mixtures: polyallyl polyisocyanate (PAPI), aromatic diisocyanates such as 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Aliphatic diisocyanates such as isocyanates, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate; isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanato Examples of the diisocyanate include alicyclic diisocyanates such as m- and p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI); trivalent or higher polyisocyanates such as lysine triisocyanate and diisocyanate-modified products of trivalent or higher alcohols; and modified products of these isocyanates, and mixtures of two or more of these may also be used.Examples of the modified isocyanate include modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, and an oxazolidone group.

[0051] (Charge control agent) A charge control agent or the like may be added to the oil phase. Any known charge control agent can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compounds, tungsten simple substance or compounds, fluorine-based activators, metal salicylate, and metal salts of salicylic acid derivatives. Specifically, these include the nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, the salicylic acid metal complex E-84, and the phenol condensate E-89 (all manufactured by Orient Chemical Industry Co., Ltd.), the quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.), the quaternary ammonium salt Copy Charge PSY VP2038, the triphenylmethane derivative Copy Blue PR, and the quaternary ammonium salt Copy Charge NEG VP2036 and Copy Charge NX. Examples of suitable charge control agents include VP434 (manufactured by Hoechst), LRA-901, the boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. The charge control agent may be used in an amount that allows the agent to exhibit its performance without interfering with fixability, etc., and is contained in the toner in an amount of 0.5 to 5% by mass, and preferably 0.8 to 3% by mass.

[0052] [Step b] (Phase inversion emulsification step) Step b is a step of adding water to the solution obtained in step a to invert the phase from a water-in-oil dispersion to an oil-in-water dispersion. In the present invention, the oil phase is neutralized with ammonia water or the like, and then ion-exchanged water is added thereto to obtain a microparticle dispersion by phase inversion emulsification, which inverts the phase from a water-in-oil dispersion to an oil-in-water dispersion.

[0053] [Step c] (solvent removal step) Step c is a step of removing the organic solvent from the oil-in-water dispersion obtained in step b to obtain a fine particle dispersion. In order to remove the organic solvent from the fine particle dispersion, a method can be employed in which the temperature of the entire system is gradually increased while being stirred, and the organic solvent in the droplets is completely evaporated and removed. Alternatively, the resulting microparticle dispersion can be sprayed into a dry atmosphere while stirring to completely remove the organic solvent from the droplets. Alternatively, the microparticle dispersion can be stirred while reducing the pressure to evaporate and remove the organic solvent. The latter two methods can be used in combination with the first method.

[0054] The drying atmosphere in which the fine particle dispersion is sprayed is generally a gas such as air, nitrogen, carbon dioxide, or a heated combustion gas, particularly a gas stream heated to a temperature equal to or higher than the boiling point of the highest boiling point solvent used. The desired quality can be obtained sufficiently by short-term treatment using a spray dryer, belt dryer, rotary kiln, or the like. By the above method, a fine particle dispersion can be obtained.

[0055] [Process d] (Agglutination process) Step d is a step of aggregating the fine particles in the fine particle dispersion obtained in step c to obtain aggregated particles. The microparticle dispersion is agitated and aggregated until the desired particle size is reached. Conventional methods, such as adding a flocculant or adjusting the pH, can be used to aggregate the particles. When adding the flocculant, it may be added directly, but it is preferable to use an aqueous solution of the flocculant, as this can prevent localized high concentrations. It is also preferable to gradually add the flocculating salt while monitoring the particle size of the aggregated particles.

[0056] The temperature of the dispersion during aggregation is preferably near the Tg of the resin used. If the liquid temperature is too low, aggregation does not proceed very well, resulting in poor efficiency, while if the liquid temperature is too high, the aggregation rate increases, resulting in the generation of coarse particles and a deterioration in particle size distribution.

[0057] When the target particle size is reached, aggregation is stopped by adding a salt or chelating agent with a low ionic valence, adjusting the pH, lowering the temperature of the dispersion, or adding a large amount of aqueous medium to dilute the concentration. By the above method, a dispersion of aggregated particles can be obtained.

[0058] In the aggregation step, wax may be added as a release agent, or a crystalline resin may be added to improve low-temperature fixability. In this case, a dispersion of wax dispersed in an aqueous medium or a dispersion of a crystalline resin may be prepared, and mixed with the fine particle dispersion, followed by aggregation, to obtain aggregated particles in which the wax or crystalline resin is uniformly dispersed.

[0059] The flocculant, wax and crystalline resin will be explained below.

[0060] (flocculant) Known flocculants can be used, such as metal salts of monovalent metals such as sodium and potassium, metal salts of divalent metals such as calcium and magnesium, and metal salts of trivalent metals such as iron and aluminum. By adding a metal salt as a flocculant, the metal ions act as a metal crosslinking agent, crosslinking the polymer chains and causing agglomeration. Metal crosslinking by the metal crosslinking agent is expected to improve hot offset resistance, storage stability, and durability.

[0061] (wax) The wax is not particularly limited and can be appropriately selected depending on the purpose, but a low-melting release agent with a melting point of 50° C. to 120° C. is preferred. The low-melting release agent, when dispersed in the resin, effectively acts as a release agent between the fixing roller and the toner interface, thereby improving hot offset resistance even in an oil-less system (where a release agent such as oil is not applied to the fixing roller).

[0062] Suitable examples of release agents include waxes. Examples of waxes include natural waxes such as plant-based waxes (e.g., carnauba wax, cotton wax, Japan wax, and rice wax); animal-based waxes (e.g., beeswax and lanolin); mineral waxes (e.g., ozokerite and cerusine); and petroleum waxes (e.g., paraffin, microcrystalline wax, and petrolatum). In addition to these natural waxes, synthetic hydrocarbon waxes (e.g., Fischer-Tropsch wax and polyethylene wax); synthetic waxes (e.g., esters, ketones, and ethers); and other synthetic waxes. Other examples include fatty acid amides (e.g., 12-hydroxystearic acid amide, stearic acid amide, phthalimide anhydride, and chlorinated hydrocarbons); low-molecular-weight crystalline polymer resins (e.g., polyacrylate homopolymers or copolymers such as poly-n-stearyl methacrylate and poly-n-lauryl methacrylate) (e.g., n-stearyl acrylate-ethyl methacrylate copolymers); and crystalline polymers having long alkyl groups in their side chains. These may be used alone or in combination of two or more.

[0063] The melting point of the wax is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 50° C. to 120° C., and more preferably from 60° C. to 90° C. A melting point of 50° C. or higher can prevent the wax from adversely affecting heat-resistant storage stability, while a melting point of 120° C. or lower can effectively prevent the problem of cold offset occurring during fixation at low temperatures.

[0064] The melt viscosity of the wax, measured at a temperature 20° C. higher than the melting point of the wax, is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps. A melt viscosity of 5 cps or higher can prevent a decrease in releasability, while a melt viscosity of 1,000 cps or lower can fully exhibit the effects of hot offset resistance and low-temperature fixability.

[0065] The wax content in the toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0% by mass to 40% by mass, more preferably 3% by mass to 30% by mass. If the wax content is 40% by mass or less, deterioration of the toner flowability can be prevented.

[0066] (Crystalline polyester resin) Crystalline polyester resins are obtained from polyhydric alcohols and polycarboxylic acids such as polycarboxylic acids, polycarboxylic anhydrides, and polycarboxylic esters, or derivatives thereof. Note that, in the present invention, the crystalline polyester resin refers to a resin obtained using a polyhydric alcohol and a polycarboxylic acid such as polycarboxylic acids, polycarboxylic anhydrides, and polycarboxylic esters, or derivatives thereof, as described above, and modified polyester resins, such as prepolymers and resins obtained by subjecting the prepolymers to crosslinking and / or elongation reactions, do not fall under the category of crystalline polyester resins.

[0067] <<Polyhydric alcohol>> The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples include diols and trihydric or higher alcohols. Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferred, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferred. If the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may decrease, resulting in a lower melting point. Furthermore, if the saturated aliphatic diol has more than 12 carbon atoms, it may be difficult to obtain a practical material.

[0068] Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosanedecanediol, etc. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred in terms of the high crystallinity and excellent sharp melt properties of the crystalline polyester resin. Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. These may be used alone or in combination of two or more.

[0069] <<Polycarboxylic Acids>> The polycarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples include dicarboxylic acids and tricarboxylic or higher carboxylic acids. Examples of the dicarboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid. Further examples include anhydrides of these compounds and lower (C1 to C3) alkyl esters of these compounds.

[0070] Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc., as well as anhydrides thereof and lower (C1 to C3) alkyl esters thereof, etc. These may be used alone or in combination of two or more.

[0071] The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. This results in high crystallinity and excellent sharp melting properties, allowing for excellent low-temperature fixability. One method for controlling the crystallinity and softening point of the crystalline polyester resin is to design and use a non-linear polyester obtained by condensation polymerization of a trivalent or higher polyhydric alcohol such as glycerin as the alcohol component or a trivalent or higher polycarboxylic acid such as trimellitic anhydride as the acid component during polyester synthesis.

[0072] The molecular structure of the crystalline polyester resin of the present invention can be confirmed by NMR measurement of a solution or a solid, as well as X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., but it can be easily confirmed by infrared absorption spectroscopy at 965±10 cm -1 Or 990±10cm -1Examples include those that have absorption based on the δCH (out-of-plane bending vibration) of olefins.

[0073] Regarding the molecular weight, from the viewpoint that those with a sharp molecular weight distribution and a low molecular weight have excellent low-temperature fixability, and that a large amount of low-molecular-weight components deteriorates heat-resistant storage stability, extensive research has revealed that, in the molecular weight distribution by GPC of the o-dichlorobenzene soluble fraction, the peak position in a molecular weight distribution diagram with the horizontal axis being log(M) and the vertical axis being weight % is in the range of 3.5 to 4.0, the half-width of the peak is 1.5 or less, the weight average molecular weight (Mw) is 3,000 to 30,000, the number average molecular weight (Mn) is 1,000 to 10,000, and Mw / Mn is 1 to 10. It is further preferred that the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and Mw / Mn is 1-5.

[0074] From the viewpoint of affinity between paper and resin, the acid value of the crystalline polyester resin is preferably 5 mgKOH / g or more to achieve the desired low-temperature fixability, and more preferably 7 mgKOH / g or more to prepare fine particles by phase inversion emulsification, while 45 mgKOH / g or less is preferred to improve hot offset resistance. Furthermore, the hydroxyl value of the crystalline polymer is preferably 0 mgKOH / g or more and 50 mgKOH / g or less, more preferably 5 mgKOH / g or more and 50 mgKOH / g or less, to achieve the desired low-temperature fixability and good charging characteristics.

[0075] (fusion process) Next, the resulting aggregated particles are fused by heat treatment to reduce the irregularities. Fusion can be achieved by heating the dispersion of the aggregated particles while stirring. The temperature of the dispersion is preferably near a temperature above the Tg of the resin used.

[0076] (Washing and drying process) The toner particle dispersion obtained by the above method contains, in addition to toner particles, secondary materials such as coagulating salts, and therefore washing is performed to extract only the toner particles from the dispersion. Methods for washing toner particles include centrifugation, vacuum filtration, and filter press, but the method is not particularly limited in the present invention. A cake of toner particles can be obtained by any of these methods, but if the toner particles cannot be sufficiently washed in one operation, the obtained cake can be dispersed again in an aqueous solvent to form a slurry, and the process of extracting the toner particles by any of the above methods can be repeated. Alternatively, if washing is performed by vacuum filtration or filter press, a method can be used in which the aqueous solvent is passed through the cake to wash out the secondary materials absorbed by the resin particles. The aqueous solvent used for this washing is water or a mixed solvent of water and an alcohol such as methanol or ethanol, but considering the cost and the environmental load due to wastewater treatment, it is preferable to use water.

[0077] Since the washed toner particles contain a large amount of aqueous medium, they can be dried to remove the aqueous medium and obtain only the toner particles. Drying methods that can be used include dryers such as spray dryers, vacuum freeze dryers, reduced-pressure dryers, stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers, and agitator dryers. It is preferable to dry the dried toner particles until the moisture content is less than 1%. If the dried resin particles are soft and agglomerated, which can cause inconvenience during use, they may be crushed using a device such as a jet mill, Henschel mixer, super mixer, coffee mill, Oster blender, or food processor to loosen the agglomerates.

[0078] (Annealing process) When a crystalline resin is added, annealing the toner after drying causes phase separation between the amorphous and crystalline resins, improving fixability. Specifically, this can be achieved by storing the toner at a temperature near its Tg for 10 hours or more.

[0079] (External addition process) In order to impart fluidity, chargeability, cleaning properties, etc. to the toner particles obtained in the present invention, inorganic fine particles, polymeric fine particles, cleaning aids, etc. may be added or mixed. Specific mixing methods include applying an impact force to the mixture with blades rotating at high speed, or throwing the mixture into a high-speed air current, accelerating it, and causing the particles or composite particles to collide with an appropriate collision plate. Examples of equipment include an Ang Mill (manufactured by Hosokawa Micron Corporation), a modified I-type Mill (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) with reduced grinding air pressure, a Hybridization System (manufactured by Nara Machinery Works, Ltd.), a Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

[0080] (external additives) The primary particle diameter of the inorganic fine particles is preferably 5 nm or more and 2 μm or less, and more preferably 5 nm or more and 500 nm or less. 2 / g or more 500m 2 / g or less. The proportion of these inorganic fine particles used is preferably 0.01 to 5% by mass of the toner. Specific examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

[0081] Examples of polymeric fine particles include polymer particles made of polystyrene, methacrylate ester or acrylate ester copolymers obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, or nylon, and thermosetting resins.

[0082] Such fluidizing agents can be surface-treated to increase their hydrophobicity and prevent deterioration of flow properties and charging properties even under high humidity. Examples of preferred surface treatment agents include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils.

[0083] Examples of cleaning improvers for removing the developer remaining on the photosensitive member or primary transfer medium after transfer include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, and polymer fine particles produced by soap-free emulsion polymerization of, for example, polymethyl methacrylate fine particles, polystyrene fine particles, etc. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

[0084] (developer) The developer of the present invention contains the toner of the present invention. The developer may be used as a single-component developer, or may be mixed with a carrier and used as a two-component developer. In particular, when used in high-speed printers that respond to recent improvements in information processing speed, the two-component developer is preferred in terms of extended life, etc. In the case of the one-component developer using the toner, even if the toner is balanced, there is little fluctuation in the particle size of the toner, and there is no toner filming on the developing roller or toner fusion to layer thickness regulating members such as blades for thinning the toner layer, and good and stable developability and images can be obtained even with long-term use (stirring) of the developing means. Furthermore, in the case of the two-component developer using the toner, even if the toner is balanced over a long period of time, there is little fluctuation in the toner particle size in the developer, and good and stable developability can be obtained even with long-term stirring in the developing means. The developer of the present invention can also be used as a replenishing developer.

[0085] <Career> The carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably one having a core material and a resin layer covering the core material.

[0086] (Developer container) The developer container for containing the developer of the present invention is not particularly limited and can be appropriately selected from known containers, for example, those having a container body and a cap. The size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably cylindrical or the like. In particular, it is preferable that spiral irregularities are formed on the inner peripheral surface so that the developer content can be transferred to the discharge port side by rotation, and that some or all of the spiral irregularities have a bellows function. It is also preferable that the material has good dimensional accuracy. Examples of such materials include resin materials such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin component ABS resin, and polyacetal resin.

[0087] The developer storage container is easy to store, transport, and handle, and can be detachably attached to a process cartridge, an image forming apparatus, or the like, which will be described later, and used to replenish the developer.

[0088] Next, regarding one embodiment of the method for forming an image using the image forming apparatus of the present invention, The description will be made with reference to Figure 1. Although a printer is shown as an example of the image forming apparatus of this embodiment, the image forming apparatus is not particularly limited as long as it is capable of forming an image using toner, such as a copier, facsimile, or multifunction machine. The image forming apparatus includes a paper feed unit 210, a conveying unit 220, an image forming unit 230, a transfer unit 240, and a fixing unit 250. The paper feed section 210 includes a paper feed cassette 211 in which the paper P to be fed is stacked, and a paper feed roller 212 that feeds the paper P stacked in the paper feed cassette 211 one sheet at a time.

[0089] The conveying section 220 includes a roller 221 that conveys the paper P fed by the paper feed roller 212 toward the transfer section 240, a pair of timing rollers 222 that hold the leading end of the paper P conveyed by the roller 221 and wait, sending the paper to the transfer section 240 at a predetermined timing, and a paper discharge roller 223 that discharges the paper P with the fixed color toner image onto a paper discharge tray 224.

[0090] The image forming section 230 includes, at predetermined intervals from left to right in the figure, an image forming unit Y that forms an image using a developer containing yellow toner, an image forming unit C that uses a developer containing cyan toner, an image forming unit M that uses a developer containing magenta toner, an image forming unit K that uses a developer containing black toner, and an exposure device 233. It should be noted that when referring to any of the image forming units (Y, C, M, K), it is referred to as an image forming unit.

[0091] The developer contains toner and carrier. Four image forming units (Y, C, M, K) differ only in the developer used, but the mechanical configuration is essentially the same.

[0092] The transfer unit 240 includes a drive roller 241 and a driven roller 242, an intermediate transfer belt 243 that can rotate counterclockwise in the figure as the drive roller 241 is driven, primary transfer rollers (244Y, 244C, 244M, 244K) that are arranged opposite the photosensitive drum 231 across the intermediate transfer belt 243, and secondary opposing rollers 245 and 246 that are arranged opposite each other across the intermediate transfer belt 243 at the position where the toner image is transferred to the paper.

[0093] The fixing unit 250 has a heater installed inside and is equipped with a fixing belt 251 that heats the paper P, and a pressure roller 252 that forms a nip by rotatably applying pressure to the fixing belt 251. This applies heat and pressure to the color toner image on the paper P, fixing the color toner image. The paper P with the fixed color toner image is discharged to a paper discharge tray 224 by a paper discharge roller 223, completing the series of image formation processes.

[0094] (Process cartridge) The process cartridge according to the present invention is molded so as to be detachably mountable to various image forming apparatuses, and includes at least an electrostatic latent image carrier that carries an electrostatic latent image, and developing means that develops the electrostatic latent image carried on the electrostatic latent image carrier with the developer of the present invention to form a toner image. The process cartridge according to the present invention may further include other means, if necessary.

[0095] The developing means includes at least a developer container that contains the developer of the present invention and a developer carrier that carries and transports the developer contained in the developer container. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

[0096] 2 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes the photosensitive drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90. [Example]

[0097] Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the following description, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0098] <Synthesis of Ketimine Compounds> A reaction vessel equipped with a stirrer and a thermometer was charged with 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone, and the mixture was reacted at 50°C for 5 hours to obtain a ketimine compound. The amine value of the ketimine compound was 418 mg KOH / g.

[0099] <Synthesis of Prepolymer A> 3-methyl-1,5-pentanediol, isophthalic acid, and plant-derived sebacic acid were added to a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet tube, along with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the hydroxyl to carboxyl molar ratio (OH / COOH) was 1.1, the diol component was 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component was 66 mol% isophthalic acid and 34 mol% sebacic acid, and the amount of trimethylolpropane in the total monomers was 1.5 mol%. The temperature was then raised to 200°C over approximately 4 hours, then to 230°C over 2 hours, and the reaction was continued until no water was discharged. The reaction was then continued for another 5 hours under a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester A].

[0100] Next, the obtained [intermediate polyester A] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [prepolymer A].

[0101] <Synthesis of amorphous polyester resin B-1> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, flake-shaped recycled PET, plant-derived propylene glycol, petroleum-derived bisphenol A ethylene oxide 2 mole adduct, plant-derived terephthalic acid, and petroleum-derived adipic acid were added, and the molar ratio of the flake-shaped recycled PET (ethylene glycol unit unit) to the plant-derived propylene glycol and bisphenol A ethylene oxide 2 mole adduct was 32 / 21 / 47, and the flake-shaped recycled PET (terephthalic acid The resin was charged with plant-derived terephthalic acid and adipic acid in a molar ratio of 32 / 21 / 47, with a molar ratio of hydroxyl groups to carboxyl groups of OH / COOH of 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at normal pressure and 230°C for 8 hours. After further reacting for 4 hours at a reduced pressure of 10 to 15 mmHg, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and the reaction was continued at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-1].

[0102] <Synthesis of amorphous polyester resin B-2> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, flake-shaped recycled PET, plant-derived propylene glycol, petroleum-derived bisphenol A ethylene oxide 2 mole adduct, plant-derived terephthalic acid, and petroleum-derived adipic acid were added, and the molar ratio of the flake-shaped recycled PET (ethylene glycol unit unit) to the plant-derived propylene glycol and bisphenol A ethylene oxide 2 mole adduct was 51 / 30 / 19, and the flake-shaped recycled PET (terephthalic acid The resin was charged with plant-derived terephthalic acid and adipic acid in a molar ratio of 51 / 30 / 19, with a molar ratio of hydroxyl groups to carboxyl groups of OH / COOH of 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at normal pressure and 230°C for 8 hours. After further reacting for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and the reaction was continued at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-2].

[0103] <Synthesis of amorphous polyester resin B-3> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, flake-shaped recycled PET, plant-derived propylene glycol, petroleum-derived bisphenol A ethylene oxide 2 mole adduct, plant-derived terephthalic acid, and petroleum-derived adipic acid were added, and the molar ratio of the flake-shaped recycled PET (ethylene glycol unit unit) to the plant-derived propylene glycol and bisphenol A ethylene oxide 2 mole adduct was 56 / 30 / 14, and the flake-shaped recycled PET (terephthalic acid The resin was charged with plant-derived terephthalic acid and adipic acid in a molar ratio of 56 / 30 / 14, with a molar ratio of hydroxyl groups to carboxyl groups of OH / COOH of 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at normal pressure and 230°C for 8 hours. After further reacting for 4 hours at a reduced pressure of 10 to 15 mmHg, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and the reaction was continued at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-3].

[0104] <Synthesis of amorphous polyester resin B-4> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, flake-shaped recycled PET, plant-derived propylene glycol, petroleum-derived bisphenol A ethylene oxide 2 mole adduct, plant-derived terephthalic acid, and petroleum-derived adipic acid were added, and the molar ratio of the flake-shaped recycled PET (ethylene glycol unit unit) to the plant-derived propylene glycol and bisphenol A ethylene oxide 2 mole adduct was 63 / 30 / 7, and the flake-shaped recycled PET (terephthalic acid The resin was charged with plant-derived terephthalic acid and adipic acid in a molar ratio of 63 / 30 / 7, with a molar ratio of hydroxyl groups to carboxyl groups of OH / COOH of 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at normal pressure and 230°C for 8 hours. After further reacting for 4 hours at a reduced pressure of 10 to 15 mmHg, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and the reaction was continued at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-4].

[0105] <Synthesis of amorphous polyester resin B-5> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, flake-shaped recycled PET, plant-derived propylene glycol, petroleum-derived bisphenol A ethylene oxide 2 mole adduct, plant-derived terephthalic acid, and petroleum-derived adipic acid were added, and the molar ratio of the flake-shaped recycled PET (ethylene glycol unit unit) to the plant-derived propylene glycol and bisphenol A ethylene oxide 2 mole adduct was 16 / 37 / 47, and the flake-shaped recycled PET (terephthalic acid The resin was charged with plant-derived terephthalic acid and adipic acid in a molar ratio of 16 / 37 / 47, with a molar ratio of hydroxyl groups to carboxyl groups of OH / COOH of 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at normal pressure and 230°C for 8 hours. After further reacting for 4 hours at a reduced pressure of 10 to 15 mmHg, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and the reaction was continued at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-5].

[0106] <Synthesis of amorphous polyester resin B-6> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, flake-shaped recycled PET, plant-derived propylene glycol, petroleum-derived bisphenol A ethylene oxide 2-mol adduct, plant-derived terephthalic acid, and petroleum-derived adipic acid were added, and the molar ratio of the flake-shaped recycled PET (ethylene glycol unit unit) to the plant-derived propylene glycol and bisphenol A ethylene oxide 2-mol adduct was 24 / 29 / 47, and the flake-shaped recycled PET (terephthalic acid The resin was charged with plant-derived terephthalic acid and adipic acid in a molar ratio of 24 / 29 / 47, with a molar ratio of hydroxyl groups to carboxyl groups of OH / COOH of 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at normal pressure and 230°C for 8 hours. After further reacting for 4 hours at a reduced pressure of 10 to 15 mmHg, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and the reaction was continued at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-6]. Table 1 shows the compositions of the amorphous polyester resins B-1 to B-6.

[0107] [Table 1]

[0108] <Synthesis of crystalline polyester resin C> Plant-derived sebacic acid and 1,6-hexanediol were placed in a 5 L four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple so that the molar ratio of hydroxyl groups to carboxyl groups, OH / COOH, was 0.9, and reacted together with titanium tetraisopropoxide (500 ppm relative to the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours, and then further reacted at a pressure of 8.3 kPa for 2 hours to obtain [Crystalline Polyester Resin C].

[0109] <Synthesis of vinyl resin dispersion> Into a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, 11 parts of sodium salt of sulfuric acid ester of ethylene oxide adduct of methacrylic acid Eremol RS-30 (manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, 138 parts of methacrylic acid and 1 part of ammonium persulfate were charged. After stirring at 400 rpm for 15 minutes, a white emulsion was obtained. Next, the temperature inside the system was raised to 75 °C and reacted for 5 hours. Then, 30 parts of 1% aqueous ammonium persulfate solution was added and aged at 75 °C for 5 hours to obtain a [vinyl resin dispersion].

[0110] <Preparation of Masterbatch (MB)> 1,200 parts of water, 500 parts of carbon black (Printex 35, manufactured by Degussa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], and 500 parts of [amorphous polyester resin B-1] were added and mixed with a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.). The obtained mixture was kneaded at 150 °C for 30 minutes using two rolls, then rolled and cooled and pulverized with a pelletizer to obtain a [masterbatch].

[0111] <Preparation of WAX Dispersion><00,00515> Into a container equipped with a stirring rod and a thermometer, 42 parts of carnauba wax (manufactured by Cerica Noda, RN-5, plant-based wax, melting point 82 °C) as a mold release agent and 420 parts of ethyl acetate were charged. The temperature was raised to 80 °C under stirring and held at 80 °C for 5 hours. Then, it was cooled to 三十 °C in 1 hour and dispersed using a bead mill (Ultraviscomill, manufactured by Aimax Co., Ltd.) under the conditions of a liquid feeding rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% by volume filling of zirconia beads with a diameter of 0.5 mm, and 3 passes to obtain a [WAX dispersion].

[0112] <Preparation of Crystalline Polyester Dispersion> It should be noted that in the original text, "三十" in item seems to be an incorrect value. It might be intended to be "30". The translation is based on the best understanding of the context with this potential correction.A vessel equipped with a stirring rod and a thermometer was charged with 308 parts of [Crystalline Polyester Resin C] and 1,900 parts of ethyl acetate. The mixture was then heated to 80°C with stirring, maintained at this temperature for 5 hours, and then cooled to 30°C over 1 hour. Furthermore, a bead mill, Ultraviscomill (manufactured by Imex Co., Ltd.), was used to fill the vessel with 80% by volume of zirconia beads with a diameter of 0.5 mm, and the mixture was dispersed under three passes to obtain a [Crystalline Polyester Dispersion].

[0113] Example 1 <Preparation of oil phase 1> 165 parts of [WAX dispersion], 245 parts of [Amorphous polyester resin B-1], 270 parts of ethyl acetate, and 75 parts of [Masterbatch] were charged into a container, and then mixed at 7000 rpm for 60 minutes using a TK Homomixer (manufactured by Primix Corporation) to obtain [Oil phase 1].

[0114] <Preparation of aqueous phase 1> 600 parts of water, 50 parts of [vinyl resin dispersion], 225 parts of a 48.5% aqueous solution of sodium dodecyldiphenyletherdisulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white [aqueous phase 1].

[0115] <Emulsification / solvent removal> To a container containing [oil phase 1], 0.2 parts of [ketimine compound] and 2000 parts of [aqueous phase 1] were added, and then mixed at 13000 rpm for 20 minutes using a TK homomixer to obtain [emulsified slurry 1]. [Emulsified slurry 1] was placed in a vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30°C for 8 hours, followed by aging at 45°C for 4 hours to obtain [Dispersed slurry 1].

[0116] <Cleaning, heating, drying> 100 parts of [Dispersion Slurry 1] were filtered under reduced pressure. Next, 100 parts of ion-exchanged water were added to the filter cake, and the mixture was mixed using a TK homomixer at 12,000 rpm for 10 minutes, followed by filtration (hereinafter referred to as washing step (1)). Furthermore, 100 parts of a 10% aqueous sodium hydroxide solution were added to the filter cake, and the mixture was mixed using a TK homomixer at 12,000 rpm for 30 minutes, followed by filtration under reduced pressure (hereinafter referred to as washing step (2)). Next, 100 parts of 10% hydrochloric acid were added to the filter cake, and the mixture was mixed using a TK homomixer at 12,000 rpm for 10 minutes, followed by filtration (hereinafter referred to as washing step (3)). Furthermore, 300 parts of ion-exchanged water were added to the filter cake, and the mixture was mixed using a TK homomixer at 12,000 rpm for 10 minutes, followed by filtration (hereinafter referred to as washing step (4)). At this time, the operations of washing steps (1) to (4) were repeated twice. 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed at 12,000 rpm for 10 minutes using a TK homomixer, heated at 50°C for 4 hours, and then filtered. The filter cake was dried using a circulating air dryer at 45° C. for 48 hours, and then sieved through a mesh with 75 μm openings to obtain [toner base particles 1].

[0117] <External additive processing process> 100 parts of [toner base particles 1] and 2.0 parts of hydrophobic silica (HDK-2000, manufactured by Clariant KK) were mixed in a Henschel mixer, and the mixture was passed through a 500 mesh sieve to obtain [toner 1].

[0118] Example 2 [Emulsified slurry 2], [Dispersed slurry 2], [Toner base particles 2], and [Toner 2] were obtained in the same manner as in Example 1, except that [Amorphous polyester B-1] in Example 1 was changed to [Amorphous polyester B-2].

[0119] Example 3 [Emulsified slurry 3], [Dispersed slurry 3], [Toner base particles 3], and [Toner 3] were obtained in the same manner as in Example 1, except that [Oil phase 1] in Example 1 was changed to the following [Oil phase 3].

[0120] <Preparation of oil phase 3> 165 parts of [WAX dispersion], 165 parts of [Crystalline polyester dispersion], 180 parts of [Amorphous polyester resin B-3], 160 parts of ethyl acetate, and 75 parts of [Masterbatch] were charged into a container, and then mixed at 7000 rpm for 60 minutes using a TK Homomixer (manufactured by Primix Corporation) to obtain [Oil phase 3].

[0121] Example 4 <Preparation of oil phase 4> 170 parts of [WAX dispersion], 160 parts of [Crystalline polyester dispersion], 175 parts of [Amorphous polyester resin B-4], 155 parts of ethyl acetate, and 75 parts of [Masterbatch] were charged into a container, and then mixed at 7000 rpm for 60 minutes using a TK Homomixer (manufactured by Primix Corporation) to obtain [Oil phase 4].

[0122] <Preparation of aqueous phase 4> 600 parts of water, 50 parts of [vinyl resin dispersion], 230 parts of a 48.5% aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white [aqueous phase 4].

[0123] <Emulsification / solvent removal> To a vessel containing [Oil Phase 4], 0.2 parts of [Ketimine Compound], 2000 parts of [Aqueous Phase 4], and 50 parts of [Prepolymer A] were added, and then mixed at 13000 rpm for 20 minutes using a TK Homomixer to obtain [Emulsified Slurry 4]. [Emulsified slurry 4] was placed in a vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30°C for 8 hours, followed by aging at 45°C for 4 hours to obtain [Dispersed slurry 4]. The obtained [Dispersion Slurry 4] was subjected to the same treatment as in Example 1 to obtain [Toner Base Particles 4], "Toner 4."

[0124] Example 5 <Preparation of oil phase 5> A four-neck flask was charged with 160 parts of [WAX dispersion], 165 parts of [Crystalline polyester dispersion], 160 parts of ethyl acetate, 75 parts of [Masterbatch], and 190 parts of [Amorphous polyester resin B-4], and stirred to dissolve and disperse. While stirring, 10 parts of ethyl acetate, 45 parts of [Prepolymer A], and 15 parts of a 20% aqueous sodium hydroxide solution were added to a neutralization rate of 75%, to prepare [Oil phase 5]. <Preparation of aqueous phase 5> Ethyl acetate was added to 1,100 parts of ion-exchanged water so that the amount was 100% of the saturated solubility, and a surfactant (sodium dodecyl sulfate) was further added so that the amount was 2% of the aqueous phase to prepare [aqueous phase 5].

[0125] <Emulsification / solvent removal> [Water Phase 5] was gradually added to [Oil Phase 5] to perform phase inversion emulsification. After that, the solvent was removed to obtain [Emulsified Slurry 5].

[0126] <Agglomeration / fusion process> 1500 parts of [Emulsified Slurry 5] and 1600 parts of ion-exchanged water were placed in a container and stirred for 5 minutes. Next, 100 parts of a 20% aqueous magnesium sulfate solution were added dropwise, and the mixture was stirred for another 5 minutes, after which the temperature was raised to 60°C. Thereafter, an additional 75 parts of a 20% aqueous magnesium sulfate solution were added dropwise, and when the particle size reached 5.0 μm, 350 parts of a 20% aqueous sodium sulfate solution was added to complete the aggregation process, thereby obtaining [Aggregated Slurry]. The aggregated slurry was heated to 70° C. while stirring, and cooled when the desired circularity of 0.960 was reached, to obtain [Dispersion Slurry 5].

[0127] <Annealing process, cleaning, drying process> [Dispersion Slurry 5] was stored at 45°C for 10 hours, filtered under reduced pressure, and washed and dried as follows. (1) 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered. (2) 900 parts of ion-exchanged water was added to the filter cake from (1), and the mixture was mixed with ultrasonic vibration in a TK homomixer (at 12,000 rpm for 30 minutes), followed by vacuum filtration. This procedure was repeated until the electrical conductivity of the reslurry liquid reached 10 μC / cm or less, and then the mixture was filtered to obtain a filter cake. The filtered cake was dried in a circulating air dryer at 45° C. for 48 hours and sieved through a 75 μm mesh to obtain [toner base particles 5].

[0128] <External additive processing process> 100 parts of [toner base particles 6] and 2.0 parts of hydrophobic silica (HDK-2000, manufactured by Clariant Co., Ltd.) were mixed in a Henschel mixer, and the mixture was passed through a 500 mesh sieve to obtain [toner 5].

[0129] (Comparative Example 1) [Emulsified slurry 6], [Dispersed slurry 6], [Toner base particles 6], and [Toner 6] were obtained in the same manner as in Example 1, except that [Amorphous polyester B-1] in Example 1 was changed to [Amorphous polyester B-5].

[0130] (Comparative Example 2) [Emulsified slurry 7], [Dispersed slurry 7], [Toner base particles 7], and [Toner 7] were obtained in the same manner as in Example 1, except that [Amorphous polyester B-1] in Example 1 was changed to [Amorphous polyester B-6].

[0131] <Evaluation> (High temperature fixability) Using the fixing unit of a color multifunction printer (imagio MP C5503, manufactured by Ricoh Co., Ltd.), a 0.6 mg / cm 2 The temperature at which hot offset occurred was measured and evaluated according to the following criteria. [Evaluation criteria] ◎: 190℃ or higher ○: 180℃ or higher but lower than 190℃ △: 170℃ or more and less than 180℃ ×: Less than 170℃

[0132] (low temperature fixability) Using the fixing unit of a color multifunction printer (imagio MP C5503, manufactured by Ricoh Co., Ltd.), a 0.6 mg / cm 2 The temperature at which cold offset occurred was measured and evaluated according to the following criteria. [Evaluation criteria] ◎: Less than 120℃ ○: 120℃ or higher but lower than 125℃ △: 125℃ or higher but lower than 130℃ ×: 130℃ or higher

[0133] (Heat-resistant storage stability) 10 g of toner was placed in a 100 ml glass bottle, and left to stand in an environment of 50° C. for 24 hours, and then evaluated according to the following evaluation criteria. [Evaluation criteria] ◎: Shake 10 times until everything turns back into powder 〇: Shake 10 times to turn half of the powder back into powder △: Shake 10 times and it will turn back into powder ×: Does not turn back into powder even after shaking 10 times

[0134] (durability) After the 100,000-sheet copy test, the toner was removed from the developer by blow-off, and the mass of the remaining carrier was measured and designated W1. Next, this carrier was placed in toluene to dissolve the molten material, washed, and dried, after which the mass was measured and designated W2. The spent rate was then calculated using the following formula and evaluated according to the following criteria. Spent rate (%) = [(W1-W2) / W1] x 100 [Evaluation criteria] ◎: 0% by mass or more and less than 0.01% by mass ○: 0.01% by mass or more and less than 0.02% by mass △: 0.02% by mass or more and less than 0.05% by mass ×: 0.05% by mass or more

[0135] Table 2 shows the evaluation results of the toners of Examples and Comparative Examples. The binder resin is the total of prepolymer A, amorphous polyester B, and crystalline polyester C. The environmentally friendly resins used in the examples and comparative examples were only amorphous polyesters B-1 to B-5. The amorphous polyester resin is made from biomass-derived resin, recycled resin, and conventional petroleum-derived resin.

[0136] [Table 2] [Explanation of symbols]

[0137] 10 Photosensitive drum 40 Developer 58 Corona charger 80 Transfer roller 90 Cleaning Device 95 Transfer paper 110 Process cartridge 180 Developer 210 Paper feed section 211 Paper cassette 212 Paper feed roller 220 Conveyor 221 Laura 222 Timing roller 223 Paper ejection roller 224 Paper output tray 230 Image creation section 231 Photosensitive drum 232 Charger 233 Exposure device 240 Transcription Unit 241 Drive roller 242 driven roller 243 Intermediate transfer belt 244 Primary transfer roller 245 Secondary opposing roller 246 Secondary transfer roller 250 Fixing unit 251 Fixing belt 252 pressure roller P paper [Prior art documents] [Patent documents]

[0138] [Patent Document 1] Patent No. 6138021 [Patent Document 2] Patent No. 3693334 [Patent Document 3] Patent No. 5473252 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-257568 [Patent Document 5] Japanese Patent Application Laid-Open No. 2004-054258

Claims

1. Resin particles containing at least a binder resin, the binder resin contains an amorphous polyester resin and a crystalline polyester resin, At least one of the amorphous polyester resin and the crystalline polyester resin contains a biomass-derived resin, The binder resin contains a recycled resin, Resin particles characterized in that the content (mass%) of the biomass-derived resin and the content (mass%) of the recycled resin in the binder resin satisfy the following relational expression (1): Recycled resin content > Biomass resin content (1)

2. The resin particles according to claim 1 , wherein the binder resin contains the recycled resin and the biomass-derived resin in an amount of 80% by mass or more.

3. The resin particles according to claim 1 or 2, wherein the recycled resin is polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT).

4. Resin particles described in any one of claims 1 to 3, wherein the amorphous polyester resin comprises a resin obtained by crosslinking and / or elongation reaction of a prepolymer having a functional group capable of reacting with an active hydrogen group.

5. Resin particles described in any one of claims 1 to 4, wherein the biomass-derived resin is a polyester resin synthesized from an alcohol component and an acid component, and at least one of the alcohol component and acid component contains a plant-derived alcohol component or a plant-derived acid component.

6. Resin particles described in Claim 5, wherein the plant-derived alcohol component is propylene glycol and the plant-derived acid component is either sebacic acid, terephthalic acid, or succinic acid.

7. The resin particles according to claim 1 , further comprising a colorant and a release agent.

8. 8. A toner comprising the resin particles according to claim 7 and an external additive added thereto.

9. A developer comprising the toner of claim 8.

10. A developer container containing the developer according to claim 9.

11. A method for producing resin particles containing at least a binder resin, comprising: The method includes a step of mixing a binder resin and / or a binder resin precursor containing at least a biomass-derived resin and a recycled-derived resin, The binder resin precursor contains a prepolymer having a functional group capable of reacting with an active hydrogen group, A method for producing resin particles, characterized in that the content (mass%) of the biomass-derived resin in the binder resin and the content (mass%) of the recycled resin in the binder resin satisfy the following relationship (1): Recycled resin content > Biomass resin content (1)

12. 12. The method for producing resin particles according to claim 11, comprising the following steps: Step a: A step of preparing a solution by dissolving or dispersing a binder resin and / or a binder resin precursor containing at least a biomass-derived resin and a recycled-derived resin in an organic solvent. Step b: adding water to the solution to invert the phase from a water-in-oil dispersion to an oil-in-water dispersion Step c: removing the organic solvent from the oil-in-water dispersion to obtain a fine particle dispersion Step d: A step of aggregating the fine particles in the fine particle dispersion to obtain aggregated particles.

13. A method for producing a toner, comprising adding an external additive to the resin particles obtained by the method for producing resin particles according to claim 11 or 12.

14. an electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier; a developing unit that develops the electrostatic latent image to form a visible image using the toner according to claim 8 or the developer according to claim 9; a transfer means for transferring the visible image onto a recording medium; a fixing means for fixing the transferred image on the recording medium; An image forming apparatus comprising:

15. an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image to form a visible image using the toner according to claim 8 or the developer according to claim 9; a transfer step of transferring the visible image onto a recording medium; a fixing step of fixing the transferred image on the recording medium; An image forming method comprising the steps of:

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