JP6540416B2 - Toner and manufacturing method thereof - Google Patents

Description

  The present invention relates to a toner for electrostatic latent image development and a method for producing the same.

  In an electrophotographic image forming method, for example, a two-component developer (toner) containing toner particles containing a colorant and carrier particles for stirring and transporting the toner particles is used. In the image forming method, for the purpose of speeding up image formation and reducing the load on the environment, reduction of heat energy at the time of fixing is required. Therefore, low temperature fixing is required for toner particles, and it is generally known to blend a crystalline resin such as crystalline polyester having excellent sharp melt properties into a binder resin.

  For example, in a binder resin containing a crystalline polyester resin and an amorphous resin, when the temperature of the binder resin exceeds the melting point of the crystalline polyester, for example, by heating at the time of fixing, the crystallinity in the binder resin is The crystalline part of the polyester resin melts. As a result, the crystalline polyester resin and the amorphous resin are compatible with each other to realize low temperature fixing of toner particles. However, in the case of the toner particles, the compatibility between the two resins proceeds at the reaction temperature at the time of production thereof, and the toner particles may be softened. As a result, the storage stability of the toner may be insufficient.

  It is known to use as a binder resin a hybrid resin formed by chemically bonding a crystalline resin unit and an amorphous resin unit as one of the measures to suppress the above-mentioned compatibilization during production. There is. The hybrid resin may be, for example, a triblock copolymer formed by linear bonding of an amorphous polyester resin unit, a crystalline acrylic resin unit, and an amorphous vinyl resin unit, and a crystalline polyester resin There are known graft copolymers comprising a unit, a polystyrene-based resin unit polymerization block grafted to the polyster resin unit, and a crystalline acrylic resin unit, and the like (see, for example, Patent Documents 1 and 2).

JP, 2013-097321, A JP, 2013-024920, A

  The toner containing the above-mentioned copolymer as a binder resin is effective from the viewpoint of suppressing unintended compatibility between the crystalline resin component and the non-crystalline resin component. However, in the above toner, it is difficult to introduce a crystalline resin component into toner base particles. For this reason, for example, the crystalline resin component is exposed on the surface of the toner base particle, and the binder resin tends to melt on the surface, and the charging uniformity of the toner particle and the high temperature storage property become insufficient. As a result, image defects may occur in the electrophotographic method using such toner particles.

  An object of the present invention is to provide a toner which is excellent in low temperature fixability, high temperature storage property and charge uniformity.

  The present invention provides a toner for developing an electrostatic latent image having toner base particles containing a binder resin, wherein the binder resin contains a hybrid crystalline resin having a main chain and two or more side chains. Provided is a toner in which at least one of the main chain and the two or more types of side chains is composed of a crystalline resin unit, and at least one of the two or more types of side chains is composed of an amorphous resin unit. Do.

  In addition, the present invention also includes the step of aggregating and fusing dispersed hybrid crystalline resin particles in an aqueous medium to produce toner base particles, for electrostatic latent image development containing the toner base particles. In the method of producing a toner according to the present invention, the hybrid crystalline resin has a main chain and two or more types of side chains, and at least one of the main chain and the two or more types of side chains is a crystalline resin unit. Provided is a method for producing a toner, which is configured, and at least one of the two or more types of side chains is a resin composed of an amorphous resin unit.

 According to the present invention, it is possible to provide a toner which is excellent in low-temperature fixability, high-temperature storage property and charge uniformity.

FIG. 1 schematically shows a configuration of an example of an image forming apparatus in which a toner according to an embodiment of the present invention is used.

Hereinafter, embodiments of the present invention will be described.
The toner according to the present embodiment contains toner base particles containing a binder resin. The toner base particles are particles mainly composed of a binder resin, and optionally containing various additives such as a colorant and a release agent. First, the binder resin will be described.

  The binder resin contains a hybrid crystalline resin. The hybrid crystalline resin may be one kind or more. The hybrid crystalline resin has a structure in which a crystalline polyester resin unit and an amorphous resin unit are chemically bonded. The hybrid crystalline resin has a main chain and two or more side chains. At least one of the main chain and the two or more types of side chains is composed of a crystalline resin unit. In addition, at least one of the two or more types of side chains is composed of an amorphous resin unit.

  For example, the main chain of the above-mentioned hybrid crystalline resin may be composed of the first non-crystalline resin unit, and the side chain may be composed of the crystalline resin unit and the second non-crystalline resin unit. The main chain may be composed of a crystalline resin unit, and its side chain may be composed of first and second amorphous resin units, and the main chain may be composed of a first crystalline resin unit The side chain may be composed of a second crystalline resin unit and an amorphous resin unit. The first and second amorphous resin units may be the same type or different types, and the first and second crystalline resin units may be the same type. It may be of different types.

  The hybrid crystalline resin is preferably a crystalline resin unit in which at least one side chain is a crystalline resin unit, from the viewpoint of improving low-temperature fixability and enhancing high-temperature storage stability and charging uniformity.

  The crystalline resin unit represents a portion derived from the crystalline resin in the hybrid crystalline resin, and the non-crystalline resin unit is a resin having no crystallinity (non-crystalline in the hybrid crystalline resin). Part, for example, a resin other than the above-mentioned crystalline resin. More specifically, the crystalline unit is a portion of a crystalline resin in which the crystalline resin is bonded to the main chain or in the side chain, and the amorphous resin unit is a crystal. A portion of the amorphous resin attached to the main chain or attached to the side chain.

  The crystalline resin in the crystalline resin unit is a resin having crystallinity. The said crystallinity means not having a stepwise endothermic change but having a clear endothermic peak in differential scanning calorimetry (DSC). The “clear endothermic peak” specifically refers to a peak whose half-width of the endothermic peak is within 15 ° C. when measured at a temperature rising rate of 10 ° C./min in DSC. The smaller the half width, the higher the crystallinity of the resin.

  The crystalline resin may be of one kind or more. The melting point of the crystalline resin is preferably 55 to 80 ° C. from the viewpoint of sufficiently softening the toner and securing a sufficient low temperature fixing property, and further from the viewpoint of improving various characteristics in a balanced manner, More preferably, the temperature is 85 ° C. Examples of crystalline resins include crystalline polyester resins and crystalline acrylic resins.

  The crystalline polyester resin is preferable because it is easy to adjust its melting point. The melting point of the crystalline polyester resin can be controlled by the resin composition (for example, the type of monomer). The crystalline polyester can be obtained, for example, by a known synthesis method by dehydration condensation reaction of polyhydric carboxylic acid and polyhydric alcohol.

  Examples of the polyvalent carboxylic acids include saturated aliphatic dicarboxylic acids such as succinic acid, sebacic acid and dodecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and aromatics such as phthalic acid, isophthalic acid and terephthalic acid Dicarboxylic acids; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; their acid anhydrides; and their C1-C3 alkyl esters are included. The polyvalent carboxylic acid is preferably an aliphatic dicarboxylic acid.

  Examples of the polyhydric alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Aliphatic diols such as 7-heptanediol, 1,8-octanediol, neopentyl glycol and 1,4-butenediol; and trivalent or higher alcohols such as glycerin, pentaerythritol, trimethylolpropane and sorbitol; included. The polyhydric alcohol is preferably an aliphatic diol.

  The above-mentioned crystalline acrylic resin can be obtained, for example, by a known method by radical addition polymerization of a monomer having a carbon-carbon unsaturated double bond. Examples of such monomers include stearyl methacrylate, decyl methacrylate and undecyl methacrylate.

  The non-crystalline resin in the non-crystalline resin unit may be one or more. The amorphous resin has substantially no crystallinity and, for example, contains an amorphous portion in the resin. Examples of the non-crystalline resin include vinyl resins, urethane resins, urea resins, non-crystalline polyester resins, and modified polyester resins partially modified. The above amorphous resin can also be obtained, for example, by a known synthesis method.

  The vinyl-based resin is a resin produced by the polymerization of a monomer containing a compound having a vinyl group or a derivative thereof, and may be one or more. Styrene (meth) acrylic resin is contained in the example of the said vinyl resin. In addition, "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid, and means one or both of them.

  The styrene- (meth) acrylic resin has a molecular structure of a radical polymer of a compound having a radically polymerizable unsaturated bond, and can be synthesized, for example, by radical polymerization of the compound. The above compounds may be one or more, and examples thereof include styrene and its derivatives, and (meth) acrylic acid and its derivatives.

  Examples of the above styrene and derivatives thereof include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n Butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, 2,4- Dimethylstyrene and 3,4-dichlorostyrene are included.

  Examples of the (meth) acrylic acid and derivatives thereof include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic Included are butyl acid, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl .beta.-hydroxyacrylate, propyl .gamma.-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

  Further, examples of polyvalent carboxylic acids constituting the non-crystalline polyester resin include terephthalic acid, fumaric acid, trimellitic acid, isophthalic acid, succinic acid and adipic acid. Further, examples of polyhydric alcohols constituting the non-crystalline polyester resin include a 2-mole adduct of bisphenol A propylene oxide, a 2-mole adduct of bisphenol A ethylene oxide and ethylene glycol.

  The non-crystalline resin unit is a vinyl resin unit, and the crystalline resin unit is sufficiently included in the toner base particles when the binder resin contains a styrene acrylic resin as a main binder. It is preferable from

  The main chain is chemically bonded to the side chain, and the chemical bond is, for example, an ester bond or a covalent bond by the addition reaction of an unsaturated group. The hybrid crystalline resin can be obtained by a known method of bonding the crystalline resin unit and the amorphous resin unit by the chemical bonding. For example, in the hybrid crystalline resin, the chemical bond may be obtained by, for example, blending both monomers for the main chain with monomers for the main chain and monomers for the side chain, which have a site to be polymerized. It is possible to produce a resin unit to be a main chain by polymerizing these monomers, and then polymerizing a side chain monomer in the presence of the resin unit.

  Furthermore, substituents such as a sulfonic acid group, a carboxyl group, and a urethane group can be further introduced into the hybrid crystalline resin. The said substituent may be introduce | transduced into the said crystalline resin unit, and may be introduce | transduced into the said amorphous resin unit.

  The structure and amount of the main chain and side chains in the above hybrid crystalline resin can be determined, for example, by a known instrumental analysis method such as NMR or electrospray ionization mass spectrometry (ESI-MS) of the binder resin or the hydrolyzate thereof. It can be confirmed or estimated by analysis.

  Moreover, in the synthesis | combination of said resin unit, the chain transfer agent for adjusting the molecular weight of resin obtained may be further contained in raw materials, such as a monomer of the said resin unit. The chain transfer agent may be used alone or in combination, and is used in an amount capable of achieving the above object within the range where the effects of the present embodiment can be achieved. Examples of the chain transfer agent include 2-chloroethanol, octylmercaptan, dodecyl mercaptan, mercaptans such as t-dodecyl mercaptan, and styrene dimer.

  The content of the crystalline resin unit in the hybrid crystalline resin can be appropriately determined as long as the effects of the present embodiment can be obtained. For example, if the content of the crystalline resin unit in the hybrid crystalline resin is too small, low temperature stability may be insufficient. If the content is too large, inclusion and dispersion of the hybrid crystalline resin in the toner base particles May be inadequate. From such a viewpoint, the content is preferably 70 to 95% by mass, and more preferably 80 to 90% by mass.

  From the same viewpoint, the content of the non-crystalline resin unit in the hybrid crystalline resin can be appropriately determined in the range where the effects of the present embodiment can be obtained. For example, if the content of the non-crystalline resin unit in the hybrid crystalline resin is too small, inclusion and dispersion of the hybrid crystalline resin in the toner base particles may be insufficient, and if too large, low temperature stability In some cases, the gender is insufficient. From such a point of view, the content is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint of enhancing high-temperature storage stability and charging uniformity.

  Moreover, the said hybrid crystalline resin may further contain other components other than the said both resin unit in the range from which the effect of this embodiment is acquired. Examples of the other components include other resin units and various additives to be added to toner base particles.

  Moreover, although the said binder resin may be comprised substantially by the said hybrid crystalline resin, in the range with the effect of this embodiment, you may further contain components other than the said hybrid crystalline resin. Examples of such other components include amorphous resins. The amorphous resin may be one or more. For the non-crystalline resin, the non-crystalline resin described above in the non-crystalline resin unit can be used. It is preferable to further contain the non-crystalline resin in the binder resin from the viewpoint of enhancing both the high-temperature storage property and the charging uniformity of the toner, and the non-crystalline resin is a vinyl resin. It is more preferable from the above viewpoint. In addition, the amorphous resin used in combination with the hybrid crystalline resin as a binder resin is the same kind as the amorphous resin unit in the hybrid crystalline resin, and the crystalline resin unit is used as a toner matrix. It is preferable from the viewpoint of inclusion in particles.

  When the binder resin further contains the other component such as the amorphous resin, the content of the hybrid crystalline resin in the binder resin is 5 to 30% by mass, It is preferable from the viewpoint of enhancing the high temperature storage stability, and more preferably 5 to 20% by mass from the viewpoint.

  The content of each resin or each unit in the binder resin is, for example, known instrumental analysis such as nuclear magnetic resonance (NMR) or methylation reaction thermal decomposition-gas chromatography / mass spectrometry (P-GC / MS). It is possible to identify or estimate using the method.

  The toner base particles may further contain other components other than the binder resin, as long as the effects of the exemplary embodiment can be achieved. Examples of the other components include a colorant, a release agent and a charge control agent. The other components may be one kind or more.

  The colorant may be one kind or more. As the colorant, known inorganic or organic colorants used for colorants of color toners are used. Examples of the colorant include carbon black, magnetic substances, pigments and dyes.

  Examples of the carbon black include channel black, furnace black, acetylene black, thermal black and lamp black. Examples of the magnetic substance include ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, and compounds of ferromagnetic metals such as ferrite and magnetite.

  Examples of the above pigments include C.I. I. Pigment red 2, 3, 5, 7, 15, 15, 16, 48: 1, 48: 3, 53: 1, 57: 1, 81: 4, 122, 123, 139, 144, 149, 166, 177, 178, 208, 209, 222, 238, 269, C.I. I. Pigment oranges 31, 43, C.I. I. Pigment yellow 3, 9, 14, 17, 35, 36, 65, 74, 83, 93, 94, 98, 110, 111, 138, 139, and the like 153, 155, 180, 181, 185, C.I. I. Pigment green 7, C.I. I. Pigment blue 15: 3, 15: 4, 60, and phthalocyanine pigments whose central metal is zinc, titanium, magnesium or the like.

  Examples of the above dyes include C.I. I. Solvent Red 1, 3, 14, 17, 18, 18, 22, 23, 49, 51, 52, 58, 63, 87, 111, 122, 127, 127 128, 131, 145, 146, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 176, 179, pyrazolotriazole Azo dye, pyrazolotriazole azomethine dye, pyrazolone azo dye, pyrazolone azomethine dye, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93 and 95 are included.

  Examples of the above releasing agent (wax) include hydrocarbon waxes and ester waxes. Examples of such hydrocarbon waxes include low molecular weight polyethylene waxes, low molecular weight polypropylene waxes, Fischer-Tropsch waxes, microcrystalline waxes and paraffin waxes. Also, examples of the ester wax include carnauba wax, pentaerythritol behenate, behenyl behenate and behenyl citrate.

  Examples of the charge control agent include nigrosine dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, and salicylic acid metal salts or metal complexes thereof. Be

  The toner base particle is preferably a polymerized toner prepared in an aqueous medium rather than a pulverized toner from the viewpoint of appropriate control of the particle diameter and the circularity, and is a toner base particle by an emulsion association aggregation method Is more preferred.

  The toner particles include, for example, the toner base particles and an external additive present on the surface thereof. It is preferable that the toner particles contain an external additive from the viewpoint of controlling the flowability and chargeability of the toner particles. The external additive may be one or more. Examples of the external additive include silica particles, titania particles, alumina particles, zirconia particles, zinc oxide particles, chromium oxide particles, cerium oxide particles, antimony oxide particles, tungsten oxide particles, tin oxide particles, tellurium oxide particles, oxide Manganese particles and boron oxide particles are included.

  The external additive more preferably contains silica particles produced by a sol-gel method. The silica particles produced by the sol-gel method are characterized in that the particle size distribution is narrow, and thus are preferable from the viewpoint of suppressing the variation in the adhesion strength of the external additive to the toner base particles.

  Moreover, it is preferable that the number average primary particle diameter of the said silica particle is 70-200 nm. The silica particles having a number average primary particle diameter in the above range are larger than other external additives. Therefore, it has a role as a spacer in a two-component developer. Therefore, it is preferable from the viewpoint of preventing the smaller external additive from being embedded in the toner base particles when the two-component developer is stirred in the developing device. Moreover, it is preferable also from the viewpoint of preventing the fusion of toner base particles.

  The number average primary particle diameter of the external additive can be determined, for example, by image processing of an image taken with a transmission electron microscope, and can be adjusted, for example, by classification, mixing of classified products, etc. .

  The surface of the external additive is preferably hydrophobized. A known surface treatment agent is used for the hydrophobization treatment. The surface treatment agent may be one or more, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminate coupling agents, fatty acids, fatty acid metal salts, esters thereof and rosins It contains an acid.

  Examples of the above silane coupling agent include dimethyldimethoxysilane, hexamethyldisilazane (HMDS), methyltrimethoxysilane, isobutyltrimethoxysilane and decyltrimethoxysilane. Examples of the silicone oil include cyclic compounds and linear or branched organosiloxanes. More specifically, organosiloxane oligomers, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyl Cyclotetrasiloxane and tetravinyl tetramethyl cyclotetrasiloxane are included.

  In addition, examples of the silicone oil include highly reactive, at least terminal-modified silicone oils in which a modifying group is introduced to a side chain or one end, both ends, side chain ends, side chain ends, etc. . The type of the above-mentioned modifying group may be one or more, and examples thereof include alkoxy, carboxyl, carbinol, higher fatty acid modification, phenol, epoxy, methacryl and amino.

  The addition amount of the external additive is preferably 0.1 to 10.0% by mass with respect to the entire toner particles. More preferably, it is 1.0-3.0 mass%.

  The toner is constituted of the toner particles itself if it is a one-component developer, and is constituted of the toner particles and carrier particles if it is a two-component developer. The content (toner concentration) of toner particles in the two-component developer may be the same as that of a normal two-component developer, and is, for example, 4.0 to 8.0% by mass.

  The carrier particles are composed of a magnetic material. In the example of the carrier particle, a coated carrier particle having a core material particle made of the magnetic substance and a layer of a coating material which coats the surface, and a fine powder of the magnetic substance dispersed in a resin Resin-dispersed carrier particles are included. The carrier particles are preferably the coated carrier particles from the viewpoint of suppressing the adhesion of the carrier particles to the photosensitive member.

  The core particles are composed of a magnetic substance, for example, a substance that is strongly magnetized in the direction by a magnetic field. The magnetic substance may be one or more, and examples thereof include metals exhibiting ferromagnetism such as iron, nickel and cobalt, alloys or compounds containing these metals, and alloys exhibiting ferromagnetism by heat treatment. , Is included.

Examples of the above-described ferromagnetic metal or a compound containing the same include iron, a ferrite represented by the following formula (a), and a magnetite represented by the following formula (b). M in Formula (a) and Formula (b) represents one or more monovalent or divalent metals selected from the group of Mn, Fe, Ni, Co, Cu, Mg, Zn, Cd and Li.
Formula (a): MO · Fe ₂ O ₃
Formula (b): MFe ₂ O ₄

  Moreover, Heusler alloys, such as manganese- copper- aluminum and manganese- copper- tin, and chromium dioxide are contained in the example of an alloy which shows ferromagnetism by heat-processing.

  The core particles are preferably the ferrite. This is because the specific gravity of the coated carrier particles is smaller than the specific gravity of the metal constituting the core particles, so that the impact force of stirring in the developing device can be further reduced.

  The covering material may be of one kind or more. For the covering material, known resins used for covering core particles of carrier particles can be used. The coating material is preferably a resin having a cycloalkyl group from the viewpoint of reducing the water adsorption of the carrier particles and the viewpoint of enhancing the adhesion of the coating layer to the core particles. Examples of the cycloalkyl group include cyclohexyl group, cyclopentyl group, cyclopropyl group, cyclobutyl group, cycloheptyl group, cyclooctyl group, cyclononyl group and cyclodecyl group. Among them, a cyclohexyl group or a cyclopentyl group is preferable, and a cyclohexyl group is more preferable from the viewpoint of the adhesion between the coating layer and the ferrite particles.

The weight average molecular weight Mw of the resin having a cycloalkyl group is, for example, 10,000 to 800,000, and more preferably 100,000 to 750,000. The content of the cycloalkyl group in the resin is, for example, 10 to 90% by mass. The content of the cycloalkyl group in the resin can be determined, for example, using a known instrumental analysis method such as P-GC / MS or ¹ H-NMR.

  The two-component developer can be produced by mixing the toner particles and the carrier particles in an appropriate amount. Examples of mixing devices used for such mixing include Nauta mixers, W-cone and V-type mixers.

  The size and shape of the toner particles can be appropriately determined within the range in which the effects of the present embodiment can be obtained. For example, the volume average particle diameter of the toner particles is 3.0 to 8.0 μm, and the average circularity of the toner particles is 0.92 to 1.000.

  The number average particle diameter of the toner particles can be measured and calculated using an apparatus in which a computer system for data processing is connected to "Multisizer 3" (manufactured by Beckman Coulter, Inc.). Further, the number average particle diameter of the toner particles can be adjusted, for example, by the temperature in the production of the toner particles and the conditions of stirring, the classification of the toner particles, and the mixing of classified particles of the toner particles.

The average circularity of the toner particles is determined, for example, by using a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation), and using a predetermined number of toner particles, the perimeter L1 of a circle having the same projected area as the particle image. From the peripheral length L2 of the particle projection image, it can be obtained by dividing the sum of the circularity C calculated from the following equation by the predetermined number. The average circularity of the toner particles can be adjusted, for example, by the degree of ripening of the resin particles in the production of the toner particles, the heat treatment of the toner particles, the mixing of toner particles having different circularities, or the like.
(Formula) C = L1 / L2

  In addition, the size and shape of the carrier particles can be appropriately determined as long as the effects of the present embodiment can be obtained. For example, the volume average particle size of the carrier particles is 15 to 100 μm. The volume average particle diameter of the carrier particles can be measured wet, for example, using a laser diffraction type particle size distribution measuring apparatus “HELOS KA” (manufactured by Nippon Laser Co., Ltd.). In addition, the volume average particle diameter of the carrier particles is adjusted by, for example, a method of controlling the particle diameter of the core particles according to the manufacturing conditions of the core particles, classification of carrier particles, mixing of classified particles of carrier particles, etc. Is possible.

  The toner can be produced, for example, by a method including the step of aggregating and fusing particles of the hybrid crystalline resin dispersed in an aqueous medium in an aqueous medium to produce the toner base particles.

  The above-mentioned production method may further include the step of dispersing, aggregating and fusing the above-mentioned other components in an appropriate form in an aqueous medium. For example, in any of the above manufacturing methods, a step of further dispersing further resin fine particles in which another component such as a colorant is dispersed in the resin component in the aqueous medium, and the resin fine particles in the aqueous medium And aggregating and fusing additional resin fine particles.

  Furthermore, any of the above manufacturing methods may further include appropriate steps depending on the form of the toner. For example, any of the above production methods may further include one or both of the step of mixing the external additive with the toner base particles and the step of mixing the toner particles with the carrier particles.

  In the present invention, a hybrid crystalline resin having a main chain and two or more side chains is used. And the said hybrid crystalline resin is a graft copolymer containing a crystalline resin unit and an amorphous resin unit, The side chain (branch) is 2 types of resin units containing an amorphous resin unit. Configured For this reason, it is possible to further improve the affinity between the main binder other than the hybrid crystalline resin usually contained in the binder resin and the hybrid crystalline resin.

  Further, since the hybrid crystalline resin is a graft copolymer, it is considered that the respective resin units introduced as side chains are likely to interact with each other. Therefore, when the crystalline resin unit is included in the side chain, the crystallinity of the hybrid crystalline resin is improved, and the low temperature fixability of the toner is further improved. Also when the crystalline resin unit is the main chain, the interaction between the side chain resin units is increased, and the effect of improving the affinity of the hybrid crystalline resin to the main binder is further easily obtained.

  As apparent from the above description, the toner has toner base particles containing a binder resin, and the binder resin includes a hybrid crystalline resin having a main chain and two or more types of side chains, At least one of the main chain and two or more types of side chains is composed of a crystalline resin unit, and at least one of the two or more types of side chains is composed of an amorphous resin unit. Therefore, the toner is excellent in low-temperature fixability, high-temperature storage property, and charging uniformity.

  Further, the content of the crystalline resin unit in the hybrid crystalline resin of 70 to 95% by mass is more effective from the viewpoint of enhancing both the low temperature fixability and the charge uniformity of the toner.

  In addition, the above-mentioned hybrid crystalline resin containing the above-mentioned crystalline resin unit in at least one of the side chains thereof is a viewpoint of improving the low temperature fixability of the toner, and a viewpoint of enhancing the high temperature storage property and charging uniformity of the toner It is even more effective from

  Further, the crystalline resin unit being a crystalline polyester resin unit is more effective from the viewpoint of facilitating setting of the low temperature fixability of the toner.

  In addition, the crystalline resin unit is sufficiently contained in the toner base particle by the binder resin containing a main binder such as a styrene acrylic resin, so that the amorphous resin unit is a vinyl resin unit. It is even more effective from the viewpoint of sufficiently developing low temperature fixability, high temperature storage property and charge uniformity.

  In addition, the content of the hybrid crystalline resin in the binder resin is 5 to 30% by mass, which is more effective from the viewpoint of enhancing the charging uniformity of the toner and the high temperature storage stability.

  In addition, it is more effective that the binder resin further contains an amorphous resin from the viewpoint of enhancing both the high temperature storage property and the charging uniformity, and the above amorphous resin is a vinyl resin, It is more effective from the above point of view.

  Further, in the method of producing a toner for developing an electrostatic latent image containing the toner base particles, the method of producing a toner includes aggregating the particles of the hybrid crystalline resin in an aqueous medium to produce toner base particles. Including the step of Therefore, the above-mentioned toner excellent in low-temperature fixability, high-temperature storage property and charging uniformity can be obtained.

  The above-mentioned toner is applied to a general electrophotographic image forming method, and is used for developing an electrostatic latent image. The toner is stored, for example, in the image forming apparatus shown in FIG. 1 and is used to form a toner image on a recording medium.

  The image forming apparatus 1 illustrated in FIG. 1 includes an image reading unit 110, an image processing unit 30, an image forming unit 40, a sheet conveyance unit 50, and a fixing device 60.

  The image forming unit 40 includes image forming units 41Y, 41M, 41C, and 41K that form images with toners of Y (yellow), M (magenta), C (cyan), and K (black). Since all of these components have the same configuration except for the toner to be stored, symbols representing colors may be omitted hereinafter. The image forming unit 40 further includes an intermediate transfer unit 42 and a secondary transfer unit 43. These correspond to transfer devices.

  The image forming unit 41 includes an exposure device 411, a developing device 412, a photosensitive drum 413, a charging device 414, and a drum cleaning device 415. The photosensitive drum 413 is, for example, a negatively charged organic photosensitive member. The surface of the photosensitive drum 413 has photoconductivity. The photosensitive drum 413 corresponds to a photosensitive member. The charging device 414 is, for example, a corona charger. The charging device 414 may be a contact charging device in which a contact charging member such as a charging roller, a charging brush, or a charging blade is brought into contact with the photosensitive drum 413 for charging. The exposure device 411 includes, for example, a semiconductor laser as a light source, and a light deflection device (polygon motor) that irradiates the photosensitive drum 413 with laser light according to an image to be formed.

  The developing device 412 is a two-component developing type developing device. The developing device 412 includes, for example, a developing container for containing a two-component developer, and a developing container capable of communicating the two-component developer with a developing roller (magnetic roller) rotatably disposed at an opening of the developing container. It has a partition dividing the inside, a conveyance roller for conveying the two-component developer on the opening side of the developing container toward the developing roller, and a stirring roller for stirring the two-component developer in the developing container. . The toner as the two-component developer is accommodated in the developer container.

  The intermediate transfer unit 42 includes an intermediate transfer belt 421, a primary transfer roller 422 for pressing the intermediate transfer belt 421 against the photosensitive drum 413, a plurality of support rollers 423 including a backup roller 423A, and a belt cleaning device 426. The intermediate transfer belt 421 is stretched around a plurality of support rollers 423 in a loop. By rotating at least one drive roller of the plurality of support rollers 423, the intermediate transfer belt 421 travels at a constant speed in the arrow A direction.

  The secondary transfer unit 43 has an endless secondary transfer belt 432 and a plurality of support rollers 431 including a secondary transfer roller 431A. The secondary transfer belt 432 is stretched in a loop by the secondary transfer roller 431A and the support roller 431.

  The fixing device 60 covers, for example, the fixing roller 62 and the outer peripheral surface of the fixing roller 62, and heats and melts toner forming the toner image on the sheet S, fixing the sheet S and the sheet S And a pressure roller 64 for pressing the roller 62 and the heat generating belt 63. The sheet S corresponds to a recording medium.

  The image forming apparatus 1 further includes an image reading unit 110, an image processing unit 30, and a sheet conveyance unit 50. The image reading unit 110 has a sheet feeding device 111 and a scanner 112. The sheet conveyance unit 50 includes a sheet feeding unit 51, a sheet discharge unit 52, and a conveyance path unit 53. In the three sheet feeding tray units 51a to 51c constituting the sheet feeding unit 51, sheets S (standard sheets and special sheets) identified based on basis weight, size and the like are stored for each preset type. . The transport path portion 53 has a plurality of transport roller pairs such as a registration roller pair 53a.

The formation of an image by the image forming apparatus 1 will be described.
The scanner 112 optically scans and reads the document D on the contact glass. Reflected light from the document D is read by the CCD sensor 112 a and becomes input image data. The input image data is subjected to predetermined image processing in the image processing unit 30 and sent to the exposure device 411.

  The photosensitive drum 413 rotates at a constant circumferential speed. The charging device 414 uniformly charges the surface of the photosensitive drum 413 to a negative polarity. In the exposure device 411, the polygon mirror of the polygon motor rotates at high speed, and the laser light corresponding to the input image data of each color component is developed along the axial direction of the photosensitive drum 413, and the photosensitive member is along the axial direction The outer peripheral surface of the drum 413 is irradiated. Thus, an electrostatic latent image is formed on the surface of the photosensitive drum 413.

  In the developing device 412, the toner particles are charged by stirring and transporting the two-component developer in the developing container, and the two-component developer is transported to the developing roller, and a magnetic brush is formed on the surface of the developing roller. The charged toner particles electrostatically adhere to the portion of the electrostatic latent image on the photosensitive drum 413 from the magnetic brush. Thus, the electrostatic latent image on the surface of the photosensitive drum 413 is visualized, and a toner image corresponding to the electrostatic latent image is formed on the surface of the photosensitive drum 413.

  The toner image on the surface of the photosensitive drum 413 is transferred to the intermediate transfer belt 421 by the intermediate transfer unit 42. The transfer residual toner remaining on the surface of the photosensitive drum 413 after transfer is removed by a drum cleaning device 415 having a drum cleaning blade in sliding contact with the surface of the photosensitive drum 413.

  When the intermediate transfer belt 421 is in pressure contact with the photosensitive drum 413 by the primary transfer roller 422, a primary transfer nip is formed for each photosensitive drum by the photosensitive drum 413 and the intermediate transfer belt 421. At the primary transfer nip, toner images of the respective colors are sequentially overlapped and transferred onto the intermediate transfer belt 421.

  On the other hand, the secondary transfer roller 431A is in pressure contact with the backup roller 423A via the intermediate transfer belt 421 and the secondary transfer belt 432. Thus, a secondary transfer nip is formed by the intermediate transfer belt 421 and the secondary transfer belt 432. The sheet S passes through the secondary transfer nip. The sheet S is conveyed by the sheet conveyance unit 50 to the secondary transfer nip. The correction of the inclination of the sheet S and the adjustment of the timing of conveyance are performed by the registration roller unit in which the registration roller pair 53a is disposed.

  When the sheet S is conveyed to the secondary transfer nip, a transfer bias is applied to the secondary transfer roller 431A. By the application of the transfer bias, the toner image carried on the intermediate transfer belt 421 is transferred to the sheet S. The sheet S on which the toner image has been transferred is conveyed by the secondary transfer belt 432 toward the fixing device 60.

  The fixing device 60 forms a fixing nip by the heat generating belt 63 and the pressure roller 64, and heats and presses the conveyed sheet S at the fixing nip portion. The toner particles constituting the toner image on the sheet S are heated, and the hybrid crystalline resin is rapidly melted therein, as a result, the entire toner particles are rapidly melted with a relatively small amount of heat, and the toner component is the sheet S Adhere to In the adhering molten toner component, the crystalline resin unit in the hybrid crystalline resin is rapidly crystallized, and the entire molten toner component is rapidly solidified. Thus, the toner image is fixed to the sheet S quickly with a relatively small amount of heat. The sheet S on which the toner image is fixed is discharged to the outside of the machine by the paper discharge unit 52 provided with the paper discharge roller 52a. Thus, a high quality image is formed.

  The transfer residual toner remaining on the surface of the intermediate transfer belt 421 after the secondary transfer is removed by a belt cleaning device 426 having a belt cleaning blade in sliding contact with the surface of the intermediate transfer belt 421.

  In the present embodiment, the above-mentioned hybrid crystalline resin is used as a constituent material of toner base particles. The hybrid crystalline resin contains a crystalline resin unit, and at least the side chain contains an amorphous resin unit. The amorphous resin unit has high affinity to the amorphous resin (main binder) in the toner base particles, generally, such as styrene-acrylic resin. As a result, the incorporation of the crystalline resin unit into the toner base particles is significantly improved, and the sharp meltability of the toner is also improved. As a result, the toner exhibits sufficient low temperature fixability, and further exhibits sufficient high temperature storage property and charge uniformity.

  The present invention will be more specifically described using the following examples and comparative examples. The present invention is not limited to the following examples and the like.

[Measuring method]
(Melting point and glass transition temperature (Tg) of each resin)
The melting point and glass transition temperature of each resin constituting the toner can be determined by performing differential scanning calorimetry on each resin. In differential scanning calorimetry, for example, a differential scanning calorimeter "diamond DSC" (manufactured by Perkin Elmer) is used. The measurement is performed by raising the temperature from room temperature (25 ° C.) to 150 ° C. at a lifting rate of 10 ° C./min and holding isothermally at 150 ° C. for 5 minutes. The measurement conditions are as follows: a cooling process that cools to 0 ° C and isothermal holding at 0 ° C for 5 minutes, and a second heating process that raises the temperature from 0 ° C to 150 ° C at a lifting speed of 10 ° C / min. Condition is performed. The above measurement is performed by enclosing 3.0 mg of toner in an aluminum pan and setting it in a sample holder of a differential scanning calorimeter "diamond DSC". Use an empty aluminum pan as a reference.

  In the above measurement, the top temperature of the melting peak of the resin (the endothermic peak whose half width is within 15 ° C.) in the first temperature raising process is taken as the melting point of the resin. Further, for the amorphous resin, in the above measurement, the onset temperature obtained from the endothermic curve obtained in the first temperature rising process is taken as the glass transition temperature Tg (° C.).

(Measurement of weight average molecular weight (Mw))
In the weight average molecular weight (Mw) (polystyrene conversion) of each resin, "HLC-8220" (made by Tosoh Corp.) is used as a GPC apparatus, and "TSKguardcolumn + TSKgelSuperHZM-M3 series" (made by Tosoh Corp.) is used as a column. The column temperature is maintained at 40 ° C., and tetrahydrofuran (THF) is flowed at a flow rate of 0.2 mL / min as a carrier solvent. The resin of the measurement sample is dissolved in tetrahydrofuran so as to have a concentration of 1 mg / mL under dissolution conditions of processing for 5 minutes using an ultrasonic disperser at room temperature. The resulting solution is treated with a membrane filter having a pore size of 0.2 μm to obtain a sample solution. Further, 10 μL of this sample solution is injected into the above-mentioned GPC apparatus together with the above-mentioned carrier solvent. Then, each component in the resin is detected using a refractive index detector (RI detector), and the molecular weight distribution of the measurement sample is calculated using a calibration curve measured using monodispersed polystyrene standard particles.

The calibration curve is, for example, a standard polystyrene sample for calibration curve measurement, which has a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5 manufactured by Pressure Chemical. Standard polystyrene of at least about 10 points using those of 1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ It is created by measuring a sample. A refractive index detector is used as a detector in this measurement.

(Average particle size of resin particles, colorant particles, etc.)
The volume average particle diameter (median diameter on a volume basis) of resin particles, colorant particles and the like was measured by "UPA-150" (manufactured by Microtrac Bell Inc.).

[Synthesis Example 1 of Side-Chain Resin Unit]
A solution Mb2-1 containing the following raw material monomers for addition polymerization resins, a bireactive monomer (2-butene-1,4-diol) and a radical polymerization initiator was placed in a dropping funnel.
Styrene 35 parts by mass Butyl acrylate 9 parts by mass 2-butene-1,4-diol 4 parts by mass Azobisisobutyl nitrile 7 parts by mass

  Next, the above Mb 2-1 is dropped into 50 parts by mass of toluene kept at 110 ° C. for 90 minutes under stirring, and after aging for 60 minutes, unreacted under the reduced pressure (8 kPa) The addition polymerization monomer was removed to obtain a side chain resin unit b2-1.

[Synthesis Example 2 of Side-Chain Resin Unit]
A solution Mb2-2 containing the following raw material monomers for addition polymerization resins, a bireactive monomer and a radical polymerization initiator was placed in the dropping funnel.
Styrene 30 parts by mass Butyl acrylate 14 parts by mass 2-butene-1,4-diol 4 parts by mass Azobisisobutyl nitrile 7 parts by mass

  Next, the above Mb2-2 is dropped into 50 parts by mass of toluene kept at 110 ° C. over 90 minutes under stirring, and after aging for 60 minutes, it is unreacted under reduced pressure (8 kPa) The addition polymerization monomer was removed to obtain a side chain resin unit b2-2.

[Synthesis example 3 of side chain resin unit]
A solution Mb2-3 containing the following raw materials of an addition polymerization resin, a bireactive monomer, and a radical polymerization initiator was placed in the dropping funnel.
Styrene 35 parts by mass Butyl acrylate 9 parts by mass Methyl methacrylate 4 parts by mass 2-butene-1,4-diol 4 parts by mass Azobisisobutyl nitrile 7 parts by mass

  Next, the above Mb 2-3 is dropped into 50 parts by mass of toluene kept at 110 ° C. over 90 minutes under stirring, aged for 60 minutes, and then unreacted under reduced pressure (8 kPa) The addition polymerization monomer was removed to obtain a side chain resin unit b2-3.

[Synthesis example 4 of side chain resin unit]
The raw material liquid Mb2-4 containing the raw material monomer of the following polycondensation resin (amorphous polyester resin) unit is put into a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, The mixture was heated to 0 C and dissolved.
Bisphenol A propylene oxide 2 mol adduct 285.7 parts by mass Terephthalic acid 66.9 parts by mass Fumaric acid 47.4 parts by mass

  Next, 100 parts by mass of a raw material monomer (solution Mb2-1) of an addition polymerization resin is dropped into the above solution Mb2-4 over 90 minutes with stirring, and after aging for 60 minutes, under reduced pressure (8 kPa) The unreacted addition polymerization monomer was removed.

Next, 0.4 parts by mass of Ti (OBu) ₄ as an esterification catalyst is added to the obtained reaction solution, the temperature is raised to 235 ° C., and under normal pressure (101.3 kPa) for 5 hours, further under reduced pressure (8 kPa The reaction was carried out for 1 hour.

  Next, the obtained reaction liquid was cooled to 200 ° C., and then the reaction was performed under reduced pressure (20 kPa) until the softening point of the produced resin component reaches a desired softening point. Subsequently, the solvent was removed to obtain a side chain resin unit b2-4.

[Synthesis of Hybrid Crystalline Resin C1]
The following raw materials monomers for addition polymerization resin, a dual reactive monomer (acrylic acid) and a radical polymerization initiator were placed in the dropping funnel.
Styrene 77 parts by mass Butyl acrylate 20 parts by mass Acrylic acid 9 parts by mass Di-t-butyl peroxide 7 parts by mass

Also, the following raw material monomers for polycondensation resin and side chain resin unit b2-1 synthesized above are put into a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, Heated to dissolve.
Sebacic acid 277 parts by mass Dodecanediol 283 parts by mass Side chain resin unit b2-1 35 parts by mass

  Subsequently, the raw material monomer of the addition polymerization resin was dropped over 90 minutes under stirring, and after aging for 60 minutes, the unreacted addition polymerization monomer was removed under reduced pressure (8 kPa).

Next, 0.8 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, the temperature was raised to 235 ° C., reaction was conducted under normal pressure (101.3 kPa) for 5 hours, and further under reduced pressure (8 kPa) for 1 hour went.

  Subsequently, the obtained reaction liquid was cooled to 200 ° C., and then reacted for 1 hour under reduced pressure (20 kPa) to obtain a hybrid crystalline resin (HB) C1. The obtained hybrid crystalline resin C1 had a weight average molecular weight (Mw) of 14,000 and a melting point of 76 ° C.

[Synthesis of Hybrid Crystalline Resin C2]
A hybrid crystalline resin C2 was synthesized in the same manner as in the synthesis of the hybrid crystalline resin C1, except that the side chain resin unit b2-2 was used instead of the side chain resin unit b2-1. The obtained hybrid crystalline resin C2 had a Mw of 13,500 and a melting point of 76 ° C.

[Synthesis of Hybrid Crystalline Resin C3]
The following raw material monomers of a polycondensation resin (amorphous polyester resin) unit are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, heated to dissolve at 170 ° C., and then The catalyst Ti (OBu) ₄ (0.003% by mass with respect to the total amount of polyvalent carboxylic acid monomers) was introduced.
Bisphenol A propylene oxide 2 mole adduct 74 parts by mass Terephthalic acid 17 parts by mass Fumaric acid 12 parts by mass Trimellitic acid 2 parts by mass

  Then, the temperature was raised to 235 ° C., and reaction was carried out under normal pressure (101.3 kPa) for 5 hours, and further under reduced pressure (8 kPa) for 1 hour. Subsequently, after cooling the obtained reaction liquid to 200 degreeC, reaction was performed under pressure reduction (20 kPa) for 3 hours, and then solvent removal was performed.

Next, the following raw material monomers for a polycondensation resin and the side chain resin unit b2-3 synthesized above were placed in the above four-necked flask and heated at 170 ° C. to be dissolved.
Sebacic acid 277 parts by mass Dodecanediol 283 parts by mass Side chain resin unit b2-3 35 parts by mass

Subsequently, 0.8 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C3. The obtained hybrid crystalline resin C3 had a Mw of 15,000 and a melting point of 75 ° C.

[Synthesis of Hybrid Crystalline Resin C4]
The following raw material monomers of a polycondensation resin (amorphous polyester resin) unit are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, heated to dissolve at 170 ° C., and then The catalyst Ti (OBu) ₄ (0.003% by mass with respect to the total amount of polyvalent carboxylic acid monomers) was introduced.
Bisphenol A propylene oxide 2 mole adduct 71 parts by mass Terephthalic acid 33 parts by mass Trimellitic acid 1 part by mass

Next, 0.4 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, the temperature was raised to 235 ° C., the reaction was conducted for 5 hours under normal pressure (101.3 kPa), and further for 1 hour under reduced pressure (8 kPa). went. Subsequently, after cooling the obtained reaction liquid to 200 degreeC, reaction was performed under pressure reduction (20 kPa) for 3 hours, and solvent removal was then performed.

Next, the following raw material monomers for a polycondensation resin and the side chain resin unit b2-4 synthesized above were placed in the above four-necked flask and heated at 170 ° C. for dissolution.
Sebacic acid 277 parts by mass Dodecanediol 283 parts by mass Side chain resin unit b2-4 35 parts by mass

Subsequently, 0.8 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C4. The obtained hybrid crystalline resin C4 had a Mw of 15,000 and a melting point of 75 ° C.

[Synthesis of Hybrid Crystalline Resin C5]
A hybrid crystalline resin C5 was synthesized in the same manner as in the synthesis of the hybrid crystalline resin C1, except that the side chain resin unit b2-4 was used in place of the side chain resin unit b2-1. The obtained hybrid crystalline resin C5 had an Mw of 14,500 and a melting point of 76 ° C.

[Synthesis of Hybrid Crystalline Resin C6]
The following raw materials monomers for addition polymerization resins, both reactive monomers and a radical polymerization initiator were placed in the dropping funnel.
Styrene 20 parts by mass Butyl acrylate 5 parts by mass Acrylic acid 2 parts by mass Di-t-butyl peroxide 2 parts by mass

Then, the following raw material monomers for a polycondensation resin and the side chain resin unit b2-1 synthesized above are put into a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, Heated to dissolve.
Sebacic acid 326 parts by mass Dodecanediol 332 parts by mass Side chain resin unit b2-1 14 parts by mass

  Subsequently, a raw material monomer of the addition polymerization resin was dropped over 90 minutes under stirring, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C6. The obtained hybrid crystalline resin C6 had a Mw of 12,000 and a melting point of 75 ° C.

[Synthesis of Hybrid Crystalline Resin C7]
The following raw materials monomers for addition polymerization resins, both reactive monomers and a radical polymerization initiator were placed in the dropping funnel.
Styrene 102 parts by mass Butyl acrylate 26 parts by mass Acrylic acid 12 parts by mass Di-t-butyl peroxide 10 parts by mass

Then, the following raw material monomers for a polycondensation resin and the side chain resin unit b2-1 synthesized above are put into a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, Heated to dissolve.
Sebacic acid 246 parts by mass Dodecanediol 251 parts by mass Side chain resin unit b2-1 63 parts by mass

  Subsequently, a raw material monomer of the addition polymerization resin was dropped over 90 minutes under stirring, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C7. The obtained hybrid crystalline resin C7 had an Mw of 13,500 and a melting point of 75 ° C.

[Synthesis of Hybrid Crystalline Resin C8]
The following raw material monomers of a polycondensation resin (crystalline polyester resin) unit are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, heated to dissolve at 170 ° C., and then The catalyst Ti (OBu) ₄ (0.003% by mass with respect to the total amount of polyvalent carboxylic acid monomers) was introduced.
Sebacic acid 235 parts by mass Dodecanediol 247 parts by mass Fumaric acid 6 parts by mass Trimellitic acid 2 parts by mass

  Next, the temperature was raised to 235 ° C., and reaction was carried out under normal pressure (101.3 kPa) for 5 hours and further under reduced pressure (8 kPa) for 1 hour. Subsequently, after cooling the obtained reaction liquid to 200 degreeC, reaction was performed under pressure reduction (20 kPa) for 3 hours, and solvent removal was then performed.

Subsequently, the following raw material monomers for a polycondensation resin and the side chain resin unit b2-3 and the side chain resin unit b2-4 synthesized above were placed in the above four-necked flask and heated at 170 ° C. to be dissolved.
Side chain resin unit b2-3 140 parts by mass Side chain resin unit b2-4 70 parts by mass

Subsequently, 0.8 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C8. The obtained hybrid crystalline resin C8 had a Mw of 14,000 and a melting point of 76 ° C.

[Synthesis of Hybrid Crystalline Resin C9]
The following raw materials monomers for addition polymerization resins, both reactive monomers and a radical polymerization initiator were placed in the dropping funnel.
Styrene 51 parts by mass Butyl acrylate 13 parts by mass Acrylic acid 6 parts by mass Di-t-butyl peroxide 7 parts by mass

In addition, the following raw materials monomers for polycondensation resins and side chain resin units b2-1 and side chain resin units b2-2 synthesized above are provided with a nitrogen introducing pipe, a dewatering pipe, a stirrer, and a thermocouple. The mixture was placed in a neck flask and heated to 170 ° C. for dissolution.
Sebacic acid 277 parts by mass Dodecanediol 283 parts by mass Side chain resin unit b2-1 35 parts by mass Side chain resin unit b2-2 35 parts by mass

  Subsequently, a raw material monomer of the addition polymerization resin was dropped over 90 minutes under stirring, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C9. The obtained hybrid crystalline resin C9 had a Mw of 14,000 and a melting point of 76 ° C.

[Synthesis of Hybrid Crystalline Resin C10]
The following raw material monomers of a polycondensation resin (crystalline polyester resin) unit are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, heated to dissolve at 170 ° C., and then The catalyst Ti (OBu) ₄ (0.003% by mass with respect to the total amount of polyvalent carboxylic acid monomers) was introduced.
Sebacic acid 67 parts by mass dodecanediol 71 parts by mass Fumaric acid 2 parts by mass Trimellitic acid 1 part by mass

  Then, the temperature was raised to 235 ° C., and reaction was carried out under normal pressure (101.3 kPa) for 5 hours, and further under reduced pressure (8 kPa) for 1 hour. Subsequently, after cooling the obtained reaction liquid to 200 degreeC, reaction was performed under pressure reduction (20 kPa) for 3 hours, and solvent removal was then performed.

Next, the following raw material monomers for a polycondensation resin and the side chain resin unit b2-3 synthesized above were placed in the above four-necked flask and heated at 170 ° C. to be dissolved.
Sebacic acid 208 parts by mass Dodecanediol 212 parts by mass Side chain resin unit b2-3 140 parts by mass

Subsequently, 0.8 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C10. The obtained hybrid crystalline resin C10 had an Mw of 13,500 and a melting point of 75 ° C.

[Synthesis of Hybrid Crystalline Resin C11]
The following raw materials monomers for addition polymerization resins, both reactive monomers and a radical polymerization initiator were placed in the dropping funnel.
Styrene 51 parts by mass Butyl acrylate 13 parts by mass Acrylic acid 6 parts by mass Di-t-butyl peroxide 7 parts by mass

Also, the following raw material monomers for polycondensation resin and side chain resin unit b2-1 synthesized above are put into a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, Heated to dissolve.
Stearyl methacrylate 560 parts by mass Side chain resin unit b2-1 70 parts by mass

  Subsequently, a raw material monomer of the addition polymerization resin was dropped over 90 minutes under stirring, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C11. The obtained hybrid crystalline resin C11 had a Mw of 12,000 and a melting point of 80 ° C.

[Synthesis of Hybrid Crystalline Resin C12]
The following raw material monomers of a polycondensation resin (amorphous polyester resin) unit are placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, heated to dissolve at 170 ° C., and then The catalyst Ti (OBu) ₄ (0.003% by mass with respect to the total amount of polyvalent carboxylic acid monomers) was introduced.
Bisphenol A propylene oxide 2 molar adduct 94 parts by mass Terephthalic acid 44 parts by mass Trimellitic acid 2 parts by mass

  Thereafter, the temperature was raised to 235 ° C., and reaction was carried out under normal pressure (101.3 kPa) for 5 hours and further under reduced pressure (8 kPa) for 1 hour. Subsequently, after cooling the obtained reaction liquid to 200 degreeC, reaction was performed under pressure reduction (20 kPa) for 3 hours, and solvent removal was then performed.

Subsequently, the following raw material monomers for polycondensation resins were placed in the above-mentioned four-necked flask and heated at 170 ° C. for dissolution.
277 parts by mass of sebacic acid 283 parts by mass of dodecanediol

Subsequently, 0.8 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, and thereafter, the same procedure as in the synthesis of the hybrid crystalline resin C1 was performed to obtain a hybrid crystalline resin C12. The obtained hybrid crystalline resin C12 had an Mw of 15,000 and a melting point of 75 ° C.

  The composition, weight average molecular weight and melting point of the hybrid crystalline resins C1 to C12 are shown in Table 1. In the table, "StAc" represents a styrene-acrylic resin, "APEs" represents amorphous polystyrene, "CPEs" represents a crystalline polyester, and "CAc" represents a crystalline acrylic resin.

[Preparation of Aqueous Dispersion Dx1 of Amorphous Resin X1 Fine Particles]
(First stage polymerization)
8 parts by mass of sodium dodecyl sulfate and 3000 parts by mass of ion-exchanged water are charged into a 5 L reaction vessel equipped with an agitator, temperature sensor, cooling pipe, and nitrogen introducing device, and are stirred at a stirring speed of 230 rpm under nitrogen stream. The temperature was raised to 80 ° C. After the temperature rise, an aqueous solution in which 10 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion-exchanged water is added, and the liquid temperature is again raised to 80 ° C. After dripping over time, polymerization was carried out by heating and stirring at 80 ° C. for 2 hours to prepare dispersion D1-1 of resin fine particles.
Styrene 480 parts by mass n-butyl acrylate 250 parts by mass methacrylic acid 68.0 parts by mass

(Second stage polymerization)
A solution of 7 parts by mass of sodium polyoxyethylene (2) dodecyl ether sulfate in 3000 parts by mass of ion-exchanged water is charged into a 5-liter reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device. A mechanical disperser having a circulation path by adding 260 parts by mass of dispersion liquid D1-1 of resin fine particles and a monomer and a releasing agent dissolved at 90 ° C. after heating to 260 ° C. The mixture was mixed and dispersed for 1 hour with “CLEARMIX” (manufactured by Em Technic Co., Ltd., “CLEARMIX” is a registered trademark of the company) to prepare a dispersion Do1-1 containing emulsified particles (oil droplets).
Styrene 284 parts by mass n-butyl acrylate 92 parts by mass methacrylic acid 13 parts by mass n-octyl 3-mercaptopropionate 1.5 parts by mass

  Then, an initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion-exchanged water is added to the dispersion Do1-1, and the dispersion is heated and stirred at 84 ° C. for 1 hour. The polymerization was carried out to prepare dispersion D1-2 of resin fine particles.

(Third stage polymerization)
Further, 400 parts by mass of ion exchange water is added to the dispersion liquid D1-2 of resin fine particles and thoroughly mixed, and then a solution of 11 parts by mass of potassium persulfate dissolved in 400 parts by mass of ion exchange water is added. Under the temperature conditions, a monomer mixture consisting of the following was added dropwise to the above dispersion over 1 hour. After completion of the dropwise addition, polymerization was carried out by heating and stirring for 2 hours, and then cooled to 28 ° C. to prepare an aqueous dispersion Dx1 of fine particles of amorphous resin X1 consisting of a vinyl resin.
Styrene 400 parts by mass n-butyl acrylate 128 parts by mass methacrylic acid 28 parts by mass methyl methacrylate 45 parts by mass n-octyl-3-mercaptopropionate 8 parts by mass

  With respect to the obtained aqueous dispersion Dx1, the volume-based median diameter of the non-crystalline resin X1 fine particles is 220 nm, the glass transition point (Tg) of the non-crystalline resin X1 is 55 ° C., and the Mw is 32,000. there were.

[Preparation of Aqueous Dispersion Dx2 of Amorphous Resin X2 Fine Particles]
An aqueous dispersion Dx2 of fine particles of the non-crystalline resin X2 was prepared in the same manner except that the amount of the monomers was changed as follows in the "third stage polymerization" of the preparation of the aqueous dispersion Dx1.
Styrene 400 parts by mass n-butyl acrylate 136 parts by mass methacrylic acid 20 parts by mass methyl methacrylate 45 parts by mass n-octyl-3-mercaptopropionate 8 parts by mass

  For the aqueous dispersion Dx2, the volume-based median diameter of the non-crystalline resin X2 fine particles was 210 nm, the Tg of the non-crystalline resin X2 was 53 ° C., and the Mw was 30,000.

[Preparation of Amorphous Resin X3]
The raw material monomers of the following polycondensation resin (amorphous polyester resin) unit were placed in a four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, and dissolved by heating to 170 ° C.
Bisphenol A propylene oxide 2 mol adduct 285.7 parts by mass Terephthalic acid 66.9 parts by mass Fumaric acid 47.4 parts by mass

  Subsequently, the raw material monomer of the addition polymerization resin was dropped over 90 minutes under stirring, and after aging for 60 minutes, the unreacted addition polymerization monomer was removed under reduced pressure (8 kPa).

Next, 0.4 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, the temperature was raised to 235 ° C., the reaction was conducted for 5 hours under normal pressure (101.3 kPa), and further for 1 hour under reduced pressure (8 kPa). went.

  Then, after cooling the obtained reaction solution to 200 ° C., the reaction was carried out under reduced pressure (20 kPa) until the desired softening point was reached. Subsequently, the solvent was removed to obtain an amorphous resin X3. The Tg of the obtained amorphous resin X3 was 61 ° C., and the Mw was 19,000.

Preparation of Aqueous Dispersion Dx3 of Amorphous Resin X3 Particles
100 parts by mass of amorphous resin X3 is dissolved in 400 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.), mixed with 638 parts by mass of 0.26% by mass aqueous solution of sodium lauryl sulfate prepared beforehand, and stirred After ultrasonic dispersion with ultrasonic homogenizer "US-150T" (made by Nippon Seiki Seisakusho Co., Ltd.) for 30 minutes at V-LEVEL 300μA while doing so, diaphragm vacuum pump "V-700" (in the state heated at 40 ° C) Ethyl acetate was completely removed using BUCHI product) while stirring under reduced pressure for 3 hours to prepare an aqueous dispersion Dx3 of amorphous resin X3 fine particles having a solid content of 13.5% by mass. The volume based median diameter of the fine particles of the amorphous resin X3 in the aqueous dispersion Dx3 was 170 nm.

[Preparation of Release Agent Particle Dispersion Liquid DW1]
The following components were mixed, and an ester wax as a release agent was dissolved at an internal liquid temperature of 120 ° C. with a pressure discharge type homogenizer (Gorin Co., Ltd., Gorin homogenizer). Thereafter, the dispersion was subjected to dispersion treatment for 120 minutes at a dispersion pressure of 5 MPa, and then for 360 minutes at 40 MPa, followed by cooling to obtain a dispersion of a release agent. The volume average particle diameter D50v (median diameter based on volume) of the particles in the dispersion was 225 nm. Thereafter, ion-exchanged water was added to the dispersion liquid to adjust the concentration of the release agent so that the solid content concentration was 20.0% by mass, and thus a dispersion DW1 of release agent particles was obtained.
Ester wax 270 parts by mass Anionic surfactant 13.5 parts by mass Ion-exchanged water 21.6 parts by mass

  The said ester wax is a Nippon Oil Co., Ltd. make, brand name: Nissan elector (the registered trademark of the company) WEP-3 (melting temperature Tw = 73 degreeC). Further, the above anionic surfactant is Neogen (registered trademark of the company) RK (the amount of the active ingredient: 60% by mass, 3.0% by mass with respect to the release agent as the active ingredient) manufactured by Daiichi Kogyo Seiyaku Co. It is.

[Preparation of aqueous dispersion liquid DCy of colorant fine particles]
90 parts by mass of sodium dodecyl sulfate was added to 1600 parts by mass of ion exchange water. While stirring this solution, 420 parts by mass of copper phthalocyanine is gradually added, and then dispersion processing is carried out using an agitator "Claremix" (manufactured by M. Technics Co., Ltd.) to obtain an aqueous dispersion DC of pigment fine particles. Was prepared.

  The average particle diameter (volume based median diameter) of the colorant fine particles in the obtained aqueous dispersion DCy was 110 nm.

[Preparation of aqueous dispersion DC1]
Dissolve 200 parts by mass of the hybrid crystalline resin C1 in 200 parts by mass of ethyl acetate, and while stirring this solution, dissolve sodium polyoxyethylene lauryl ether sulfate in 800 parts by mass of ion-exchanged water to a concentration of 1% by mass The aqueous solution was slowly dropped into the above solution. The resulting solution was adjusted to pH 8.5 with ammonia after removing ethyl acetate under reduced pressure. Thereafter, the solid content concentration was adjusted to 30% by mass. Thus, a dispersion liquid DC1 in which fine particles of the hybrid crystalline resin C1 were dispersed in an aqueous medium was prepared. The volume-based median diameter of the particles contained in the dispersion DC1 was 205 nm.

[Preparation of aqueous dispersions DC2 to DC12]
The preparation of dispersion DC1 is carried out in the same manner as in the preparation of dispersion DC1 except that each of hybrid crystalline resins C2 to C12 is used instead of hybrid crystalline resin C1. Dispersions DC2 to DC12 in which the respective fine particles were dispersed were obtained respectively. The volume-based median diameters of the particles contained in the dispersions DC2 to DC12 were all in the range of 190 to 230 nm.

Example 1 Production of Cyan Developer 1
360 parts by mass (in terms of solid content) of the aqueous dispersion Dx1, 40 parts by mass (in terms of solid content) of the dispersion DC1, and 2000 parts by mass of ion exchange water are introduced into a reaction vessel equipped with a stirrer, temperature sensor and cooling pipe Then, the pH of the above dispersion was adjusted to 10 by addition of 5 mol / L aqueous sodium hydroxide solution.

  Next, an aqueous solution in which 30 parts by mass (in terms of solid content) of the aqueous dispersion DCy and 56 parts by mass (in terms of solid content) of the dispersion DW1 is added, and then 60 parts by mass of magnesium chloride is dissolved in 60 parts by mass of ion exchanged water Was added over 10 minutes at 30.degree. C. under stirring. Then, after standing for 3 minutes, the temperature rise was started, and the obtained dispersion was heated to 80 ° C. over 60 minutes, and the particle growth reaction was continued while maintaining 80 ° C.

  In this state, the particle size of the associated particles is measured with "Coulter Multisizer 3" (manufactured by Coulter Beckman), and 190 parts by mass of sodium chloride is ion-exchanged when the volume-based median diameter reaches 6.4 μm. Particle growth was stopped by adding an aqueous solution dissolved in 760 parts by mass of water.

  Further, the temperature is raised, and heat fusion is carried out by heating and stirring in a state of 90 ° C., thereby promoting fusion of particles, and using a measuring device “FPIA-2100” (manufactured by Sysmex) of average toner circularity (HPF detection) When the average circularity was 0.945, the dispersion in the reaction vessel was cooled to 30 ° C. at a cooling rate of 2.5 ° C./min.

  Next, after repeating the solid-liquid separation and dewatering toner cake re-dispersion in ion-exchange water and solid-liquid separation three times, cyan toner mother particles 1X are obtained by drying at 40 ° C. for 24 hours. The

  0.6 parts by mass of hydrophobic silica (number average primary particle diameter = 12 nm, degree of hydrophobization = 68) and hydrophobic titanium oxide (number average primary particle diameter = 20 nm) in 100 parts by mass of the cyan toner base particle 1X obtained Degree of hydrophobization = 63) 1.0 part by mass is added, and after mixing for 20 minutes at 32 ° C and a rotor peripheral speed of 35 mm / sec using a "Henshell mixer" (manufactured by Nippon Coke Industry Co., Ltd.), 45 μm opening Cyan toner particles 1 were produced by the external additive treatment of removing coarse particles using a sieve. The volume average particle diameter of each of the cyan toner base particle 1 and the cyan toner particle 1 was 6.3 μm.

  A cyan developer 1 was produced by adding and mixing ferrite carrier coated with a silicone resin to a cyan toner particle 1 so that the volume concentration is 35 μm so that the toner concentration is 8% by mass.

[Examples 2 to 7: Production of cyan developers 2 to 7]
A cyan developer 2 was produced in the same manner as in Example 1 except that the aqueous dispersion DC2 was used instead of the aqueous dispersion DC1 and the aqueous dispersion Dx2 was used instead of the aqueous dispersion Dx1. Further, cyan developers 3, 6 and 7 were produced in the same manner as in Example 1 except that aqueous dispersions DC3, C6 and C7 were used in place of the aqueous dispersion DC1, respectively. Further, cyan developers 4 and 5 are respectively prepared in the same manner as in Example 1 except that the aqueous dispersion DC4 and DC5 are used instead of the aqueous dispersion DC1 and the aqueous dispersion Dx3 is used instead of the aqueous dispersion Dx1. Manufactured. The volume average particle diameters of the cyan toner particles 2 to 7 in the obtained cyan developers 2 to 7 were all in the range of 6.0 to 6.5 μm.

[Examples 8 and 9: Production of cyan developers 8 and 9]
A cyan developer 8 was produced in the same manner as in Example 1 except that the amount of the aqueous dispersion DC1 added was changed to 20 parts by mass and the amount of the aqueous dispersion Dx1 added was changed to 380 parts by mass. Further, cyan development is performed in the same manner as in Example 1, except that the aqueous dispersion DC2 of 120 parts by mass is used instead of the aqueous dispersion DC1 of 40 parts by mass and the addition amount of the aqueous dispersion Dx1 is changed to 280 parts by mass. Agent 9 was prepared. The volume average particle diameters of cyan toner particles 8 and 9 in the obtained cyan developers 8 and 9 were all in the range of 6.0 to 6.5 μm.

[Examples 10 and 11: Production of cyan developers 10 and 11]
An example except using the aqueous dispersion DC8 instead of the aqueous dispersion DC1 and changing the addition amount of the aqueous dispersion Dx1 to 320 parts by mass and further adding 40 parts by mass of the aqueous dispersion Dx3 before the above-mentioned pH adjustment In the same manner as in 1, a cyan developer 10 was produced. Further, a cyan developer 11 was produced in the same manner as in Example 10 except that the aqueous dispersion Dx2 was used instead of the aqueous dispersion Dx3. The volume average particle diameters of the cyan toner particles 10 and 11 in the obtained cyan developers 10 and 11 were all in the range of 6.0 to 6.5 μm.

[Examples 12 and 13: Production of cyan developers 12 and 13]
Cyan developers 10 and 11 were produced in the same manner as in Example 1 except that aqueous dispersions DC10 and C11 were used instead of the aqueous dispersion DC1. The volume average particle diameters of the cyan toner particles 10 and 11 in the obtained cyan developers 10 and 11 were all in the range of 6.0 to 6.5 μm.

Comparative Example 1: Production of Cyan Developer 14
A cyan developer 14 was produced in the same manner as in Example 1 except that the aqueous dispersion DC12 was used instead of the aqueous dispersion DC1 and the aqueous dispersion Dx3 was used instead of the aqueous dispersion Dx1. The volume average particle diameter of cyan toner particles 14 of the obtained cyan developer 14 was 6.1 μm.

Comparative Example 2: Production of Black Developer 1
The resin particle dispersion 1 described in Patent Document 1 was prepared based on the description of the example of Patent Document 1, and the black developer 1 was manufactured based on the description of Example 1 of Patent Document 1. The volume average particle diameter of the black toner particles 1 of the obtained black developer 1 was 6.0 μm.

[Evaluation of cyan developers 1 to 14 and black developer 1]
(1) Low-Temperature Fixing Evaluation Machine Evaluated by fixing the fixing device of the copying machine "bizhub PRO C6501" (manufactured by Konica Minolta) so that the surface temperature of the fixing heat roller can be changed in the range of 100 to 210 ° C. Was filled with cyan developer 1. Next, a fixing experiment was performed in which a solid image with a toner adhesion amount of 11 mg / 10 cm ² was fixed on OK embossed cloth made by Oji Paper Co., Ltd. (basis weight 104.7 g / m ² ), with the fixing temperature set at 140 ° C. . The test was performed for each of cyan developers 2 to 14 and black developer 1.

Then, the printed matter obtained in the above experiment was folded by a folding machine so as to apply a load to the solid image, a compressed air of 0.35 MPa was blown thereto, and the fold was evaluated based on the following evaluation criteria. The results are shown in Table 2. If it is rank 3 or more, there is no problem in practical use and it is judged as a pass.
(Evaluation criteria)
Rank 5: No crease at all Rank 4: Peeling according to part of the fold Rank 3: Fine linear peeling according to the fold Rank 2: Thick linear peeling according to the fold Rank 1: There is a big peeling.

(2) Evaluation of high temperature storage property 0.5 g of each of cyan developers 1 to 14 and black developer 1 is put into a 10 mL glass bottle with an inner diameter of 21 mm, the lid is closed, and tap denser KYT-2000 (manufactured by Seishin Enterprise Co., Ltd.) After shaking at room temperature for 600 times at room temperature, it was left in an environment of 55.degree. C. and 35% RH with the lid removed for 2 hours.

Next, place the above developer after standing on a 48 mesh (350 μm mesh) sieve carefully taking care not to crush aggregates of the developer, and set it in a powder tester (manufactured by Hosokawa Micron Corporation), After fixing with a presser bar and a knob nut, adjusting the vibration intensity to a feed width of 1 mm, applying vibration for 10 seconds, the ratio of the amount of developer remaining on the sieve (toner aggregation ratio At, mass%) was measured. At is a value calculated by the following equation.
At (mass%) = (remaining developer mass on sieve (g)) / 0.5 (g) × 100

From the determined At, the high temperature storage stability of the developer was evaluated according to the following criteria. If 判断 to △, it is judged as a pass.
(Evaluation criteria)
:: Toner aggregation rate is less than 15% by mass (heat-resistant storage stability of developer is extremely good)
○: Toner aggregation rate is 15% by mass or more and less than 20% by mass (the heat resistant storage stability of the developer is good)
:: Toner aggregation rate is 20% by mass or more and less than 25% by mass (the heat resistant storage stability of the developer is a little bad)
X: Toner aggregation rate is 25% by mass or more (heat storage stability of the developer is poor and can not be used)

(3) Charging uniformity (halftone reproducibility)
Using the cyan developers 1 to 14 and the black developer 1 respectively, copy the halftone chart with the above evaluation machine, measure the image density of this image at 5 points in the axial direction of the photoreceptor, and scatter the image density I asked for. Image density was measured using an image densitometer (Macbeth RD 914). The variation of the image density was calculated as the ratio (%) of the difference to the average value of the five points, by calculating the difference between the maximum value and the minimum value among the measured values of the five points. From the variation of the image density, the reproducibility of the halftone was evaluated based on the following evaluation criteria, and thereby the charging uniformity of the toner was evaluated. If 判断 to △, it is judged as a pass.
(Evaluation criteria)
:: Variation of image density is less than 10% (very good)
○: 10% or more but less than 15% (good)
Δ: Variation of image density is 15% or more and less than 20% ×: Variation of image density is 20% or more

  Table 2 shows the compositions and evaluation results of the binder resins of cyan developers 1 to 14 and black developer 1. In the table, the amount of the resin component represents the ratio (mass%) to the total amount of the binder resin.

  As is clear from Table 2, all of the cyan developers 1 to 13 in Examples 1 to 13 are hybrid crystalline resins in which the binder resin constituting the toner base particles has a main chain and two or more types of side chains. And at least one of the main chain and the two or more types of side chains is composed of a crystalline resin unit, and at least one of the two or more types of side chains is composed of an amorphous resin unit . The cyan developers 1 to 13 all exhibit sufficient performance in low-temperature fixability, high-temperature storage stability, and charge uniformity.

  On the other hand, Comparative Example 1 is insufficient in both high temperature storage stability and charging uniformity. This is because the side chain of the hybrid crystalline resin is only one type composed of the crystalline polyester resin unit, and the side chain does not contain the second side chain composed of the amorphous resin unit. It is considered that the crystalline polyester resin unit was not sufficiently dispersed inside the toner base particles and was unevenly distributed on the surface of the toner base particles and in the vicinity thereof.

  Further, Comparative Example 2 is insufficient in high-temperature storage stability. This is because the crystalline resin unit and the amorphous resin unit are linearly bonded in the binder resin, so that a part of the crystalline resin unit must be disposed on the surface of the toner base particle and in the vicinity thereof. As a result, it is considered that sufficient high temperature stability was not obtained.

  According to the present invention, the low temperature fixability and the charge uniformity of the toner are exhibited, and the compatibility of the binder resin component by the unintended external heat is suppressed. According to the present invention, it is expected that the versatility of the toner will be improved as well as performance improvement, speeding up and energy saving in the electrophotographic image forming technology, and further spread of the image forming technology is expected.

Reference Signs List 1 image forming apparatus 30 image processing unit 40 image forming units 41Y, 41M, 41C, 41K image forming unit 42 intermediate transfer unit 43 secondary transfer unit 50 sheet conveying unit 51 sheet feeding unit 51a, 51b, 51c sheet feeding tray unit 52 Paper portion 52a Paper discharge roller 53 Transport path portion 53a Registration roller pair 60 Fixing device 62 Fixing roller 63 Heat generation belt 64 Pressure roller 110 Image reading portion 111 Paper feeding device 112 Scanner 112a CCD sensor 411 Exposure device 412 Development device 413 Photosensitive drum 414 charging device 415 drum cleaning device 421 intermediate transfer belt 422 primary transfer roller 423, 431 support roller 423A backup roller 426 belt cleaning device 431A secondary transfer roller 43 2 Secondary Transfer Belt D Original S Paper

Claims (8)

In a toner for electrostatic latent image development having toner base particles containing a binder resin,
The binder resin includes a hybrid crystalline resin having a main chain and two or more side chains,
At least one of the main chain and the two or more types of side chains is composed of a crystalline resin unit,
At least one of the two or more side chains is composed of the amorphous resin unit,
The content of the crystalline resin unit in the hybrid crystalline resin is 70 to 95% by mass.
toner. The toner according to claim 1, wherein the hybrid crystalline resin contains the crystalline resin unit in at least one side chain thereof. The crystalline resin unit is a crystalline polyester resin unit, toner according to claim 1 or 2. The toner according to any one of claims 1 to 3 , wherein the amorphous resin unit is a vinyl resin unit. The toner according to any one of claims 1 to 4 , wherein a content of the hybrid crystalline resin in the binder resin is 5 to 30% by mass. The toner according to any one of claims 1 to 5 , wherein the binder resin further contains an amorphous resin. The toner according to claim 6 , wherein the amorphous resin is a vinyl resin. Toner for developing an electrostatic latent image containing toner base particles, comprising the steps of aggregating and fusing particles of hybrid crystalline resin dispersed in aqueous medium in an aqueous medium to produce toner base particles In the method of manufacturing
The hybrid crystalline resin has a main chain and two or more types of side chains, and at least one of the main chain and the two or more types of side chains is composed of a crystalline resin unit, and the two types At least one of the above side chains is composed of an amorphous resin unit, and a resin having a content of the crystalline resin unit in the hybrid crystalline resin of 70 to 95% by mass is used.
Method of manufacturing toner.

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