JP5407377B2 - Electrostatic image developing toner, electrostatic image developer, process cartridge, image forming method, and image forming apparatus - Google Patents

Description

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

Conventional dry developers used in electrophotography are largely divided into a one-component developer using a toner itself in which a colorant is dispersed in a binder resin and a two-component developer in which the toner is mixed with a carrier. Separated. However, these developers alone are not sufficient in characteristics such as storage stability, transportability, developability, transferability, and chargeability. In order to improve these characteristics, an additive is often externally added to the toner. As additives, hydrophobic silica fine powder (see Patent Document 1), silica fine particles added with aluminum oxide or titanium oxide fine particles (see Patent Document 2), and vapor-phase-processed titanium oxide hydrophobized. (Refer patent document 3), anatase type titanium oxide (refer patent document 4), aluminum oxide covering titanium oxide (refer patent document 5), etc. are proposed. Furthermore, an external additive that has been surface-treated with an inorganic compound, for example, a titanium oxide fine particle that has been surface-treated with a coupling agent (see Patent Documents 6 and 7), a material that has been added with hydrophobic silica and hydrophobic titania (Patent Document) 8) etc. have been proposed.
In the past, hydrophobic fine powders such as silica have often been used as additives, and as a result, storage stability, transportability, developability, transferability, etc. are considerably improved. If a sufficient amount is used, the chargeability is not sufficient. In other words, with respect to the chargeability, it is required to satisfy the requirements such as charge amount, charge speed, charge amount distribution, toner admixability (addition of toner), and environmental stability of charge. When a sufficient amount of silica or the like is used to improve the toner, the charging speed, the distribution of the charge amount, the admixability of the toner, or the environmental stability of the charging may be lowered.
In addition, when a polyester resin is used as a binder resin for the toner, the polyester resin itself has a negative chargeability. Therefore, if a charge control agent is not used or if a small amount is used, a negative chargeability can be obtained. Has been. However, the polyester resin has an environmental dependency of charging, that is, a large difference in charge amount between high temperature and high humidity and low temperature and low humidity, and a wide distribution of charge amount. In particular, when a pigment other than carbon black is used as a toner colorant, these are remarkable.

JP 56-128956 A JP-A-60-238847 JP 59-52255 A JP 60-112052 A JP-A-57-79961 JP-A-4-40467 JP-A-4-348354 Japanese Patent Laid-Open No. 10-186711

  The present invention has been made in view of the above situation in the prior art. An object of the present invention is to provide a toner for developing an electrostatic image having excellent charging stability even when the toner consumption is low. It is another object of the present invention to provide an electrostatic image developer, a process cartridge, an image forming method, and an image forming apparatus using the electrostatic image developing toner.

As a result of intensive studies to solve the problems of the prior art, the present inventors have found that the above problems can be solved by the means described in the following <1> and <6> to <9>. It was. It describes below with <2>-<5> which is a preferable embodiment.
<1> An inorganic particle is externally added to a toner base particle containing at least a binder resin and a colorant, the surface of the toner base particle is coated with a silane compound, and the inorganic particle contains silica and titania. Toner for electrostatic charge image development,
<2> The toner for developing an electrostatic charge image according to <1>, wherein the toner base particles have a core-shell structure, and the shell layer is further coated with a silane compound,
<3> The electrostatic image developing toner according to <1> or <2>, wherein the silane compound includes a silane compound derived from an organic silane compound having an ethylenically unsaturated bond,
<4> Any one of <1> to <3> satisfying the following formula (1), where a is an addition amount of the silica to the toner base particles and b is an addition amount of the titania to the toner base particles. Toner for developing an electrostatic image according to claim 1,
0.2 ≦ b / a ≦ 0.5 (1)
<5> The electrostatic image developing toner according to any one of <1> to <4>, wherein the inorganic particles contain conductive particles in addition to silica and titania.
<6> The electrostatic charge image developer comprising the electrostatic charge image developing toner and the carrier according to any one of <1> to <5>,
<7> The toner for developing an electrostatic charge image according to any one of <1> to <5> or the electrostatic charge image developer according to <6> is housed and formed on the surface of the image carrier. Developing means for developing the electrostatic latent image with the electrostatic image developing toner or the electrostatic image developer to form a toner image, an image holding member, and a charging means for charging the surface of the image holding member, And at least one selected from the group consisting of cleaning means for removing the toner remaining on the surface of the image carrier, and a process cartridge that is detachable from the image forming apparatus,
<8> At least a charging step for charging the image carrier, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and an electrostatic latent image formed on the surface of the image carrier. Developing with a developing toner or an electrostatic charge image developer to form a toner image, a transfer step for transferring the toner image formed on the surface of the image holding member to the surface of the transfer target, and fixing the toner image The electrostatic charge image developing toner according to any one of <1> to <5>, or the electrostatic charge image developer according to <6>. An image forming method characterized by being an electrostatic charge image developer of
<9> Image carrier, charging unit for charging the image carrier, exposure unit for exposing the charged image carrier to form an electrostatic latent image on the image carrier, and electrostatic image development Developing means for developing the electrostatic latent image with toner for developing or electrostatic charge image developer to form a toner image, transfer means for transferring the toner image from the image holding member to a transfer target, and the toner image <6> as the electrostatic charge image developing toner according to any one of <1> to <5> or the electrostatic charge image developer as the electrostatic charge image developing toner. An image forming apparatus using the described electrostatic charge image developer.

According to the invention described in <1> above, the surface of the toner base particles is not coated with a silane compound and silica and titania are not externally added as inorganic particles for a long time. Fog is suppressed even when used.
According to the above invention <2>, fogging is further suppressed as compared with the case where the toner base particles do not have a core-shell structure.
According to the invention described in the above <3>, fog is further suppressed as compared with the case where the silane compound does not contain a silane compound derived from an organic silane compound having an ethylenically unsaturated bond.
According to the invention described in <4> above, fogging is further suppressed as compared with the case where the present configuration is not provided.
According to the above invention <5>, the charge exchange between the toners is promoted as compared with the case where the present configuration is not provided.
According to the invention described in <6>, fogging is further suppressed as compared with the case where the present configuration is not provided.
According to the invention described in <7> above, fogging is further suppressed as compared with the case where the present configuration is not provided.
According to the invention described in <8> above, fogging is further suppressed as compared with the case where the present configuration is not provided.
According to the invention described in <9>, fogging is further suppressed as compared with the case where the present configuration is not provided.

(Static image developing toner)
The toner for developing an electrostatic charge image of the present embodiment (hereinafter also simply referred to as “toner”) is obtained by externally adding inorganic particles to toner base particles containing at least a binder resin and a colorant. The surface is coated with a silane compound, and the inorganic particles contain silica and titania.
“The surface of the toner base particles is covered with the silane compound” is not limited to the case where the entire surface of the toner base particles is covered with the silane compound. At least the silane compound forms a continuous phase. Then, it is only necessary to coat the toner base particles. That is, a part of the surface of the toner base particle that is not coated with the silane compound may exist.
Here, in the following description, the “toner core particle” means a part of the toner base particle excluding the coating with the silane compound. That is, the toner base particles are formed by coating toner core particles with a silane compound.
Moreover, in the following description, the description of “A to B” indicating a numerical range represents “A or more and B or less” unless otherwise specified, and means a numerical range including A and B as end points.
Hereinafter, the electrostatic image developing toner of this embodiment will be described in detail.

Conventionally, additive particles have been used in order to give toner properties such as storability, transportability, developability, transferability, and chargeability. The additive particles are attached to the surface of the toner base particles by a mechanical method or a chemical method. The state of the additive particles on the surface of the toner base particles varies depending on use. For example, in order to develop an electrostatic latent image on an image carrier (photoreceptor) with a two-component developer using a mixture of toner and carrier, the toner and carrier are machined in a developing machine to charge the toner. Clash. At this time, the toner collides with the inner wall of the developing machine.
When the consumption of developed toner continues to be low, such as when copying or printing an image with a low image area, most of the toner is agitated in the developing machine for a long time. As a result, a phenomenon occurs in which the additive particles are embedded in the toner base particles. The toner in which the additive particles are embedded on the surface of the toner base particles is different in surface condition from the toner that has not been subjected to initial stress. When a new toner that does not have additive particles embedded therein is added to the developer including the toner in which the additive particles are embedded, the additive particles are embedded in addition to the charge exchange between the toner and the carrier. Charge exchange occurs between the toner and the non-embedded toner, resulting in a mixture of toners with different charge levels. As a result, the resulting image may be fogged or the highlight image density may vary. It occurs. Here, the fog means a stain due to toner generated by developing and transferring a low-charge / reverse-charge toner on an area other than the original image area on a recording medium such as a copy sheet.

  In the toner of this embodiment, the surface of the toner base particles is coated with a silane compound that is not silica particles, and as a result, the silicon element of the silane compound also contributes to charge exchange. In this embodiment, silica particles containing silicon element are added to the surface of the toner base particles as an external additive. However, when external stress such as collision is applied to the toner, the silica particles are also embedded in the toner base particles. However, since the surface of the toner base particles is coated with a silane compound, which is a silicon compound, even if silica particles are embedded, when viewed as elemental silicon, the embedded silicon and the non-embedded toner are used for the surface silicon. The element ratio does not change greatly, the charge exchange between the toner and the toner is slight, and the toner charge amount level difference between the two is also small.

Further, by using titania as an external additive, the toner charge maintaining property after long-term use is improved. In the case of a two-component developer composed of a toner and a carrier, the toner is charged by the carrier, but the ability of the carrier deteriorates due to contamination by the toner component as well as surface destruction and wear.
Constituent elements of the toner include toner base particles and external additives. When the surface of the toner base particle is coated with a silane compound, if only silica is used as an external additive, the binding force of silica on the surface of the toner base particle is because the surface of the toner base particle has silicon element as a component. The electrostatic binding force is not sufficient, and the carrier surface is moved and contaminated. As a result, it is difficult to maintain good toner chargeability over a long period of time. On the other hand, when another additive particle, which is another component, is added to the combination of the toner base particle and silica, a binding force is generated between the separate additive particle and silica, and the separate additive particle and toner base particle. Is stably attached to the surface of the toner base particles, the movement to the carrier surface and contamination are suppressed, and good toner chargeability is maintained over a long period of time.

  Here, the additional additive particles contain at least titania. Since titania is different from silica in a charge train, there is electrostatic interaction, and not only can silica and titania be stably present on the surface of the toner base particles, but also the semiconductive properties of titania. As a result, fluctuations in the toner charge amount due to environmental changes such as a high temperature and high humidity environment and a low temperature and low humidity environment are suppressed, and the toner chargeability becomes stable.

  Japanese Patent Application Laid-Open No. 2008-46416 describes a toner for developing an electrostatic image that contains hydrophobic silica particles in a layer of 0.04 to 1 μm from the surface of the toner base particles. In this embodiment, by covering the surface of the toner base particles with a silane compound, the surface coverage of the toner base particles can be improved and the surface can be uniformly coated with less unevenness than when silica particles are contained. Is advantageous. Further, the hydrophobic silica particles added in the 0.04 to 1 μm layer from the surface are buried in the toner base particles. When the silica particles externally added to the toner base particles are buried in the toner base particles, if the toner base particles are coated with a silane compound as in this embodiment, the silane compound of the toner base particles is formed on the toner core particles. Since it is bonded, burying is suppressed. As a result, even when the external additive is buried, silicon on the surface does not disappear, and a more stable chargeability can be obtained.

Next, the toner manufacturing method and constituent materials of the present embodiment will be described in detail.
The method for producing the toner of the present exemplary embodiment is not particularly limited, and a known method is used, but a method of coating the toner core particles with a silane compound after producing the toner core particles is preferable.
Below, the manufacturing method of a toner core particle is demonstrated.
In the present embodiment, the production method of the toner core particles is not particularly limited, and a known method is used. Preferably, an aqueous system such as a suspension polymerization method, an emulsion polymerization aggregation method, a seed polymerization method, or a swelling polymerization method is used. Examples thereof include a method for producing toner core particles by forming polymerizable monomer particles and / or polymer particles in a medium. Moreover, the emulsion aggregation method mentioned later is also preferable and you may manufacture by mechanical methods, such as a kneading | pulverization grinding | pulverization method.

  In the exemplary embodiment, it is preferable that the toner base particles have a core-shell structure, and the shell layer of the core-shell structure is further coated with a silane compound. That is, it is preferable that the toner base particles have a configuration in which toner core particles having a core-shell structure are coated with a silica compound. It is preferable that the toner base particles have a core-shell structure because exposure of the release agent to the toner surface is suppressed.

  From the viewpoint of easy preparation of toner core particles having a core-shell structure, it is preferable to use a wet manufacturing method, particularly an emulsion aggregation method. The emulsion aggregation method is an emulsion polymerization, or an additive for imparting functions required for a toner, such as an aqueous dispersion such as a colorant, a charge control agent, and a release agent, to a resin particle dispersion prepared by emulsion. The dispersion liquid is mixed in an aqueous medium, and the toner core is formed by aggregating and growing with an aggregating agent while mechanically shearing in an aqueous medium using various dispersing machines such as a homomixer, and further fusing resin particles. This is a method for obtaining particles.

The emulsion aggregation method includes a first resin particle dispersion liquid in which first resin particles having a volume average particle diameter of 1 μm or less, which is made of a first binder resin, and a colorant dispersion liquid in which a colorant is dispersed. An aggregating step in which a core particle is formed by adding a flocculant and heating to a mixed dispersion at least mixed, and the mixed dispersion in which the core particle is formed is composed of a second binder resin and has a volume average Addition of second resin particle dispersion in which second resin particles having a particle diameter of 1 μm or less are dispersed, and the second resin particles are attached to the surface of the core particles to form attached resin agglomerated particles Preferably, the method includes a step and a fusion step of fusing the adhered resin aggregated particles. Further, in the aggregation step for forming the core particles, it is preferable to mix a release agent dispersion in addition to the resin particle dispersion and the colorant dispersion.
In the agglomeration step, core particles (core agglomerated particles) obtained by aggregating various particle components in the mixed dispersion liquid may be formed, and the heating temperature is set to the glass transition temperature or melting point of the first binder resin. It is possible to form a core particle (core fused particle) that is made higher than the temperature of the particle and fused at the same time as aggregation. The fusing step may be carried out by heating to a temperature higher than the glass transition temperature or melting point of the first or second binder resin, whichever is higher. When formed using, mechanical fusion may be used. Details of these steps will be described later.

Each component constituting the toner core particle in the present embodiment will be described. The toner core particles of the exemplary embodiment preferably contain a binder resin and a colorant, and further contain a release agent and other various internal additives.
<Release agent>
The toner core particles of the present embodiment preferably contain a release agent.
In a full-color copying machine or printer that has become widespread in recent years, an apparatus for supplying an anti-offset liquid to a heat fixing roll or fixing belt is required in order to prevent contamination by toner components and offset in the fixing process. Is a problem. This is in the opposite direction to the reduction in size and weight, and the anti-offset liquid may be heated and evaporated to give an unpleasant odor or cause in-flight contamination. Therefore, it is preferable that the toner contains a release agent (wax) in order to obtain good fixability in a state where there is substantially no anti-offset liquid.
The mold release agent melts at a temperature of 70 to 140 ° C. and preferably exhibits a melt viscosity of 1 to 200 centipoise, more preferably 1 to 100 centipoise. When the melting temperature is 70 ° C. or higher, the change temperature of the release agent is appropriate, and good blocking resistance is obtained. Also, good developability can be obtained even when the temperature in the copying machine increases. When the melting temperature is 140 ° C. or lower, the changing temperature of the wax is appropriate, which is preferable from the viewpoint of energy saving. Further, when the melt viscosity is 200 centipoises or less, elution from the toner is appropriate and fixing releasability is good.

  The addition amount of the release agent to the toner core particles is preferably 1 to 15% by weight, more preferably 3 to 10% by weight, by weight. When the amount of the release agent added to the toner core particles is 1% by weight or more, sufficient fixing latitude (fixing roll or fixing belt temperature range fixed without toner offset) is obtained, and 15% by weight. When the amount is less than the above, the amount of the wax released from the toner is small, and the developer holding member is not contaminated. In addition, the powder fluidity of the toner is good, and there is little adhesion of free wax to the surface of the image carrier (photoconductor) that forms the electrostatic latent image, so that the electrostatic latent image is formed accurately. In addition, the release agent is inferior in transparency as compared with the binder resin, but even when an image is formed on OHP or the like, the transparency is not lowered and a dark projection image is not obtained.

  The mold release agent used in this embodiment is obtained from the following wax. Specific examples include paraffin wax and derivatives thereof, montan wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, and polyolefin wax and derivatives thereof. Derivatives include oxides, polymers with vinyl monomers, and graft modified products. In addition, alcohols, fatty acids, plant waxes, animal waxes, mineral waxes, ester waxes, acid amides and the like are also used.

<Binder resin>
The toner core particles used in this embodiment contain at least a binder resin.
Binder resins include styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene, and isoprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl acetate; methyl acrylate, acrylic Α-methylene aliphatic monocarboxylic acid esters such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate; vinyl methyl ether, Homopolymers or copolymers of vinyl ethers such as vinyl ethyl ether and vinyl butyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone; Polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyethylene, polypropylene Is mentioned. Further examples include polyester, polyurethane, epoxy resin, silicon resin, polyamide, modified rosin, paraffin, and waxes. Among these, it is particularly effective to use polyester as a binder resin.

The polyester resin used in this embodiment is synthesized from a polyol component and a polycarboxylic acid component by polycondensation. In addition, in this embodiment, a commercial item may be used as said polyester resin, and what was synthesize | combined suitably may be used.
Examples of the polycarboxylic acid component (polyvalent carboxylic acid component) include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decane. Aliphatic dicarboxylic acids such as dicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid , Aromatic dicarboxylic acids such as dibasic acids such as malonic acid and mesaconic acid, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  Furthermore, it is more preferable to contain a dicarboxylic acid component having a double bond in addition to the aforementioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid. A dicarboxylic acid having a double bond is preferably used in order to prevent hot offset at the time of fixing because it can be radically cross-linked through the double bond. Examples of such dicarboxylic acids include, but are not limited to, maleic acid, fumaric acid, 3-hexenedioic acid, and 3-octenedioic acid. In addition, these lower esters, acid anhydrides and the like are also included. Among these, fumaric acid and maleic acid are preferable from the viewpoint of cost.

As the polyhydric alcohol component (polyol component), as the divalent polyhydric alcohol, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) Alkylene (2 to 4 carbon atoms) oxide adducts (average number of moles added 1.5 to 6) of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, propylene glycol, neopentyl glycol 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol and the like.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, pentaerythritol, glycerol, trimethylolpropane and the like.

  In the amorphous polyester resin, it is preferable to use a dihydric or higher secondary alcohol and / or a divalent or higher aromatic carboxylic acid compound among the raw material monomers described above. Examples of the dihydric or higher secondary alcohol include propylene oxide adducts of bisphenol A, propylene glycol, 1,3-butanediol, glycerol and the like. Among these, propylene oxide adducts of bisphenol A are preferable and divalent. As the above aromatic carboxylic acid compound, terephthalic acid, isophthalic acid, phthalic acid and trimellitic acid are preferable, and terephthalic acid and trimellitic acid are more preferable.

  The amorphous polyester resin has a softening point of 90 to 150 ° C, a glass transition temperature of 55 to 75 ° C, a number average molecular weight of 2,000 to 10,000, a weight average molecular weight of 8,000 to 150,000, and an acid value of 5 to 30 mgKOH. / G and a hydroxyl value of 5 to 40 mgKOH / g.

Further, it is preferable to use a crystalline polyester resin as a part of the binder resin in order to give the toner low temperature fixability.
The crystalline polyester resin is preferably composed of an aliphatic dicarboxylic acid and an aliphatic diol, and more preferably a linear dicarboxylic acid or a linear aliphatic diol having 4 to 20 carbon atoms in the main chain portion. The straight-chain type is preferable because the polyester resin has high crystallinity and a high melting point, and is excellent in toner blocking resistance, image storage stability, and low-temperature fixability. Further, when the number of carbon atoms is 4 or more, a low ester bond group concentration can be obtained, so that the electric resistance is high, and as a result, good toner chargeability can be obtained. On the other hand, it is preferable that the number of carbon atoms is 20 or less because practical materials are easily available. The carbon number is more preferably 14 or less.

  Examples of the aliphatic dicarboxylic acid suitably used for the synthesis of the crystalline polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelinic acid, sebacic acid, 1,9-nonane. Dicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid An acid, 1,18-octadecanedicarboxylic acid or the like, or a lower alkyl ester or an acid anhydride thereof may be mentioned, but not limited thereto. Among these, considering availability, sebacic acid and 1,10-decanedicarboxylic acid are preferable.

Specific examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol 1,18-octadecanediol, 1,14-eicosandecanediol and the like, but are not limited thereto. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.
Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

  Among the polyvalent carboxylic acid components, the content of the aliphatic dicarboxylic acid is preferably 80 mol% or more, and more preferably 90% or more. When the content of the aliphatic dicarboxylic acid is 80 mol% or more, the crystallinity of the polyester resin is good and a high melting point is obtained. As a result, the toner blocking resistance, the image storage stability and the low-temperature fixability are excellent. Among the polyhydric alcohol components, the content of the aliphatic diol component is preferably 80 mol% or more, and more preferably 90% or more. When the content of the aliphatic diol component is 80 mol% or more, the crystallinity of the polyester resin is good, and a high melting point is obtained. As a result, the toner blocking resistance, the image storage stability, and the low-temperature fixability are excellent. .

  Moreover, it is preferable that crystalline polyester resin is 45-110 degreeC of melting | fusing point, More preferably, it is 50-100 degreeC, More preferably, it is 55-90 degreeC. The number average molecular weight is preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. The weight average molecular weight is preferably 8,000 to 150,000, the acid value is preferably 5 to 30 mgKOH / g, and the hydroxyl value is preferably 5 to 40 mgKOH / g.

  If necessary, monovalent acids such as acetic acid and benzoic acid and monovalent alcohols such as cyclohexanol benzyl alcohol may be used for the purpose of adjusting the acid value and hydroxyl value.

The production method of the polyester resin is not particularly limited, and is produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification methods. Produced separately.
The polyester resin may be produced by subjecting the polyhydric alcohol and polyhydric carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid, if necessary, a catalyst, and blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heat at 150 to 250 ° C. to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant It may be manufactured by.

<Colorant>
In this embodiment, the toner core particles contain a colorant.
Colorants used for toner core particles include carbon black, nigrosine, aniline blue, calcoil blue, chrome yellow, ultramarine blue, duPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, and lamp black. Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 238, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 180, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 is exemplified as a typical example.

<Other ingredients>
In addition to a binder resin, a colorant such as carbon black, and a release agent, one or more charge control agents that adjust charge as an internal additive may be included. Further, a petroleum resin may be included in order to satisfy the pulverization property and heat storage property of the toner. Petroleum resins are synthesized from diolefins and monoolefins contained in cracked oil fractions by-produced from an ethylene plant that produces ethylene, propylene, and the like by steam cracking of petroleum.

<Method for producing toner core particles>
(Emulsion aggregation method)
As described above, the toner core particles are preferably produced by an emulsion aggregation method.
In the emulsion aggregation method, a resin particle dispersion is prepared by emulsion polymerization or emulsification, while a colorant particle dispersion in which a colorant is dispersed in a solvent, and a release agent particle dispersion in which a release agent is dispersed. Then, these are mixed to form aggregated particles corresponding to the toner particle size (aggregation step) and then fused by heating (fusion step) to obtain toner particles. In addition, it is preferable to have the adhesion process of attaching resin particles to the aggregated particles after the aggregation process and before the fusion process.
A method for producing toner core particles suitably used in the present embodiment, including the above-described aggregation process, adhesion process, and fusion process, will be described in detail for each process.

-Aggregation process-
In the aggregating step, first, the first binder resin dispersion, the colorant dispersion, further the release agent dispersion used as necessary, and the mixed dispersion obtained by mixing other components are used. By adding a flocculant and heating at a temperature slightly lower than the melting point of the first binder resin, agglomerated particles (core agglomerated particles) are formed by aggregating particles composed of the respective components. The fused particles (core fused particles) may be formed by heating at a temperature equal to or higher than the glass transition temperature of the first binder resin and performing fusion at the same time as aggregation.

The formation of the agglomerated particles is preferably performed by adding an aggregating agent at room temperature while stirring with a rotary shearing homogenizer. As the aggregating agent used in the aggregating step, a surfactant having a reverse polarity to the surfactant used as a dispersing agent for various dispersions, an inorganic metal salt, and a divalent or higher-valent metal complex are preferably used.
In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used is reduced and the charging characteristics are improved.

  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 polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

-Adhesion process-
In the attaching step, resin particles made of the second binder resin are attached to the surface of the core particles (core aggregated particles or core fusion particles) containing the first binder resin formed through the above-described aggregation step. Thus, the coating layer is formed (hereinafter, the agglomerated particles provided with the coating layer on the surface of the core particles are referred to as “adhesive resin aggregated particles”). Here, this coating layer corresponds to the shell layer of the toner base particles of the present embodiment formed through a fusion process described later.
The coating layer (shell layer) is formed by adding the second resin particle dispersion liquid to the dispersion liquid in which the core particles are formed in the aggregation step, and simultaneously adding other components as necessary. May be.

When the adhesion resin particles are uniformly adhered to the surface of the core particles to form a coating layer, and the adhesion resin particles are heat-fused in a fusion process described later, a second layer contained in the coating layer on the surface of the core particles Resin particles made of the binder resin are melted to form a shell layer. For this reason, the components such as the release agent contained in the core layer located inside the shell layer are effectively prevented from being exposed to the toner surface.
There is no restriction | limiting in particular as the method of addition mixing of the 2nd resin particle dispersion liquid in an adhesion process, For example, you may carry out gradually continuously and may carry out in steps divided into several times. In this way, by adding and mixing the second resin particle dispersion, the generation of fine particles is suppressed, and the particle size distribution of the obtained toner becomes sharp.
In the present embodiment, the number of times that this adhesion step is performed may be one or a plurality of times. In the former case, only one layer mainly composed of the second binder resin is formed on the surface of the core aggregated particles. On the other hand, in the latter case, if not only the second resin particle dispersion but also a plurality of release agent dispersions and particle dispersions composed of other components are used, a specific component is applied to the surface of the core aggregated particles. A layer having the main component is laminated.

  The latter case is advantageous in that a toner having a complicated and precise hierarchical structure can be obtained and a desired function can be imparted to the toner. When the adhesion process is performed a plurality of times or in multiple stages, the composition and physical properties of the obtained toner from the surface to the inside can be changed in stages, and the structure of the toner can be easily controlled. In this case, a plurality of layers are laminated stepwise on the surface of the core particle, and a structural change or composition gradient is given from the inside to the outside of the toner particle, thereby changing the physical properties. In this case, the shell layer corresponds to all the layers laminated on the surface of the core particle, and the outermost layer is composed of a layer mainly composed of the second binder resin. In the following explanation, explanation will be made on the assumption that the adhesion process is performed only once.

  Conditions for attaching the resin particles made of the second binder resin to the core particles are as follows. That is, the heating temperature in the adhesion step is preferably a temperature in the vicinity of the melting point of the first binder resin contained in the core aggregated particles, and specifically, a temperature range within a melting point ± 10 ° C. preferable. In the case where the first binder resin is an amorphous resin, the heating temperature in the attaching step is preferably a temperature in the vicinity of the glass transition temperature, and specifically, a temperature within the glass transition temperature ± 10 ° C. A range is preferable.

When the heating temperature is equal to or higher than the melting point (or glass transition temperature) of −10 ° C. of the first binder resin, the resin particles composed of the first binder resin present on the core particle surface and the surface of the core aggregated particle are adhered. Adhesion with the resin particles made of the second binder resin is good, and the thickness of the formed shell layer becomes more uniform, which is preferable.
In addition, when the heating temperature is the melting point (or glass transition temperature) of the first binder resin + 10 ° C. or lower, the resin particles made of the first binder resin existing on the core particle surface and attached to the core particle surface Excessive adhesion of resin particles made of the second binder resin is suppressed. As a result, adhesion between the adhering resin and the aggregated particles due to excessive adhesion is suppressed, and the obtained toner core particles are preferable because of excellent particle size / particle size distribution.
The heating time in the attaching step depends on the heating temperature and is difficult to define in general, but is about 5 minutes to 2 hours.

  In addition, in the attaching step, the dispersion obtained by additionally adding the second resin particle dispersion to the mixed dispersion formed with the core particles may be allowed to stand or be gently stirred by a mixer or the like. Also good. The latter case is advantageous in that uniform adhered resin aggregated particles are easily formed.

-Fusion process-
In the fusion process, the adhered resin aggregated particles obtained in the adhesion process are fused by heating. The fusing step is preferably performed at a higher temperature or higher of the glass transition temperatures of the first binder resin and the second binder resin. As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is necessary if the heating temperature is low. That is, since the fusion time depends on the heating temperature, it is difficult to define it unconditionally, but it is preferably 30 minutes to 10 hours.

When the core particles are core fusion particles, resin particles made of the second binder resin may be attached. In this case, the dispersion containing the core fusion particles is once filtered, and after the water content of the dispersion is controlled to 30% to 50% by weight, the second resin particle dispersion is further added. Thereby, the particle | grains which consist of 2nd binder resin are made to adhere to the surface of a core fusion particle.
It is preferable that the water content of the dispersion is 30% by weight or more because the adhesion of the particles made of the second binder resin is good and the detachment of the particles from the core fused particles is suppressed. Further, it is preferable that the water content is 50% by weight or less because stirring is easy and particles made of the second binder resin are uniformly attached to the surface of the core fusion particles.

  In addition, mechanical stress by a Henschel mixer or the like is applied to the adhered resin agglomerated particles obtained by adhering the particles made of the second binder resin to the surface of the core fused particles after the washing / drying process described below. Thus, the particles made of the second binder resin attached to the surface of the core fusion particles can be fused. Thus, the fusion process may be performed by applying mechanical stress instead of heating in the liquid phase.

-Washing / drying process-
The fused particles obtained through the fusion process are subjected to solid-liquid separation such as filtration, washing, and drying. Thereby, toner core particles are obtained.
The solid-liquid separation is not particularly limited, but suction filtration, pressure filtration and the like are preferable from the viewpoint of productivity. The washing is preferably performed with substitution washing with ion-exchanged water from the viewpoint of chargeability. In the drying step, an arbitrary method such as a normal vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like is employed. The toner core particles preferably have a moisture content after drying of preferably 1.0% by weight or less, more preferably 0.5% by weight or less.

-Preparation of dispersion-
A known emulsification method is used to prepare the binder resin dispersion, but the obtained particle size distribution is sharp and the phase inversion emulsification is easily obtained in the range of volume average particle size of 0.08 to 0.40 nm. The law is effective.
In the phase inversion emulsification method, the resin is dissolved in an organic solvent for dissolving the resin, an amphiphilic organic solvent alone, or a mixed solvent to obtain an oil phase. A small amount of a basic compound is dropped while stirring the oil phase, and water is dropped little by little while stirring, and water droplets are taken into the oil phase. Next, when the dripping amount of water exceeds a certain amount, the oil phase and the water phase are reversed and the oil phase becomes oil droplets. Thereafter, an aqueous dispersion is obtained through a desolvation step of depressurization.
Here, the amphiphilic organic solvent means a solvent having a solubility in water at 20 ° C. of preferably 5 g / L or more, more preferably 10 g / L or more. It is preferable for the solubility to be 5 g / or more because the effect of accelerating the aqueous treatment speed is excellent and the storage stability of the resulting aqueous dispersion is excellent. Examples of such organic solvents include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1 -Alcohols such as ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and isophorone, ethers such as tetrahydrofuran and dioxane , Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, Esters such as ethyl lopionate, diethyl carbonate, dimethyl carbonate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene group Examples include glycol derivatives such as coal methyl ether acetate and dipropylene glycol monobutyl ether, and 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, etc. Is done. These solvents may be used singly or in combination of two or more.

Next, regarding the basic compound, when a polyester resin is used as the binder resin in this embodiment, the polyester resin is preferably neutralized with a basic compound when dispersed in an aqueous medium. The neutralization reaction with the carboxyl group of the polyester resin is a starting force for aqueous formation, and the electric repulsion between the generated carboxyl anions prevents aggregation between the particles, which is preferable.
Examples of the basic compound include ammonia and organic amine compounds having a boiling point of 250 ° C. or lower. Examples of preferred organic amine compounds include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine , Diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, Examples include triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like.

  The basic compound is preferably added in an amount that can be at least partially neutralized according to the carboxyl group contained in the polyester resin, that is, 0.2 to 9.0 times equivalent to the carboxyl group. It is more preferable to add 6 to 2.0 times equivalent. If it is 0.2 times equivalent or more, the effect of adding a basic compound is obtained, and if it is 9.0 times equivalent or less, a sharp particle size distribution is obtained and a good dispersion is obtained. This is presumably because the improvement in hydrophilicity of the oil phase is within an appropriate range.

The colorant dispersion is formed by dispersing at least a colorant. The colorant is dispersed by a known method. For example, a rotary-type homogenizer, a ball-type mill, a sand mill, an attritor-type media type disperser, a high-pressure counter-collision type disperser, or the like is preferably used. The colorant is an ionic surfactant having polarity and is dispersed in an aqueous solvent using a homogenizer as described above to produce a colorant particle dispersion. A coloring agent may be used individually by 1 type, and may use 2 or more types together.
The volume average particle size of the colorant (hereinafter sometimes simply referred to as an average particle size) is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.01 to 0.5 μm.

  The release agent dispersion is formed by dispersing at least a release agent. The release agent is dispersed by a known method. For example, a rotary shearing homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used. The release agent is an ionic surfactant having polarity and dispersed in an aqueous solvent using a homogenizer as described above to produce a release agent particle dispersion. In this embodiment, a mold release agent may be used individually by 1 type, and may be used in combination of 2 or more type. The average particle size of the release agent particles is preferably 1 μm or less, and more preferably 0.01 to 1 μm.

There is no restriction | limiting in particular as a combination of resin of the said resin particle, the said coloring agent, and the said mold release agent, According to the objective, it selects and uses suitably suitably.
In the present embodiment, depending on the purpose, at least one of the binder resin dispersion, the colorant dispersion, and the release agent dispersion includes an internal additive, a charge control agent, inorganic particles, and organic particles. It is possible to disperse other components (particles) such as bodies, lubricants, and abrasives. In that case, other components (particles) may be dispersed in at least one of the binder resin dispersion, the colorant dispersion, and the former agent dispersion, or the resin particle dispersion and the colorant. You may mix the dispersion liquid which disperse | distributes another component (particle | grains) in the liquid mixture formed by mixing a dispersion liquid and a mold release agent dispersion liquid.

Examples of the dispersion medium in the binder resin dispersion, the colorant dispersion, the release agent dispersion, and the other components include an aqueous medium. Examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together. As a suitable combination, distilled water and ion exchange water are preferably used. That's right. The addition of a surfactant is not only advantageous in terms of the stability of each dispersed particle, such as resin particles, colorant particles, and release agent particles, in the aqueous medium, and thus the storage stability of the dispersion, but also in the aggregation process. This is also advantageous from the viewpoint of the stability of the aggregated particles.
In addition, rosin, rosin derivatives, coupling agents, polymer dispersions are added as dispersants to further stabilize the dispersion stability of the colorant in the aqueous medium and lower the energy of the colorant in the toner. Agents and the like.

In the present embodiment, it is preferable to add and mix a surfactant in an aqueous medium in order to improve dispersion stability.
The volume average primary particle size of the fine particle dispersion thus obtained is measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.). As a measurement method, a sample in a dispersion is adjusted to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The volume-volume average primary particle size of each obtained channel was accumulated from the smaller volume-volume average primary particle size, and the volume-average primary particle size when the accumulation reached 50%.

  In the toner of the exemplary embodiment, the colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, transparency when printed on OHP, and dispersibility in the toner. The amount of the colorant added to the toner of this embodiment is preferably in the range of 4 to 20 parts by weight with respect to 100 parts by weight of the resin contained in the toner. The release agent is selected from the viewpoints of fixing properties, toner storage stability, toner strength, and the like. The amount of the release agent added to the toner of this embodiment is preferably in the range of 2 to 20 parts by weight with respect to 100 parts by weight of the resin contained in the toner.

<Coating with silane compound>
In the present embodiment, the toner core particles are coated with a silane compound. The method of coating with the silane compound is not particularly limited and may be appropriately selected from known coating methods with a silane compound, and it is preferable to coat with an organic silane compound. Specifically, a radical-reactive organosilane compound having at least one ethylenically unsaturated bond (unsaturated carbon bond) is added to the toner core particle dispersion, and the system is gently mixed to make the system uniform. A method of polymerizing while stirring is exemplified. At this time, the polymerization temperature may be appropriately selected depending on the polymerization initiator used, and is not particularly limited, but is preferably 40 to 90 ° C.

  The organic silane compound of the present embodiment is generally called a silane coupling agent and is represented by the following formula (I).

  In the above formula, R, X, Y and Z are each composed of a hydrophobic organic group and / or a hydrophilic hydrolyzable group, and a functional group such as an alkyl group, a vinyl group, an epoxy group, an acrylic group, Contains amino groups and the like.

Here, the silane coupling agent is preferably a compound represented by the following formula (II).
R ' _n SiX' _(4-n) (II)
However, R ′: unsubstituted or substituted hydrocarbon group, acryloxy group (also referred to as acryloyloxy group), methacryloxy group (also referred to as methacryloyloxy group), epoxy group, or amino group, X ′: 1 to 1 carbon atoms 6 alkoxy groups, hydroxyl groups, halogen atoms or hydrogen atoms, n: an integer of 0 to 3.

Here, R ′ is an unsubstituted or substituted hydrocarbon group, acryloxy group, methacryloxy group, epoxy group, or amino group, and examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Is exemplified.
The alkyl group preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms. The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms. The alkyl group, alkenyl group and alkynyl group may be linear, branched or cyclic, and further an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms). May be substituted to form an aralkyl group or the like.
The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group further includes an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms), and an alkynyl group. (Preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms) may be substituted.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, and examples of the alkenyl group include a vinyl group. A phenyl group is illustrated as an aryl group.
Furthermore, the alkyl group, alkenyl group, alkynyl group, and aryl group may be partially or fully substituted with halogen atoms such as fluorine atoms, and may be amino groups, epoxy groups, glycidyloxy groups (glycidoxy groups), acryloxy groups, and the like. A group, a methacryloxy group, or a mercapto group may be substituted, and a part of the hydrocarbon group may form an epoxy group together with an oxygen atom.
The amino group may be a substituted amino group, and examples of the substituted amino group include a monoalkylamino group and a dialkylamino group.
If possible, the substituent may be further substituted with an arbitrary substituent selected from the substituents. For example, the 3-aminopropyl group may be an N-ethyl-3-aminopropyl group in which the amino group is substituted with an ethyl group, and further an N-2-aminoethyl group in which the ethyl group is substituted with an amino group. It may be a -3-aminopropyl group.

Among these, R ′ is preferably an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, more preferably an unsubstituted or substituted hydrocarbon group having 1 to 5 carbon atoms, and further preferably a carbon number. 1 to 3 unsubstituted or substituted hydrocarbon groups. R ′ preferably has an ethylenically unsaturated bond, more preferably has an acryloxy group, a methacryloxy group or a vinyl group, more preferably has an acryloxy group or a methacryloxy group, and particularly preferably has an acryloxy group. preferable.
When n is 2 or 3, the plurality of R ′ may be the same or different.

Said X represents a C1-C4 alkoxy group, a hydroxyl group, a halogen atom, or a hydrogen atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these, it is preferable that X is a C1-C4 alkoxy group or a halogen atom.
When n is 0 to 2, a plurality of Xs may be the same or different from each other, but are preferably the same from the viewpoint of easy availability.

  This type of organosilane compound is excellent in compatibility with the toner core particles, and a thin film of a silane compound having a thickness of several nanometers to several tens of nanometers can be easily and effectively formed by using a very small amount. In this embodiment, it is particularly preferable to use a radical-reactive organosilane compound in which one or more organic groups having an ethylenically unsaturated bond (unsaturated carbon bond) are present. Such an organic silane compound is bonded to a radical polymerizable group present in the toner core particle by radical polymerization to form a thin film, or the toner core particle is coated with a polymer of the organic silane compound.

In the present embodiment, in the coating of the toner core particles, the above organosilane compound having an ethylenically unsaturated bond and other ethylenically unsaturated compounds may be used in combination. Examples of other ethylenically unsaturated compounds include known ethylenically unsaturated compounds. For example, at least a polymerizable functional group such as (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, vinyloxy group, etc. A radically polymerizable compound having one is mentioned.
The amount of other ethylenically unsaturated compounds used is preferably 25% by weight or less based on the total amount of the organic silane compound and other ethylenically unsaturated compounds used for coating the toner core particles. More preferably, it is more preferably 5% by weight or less, and most preferably not used. It is preferable that the amount of other ethylenically unsaturated compound used be within the above range since the silicon content of the coating layer is appropriate.

Although it does not specifically limit as an appropriate thing of such an organosilane compound, The following compounds are illustrated. Specific examples include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, allyltrimethylsilane, methacryloxymethyltrimethoxysilane, and the like.
These organosilane compounds are usually hydrophobic and have low solubility in water at pH = 7. Therefore, when using such an organic silane compound, it is possible to adjust the pH according to each type, and to hydrolyze the hydrolyzable group contained in the molecule to a silanol group and to perform water-solubilization treatment, toner base particles It is preferable to make the surface homogeneous. More preferably, the pH is set to 3 to 5 with hydrochloric acid, formic acid, acetic acid, nitric acid or the like. A pH within the above range is preferable because the reactivity of the silanol group is low and the formation of a water-insoluble siloxane oligomer by the condensation reaction is suppressed. If necessary, a small amount of a solvent such as alcohol, acetone, or toluene may be added to improve the solubility of the organosilane compound.

  The amount of the organosilane compound added may be added all at once, or may be gradually added little by little. The total amount of the organosilane compound added is preferably 10% by weight or less based on the weight of the toner core particles. When the addition amount is within the above range, polymerization precipitation is suppressed in an aqueous medium, and aggregation and fusion of toner core particles or toner base particles are suppressed at the time of polymerization, which is preferable because manufacturing problems are suppressed. . Although the lower limit of the addition amount of the organosilane compound is not particularly defined, it is preferably 0.1% by weight or more based on the toner core particles.

  In order to polymerize the organosilane compound having an ethylenically unsaturated bond by the above method, it is preferable to add a polymerization initiator. For example, azo such as 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2-azobis (isobutyronitrile) widely used as a polymerization initiator in suspension polymerization method and swelling polymerization method. System initiators; peroxide initiators such as benzoyl peroxide and lauroyl peroxide; oil-soluble polymerization initiators; and the like may be used. Further, water-soluble initiators such as persulfates such as potassium persulfate and ammonium persulfate and peroxides used as polymerization initiators in the seed polymerization method and the emulsion polymerization method may be used. In addition to the polymerization initiator, a polymerization regulator such as tert-dodecanethiol may be added as necessary.

<Toner particle size>
In the exemplary embodiment, the volume average particle size of the toner base particles is preferably 2 to 9 μm, and more preferably 3 to 7 μm. It is preferable that the toner has a volume average particle diameter of 2 μm or more because good chargeability is obtained and high developability is obtained. Moreover, since it is excellent in the resolution of an image as it is 9 micrometers or less, it is preferable.

In this embodiment, the toner base particles preferably have a volume average particle size distribution index GSDv of 1.30 or less.
It is preferable that the volume average particle size distribution index GSDv of the toner base particles is 1.30 or less because the remodelability of the image is good.
In this embodiment, the particle size of the toner base particles and the value of the volume average particle size distribution index GSDv are measured and calculated as follows. First, with respect to the divided particle size range (channel), the particle size distribution of toner base particles measured using a measuring instrument such as Coulter Counter TAII (manufactured by Beckman Coulter), Multisizer II (manufactured by Beckman Coulter), etc. A cumulative distribution is drawn from the small-diameter side with respect to the volume of each toner base particle, and the particle size at which accumulation is 16% is defined as volume average particle size D16v, and the particle size at which accumulation is 50% is defined as volume average particle size D50v. To do. Similarly, the particle diameter that is 84% cumulative is defined as the volume average particle diameter D84v. At this time, the volume average particle size distribution index (GSDv) is calculated using these relational expressions defined as D84v / D16v.

The toner base particles of the present embodiment have a shape factor SF1 (= ((absolute maximum length of toner base particles) ² / projection area of toner base particles) × (π / 4) × 100) of 110 to 160. A range is preferred. The shape factor SF1 is more preferably in the range of 125 to 140.
The value of the shape factor SF1 indicates the roundness of the particle, and is 100 in the case of a true sphere, and increases as the shape of the toner base particle becomes indefinite. Further, values required for calculation using the shape factor SF1, that is, the absolute maximum length of the toner base particles and the projected area of the toner base particles are 500 magnifications using an optical microscope (Nikon Corporation, Microphoto-FXA). A toner base particle image magnified twice is taken, and the obtained image information is introduced into, for example, an image analysis apparatus (Luxex III) manufactured by Nireco Co., Ltd. via an interface and obtained by image analysis. The average value of the shape factor SF1 is calculated based on data obtained by measuring 1,000 toner mother particles randomly sampled.
Note that the volume average particle size, volume average particle size distribution index, shape factor, and the like of the toner base particles may be approximated by measuring the toner particles. This is because the volume average particle size, the volume average particle size distribution index, the shape factor, and the like are less changed by the addition of external additives (silica particles, titania particles, etc.).

  A shape factor of SF1 of 110 or more is preferable because residual toner is likely to be generated in the transfer step during image formation and the residual toner needs to be removed, but it is excellent in cleaning properties and as a result hardly causes image defects. On the other hand, it is preferable that the shape factor SF1 is 160 or less because when the toner is used as a developer, the toner is not destroyed by collision with the carrier in the developing machine. As a result, generation of fine powder is suppressed, exposure of the release agent component to the toner surface is small, contamination of the surface of the photoreceptor is prevented, good charging characteristics are maintained, and fog caused by the fine powder is further prevented. Since generation | occurrence | production of is suppressed, it is preferable.

<External additive>
In this embodiment, after drying like a normal toner for the purpose of imparting chargeability, fluidity and improving cleaning properties, inorganic particles such as silica, alumina, titania and calcium carbonate, resins such as vinyl resins, polyesters and silicones are used. The particles may be added to the surface of the toner base particles by being sheared in a dry state as a fluidity aid or a cleaning aid.
Inorganic oxide particles added to the toner include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na _2. Examples include 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.
Among these, in the toner of the present embodiment, it is necessary to use at least silica particles and titania particles in combination. As for the addition amount of silica and titania to the toner base particles, it is preferable that silica is mainly added, and the addition amount of titania is preferably smaller than that of silica. It is preferable that the amount of titania added is smaller than that of silica because the interaction between titania and toner particles does not become excessive and the charging property is good.

Further, when the addition amount of silica to the toner base particles is a and the addition amount of titania toner base particles is b, it is preferable to satisfy the following formula (1).
0.2 ≦ b / a ≦ 0.5 (1)
When the above b / a is 0.2 or more, the abundance ratio of titania is high, the binding force to the silica particles is high, the release of the silica particles from the toner is suppressed, the carrier contamination is suppressed, and the charging during long-term use is suppressed. Good properties. Further, when the b / a is 0.5 or less, the ratio of titania is low, the charge exchange between the toner and titania does not prevail, the mixture of toners having different chargeability levels is suppressed, and image fogging is suppressed. Is suppressed.
b / a is more preferably 0.25 or more and 0.45 or less, further preferably 0.3 or more and 0.45 or less, and particularly preferably 0.3 or more and 0.4 or less.
Here, as a silica particle and a titania particle, when using several particle | grains from which an average particle diameter and a surface treatment state differ, it is preferable to set it as said range as the total amount.

The total amount of silica particles added to the toner base particles is preferably 2 / D50v (μm) wt% or more and 50 / D50 v (μm) wt%, where D50v is the volume average diameter of the toner base particles. D50v (μm) wt% or more and 30 / D50v (μm) wt% or less are more preferable. When the addition amount of the silica particles in the toner is 2 / D50v (μm) weight% or more, sufficient fluidity is imparted. Further, it is preferable that the amount is 50 / D50v (μm) wt% or less because charging is less dependent on the environment and wear of the photoreceptor is suppressed.
The addition amount of the titania particles to the toner base particles is preferably 2 / D50v (μm) wt% or more and 20 / D50v (μm) wt% or less, preferably 3 / D50v (μm) wt% or more and 12 / D50v (μm) weight. % Or less is more preferable. When the addition amount of the titania particles in the toner is 2 / D50v (μm) weight% or more, the release of silica particles from the toner is suppressed, carrier contamination is suppressed, and good chargeability is obtained even in long-term use. Maintained. Further, it is preferable that the amount is 20 / D50v (μm) wt% or less because the OHP transparency of the color toner is good.

Moreover, in this embodiment, it is preferable to contain the inorganic particle which shows electroconductivity other than a silica and a titania.
It is preferable that inorganic particles exhibiting electrical conductivity are contained because charge exchange is performed in a direction in which the charge amount between toners becomes uniform, and the toner charge amount distribution becomes sharp.
Here, showing conductivity means that the volume resistivity is 10 ⁴ Ωcm or less. The volume resistivity is measured as follows.
A measuring jig comprising a pair of 20 cm ² circular electrode plates (made of steel) connected to an electrometer (manufactured by KEITHLEY, trade name: KEITHLEY 610C) and a high-voltage power supply (trade name: FLUKE 415B). The sample is placed on the lower electrode plate so as to form a flat layer having a thickness of about 1 mm to 3 mm. Next, after placing the upper electrode plate on the sample, a 4 kg weight is placed on the upper electrode plate in order to eliminate the gap between the samples. In this state, the thickness of the sample layer is measured. Next, the current value is measured by applying a voltage to the bipolar plate, and the volume resistivity is calculated based on the following equation.
Volume resistivity = applied voltage × 20 ÷ (current value−initial current value) ÷ sample thickness In the above formula, the initial current is the current value when the applied voltage is 0, and the current value indicates the measured current value.

  Examples of the conductive particles include metal particles such as gold, silver, and copper, carbon black particles, and surfaces of titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate powder, tin oxide, carbon black, metal And particles covered with the like, titanium oxide, zinc oxide or the like doped with a different element. These may be used individually by 1 type and may use 2 or more types together. Among these, particles in which a different element is doped into zinc oxide are preferable from the viewpoints of production stability, cost, conductivity, and the like. The amount of the conductive particles added to the toner base particles is preferably 0.5 to 4.0 wt%, more preferably 0.7 to 2.0 wt%.

It is preferable that the surface of the inorganic oxide particles is previously hydrophobized. This hydrophobization treatment is more effective for improving the powder fluidity of the toner, as well as the environmental dependency of charging and the resistance to carrier contamination.
The hydrophobizing treatment may be performed by immersing the inorganic oxide particles in a hydrophobizing agent. Although there is no restriction | limiting in particular as said hydrophobic treatment agent, For example, a silane coupling agent, a silicone oil, a titanate coupling agent, an aluminum coupling agent etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, silane coupling agents are preferable.
As the silane coupling agent, for example, any one of chlorosilane, alkoxysilane, silazane, and a special silylating agent can be used. Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltriethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N- ( Trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane , Γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercapto Examples thereof include propyltrimethoxysilane and γ-chloropropyltrimethoxysilane. The amount of the hydrophobizing agent varies depending on the kind of the inorganic oxide particles and it is difficult to define it unconditionally. Preferably there is. More preferably, it is about 5 to 20 parts by weight. In the present embodiment, commercially available products are preferably used as the hydrophobic silica particles.

In this embodiment, silica and titania may be used in combination.
In particular, the silica is preferably used in combination with a plurality of silica particles having different average particle diameters. Specifically, it is preferable to use silica having an average particle diameter of 20 to 50 nm and silica having an average particle diameter of 70 to 140 nm in combination.

(Electrostatic image developer)
The electrostatic image developing toner of this embodiment is used as an electrostatic image developer.
The electrostatic image developer of the exemplary embodiment is not particularly limited except that it contains the electrostatic image developing toner of the exemplary embodiment, and can take an appropriate component composition according to the purpose. When the electrostatic image developing toner of this embodiment is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development is performed according to an electrostatic latent image is also applied.

  In the present embodiment, the development method is not particularly defined, but the two-component development method is preferable. Also, if the above conditions are satisfied, the carrier is not particularly defined, but as the core material of the carrier, for example, magnetic metals such as iron, steel, nickel, cobalt, alloys of these with manganese, chromium, rare earth, etc., and ferrite, Examples thereof include magnetic oxides such as magnetite. From the viewpoint of core material surface properties and core material resistance, ferrite, particularly alloys with manganese, lithium, strontium, magnesium and the like are preferable.

The carrier used in this embodiment is preferably formed by coating a resin on the surface of the core, and the resin is not particularly limited and is appropriately selected according to the purpose. For example, polyolefin resins such as polyethylene and polypropylene; polyvinyl resins and polyvinylidene resins such as polystyrene, acrylic resins, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone Vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of organosiloxane bond or modified product thereof; polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. Fluorine resin; Silicone resin; Polyester; Polyurethane; Polycarbonate; Phenol resin; Urea-formaldehyde resin, Melamine tree , Benzoguanamine resins, urea resins, amino resins such as polyamide resins, epoxy resins, per se known resins and the like. These may be used individually by 1 type and may use 2 or more types together. In the present embodiment, among these resins, it is preferable to use at least a fluorine resin and / or a silicone resin. Use of at least a fluorine-based resin and / or a silicone resin as the resin is advantageous in that the effect of preventing carrier contamination (impaction) due to toner and external additives is high.
The resin film may be obtained by dispersing resin particles and / or conductive particles in the resin. Examples of the resin particles include thermoplastic resin particles and thermosetting resin particles. Among these, thermosetting resins are preferable from the viewpoint of relatively easily increasing the hardness, and resin particles made of nitrogen-containing resin containing N atoms are preferable from the viewpoint of imparting negative chargeability to the toner. In addition, these resin particles may be used individually by 1 type, and may use 2 or more types together. The average particle size of the resin particles is preferably about 0.1 to 2 μm, more preferably 0.2 to 1 μm. It is preferable that the average particle diameter of the resin particles is 0.1 μm or more because the resin particles are excellent in dispersibility in the coating. Moreover, since it is hard to produce detachment | desorption of the resin particle from the said film as it is 2 micrometers or less, it is preferable.

  Examples of the conductive particles include metal particles such as gold, silver, and copper, carbon black particles, and surfaces of titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate powder, tin oxide, carbon black, metal And particles covered with the like, titanium oxide, zinc oxide or the like doped with a different element. These may be used individually by 1 type and may use 2 or more types together. Among these, carbon black particles are preferable from the viewpoints of production stability, cost, conductivity, and the like. The type of carbon black is not particularly limited, but carbon black having a DBP oil absorption of about 50 to 250 ml / 100 g is preferable because of excellent production stability. The coating amount on the surface of the core material by the resin, the resin particles, and the conductive particles is preferably 0.5 to 5.0 wt%, more preferably 0.7 to 3.0 wt%.

The method for forming the coating is not particularly limited. For example, the resin particles such as crosslinkable resin particles and / or the conductive particles, and a styrene acrylic resin, a fluorine resin, a silicone resin as a matrix resin, etc. And a method of using a film-forming solution containing the above resin in a solvent.
Specifically, the carrier core material is immersed in the film forming liquid, a spray method in which the film forming liquid is sprayed on the surface of the carrier core material, and the carrier core material is floated by flowing air And kneader coater method in which the film forming solution is mixed and the solvent is removed. Among these, the kneader coater method is preferable in the present embodiment.

  The solvent used for the film forming liquid is not particularly limited as long as it can dissolve only the resin as a matrix resin, and is selected from known solvents such as toluene, Aromatic hydrocarbons such as xylene, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and the like. When the resin particles are dispersed in the coating, since the resin particles and the particles as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface, the carrier is used for a long time. Even when the coating is worn, the surface formation is always maintained as when the coating is not used, and a good charge imparting ability is maintained for the toner over a long period of time. In the case where the conductive particles are dispersed in the coating, the conductive particles and the resin as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface. Even if the coating is worn out over a long period of time, the same surface formation as when not in use is always maintained, and carrier deterioration is prevented for a long period of time. In addition, when the said resin particle and the said electroconductive particle are disperse | distributed to the said film, the above-mentioned effect is exhibited simultaneously.

The electric resistance of the magnetic carrier formed as described above in the state of a magnetic brush under an electric field of 10 ⁴ V / cm is preferably 10 ⁸ to 10 ¹³ Ωcm. It is preferable that the electric resistance of the magnetic carrier is 10 ⁸ Ωcm or more because adhesion of the carrier to the image portion on the image holding member is suppressed and a brush mark is difficult to appear. On the other hand, it is preferable that the electrical resistance of the magnetic carrier is 1 × 10 ¹³ Ωcm or less because the generation of the edge effect is suppressed and a good image quality can be obtained.
The volume resistivity is measured as follows.
A measuring jig comprising a pair of 20 cm ² circular electrode plates (made of steel) connected to an electrometer (manufactured by KEITHLEY, trade name: KEITHLEY 610C) and a high-voltage power supply (trade name: FLUKE 415B). The sample is placed on the lower electrode plate so as to form a flat layer having a thickness of about 1 mm to 3 mm. Next, after placing the upper electrode plate on the sample, a 4 kg weight is placed on the upper electrode plate in order to eliminate the gap between the samples. In this state, the thickness of the sample layer is measured. Next, the current value is measured by applying a voltage to the bipolar plate, and the volume resistivity is calculated based on the following equation.
Volume resistivity = applied voltage × 20 ÷ (current value−initial current value) ÷ sample thickness In the above formula, the initial current is the current value when the applied voltage is 0, and the current value indicates the measured current value.

  In the two-component electrostatic image developer, the mixing ratio of the toner and the carrier of this embodiment is usually 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method)
The electrostatic image developer (electrostatic image developing toner) is used in an image forming method of a normal electrostatic image developing system (electrophotographic system).
The image forming method of the present embodiment includes a charging step for charging the image carrier, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and an electrostatic latent image formed on the surface of the image carrier. A development step of developing the image with an electrostatic charge image developing toner or an electrostatic charge image developer to form a toner image, and a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the transfer target; And a fixing step for fixing the toner image. In addition, a cleaning process or the like may be included as necessary.
Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. Note that the image forming method of the present embodiment is carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.
The latent image forming step is a step of forming an electrostatic latent image on the surface of the image carrier.
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer holder to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of this embodiment containing the electrostatic image developer of the present embodiment.
The transfer step is a step of transferring the toner image onto a transfer target.
The fixing step is a step of forming a copy image by fixing the toner image transferred onto a recording medium such as recording paper by an optical fixing device or a thermal fixing device.
The cleaning step is a step of removing the electrostatic charge image developer remaining on the image carrier. In the image forming method of the present embodiment, an aspect that further includes a recycling step is preferable.
The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling process is performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention is also applicable to a recycling system in which the cleaning step is omitted and toner is collected simultaneously with development.
Through such a series of processing steps, a desired duplicate product (printed matter or the like) can be obtained.

(Image forming device)
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the image carrier, and an exposure unit that exposes the charged image carrier to form an electrostatic latent image on the image carrier. A developing means for developing the electrostatic latent image with an electrostatic charge image developing toner or an electrostatic charge image developer to form a toner image; and a transfer means for transferring the toner image from the image carrier to a transfer target. It is preferable to have. In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member. Further, it may have a cleaning means for removing toner remaining on the image carrier.

As the image carrier and each of the above-described units, the configurations described in the respective steps of the image forming method are preferably used.
As each of the above-described means, a well-known means is used in the image forming apparatus. Further, the image forming apparatus used in the present embodiment may include means and devices other than the above-described configuration. Further, the image forming apparatus used in the present embodiment may simultaneously perform a plurality of the above-described means.

  In addition, a known fixing device is used for fixing in the present embodiment. For example, a fixing belt having a low surface energy material typified by a fluororesin component and a silicone resin on the surface and a belt shape, Examples include a fixing roll having a low surface energy material typified by a fluororesin component and a silicone resin on the surface and exhibiting a cylindrical roll shape.

  The surface of the fixing roll or the fixing belt may be formed of a material having excellent releasability from the toner, for example, silicon rubber or fluorine resin, for the purpose of preventing toner from adhering. preferable. At this time, it is effective that the releasable liquid such as silicone oil applied to the fixing roll is infinitely small. The releasable liquid is effective for fixing latitude, but because it is transferred to the transfer material to be fixed, there are stickiness, tape cannot be applied, and characters cannot be written by magic. is there. This is remarkable for OHP. In addition, since the releasing liquid cannot smooth the fixing surface, it also causes a decrease in OHP transparency.

  Since the toner configuration of the present embodiment exhibits a sufficient fixing latitude, a small amount of releasable liquid such as silicone oil applied to the fixing roll or fixing belt is sufficient. For example, it is preferably 1 μl or less per A4 sheet. Within this range, the aforementioned problems are substantially avoided.

(Toner cartridge and process cartridge)
The toner cartridge of the present embodiment is a toner cartridge that contains at least the electrostatic image developing toner of the present embodiment. The toner cartridge of this embodiment may contain the electrostatic image developing toner of this embodiment as an electrostatic image developer.
In addition, the process cartridge of the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, a developing unit that develops an electrostatic latent image with a developer containing toner, and forms a toner image, and an image holding unit At least one selected from the group consisting of cleaning means for removing toner remaining on the body surface, and the electrostatic charge image developing toner of the present embodiment or the electrostatic charge image developer of the present embodiment. At least the process cartridge accommodated.

The toner cartridge of this embodiment is preferably detachable from the image forming apparatus. That is, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner cartridge of the present embodiment in which the toner of the present embodiment is stored is preferably used.
Further, the toner cartridge may be a cartridge that stores toner and a carrier, or a cartridge that stores toner alone and a cartridge that stores a carrier independently.

It is preferable that the process cartridge of the present embodiment is attached to and detached from the image forming apparatus.
In addition, the process cartridge according to the present embodiment may include other members such as a static elimination unit as necessary.
As the toner cartridge and the process cartridge, known configurations may be adopted. For example, Japanese Patent Application Laid-Open Nos. 2008-209489 and 2008-233736 are referred to.

Hereinafter, the present embodiment will be described in detail with reference to examples, but the present embodiment is not limited in any way.
The color toner core particles 1 and 2 of the present embodiment were obtained by the following method.
That is, the following resin particle dispersion, colorant particle dispersion, and release agent particle dispersion were prepared. Next, while a predetermined amount of these were mixed and stirred, a polymer of an inorganic metal salt was added thereto and ionically neutralized to form aggregates of the particles. Before reaching the desired toner particle size, a resin particle dispersion was added to obtain a toner particle size. Next, the pH of the system was adjusted from a weakly acidic to a neutral range with an inorganic hydroxide, and then heated to a temperature higher than the glass transition temperature of the resin particles so as to fuse together. After completion of the reaction, desired toner core particles 1 and 2 were obtained through sufficient washing, solid-liquid separation and drying processes.
Hereinafter, preparation examples of a method for preparing each material and a method for preparing aggregated particles will be described.

(Toner preparation)
<Synthesis of crystalline polyester resin (1)>
Decanedicarboxylic acid: 100 mol%
-Nonanediol: 100 mol%
Dibutyltin oxide: 0.25% by weight based on the total monomer weight
After putting the above components into a heat-dried three-necked flask, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring.
Then, it heated up gradually to 230 degreeC under pressure reduction, stirred for 2 hours, and air-cooled when it became a viscous state, the reaction was stopped, and the crystalline polyester resin (1) was synthesize | combined.
The weight average molecular weight (Mw) of the crystalline polyester resin (1) obtained by molecular weight measurement (polystyrene conversion) by gel permeation chromatography was 22,000, and the number average molecular weight (Mn) was 7,400. . The acid value was 10.7 mgKOH / g, and the hydroxyl value was 20.5 mgKOH / g.
Further, when the melting point (Tm) of the crystalline polyester resin (1) was measured using a differential scanning calorimeter (DSC) by the above-described measuring method, it showed a clear endothermic peak, and the endothermic peak temperature (melting point) was 72.1 ° C.

<Synthesis of Amorphous Polyester Resin (1)>
-Bisphenol A ethylene oxide 2-mol adduct: 10 mol%
(2-mole adduct in terms of both ends)
-Bisphenol A propylene oxide 2 mol adduct: 90 mol%
(2-mole adduct in terms of both ends)
・ Terephthalic acid: 50 mol%
・ Fumaric acid: 30 mol%
-Dodecenyl succinic acid: 20 mol%
Charge the above monomer into a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectification tower, increase the temperature to 190 ° C over 1 hour, and confirm that the reaction system is uniformly stirred. Thereafter, 0.8% by weight of tin distearate was added to the total weight of these monomers. Further, while distilling off the generated water, the temperature was raised to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. As a result, the glass transition temperature is 62 ° C., the acid value is 13.2 mg KOH / g, the hydroxyl value is 27.5 mg KOH / g, the weight average molecular weight is 15,000, the number average molecular weight is 5,000, and the softening point is 101 ° C. Amorphous polyester resin (1) was obtained.

<Synthesis of Amorphous Polyester Resin (2)>
-Bisphenol A ethylene oxide 2-mol adduct: 50 mol%
(2-mole adduct in terms of both ends)
Bisphenol A propylene oxide 2 mol adduct: 50 mol%
(2-mole adduct in terms of both ends)
-Trimellitic anhydride: 7 mol%
・ Terephthalic acid: 65 mol%
・ Dodecenyl succinic acid: 28 mol%
Using a monomer other than trimellitic anhydride, the reaction was continued in the same manner as in the amorphous polyester resin (1) until the softening point reached 110 ° C. Next, the temperature was lowered to 190 ° C., 7 mol% of trimellitic anhydride was gradually added, and the reaction was continued at that temperature for 1 hour. As a result, the glass transition temperature was 56 ° C., the acid value was 11.3 mg KOH / g, the hydroxyl value was 23.8 mg KOH / g, the weight average molecular weight was 58,000, the number average molecular weight was 7,800, and the softening point was 114 ° C. A crystalline polyester resin (2) was obtained.

<Preparation of resin particle dispersion (1)>
・ Crystalline polyester resin (1): 100 parts by weight ・ Methyl ethyl ketone: 60 parts by weight ・ Isopropyl alcohol: 15 parts by weight Stirring was carried out to completely dissolve the oil phase. This separable flask containing the oil phase is set to 65 ° C. with a water bath, and a 10% aqueous ammonia solution is gradually added dropwise to the stirred oil phase with a dropper so that the total amount becomes 5 parts by weight. 230 parts by weight of water are gradually added dropwise at a rate of 10 ml / min to cause phase inversion emulsification, and solvent removal is performed while reducing the pressure with an evaporator, and a resin particle dispersion (1) made of crystalline polyester resin (1) Obtained. The resin particles had a volume average particle size of 150 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

<Preparation of resin particle dispersion (2)>
-Amorphous polyester resin (1): 100 parts by weight-Methyl ethyl ketone: 60 parts by weight-Isopropyl alcohol: 15 parts by weight Methyl ethyl ketone and isopropyl alcohol are charged into a separable flask, and then the above resins are gradually added to provide a three-one motor. Was stirred and completely dissolved to obtain an oil phase. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount was 3.5 parts by weight. 230 parts by weight of ion-exchanged water is gradually added dropwise at a rate of 10 ml / min to carry out phase inversion emulsification, and solvent removal is performed while reducing the pressure with an evaporator. 2) was obtained. The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

<Preparation of resin particle dispersion (3)>
The resin particle dispersion (3) was obtained in the same manner as in the preparation of the resin particle dispersion (2) except that the amorphous polyester resin (1) was changed to the amorphous polyester resin (2). The volume average particle diameter of the resin particles was 165 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

<Preparation of Colorant Particle Dispersion 1>
Cyan pigment (Daiichi Seika Kogyo Co., Ltd .: ECB-301): 50 parts by weight Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts by weight Part After mixing the above components and dispersing for 10 minutes with a homogenizer (IKA Ultra Tarrax), using an optimizer (counter-impact collision type wet crusher: manufactured by Sugino Machine Co., Ltd.) for 15 minutes at a pressure of 250 MPa, A colorant particle dispersion 1 having a volume average particle size of the colorant particles of 130 nm and a solid content of 20% was obtained.

<Preparation of Colorant Particle Dispersion 2>
In the preparation of the colorant particle dispersion 1, the same procedure was performed except that the colorant was changed to magenta R122 pigment (manufactured by Dainichi Seika Kogyo Co., Ltd .: ECR-186Y), and the volume average particle diameter of the colorant particles was 120 nm. To obtain a colorant particle dispersion 2 having a solid content of 20.0%.

<Preparation of release agent particle dispersion>
-Olefin wax (melting point: 88 ° C): 60 parts by weight-Ionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1.8 parts by weight-Ion exchange water: 238 parts by weight Heat and thoroughly disperse with IKA Ultra Turrax T50, then heat to 110 ° C. with a pressure discharge type gorin homogenizer and perform dispersion treatment for 1 hour, release with volume average particle size of 180 nm and solid content of 20% An agent particle dispersion was obtained.

<Preparation of Color Toner Core Particle 1>
Resin particle dispersion (1): 150 parts by weight Resin particle dispersion (2): 300 parts by weight Resin particle dispersion (3): 250 parts by weight Colorant particle dispersion 1:50 parts by weight Agent particle dispersion: 50 parts by weight The above was added in an amount of 2.0 parts by weight of the ionic surfactant Neogen RK in a round stainless steel flask, and then sufficiently mixed and dispersed. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part by weight of polyaluminum sulfate was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts by weight of the resin particle dispersion (2) and 100 parts by weight of the resin particle dispersion (3) was slowly added thereto.
Thereafter, a 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the reaction mixture was cooled and subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 5 L of ion exchange water at 40 ° C., stirred with a stirring blade (300 rpm) for 15 minutes, and solid-liquid separation was performed by Nutsche suction filtration.
This redispersion and solid-liquid separation washing were repeated, and when the electric conductivity reached 7.0 μS / cm or less, the washing was terminated to obtain color toner core particles 1.
When the particle size at this time was measured with a Coulter counter, the volume average particle size D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Further, the shape factor SF1 of the particle obtained from the shape observation by Luzex was 137, which was a potato shape.

<Preparation of Color Toner Core Particle 2>
In the production of the color toner core particles 1, 150 parts by weight of the resin particle dispersion (1) is 50 parts by weight, 300 parts by weight of the resin particle dispersion (2) is 370 parts by weight, and 50 of the colorant particle dispersion 1 is prepared. A color toner core particle 2 was obtained in the same manner except that the weight part was changed to 80 parts by weight of the colorant particle dispersion 2. The color toner core particles 2 had a volume average particle diameter D50v of 4.8 μm and a particle size distribution coefficient GSDv of 1.27. Further, the shape factor SF1 of the particles obtained from the shape observation by Luzex was 129, which was a potato shape.

<Preparation of Color Toner Core Particle 3>
Amorphous polyester resin (1): 30 parts by weight Amorphous polyester resin (2): 50 parts by weight Crystalline polyester resin (1): 7 parts by weight Cyan pigment (manufactured by Dainichi Seika Kogyo) : ECB-301): 5 parts by weight • Olefin wax (melting point: 88 ° C.): 8 parts by weight The coarse particles were classified to obtain color toner core particles 3. The toner core particles had a volume average particle diameter D50v of 6.5 μm and a particle size distribution coefficient GSDv of 1.26. Further, the shape factor SF1 of the particle obtained by shape observation with Luzex was 136, which was indefinite.

<Preparation of color toner mother particle 1>
-Color toner core particles 1: 100 parts by weight-Ion exchange water: 400 parts by weight The above is stirred in a round glass flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, rectifying tower, and 25 ° C is sufficient. Mixed and dispersed.
Next, a mixed solution of 20 parts by weight of methanol and 6 parts by weight of γ-methacryloxypropyltrimethoxysilane was added dropwise at a rate of 5 ml / min. After completion of the addition, the mixture was mixed for 2 hours with mechanical stirring. At this time, the pH was adjusted to 4.5 with nitric acid. Next, the air in the container was brought into an inert atmosphere with nitrogen gas, and after gradually raising the temperature to 60 ° C. while continuing mechanical stirring, 0.05 parts of catalyst KPS (potassium persulfate) was added to 1 part by weight of ion exchange water. The aqueous solution charged in parts by weight was dropped at a rate of 5 ml / min, and the reaction of the methacryloxy part was advanced while stirring for 3 hours. Next, the mixture was cooled and subjected to solid-liquid separation by Nutsche suction filtration. Thereafter, vacuum drying was continued for 12 hours to obtain color toner mother particles 1 whose surfaces were coated with a silane coupling agent. The color toner base particles had a volume average particle diameter D50v of 6.1 μm and a particle size distribution coefficient GSDv of 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.

<Preparation of color toner mother particles 2>
-Color toner core particles 2: 100 parts by weight-Ion exchange water: 400 parts by weight The above is stirred in a round glass flask equipped with a stirrer, nitrogen introduction tube, temperature sensor, and rectifying tower, and 25 ° C is sufficient. Mixed and dispersed. Next, a mixed solution of 3 parts by weight of γ-methacryloxypropyltrimethoxysilane was added dropwise to 20 parts by weight of methanol at a rate of 5 ml / min. After completion of the dropwise addition, the mixture was mixed for 2 hours with mechanical stirring. At this time, the pH was adjusted to 4.0 with nitric acid. Next, the air in the container was brought into an inert atmosphere with nitrogen gas, and the temperature was gradually raised to 60 ° C. while continuing mechanical stirring. Then, 0.03 wt. The aqueous solution charged in parts by weight was dropped at a rate of 5 ml / min, and the reaction of the methacryloxy part was advanced while stirring for 3 hours. Next, the mixture was cooled and subjected to solid-liquid separation by Nutsche suction filtration. Thereafter, vacuum drying was continued for 12 hours to obtain color toner particles 2 whose surface was coated with a silane coupling agent. The volume average particle diameter D50v of the color toner particles was 4.9 μm, and the particle size distribution coefficient GSDv was 1.27. Further, the shape factor SF1 of the particles obtained by shape observation with Luzex was 128, which was a potato shape.

<Preparation of color toner mother particles 3>
-Color toner core particles 3: 100 parts by weight-Ion exchange water: 400 parts by weight-Methanol: 50 parts by weight The above is stirred in a round glass flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying tower. The mixture was sufficiently mixed and dispersed at 25 ° C. Next, a mixed solution of 5 parts by weight of γ-methacryloxypropyltrimethoxysilane was added dropwise to 20 parts by weight of methanol at a rate of 5 ml / min. After completion of the dropwise addition, the mixture was mixed for 2 hours with mechanical stirring. At this time, the pH was adjusted to 4.0 with nitric acid. Next, the air in the container was brought into an inert atmosphere with nitrogen gas, and the temperature was gradually raised to 60 ° C. while continuing mechanical stirring. Then, 0.03 wt. The aqueous solution charged in parts by weight was dropped at a rate of 5 ml / min, and the reaction of the methacryloxy part was advanced while stirring for 3 hours. Next, the mixture was cooled and subjected to solid-liquid separation by Nutsche suction filtration. Thereafter, vacuum drying was continued for 12 hours to obtain color toner particles 2 whose surface was coated with a silane coupling agent. The volume average particle diameter D50v of the color toner particles was 6.6 μm, and the particle size distribution coefficient GSDv was 1.25. Further, the shape factor SF1 of the particle obtained by shape observation with Luzex was 136, which was indefinite.

<Addition of external additives>
0.8% by weight of hydrophobic titania treated with decylsilane having an average particle size of 15 nm, 1.1% by weight of hydrophobic silica (NY50, manufactured by Nippon Aerosil Co., Ltd.) After blending for 10 minutes at a peripheral speed of 32 m / s using a Henschel mixer so that the average particle size of 100 nm hydrophobic silica (X24, manufactured by Shin-Etsu Chemical Co., Ltd.) was 1.0% by weight, a 45 μm mesh sieve was obtained. Coarse particles were removed using a toner to obtain an external color toner 1. The color toner base particles 1 to 3 were prepared in the same manner to obtain external color toners 2 to 14. The configuration is shown in Table 1.

The inorganic particles used are as follows.
NY50: manufactured by Nippon Aerosil Co., Ltd., silica particles (average particle size: 30 nm, surface treatment: silicone oil treatment)
R812: manufactured by Nippon Aerosil Co., Ltd., silica particles (average particle size: 7 nm, surface treatment: hexamethyldisilazane treatment)
X-24: Shin-Etsu Chemical Co., Ltd., silica particles (average particle size: 100 nm, surface treatment: silane coupling treatment)
RX-50: manufactured by Nippon Aerosil Co., Ltd., silica particles (average particle size: 40 nm, surface treatment: hexamethyldisilazane treatment)
Hydrophobic titania: titania particles (average particle size: 15 nm, surface treatment: decylsilane treatment)
23-K: Conductive zinc oxide particles (average particle size: 120 to 250 nm, volume resistivity: 10 ² Ωcm) manufactured by Hakusui Tech Co., Ltd.
・ Pazette CK: conductive zinc oxide particles (average particle size: 20 to 40 nm, volume resistivity: 10 ^1.3 Ωcm), manufactured by Hakusui Tech Co., Ltd.

<Career production>
Ferrite (trade name EFC-35B, manufactured by Powdertech Co., Ltd., weight average particle size: 35 μm): 100 parts by weight Toluene: 13.5 parts by weight Methyl methacrylate / perfluorooctyl methacrylate copolymer (polymerization ratio) 90:10, weight average molecular weight 49,000): 2.3 parts by weight, carbon black (trade name: VXC72, manufactured by Cabot Corporation): 0.3 parts by weight, Eposter S (melamine resin particles, manufactured by Nippon Shokubai Co., Ltd.) ): 0.3 part by weight The above components excluding ferrite were dispersed in a sand mill for 1 hour to prepare a resin coating layer forming solution. Next, this resin coating layer forming solution and ferrite were put in a vacuum degassing kneader and stirred for 20 minutes while reducing the pressure at a temperature of 60 ° C. to form a resin coating layer on the ferrite to obtain a carrier. The volume resistance was 2 × 10 ¹¹ Ωcm.

<Developing developer>
100 parts of a carrier was added to 7 parts of the externally added color toner 1, and mixed for 5 minutes by a ball mill to obtain a color developer 1. Externally added color toners 2 to 11 were produced in the same manner to obtain color developers 2 to 11.

<Evaluation>
[Chargeability]
The charge amount, charge distribution, and reverse polarity toner amount were measured. The measurement is a value obtained by image analysis of CSG (charge spectrograph method), the charge amount is a 50% charge amount Q (50) (μC / g) of the cumulative integration of the charge distribution, and the charge distribution is the charge distribution. Is the value obtained by dividing the difference between 20% charge amount Q (20) and 80% charge amount Q (80) by 50% charge amount Q (50), that is, [Q (80) −Q (20)]. / Q (50). The reverse polarity toner amount is an accumulated cumulative weight% with respect to the total amount of toner having a reverse charge polarity.

[Initial charging]
7 parts of externally added toner and 100 parts of carrier were mixed for 5 minutes by a ball mill, and the charge amount, charge distribution, and reverse polarity toner amount were measured.

[Admixability]
7 parts of the externally added toner and 100 parts of the carrier were mixed with a ball mill for 100 minutes, 2 parts of the externally added toner were further added and mixed for 5 minutes, and the charge amount, charge distribution, and reverse polarity toner amount were measured.

[Evaluation of actual machine]
The produced color developers 1 to 9 were subjected to a long-term print test using Doccolor 500 (Fuji Xerox Co., Ltd.).
The color developer was set at the position of the cyan developing machine, and the image quality was evaluated by continuously printing a print image in which the toner consumption per print was 10 mg.
-Image quality evaluation-
≪Image quality evaluation standard≫
○: No fogging, no problem in fluctuation of Cin 10% halftone image density Δ: Cin 10% halftone image density fluctuation ×: Ground fogging, impractical use

  The evaluation results of Examples 1 to 11 and Comparative Examples 1 to 3 are shown in Tables 2 and 3. Table 2 shows the results in a 28 ° C., 85% RH environment, and Table 3 shows the results in a 10 ° C., 15% RH environment.

In Examples 1 to 11, the charge distribution was narrow in initial chargeability and admixability in either environment, there was no reverse polarity toner, and there was no fog in the actual machine evaluation.
On the other hand, in Comparative Example 1 in an environment of 28 ° C. and 85% RH, an admix property, a wide charge distribution and a reverse polarity toner were confirmed. In the actual machine evaluation, the density of the halftone image portion of Cin 10% was obtained on the 1,000th print. It became darker than the initial one, and clear and fogging was confirmed on the 10,000th sheet. In Comparative Example 2, initial chargeability and admixability were good without reverse polarity toner, but fogging was confirmed on the 10,000th print in the actual machine evaluation. In Comparative Example 3, toner having an admix property, a wide charge distribution, and a reverse polarity toner was confirmed, and fogging was confirmed on the 1,000th print in the actual machine evaluation. Even in the environment of 10 ° C. and 15% RH, Comparative Examples 1 to 3 were less favorable in the evaluation of the actual machine than in the case of 28 ° C. and 85% RH environment, but were not good.
From the above results, according to the present embodiment, the chargeability is stable even during long-term use with a very small amount of toner consumption, and a static image can be obtained that does not cause fogging or density fluctuation in the halftone image portion. A toner for developing charge images has been provided.

Claims (9)

Inorganic particles are externally added to toner base particles containing at least a binder resin and a colorant,
The surface of the toner base particles is coated with a silane compound,
Inorganic particles are viewing contains a silica and titania,
The silane compound includes a silane compound derived from an organic silane compound having an ethylenically unsaturated bond,
An electrostatic charge image developing toner , wherein the addition amount of the silica to the toner base particles is a and the addition amount of the titania toner base particles is b, the following formula (1) is satisfied .
0.2 ≦ b / a ≦ 0.5 (1)   The electrostatic image developing toner according to claim 1, wherein the silica uses silica having an average particle diameter of 20 to 50 nm in combination with silica having an average particle diameter of 70 to 140 nm. It said toner base particles have a core-shell structure, the shell layer is further coated with a silane compound, toner according to claim 1 or 2.   The electrostatic charge image developing toner according to claim 3, wherein the core-shell structure of the toner base particles is prepared by an emulsion aggregation method.   The electrostatic image developing toner according to claim 1, wherein the inorganic particles contain conductive particles in addition to silica and titania.   An electrostatic image developer comprising the electrostatic image developing toner according to claim 1 and a carrier. An electrostatic latent image formed on the surface of an image carrier, containing the electrostatic image developing toner according to claim 1 or the electrostatic charge image developer according to claim 6. Developing means for developing a toner image by developing with the electrostatic image developing toner or the electrostatic image developer;
And at least one selected from the group consisting of an image carrier, a charging unit for charging the surface of the image carrier, and a cleaning unit for removing toner remaining on the surface of the image carrier,
A process cartridge which is detachable from an image forming apparatus. A charging step for charging at least the image carrier;
A latent image forming step of forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image formed on the surface of the image carrier with an electrostatic charge image developing toner or an electrostatic charge image developer to form a toner image;
A transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the transfer target;
A fixing step for fixing the toner image,
The electrostatic charge image developing toner according to any one of claims 1 to 5, or the electrostatic charge image developer according to any one of claims 1 to 5. Image forming method. An image carrier,
Charging means for charging the image carrier;
Exposure means for exposing the charged image carrier to form an electrostatic latent image on the image carrier;
Developing means for developing the electrostatic latent image with an electrostatic charge image developing toner or an electrostatic charge image developer to form a toner image;
Transfer means for transferring the toner image from the image carrier to a transfer medium;
Fixing means for fixing the toner image;
Use of the electrostatic image developing toner according to any one of claims 1 to 5 as the electrostatic charge image developing toner or the electrostatic image developer according to claim 6 as the electrostatic image developer. An image forming apparatus.