JP2009192991A - Liquid developer and image forming apparatus - Google Patents

Abstract

To provide a liquid developer excellent in positive charging characteristics and to provide an image forming apparatus using the liquid developer.
The liquid developer of the present invention has an insulating liquid and toner particles containing a polyester resin dispersed in the insulating liquid, and the polyester resin has a polarity out of its surface free energy. The proportion of the component is 25% or more. The polyester resin is preferably a rosin-modified polyester resin and / or a urethane-modified polyester resin. The surface free energy of the polyester resin is preferably 50 mJ / m ² or more. The polar component of the surface free energy of the polyester resin is preferably 13 mJ / m ² or more.
[Selection figure] None

Description

  The present invention relates to a liquid developer and an image forming apparatus.

As a developer used to develop the electrostatic latent image formed on the latent image carrier, a toner composed of a material containing a colorant such as a pigment and a binder resin is used as an electrically insulating carrier liquid (insulating property). Liquid developers dispersed in (liquid) are known.
In general, a polyester resin is widely used as a binder resin used for toner particles constituting such a liquid developer. The polyester resin has high transparency, and when used as a binder resin, it has characteristics that the resulting image has good color developability and high fixing characteristics.

By the way, examples of the liquid developer include a negatively chargeable liquid developer and a positively chargeable liquid developer. When a negatively chargeable liquid developer is used, an image forming apparatus is used for image formation. There was a problem that ozone was generated inside and adversely affected peripheral parts in the image forming apparatus.
Therefore, in recent years, since it is possible to perform image formation by reducing the amount of discharge products such as ozone, development of a method for forming an image using a positively chargeable liquid developer has been promoted (for example, Patent Document 1).

  However, since the polyester resin conventionally used for toner particles generally has high negative chargeability, it has been difficult to apply it to positively charged toner particles (liquid developer). In addition, it is conceivable to add a charge control agent to toner particles using a conventional polyester resin as a binder resin for positive charging, but it is difficult to obtain a sufficient charge amount.

JP 2002-214849 A

  An object of the present invention is to provide a liquid developer excellent in positive charge characteristics and to provide an image forming apparatus using the liquid developer.

Such an object is achieved by the present invention described below.
The liquid developer of the present invention includes an insulating liquid,
Toner particles containing a polyester resin dispersed in the insulating liquid;
The polyester resin is characterized in that the proportion of the polar component in the surface free energy of the polyester resin is 25% or more.

In the liquid developer of the present invention, the polyester resin is preferably a rosin-modified polyester resin and / or a urethane-modified polyester resin.
In the liquid developer of the present invention, the surface free energy of the polyester resin is preferably 50 mJ / m ² or more.
In the liquid developer of the present invention, the polar component of the surface free energy of the polyester resin is preferably 13 mJ / m ² or more.

In the liquid developer of the present invention, the hydrogen bonding component in the surface free energy of the polyester resin is preferably ² mJ / m ² or less.
The liquid developer of the present invention preferably contains a dispersant having an amine value of 1 to 100 mgKOH / g.
In the liquid developer according to the aspect of the invention, it is preferable that the insulating liquid contains a vegetable oil.
In the liquid developer of the present invention, it is preferable that the insulating liquid contains a fatty acid monoester.

The image forming apparatus of the present invention includes a plurality of developing units that form a single color image corresponding to the plurality of liquid developers by using a plurality of liquid developers having different colors.
An intermediate transfer unit that sequentially transfers a plurality of the single-color images formed by the plurality of developing units, and forms an intermediate transfer image formed by superimposing the transferred single-color images;
A secondary transfer unit that transfers the intermediate transfer image to a recording medium and forms an unfixed color image on the recording medium;
A fixing unit for fixing the unfixed color image on the recording medium,
The liquid developer has an insulating liquid and toner particles containing a polyester resin dispersed in the insulating liquid;
The polyester resin is characterized in that the proportion of the polar component in the surface free energy of the polyester resin is 25% or more.
By satisfying the above configuration, it is possible to provide a liquid developer having excellent positive charge characteristics. In addition, an image forming apparatus using such a liquid developer can be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail.
First, the liquid developer of the present invention will be described.
The liquid developer of the present invention is one in which toner particles are dispersed in an insulating liquid.
<Toner particles>
First, toner particles will be described.
[Component material of toner particles]
The toner particles are mainly composed of a binder resin (resin material).

1. Resin material (binder resin)
The toner particles are made of a material containing a resin material as a main component.
In the present invention, the resin material is mainly composed of a polyester resin. The polyester resin has high transparency, and when used as a binder resin, it has characteristics that the resulting image has good color developability and high fixing characteristics. However, since conventionally used polyester resins generally have high chargeability, it has been difficult to apply them to positively charged toner particles (liquid developer). In addition, it is conceivable to add a charge control agent to toner particles using a conventional polyester resin as a binder resin for positive charging, but it is difficult to obtain a sufficient charge amount.

By the way, the resin material generally has surface free energy. This surface free energy can be divided into a dispersion force component derived from van der Waals force, a hydrogen bond component derived from hydrogen bond, and a polar component derived from intramolecular polarization.
The present inventor pays attention to the above polar component in the surface free energy of the polyester resin, and as the polyester resin, by using the surface free energy in which the proportion of the polar component is 25% or more, The inventors have found that the positive charging characteristics of the developer can be made excellent, and have completed the present invention.

That is, the liquid developer of the present invention is characterized in that toner particles mainly composed of a special polyester resin in which the proportion of the polar component in the surface free energy is 25% or more are dispersed in the insulating liquid. Thus, the positive charging characteristics are excellent. This is because there are a lot of polarized parts in the polyester resin molecules on the surface of the toner particles, and these parts attract charged substances in the liquid developer, such as protons (H ⁺ ), and are stably positive. This is thought to be due to charging.

As described above, in the present invention, a polyester resin in which the proportion of the polar component in the surface free energy is 25% or more is used as the resin material, but the proportion of the polar component is 30% or more. Is more preferable, and it is still more preferable that it is 50% or more. As a result, the charging property of the positive charge of the liquid developer can be further improved.
As such a polyester resin, it is preferable to use a rosin-modified polyester resin subjected to a rosin-modified treatment or a urethane-modified polyester resin subjected to a urethane-modified treatment. Such a polyester resin tends to have a relatively high proportion of the polar component in the surface free energy, and can be suitably used for the liquid developer of the present invention.

Surface free energy of the polyester resin used in the present invention is preferably at 50 mJ / ^{m 2} or more, more preferably 70 mJ / ^{m 2} or more. Thereby, more stable positive charging characteristics can be exhibited.
Further, the polar component of the surface free energy of the polyester resin used in the present invention is preferably at 13 mJ / m ² or more, more preferably 30 mJ / m ² or more. Thereby, it is possible to further improve the positively charged characteristics.

Moreover, it is preferable that the hydrogen bond component of the surface free energy of a polyester resin is ² mJ / m < ² > or less, and it is more preferable that it is 1 mJ / m < ² > or less. As a result, positive charges can be stably held on the surface of the toner particles, and more stable positive charging characteristics can be exhibited.
Moreover, it is preferable that it is 15-70 degreeC, and, as for the glass transition point (Tg) of a polyester resin, it is more preferable that it is 20-55 degreeC. In this specification, the glass transition point is a measurement condition in a differential scanning calorimeter DSC-220C (manufactured by SII): a sample amount of 10 mg, a heating rate of 10 ° C./min, and a measurement temperature range of 10 to 150 ° C. The temperature at the intersection of the base line extension below the glass transition point and the tangent that indicates the maximum slope from the peak rise to the peak apex.

Although the softening temperature (T1 _{/ 2} ) of a polyester resin is not specifically limited, It is preferable that it is 50-130 degreeC, It is more preferable that it is 50-120 degreeC, It is further more preferable that it is 60-115 degreeC. In the present specification, the softening temperature is a measurement condition in a Koka type flow tester (manufactured by Shimadzu Corporation): temperature increase rate: 5 ° C./min, softening start temperature defined by a die hole diameter of 1.0 mm. Point to.
The toner particles may include a resin material other than the polyester resin as described above.
In addition, the content of the polyester resin in the resin material is preferably 50 wt% or more, and more preferably 80 wt% or more.

2. Colorant The toner particles may contain a colorant. The colorant is not particularly limited, and for example, known pigments and dyes can be used.

3. Other Components The toner may contain components other than those described above. Examples of such components include known waxes and magnetic powders.
In addition to the above materials, the toner particle constituent material (component) is, for example, metal soap such as zinc stearate, zinc oxide, cerium oxide, silica, titanium oxide, iron oxide, fatty acid, fatty acid metal. A salt or the like may be used.

[Toner particle shape]
The average particle size of the toner particles in the present invention composed of the above materials is preferably 0.7 to 3 μm, more preferably 0.8 to 2.5 μm, and 0.8 to More preferably, it is 2.0 μm. When the average particle diameter of the toner particles is within the above range, the variation in characteristics among the toner particles is small, and the liquid developer as a whole is made highly reliable while being formed with the liquid developer. The resolution of the toner image can be made sufficiently high. Further, it is possible to improve the dispersion of the toner particles in the insulating liquid and to improve the storage stability of the liquid developer. In the present specification, “average particle diameter” refers to an average particle diameter based on volume.
The content ratio of the toner particles in the liquid developer is preferably 10 to 60 wt%, and more preferably 20 to 50 wt%.

<Insulating liquid>
Next, the insulating liquid will be described.
The insulating liquid is not particularly limited as long as it has a sufficiently high insulating property. Specifically, the electrical resistance at room temperature (20 ° C.) is preferably 10 ¹¹ Ωcm or more, and preferably 10 ¹² Ωcm or more. More preferably, it is more preferably 10 ¹³ Ωcm or more.
The dielectric constant of the insulating liquid is preferably 3.5 or less.

  Examples of the insulating liquid that satisfies such conditions include Isopar E, Isopar G, Isopar H, Isopar L (Isopar; trade name of Exxon Chemical), Cielsol 70, Cielsol 71 (Cielsol; Commodity of Ciel Oil) Name), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits), mineral oil (hydrocarbon liquid) such as low viscosity / high viscosity liquid paraffin (Wako Pure Chemical Industries), fatty acid glyceride, medium chain fatty acid ester Etc. vegetable oils, fatty acid monoesters that are esters between fatty acids and monohydric alcohols, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene , Mesitylene, etc. , It can be used singly or in combination of two or more of them. Among the above-mentioned, in particular, vegetable oil has particularly high affinity (compatibility) with the above-mentioned polyester resin, so that the dispersion stability of toner particles can be improved. As a result, variation in charging characteristics can be prevented. Vegetable oil is an environmentally friendly component. Therefore, it is possible to reduce the load on the environment of the insulating liquid due to leakage of the insulating liquid to the outside of the image forming apparatus and disposal of the used liquid developer. As a result, an environmentally friendly liquid developer can be provided.

  Moreover, among the above-mentioned, it is preferable to use what contains a fatty acid monoester as an insulating liquid. Since the fatty acid monoester has a molecular structure similar to that of the polyester resin, the affinity (compatibility) with the polyester resin is particularly high. As a result, the dispersion stability of the toner particles can be improved. As a result, variation in charging characteristics can be prevented. In particular, the above effects can be made more remarkable by using in combination with the above-described vegetable oil.

  The fatty acid monoester is a component having an effect (plastic effect) of plasticizing toner particles during fixing. The plasticized toner particles can be easily adhered to a recording medium, and the toner particles can have a higher fixability. Further, by plasticizing in this way, a dispersant as described later can be firmly attached (adsorbed) to the surface, and the positive charging characteristics of the toner particles can be further improved.

Examples of such fatty acid monoesters include oleic acid, palmitoleic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, arachidonic acid, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and the like. Unsaturated fatty acid alkyl (methyl, ethyl, propyl, butyl, etc.) monoester, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc. And alkyl (methyl, ethyl, propyl, butyl, etc.) monoesters of saturated fatty acids, and the like, and one or more selected from these can be used in combination.
When the fatty acid monoester is contained in the insulating liquid, the content of the fatty acid monoester in the insulating liquid is preferably 1 to 50 wt%, and more preferably 5 to 45 wt%. Thereby, the dispersion stability of the toner particles can be further improved, and variation in charging can be more reliably prevented.

  The viscosity of the insulating liquid is not particularly limited, but is preferably 5 to 1000 mPa · s, more preferably 50 to 800 mPa · s, and still more preferably 50 to 500 mPa · s. When the viscosity of the insulating liquid is within the above range, when the liquid developer is squeezed out from the developer container onto the application roller, an appropriate amount of the insulating liquid adheres to the toner particles, and the developability of the toner image. , Transferability can be made particularly excellent. Further, the toner particles can be made more highly dispersible, and in an image forming apparatus as described later, the liquid developer can be supplied more uniformly to the application roller. It is possible to more effectively prevent the liquid developer from dripping. In addition, aggregation and sedimentation of the toner particles can be more effectively prevented, and the dispersibility of the toner particles in the insulating liquid can be made higher. On the other hand, when the viscosity of the insulating liquid is less than the lower limit value, there is a possibility that problems such as dripping of the liquid developer from the application roller or the like may occur in the image forming apparatus described later. On the other hand, if the viscosity of the insulating liquid exceeds the upper limit, the dispersibility of the toner particles cannot be sufficiently increased, and the liquid developer cannot be more uniformly supplied to the application roller in an image forming apparatus as described later. There is a case. However, the viscosity in this specification refers to a value measured at 25 ° C.

<Other ingredients>
In addition to the above components, the liquid developer may contain a dispersant.
Although it does not specifically limit as a dispersing agent used by this invention, It is preferable to use the dispersing agent which has an amine value.
The dispersant having an amine value has high compatibility (affinity) with the polyester resin as described above, and is firmly attached or adsorbed on the surface of the toner particles. As a result, the dispersion stability of the toner particles can be made particularly excellent. Further, in the image forming apparatus described later, when the liquid developer collected in the developing unit or the like is reused, the toner particles in the collected liquid developer can be easily redispersed, and easily Can be reused.

Further, the dispersant having an amine value has a property of being easily positively charged, that is, a property of easily attracting protons (H ⁺ ). Therefore, when such a dispersant is adsorbed on the surface of the toner particles, the positive charging characteristics of the toner particles can be made particularly excellent.
The dispersant having an amine value is highly compatible with insulating liquids such as vegetable oils and fatty acid monoesters as described above, and adheres (adsorbs) to the surface of the toner particles, whereby the dispersion stability of the toner particles. Can be further improved.

The dispersant having an amine value preferably has at least one structure selected from the group consisting of a secondary amine structure, a tertiary amine structure, and an amide bond structure in the molecule. As a result, the dispersant can be more firmly adsorbed on the surface of the toner particles, and the long-term dispersion stability and positive charging characteristics of the toner particles can be further improved.
The amine value of the dispersant having an amine value is preferably 1 to 100 mgKOH / g, more preferably 10 to 80 mgKOH / g. Thereby, the toner particles can be positively charged more reliably and the dispersion stability of the toner particles can be further increased. On the other hand, if the amine value of the dispersant is less than the lower limit, the effect of further improving the positive charge characteristics may not be obtained sufficiently. Moreover, when the amine value of the said dispersing agent exceeds the said upper limit, dispersing agents will aggregate, and sufficient dispersion stability may not be obtained.

  Examples of the dispersant having an amine value include EFKA-5044, EFKA-5244, EFKA-6220, EFKA-6225, EFKA-7564, and EFKA-4080 manufactured by Ciba Specialty Chemicals. Tera-U, Disperbyk-101, Disperbyk-106, Disperbyk-108, Disperbyk-109, Disperbyk-116, Disperbyk-140 (“Disperbyk” is a registered trademark of BYK Chemie), New Century FA , Agrisperse 712 and the like, and one or more of them can be used in combination.

The content of the dispersant having an amine value in the liquid developer is preferably 0.2 to 10 parts by weight, more preferably 1 to 8 parts by weight with respect to 100 parts by weight of the toner particles. More preferably, it is 3 to 6 parts by weight. When the content of the dispersing agent is in the above range, the long-term dispersion stability of the toner particles can be effectively improved, and the positive charging characteristics can be further improved.
Further, the liquid developer (insulating liquid) may contain a known antioxidant, a charge control agent and the like in addition to the components described above.

≪Liquid developer manufacturing method≫
Next, a preferred embodiment of the liquid developer manufacturing method as described above will be described.
The liquid developer manufacturing method according to the present embodiment includes a dispersion preparation step of preparing a dispersion in which a resin material and a colorant as described above are dispersed in an aqueous dispersion medium, and a plurality of dispersoids. Insulating the toner particles and the dispersing agent as described above, a coalescing step for obtaining one particle, a desolvating step for removing the organic solvent contained in the coalesced particle to obtain toner particles containing a resin material and a colorant A dispersion step of dispersing in a liquid.
Hereafter, each process which comprises the manufacturing method of a liquid developer is demonstrated in detail.

[Dispersion Preparation Step (Aqueous Dispersion Preparation Step)]
First, a dispersion (aqueous dispersion) is prepared.
The aqueous dispersion may be prepared by any method. For example, a resin material (polyester resin and other resin materials), a toner particle constituent material (toner material) such as a colorant, etc. in an organic solvent. A resin liquid is obtained by dissolving and dispersing in (resin liquid preparation process), and an aqueous dispersion medium composed of an aqueous liquid is added to the resin liquid, whereby the dispersoid containing the toner material (liquid dispersoid) is converted into an aqueous liquid. A dispersion liquid (water-based dispersion liquid) formed therein and having a dispersoid dispersed therein is obtained (dispersoid formation treatment).

(Resin liquid preparation process)
First, a resin liquid in which a toner material is dissolved or dispersed in an organic solvent is prepared.
The prepared resin liquid contains the constituent material of the toner particles as described above and the organic solvent as described below.
The organic solvent may be any as long as it dissolves at least a part of the resin material, but it is preferable to use an organic solvent having a boiling point lower than that of the aqueous liquid described later. Thereby, the organic solvent can be easily removed.

The organic solvent is preferably one having low compatibility with an aqueous dispersion medium (aqueous liquid) described later (for example, one having a solubility in 100 g of the aqueous dispersion medium at 25 ° C. of 30 g or less). Thereby, the toner material can be finely dispersed in a stable state in the aqueous emulsion.
Further, the composition of the organic solvent can be appropriately selected according to, for example, the resin material, the composition of the colorant, the composition of the aqueous dispersion medium, and the like as described above.

Such an organic solvent is not particularly limited, and examples thereof include ketone solvents such as MEK and aromatic hydrocarbon solvents such as toluene.
The resin liquid can be obtained, for example, by mixing a resin material, a colorant, an organic solvent, etc. with a stirrer or the like. Examples of the stirrer that can be used for preparing the resin liquid include DESPA (manufactured by Asada Tekko Co., Ltd.), T.C. K. Robotics / T. K. Examples thereof include a high-speed stirrer such as a homodisper 2.5-type blade (manufactured by Primex).

Moreover, it is preferable that the material temperature at the time of stirring is 20-60 degreeC, and it is more preferable that it is 30-50 degreeC.
Although the content rate of solid content in a resin liquid is not specifically limited, It is preferable that it is 40-75 wt%, it is more preferable that it is 50-73 wt%, and it is further more preferable that it is 50-70 wt%. When the solid content is within the above range, the dispersoid constituting the dispersion (emulsion suspension) described later may have a higher sphericity (a shape close to a true sphere). The shape of the toner particles finally obtained can be made more surely suitable.
In the preparation of the resin liquid, all the components of the resin liquid to be prepared may be mixed at the same time, or a part of the components of the resin liquid to be prepared may be mixed in advance to prepare a mixture (master). After that, the mixture (master) may be mixed with other components.

(Dispersoid formation processing)
Next, an aqueous dispersion (dispersion) is prepared.
By adding an aqueous dispersion medium composed of an aqueous liquid to the resin liquid, a dispersoid containing the toner material (liquid dispersoid) is formed in the aqueous liquid, and the dispersion in which the dispersoid is dispersed (aqueous dispersion) Get.
The aqueous dispersion medium is composed of an aqueous liquid.

As the aqueous liquid, a liquid mainly composed of water can be used.
The aqueous liquid may contain, for example, a solvent having excellent compatibility with water (for example, a solvent having a solubility in 100 parts by weight of water at 25 ° C. of 50 parts by weight or more).
Further, an emulsifying dispersant may be added to the aqueous dispersion medium as necessary. By adding an emulsifying dispersant, an aqueous emulsion can be prepared more easily.

The emulsifying dispersant is not particularly limited, and for example, a known emulsifying dispersant can be used.
In preparing the aqueous dispersion, for example, a neutralizing agent may be used. Thereby, for example, the functional group (for example, carboxyl group) of the resin material can be neutralized, and the shape, size uniformity, and dispersibility of the dispersoid in the prepared aqueous dispersion liquid. Can be particularly excellent. For this reason, the obtained toner particles have a particularly narrow particle size distribution.

For example, the neutralizing agent may be added to the resin liquid or may be added to the aqueous liquid.
Further, the neutralizing agent may be added in a plurality of times in the preparation of the aqueous dispersion.
As the neutralizing agent, a basic compound can be used. More specifically, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia, and organic bases such as diethylamine, triethylamine, and isopropylamine are used. 1 type selected from these, or 2 or more types can be used in combination. The neutralizing agent may be an aqueous solution containing the above compound.

  Moreover, the usage-amount of a basic compound has the preferable amount (1-3 equivalent) equivalent to 1-3 times the amount required in order to neutralize all the carboxyl groups which a resin material has, and is equivalent to 1-2 times The amount (1 to 2 equivalents) is more preferred. Thereby, it is possible to effectively prevent the formation of irregular dispersoids, and it is possible to make the particle size distribution of the particles obtained in the coalescence step described in detail later sharper.

  The aqueous liquid may be added to the resin liquid by any method, but it is preferable to add the aqueous liquid containing water to the resin liquid while stirring the resin liquid. That is, it is performed by gradually adding (dropping) an aqueous liquid into the resin liquid while applying shear to the resin liquid with a stirrer or the like, and phase-inverting from a W / O type emulsion to an O / W type emulsion. Finally, it is preferable to obtain an aqueous dispersion in which the dispersoid derived from the resin liquid is dispersed in the aqueous liquid.

Examples of the stirrer that can be used for the preparation of the aqueous dispersion include DESPA (manufactured by Asada Tekko Co., Ltd.), T.C. K. Robotics / T. K. Examples thereof include a high-speed stirrer such as a homodisper 2.5-type blade (manufactured by Primics), a slasher (manufactured by Mitsui Mining Co., Ltd.), a Cavitron (manufactured by Eurotech), or a high-speed disperser.
Further, at the time of adding the aqueous liquid to the resin liquid, stirring is preferably performed so that the blade tip speed is 10 to 20 m / sec, and more preferably 12 to 18 m / sec. When the blade tip speed is a value within the above range, an aqueous dispersion can be obtained efficiently, and the dispersion of the shape and size of the dispersoid in the aqueous dispersion can be made particularly small. In particular, the uniform dispersibility of the dispersoid can be made excellent while preventing the generation of fine dispersoids and coarse particles.

The solid content in the aqueous dispersion is not particularly limited, but is preferably 5 to 55 wt%, and more preferably 10 to 50 wt%. Thereby, the productivity of toner particles can be made particularly excellent while preventing unintentional aggregation of the dispersoids in the aqueous dispersion more reliably.
Moreover, it is preferable that the material temperature in this process is 20-60 degreeC, and it is more preferable that it is 20-50 degreeC.

[Joint process]
Next, a plurality of dispersoids are coalesced to obtain coalesced particles (a coalescence step). The coalescence of dispersoids usually proceeds as a result of collision of dispersoids containing an organic solvent so that they are integrated.
The coalescence of a plurality of dispersoids is performed by adding an electrolyte to the dispersion while stirring the dispersion. Thereby, coalesced particles can be obtained easily and reliably. Moreover, the particle diameter and particle size distribution of the coalesced particles can be controlled easily and reliably by adjusting the amount of electrolyte added.

It does not specifically limit as electrolyte, Well-known organic and inorganic water-soluble salt etc. can be used 1 type or in combination of 2 or more types.
The electrolyte is preferably a monovalent cation salt. Thereby, the particle size distribution of the obtained coalesced particles can be narrowed. In addition, by using a monovalent cation salt, it is possible to reliably prevent generation of coarse particles in this step.
Moreover, among the above-mentioned, it is preferable that electrolyte is a sulfate (for example, sodium sulfate, ammonium sulfate) or carbonate, and it is especially preferable that it is a sulfate. Thereby, the particle diameter of the coalesced particles can be controlled particularly easily.

The amount of the electrolyte added in this step is preferably 0.5 to 3 parts by weight, preferably 1 to 2 parts by weight, based on 100 parts by weight of the solid content in the dispersion to which the electrolyte is added. Is more preferable. As a result, the particle diameter of the coalesced particles can be controlled particularly easily and reliably, and the generation of coarse particles can be reliably prevented.
The electrolyte is preferably added in the form of an aqueous solution. As a result, the electrolyte can be quickly diffused throughout the dispersion, and the amount of electrolyte added can be easily and reliably controlled. As a result, coalesced particles having a desired particle size and a particularly narrow particle size distribution can be obtained.

  Moreover, when adding electrolyte in the state of aqueous solution, it is preferable that the density | concentration of the electrolyte in aqueous solution is 2-10 wt%, and it is more preferable that it is 2.5-6 wt%. As a result, the electrolyte can be diffused through the entire dispersion particularly quickly, and the amount of electrolyte added can be easily and reliably controlled. Further, by adding such an aqueous solution, the content of water in the dispersion when the addition of the electrolyte is completed becomes suitable. For this reason, the growth rate of the coalesced particles after the addition of the electrolyte can be made moderately slow to the extent that productivity does not decrease. As a result, the particle size can be controlled more reliably. In addition, unintentional coalescence of coalesced particles can be reliably prevented.

  When the electrolyte is added as an aqueous solution, the rate of addition of the aqueous electrolyte solution is 0.5 to 10 parts by weight / minute with respect to 100 parts by weight of the solid content in the dispersion to which the aqueous electrolyte solution is added. Is preferable, and it is more preferable that it is 1.5-5 weight part / min. As a result, it is possible to prevent the uneven concentration of the electrolyte from occurring in the dispersion, and reliably prevent the generation of coarse particles. Further, the particle size distribution of the coalesced particles is particularly narrow. Furthermore, by adding the electrolyte at such a rate, the coalescing rate can be controlled particularly easily, the average particle size of the coalesced particles can be controlled particularly easily, and the toner productivity is particularly excellent. Can be.

The addition of the electrolyte may be performed in a plurality of times. As a result, coalescent particles having a desired size can be obtained easily and reliably, and the circularity of the obtained coalescent particles can be surely made sufficiently large.
Moreover, this process is performed in the state which stirred the dispersion liquid. Thereby, coalesced particles with particularly small variations in shape and size among the particles can be obtained. As a result, the obtained toner particles have small variations in characteristics (particularly charging characteristics) among the toner particles.

  For stirring the dispersion, for example, an agitation blade such as an anchor blade, a turbine blade, a fiddler blade, a full zone blade, a max blend blade, or a half moon blade may be used, and among these, a max blend blade or a full zone blade is preferable. As a result, the added electrolyte can be quickly and uniformly dispersed and dissolved to reliably prevent the uneven concentration of the electrolyte from occurring. In addition, it is possible to more reliably prevent the coalesced particles once formed from collapsing while efficiently coalescing the dispersoid. As a result, coalesced particles with small variations in shape and particle size among the particles can be obtained efficiently.

The blade tip speed of the stirring blade is preferably from 0.1 to 10 m / second, more preferably from 0.2 to 8 m / second, and even more preferably from 0.2 to 6 m / second. When the blade tip speed is a value within the above range, the added electrolyte can be uniformly dispersed and dissolved, and the occurrence of uneven concentration of the electrolyte can be reliably prevented. In addition, it is possible to more reliably prevent the coalesced particles once formed from collapsing while more efficiently coalescing the dispersoid.
The average particle diameter of the obtained coalesced particles is preferably 0.5 to 5 μm, and more preferably 1.5 to 3 μm. Thereby, the particle diameter of the toner particles finally obtained can be made moderate.

[Desolvation (desolvation) step]
Thereafter, the organic solvent contained in the dispersion is removed. Thereby, resin fine particles (toner particles) dispersed in the dispersion are obtained.
The removal of the organic solvent may be performed by any method, but can be performed, for example, under reduced pressure. Thereby, the organic solvent can be efficiently removed while sufficiently preventing the modification of the constituent material such as the resin material.

Moreover, it is preferable that the process temperature in this process is temperature lower than the glass transition point (Tg) of the resin material which comprises coalesced particle.
Moreover, you may perform this process in the state which added the antifoamer to the dispersion liquid. Thereby, an organic solvent can be removed efficiently.
Antifoaming agents include, for example, mineral oil-based antifoaming agents, polyether-based antifoaming agents, silicone-based antifoaming agents, lower alcohols, higher alcohols, fats and oils, fatty acids, fatty acid esters, phosphoric acid Esters can be used.

Although the usage-amount of an antifoamer is not specifically limited, It is preferable that it is 20-300 ppm by weight ratio with respect to the solid content contained in a dispersion liquid, and it is more preferable that it is 30-100 ppm.
In this step, at least a part of the aqueous liquid may be removed together with the organic solvent.
In this step, it is not always necessary to remove all of the organic solvent (the total amount of the organic solvent contained in the dispersion). Even in such a case, the remaining organic solvent can be sufficiently removed in other steps described later.

[Washing process]
Next, the resin fine particles (toner particles) obtained as described above are cleaned (cleaning step).
By performing this step, even if an organic solvent or the like is contained as an impurity, these can be efficiently removed. As a result, the amount of volatile organic compound (TVOC) in the resin fine particles finally obtained can be made particularly small.
In this step, for example, resin fine particles are separated by solid-liquid separation (separation from an aqueous liquid), and then solid dispersion (resin fine particles) is redispersed in water and solid-liquid separation (resin fine particles from an aqueous liquid is separated). Separation). The redispersion of solids in water and solid-liquid separation may be repeated a plurality of times.

[Drying process]
Thereafter, toner particles can be obtained by performing a drying process (drying step).
The drying step can be performed using, for example, a vacuum dryer (for example, ribocorn (manufactured by Okawara Seisakusho), nauter (manufactured by Hosokawa Micron) etc.), fluidized bed dryer (manufactured by Okawara Seisakusho), etc.

[Dispersion process]
Next, the toner particles obtained as described above and, if necessary, the dispersant as described above are dispersed in the insulating liquid. Thereby, a liquid developer is obtained.
Any method may be used for dispersing the toner particles and the dispersant in the insulating liquid. For example, the insulating liquid, the toner particles, and the dispersant can be mixed by a bead mill, a ball mill, or the like. . By mixing by such a method, the dispersant can be reliably attached or adsorbed on the surface of the toner particles.

Further, at the time of dispersion, components other than the insulating liquid, toner particles, and the dispersant may be mixed.
Further, the dispersion of the toner particles and the dispersant in the insulating liquid may be performed using the entire amount of the insulating liquid constituting the finally obtained liquid developer. It may be performed using

  Further, when the toner particles and the dispersant are dispersed using a part of the insulating liquid, the same liquid as the liquid used for dispersion may be added as the insulating liquid after the dispersion. After dispersion, a liquid different from the liquid used for dispersion may be added as an insulating liquid. In the latter case, characteristics such as the viscosity of the finally obtained liquid developer can be easily adjusted.

  When the liquid developer is produced by the method as described above, the toner particles contained therein are those in which the constituent materials are uniformly dispersed and the shape variation among the toner particles is small. Thereby, variation in charging characteristics among toner particles can be reduced. In addition, when the surface area of the particle surface is relatively uniform among the particles, and the dispersant is contained in the liquid developer, the dispersant can be adhered or adsorbed more uniformly on the surface of the toner particles. it can. As a result, it is possible to improve the long-term dispersion stability of the toner particles and to further reduce the variation in charging characteristics among the toner particles.

≪Image forming device≫
Next, a preferred embodiment of the image forming apparatus of the present invention will be described. The image forming apparatus of the present invention forms a color image on a recording medium using the liquid developer of the present invention as described above.
FIG. 1 is a schematic view showing a second embodiment of an image forming apparatus to which the liquid developer of the present invention is applied, and FIG. 2 is an enlarged view of a part of the image forming apparatus shown in FIG.

As shown in FIGS. 1 and 2, the image forming apparatus 1000 includes four developing units 30Y, 30M, 30C, and 30K, an intermediate transfer unit 40, a secondary transfer unit (secondary transfer unit) 60, and a fixing unit. (Fixing device) F40 and four liquid developer supply portions 80Y, 80M, 80C, and 80K are provided.
The developing units 30Y, 30M, and 30C develop a latent image with a yellow liquid developer (Y), a magenta liquid developer (M), and a cyan liquid developer (C), respectively, and correspond to each color. It has a function of forming a single color image. The developing unit 30K has a function of developing a latent image with a black liquid developer (K) to form a black single color image.

Since the developing units 30Y, 30M, 30C, and 30K have the same configuration, the developing unit 30Y will be described below.
As shown in FIG. 2, the developing unit 30Y includes a photoconductor 10Y as an example of an image carrier, a charging roller 11Y, an exposure unit 12Y, a development unit 100Y, and a photoconductor along the rotation direction of the photoconductor 10Y. The image forming apparatus includes a body squeeze device 101Y, a primary transfer backup roller 51Y, a charge removal unit 16Y, a photoreceptor cleaning blade 17Y, and a developer recovery unit 18Y.

The photoreceptor 10Y is formed on a cylindrical base material and an outer peripheral surface thereof, has a photosensitive layer made of a material such as amorphous silicon, and is rotatable about a central axis. Rotate clockwise as indicated by the arrow in FIG.
The photoreceptor 10Y is supplied with a liquid developer by a developing unit 100Y described later, and a layer of the liquid developer is formed on the surface.

  The charging roller 11Y is a device for charging the photoconductor 10Y, and the exposure unit 12Y is a device for forming a latent image on the photoconductor 10Y charged by irradiating a laser. The exposure unit 12Y includes a semiconductor laser, a polygon mirror, an F-θ lens, and the like, and charges a modulated laser based on an image signal input from a host computer (not shown) such as a personal computer or a word processor. Irradiate onto the photoconductor 10Y.

The developing unit 100Y is a device for developing the latent image formed on the photoreceptor 10Y using the liquid developer of the present invention. Details of the developing unit 100Y will be described later.
The photoconductor squeeze device 101Y is disposed on the downstream side of the developing unit 100Y in the rotation direction so as to face the photoconductor 10Y. The photoconductor squeeze roller 13Y and the photoconductor squeeze roller 13Y are pressed and slidably attached to the surface. The cleaning blade 14Y removes the liquid developer and the developer collection unit 15Y that collects the removed liquid developer. The photoreceptor squeeze device 101Y has a function of collecting excess carrier (insulating liquid) and originally unnecessary fog toner from the developer developed on the photoreceptor 10Y, and increasing the ratio of toner particles in the visible image.

The primary transfer backup roller 51Y is a device for transferring a single color image formed on the photoreceptor 10Y to an intermediate transfer unit 40 described later.
The neutralization unit 16Y is a device that removes residual charges on the photoreceptor 10Y after the intermediate transfer image is transferred onto the intermediate transfer unit 40 by the primary transfer backup roller 51Y.
The photoconductor cleaning blade 17Y is a rubber member that is in contact with the surface of the photoconductor 10Y, and remains on the photoconductor 10Y after the image is transferred onto the intermediate transfer portion 40 by the primary transfer backup roller 51Y. It has a function of scraping off and removing the liquid developer.

The developer recovery unit 18Y has a function of recovering the liquid developer removed by the photoconductor cleaning blade 17Y.
The intermediate transfer unit 40 is an endless elastic belt member, and is stretched around a belt driving roller 41 and a pair of driven rollers 42 and 43 to which a driving force of a motor (not shown) is transmitted. The intermediate transfer unit 40 is driven to rotate counterclockwise by the belt driving roller 41 while being in contact with the photoreceptors 10Y, 10M, 10C, and 10K by the primary transfer backup rollers 51Y, 51M, 51C, and 51K.

Further, the intermediate transfer unit 40 is applied with a predetermined tension by the tension roller 44 so that the slack is removed. The tension roller 44 is disposed downstream of the one driven roller 42 in the rotation (movement) direction of the intermediate transfer unit 40 and upstream of the other driven roller 43 in the rotation (movement) direction of the intermediate transfer unit 40. .
A single color image corresponding to each color formed by the developing units 30Y, 30M, 30C, and 30K is sequentially transferred to the intermediate transfer unit 40 by the primary transfer backup rollers 51Y, 51M, 51C, and 51K, and a single color corresponding to each color is transferred. The images are superimposed. As a result, a full-color developer image (intermediate transfer image) is formed on the intermediate transfer portion 40.

  In the intermediate transfer unit 40, the single-color images formed on the plurality of photoconductors 10Y, 10M, 10C, and 10K are secondarily transferred and superposed one after another. Secondary transfer is performed on a recording medium F5 such as paper, film, or cloth. Therefore, when the toner image is transferred to the recording medium F5 in the secondary transfer process, even if the surface of the recording medium F5 is a sheet material that is not smooth due to fiber or the like, the secondary transfer characteristics follow the surface of the non-smooth sheet material. An elastic belt member is employed as means for improving the above.

The intermediate transfer unit 40 is provided with a cleaning device including an intermediate transfer unit cleaning blade 46, a developer recovery unit 47, and a non-contact type bias applying member 48.
The intermediate transfer portion cleaning blade 46 and the developer recovery portion 47 are arranged on the driven roller 43 side.
The intermediate transfer portion cleaning blade 46 scrapes and removes the liquid developer adhering to the intermediate transfer portion 40 after the image is transferred onto the recording medium F5 by the secondary transfer unit (secondary transfer portion) 60. have.

The developer recovery unit 47 has a function of recovering the liquid developer removed by the intermediate transfer unit cleaning blade 46.
The non-contact type bias applying member 48 is disposed away from the intermediate transfer unit 40 at a position facing the tension roller 44. The non-contact type bias applying member 48 applies a bias voltage having a polarity opposite to that of the toner to the liquid developer toner (solid content) remaining on the intermediate transfer portion 40 after the secondary transfer. As a result, the toner is discharged, and the electrostatic adhesion force of the toner to the intermediate transfer unit 40 is reduced. In this example, a corona charger is used as the non-contact type bias applying member 48.

  The non-contact type bias applying member 48 is not necessarily disposed at a position facing the tension roller 44. For example, a position between the driven roller 42 and the tension roller 44, such as a position between the driven roller 42 and the intermediate transfer unit. It can be disposed at any position downstream in the movement direction and upstream of the driven roller 43 in the movement direction of the intermediate transfer portion. The non-contact type bias applying member 48 may be a known non-contact type charger other than the corona charger.

An intermediate transfer unit squeeze device 52Y is disposed downstream of the primary transfer backup roller 51Y in the moving direction of the intermediate transfer unit 40.
The intermediate transfer unit squeeze device 52Y is provided as a means for removing excess insulating liquid from the transferred liquid developer when the liquid developer transferred onto the intermediate transfer unit 40 has not reached the desired dispersion state. ing.

The intermediate transfer unit squeeze device 52Y is removed by an intermediate transfer unit squeeze roller 53Y, an intermediate transfer unit squeeze cleaning blade 55Y that presses and slides against the intermediate transfer unit squeeze roller 53Y, and an intermediate transfer unit squeeze cleaning blade 55Y. The developer collecting section 56Y collects the liquid developer.
The intermediate transfer unit squeeze device 52Y has a function of recovering excess insulating liquid from the developer primarily transferred to the intermediate transfer unit 40, increasing the toner particle ratio in the image, and recovering originally unwanted toner. Have.

  The secondary transfer unit 60 includes a pair of secondary transfer rollers that are spaced apart from each other by a predetermined distance along the transfer material movement direction. Of the pair of secondary transfer rollers, the secondary transfer roller disposed on the upstream side in the moving direction of the intermediate transfer unit 40 is the upstream secondary transfer roller 61. The upstream secondary transfer roller 61 can be brought into pressure contact with the belt driving roller 41 via the intermediate transfer unit 40.

Of the pair of secondary transfer rollers, the secondary transfer roller disposed downstream of the transfer material in the moving direction is the downstream secondary transfer roller 62. The downstream secondary transfer roller 62 can be brought into pressure contact with the driven roller 42 via the intermediate transfer unit 40.
That is, the upstream side secondary transfer roller 61 and the downstream side secondary transfer roller 62 bring the recording medium F5 into contact with the intermediate transfer unit 40 that is hung on the belt driving roller 41 and the driven roller 42, respectively. The intermediate transfer image formed by superimposing colors on 40 is secondarily transferred to the recording medium F5.

  In this case, the belt driving roller 41 and the driven roller 42 also function as backup rollers for the upstream side secondary transfer roller 61 and the downstream side secondary transfer roller 62, respectively. In other words, the belt driving roller 41 is also used as an upstream backup roller disposed in the secondary transfer unit 60 on the upstream side of the driven roller 42 in the moving direction of the recording medium F5. The driven roller 42 is also used as a downstream backup roller disposed in the secondary transfer unit 60 on the downstream side in the moving direction of the recording medium F5 from the belt driving roller 41.

  Therefore, the recording medium F5 conveyed to the secondary transfer unit 60 is moved from the pressure contact start position (nip start position) between the upstream secondary transfer roller 61 and the belt drive roller 41 to the downstream secondary transfer roller 62 and the driven roller. 42 is in close contact with the intermediate transfer section 40 in a predetermined movement region of the transfer material up to the press-contact end position (nip end position) with 42. As a result, the full-color intermediate transfer image on the intermediate transfer unit 40 is secondarily transferred to the recording medium F5 in close contact with the intermediate transfer unit 40 over a predetermined time, so that good secondary transfer is performed.

  Further, the secondary transfer unit 60 includes a secondary transfer roller cleaning blade 63 and a developer recovery unit 64 for the secondary transfer roller 61. Further, the secondary transfer unit 60 includes a secondary transfer roller cleaning blade 65 and a developer recovery unit 66 for the secondary transfer roller 62. The secondary transfer roller cleaning blades 63 and 65 are in contact with the secondary transfer rollers 61 and 62, respectively, and scrape and remove the liquid developer remaining on the surfaces of the secondary transfer rollers 61 and 62 after the secondary transfer. To do. The developer recovery units 64 and 66 collect and store the liquid developer scraped off from the secondary transfer rollers 61 and 62 by the secondary transfer roller cleaning blades 63 and 65, respectively.

The toner image (transfer image) F5a transferred onto the recording medium F5 by the secondary transfer unit 60 is sent to a fixing unit (fixing device) F40, and is heated and pressurized to be fixed on the recording medium F5.
Specifically, the fixing temperature is preferably 80 to 160 ° C., more preferably 100 to 150 ° C., and further preferably 100 to 140 ° C.

Next, the developing units 100Y, 100M, 100C, and 100K will be described in detail. In the following description, the developing unit 100Y will be typically described.
As shown in FIG. 2, the developing unit 100Y includes a liquid developer storage unit 31Y, a coating roller 32Y, a regulating blade 33Y, a developer stirring roller 34Y, a developing roller 20Y, and a developing roller cleaning blade 21Y. is doing.
The liquid developer storage unit 31Y has a function of storing a liquid developer for developing the latent image formed on the photoreceptor 10Y.

The coating roller 32Y has a function of supplying a liquid developer to the developing roller 20Y.
The application roller 32Y is a so-called anilox roller in which grooves are uniformly and spirally formed on the surface of a metallic roller such as iron and nickel-plated, and has a diameter of about 25 mm. . In the present embodiment, a plurality of grooves are formed obliquely with respect to the rotation direction of the application roller 32Y by so-called cutting or rolling. The application roller 32Y contacts the liquid developer while rotating counterclockwise, thereby supporting the liquid developer in the liquid developer storage section 31Y in the groove, and the supported liquid developer is transferred to the developing roller. Transport to 20Y.

  The regulating blade 33Y is in contact with the surface of the coating roller 32Y and regulates the amount of liquid developer on the coating roller 32Y. That is, the regulation blade 33Y plays a role of scraping off the excess liquid developer on the application roller 32Y and measuring the liquid developer on the application roller 32Y supplied to the development roller 20Y. The restriction blade 33Y is made of urethane rubber as an elastic body, and is supported by a restriction blade support member made of metal such as iron. The regulating blade 33Y is provided on the side where the application roller 32Y rotates and advances from the liquid developer (that is, the right side in FIG. 2). The rubber hardness of the regulation blade 33Y is about 77 degrees according to JIS-A, and the hardness (about 77 degrees) of the contact portion of the regulation blade 33Y with the surface of the coating roller 32Y is about the elasticity of the developing roller 20Y described later. It is lower than the hardness (about 85 degrees) of the pressure contact portion of the body layer to the surface of the application roller 32Y. Further, the excess liquid developer scraped off is collected in the liquid developer storage unit 31Y and reused.

  The developer stirring roller 34Y has a function of stirring the liquid developer in a uniformly dispersed state. Thus, even when a plurality of toner particles 1 are aggregated, the toner particles 1 can be suitably dispersed. In particular, the liquid developer of the present invention can be more suitably dispersed because of high dispersibility of toner particles. Even a reused liquid developer can be easily dispersed.

In the liquid developer storage unit 31Y, the toner particles 1 in the liquid developer have a positive charge, and the liquid developer is stirred by the developer stirring roller 34Y to be in a uniformly dispersed state, and the coating roller 32Y. , The liquid developer is stored in the liquid developer reservoir 31Y, and the amount of liquid developer is regulated by the regulating blade 33Y and supplied to the developing roller 20Y.
The developing roller 20Y carries the liquid developer and conveys it to the developing position facing the photoconductor 10Y in order to develop the latent image carried on the photoconductor 10Y with the liquid developer.

A liquid developer layer is formed on the surface of the developing roller 20Y by supplying the liquid developer from the coating roller 32Y described above.
The developing roller 20Y includes a conductive elastic layer on the outer peripheral portion of an inner core made of metal such as iron, and has a diameter of about 20 mm. The elastic body layer has a two-layer structure. As the inner layer, urethane rubber having a rubber hardness of about 30 degrees JIS-A and a thickness of about 5 mm is used, and as the surface layer (outer layer), the rubber hardness is JIS. A urethane rubber having a thickness of about 30 μm at about 85 ° A is provided. The developing roller 20Y is in pressure contact with the coating roller 32Y and the photoreceptor 10Y in a state of being elastically deformed with the surface layer serving as a pressure contact portion.

  Further, the developing roller 20Y can rotate around its central axis, and the central axis is below the rotational central axis of the photoconductor 10Y. Further, the developing roller 20Y rotates in a direction (counterclockwise in FIG. 2) opposite to the rotation direction of the photoreceptor 10Y (clockwise in FIG. 2). When developing the latent image formed on the photoconductor 10Y, an electric field is formed between the developing roller 20Y and the photoconductor 10Y.

In the developing unit 100Y, the coating roller 32Y and the developing roller 20Y are separately driven by different power sources (not shown). The amount of the liquid developer supplied onto the developing roller 20Y can be adjusted by changing the rotation speed (linear speed) ratio between the application roller 32Y and the developing roller 20Y.
The developing unit 100Y includes a rubber developing roller cleaning blade 21Y that is in contact with the surface of the developing roller 20Y, and a developer recovery unit 22Y. The developing roller cleaning blade 21Y is a device for scraping off and removing the liquid developer remaining on the developing roller 20Y after development is performed at the developing position. The liquid developer removed by the developing roller cleaning blade 21Y is collected in the developer collecting unit 22Y.

  As shown in FIGS. 1 and 2, the image forming apparatus 1000 includes liquid developer replenishing units 80Y, 80M, 80C, and 80K that replenish liquid developer to the developing units 30Y, 30M, 30C, and 30K. . These liquid developer replenishers 80Y, 80M, 80C, and 80K are respectively provided with liquid developer tanks 81Y, 81M, 81C, and 81K, insulating liquid tanks 82Y, 82M, 82C, and 82K, and stirring devices 83Y, 83M, 83C and 83K.

  Each of the liquid developer tanks 81Y, 81M, 81C, 81K contains a high concentration liquid developer corresponding to each color. Insulating liquid tanks 82Y, 82M, 82C, and 82K contain insulating liquids, respectively. Furthermore, each stirring device 83Y, 83M, 83C, 83K includes a predetermined amount of each high-concentration liquid developer from each liquid developer tank 81Y, 81M, 81C, 81K, and each insulating liquid tank 82Y, 82M, 82C. A predetermined amount of each insulating liquid from 82K is supplied.

  The stirrers 83Y, 83M, 83C, and 83K mix and stir the supplied high-concentration liquid developer and the insulating liquid, respectively, and respectively store the liquid developer reservoirs 31Y, 31M, 31C, and 31K. A liquid developer corresponding to each color used in the above is prepared. Each liquid developer produced by each stirring device 83Y, 83M, 83C, 83K is supplied to each liquid developer reservoir 31Y, 31M, 31C, 31K.

Further, as shown in FIGS. 1 and 2, the liquid developer replenishing units 80Y, 80M, 80C, and 80K include the liquid developers collected by the developer collecting units 15Y, 15M, 15C, and 15K, respectively. Each liquid developer recovered by the developer recovery units 22Y, 22M, 22C, and 22K is recovered and reused.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, the liquid developer of the present invention is not limited to that applied to the image forming apparatus as described above.

Further, the liquid developer of the present invention is not limited to those produced by the production method as described above.
Moreover, although embodiment mentioned above demonstrated as what obtains the coalesced particle by obtaining aqueous emulsion and adding electrolyte to this aqueous emulsion, this invention is not limited to this. For example, the coalesced particles are prepared by dispersing a colorant, a monomer, a surfactant, and a polymerization initiator in an aqueous liquid, preparing an aqueous emulsion by emulsion polymerization, and adding an electrolyte to the aqueous emulsion to associate. The emulsion may be prepared using an emulsion polymerization association method, or may be obtained by spray-drying the obtained aqueous emulsion to obtain coalesced particles.
In the embodiment described above, the coalesced particles are dispersed in the insulating liquid to obtain a liquid developer. However, the present invention is not limited to this. For example, the coalesced particles are crushed in a fatty acid monoester. Thus, the obtained crushed particles may be used as toner particles.

[1] Synthesis of polyester resin (Synthesis of resin A)
First, a nitrogen gas inlet tube, a thermometer and a stirring device are attached to a four-necked flask with a capacity of 2000 mL, gum rosin: 1060 g, fumaric acid: 117 g are added, and the mixture is stirred for 2 hours at 200 ° C. in a nitrogen stream. Liquid A which is a reaction mixture of unreacted gum rosin was obtained.

  On the other hand, a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were attached to a 2000 mL four-necked flask, 1,8-octanediol: 296 g, pentaerythritol: 83 g, ethylene glycol: 138 g, Terephthalic acid: 235 g, isophthalic acid: 101 g, and dibutyltin oxide: 2 g were added, and the mixture was esterified by maintaining the temperature at 240 ° C. for 4 hours while stirring under a nitrogen stream to obtain liquid B.

Next, the liquid B was transferred to an autoclave having a capacity of 5000 mL, and the entire amount of the liquid A was gradually poured while stirring. After mixing of liquids A and B was completed, the temperature in the kettle was raised to 245 ° C., and then the internal pressure was reduced to 300 Pa over 1 hour. When the condensation reaction was carried out for 2 hours while maintaining the pressure in the kettle at a predetermined pressure, a tan resin was obtained.
A solution obtained by dissolving the obtained resin in methyl ethyl ketone is added dropwise to ion-exchanged water while stirring to obtain a resin agglomerate. The agglomerate is collected with a filter paper and dried by vacuum heating at a temperature of 55 ° C. and an atmospheric pressure of 0.1 MPa. Drying was performed in an oven for 48 hours to obtain Resin A.

(Synthesis of Resin B)
First, a nitrogen gas inlet tube, a thermometer and a stirring device are attached to a four-necked flask with a capacity of 2000 mL, gum rosin: 1060 g, fumaric acid: 117 g are added, and the mixture is stirred for 2 hours at 200 ° C. in a nitrogen stream. Liquid C which is a reaction mixture of unreacted gum rosin was obtained. On the other hand, a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were attached to a 2000 mL four-necked flask, and 1,8-octanediol was obtained. : 355 g, pentaerythritol: 83 g, ethylene glycol: 113 g, terephthalic acid: 235 g, isophthalic acid: 101 g, dibutyltin oxide: 2 g are added, and the temperature is maintained at 240 ° C. while stirring with a nitrogen stream, and esterification is performed at normal pressure for 4 hours. Reaction D was obtained.

Next, the liquid D was transferred to an autoclave having a capacity of 5000 mL, and the entire amount of the liquid C was gradually poured while stirring. After mixing of liquids C and D was finished, the temperature in the kettle was raised to 245 ° C., and then the internal pressure was reduced to 300 Pa over 1 hour. When the condensation reaction was carried out for 2 hours while maintaining the pressure in the kettle at a predetermined pressure, a tan resin was obtained.
A solution obtained by dissolving the obtained resin in methyl ethyl ketone is added dropwise to ion-exchanged water while stirring to obtain a resin agglomerate. The agglomerate is collected with a filter paper and dried by vacuum heating at a temperature of 55 ° C. and an atmospheric pressure of 0.1 MPa. Drying was performed in an oven for 48 hours to obtain Resin B.

(Synthesis of Resin C)
First, a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were attached to a 2000 mL four-necked flask, pentaerythritol: 110 g, ethylene glycol: 113 g, terephthalic acid: 370 g, trimellitic anhydride : 350 g, polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane: 978 g, 1,6-hexamethylene diisocyanate: 30 g, antimony trioxide: 1.5 g, zinc acetate: 0. 7 g was added to conduct esterification reaction. There was no irritating odor during the esterification reaction. The reaction was terminated when there was almost no distillation of water produced by the reaction. Next, the entire amount of the liquid obtained by the esterification reaction was transferred to an autoclave having a capacity of 5000 mL, and a polycondensation reaction was performed under the conditions of a temperature of 245 ° C. and an internal pressure of 300 Pa to obtain a resin composition.

Two separable covers were attached to a separable flask having a volume of 2000 ml, and a stirrer was attached to the central neck. The resin composition: 100 g and tetrahydrofuran: 900 g were added to dissolve the resin composition. After the resin composition was completely dissolved, 8.5 g of 1,6-hexamethylene diisocyanate was added and stirred continuously at 23 ° C. for 24 hours to obtain a resin composition solution.
This resin composition solution was dropped into ion-exchanged water while stirring to obtain a resin precipitate, and then filtered to collect the precipitate. This precipitate was dried for 48 hours in a vacuum heating and drying furnace set at a temperature of 55 ° C. and an atmospheric pressure of 0.1 MPa, to obtain Resin C.

(Synthesis of Resin D)
First, a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were attached to a 2000 mL four-necked flask, terephthalic acid: 250 g, trimellitic anhydride: 257 g, 2,2-diethyl-1 , 3-propanediol: 111 g, polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane: 1457 g, dibutyltin oxide: 2.1 g, and the temperature inside the nitrogen gas flow vessel is 190 ° C. The esterification reaction was carried out for 3 hours. Next, the total amount of the liquid obtained by the esterification reaction was transferred to a 5000 mL autoclave and subjected to a polycondensation reaction for 2 hours under the conditions of a temperature of 245 ° C. and an internal pressure of 300 Pa to obtain a resin composition.
This resin composition was dissolved in methyl ethyl ketone, dropped into ion-exchanged water with stirring, and filtered to collect a precipitate. This precipitate was dried for 48 hours in a vacuum heating and drying furnace set at a temperature of 55 ° C. and an atmospheric pressure of 0.1 MPa, to obtain Resin D.

(Synthesis of Resin E)
A reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were attached to a four-necked flask with a capacity of 2000 mL, terephthalic acid: 323 g, trimellitic anhydride: 204 g, 2,2-diethyl-1,3 -Propanediol: 140 g, polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane: 1368 g, dibutyltin oxide: 2 g were charged, and the temperature in the nitrogen gas flow vessel was 200 ° C for 3 hours. An esterification reaction was performed. Next, the total amount of the liquid obtained by the esterification reaction was transferred to a 5000 mL autoclave and subjected to a polycondensation reaction for 2 hours under the conditions of a temperature of 245 ° C. and an internal pressure of 300 Pa to obtain a resin composition.
This resin composition was dissolved in methyl ethyl ketone and dropped into ion-exchanged water with stirring to obtain a resin precipitate, which was then filtered to collect the precipitate. This precipitate was dried for 48 hours in a vacuum heating and drying oven set at a temperature of 55 ° C. and an atmospheric pressure of 0.1 MPa to obtain a white resin E.

(Synthesis of Resin F)
Attach a reflux condenser, water separator, nitrogen gas inlet tube, thermometer and stirrer to a 2000 mL four-necked flask, pentaerythritol: 65 g, ethylene glycol: 192 g, terephthalic acid: 316 g, isophthalic acid: 396 g, poly Oxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane: 1009 g, both-end carboxyl-modified silicone oil X-22-162C (Shin-Etsu Chemical Co., Ltd.): 60 g, dibutyltin oxide: 2 g Then, the esterification reaction was carried out for 3 hours at a temperature of 180 ° C. in the nitrogen stream. Next, the total amount of the liquid obtained by the esterification reaction was transferred to an autoclave having a capacity of 5000 mL, and a polycondensation reaction was performed for 2 hours under the conditions of a temperature of 230 ° C. and an internal pressure of 300 Pa to obtain a resin composite.
This resin composition was dissolved in methyl ethyl ketone, dropped into ion-exchanged water with stirring, and filtered to collect a precipitate. This precipitate was dried for 48 hours in a vacuum heating and drying furnace set at a temperature of 55 ° C. and an atmospheric pressure of 0.1 MPa, to obtain Resin F.

[2] Measurement of surface free energy For the resins A to F obtained as described above, the surface free energy and each component of the surface free energy (dispersion component, hydrogen bond component and polar component) are measured as follows. did.
Resins A to F obtained as described above were dissolved in THF, filtered with pressure through a membrane filter having a pore size of 10 μm, and then filtered with pressure through a membrane filter with a pore size of 3 μm to obtain a THF solution of each resin. . Using this resin solution, coating was performed on a PET substrate having a thickness of 100 μm by a spin coater, and this was dried in a heating and drying furnace at 80 ° C. for 1 hour to obtain a resin film sample having a thickness of about 8 μm.

Next, after the obtained resin film sample was left in an environment of 24 ° C./55% RH for 24 hours, the contact angle was measured with a fully automatic contact angle meter DM700 (Kyowa Interface Science Co., Ltd.). The liquid used for the contact angle measurement was 1-bromonaphthalene, formamide, and ion-exchanged water. The measurement was performed five times while changing the position of each liquid, and the average was taken. From the average value, surface free energy, dispersion force component, hydrogen bond component, and polar component were calculated and shown in Table 1.
The calculation of the surface free energy, the dispersion force component, the hydrogen bond component, and the polar component was performed by using the contact angle measurement value of each liquid and the physical property values of Table 2 in the extended Fowkes equation.
In addition, Table 2 shows the glass transition point (Tg), softening temperature (T _1/2 ), and weight average molecular weight (Mw) of each resin.

[3] Production of Liquid Developer A liquid developer was produced as follows.
(Example 1)
First, toner particles were manufactured. In addition, about the process in which temperature is not described, it performed at room temperature (25 degreeC).

<Dispersion adjustment process>
(Preparation of colorant master solution)
First, a mixture (mass ratio 50:50) of the resin A and a cyan pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3) was prepared. These components were mixed using a 20 L type Henschel mixer to obtain a raw material for toner production.
Next, this raw material (mixture) was kneaded using a twin-screw kneading extruder. The kneaded product extruded from the extrusion port of the biaxial kneading extruder was cooled.
The kneaded material cooled as described above was coarsely pulverized to obtain a colorant master batch having an average particle size of 1.0 mm or less. A hammer mill was used for coarse pulverization of the kneaded product.

(Resin liquid preparation process)
The colorant masterbatch: 97.5 parts by weight, methyl ethyl ketone: 175 parts by weight, the polyester resin: 172.3 parts by weight, and the resin A: 55.3 parts by weight were added to a high-speed disperser (Primix Corporation, TK ROBOMIX / TK homodisper 2.5 type wing), and 1.38 parts by weight of Neogen SC-F (Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier was added to prepare a resin liquid. In this solution, the pigment was uniformly finely dispersed.

(Dispersoid formation processing)
Next, 72.8 parts by weight of 1N ammonia water was added to the resin liquid in the container, and the mixture was stirred with a high-speed disperser (Primics Co., Ltd., TK Robotics / TK Homo Disperser 2.5 type blade). The blade tip speed of the wing was sufficiently stirred at 7.5 m / s, the temperature of the solution in the flask was adjusted to 25 ° C., and the stirring blade blade speed was then 14.7 m / s while stirring. Part by weight of deionized water was added dropwise to cause phase inversion emulsification. While continuing the stirring, 100 parts by weight of deionized water was further added to the resin liquid. As a result, an aqueous dispersion in which the dispersoid containing the resin material was dispersed was obtained.

<Joint process>
Next, the aqueous dispersion was transferred to a stirring vessel having a Max Blend blade, and the temperature of the aqueous dispersion was adjusted to 25 ° C. while stirring at a blade tip speed of 1.0 m / s.
Next, while maintaining the same temperature and stirring conditions, 200 parts by weight of a 5.0% aqueous sodium sulfate solution was added dropwise to coalesce the dispersoids to form coalesced particles. After the dropping, stirring was continued until the 50% volume particle diameter Dv (50) [μm] of the coalesced toner particles grew to 3.4 μm. When the Dv (50) of the coalesced particles reached 3.4 μm, 200 parts by weight of deionized water was added to complete the coalescence.

<Desolvation process>
The organic solvent was distilled off under reduced pressure until the solid content was 23 wt%, to obtain a slurry of resin fine particles.
<Washing process>
Next, the slurry was subjected to solid-liquid separation, and further subjected to washing treatment by redispersion in water (reslurry) and repeated solid-liquid separation. Thereafter, a wet cake (resin fine particle cake) of colored resin fine particles was obtained by suction filtration. The moisture content of the wet cake was 35 wt%.

<Drying process>
Thereafter, the obtained wet cake was dried using a vacuum dryer to obtain toner particles.
<Dispersing process>
Toner particles obtained by the above method: 20 parts by weight, rapeseed oil (manufactured by Nisshin Oilio Co., Ltd., trade name “High Oleic Rapeseed Oil”): 48 parts by weight, methyl soybean fatty acid (manufactured by Nisshin Oilio Co., Ltd.): 32 parts by weight, Dispersbyk-116 as a dispersant (by Big Chemie, amine value: 65 mgKOH / g): 1 part by weight is placed in a ceramic pot (internal volume 600 ml), and zirconia balls (ball diameter: 1 mm) are filled in a volume of 85%. In a ceramic pot, dispersion was performed for 24 hours at a rotational speed of 250 rpm in a desktop pot mill. As a result, a liquid developer was obtained.

  The Dv (50) of the toner particles in the obtained liquid developer was 3.0 μm. The 50% volume particle diameter Dv (50) [μm] of the obtained toner particles was measured with a Mastersizer 2000 particle analyzer (manufactured by Malvern Instruments Ltd.). Moreover, the particle diameter was similarly calculated | required about the particle | grains obtained by each Example and each comparative example demonstrated below.

  Further, instead of cyan pigment, magenta pigment: Pigment Red 238 (manufactured by Sanyo Dye), yellow pigment: Pigment Yellow 180 (manufactured by Clariant), black pigment: carbon black (printex L, manufactured by Degussa) In addition, a magenta liquid developer, a yellow liquid developer, and a black liquid developer were produced in the same manner as described above except that the respective changes were made.

(Example 2)
A liquid developer corresponding to each color was produced in the same manner as in Example 1 except that the resin B was used instead of the resin A as the resin material.
(Example 3)
A liquid developer corresponding to each color was produced in the same manner as in Example 1 except that the resin C was used instead of the resin A as the resin material.

Example 4
A liquid developer corresponding to each color is produced in the same manner as in Example 1 except that EFKA-4080 (manufactured by Ciba Specialty Chemicals, amine value: 4 mgKOH / g) is used as a dispersant having an amine value. did.
(Example 5)
A liquid developer corresponding to each color was produced in the same manner as in Example 1 except that Agrisperse 712 (manufactured by New Century Coatings, amine value: 100 mgKOH / g) was used as the dispersant having an amine value.

(Examples 6 and 7)
Liquid developers corresponding to the respective colors were produced in the same manner as in Example 1 except that the content of the dispersant having an amine value was changed as shown in Table 1.
(Example 8)
Liquid developers corresponding to the respective colors were produced in the same manner as in Example 1 except that both rapeseed oil and soybean oil fatty acid methyl were changed to Isopar H (trade name of Exxon Chemical Co., Ltd.).

Example 9
Liquid developers corresponding to the respective colors were produced in the same manner as in Example 1 except that the methyl soybean fatty acid was changed to Isopar H (trade name of Exxon Chemical Co., Ltd.).
(Example 10)
A liquid developer corresponding to each color was produced in the same manner as in Example 1 except that no dispersant having an amine value was added.

(Comparative Example 1)
A liquid developer corresponding to each color was produced in the same manner as in Example 1 except that the resin D was used instead of the resin A as the resin material.
(Comparative Example 2)
A liquid developer corresponding to each color was produced in the same manner as in Example 1 except that the resin E was used instead of the resin A as the resin material.

(Comparative Example 3)
A liquid developer corresponding to each color was produced in the same manner as in Example 1 except that the resin F was used instead of the resin A as the resin material.
(Comparative Example 4)
Resin F was used instead of Resin A as the resin material, Nikka Octix Zirconium (Nippon Kagaku Sangyo Co., Ltd., containing zirconium octylate) as a charge control agent was added, and no dispersant was added. Produced liquid developers corresponding to the respective colors in the same manner as in Example 1.

  For each of the above examples and comparative examples, the composition of the liquid developer, the type of resin of the toner particles and the average particle size of the toner particles, the type of dispersant, the value and content of the amine value, the type of insulating liquid, etc. Are shown in Table 3. In the table, Disperbyk-116 is indicated as D116, EFKA-4080 as E4080, Agrisperse 712 as A712, rapeseed oil as NT, soybean oil fatty acid methyl as ME, and isoper as AP.

[4] Evaluation Each liquid developer obtained as described above was evaluated as follows.
[4.1] Development efficiency Liquid developer using the liquid developer obtained in each of the examples and comparative examples on the developing roller of the image forming apparatus using the image forming apparatus as shown in FIGS. A layer was formed. Next, the surface potential of the developing roller was set to 300V, the surface potential of the photoconductor was uniformly charged at 500V, the photoconductor was exposed, the charge on the surface of the photoconductor was attenuated, and the surface potential was set to 50V. The toner particles on the developing roller and the toner particles on the photosensitive member after the liquid developer layer passed between the photosensitive member and the developing roller were collected with a tape. Each tape used for sampling was affixed on a recording paper, and the concentration of each toner particle was measured. After the measurement, the value obtained by dividing the concentration of toner particles collected on the photoreceptor by the sum of the concentration of toner particles collected on the photoreceptor and the concentration of toner particles collected on the developing roller is multiplied by 100. Was determined as development efficiency, and evaluated according to the following four-stage criteria.
A: The development efficiency is 95% or more, and the development efficiency is particularly excellent.
B: The development efficiency is 90% or more and less than 95%, and the development efficiency is excellent.
C: The development efficiency is 80% or more and less than 90%, and there is no practical problem.
D: The development efficiency is less than 80% and the development efficiency is inferior.

[4.2] Transfer efficiency Using the image forming apparatus as shown in FIGS. 1 and 2, the liquid developer using the liquid developer obtained in each of the examples and comparative examples on the photoreceptor of the image forming apparatus. A layer was formed. Next, the toner particles on the photoconductor and the toner particles on the intermediate transfer portion after the liquid developer layer passed between the photoconductor and the intermediate transfer portion were collected with a tape. Each tape used for sampling was affixed on a recording paper, and the concentration of each toner particle was measured. After the measurement, a value obtained by dividing the concentration of the toner particles collected on the intermediate transfer portion by the sum of the concentration of the toner particles collected on the photoconductor and the concentration of the toner particles collected on the intermediate transfer portion is 100. A value obtained by multiplying by is obtained as transfer efficiency, and evaluated according to the following four criteria.
A: The transfer efficiency is 95% or more, and the transfer efficiency is particularly excellent.
B: The transfer efficiency is 90% or more and less than 95%, and the transfer efficiency is excellent.
C: The transfer efficiency is 80% or more and less than 90%, and there is no practical problem.
D: Transfer efficiency is less than 80% and inferior to transfer efficiency.

[4.3] Charging characteristics of positive charge For the liquid developer obtained in each example and each comparative example, the potential difference was measured using a “microscopic laser zeta electrometer” ZC-2000 manufactured by Microtick Nithion. The evaluation was made according to the following five criteria.
Measurement is performed by diluting the liquid developer with a diluting solvent, placing it in a 10 mm transparent cell, applying a voltage of 300 V at 9 mm between the electrodes, and simultaneously observing the moving speed of the particles in the cell with a microscope. Was obtained by calculating the zeta potential from the calculated value.

A: Potential difference is +150 mV or more (very good).
B: The potential difference is +125 mV or more and less than +150 mV (good).
C: The potential difference is +100 mV or more and less than +125 mV (normal).
D: The potential difference is +75 mV or more and less than +100 mV (somewhat bad).
E: Potential difference is less than +75 mV (very bad).

[4.4] Fixing Strength Using an image forming apparatus as shown in FIGS. 1 and 2, an image of a predetermined pattern by the liquid developer obtained in each of the examples and the comparative examples is recorded on a recording paper (Seiko Epson). It was formed on high-quality paper LPCPPA4) manufactured by the same company, and heat fixing was performed at a fixing temperature of 100 ° C.
Then, after confirming the non-offset area, the fixed image on the recording paper is erased twice (rubber eraser “LION 261-11” manufactured by Lion Business Machine Co., Ltd.) twice with a pressing load of 1.2 kgf, and the remaining ratio of image density Was measured by “X-Rite model 404” manufactured by X-Rite Inc, and evaluated according to the following five-step criteria.

A: Image density residual ratio is 95% or more (very good).
B: Image density remaining rate is 90% or more and less than 95% (good).
C: Image density remaining rate is 80% or more and less than 90% (normal).
D: Image density residual ratio is 70% or more and less than 80% (slightly bad).
E: Image density residual ratio is less than 70% (very bad).
These results are shown in Table 4.

表４から明らかなように、本発明の液体現像剤は、帯電特性（正帯電の帯電特性）、現像効率、転写効率に優れていた。また、本発明の液体現像剤は、定着強度にも優れていた。これに対し、比較例の液体現像剤では、満足な結果が得られなかった。

As is apparent from Table 4, the liquid developer of the present invention was excellent in charging characteristics (positive charging characteristics), development efficiency, and transfer efficiency. Further, the liquid developer of the present invention was excellent in fixing strength. On the other hand, satisfactory results were not obtained with the liquid developer of the comparative example.

1 is a schematic diagram illustrating an example of an image forming apparatus to which a liquid developer of the present invention is applied. FIG. 2 is an enlarged view of a part of the image forming apparatus shown in FIG. 1.

Explanation of symbols

  1000: Image forming apparatus 10Y, 10M, 10C, 10K ... Photoconductor 11Y ... Charging roller 12Y ... Exposure unit 13M, 13Y ... Photoconductor squeeze roller 14Y, 14M ... Cleaning blade 15M, 15Y ... Developer recovery unit 16Y ... Static elimination unit 17Y ... Photoconductor cleaning blade 18Y ... Developer collection unit 20Y, 20M, 20C, 20K ... Development roller 21Y ... Development roller cleaning blade 22Y ... Developer collection unit 30Y, 30M, 30C, 30K ... Development unit 31Y ... Liquid developer storage unit 32Y ... coating roller 33Y ... regulating blade 34Y ... developer stirring roller 40 ... intermediate transfer unit 41 ... belt drive rollers 42, 43 ... driven roller 44 ... tension roller 46 ... intermediate transfer unit cleaning blade 47 ... developer collecting unit 8: Non-contact type bias applying member 51Y, 51M, 51C, 51K ... Primary transfer backup roller 52Y, 52M, 52C, 52K ... Intermediate transfer unit squeeze device 53Y ... Intermediate transfer unit squeeze roller 55Y ... Intermediate transfer unit squeeze cleaning blade 56Y ... Developer recovery unit 60 ... Secondary transfer unit 61 ... Upstream secondary transfer roller 62 ... Downstream secondary transfer roller 63, 65 ... Secondary transfer roller cleaning blades 64, 66 ... Developer recovery unit 80Y, 80M, 80C , 80K ... Liquid developer replenishment section 81Y, 81M, 81C, 81K ... Liquid developer tank 82Y, 82M, 82C, 82K ... Insulating liquid tank 83Y, 83M, 83C, 83K ... Stirrer 100Y ... Development unit 101Y ... Photoconductor Squeeze device F40 ... Fixing part (fixed Device) F5 ... recording medium F5a ... toner image

Claims (9)

An insulating liquid;
Toner particles containing a polyester resin dispersed in the insulating liquid,
The liquid developer, wherein the polyester resin has a polar component occupying 25% or more of the surface free energy of the polyester resin.   The liquid developer according to claim 1, wherein the polyester resin is a rosin-modified polyester resin and / or a urethane-modified polyester resin. The liquid developer according to claim 1, wherein the surface free energy of the polyester resin is 50 mJ / m ² or more. The liquid developer according to any one of claims 1 to 3, wherein a polar component of the surface free energy of the polyester resin is 13 mJ / m ² or more. 5. The liquid developer according to claim 1, wherein a hydrogen bond component in the surface free energy of the polyester resin is ² mJ / m ² or less.   The liquid developer according to claim 1, comprising a dispersant having an amine value of 1 to 100 mg KOH / g.   The liquid developer according to claim 1, wherein the insulating liquid contains vegetable oil.   The liquid developer according to claim 1, wherein the insulating liquid contains a fatty acid monoester. A plurality of developing units that form a single color image corresponding to the plurality of liquid developers using a plurality of liquid developers having different colors;
An intermediate transfer unit that sequentially transfers a plurality of the single-color images formed by the plurality of developing units, and forms an intermediate transfer image formed by superimposing the transferred single-color images;
A secondary transfer unit that transfers the intermediate transfer image to a recording medium and forms an unfixed color image on the recording medium;
A fixing unit for fixing the unfixed color image on the recording medium,
The liquid developer has an insulating liquid and toner particles containing a polyester resin dispersed in the insulating liquid;
The polyester resin is characterized in that the proportion of the polar component in the surface free energy of the polyester resin is 25% or more.

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