JP5707987B2 - Electrostatic image developing toner, electrostatic image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  A method of visualizing image information through an electrostatic latent image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic latent image formed on a photoreceptor by a charging process and an exposure process is developed with a developer containing toner, and visualized through a transfer process and a fixing process.

  For example, Patent Document 1 states that “a toner in which core particles containing a binder resin and a colorant are coated with shell particles, and has a volume average particle diameter of 4.0 μm or more and 8.0 μm or less. The toner having a particle size of 3.0 μm or less is contained in a ratio of 8% or more and less than 25% by number of the whole toner, and a part of the shell particles is fused with at least one of the core particles and the shell particles. Thus, a “toner characterized by forming protrusions” has been proposed.

  Patent Document 2 states that “a resin composition protrusion having an outer diameter ra is provided on the surface of the toner, the resin composition protrusion has a cross-linking structure, and the outer diameter ra of the resin composition protrusion and the toner The relationship between the volume average particle diameter D50 of the base particles satisfies a specific relationship, and the relationship between the solubility parameter of the resin composition protrusion and the solubility parameter of the resin composition of the toner base particle satisfies the specific relationship, and An electrostatic charge developing toner having a toner shape factor SF1 in the range of 110 to 120 has been proposed.

  Patent Document 3 states that “a toner composed of at least a binder resin, a colorant, and resin fine particles, and a ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner. Is in the range of 1.00 to 1.40, the glass transition point (Tg) of the resin fine particles is 50 to 90 ° C., and the coverage of the resin fine particles existing on the surface of the toner particles is in the range of 5 to 85%. Toner characterized by the above has been proposed.

JP 2009-15175 A JP 2008-158319 A JP 2009-134311 A

  An object of the present invention is to provide a toner for developing an electrostatic charge image that maintains filming and transferability while suppressing inhibition of low-temperature fixability.

The above problem is solved by the following means. That is,
The invention according to claim 1
Toner particles,
Resin particles partially embedded in the toner particles so as to protrude from the surface of the toner particles, comprising a core portion containing a non-crosslinked resin and a coating layer containing a crosslinked resin, and having a toluene insoluble content of 10 Resin particles having a volume average particle diameter of 200 nm or more and 400 nm or less,
A toner for developing an electrostatic charge image.

The invention according to claim 2
The electrostatic charge image developing toner according to claim 1, wherein the cross-linked resin is a cross-linked product of a tri- or higher functional cross-linking agent.

The invention according to claim 3
An electrostatic charge image developer comprising at least the electrostatic charge image developing toner according to claim 1.

The invention according to claim 4
Containing the electrostatic image developing toner according to claim 1,
A toner cartridge to be attached to and detached from the image forming apparatus.

The invention according to claim 5
A developer that contains the electrostatic charge image developer according to claim 3 and that develops the electrostatic charge image formed on the image carrier as a toner image with the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 6
An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 3 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer,
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
Image forming apparatus comprising

The invention according to claim 7 provides:
A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer according to claim 3;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
An image forming method comprising:

According to the first aspect of the present invention, the resin particles are not composed of the core portion containing the non-crosslinked resin and the coating layer containing the crosslinked resin, compared with the case where the toluene insoluble matter and the volume average particle diameter do not satisfy the above range. In addition, it is possible to provide a toner for developing an electrostatic charge image that maintains filming and transferability while suppressing inhibition of low-temperature fixability.
According to the second aspect of the invention, it is possible to provide a toner for developing an electrostatic charge image in which inhibition of low-temperature fixability is suppressed as compared with a case where the cross-linked resin is a cross-linked product of a trifunctional cross-linking agent and a resin.
According to the invention of claim 3, a toner is used in which the resin particles are not composed of a core portion containing a non-crosslinked resin and a coating layer containing a crosslinked resin, and the toluene insoluble content and the volume average particle diameter do not satisfy the above ranges. As compared with the above case, it is possible to provide a toner for developing an electrostatic charge image that maintains filming and transferability while suppressing inhibition of low-temperature fixability.

  According to the inventions according to claims 4, 5, 6, and 7, the resin particles are not composed of the core portion containing the non-crosslinked resin and the coating layer containing the crosslinked resin, and the toluene insoluble content and the volume average particle size are in the above range. As compared with the case where a toner that does not satisfy the above condition is applied, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method capable of obtaining an image in which filming and transfer defects are suppressed while realizing low-temperature fixing can be provided.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment. 1 is a schematic configuration diagram illustrating an electrostatic charge image developing toner according to an exemplary embodiment. FIG. 2 is a schematic partial cross-sectional view illustrating an electrostatic charge image developing toner according to an exemplary embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

(Static image developing toner)
FIG. 3 is a schematic configuration diagram showing the electrostatic image developing toner according to the present embodiment. FIG. 4 is a schematic partial cross-sectional view showing the electrostatic image developing toner according to this embodiment.

As shown in FIG. 3, the electrostatic image developing toner 100 according to the present embodiment (hereinafter sometimes referred to as toner 100) is, for example, a toner particle 101 and a toner particle 101 that protrudes from the surface of the toner particle 101. And the resin particles 102 embedded in the toner particles 101 (hereinafter referred to as protrusion resin particles 102).
And, as shown in FIG. 4, the resin particle 102 is composed of a core portion 102A containing a non-crosslinked resin and a coating layer 102B containing a crosslinked resin, and a toluene insoluble content is 10 mass% or more and 70 mass% or less, and The volume average particle size is 200 nm or more and 400 nm or less.
The toner 100 according to the present exemplary embodiment has a configuration in which a plurality of protrusions by the protrusion resin particles 102 are provided on the surface of the toner particles 101.

Here, for the purpose of improving the transferability, a toner having a projection portion made of resin particles on the surface of toner particles is known.
The toner having protrusions made of resin particles on the surface of the toner particles is crushed by a mechanical load during development, and the protrusions (resin particles) disappear and it is difficult to maintain transferability.
Therefore, in order to prevent the protrusions from being crushed, the use of crosslinked resin particles having a crosslinked structure as the resin particles constituting the protrusions suppresses crushing due to a mechanical load during development, thereby maintaining transferability. Is realized.
On the other hand, when cross-linked resin particles having a cross-linked structure are used as the resin particles constituting the protrusion, the non-cross-linked resin is higher than the glass transition temperature of the binder resin constituting the toner particles, and the low-temperature fixability as a toner is improved. It becomes easy to lose. This is particularly likely to occur when fixing energy is required as in a high-speed machine, such as fixing failure.

Therefore, in the toner 100 according to the present embodiment, the specific protrusion resin particles 102 are used as resin particles that form protrusions on the surface of the toner particles 101, thereby suppressing the low-temperature fixability. , Filming and transferability are maintained.
Although this reason is not certain, it is thought to be due to the following reasons.

The protruding portion resin particles 102 composed of the core portion 102A containing the non-crosslinked resin and the coating layer 102B containing the cross-linked resin have a three-dimensional network in which the periphery (surface) of the core portion 102A containing the non-crosslinked resin is a cross-linked resin. Since the structure is covered with the coating layer 102B having a high hardness, the strength is easily maintained as compared with the resin particles composed of only the non-crosslinked resin, and the mechanical load during development is increased. It is thought that crushing is suppressed.
On the other hand, the amount of the cross-linking resin that tends to hinder the low-temperature fixability compared to the cross-linked resin that hardly has a difference from the glass transition temperature of the binder resin constituting the toner particles and hardly hinders the low-temperature fixability; By setting the toluene-insoluble content of the particles 102 within the above range, it is considered that the amount of the crosslinked resin that inhibits the low-temperature fixability can be suppressed while maintaining the intended strength of the resin particles 102 for protrusions.
Then, by setting the volume average particle size of the protruding portion resin particles 102 in the above-mentioned range, the embedding of the external additive in the toner particles 101 is suppressed, while the protruding portion resin particles 102 themselves from the toner particles 101. It is thought that the withdrawal of is suppressed.

For this reason, it is considered that the toner 100 according to the present embodiment maintains the transferability while suppressing the inhibition of the temperature fixability.
By using the toner 100 according to the present embodiment for image formation, an image in which transfer defects are suppressed while low-temperature fixing is realized can be obtained.

  Hereinafter, each component of the toner 100 according to the exemplary embodiment will be described in detail. In the following description, reference numerals are omitted.

The toner according to the exemplary embodiment includes toner particles and, if necessary, an external additive.
Further, the surface of the toner particle has a protruding portion made of the protruding portion resin particles.

The toner particles will be described.
The toner particles include, for example, a binder resin and, if necessary, other additives such as a colorant and a release agent.

  The binder resin is not particularly limited, but styrenes (eg, styrene, chlorostyrene, etc.), monoolefins (eg, ethylene, propylene, butylene, isoprene, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, Vinyl benzoate, vinyl butyrate, etc.), α-methylene aliphatic monocarboxylic acid esters (eg methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, methacrylic acid) Ethyl acetate, butyl methacrylate, dodecyl methacrylate, etc.), vinyl ethers (eg, vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether), vinyl ketones (eg, vinyl methyl ketone, vinyl hexyl ketone, vinyl isopro) Homopolymers and copolymers of Niruketon etc.), etc., and polyester resins by copolymerization of dicarboxylic acids and diols.

Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. Examples thereof include a polymer, a polyethylene resin, a polypropylene resin, and a polyester resin.
Typical binder resins include polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

  The colorant is not particularly limited as long as it is a known colorant. For example, carbon black such as furnace black, channel black, acetylene black, and thermal black, inorganic pigments such as bengara, bitumen, and titanium oxide, fast yellow, disazo Azo pigments such as yellow, pyrazolone red, chelate red, brilliant carmine, para brown, phthalocyanine pigments such as copper phthalocyanine, metal-free phthalocyanine, flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, dioxazine violet Examples thereof include cyclic pigments.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  As content of a coloring agent, the range of 1 to 30 mass parts is desirable with respect to 100 mass parts of binder resin.

  Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; ester types such as fatty acid esters and montanic acid esters. Wax; and the like, but is not limited thereto.

  The melting point of the release agent is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoint of storage stability. Further, from the viewpoint of offset resistance, the temperature is desirably 110 ° C. or less, and more desirably 100 ° C. or less.

  As content of a mold release agent, the range of 2 to 30 mass parts is desirable with respect to 100 mass parts of binder resin, for example.

  Examples of other additives include magnetic substances, charge control agents, inorganic powders, and the like.

The characteristics of the toner particles will be described.
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
The toner particles having a core / shell structure include, for example, a core that includes a binder resin and, if necessary, other additives such as a colorant and a release agent, and a binder resin. And a coating layer.
The toner particles having a core / shell structure may have a configuration in which part of the resin particles for protrusions is buried in the coating layer to form protrusions.

The volume average particle diameter of the toner particles (excluding protrusions) is, for example, 2.0 μm or more and 10 μm or less, and desirably 3.5 μm or more and 7.0 μm or less.
As a method for measuring the volume average particle diameter of the toner particles, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5% by weight aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. The electrolyte was added to 100 ml to 150 ml. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the above-mentioned Coulter Multisizer II type (manufactured by Beckman-Coulter) is used to produce particles using an aperture having an aperture diameter of 100 μm. The particle size distribution of particles having a diameter in the range of 2.0 μm to 60 μm is measured. The number of particles to be measured is 50,000.
For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is defined as the volume average particle size D50v.

Next, the resin particles for protrusions will be described.
The resin particles for protrusions are composed of a core portion containing a non-crosslinked resin and a coating layer containing a crosslinked resin.
In addition to the resin, the core part and the coating layer may contain other additives (for example, a polymerization initiator, a surfactant, a chain transfer agent, etc.) as necessary.

The non-crosslinked resin constituting the core part will be described.
Examples of the non-crosslinked resin constituting the core include a polymer of a monomer containing at least one or more polymerizable monomers having a vinyl double bond.

Examples of the polymer monomer having a vinyl double bond include a monomer containing a radical polymerizable vinyl group.
As monomers containing radically polymerizable vinyl groups, aromatic vinyl monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers Body, diolefin monomer, halogenated olefin monomer and the like.
In addition, (meth) acryl means that it is either or both of acryl and methacryl.

Examples of the aromatic vinyl monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2, Examples thereof include styrene monomers such as 4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof.
Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples include butyl, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.
Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate.
Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like. Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.
Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like. Examples of halogenated olefin monomers include vinyl chloride, vinylidene chloride, vinyl bromide, etc.
These monomers are not limited to these, and these monomers may be used alone or in combination of two or more.

A chain transfer agent may be used for the polymerization of these monomers.
The chain transfer agent is not particularly limited, and examples thereof include compounds having a thiol component, specifically, for example, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan, etc. Alkyl mercaptans are preferred, and the molecular weight distribution is particularly narrow, so that the storage stability of the toner at high temperatures is good.

When performing radical polymerization as polymerization of these monomers, an initiator for radical polymerization may be used.
There is no restriction | limiting in particular as an initiator for radical polymerization. Specifically, for example, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, Lauroyl oxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid tert-butyl hydroperoxide, formic acid tert- Peroxides such as butyl, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl permethoxyacetate, tert-butyl per-N- (3-toluyl) carbamate, , 2'-azo Bispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2 '-Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2 -Methyl methyl propionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis ( 1-methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4′-azobis-4-cyanovaleric acid, 3,5-dihydroxymethyl Enylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyano Dimethyl herbate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azobis-1 -Chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-nitrophenylazobenzylcyanoacetate ethyl, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenyla Triphenylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2′-azo Azo compounds such as bisisobutyrate), 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like.

The resin constituting the coating layer will be described.
Examples of the cross-linked resin constituting the coating layer include a cross-linked product of a resin with a cross-linking agent (for example, a non-cross-linked resin constituting the core), and in particular, from the viewpoint of suppressing inhibition of low-temperature fixability. It is preferable that the resin is a cross-linked product of the cross-linking agent.
The cross-linked product of the resin with a tri- or higher functional cross-linking agent has a higher cross-linking hardness than the cross-linked product of a bi-functional or lower functional cross-linking agent, and the strength of the coating layer is increased with a small amount of cross-linked resin (toluene insoluble matter) Conceivable. As a result, it becomes easy to suppress inhibition of low-temperature fixability while maintaining the strength of the protrusion resin particles.

Specifically, as a cross-linked product of a resin by a cross-linking agent, for example, a monomer for forming a non-cross-linked resin (for example, a vinyl double bond exemplified for forming a non-cross-linked resin constituting a core part) And a crosslinked polymer obtained by polymerizing and crosslinking a monomer having at least one or more polymerizable monomers) together with a crosslinking agent.
The cross-linked product of the resin by the cross-linking agent may be a cross-linked product of a resin in which a cross-linking reaction is caused by the cross-linking agent with respect to the formed non-cross-linked resin (for example, non-cross-linked resin constituting the core part).
In addition, a crosslinking agent can be used individually or in combination of 2 or more types.

Examples of the crosslinking agent (crosslinkable monomer) include a crosslinkable monomer having two or more polymerizable carbon-carbon unsaturated double bonds.
Examples of such crosslinkable monomers include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; dimethacrylate compounds such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate, and divinyl ether. And compounds having two vinyl groups in the molecule; compounds having three or more vinyl groups in the molecule such as pentaerythritol triallyl ether and trimethylolpropane triacrylate.
Among these, compounds having three or more vinyl groups in the molecule such as pentaerythritol triallyl ether and trimethylolpropane triacrylate, that is, “trifunctional or higher functional crosslinking agent” are preferable.

  Specifically, when the functional group of the non-crosslinked resin (its monomer) has a carboxyl group, examples of the crosslinking agent include compounds having an epoxy group or an isocyanate group, metal compounds, and the like.

  As the compound having an epoxy group, a compound having two or more epoxy groups, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, 1,3,4-diepoxybutane, allyl glycidyl ether, glycidyl acrylate, β-methylglycidyl acrylate, glycidyl methacrylate, β-methyl methacrylate Glycidyl, etc.

As the compound having an isocyanate group, a polyisocyanate compound such as tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, a prepolymer having an isocyanate group (hydroxyl-containing polyester, hydroxyl-containing polyether, etc.) And a polymer having an isocyanate group at the terminal obtained by reacting the above polyisocyanate with an excess amount of the above-mentioned polyisocyanate).
The metal compound is preferably a water-soluble metal compound having a valence of 2 or more, and a halide of a metal such as boron, aluminum, iron, copper, zinc, tin, titanium, nickel, magnesium, vanadium, chromium, zirconium, etc. , Salts (carbonates, nitrates, sulfates, etc.), oxides or hydroxides. Among these, boric acid, borax, aluminum chloride, aluminum sulfate, ammonium zirconium carbonate, zirconium chloride, iron alum and the like are particularly preferable.

  When there is a hydroxyl group in the functional group of the non-crosslinked resin (its monomer), examples of the crosslinking agent include compounds having a carboxyl group or acid anhydride group, compounds having an aldehyde group, compounds having an epoxy group, nitrogen Examples of the compound include a compound having an acrylamide moiety, a compound having an isocyanate group, and a metal compound. Among these, a compound having a carboxyl group or an acid anhydride group (particularly a polyvalent carboxylic acid or acid anhydride thereof) and a metal compound are preferable.

Examples of the polyvalent carboxylic acid include aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, aromatic polycarboxylic acid, oxypolycarboxylic acid, and heterocyclic polycarboxylic acid.
Examples of the aliphatic polycarboxylic acid include aliphatic saturated polycarboxylic acids having 2 to 10 carbon atoms (for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid). Etc.), or aliphatic unsaturated polycarboxylic acids having 4 to 6 carbon atoms (fumaric acid, maleic acid, maleic anhydride, citraconic acid, mesaconic acid, itaconic acid, etc.).
Examples of the alicyclic polycarboxylic acid include alicyclic polycarboxylic acids having 8 to 10 carbon atoms (for example, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc.).
As the aromatic polycarboxylic acid, an aromatic polycarboxylic acid having 8 to 12 carbon atoms or an acid anhydride thereof (for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) Is mentioned.
Examples of the oxypolycarboxylic acid include oxypolycarboxylic acids having 3 to 6 carbon atoms (for example, tartronic acid, malic acid, tartaric acid, citric acid, etc.).
The heterocyclic polyvalent carboxylic acid is a polyvalent carboxylic acid having at least one heteroatom selected from nitrogen, oxygen and sulfur atoms (for example, pyridinedicarboxylic acid, pyridinetricarboxylic acid, pyridinetetracarboxylic acid, tropic acid, etc.) Etc. As the polyvalent carboxylic acid in the heterocyclic polyvalent carboxylic acid, an aliphatic, alicyclic or aromatic polycarboxylic acid (particularly a polycarboxylic acid having 3 to 10 carbon atoms) is preferably used.
Here, examples of the polyvalent carboxylic acid include salts or partial salts of polyvalent carboxylic acids. Examples of the polyvalent carboxylates include inorganic salts such as ammonium salts and alkali metal salts (potassium salts, sodium salts, etc.) and organic salts such as tertiary amines. As the polyvalent carboxylic acid, maleic acid or its acid anhydride (maleic anhydride) is particularly preferable.

  Examples of the compound having an aldehyde group include compounds having a plurality of aldehyde groups, such as glyoxal, malonaldehyde, glutaraldehyde, terephthalaldehyde, dialdehyde starch, and acrolein copolymer acrylic resin.

  Examples of nitrogen-containing compounds include C1-C4 alkoxymelamines such as methoxymethylmelamine, methylol group-containing compounds such as N-methylolmelamine and N-methylolurea, guanamines such as acetoguanamine and benzoguanamine, melamine-formalin resin, urea -Formalin resin etc. are mentioned.

  Examples of the compound having an acrylamide group include methylene-bis (meth) acrylamide, N, N′-dimethylol-methylene-bisacrylamide, 1,1-bisacrylamide-ethane, and the like.

  About the compound and metal compound which have an epoxy group or an isocyanate group, what was mentioned above is mentioned.

  In the case where the functional group of the non-crosslinked resin (its monomer) is a functional group other than a carboxyl group and a hydroxyl group, a crosslinking agent having a functional group capable of reacting with the functional group should be selected in consideration of the above explanation. That's fine. For example, when the functional group is an amide group, a dihydroxy compound may be used.

  The mass ratio between the non-crosslinked resin (its monomer) and the crosslinking agent is, for example, 11 parts by mass or more and 233 parts by mass or less, preferably 67 with respect to 100 parts by mass of the non-crosslinked resin (its monomer). The above is 150 parts by mass.

The characteristic of the resin particle for protrusion parts is demonstrated.
The toluene-insoluble content (that is, the content of the crosslinked resin constituting the coating layer) of the resin particles for protrusions is, for example, 10% by mass to 70% by mass, and preferably 40% by mass to 60% by mass. .
When there is too little toluene insoluble content, it becomes difficult to maintain the strength of the resin particles for protrusions, and crushing tends to occur. On the other hand, when there is too much toluene insoluble matter, the low-temperature fixability tends to be hindered.

A method for measuring the toluene insoluble content of the resin particles for the protrusion is performed as follows.
(1) The resin particles for protrusions were separated at 13,000 rpm for 30 minutes with a centrifugal freeze dryer, and the separated cake was dried with a vacuum dryer at 40 ° C. for 24 hours. 0.2 g to 0.3 g of resin particles for protrusions after drying are weighed directly into a 25 ml Erlenmeyer flask, sealed with 20 ml of toluene, and allowed to stand for 24 hours.
(2) Transfer (1) to a glass tube for centrifugation.
(3) 20 ml of toluene is again added to (1), the Erlenmeyer flask is washed, transferred to the glass tube of (2), and sealed.
(4) Centrifuge (3) for 30 minutes under the conditions of 20,000 rpm and -10 ° C.
(5) Take out (4) and leave it until it reaches room temperature.
(6) Weigh 5 ml of the supernatant in (5), take out into a measured aluminum dish, and heat the aluminum dish on the pot plate to evaporate toluene.
(7) (6) is dried with a vacuum dryer at 50 ° C. for 24 hours, and this is weighed together with the mass of the aluminum dish as toluene-insoluble matter in 5 ml.
(8) The toluene insoluble matter is calculated by the following formula.
Formula: {sample amount-[(toluene-dissolved portion and aluminum dish mass) -aluminum dish mass] × (40 ÷ 5)} ÷ sample amount × 100 = toluene insoluble content (mass%)

The average particle size of the resin particles for protrusions (that is, the size of the protrusions formed by the resin particles for protrusions) is, for example, 200 nm or more and 400 nm or less, and preferably 250 nm or more and 350 nm or less. It is said.
If the volume average particle size is too small, the external additive tends to be buried in the toner particles. On the other hand, if the average particle size is too large, the protrusion resin particles themselves tend to be detached from the toner particles. The detached resin particles for protrusions cause a phenomenon of fixing on the surface of the image carrier (so-called filming).

The measuring method of the average particle diameter of the resin particles for protrusions is performed as follows.
The toner is observed with a scanning electron microscope (SEM), the number average value of 100 protrusions is obtained, and the number average value of the outer diameters is set as the average particle diameter of the resin particles for the protrusions.

The content of the resin particles for protrusions is, for example, preferably from 1% by mass to 23% by mass, and more preferably from 2% by mass to 11% by mass with respect to the toner particles.
That is, when the surface area of the toner particles is 100, the ratio of the surface area occupied by the protrusions due to the resin particles for protrusions is preferably 4 or more and 80 or less, and more preferably 8 or more and 40 or less.
By setting the content of the resin particles for the protrusions in the above range, it becomes easy to improve transferability while suppressing the inhibition of low-temperature fixability.

Next, the manufacturing method of the resin particle for protrusion parts is demonstrated.
Specifically, for example, the resin particles for protrusions are
Monomer for forming a non-crosslinked resin constituting the core (for example, a monomer containing at least one or more polymerizable monomers having a vinyl double bond) An aqueous medium) a step of polymerizing to form non-crosslinked resin particles as a core;
A monomer (for example, having a vinyl double bond) for forming a crosslinked resin constituting the coating layer with respect to the dispersion in which the non-crosslinked resin particles in which the non-crosslinked resin particles serving as the core are dispersed is dispersed. A monomer containing at least one or more polymerizable monomers)) and a crosslinking agent are mixed, and the monomer is crosslinked and polymerized together with the crosslinking agent on the surface of the non-crosslinked resin particles as the core. Forming a cross-linked resin, and forming a coating layer containing the cross-linked resin on the surface of the non-cross-linked resin particles serving as the core;
It is better to manufacture after going through.

  As a method for producing the resin particles for the protrusions, for example, a known polymerization method such as an emulsion polymerization method, a mini-emulsion method, a suspension polymerization method, a dispersion polymerization method may be used. , Surfactants, initiators, emulsifiers, stabilizers, etc. are used in combination.

Next, the external additive will be described.
Examples of the external additive include inorganic particles. Examples of the inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, and CaO. , K ₂ O, Na ₂ O, ZrO ₂ , CaO.SiO ₂ , K ₂ O. (TiO ₂ ) _n , Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO _{4 and the} like. .

The surface of the external additive may be hydrophobized in advance. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually about 1 part by mass or more and about 10 parts by mass with respect to 100 parts by mass of the inorganic particles, for example.

  The external addition amount of the external additive is preferably 0.5 parts by mass or more and 2.5 parts by mass or less with respect to 100 parts by mass of the toner particles.

Hereinafter, a toner manufacturing method according to the exemplary embodiment will be described.
First, toner particles may be produced by a dry process (for example, a kneading and pulverization method), a wet process (for example, an aggregation coalescence method, a suspension polymerization method, a solution suspension granulation method, a solution suspension method, a solution emulsion aggregation method, or the like. ). There is no restriction | limiting in particular in these manufacturing methods, A well-known manufacturing method is employ | adopted.

Specifically, for example, when producing toner particles (toner particles having a core / shell structure) by an aggregation coalescence method,
At least a first resin particle dispersion in which first resin particles (first resin particles for binder resin constituting the core of toner particles) are dispersed is prepared, and at least the first resin particles are aggregated to form a first resin particle dispersion. A step of forming aggregated particles (first aggregation step);
A first agglomerated particle dispersion in which the first agglomerated particles are dispersed; a second resin particle dispersion in which the second resin particles (second resin particles for the binder resin constituting the coating layer of the toner particles) are dispersed; , The protrusion resin particle dispersion in which the protrusion resin particles are dispersed, and agglomerated so that the second resin particles and the protrusion resin particles adhere to the surface of the first agglomerated particles, A step of forming second agglomerated particles (second agglomeration step);
Heating the second agglomerated particle dispersion in which the second agglomerated particles are dispersed, fusing and coalescing the second agglomerated particles to form toner particles (fusing and coalescing step);
Through this process, it is preferable to produce toner particles.

The method for producing toner particles is not limited to the above method. For example, in the case of producing single-layer toner particles, resin particles (resin particles for binder resin constituting the toner particles) are dispersed. A step of preparing at least a dispersion and a resin particle dispersion for protrusions in which resin particles for protrusions are dispersed, mixing them, and then aggregating the resin particles and the resin particles for protrusions to form aggregated particles And heating the agglomerated particle dispersion in which the agglomerated particles are dispersed, fusing and coalescing the agglomerated particles to form toner particles (fusing and fusing step), It may be manufactured.
However, from the viewpoint of efficiently forming the protrusions by the resin particles for the protrusions on the surface of the toner particles, it is preferable to employ an agglomeration and coalescence method for the toner particles (toner particles having a core / shell structure).

Details of each step will be described below.
In the following description, a method of obtaining toner particles containing a colorant and a release agent will be described. However, the colorant and the release agent are used as necessary. Of course, you may use other additives other than a coloring agent and a mold release agent.

-First aggregated particle forming step-
First, together with the first resin particle dispersion in which the first resin particles are dispersed, for example, a colorant particle dispersion in which the colorant particles are dispersed and a release agent dispersion in which the release agent particles are dispersed are prepared.

The first resin particles dispersed in the first resin particle dispersion are resin particles for the binder resin that constitute the core of the toner particles.
The first resin particle dispersion may be prepared as a single resin particle dispersion by preparing and mixing each resin particle dispersion when applying two or more kinds of first resin particles. You may mix each resin particle dispersion | distribution when mixing with a coloring agent particle dispersion and a mold release agent particle dispersion.

  The first resin particle dispersion is prepared, for example, by dispersing the first resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the first resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

The surfactant is not particularly limited. For example, anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; amine salt type, quaternary ammonium salt type Nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and the like. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of a method for dispersing the first resin particles in the dispersion medium in the first resin particle dispersion include general dispersion methods such as a rotary shear type homogenizer, a ball mill having media, a sand mill, and a dyno mill. Further, depending on the type of resin particles used, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

Examples of the volume average particle diameter of the first resin particles dispersed in the first resin particle dispersion include a range of 0.01 μm to 1 μm, and may be 0.08 μm to 0.8 μm. It may be 1 μm or more and 0.6 μm.
The volume average particle diameter of the resin particles is measured with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.). Hereinafter, unless otherwise specified, the volume average particle diameter of the particles is measured in the same manner.

  As content of the 1st resin particle contained in 1st resin particle dispersion liquid, 5 mass% or more and 50 mass% or less are mentioned, for example, and 10 mass% or more and 40 mass% or less may be sufficient.

In addition, similarly to the first resin particle dispersion, for example, a colorant dispersion and a release agent dispersion are also prepared. In other words, regarding the volume average particle diameter of the particles in the first resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the colorant particles dispersed in the colorant dispersion and the dispersion in the release agent dispersion The same applies to the release agent particles.
The same applies to the second resin particles and the protrusion resin particles (except for the particle diameter of the protrusion resin particles).

Next, the colorant particle dispersion and the release agent dispersion are mixed together with the first resin particle dispersion.
Then, the first resin particles, the colorant particles, and the release agent particles are hetero-aggregated in the mixed dispersion, and the first resin particles, the colorant particles, and the release agent have a diameter close to the diameter of the target toner particles. First aggregated particles (core aggregated particles) including agent particles are formed.

Specifically, for example, a flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. Then, the glass transition temperature of the first resin particles (specifically, for example, the glass transition temperature of the first resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less) is heated and dispersed in the mixed dispersion. The agglomerated particles are agglomerated to form first agglomerated particles.
In the first agglomerated particle forming step, for example, the flocculant is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, pH is 2 or more). 5 or less) and, if necessary, after adding a dispersion stabilizer, the heating may be performed.

Examples of the flocculant include surfactants having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, for example, inorganic metal salts and divalent or higher-valent metal complexes. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
Examples of the addition amount of the chelating agent include a range of 0.01 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin particles, and 0.1 parts by mass or more and less than 3.0 parts by mass. There may be.

-Second aggregated particle forming step-
Next, the obtained first aggregated particle dispersion in which the first aggregated particles are dispersed and the second resin particles (second resin particles for the binder resin constituting the coating layer of the toner particles) are dispersed. (2) The resin particle dispersion and the protrusion resin particle dispersion in which the protrusion resin particles are dispersed are mixed. The second resin particle dispersion and the protrusion resin particle dispersion may be mixed in advance and mixed with the first aggregated particle dispersion.
Then, in this mixed dispersion, the second resin particles and the protrusion resin particles are aggregated so as to adhere to the surface of the first aggregate particles, and the second resin particles and the protrusion portions are adhered to the surface of the first aggregate particles. Second agglomerated particles with resin particles adhered thereto are formed.

Specifically, for example, in the first aggregated particle forming step, the first aggregated particles reach the target particle size (for example, the volume average particle size is 1.5 μm or more, desirably 2.5 μm or more and 6.5 μm or less). In this case, the first aggregated particle dispersion is mixed with the second resin particle dispersion and the protrusion resin particle dispersion, and the first aggregated particle and the second resin particle glass are mixed with the mixed dispersion. Heating is performed below the lower glass transition temperature of the transition temperatures.
Then, the progress of aggregation is stopped by setting the pH of the mixed dispersion to a range of, for example, about 6.5 to 8.5.

  Here, in the second resin particle dispersion liquid, the volume average particle size of the second resin particles to be dispersed is smaller than the resin particles for the protrusions, for example, a range of 0.01 μm or more and 1 μm or less, and 0.05 μm. It may be 0.8 μm or less and may be 0.1 μm or more and 0.6 μm, but particularly preferably less than 0.3 μm (300 nm).

  By the second aggregated particle forming step, second aggregated particles aggregated so that the second resin particle dispersion and the protrusion resin particles adhere to the surface of the first aggregated particles are obtained.

-Fusion / unification process-
Next, with respect to the second aggregated particle dispersion in which the second aggregated particles are dispersed, for example, the glass transition temperature of the second resin particles or higher (for example, the temperature of 10 to 30 ° C. higher than the glass transition temperature of the second resin particles) And the second aggregated particles are fused and united to form toner particles.

  Through the above steps, toner particles (core / core) comprising a core part and a coating layer covering the core part, in which part of the resin particles for protrusions are buried in the coating layer and protrusions formed by the particles are formed. Shell structure toner particles) are obtained.

After the fusion and coalescence process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, although the drying process is not particularly limited, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing is preferably performed by, for example, a V blender, a Henshur mixer, a ladyge mixer or the like. Further, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

  There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. Examples of the carrier include a resin-coated carrier, a magnetic dispersion carrier, a resin dispersion carrier, and the like.

  In the two-component developer, the mixing ratio (mass ratio) of the toner according to the exemplary embodiment and the carrier is preferably in the range of toner: carrier = 1: 100 to 30: 100, and about 3: 100 to 20: 100. The range of is more desirable.

(Image forming apparatus / image forming method)
Next, the image forming apparatus / image forming method according to the present embodiment will be described.
An image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic image development. A developing means for accommodating the developer and developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer, and transferring the toner image formed on the image carrier onto the transfer target And a fixing unit that fixes the toner image transferred onto the transfer target. The electrostatic image developer according to the present embodiment is applied as the electrostatic image developer.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, A process cartridge that accommodates the electrostatic charge image developer according to the exemplary embodiment and includes a developing unit is preferably used.

  The image forming method according to the present embodiment contains a charging step for charging the image carrier, an electrostatic charge image forming step for forming an electrostatic charge image on the surface of the charged image carrier, and an electrostatic charge image developer. A developing step of developing the electrostatic image formed on the image carrier as a toner image with an electrostatic charge image developer, and a transfer step of transferring the toner image formed on the image carrier onto the transfer target; And a fixing step of fixing the toner image transferred onto the transfer medium. And as the electrostatic charge image developer, the electrostatic charge image developer according to the present embodiment is applied.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

  FIG. 1 is a schematic configuration diagram showing a four-tandem color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. The vehicle travels in the direction toward the unit 10K. A force is applied to the support roller 24 in a direction away from the drive roller 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners can be supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first image that forms the yellow image disposed on the upstream side in the intermediate transfer belt traveling direction is formed. The unit 10Y will be described as a representative. Note that the second to fourth components are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photosensitive member 1Y, a charging roller 2Y for charging the surface of the photosensitive member 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal to form an electrostatic charge image. An exposure device (electrostatic image forming means) 3 for forming, a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image, and transferring the developed toner image onto the intermediate transfer belt 20 A primary transfer roller 5Y (primary transfer unit) that performs the transfer and a photoconductor cleaning device (cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer are sequentially arranged.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer according to the present embodiment including at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a primary transfer bias is applied to the primary transfer roller 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roller 5Y acts on the toner image. Then, the toner image on the photoreceptor 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner. The

  The intermediate transfer belt 20 onto which the four color toner images have been transferred in multiple layers through the first to fourth units is arranged on the image transfer surface side of the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording paper (transfer object) P is fed at a predetermined timing to the gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via the supply mechanism, and the secondary transfer bias is supported. Applied to the roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is sent to the pressure contact portions (nip portions) of the pair of fixing rolls in the fixing device (roll-type fixing unit) 28, and the toner image is fixed on the recording paper P, thereby forming a fixed image.

Examples of the transfer target to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers.
In order to further improve the smoothness of the image surface after fixing, it is desirable that the surface of the transfer target is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with resin, art for printing Paper or the like is preferably used.

The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but is not limited to this configuration, and the toner image is directly transferred from the photoreceptor. It may be a structure that is transferred to a recording sheet.

(Process cartridge, toner cartridge)
FIG. 2 is a schematic configuration diagram showing an embodiment of a preferred example of a process cartridge containing an electrostatic charge image developer according to this embodiment. In the process cartridge 200, a charging roller 108, a developing device 111, a photoconductor cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are combined using a mounting rail 116 together with the photoconductor 107. , And integrated. In FIG. 2, reference numeral 300 denotes a transfer target.
The process cartridge 200 is detachable from an image forming apparatus including a transfer device 112, a fixing device 115, and other components not shown.

  The process cartridge 200 shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. Can be combined. In the process cartridge according to the present embodiment, in addition to the photosensitive member 107, the charging device 108, the developing device 111, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. At least one selected from the group consisting of:

  Next, the toner cartridge according to this embodiment will be described. The toner cartridge according to the present exemplary embodiment is a toner cartridge that is detachably attached to the image forming apparatus and stores at least a replenishment electrostatic image developing toner to be supplied to a developing unit provided in the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K can be attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are respectively the developing devices ( And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention. In the text, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

[Preparation of polyester resin particles (dispersion liquid)]
(Preparation of polyester resin (A1) and polyester resin particle dispersion (a1))
In a heat-dried two-necked flask, 15 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (2,2) -2,2-bis (4 -Hydroxyphenyl) propane 85 mol part, terephthalic acid 10 mol part, fumaric acid 67 mol part, n-dodecenyl succinic acid 3 mol part, trimellitic acid 20 mol part, and these acid components (terephthalic acid, n After adding 0.05 mol part of dibutyltin oxide to the total number of moles of dodecenyl succinic acid, trimellitic acid and fumaric acid), introducing nitrogen gas into the container and maintaining the inert atmosphere to raise the temperature The copolycondensation reaction was carried out at 150 to 230 ° C. for 12 to 20 hours. Thereafter, the pressure was gradually reduced at 210 ° C. to 250 ° C. to synthesize a polyester resin (A1). This resin had a weight average molecular weight Mw of 65000 and a glass transition temperature Tg of 65 ° C.

  In an emulsification tank of a high-temperature / high-pressure emulsification apparatus (Cabitron CD1010, slit: 0.4 mm), 3000 parts by mass of the obtained polyester resin, 10000 parts by mass of ion-exchanged water, and 90 parts by mass of a surfactant sodium dodecylbenzenesulfonate were added. Then, after heating and melting at 130 ° C., it was dispersed at 110 ° C. at a flow rate of 3 L / m at 10,000 rpm for 30 minutes, passed through a cooling tank, and then passed through an amorphous resin particle dispersion (high temperature / high pressure emulsifier (Cabitron CD1010 slit 0 .4 mm) was recovered to obtain a polyester resin particle dispersion (a1).

(Preparation of polyester resin (B1) and polyester resin particle dispersion (b1))
Into a heat-dried three-necked flask, 45 mol parts of 1,9-nonanediol, 55 mol parts of dodecanedicarboxylic acid and 0.05 mol parts of dibutyltin oxide as a catalyst were added, and the air in the container was then decompressed. Was placed in an inert atmosphere with nitrogen gas, and stirred at 180 ° C. for 2 hours with mechanical stirring. Then, it heated up gradually to 230 degreeC under pressure reduction, stirred for 5 hours, air-cooled when it became a viscous state, the reaction was stopped, and the polyester resin (B1) was synthesize | combined. This resin had a weight average molecular weight Mw of 25000 and a melting temperature Tm of 73 ° C.
Thereafter, a polyester resin dispersion (b1) was obtained using a high-temperature and high-pressure emulsification apparatus (Cabitron CD1010, slit: 0.4 mm) under the same conditions as those for preparing the polyester resin dispersion (A1).

[Preparation of colorant particle dispersion]
Cyan pigment: 100 parts by mass (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine))
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R): 15 parts by mass-Ion-exchanged water: 900 parts by mass , HJP30006) for about 1 hour to prepare a colorant dispersion liquid in which a colorant (cyan pigment) is dispersed. The average particle diameter of the colorant (cyan pigment) in the colorant dispersion was 0.13 μm, and the colorant particle concentration was 25% by mass.

[Preparation of release agent particle dispersion]
-Ester wax WEP-5 (manufactured by NOF Corporation): 50 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5 parts by mass-Ion-exchanged water: 200 parts by mass A mold release agent having an average particle size of 0.21 μm after being heated to 110 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50) and then dispersed by a Manton Gorin high-pressure homogenizer (Gorin). A release agent dispersion liquid (release agent concentration: 26% by mass) was prepared.

[Preparation of resin particle dispersion for protrusions]
(Preparation of resin particle dispersion (1) for protrusions)
First, 32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 7 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Turrax T50). After adding 0.8 parts by mass of ammonium sulfate, the reaction kettle was heated to 75 ° C. in a nitrogen atmosphere and reacted for 12 hours. Thereby, resin particles were formed.
Next, 28 parts by mass of styrene, 65 parts by mass of trimethylolpropane trimethacrylate (trifunctional crosslinking agent), 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were combined with a homogenizer (manufactured by IKA). : After emulsification with Ultra Turrax T50) and adding 0.2 parts by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed over 3 hours in a nitrogen atmosphere. The reaction was further continued for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (1) [solid content concentration: 17% by mass] having a volume average particle diameter D50 of 310 nm measured by a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (2) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 2.8 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Tarrax T50). After adding 0.8 parts by mass of ammonium sulfate, the reaction kettle was heated to 75 ° C. in a nitrogen atmosphere and reacted for 12 hours. Thereby, resin particles were formed.
Next, 79 parts by mass of styrene, 14 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (2) [solid content concentration of 17% by mass] for protrusions having a volume average particle diameter D50 of 396 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (3) for protrusions)
19 parts by mass of styrene, 5 parts by mass of butyl acrylate, 16 parts of trimethylolpropane trimethacrylate, 2.8 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were homogenizer (manufactured by IKA: Ultra Turrax) After emulsification in T50) and addition of 0.8 part by mass of ammonium persulfate, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 19 parts by mass of styrene, 75 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (3) [solid content concentration of 16% by mass] for protrusions having a volume average particle diameter D50 of 396 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (4) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 25 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Tarrax T50) to give ammonium persulfate. After adding 0.8 part by mass, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 79 parts by mass of styrene, 14 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion liquid (4) [solid content concentration of 17% by mass] having a volume average particle diameter D50 measured by a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.) of 208 nm is obtained. Obtained.

(Preparation of resin particle dispersion (5) for protrusions)
Homogenizer (manufactured by IKA: Ultra Turrax T50) 19 parts by mass of styrene, 5 parts by mass of butyl acrylate, 16 parts of trimethylolpropane trimethacrylate, 25 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) After adding 0.8 parts by mass of ammonium persulfate, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 19 parts by mass of styrene, 75 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (5) [solid content concentration of 16% by mass] for protrusions having a volume average particle diameter D50 of 209 nm measured by a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (6) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 7 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and ammonium persulfate was added. After adding 0.8 part by mass, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 28 parts by mass of styrene, 65 parts by mass of divinylbenzene, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Turrax T50). Then, 0.2 parts by mass of ammonium persulfate was added, and then the total amount of the emulsified dispersion was added dropwise to the dispersion in which the resin particles were dispersed over 3 hours in a nitrogen atmosphere, followed by further reaction for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion liquid (6) [solid content concentration of 17% by mass] having a volume average particle diameter D50 of 311 nm measured by a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.) was obtained. Obtained.

(Preparation of resin particle dispersion (7) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 2 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Turrax T50), and ammonium persulfate was added. After adding 0.8 part by mass, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 79 parts by mass of styrene, 14 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (7) [solid content concentration of 17% by mass] for protrusions having a volume average particle diameter D50 of 418 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (8) for protrusions)
Homogenizer (manufactured by IKA: Ultra Turrax T50) 19 parts by mass of styrene, 5 parts by mass of butyl acrylate, 16 parts of trimethylolpropane trimethacrylate, 2 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) After adding 0.8 parts by mass of ammonium persulfate, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 19 parts by mass of styrene, 75 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (8) [solid content concentration of 16% by mass] for protrusions having a volume average particle diameter D50 of 418 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (9) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 2.8 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Tarrax T50). After adding 0.8 parts by mass of ammonium sulfate, the reaction kettle was heated to 75 ° C. in a nitrogen atmosphere and reacted for 12 hours. Thereby, resin particles were formed.
Next, 82 parts by mass of styrene, 11 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion liquid (9) [solid content concentration of 17% by mass] having a volume average particle diameter D50 of 395 nm measured by a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.) was obtained. Obtained.

(Preparation of resin particle dispersion (10) for protrusions)
13 parts by weight of styrene, 3 parts by weight of butyl acrylate, 24 parts of trimethylolpropane trimethacrylate, 2.8 parts by weight of sodium dodecylbenzenesulfonate, and 560 parts by weight of ion-exchanged water (DIW) were homogenizer (manufactured by IKA: Ultra Turrax) After emulsification in T50) and addition of 0.8 part by mass of ammonium persulfate, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 23 parts by mass of styrene, 70 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (10) [solid content concentration of 15% by mass] for protrusions having a volume average particle diameter D50 of 396 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (11) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 25 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Tarrax T50) to give ammonium persulfate. After adding 0.8 part by mass, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 82 parts by mass of styrene, 11 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (11) [solid content concentration of 17% by mass] for protrusions having a volume average particle diameter D50 of 210 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (12) for protrusions)
Homogenizer (manufactured by IKA: Ultra Turrax T50) 13 parts by mass of styrene, 3 parts by mass of butyl acrylate, 24 parts of trimethylolpropane trimethacrylate, 25 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) After adding 0.8 parts by mass of ammonium persulfate, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 23 parts by mass of styrene, 70 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (12) [solid content concentration of 15% by mass] for protrusions having a volume average particle diameter D50 of 209 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (13) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 40 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Turrax T50), and ammonium persulfate was added. After adding 0.8 part by mass, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 79 parts by mass of styrene, 14 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (13) [solid content concentration of 17% by mass] for protrusions having a volume average particle diameter D50 of 178 nm measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (14) for protrusions)
Homogenizer (manufactured by IKA: Ultra Turrax T50) 19 parts by mass of styrene, 5 parts by mass of butyl acrylate, 16 parts of trimethylolpropane trimethacrylate, 40 parts by mass of sodium dodecylbenzenesulfonate and 560 parts by mass of ion-exchanged water (DIW) After adding 0.8 parts by mass of ammonium persulfate, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 19 parts by mass of styrene, 75 parts by mass of trimethylolpropane trimethacrylate, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were added to a homogenizer (manufactured by IKA: Ultra Turrax T50). After emulsifying and adding 0.2 part by mass of ammonium persulfate, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed in a nitrogen atmosphere over 3 hours, and further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (14) [solid content concentration of 16% by mass] for protrusions having a volume average particle diameter D50 of 179 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (15) for protrusions)
32 parts by mass of styrene, 8 parts by mass of butyl acrylate, 5 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and ammonium persulfate was added. After adding 0.8 part by mass, the reaction kettle was heated to 75 ° C. and reacted for 12 hours in a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 80 parts by mass of styrene, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Tarrax T50). After the addition of 2 parts by mass, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed over 3 hours in a nitrogen atmosphere, and then further reacted for 6 hours. Thus, the surface of the resin particles was formed so as to cover the crosslinked styrene resin.
As a result, a resin particle dispersion (15) [solid content concentration of 15% by mass] for protrusions having a volume average particle diameter D50 of 290 nm measured with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

(Preparation of resin particle dispersion (16) for protrusions)
40 parts by mass of trimethylolpropane trimethacrylate, 5 parts by mass of sodium dodecylbenzenesulfonate, and 560 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Turrax T50), and ammonium persulfate was 0.8. After the addition of parts by mass, the reaction kettle was heated to 75 ° C. and reacted for 12 hours under a nitrogen atmosphere. Thereby, resin particles were formed.
Next, 60 parts by mass of trimethylolpropane trimethacrylate, 5 parts by mass of sodium dodecylbenzenesulfonate, and 105 parts by mass of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Turrax T50), and ammonium persulfate was added. After adding 0.2 part by mass, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed over 3 hours in a nitrogen atmosphere. Further, 60 parts of trimethylolpropane trimethacrylate, 5 parts by weight of sodium dodecylbenzenesulfonate, and 105 parts by weight of ion-exchanged water (DIW) were emulsified with a homogenizer (manufactured by IKA: Ultra Turrax T50), and 0.2 per cent ammonium persulfate was added. After the addition of parts by mass, the total amount of the emulsified dispersion was dropped into the dispersion in which the resin particles were dispersed over 3 hours, and further reacted for 6 hours. Thereby, crosslinked particles were formed.
As a result, a resin particle dispersion (16) [solid content concentration of 11% by mass] for protrusions having a volume average particle diameter D50 of 270 nm measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.) is obtained. Obtained.

[Example 1]
(Production of toner particles)
Polyester resin particle dispersion (a1): 340 parts by mass Polyester resin particle dispersion (b1): 160 parts by weight Colorant particle dispersion: 50 parts by weight Release agent particle dispersion: 60 parts by weight Surface activity Aqueous solution: 10 parts by mass, 0.3 M nitric acid aqueous solution: 50 parts by mass, ion-exchanged water: 500 parts by mass

After containing the above components in a round stainless steel flask and dispersing using a homogenizer (IKA, Ultra Tarrax T50), heating to 42 ° C. in a heating oil bath and holding for 30 minutes, After confirming that aggregated particles are formed, add additional polyester resin particle dispersion (a1): 100 parts by mass and 105 parts by mass of resin particle dispersion for protrusions (1) and hold for another 30 minutes did.
Subsequently, nitrilotriacetic acid Na salt (manufactured by Chubu Kirest Co., Ltd., Kirest 70) was added so as to be 3% of the total liquid. Thereafter, a 1N aqueous sodium hydroxide solution was gently added until pH 7.2 was reached, and then the mixture was heated to 85 ° C. while continuing stirring and maintained for 3.0 hours. Thereafter, the reaction product was filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain toner particles 1.
On the surface of the toner particle 1, a plurality of protrusions made of protrusion resin particles were formed.

  When the particle size (excluding the protrusions) at this time was measured with a Coulter Multisizer, the volume average particle size D50 was 3.9 μm, and the particle size distribution coefficient GSD was 1.22.

(Production of toner)
Toner particles: 100 parts by mass, silica particles (silica particles obtained by a sol-gel method, having a surface treatment amount of 5% by mass with hexamethyldisilazane, and an average primary particle size of 120 nm): 3 parts by mass and silica particles (R972) (Nippon Aerosil Co., Ltd.)): 1 part by mass is added and blended for 15 minutes at a peripheral speed of 30 m / s using a 5 liter Henschel mixer, and then coarse particles are removed using a 45 μm sieve. A toner was prepared.

[Example 2]
A toner was prepared in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (2) and the addition amount was 134 parts by mass.

[Example 3]
A toner was produced in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (3) and the addition amount was 134 parts by mass.

[Example 4]
A toner was prepared in the same manner as in Example 1, except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (4) and the addition amount was 71 parts by mass.

[Example 5]
A toner was prepared in the same manner as in Example 1, except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (5) and the addition amount was 71 parts by mass.

Example 6
A toner was produced in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (6) and the addition amount was 105 parts by mass.

[Comparative Example 1]
A toner was prepared in the same manner as in Example 1, except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (7) and the addition amount was 142 parts by mass.

[Comparative Example 2]
A toner was prepared in the same manner as in Example 1, except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (8) and the addition amount was 142 parts by mass.

[Comparative Example 3]
A toner was prepared in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (9) and the addition amount was 134 parts by mass.

[Comparative Example 4]
A toner was produced in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (10) and the addition amount was 134 parts by mass.

[Comparative Example 5]
A toner was prepared in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (11) and the addition amount was 71 parts by mass.

[Comparative Example 6]
A toner was prepared in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (12) and the addition amount was 71 parts by mass.
[Comparative Example 7]
A toner was prepared in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (13) and the addition amount was 61 parts by mass.

[Comparative Example 8]
A toner was prepared in the same manner as in Example 1, except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (14) and the addition amount was 61 parts by mass.

[Comparative Example 9]
A toner was produced in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (15) and the addition amount was 98 parts by mass.

[Comparative Example 10]
A toner was prepared in the same manner as in Example 1 except that the resin particle dispersion liquid for protrusions (1) was replaced with the resin particle dispersion liquid for protrusions (15) and the addition amount was 92 parts by mass.

[Evaluation]
A developer was prepared using the toner obtained in each example, and the following evaluation was performed. The evaluation results are shown in Table 1.

The developer was produced as follows.
100 parts of ferrite particles (manufactured by Powder Tech Co., Ltd., average particle size 50 μm) and 1.5 parts of methyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight 95000) are placed in a pressure kneader together with 500 parts of toluene, and are allowed to stand at room temperature for 15 minutes. After stirring and mixing, the temperature was raised to 70 ° C. while mixing under reduced pressure to distill off toluene, followed by cooling and classification using a 105 μm sieve to obtain a resin-coated ferrite carrier.
The resin-coated ferrite carrier and the toner obtained in each example were mixed to prepare a developer (two-component electrostatic charge image developer) having a toner concentration of 7% by mass.

(Filming evaluation)
DocuPrint C3200 (Fuji Xerox Co., Ltd.) remodeling machine (process speed 300mm / s, remodeled to operate as usual until transfer even if the fixing device is removed) The developer is filled, and the amount of toner on the paper is set to 0.15 g / m ² , and 5000 sheets are output in an environment of 10 ° C. and 20% RH, and then 0.15 g / m ² in an environment of 28 ° C. and 85% RH. Printing was continuously performed with a toner amount of 5000 sheets, and the number of prints on which image defects were caused by filming was quantified in percentage.
The evaluation criteria are as follows.
◎: Less than 0.5% ○: 0.5% or more and less than 1.0% Δ: 1.0% or more and less than 5.0% ×: 5.0% or more

(Transfer maintenance evaluation)
The developer of the modified DocuPrint C3200 is filled with the obtained developer, and 5,000 sheets of solid image and character mixing charts are continuously printed in an environment of 10 ° C and 20% RH at a process speed of 300 mm / sec. The residue on the surface of the photoreceptor was transferred with a tape and evaluated by visual observation.
The evaluation criteria are as follows.
◎: Transfer residue cannot be confirmed ○: Transfer residue is almost inconspicuous △: Transfer residue is confirmed slightly and there is a problem in practical use ×: Transfer residue is large and there are serious problems in actual use

(Evaluation of low-temperature fixability)
The developer obtained in a modified DocuCentor Color f450 (Fuji Xerox Co., Ltd.) with the fixing device removed was filled with the obtained developer, and an unfixed image was collected. The image condition was a solid image of 40 mm × 50 mm, the toner amount was 1.5 mg / cm ² , and the paper was J paper (manufactured by Fuji Xerox).
Next, the fixing device of DocuPrint C2220 was modified so that the fixing temperature was variable, and the low-temperature fixing property of the image was evaluated while the fixing temperature was increased stepwise from 100 ° C. to 200 ° C.
The low-temperature fixability is obtained by bending a good fixed image having no image defect due to defective release using a constant load weight, and grading the image defect degree of the portion, and the width of the image defect is 0.3 mm or less. The fixing temperature was taken as the minimum fixing temperature and used as an index for low-temperature fixing properties.
The criteria are as follows.
◎: Less than 130 ° C ○: 130 ° C or more and less than 140 ° C Δ: 140 ° C or more and less than 150 ° C x: 150 ° C or more

  From the above results, in this example, filming, transferability maintenance, and low-temperature fixability were all good as compared with the comparative example.

  In addition, Examples 1 to 5 using a trifunctional or higher functional crosslinking agent as the crosslinking agent for forming the crosslinked resin of the coating layer of the resin particles for the protrusions are the same as Example 6 using a bifunctional crosslinking agent. In comparison, it can be seen that good results were obtained for low-temperature fixability as well as transfer maintenance.

1Y, 1M, 1C, 1K, 107 photoconductor (an example of an image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller (an example of charging means)
3Y, 3M, 3C, 3K Laser beam 3, 110 Exposure device (an example of electrostatic charge image forming means)
4Y, 4M, 4C, 4K, 111 developing device (an example of developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning devices 8Y, 8M, 8C, 8K Developer cartridges 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt 22 Drive Roller 24 Support roller 26 Secondary transfer roller (an example of transfer means)
28, 115 Fixing device (an example of fixing means)
30 Intermediate transfer member cleaning device 112 Transfer device 116 Mounting rail 117 Opening 118 for static elimination exposure Opening 200 for exposure Process cartridge,
P, 300 Recording paper (transfer object)

Claims (7)

Toner particles,
Resin particles partially embedded in the toner particles so as to protrude from the surface of the toner particles, comprising a core portion containing a non-crosslinked resin and a coating layer containing a crosslinked resin, and having a toluene insoluble content of 10 Resin particles having a volume average particle diameter of 200 nm or more and 400 nm or less,
A toner for developing an electrostatic charge image.   The electrostatic charge image developing toner according to claim 1, wherein the cross-linked resin is a cross-linked product of a tri- or higher functional cross-linking agent.   An electrostatic charge image developer comprising at least the electrostatic charge image developing toner according to claim 1. Containing the electrostatic image developing toner according to claim 1,
A toner cartridge to be attached to and detached from the image forming apparatus. A developer that contains the electrostatic charge image developer according to claim 3 and that develops the electrostatic charge image formed on the image carrier as a toner image with the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 3 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer,
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
Image forming apparatus comprising A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer according to claim 3;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
An image forming method comprising:

Images