JP2011203511A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development, the toner suppressing defects in a fixed image.SOLUTION: The toner for electrostatic charge image development comprises toner particles comprising a binder resin, a polysiloxane modified resin and an organopolysiloxane resin.

Description

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

In electrophotography, generally, a latent image is electrically formed on the surface of a photoconductor (image carrier) using a photoconductive substance by various means, and the formed latent image is replaced with toner. After developing with a developer containing the developer, a developed image is formed, and then the developed image is transferred to a surface of a transfer medium such as paper via an intermediate transfer body as necessary, and then heated, pressurized, and heated and pressed. An image is formed through a plurality of steps of fixing by, for example. In addition, the toner remaining on the surface of the photoreceptor is cleaned by various methods as necessary, and is used again for development.
In recent years, the electrophotographic method has been improved in image quality, and has spread to high image quality and high added value applications such as photographic images and printing.

By the way, Patent Document 1 states that “the toner resin contains more than 3 wt% of the polysiloxane-modified resin, and the polysiloxane part is bonded to another polymer part on the ether group or ester group, Has proposed a dry toner particle characterized by comprising a polymer containing an oxygen-containing group.
Patent Document 2 discloses that “a modified polyester for electrophotographic toner, characterized by reacting a polyester resin (A) with a vinyl polymer (B) having an epoxy group and a polysiloxane segment in the side chain”. A method for producing the resin (C) and an electrophotographic toner containing the resin (C) as an essential component have been proposed.
Patent Document 3 discloses “a polyester resin (A) and a polysiloxane-modified polyester resin for electrophotographic toner in which a polysiloxane (B) having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom is reacted. A manufacturing method and an electrophotographic toner containing the same as an essential component have been proposed.
Patent Document 4 proposes "a toner composition or a capsule toner composition characterized by containing a binder resin, a colorant, silicone oil, and a silicone-modified resin.""Siliconcopolymer" is disclosed.
Patent Document 5 discloses that “a color toner for developing an electrostatic image, comprising at least a binder resin, a colorant, and a hydrophobic polysiloxane compound having a melting point of 30 to 150 ° C. having the structure shown below”. Has been proposed.

Japanese Patent Laid-Open No. 08-297380 JP 2001-296695 A JP 2000-338720 A Japanese Patent Laid-Open No. 08-087127 JP 05-289408 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image in which a fixed image is flexible and suppresses defects such as cracking compared to a case where a polysiloxane-modified resin and an organopolysiloxane resin are not included.

The above problem is solved by the following means. That is,
The invention according to claim 1
An electrostatic charge image developing toner comprising a binder resin, a polysiloxane-modified resin, an organopolysiloxane resin, and a colorant.

The invention according to claim 2
2. The electrostatic image developing toner according to claim 1, wherein the total content of the polysiloxane-modified resin and the organopolysiloxane resin is 5% by weight or more and 50% by weight or less based on the binder resin.

The invention according to claim 3
The electrostatic image developing toner according to claim 1, wherein the polysiloxane-modified resin is a polysiloxane-modified polyester resin obtained by modifying a crystalline polyester.

The invention according to claim 4
The electrostatic image developing toner according to claim 3, wherein the polysiloxane-modified polyester resin is contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin.

The invention according to claim 5
The toner particles are composed of a core part and a coating layer covering the core part,
The electrostatic charge image developing toner according to claim 1, wherein the coating layer includes the binder resin, the polysiloxane-modified resin, and the organopolysiloxane resin.

The invention according to claim 6
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 7 provides:
A toner cartridge that accommodates the electrostatic image developing toner according to claim 1 and is detachable from an image forming apparatus.

The invention according to claim 8 provides:
A developing means for accommodating the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image holding member as a toner image by the electrostatic charge image developer,
A process cartridge that is detachable from the image forming apparatus.

The invention according to claim 9 is:
An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring the toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer target;
An image forming apparatus.

According to the first aspect of the present invention, there is provided a toner for developing an electrostatic charge image in which a fixed image is supple and suppresses defects such as cracking compared to a case where a polysiloxane-modified resin and an organopolysiloxane resin are not included.
According to the second aspect of the present invention, there is provided an electrostatic image developing toner in which the total content of the polysiloxane-modified resin and the organopolysiloxane resin is less than the above range, and the fixed image is supple and cracks are suppressed such as cracking. Provided.
According to the third aspect of the invention, compared to the case where the polysiloxane-modified resin is not a polysiloxane-modified polyester resin obtained by modifying a crystalline polyester resin, the fixed image is supple and has a suppleness and is free from defects such as cracking. Toner is provided.
According to the fourth aspect of the present invention, there is provided a toner for developing an electrostatic charge image in which the content of the polysiloxane-modified polyester resin with respect to the binder resin is out of the above range, and the fixed image is less pliable and cracked. Is done.
According to the invention of claim 5, when the toner particles are constituted by the core portion and the covering portion, the fixed image is supple as compared with the case where the core portion contains the polysiloxane-modified resin and the organopolysiloxane resin. Thus, a toner for developing an electrostatic image in which defects such as cracks are suppressed is provided.
According to the inventions according to claims 6, 7, 8, and 9, it is possible to suppress defects such as cracks as compared with the case where toner particles are used that do not contain polysiloxane-modified resin and organopolysiloxane resin. A fixed image is obtained.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge of this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail.

(Static image developing toner)
The electrostatic image developing toner according to the exemplary embodiment (hereinafter sometimes referred to as “toner”) includes, for example, toner particles and external additives as necessary.
The toner particles include a binder resin, a polysiloxane-modified resin, an organopolysiloxane resin, and a colorant.

In the toner according to the exemplary embodiment, the above-described configuration suppresses a defect such as a crack in the fixed image with flexibility. The reason for this is not clear, but is thought to be due to the following reasons.
If a resin having a polysiloxane structure is blended in the toner particles, it is considered that the flexibility of the toner particles is increased by the polysiloxane structure.
On the other hand, organopolysiloxane resins having a polysiloxane structure are easy to separate because of their poor compatibility with binder resins (especially ester resins such as polyester resins). Simply put organopolysiloxane resin in the toner particles. By simply blending, there may occur a phenomenon that the organopolysiloxane resin is unevenly distributed in the toner particles or not blended in the toner particles.
Therefore, it is considered that the compatibility of the organopolysiloxane resin with the binder resin is improved by using the polysiloxane-modified resin together with the organopolysiloxane resin.

For this reason, in the toner according to the present embodiment, the polysiloxane-modified resin is contained in the toner particles in a more uniformly distributed manner together with the organopolysiloxane resin that imparts flexibility to the toner particles. Defects such as cracks are suppressed. Specifically, for example, even when a physical excessive load is applied to the fixed image such as when the fixed image is folded, the bending load increases on the fixed image, and Even if a scratch load is applied, the loss of a fixed image such as wear, cracking, and chipping is suppressed.
In addition, in the toner according to the exemplary embodiment, it is considered that heat resistance and releasability are imparted to a fixed image by including in the toner particles a polysiloxane-modified resin together with an organopolysiloxane resin.

In particular, in the toner according to the exemplary embodiment, when the toner particles are configured by a core portion and a coating layer that covers the core portion (when the so-called toner particles have a core / shell structure), the coating layer is bound. It is preferable to include a resin, a polysiloxane-modified resin, and an organopolysiloxane resin. Thereby, it is considered that the defect of the fixed image is further suppressed.
This is because a fixed image is likely to be covered with a coating layer (shell layer) of toner particles, so that the defect of the fixed image is suppressed by providing the coating layer with the above-described configuration and providing flexibility. It is because it is considered.
In addition, since the polysiloxane-modified resin and the organopolysiloxane resin are considered to also have a function as a release agent, by including the resin in the coating layer, when fixing the toner image, the toner particles are externally applied from the toner particles. It is considered that the releasability of the fixed image is improved because the resin is easily oozed out.

  From the above, the toner according to the present embodiment enables handling equivalent to gravure printing in electrophotographic printing, and expands the use of electrophotography such as insert advertisements, magazine insert pages, and posters.

Hereinafter, the toner according to the exemplary embodiment will be described in detail.
First, toner particles will be described.
The toner particles include, for example, a binder resin, a polysiloxane-modified resin, an organopolysiloxane resin, a colorant, and, if necessary, other additives such as a release agent.

The binder resin will be described.
The binder resin is not particularly limited. For example, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, acrylic Esters having vinyl groups such as lauryl acid, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; single quantities of polyolefins such as ethylene, propylene and butadiene Homopolymer consisting of, or copolymers obtained by combining two or more of these, more mixtures thereof. In addition, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or a mixture of these with the vinyl resin, or vinyl monomers in the presence of these resins Examples thereof include a graft polymer obtained by polymerization.

Styrene resin, (meth) acrylic resin, and styrene- (meth) acrylic copolymer resin are obtained by known methods, for example, by combining styrene monomers and (meth) acrylic acid monomers alone or in appropriate combination. It is done. “(Meth) acryl” is an expression including both “acryl” and “methacryl”.
The polyester resin can be obtained by selecting and combining suitable ones from a polyvalent carboxylic acid and a polyhydric alcohol and synthesizing them using a conventionally known method such as a transesterification method or a polycondensation method.

  When using a styrene resin, a (meth) acrylic resin or a copolymer resin thereof as a binder resin, the weight average molecular weight Mw is 20,000 or more and 100,000 or less, and the number average molecular weight Mn is 2,000 or more and 30,000 or less. It is preferable to use the thing of the range. On the other hand, when a polyester resin is used as the binder resin, a resin having a weight average molecular weight Mw of 5,000 or more and 40,000 or less and a number average molecular weight Mn of 2,000 or more and 10,000 or less may be used. preferable.

  The glass transition temperature of the binder resin is desirably in the range of 40 ° C. or higher and 80 ° C. or lower. When the glass transition temperature is in the above range, the heat-resistant blocking property and the minimum fixing temperature are maintained.

The polysiloxane modified resin will be described.
The polysiloxane-modified resin is a modified resin into which a polysiloxane structure is introduced. Specifically, for example, a repeating unit derived from a base resin (a resin having no polysiloxane structure introduced), a repeating unit derived from a polysiloxane, and , Copolymerized, block copolymer, graft copolymer and the like.

  Examples of the repeating unit derived from the base resin include the repeating units derived from the binder resin. As the repeating unit derived from the base resin, a repeating unit derived from the same resin as the binder resin to be applied is preferably selected from the viewpoint of improving the compatibility of the polysiloxane-modified resin with the binder resin.

Examples of the repeating unit derived from polysiloxane include unmodified polysiloxane, polyalkyl-modified siloxane (for example, polysiloxane modified with an alkyl group having 0 to 18 carbon atoms (preferably 1 to 4 carbon atoms): for example, polymethyl Siloxane, polydimethylsiloxane, polyethylsiloxane, polybutylsiloxane, polydibutylsiloxane, etc.), polyaryl-modified siloxane (for example, polysiloxane modified with an aryl group having 6 to 18 carbon atoms (preferably 6 to 10 carbon atoms): For example, polyphenylsiloxane, polymethylphenylsiloxane, polyethylphenylsiloxane, etc.) Aralkyl-modified siloxane, alkenyl-modified siloxane, hydroxyalkyl-modified siloxane, carboxyalkyl group-modified siloxane, epoxy alkyl And repeating units such as alkenyl group-modified siloxane, polyoxyalkyl group-modified siloxane, and the like.
As the repeating unit derived from polysiloxane, it is preferable to select a repeating unit derived from a resin similar to the applied organopolysiloxane resin from the viewpoint of improving the compatibility of the organopolysiloxane resin with the binder resin.

Specific examples of polysiloxane-modified resins include polysiloxane-modified polyester resins, polysiloxane-modified polyurethane resins, polysiloxane-modified polyurea resins, polysiloxane-modified styrene resins, polysiloxane-modified polystyrene / alkyl methacrylate copolymers, and polysiloxanes. Examples thereof include a modified polystyrene / alkyl methacrylate copolymer and a polysiloxane-modified polystyrene / alkyl acrylate copolymer.
Any polysiloxane-modified resin can be used as long as it is compatible with the silicone-modified resin.

Among these, from the viewpoint of compatibility with low-temperature fixability, the polysiloxane-modified resin is preferably a polysiloxane-modified polyester resin obtained by modifying a crystalline polyester.
Here, the crystalline polyester resin refers to a resin having a clear endothermic peak rather than a stepwise endothermic amount change in differential scanning calorimetry (DSC), and any resin having the endothermic peak may be used. In the case of a polymer in which other components are copolymerized with respect to the crystalline polyester main chain, this copolymer is also a crystalline polyester resin if the other components are 50 constituent mol% or less. That is, a crystalline polyester resin is obtained by showing an endothermic peak.

  The amount of modification of the polysiloxane-modified resin is preferably 0.01% by weight or more and 3% by weight or less, and more preferably 0.05% by weight or more and 1% by weight or less from the viewpoint of flexibility of the fixed image.

The weight average molecular weight of the polysiloxane-modified resin is, for example, preferably from 3500 to 100,000, and more preferably from 5000 to 30000.
The weight average molecular weight is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC was performed with a THF solvent using a Tosoh column / TSKgel Super HM-M (15 cm) using a Tosoh GPC / HLC-8120 as a measuring device. The weight average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. The same applies hereinafter.

The organopolysiloxane resin will be described.
Examples of the organopolysiloxane resin include, as an organic group, an alkyl group (an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms); for example, a methyl group, a methyl group, and a butyl group), an aryl group ( For example, a siloxane resin modified with an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms): a carbonylaryl group or a hydroxylaryl group (for example, a hydroxyphenyl group) is available. Can be mentioned.

Specific examples of the organopolysiloxane resin include polyalkyl-modified siloxanes (for example, polyalkylpolysiloxanes having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms): for example, polymethylsiloxane, polydimethylsiloxane, and polyethylsiloxane. , Polybutylsiloxane, polydibutylsiloxane, etc.), polyarylsiloxane (for example, polysiloxane modified with an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms): for example, polyphenylsiloxane, polymethyl Examples include phenylsiloxane.
Of these, polydimethylsiloxane is desirable as the organopolysiloxane resin.

  The weight average molecular weight of the organopolysiloxane resin is, for example, from 1500 to 50,000, preferably from 5,000 to 30,000, more preferably from 8,000 to 20,000.

Here, the total content of the polysiloxane-modified resin and the organopolysiloxane resin is, for example, preferably 5 to 50% by weight, and preferably 10 to 40% by weight with respect to the binder resin. More desirably, it is 15 wt% or more and 35 wt% or less. By setting the total content within the above range, defects in the fixed image are easily suppressed.
The content of the polysiloxane-modified resin, particularly the polysiloxane-modified polyester resin obtained by modifying the crystalline polyester, is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. By setting the content within the above range, defects in the fixed image are easily suppressed.

  The ratio of the polysiloxane-modified resin to the organopolysiloxane resin (polysiloxane-modified resin: organopolysiloxane resin) is, for example, preferably from 1:99 to 10:90, preferably 2 : 98 or more and 30:70 or less, more preferably 5:95 or more and 40:60 or less. By setting the total content within the above range, defects in the fixed image are easily suppressed.

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

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

  The content of the colorant is preferably in the range of 1 part by weight to 30 parts by weight with respect to 100 parts by weight of the binder resin.

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

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

  The content of the release agent is preferably 1% by weight to 15% by weight, more preferably 2% by weight to 12% by weight, and even more preferably 3% by weight to 10% by weight.

Other additives will be described.
Examples of other internal additives include magnetic materials, charge control agents, inorganic powders, and the like.

The characteristics of the toner particles will be described.
The toner particles may have a single-layer structure, but preferably have a structure (so-called core / shell structure) composed of a core part and a coating layer covering the core part. In this core / shell structure, the shell portion (coating layer) is preferably configured to include a binder resin, a polysiloxane-modified resin, and an organopolysiloxane resin, thereby fixing the fixed image as described above. It is thought that the deficiency of is further suppressed.
Specific examples of the toner particles having a core / shell structure include, for example, a core (core) including a binder resin and, if necessary, a colorant, a release agent, and other additives, and a binder resin. Examples thereof include a two-layer structure including a polysiloxane-modified resin, an organopolysiloxane resin, and a coating layer (shell) including a colorant, a release agent, and other additives as necessary.

The volume average particle diameter of the toner particles is, for example, 4 μm or more and 15 μm or less, and desirably 5 μm or more and 10 μm or less.
As a method for measuring the volume average particle diameter of the toner particles, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5 wt% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. The electrolyte was added to 100 ml to 150 ml. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the above-mentioned Coulter Multisizer II type (manufactured by Beckman-Coulter) is used to produce particles using an aperture having an aperture diameter of 100 μm. The particle size distribution of particles having a diameter in the range of 2.0 μm to 60 μm is measured. The number of particles to be measured is 50,000.
For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is defined as the volume average particle size D50v.

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

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

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

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

  When the toner particles are produced by an aggregation coalescence method, for example, a dispersion containing binder resin particles, a dispersion containing siloxane-modified resin particles, a dispersion containing polysiloxane resin particles, and, if necessary, Then, a dispersion liquid containing the colorant particles and a dispersion liquid containing the release agent particles are prepared, and these dispersion liquids are mixed to form a dispersion liquid in which the aggregated particles are dispersed by aggregating the particles. Subsequently, for example, the particles are heated to a temperature equal to or higher than the glass transition temperature of the binder resin, and the aggregated particles are fused and united to obtain toner particles.

  In the case where toner particles having a core / shell structure are produced by an aggregation and coalescence method, for example, a dispersion containing binder resin particles, and a dispersion and release agent containing colorant particles as necessary And a dispersion liquid in which the aggregated particles are dispersed by preparing these dispersion liquids and mixing the dispersion liquids. A dispersion containing the binder resin particles, a dispersion containing the siloxane-modified resin particles, and a dispersion containing the polysiloxane resin particles are mixed with the dispersion in which the aggregated particles are dispersed, and the aggregated particles are mixed. Each particle is made to adhere to the surface. Subsequently, for example, the particles are heated to a temperature equal to or higher than the glass transition temperature of the binder resin, and the agglomerated particles having these particles attached to the surface are fused and united to obtain toner particles.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Thereafter, the recording paper P is fed to the pressure contact portion (nip portion) of the pair of fixing rolls in the fixing device (roll-type fixing means) 28, the toner image is heated, and the color-superposed toner image is melted to record the recording paper. Fixed onto P.

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

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

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

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

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

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

  Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to these examples. In the following description, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

[Preparation of polyester resin dispersion]
(Preparation of polyester resin dispersion (1))
-Synthesis of polyester resin (1)-
Dimethyl adipate: 74 parts Dimethyl terephthalate: 192 parts Bisphenol A ethylene oxide adduct: 216 parts Ethylene glycol: 38 parts Tetrabutoxy titanate (catalyst): 0.037 parts
The above components are placed in a heat-dried two-necked flask, and nitrogen gas is introduced into the container and heated while stirring in an inert atmosphere, and then subjected to a copolycondensation reaction at 160 ° C. for 7 hours, and then gradually up to 10 Torr. The temperature was raised to 220 ° C. while reducing the pressure to 4 hours. The pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced to 10 Torr, and the pressure was maintained at 220 ° C. for 1 hour to synthesize polyester resin (1).
It was 65 degreeC when the glass transition temperature of the obtained polyester resin (1) was measured using the differential scanning calorific value system (DSC) by the above-mentioned measuring method. When the molecular weight of the obtained polyester resin (1) was measured using GPC by the above-described measurement method, the weight average molecular weight (Mw) was 12,000 and the number average molecular weight (Mn) was 4,000. .

-Preparation of polyester resin dispersion (1)-
Polyester resin (1) (Mw: 12,000): 160 parts Ethyl acetate: 233 parts Sodium hydroxide aqueous solution (0.3N): 0.1 part The above ingredients are put in a 1000 ml separable flask, 70 ° C And stirred with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added to effect phase inversion emulsification and solvent removal to obtain a polyester resin dispersion (1) (solid content concentration: 30%). The volume average particle size of the resin particles in the dispersion was 160 nm.

(Preparation of polyester resin dispersion (2))
-Synthesis of polyester resin (2)-
-Bisphenol A ethylene oxide 2-mole adduct: 114 parts-Bisphenol A propylene oxide 2-mole adduct: 84 parts-Fumaric acid dimethyl ester: 75 parts-Dodecenyl succinic acid: 19.5 parts-Dimethyl terephthalate: 90 parts-Trimerit Acid: 7.5 parts The above components were placed in a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature was raised to 190 ° C over 1 hour. After stirring the interior, 3.0 parts of dibutyltin oxide was added. Further, 6 hours were required while distilling off the generated water, the temperature was raised from 190 ° C. to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours to synthesize polyester resin (2).
The obtained polyester resin (2) had a glass transition temperature of 57 ° C., an acid value of 15.0 mgKOH / g, a weight average molecular weight (Mw) of 58,000, and a number average molecular weight (Mn) of 5,600.

-Preparation of polyester resin dispersion (2)-
A polyester resin dispersion (2) (solid content concentration: 30%) was prepared in the same manner as the polyester resin dispersion (1) except that the polyester resin (2) was used instead of the polyester resin (1). The volume average particle size of the resin particles in the dispersion was 160 nm.

(Preparation of polyester resin dispersion (3))
-Synthesis of polyester resin (3)-
-1,10-decanediol: 454 parts-Adipic acid: 600 parts The above components are placed in a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is increased to 180 ° C. The reaction system was stirred and 0.43 parts of dibutyltin oxide was added. Furthermore, the dehydration condensation reaction was continued at 200 ° C. for 6 hours while distilling off the generated water to synthesize a polyester resin (3).
The obtained polyester resin (3) had a melting point of 67 ° C., a weight average molecular weight (Mw) of 27,500, and a number average molecular weight (Mn) of 13,600.

-Preparation of polyester resin dispersion (3)-
A polyester resin dispersion (3) (solid content concentration: 30%) was prepared in the same manner as the polyester resin dispersion (1) except that the polyester resin (3) was used instead of the polyester resin (1). The volume average particle size of the resin particles in the dispersion was 160 nm.

[Preparation of polysiloxane-modified resin dispersion]
(Preparation of polysiloxane-modified resin dispersion (1))
-Synthesis of polysiloxane modified resin (1)-
-Dimethyl terephthalate: 264 parts-Propylene glycol: 240 parts-Modified silicone compound (FM4411 manufactured by Chisso Corporation): 5 parts Made of 1L glass equipped with a stirrer, thermometer, condenser ester adapter, and decompressor The above components were added to the flask, and the temperature was raised to 180 ° C. over 1 hour. After stirring the reaction system, tetrabutyl titanate was added. Further, while the methanol produced was distilled off and weighed every 20 minutes, the temperature was raised to 220 ° C. over 1 hour, and the transesterification reaction was continued at 220 ° C. for an additional hour. Then, 0.2 part of germanium oxide was slowly added, the temperature was raised to 280 ° C. over 3 hours, and the pressure was reduced to 200 Pa over 2 to 3 hours to maintain the state.
When the stirring torque was increased and the desired molecular weight was reached, the system was evacuated and the system was purged with nitrogen to stop stirring and obtain a polysiloxane-modified resin (1). The amount of siloxane modification was estimated by fluorescent X-ray and HNMR analysis.

-Production of polysiloxane-modified resin dispersion (1)-
A polysiloxane modified resin dispersion (1) (solid content concentration: 25%) was obtained in the same manner as the polyester resin dispersion (1) except that the polysiloxane modified resin (1) was used in place of the polyester resin (1). Prepared. The volume average particle size of the resin particles in the dispersion was 190 nm.

(Preparation of polysiloxane-modified resin dispersion (2))
As shown in Table 1, the modified siloxane content (modified amount) was prepared in the same manner as the polysiloxane-modified resin dispersion (1) except that the blending amount of the modified silicone compound was changed to 20 parts.

(Preparation of polysiloxane-modified resin dispersion (3))
As shown in Table 1, the modified siloxane content (modified amount) was prepared in the same manner as the polysiloxane-modified resin dispersion (1) except that the blending amount of the modified silicone compound was changed to 50 parts.

(Preparation of polysiloxane-modified resin dispersion (4))
As shown in Table 1, the modified siloxane content (modified amount) was prepared in the same manner as the polysiloxane-modified resin dispersion (1) except that the blending amount of the modified silicone compound was changed to 100 parts.

(Preparation of polysiloxane-modified resin dispersion (5))
As shown in Table 1, the modified siloxane content (modified amount) was prepared in the same manner as the polysiloxane-modified resin dispersion (1) except that the amount of the modified silicone compound was changed to 200 parts.

(Preparation of polysiloxane-modified resin dispersion (6))
As shown in Table 1, the modified siloxane content (modified amount) was prepared in the same manner as the polysiloxane-modified resin dispersion (1) except that the amount of the modified silicone compound was changed to 1 part.

(Preparation of polysiloxane-modified resin dispersion (7))
As shown in Table 1, the modified siloxane content (modified amount) was prepared in the same manner as the polysiloxane-modified resin dispersion (1) except that the blending amount of the modified silicone compound was changed to 500 parts.

(Preparation of polysiloxane-modified resin dispersion (8))
-Synthesis of polysiloxane modified resin (8)-
-1,10-decanediol: 250 parts-Adipic acid: 220 parts-Modified silicone compound (FM4411 manufactured by Chisso Corporation): 5 parts Contents equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column The above components were placed in a 5 liter flask, the temperature was raised to 180 ° C., the inside of the reaction system was stirred, an aqueous solution in which dibutyltin oxide was dissolved was slowly added, and 0.43 part was added. Further, while distilling off the generated water, the pressure was further reduced to 200 Pa at 280 ° C. over 2 to 3 hours, and the dehydration condensation reaction was continued for 6 hours to synthesize a polysiloxane-modified resin (8).
When the stirring torque increased and the desired molecular weight was reached, the system was evacuated and purged with nitrogen to stop stirring.

-Preparation of polysiloxane-modified resin dispersion (8)-
A polysiloxane-modified resin dispersion (8) (solid content concentration: 20%) was obtained in the same manner as the polyester resin dispersion (1) except that the polysiloxane-modified resin (8) was used instead of the polyester resin (1). Prepared. The volume average particle size of the resin particles in the dispersion was 118 nm.

[Preparation of organopolysiloxane resin dispersion]
(Preparation of organopolysiloxane resin dispersion (1))
-Tetramethoxysilane: 60 parts-Monomethyltrimethoxysilane: 150 parts-Dimethyldimethoxysilane: 40 parts-Toluene: 300 parts-Concentrated hydrochloric acid: 10 parts-Water: 100 parts The above ingredients are placed in a 1 L glass flask at 40 ° C. And stirred for 6 hours. It was confirmed that the pH reached 7 repeatedly by washing with water three times. The solid concentration was adjusted to 20%.

(Preparation of organopolysiloxane resin dispersion (2))
Tetramethoxysilane: 60 parts Monoethyltriethoxysilane: 200 parts Diethyldiethoxysilane: 50 parts Toluene: 300 parts Concentrated hydrochloric acid: 10 parts Water: 100 parts Ingredients added to a 1 L glass flask Except having changed as mentioned above, it was prepared in the same procedure as the organopolysiloxane resin dispersion (1).

(Preparation of organopolysiloxane resin dispersion (3))
Tetramethoxysilane: 60 parts Monobutyltrimethoxysilane: 50 parts Dibutyldimethoxysilane: 10 parts Concentrated hydrochloric acid: 10 parts Water: 100 parts The components added to a 1 L glass flask were changed as described above. The same procedure as for the siloxane resin dispersion (1) was used.

[Preparation of release agent dispersion]
(Preparation of release agent dispersion (1))
-Ester wax WEP5 (manufactured by NOF Corporation): 500 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 50 parts-Ion-exchanged water: 1700 parts Then, after dispersing using a homogenizer (manufactured by IKA: Ultra Tarrax T50), dispersion processing is performed using a Menton Gorin high-pressure homogenizer (Gorin) to disperse a release agent having an average particle size of 0.180 μm. A release agent dispersion (1) (release agent concentration: 31.1% by weight) was prepared.

[Preparation of colorant dispersion]
(Preparation of colorant dispersion (1))
-Cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 1000 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 150 parts-Ion-exchanged water: 9000 Part of the above is mixed, dissolved, and dispersed for 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006) to disperse the colorant (cyan pigment). 1) was prepared. The average particle diameter of the colorant (cyan pigment) in the colorant dispersion was 0.136 μm, and the colorant particle concentration was 25.1% by weight.

[Example 1]
(Production of toner)
・ Polyester resin dispersion (1) 57 parts ・ Polyester resin dispersion (2) 310 parts ・ Polyester resin dispersion (3) 20 parts ・ Colorant dispersion (1) 62 parts ・ Anionic surfactant (Dowfax2A1 20% Aqueous solution) 15 parts, 77 parts of release agent dispersion (1)

  Among the above raw materials, a polyester resin dispersion (1), a polyester resin dispersion (2), a polyester resin dispersion (3), an anionic surfactant, 250 parts of ion-exchanged water was added, and the surfactant was blended with the polyester resin particle dispersion while stirring at 130 rpm for 15 minutes. The colorant dispersion (1) and release agent dispersion (1) were added to and mixed with this, and then a 0.3 M nitric acid aqueous solution was added to the raw material mixture to adjust the pH to 4.8. Subsequently, 13 parts of a 10% nitric acid aqueous solution of aluminum sulfate was added dropwise as a flocculant while applying a shearing force at 3000 rpm with an ultra turrax. When the dropping of the flocculant was completed, the rotation speed was further increased to 5000 rpm, and the mixture was stirred for 5 minutes to sufficiently mix the flocculant and the raw material mixture.

  Subsequently, the raw material mixture was stirred at 500 rpm while being heated to 25 ° C. with a mantle heater. After stirring for 10 minutes, it was confirmed that a primary particle size was formed using a Coulter Multisizer II (aperture diameter: 50 μm; manufactured by Coulter, Inc.), and then 43 ° C. at 0.1 ° C./min for growing aggregated particles. The temperature was raised to. The growth of aggregated particles was confirmed using a Coulter Multisizer, and the aggregation temperature and the number of rotations of stirring were changed depending on the aggregation rate.

  On the other hand, for coating aggregated particles, 70 parts of polyester resin dispersion (2), 15 parts of polysiloxane-modified resin dispersion (1), 150 parts of organopolysiloxane resin dispersion (1), 118 parts of ion-exchanged water, and anions 8.2 parts of a surfactant (Dowfax 2A1 20% aqueous solution) was mixed and adjusted to pH 3.8 in advance to obtain a coating resin dispersion. When the aggregated particles grew to 5.2 μm in the aggregation step, a coating resin particle dispersion prepared in advance was added and held for 20 minutes with stirring. Thereafter, in order to stop the growth of the coated aggregated particles, 1.5 pph of EDTA (ethylenediaminetetraacetic acid) was added, and then a 1M sodium hydroxide aqueous solution was added to control the pH of the raw material mixture to 7.6. Subsequently, in order to fuse the aggregated particles, the temperature was raised to 85 ° C. at a temperature raising rate of 1 ° C./min while adjusting the pH to 7.6. After reaching 85 ° C., the pH is adjusted to 7.6 or less in order to proceed with the fusion, and after confirming that the aggregated particles have fused with an optical microscope, ice water is used to stop the growth of the particle size. Was injected and quenched at a temperature lowering rate of 10 ° C./min.

  Subsequently, the obtained particles were sieved once with a 15 μm mesh for the purpose of washing. Thereafter, approximately 10 times the amount of ion-exchanged water (30 ° C.) was added to the solid content, stirred for 20 minutes, and then once filtered. Further, the solid content remaining on the filter paper was dispersed in a slurry, washed with ion exchange water at 30 ° C. four times and dried to obtain toner particles having a volume average particle diameter of 5.8 μm.

  To 100 parts of the toner particles prepared above, 0.8 parts of titania treated with decyltrimethoxysilane having a volume average particle diameter of 30 nm and 1.2 parts of silica treated with hexamethyldisilazane having a volume average particle diameter of 100 nm were added. Externally added with a 5 L Henschel mixer stirring mixer (Mitsui Miike Processing Co., Ltd.), and further sieved with a wind sieving machine Hivolta NR300 (Tokyo Kikai) (mesh opening 45 μm) to obtain a toner. .

(Developer)
4 parts of each toner obtained in each example and 96 parts of carrier A described below were stirred for 5 minutes with a V-type blender to prepare a developer.
In addition, the carrier produced as follows was used. 1,000 parts of Mn—Mg ferrite (volume average particle size: 50 μm, manufactured by Powder Tech Co., Ltd., shape factor SF1: 120) were added to a kneader, and a perfluorooctylmethyl acrylate-methyl methacrylate copolymer (polymerization ratio: 20 / 80, Tg: 72 ° C., weight average molecular weight: 72,000, manufactured by Soken Chemical Co., Ltd.) 150 parts dissolved in 700 parts of toluene, mixed at room temperature for 20 minutes, then heated to 70 ° C. under reduced pressure After drying, it was taken out to obtain a coat carrier. Furthermore, the obtained coated carrier was sieved with a mesh having an opening of 75 μm, and coarse powder was removed to obtain a carrier. The shape factor SF1 of the carrier was 122.

[Examples 2 to 11, 13 to 16]
A toner was obtained in the same manner as in Example 1 except that the composition and blending amount in the coating resin particle dispersion were changed according to Table 1.

[Example 12]
(Production of toner)
Polyester resin (1): 87 parts Polyester resin (2): 172 parts Polyester resin (3): 11 parts Colorant cyan pigment: 15 parts (Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.)
・ Anionic surfactant (20% aqueous solution of Dowfax2A1): 23.2 parts ・ Ester wax WEP5: 20 parts ・ Polysiloxane-modified resin (1): 27 parts ・ The solvent of the organopolysiloxane resin dispersion (1) is distilled off. 3 parts After mixing the above raw materials, melt kneaded at 160 ° C. with a twin-screw kneader, cooled, coarsely pulverized, further finely pulverized with a jet mill, and toner particles having an average particle diameter of 6 μm with an air classifier It adjusted so that it might become.

[Comparative Example 1]
A toner was obtained in the same manner as in Example 1 except that the organopolysiloxane resin dispersion (1) was not used for coating the aggregated particles of Example 1.

[Comparative Example 2]
A toner was obtained in the same manner as in Example 1 except that the polysiloxane-modified resin dispersion liquid (1) was not used for covering the aggregated particles in Example 1.

[Evaluation]
The developer obtained in each example was filled in a developer of a modified Docucolor 500 (manufactured by Fuji Xerox Co., Ltd.), and the following evaluation was performed.

(Folding evaluation of fixed images)
The evaluation of bending of the fixed image was performed as follows.
First, a color paper (J paper) manufactured by Fuji Xerox Co., Ltd. was used for the facsimile test chart No. 11 was output as an unfixed image. Using an external fixing device, fixing was performed at a fixing temperature of 160 ° C. with a nip width of 6.5 mm and a fixing speed of 180 mm / sec, and a paper on which an image was formed was prepared. Three of the 20 images including the portion on which the human image was placed were folded in three, loaded with a load of 40 gw / cm 2 and left in a 50 ° C. chamber for 3 days. The image defect of the fold was evaluated according to the following criteria. Acceptable are G2 to G5. The evaluation criteria are as follows.
G5: No image defect is found G4: Less than 20% of the number of images in which a defect part with a width of 0.5 mm or less is seen G3: The number of images in which a defect part with a width of 0.5 mm or less is seen is 20% or more G2: Less than 20% of the number of images in which a defect portion with a width of more than 0.5 mm and less than or equal to 1 mm is seen G1: The number of images in which a defect portion with a width of more than 0.5 mm and less than 1 mm is seen

  From the above evaluation results, it can be seen that in this embodiment, the evaluation of bending of the fixed image is better than in the comparative example, and the image is more flexible.

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

Claims (9)

  An electrostatic charge image developing toner comprising a binder resin, a polysiloxane-modified resin, an organopolysiloxane resin, and a colorant.   2. The electrostatic image developing toner according to claim 1, wherein the total content of the polysiloxane-modified resin and the organopolysiloxane resin is 5% by weight or more and 50% by weight or less based on the binder resin.   The electrostatic image developing toner according to claim 1, wherein the polysiloxane-modified resin is a polysiloxane-modified polyester resin obtained by modifying a crystalline polyester.   The electrostatic image developing toner according to claim 3, wherein the polysiloxane-modified polyester resin is contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. The toner particles are composed of a core part and a coating layer covering the core part,
The electrostatic charge image developing toner according to claim 1, wherein the coating layer includes the binder resin, the polysiloxane-modified resin, and the organopolysiloxane resin.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.   A toner cartridge that accommodates the electrostatic image developing toner according to claim 1 and is detachable from an image forming apparatus. A developing means for accommodating the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image holding member as a toner image by the electrostatic charge image developer,
A process cartridge that is detachable from the image forming apparatus. An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring the toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer target;
An image forming apparatus.