JP2011150285A - Toner, fixing method, image forming method, and image forming apparatus - Google Patents

Abstract

A fixing solution containing at least a plasticizer that softens or swells at least a part of the toner has a short permeation time, and an appropriate softened toner can be obtained in a short time. Provided are a toner capable of forming an image and capable of forming a high-quality image, and a fixing method using the toner.
A toner used for fixing a toner to a recording medium by applying a fixing liquid containing a diluent and a plasticizer that softens or swells at least a part of the toner to the toner on the recording medium. A toner containing at least a resin having a polyhydroxycarboxylic acid skeleton and a colorant. The polyhydroxycarboxylic acid skeleton has an optical purity X (%) in terms of monomer component = | X (L form) −X (D form) | [where X (L form) is an L form in terms of an optically active monomer. The ratio (mol%) and X (D isomer) represent the D isomer ratio (mol%) in terms of optically active monomer] is preferably 80% or less.
[Selection figure] None

Description

  The present invention relates to a toner, a fixing method, an image forming method, and an image forming apparatus.

  In an electrophotographic image forming apparatus, a thermal fixing system in which toner on a recording medium is fixed by heating and melting and pressurizing is widely used from the viewpoint of fixing speed, fixed image quality, and the like. However, about half or more of the power consumption in such an electrophotographic image forming apparatus is consumed for heating the toner. From the viewpoint of environmental problems, a low power consumption (energy saving) fixing device is desired. Yes.

As such a fixing device, for example, Patent Document 1 proposes a method of fixing a toner by dissolving or swelling the toner with a fixing solution and drying it.
Patent Document 2 discloses a method of preparing a foam-like fixing solution containing a plasticizer that dissolves or swells a toner resin, and uniformly applying the foam-like fixing solution to fix the toner image without disturbing the toner image. Has been proposed.
This fixing method is a fixing method that is low in power consumption and excellent as an energy saving measure because a heat treatment for melting the toner is not required unlike the heat fixing method.

  However, when the conventional fixing methods are used, there is a problem that the progress of softening of the toner is slow, and it is insufficient to fix the toner on the recording medium in a short fixing process. In particular, when a halftone image is fixed on a recording medium, there is a problem that the fixing strength is insufficient and the image is easily peeled off when the image portion of the recording medium is rubbed by some contact.

Further, Patent Document 3 provides a fixing method capable of fixing toner at high speed and in a small amount in a fixing method in which toner is fixed to a recording medium using a fixing liquid containing a plasticizer that softens the toner. Thus, a fixing method using a plasticizer and a toner, in which the shift width ΔT of the endothermic shoulder of the toner is 30 ° C. or more when the DSC measurement is performed with the plasticizer added at 3% by mass with respect to the toner mass, ing. In this proposal, by using a toner and a plasticizer that satisfy the above conditions, the compatibility between the toner and the plasticizer is sufficient even when the amount of the plasticizer is small, so that the toner can be sufficiently softened, and the fixing speed can be reduced. It is possible to cope with high speed.
In the proposed toner, in order to obtain a sufficiently softened state, it has been a problem that the plasticizer penetrates quickly into the toner. Although the proposed toner can sufficiently change the glass transition temperature even if a small amount is added after the plasticizer has sufficiently penetrated into the toner, high-speed image formation required for recent electrophotographic printing systems is possible. In order to cope with the above, it is required that the speed of penetration is sufficiently high.

  Therefore, as in the prior art document, when the speed of penetration of the plasticizer into the toner is low, sufficient fixing strength of the toner to the recording medium such as paper cannot be obtained, so that a high quality image cannot be formed. There is a problem that a plasticizer penetrates into a recording medium such as paper and wrinkles and curls are generated, and the present situation is that a quick solution is desired.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, according to the present invention, a permeation time of a fixing solution containing at least a plasticizer that softens or swells at least a part of the toner is short, and an appropriately softened toner can be obtained in a short time, and an image is firmly fixed on a recording medium. It is an object of the present invention to provide a toner capable of high-speed image formation and capable of forming a high-quality image, and a fixing method, an image forming method, and an image forming apparatus using the toner.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a toner capable of promptly penetrating a plasticizer in a fixing solution by appropriately selecting the composition of the binder resin of the toner is obtained. It was found that it was obtained. That is, it is the selection of the type of monomer used when synthesizing the polyester resin that is more dominant than the minute fluctuations in the content of acid and alcohol constituting the polyester resin and the difference in the mixing ratio. Lactic acid and lactide are preferred, and by selecting the monomer type in this way, the toner softening speed and toner of the fixing solution are affected even if other physical properties such as weight average molecular weight and glass transition temperature (Tg) are affected. It was found that the permeation rate into the water can be controlled within an appropriate range.

  As a result of further intensive studies by the present inventors, the plasticizer in the fixing solution has many structural components that are common in terms of the skeleton, such as aliphatic alkyl chain sites, ester bond sites, and alcohol group sites. In the case of toners using lactic acid resin as the main binder resin, the penetration of the plasticizer into the binder resin starts because the penetration of the plasticizer is rapid and the polylactic acid itself has a high affinity for paper. At the same time, it was found that good fixability was obtained, the image was firmly fixed on the recording medium, high-speed image formation was possible, and a toner capable of forming a high-quality image was obtained.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner used for fixing a toner onto a recording medium by applying a fixing liquid containing a diluent and a plasticizer that softens or swells at least a part of the toner to the toner on the recording medium. And
A toner comprising at least a resin having a polyhydroxycarboxylic acid skeleton and a colorant.
<2> The polyhydroxycarboxylic acid skeleton has an optical purity X (%) in terms of monomer component = | X (L form) −X (D form) | [where X (L form) is in terms of optically active monomer. The toner according to <1>, wherein the L-form ratio (mol%) and X (D-form) represent the D-form ratio (mol%) in terms of optically active monomer] is 80% or less.
<3> The toner according to any one of <1> to <2>, wherein the polyhydroxycarboxylic acid skeleton has a weight average molecular weight of 7,000 to 60,000.
<4> The toner according to any one of <1> to <3>, wherein the polyhydroxycarboxylic acid skeleton is a skeleton obtained by polymerization or copolymerization of a hydroxycarboxylic acid having 3 to 6 carbon atoms.
<5> The toner according to any one of <1> to <4>, wherein the toner further contains a charge control agent.
<6> The toner according to <5>, wherein the charge control agent is a fluorine-containing quaternary ammonium salt.
<7> The toner according to <1> to <6>, wherein the toner further contains a modified layered inorganic mineral, and the modified layered inorganic mineral is obtained by modifying at least part of ions between layers of the layered inorganic mineral with organic ions. The toner according to any one of the above.
<8> A toner is a water-based toner material solution in which a toner material containing at least a binder resin, a resin having a polyhydroxycarboxylic acid skeleton, a colorant, a charge control agent, and a modified layered inorganic mineral is dissolved or dispersed in an organic solvent. The toner according to any one of <1> to <7>, which is obtained by dispersing and granulating in a medium.
<9> Resin particles (A) containing at least the first resin (a), or the coating particles (P) containing the first resin (a) are resin particles containing the second resin (b) ( B) a toner adhered to the surface of
The resin particles (B) are particles comprising the toner according to any one of <1> to <8>,
The toner according to claim 1, wherein the first resin (a) is a polyester resin containing a polybasic acid and a polyhydric alcohol.
<10> A toner comprising first resin (a1) and second resin (a2) having different glass transition temperatures, and resin particles (B) containing a third resin (b),
The first resin (a1) and the second resin (a2) are both attached to the surface of the resin particles (B),
The first resin (a1) and the second resin (a2) are composed of at least one of a styrene monomer and an acrylic monomer,
The resin particle (B) is a toner comprising the toner according to any one of <1> to <8>.
<11> A toner having a first resin (a) and resin particles (B) containing a second resin (b),
The first resin (a) is composed of a polyurethane-acrylic polymer composite, and is attached to the surface of the resin particles (B).
The resin particle (B) is a toner comprising the toner according to any one of <1> to <8>.
<12> In the developer comprising the toner according to any one of <1> to <11> and a carrier,
The carrier has at least a core material and a coating layer containing fine particles on the surface of the core material, and the average particle diameter (D) of the fine particles and the average thickness (h) of the coating layer are 1 <[D / h]. <10, and the content of the fine particles is 40% by mass to 95% by mass.
<13> The developer according to <12>, wherein the coating layer contains at least a silicone resin.
<14> The developer according to any one of <12> to <13>, wherein the fine particles in the coating layer are at least one of alumina and surface-treated alumina.
<15> A fixing method in which a fixing liquid containing a plasticizer that softens the toner by dissolving or swelling at least a part of the toner is applied to the toner on the recording medium to fix the toner on the recording medium.
The fixing method is characterized in that the toner is the toner according to any one of <1> to <11>.
<16> A fixing method for fixing toner on a recording medium using the toner according to any one of <1> to <11>,
A foamed fixing solution generating step for producing a foamed fixing solution by foaming a fixing solution containing a diluent containing water, a foaming agent, and a plasticizer;
A film thickness adjusting step for forming the foamy fixer to a desired thickness on the contact surface of the foamy fixer applying means,
A foam-like fixing solution applying step for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
A fixing method comprising:
<17> The fixing method according to any one of <15> to <16>, wherein the plasticizer is a dialkoxyalkyl aliphatic dicarboxylate.
<18> The fixing method according to any one of <15> to <16>, wherein the plasticizer is a compound represented by the following general formula.
R ⁸ (COO— (R ⁹ —O) _n —R ¹⁰ ) ₂
In the general formula, n is 1 to 3, R ⁸ is an alkylene group having 2 to 8 carbon atoms, R ⁹ is an alkylene group having 1 to 3 carbon atoms, R ¹⁰ Is an alkyl group having 1 to 4 carbon atoms.
<19> an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
Developing the electrostatic latent image using a developer containing toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A fixing step of fixing the transferred image transferred to the recording medium;
An image forming method comprising:
An image forming method, wherein the fixing step is performed by the fixing method according to any one of <15> to <18>.
<20> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing a developer containing toner A developing unit that develops the electrostatic latent image using a developer containing toner and forms a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
The fixing unit includes a fixing solution applying unit that applies a fixing solution to a toner layer on a recording medium,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <11>.
<21> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer containing toner to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing toner. A developer container for storing, and developing means for developing the electrostatic latent image with a developer containing toner to form a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
A foaming fixer generating means for generating a foamy fixer by foaming a fixer containing a diluent containing water, a foaming agent, and a plasticizer;
Film thickness adjusting means for forming the foamy fixer on the contact surface of the foamy fixer applying means to a desired thickness;
A foam-like fixing solution applying means for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <11>.

  According to the present invention, the conventional problems can be solved, and the penetration time of the fixing solution containing at least a plasticizer that softens or swells at least a part of the toner is short, and a toner in an appropriate softened state can be obtained in a short time. Further, it is possible to provide a toner capable of firmly fixing an image on a recording medium, forming a high-speed image, and forming a high-quality image, and a fixing method, an image forming method, and an image forming apparatus using the toner. .

FIG. 1 is a schematic cross-sectional view showing how toner is fixed after the fixing solution is applied. FIG. 2 is a schematic diagram showing a layer configuration example of the foamy fixing solution at the time of application. FIG. 3 is a schematic diagram showing the configuration of the foamy fixing solution generating means in the fixing device. FIG. 4A is a schematic configuration diagram illustrating an example of a film thickness adjusting unit and a foamy fixing solution applying unit in the fixing device. FIG. 4B is an enlarged schematic view of a coating roller and a film thickness adjusting blade in the fixing device. FIG. 5A is a schematic diagram illustrating a method for adjusting the film thickness of the foamy fixing solution on the application roller. FIG. 5B is a schematic diagram showing a method for adjusting the film thickness of the foamy fixing solution on the application roller. FIG. 6 is a schematic diagram illustrating an example of a fixing device. FIG. 7 is a schematic diagram illustrating another example of the fixing device. FIG. 8 is a schematic view showing another example of a fixing device provided with a heating means. FIG. 9 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 10 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 11 is a schematic diagram of one image forming unit provided in the image forming apparatus shown in FIG. 12 is an enlarged view of the fixing device of the image forming apparatus shown in FIG. FIG. 13 is a schematic diagram illustrating an example of an image forming apparatus including a fixing unit. FIG. 14 is a schematic diagram illustrating another example of the image forming apparatus. FIG. 15 is a schematic view showing an apparatus for measuring the penetration time of the fixing liquid into the toner layer in the embodiment.

(toner)
The toner of the present invention is used to fix a toner on a recording medium by applying a fixing liquid containing a diluent and a plasticizer that softens or swells at least a part of the toner to the toner on the recording medium. ,
It contains at least a resin having a polyhydroxycarboxylic acid skeleton and a colorant, and contains a charge control agent, a modified layered inorganic mineral, and other components as required.

<Resin having a polyhydroxycarboxylic acid skeleton>
The polyhydroxycarboxylic acid skeleton in the resin having a polyhydroxycarboxylic acid skeleton has a skeleton obtained by polymerization or copolymerization of hydroxycarboxylic acid, and a method of directly dehydrating and condensing the hydroxycarboxylic acid, or opening a corresponding cyclic ester. It can be formed by a polymerization method.

  The polymerization method is preferably ring-opening polymerization of a cyclic ester from the viewpoint of increasing the molecular weight of the polyhydroxycarboxylic acid to be polymerized. A resin having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer is excellent in transparency, heat resistance and durability, but from the viewpoint of transparency as a toner resin and penetration rate of a plasticizer in a fixing solution to be used. As the monomer for forming the polyhydroxycarboxylic acid skeleton, aliphatic hydroxycarboxylic acids and cyclic esters are preferable, and also include hydroxycarboxylic acids having 3 to 6 carbon atoms (including cyclic esters corresponding to hydroxycarboxylic acids having 3 to 6 carbon atoms). ) Is more preferable, and lactic acid and lactide are particularly preferable.

  When a cyclic ester of hydroxycarboxylic acid is used as the optically active monomer, the hydroxycarboxylic acid skeleton of the resin obtained by polymerization is a skeleton obtained by polymerizing the hydroxycarboxylic acid constituting the cyclic ester. For example, the polyhydroxycarboxylic acid skeleton of a resin obtained using lactide is a skeleton obtained by polymerizing lactic acid.

The optically active monomer forming the polyhydroxycarboxylic acid skeleton has an optical purity X (%) = | X (L form) −X (D form) | [where X (L form) is an optically active monomer in terms of monomer components The L-form ratio (mol%) in terms of conversion and X (D-form) represent the D-form ratio (mol%) in terms of optically active monomer] are preferably 80% or less, and preferably 60% or less. More preferred. When the optical purity X is within this range, solvent solubility and resin transparency are improved.
If the optical purity is not within this range, the resin is insufficiently amorphized and crystallinity remains, so that fine crystals are generated in the resin, and light scattering occurs at the crystal interface. The transparency of the resin is impaired, and the penetration of the plasticizer in the fixing solution is slowed because the crystal portion is difficult to penetrate the solvent or plasticizer. In addition, the pigment and wax in the toner are excluded from the microcrystals, and the aggregation and uneven distribution of the pigment and wax in the toner are likely to occur, so that the gloss uniformity and color reproducibility deteriorate.
Of course, the L-form and D-form used in the raw materials are optical isomers, and the optical isomers have the same physical and chemical properties other than the optical characteristics. The reactivity is equal, and the component ratio of the monomer and the component ratio of the monomer in the polymer are the same.

  Here, the optical purity of the polyhydroxycarboxylic acid skeleton-containing resin is obtained by, for example, heating a resin containing a polyhydroxycarboxylic acid skeleton in an aqueous alkaline solution for a long time and decomposing it into monomer units through a semipermeable membrane. Only the low molecular weight monomer part can be extracted and measured by an HPLC method equipped with an optical resolution column.

  The hydroxycarboxylic acid that forms the polyhydroxycarboxylic acid skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic hydroxycarboxylic acids (such as glycolic acid, lactic acid, and hydroxybutyric acid), and aromatics. Examples thereof include hydroxycarboxylic acids (salicylic acid, creosote acid, mandelic acid, burric acid, syringic acid, etc.) or a mixture thereof. Examples of the corresponding cyclic ester include glycolide, lactide, γ-butyrolactone, and 6-valerolactone. Among these, from the viewpoint of the transparency and thermal characteristics of the toner, the resin contained in the toner contains a polyhydroxycarboxylic acid skeleton composed of an optically active monomer. Examples of the optically active monomer include aliphatic hydroxycarboxylic acids and cyclic esters. Are preferred, hydroxycarboxylic acids having 3 to 6 carbon atoms are more preferred, and lactic acid and lactide are particularly preferred.

Also, alcohols and lactones may be used as coinitiators during polymerization of a resin containing a polyhydroxycarboxylic acid skeleton.
As the alcohols, known alcohols can be used, but 1,2-propanediol and 1,3-propanediol are preferable in view of the heat melting characteristics of the obtained resin. As the lactones, known lactones can be used, but ε-caprolactone is preferable in terms of the heat melting characteristics of the obtained resin.

The weight average molecular weight (Mw) of the polyhydroxycarboxylic acid skeleton composed of the optically active monomer in the resin is preferably 7,000 to 60,000, and more preferably 10,000 to 20,000. When the weight average molecular weight is lower than this range, storage stability deteriorates, and when the molecular weight is higher than this range, solvent solubility is impaired, making it difficult to produce an aqueous granulated toner.
Here, the weight average molecular weight (Mw) of the polyhydroxycarboxylic acid skeleton can be measured, for example, by being able to be measured by a GPC method described later.

  In addition, the resin having a polyhydroxycarboxylic acid skeleton may be extended at the time of toner preparation. In that case, the resin having a polyhydroxycarboxylic acid skeleton preferably has an isocyanate group, and an amine is used as an extender. Etc.

In the present invention, a second resin other than the resin having a polyhydroxycarboxylic acid skeleton can be used in combination.
The second resin is not particularly limited, and any known resin may be used in combination, and the resin used in combination may be appropriately selected according to the use and purpose. For example, vinyl resin, polyester resin , Polyurethane resin, epoxy resin, styrene copolymer such as styrene-maleic acid ester copolymer, polymethacrylate resin, polybutyl methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polyvinyl butyral resin , Polyacrylic acid resin, rosin resin, modified rosin resin, terpene resin, phenol resin and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, polyurethane resins and polyester resins are preferable, polyester resins and polyurethane resins containing 1,2-propylene glycol as structural units are more preferable, and physical properties such as toner storage stability and ease of aqueous granulation. From the viewpoint of adjustment, a linear polyester resin is particularly preferable.

  The content of the resin having a polyhydroxycarboxylic acid skeleton is not particularly limited and can be appropriately selected depending on the purpose. The resin is contained in the toner from the viewpoint of transparency of the toner and a plasticizer in the fixing solution. The ratio of the polyhydroxycarboxylic acid skeleton to the total resin is preferably 50% by mass to 90% by mass, and more preferably 65% by mass to 85% by mass. When the ratio of the polyhydroxycarboxylic acid skeleton is less than 50% by mass, the plasticizer in the fixing solution does not penetrate rapidly and at the same time, transparency may not be obtained. When the granular toner is produced, the oil phase viscosity becomes high, and it may be difficult to produce the toner.

<Charge control agent>
The charge control agent is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include quaternary ammonium salts such as benzoylmethylhexadecyl ammonium chloride and decyltrimethyl chloride, dialkyltin compounds such as dibutyl and dioctyl, Examples include dialkyltin borate compounds, guanidine derivatives, vinyl polymers containing amino groups, polyamine resins such as condensation polymers containing amino groups, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, the use of a colored charge control agent should be avoided, and white metal salts of salicylic acid derivatives and fluorine-containing quaternary ammonium salts are preferred, and fluorine-containing quaternary ammonium salts are particularly preferred. By using a fluorine-containing quaternary ammonium salt as the charge control agent, the charge of the toner can be quickly increased to a desired charge amount, and the transparency of the resin is not impaired.

  The content of the charge control agent is preferably 0.01 parts by mass to 2 parts by mass and more preferably 0.02 parts by mass to 1 part by mass with respect to 100 parts by mass of the resin. When the content is 0.01 parts by mass or more, charge controllability is obtained, and when the content is 2 parts by mass or less, the chargeability of the toner is not excessively increased and the effect of the main charge control agent is reduced. In other words, the electrostatic attraction force with the developing roller is not increased and the fluidity of the toner and the image density are not lowered.

<Modified layered inorganic mineral>
The toner of the present invention preferably contains a modified layered inorganic mineral obtained by modifying at least part of ions between layers of the layered inorganic mineral with organic ions in order to stabilize the chargeability.

  As the modified layered inorganic mineral, a material having a smectite basic crystal structure modified with an organic cation can be preferably used. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is preferable when used.

Examples of the organic cation modifier of the modified layered inorganic mineral include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like. Among these, quaternary alkyl ammonium salts are particularly preferable.
The quaternary alkylammonium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimethylstearylammonium, dimethylstearylbenzylammonium and oleylbis (2-hydroxyethyl) methylammonium.

  Examples of the organic anion modifier include branched, unbranched, or cyclic alkyl (C1 to C44), alkenyl (C1 to C22), alkoxy (C8 to C32), hydroxyalkyl (C2 to C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates, or phosphates having Among these, carboxylates having an ethylene oxide skeleton are preferable.

  By modifying at least a part of the layered inorganic mineral with organic ions, the organic solvent phase containing the toner composition has an appropriate hydrophobicity, has a non-Newtonian viscosity, and can deform the toner. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.

  The modified layered inorganic mineral is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include montmorillonite, bentonite, hectorite, attapulgite, and sepiolite. These may be used individually by 1 type and may use 2 or more types together. Among these, organically modified montmorillonite or bentonite is particularly preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

  Commercially available products can be used as the modified layered inorganic mineral partially modified with an organic cation. Examples of the commercially available products include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (United). quaternium 18 bentonite such as Clayton 34, Clayton 40, Clayton XL (above, Southern Clay), Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by catalyst) As mentioned above, stearalkonium bentonite such as Southern Clay, etc .; quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (above, Southern Clay) are listed. These may be used individually by 1 type and may use 2 or more types together. Among these, Clayton AF and Clayton APA are particularly preferable.

As a layered inorganic mineral partially modified with an organic anion, for example, one obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable.
R ¹ (OR ² ) nOSO ₃ M—General formula (1)
However, the general formula (1), ^{R 1} represents an alkyl group having a carbon number of 13, ^{R 2} represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element.
Examples of the organic anion represented by the general formula (1) include Hitenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).

<Colorant>
As the colorant, known pigments and dyes capable of obtaining yellow, magenta, cyan, and black toners can be used.
Examples of the colorant include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow GR, quinoline yellow lake, and permanent yellow. NCG, tartrazine lake, etc. are mentioned.
Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK and the like.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B and the like. It is done.
Examples of purple pigments include Fast Violet B and Methyl Violet Lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.
Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.
Examples of the black pigment include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass.
The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene Examples thereof include resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffins. These may be used individually by 1 type and may use 2 or more types together.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, an inorganic fine particle, a mold release agent, a fluid improvement agent, a magnetic body etc. are mentioned.

-Inorganic fine particles-
Examples of the inorganic fine particles include silica, titania, alumina, cerium oxide, strontium titanate, calcium carbonate, magnesium carbonate, calcium phosphate, etc., and silica fine particles hydrophobized with silicone oil, hexamethyldisilazane, or the like. It is more preferable to use titanium oxide that has been subjected to a specific surface treatment.
Examples of the silica fine particles include Aerosil (Product Nos .: 130, 200 V, 200 CF, 300, 300 CF, 380, OX50, TT600, MOX80, MOX170, COK84, RX200, RY200, R972, R974, R976, R805, R811, R812, T805. , R202, VT222, RX170, RXC, RA200, RA200H, RA200HS, RM50, RY200, REA200) (all manufactured by Nippon Aerosil Co., Ltd.), HDK (part numbers: H20, H2000, H3004, H2000 / 4, H2050EP, H2015EP, H3050EP, KHD50), HVK2150 (all manufactured by Wacker Chemical Co., Ltd.), Cabozil (Part No .: L-90, LM-130, LM-150, M-5, PTG, S-55, H-5, HS-5, EH-5, LM-150D, M-7D, MS-75D, TS-720, TS-610, TS-530) (all manufactured by Cabot) Can be used. These may be used alone or in combination of two or more.
The addition amount of the inorganic fine particles is preferably 0.1 parts by mass to 5.0 parts by mass, and more preferably 0.8 parts by mass to 3.2 parts by mass with respect to 100 parts by mass of the toner base particles.

-Release agent-
As the release agent, for example, carbonyl group-containing wax, polyolefin wax, long chain hydrocarbon, and the like may be used, but it is preferable not to use a release agent. The toner used in the conventional heat and pressure fixing system is called a release agent and melts when performing hot roller fixing for the purpose of preventing hot offset at the time of fixing. Substances having an effect of preventing adhesion with the above toner (low molecular weight polyolefin, wax, etc.) have been used. However, it is difficult for the release agent to uniformly disperse the toner in the binder resin, and when the release agent is present in a large amount on the toner surface or the like, the anti-blocking property decreases, and the photosensitive member, carrier, etc. May cause problems such as filming, spenting, and contamination of members over time.
The toner used in the method of fixing the toner to the recording medium using the fixer containing the plasticizer that softens the toner of the present invention is used in a non-heating fixing method, and therefore, heat roller fixing is performed. It is not necessary to have a substance that has an effect of preventing the adhesion between the roller and the toner on the fixing material, and it is not necessary to use a release agent.

-Magnetic material-
Examples of the magnetic material include (1) magnetic iron oxide such as magnetite, maghemite, and ferrite, or iron oxide containing other metal oxides, (2) metals such as iron, cobalt, and nickel, or these metals. And alloys of aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, etc. (3) or mixtures thereof, etc. Is used.

Examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , and PbFe _12. Examples thereof include O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, and nickel powder. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of iron trioxide and γ-iron trioxide are particularly preferable.

  Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Among these, magnesium, aluminum, silicon, phosphorus, or zirconium is particularly preferable. The heterogeneous element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Although it is good, it is preferably contained as an oxide.

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.
The amount of the magnetic material used is preferably 10 parts by mass to 200 parts by mass, and more preferably 20 parts by mass to 150 parts by mass with respect to 100 parts by mass of the binder resin. The number average particle diameter of these magnetic materials is preferably 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.5 μm.
The number average particle diameter can be obtained, for example, by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

Further, the magnetic properties of the magnetic material are as follows: when the magnetic field is 10 k Oersted, the coercive force is 20 Oersted to 150 Oersted, the saturation magnetization is 50 emu / g to 200 emu / g, and the residual magnetization is 2 emu / g to 20 emu / g. Is preferred.
The magnetic material can also be used as a colorant.

The toner of the present invention can be the core-shell type toner of the following first to third aspects.
In the core-shell type toner of the first aspect, the resin particles (A) containing at least the first resin (a) or the coating (P) containing the first resin (a) is contained in the second resin (b). ) Attached to the surface of the resin particles (B) containing
The resin particles (B) are particles made of the toner of the present invention containing at least a resin having a polyhydroxycarboxylic acid skeleton,
The first resin (a) is a polyester resin containing a polybasic acid and a polyhydric alcohol.

Examples of the polybasic acid include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher polybasic acids.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and the like. Acid or 5-hydroxyisophthalic acid can be used.
Examples of the aliphatic dicarboxylic acid include oxalic acid, (anhydrous) succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer acid, and other saturated dicarboxylic acids, fumaric acid, (anhydrous) maleic acid, Examples thereof include unsaturated dicarboxylic acids such as (anhydrous) itaconic acid, (anhydrous) citraconic acid and dimer acid.
Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid (anhydride), tetrahydrophthalic acid ( Anhydride) and the like.
Examples of the tribasic or higher polybasic acid include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (Anhydro trimellitate), 1,2,3,4-butanetetracarboxylic acid and the like.

As said polyhydric alcohol, C2-C10 aliphatic glycol, C6-C12 alicyclic glycol, ether bond containing glycol etc. are mentioned as glycol.
Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1 , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol and the like.
Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol.
Examples of the ether bond-containing glycol include glycols obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of diethylene glycol, triethylene glycol, dipropylene glycol, and bisphenol, for example, 2, Examples include 2-bis (4-hydroxyethoxyphenyl) propane. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used as necessary. However, since the ether structure reduces the water resistance and weather resistance of the polyester resin coating, the amount used is preferably 10% by mass or less, more preferably 5% by mass or less of the total polyhydric alcohol component.
Examples of the trifunctional or higher functional polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
The tribasic or higher polybasic acid and / or polyhydric alcohol is copolymerized in the range of 10 mol% or less, preferably 5 mol% or less, based on the total acid component or the total alcohol component. The high processability of the film, which is an advantage of the polyester resin, is not expressed.

The core-shell type toner of the second aspect has resin particles (B) containing the first resin (a1) and the second resin (a2) having different glass transition temperatures and the third resin (b). And
The first resin (a1) and the second resin (a2) are attached to the surface of the resin particles (B),
The first resin (a1) and the second resin (a2) are composed of at least one of a styrene monomer and an acrylic monomer,
The resin particles (B) are particles made of the toner of the present invention containing at least a resin having a polyhydroxycarboxylic acid skeleton.

Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p. -Tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene , P-chlorostyrene, 3,4-dichlorostyrene, and the like.
Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, Stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate Octyl, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Such as α- methyl fatty monocarboxylic acid esters and the like.

The core-shell type toner of the third aspect comprises resin particles (B) containing a first resin (a) and a second resin (b),
The first resin (a) is composed of a polyurethane-acrylic polymer composite, and is attached to the surface of the resin particles (B).
The resin particles (B) are particles made of the toner of the present invention containing at least a resin having a polyhydroxycarboxylic acid skeleton.

As the polyurethane-acrylic polymer composite, for example, a prepolymer is first prepared by a urethanization reaction in an organic solvent of a diisocyanate compound, a diol compound, a diol compound having a carboxyl group, and a hydroxyl compound having a polymerizable unsaturated group. . Thereafter, the obtained NCO-terminated prepolymer is neutralized with a neutralizing agent such as a tertiary amine. Subsequently, (1) the polyfunctional carboxylic acid polyhydrazide compound is reacted with the terminal NCO group of the prepolymer, or (2) the chain is elongated with a polyfunctional amine and / or polyfunctional carboxylic acid polyhydrazide, The NCO end group to be reacted with a polyfunctional carboxylic acid polyhydrazide is converted into an aqueous polyurethane resin having a —CONHNH ₂ group at the end. Thereby, an aqueous polyurethane dispersion is obtained.
Subsequently, an acrylic monomer is polymerized in the presence of the aqueous polyurethane dispersion produced by the above-described method to produce an aqueous dispersion of a polyurethane-acrylic polymer composite. Examples of acrylic monomers used include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, acrylic acid esters such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid. Examples of the monomer mixture include methacrylic acid esters such as hexyl acid and glycidyl methacrylate, and styrene.

<Developer>
The developer contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

-Career-
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the coating layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.
The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D ₅₀ )) of 10 μm to 200 μm, and more preferably 40 μm to 100 μm. When the average particle diameter (weight average particle diameter (D ₅₀ )) is less than 10 μm, in the carrier distribution, the number of fine powder systems increases, and the magnetization per particle may be lowered, causing carrier scattering. If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur.

The material of the coating layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.
The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.
The coating layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the coating layer is prepared by dissolving the silicone resin or the like in an organic solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. Can be formed. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
The amount of the coating layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, it may not be possible to form the uniform coating layer on the surface of the core. When the amount exceeds 5.0% by mass, the coating layer becomes thick. In some cases, the carriers may be granulated, and a uniform carrier may not be obtained.
When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the purpose. The toner is preferably 1 part by mass to 10.0 parts by mass.

The coating layer may contain fine particles from the viewpoint of adjusting physical properties. The fine particles can significantly improve the strength of the coating layer by selecting an appropriate content and average particle diameter with respect to the average thickness of the coating layer.
The fine particles are not particularly limited and can be appropriately selected from conventionally known materials according to the purpose. For example, alumina, titanium oxide, zinc oxide, silica, potassium titanate, aluminum borate, calcium carbonate, Examples thereof include tin oxide and indium oxide. These may be used individually by 1 type and may use 2 or more types together. Among these, titanium oxide fine particles and alumina fine particles are particularly preferable in that the toner is negatively charged and the resistance value of the coating layer can be easily controlled within a desired range. The fine particles may be surface-treated, and surface-treated alumina fine particles are preferable.

As the binder resin constituting the coating layer, one or more resins other than the silicone resin may be contained. Among these, acrylic resins are particularly preferable because they have excellent adhesion to the fine particles contained in the core material and the coating layer and have low brittleness, and thus have very excellent properties against peeling of the coating layer.
The fine particles can remarkably improve the strength of the coating layer by selecting an appropriate content and average particle diameter with respect to the thickness of the coating layer.
In the carrier, the average particle diameter (D) of the fine particles and the average thickness (h) of the coating layer are preferably 1 <[D / h] <10, and 1 <[D / h]. More preferably, it is <5. This is because, when 1 <[D / h] <10, the fine particles are more convex than the coating layer. Therefore, the friction with the toner or between the carriers is increased by stirring for tribocharging the developer. With this friction, contact with a strong impact on the binder resin can be eased. As a result, it is possible to prevent toner spent on the carrier, and it is also possible to suppress film abrasion of the binder resin, which is a location where charging occurs. When the [D / h] is 1 or less, the fine particles are buried in the binder resin, which is not preferable because the effect is remarkably lowered. On the other hand, when the [D / h] is 10 or more, the contact area between the fine particles and the binder resin is small, so that a sufficient binding force cannot be obtained and the fine particles are easily detached.

  Furthermore, the effect is remarkable because content of the fine particles in the coating layer is in the range of 40% by mass to 95% by mass of the entire coating layer. The content is preferably 50% by mass to 80% by mass. When the content is less than 40% by mass, since the proportion of the fine particles is smaller than the proportion of the binder resin on the carrier surface, the contact with a strong impact on the binder resin is alleviated. Since the effect is small, sufficient durability cannot be obtained, which is not preferable. On the other hand, when the content exceeds 95% by mass, the proportion of the fine particles is excessive compared to the proportion of the binder resin on the surface of the carrier. Insufficient charge capacity cannot be exhibited. In addition, since the content of fine particles is too much compared to the amount of the binder resin, the ability to hold the fine particles by the binder resin becomes insufficient, and the fine particles are easily detached, so that sufficient durability cannot be obtained. is there.

There is no restriction | limiting in particular in the average thickness h of the said coating layer, According to the objective, it can select suitably, 1.0 micrometer or less is preferable and 0.02 micrometer-0.8 micrometer are more preferable.
The average particle diameter D of the fine particles is appropriately selected according to the average thickness h of the coating layer, but is preferably 0.1 μm to 1.5 μm.
Here, the average thickness h of the coating layer and the average particle diameter D of the fine particles can be measured, for example, by observing the cross section of the carrier using a transmission electron microscope (TEM).

  In the present invention, an aminosilane coupling agent can be contained in the coating layer in order for the carrier to stably charge the toner over a long period of time. The content in the coating layer is preferably 0.001% by mass to 30% by mass, and more preferably 0.001% by mass to 10% by mass. When the content is less than 0.001% by mass, the chargeability is easily affected by the environment, and the product yield may be easily reduced. When the content exceeds 30% by mass, the coating layer becomes brittle. The wear resistance of the coating layer may decrease.

There is no restriction | limiting in particular as a formation method of the said coating layer, A conventionally well-known method can be used, The method of apply | coating the said coating layer liquid to a core material surface by means, such as a spraying method or a dipping method, is mentioned.
For the purpose of promoting the polymerization reaction of the coating layer, the carrier on which the coating layer is formed may be heat-treated. The heating may be performed subsequently in the coating layer forming apparatus after the coating layer is formed, or may be performed by another heating means such as a normal electric furnace or a firing kiln after the coating layer is formed. The heating temperature varies depending on the coating layer resin to be used, and is not generally determined, but is preferably 120 ° C to 350 ° C, preferably a temperature equal to or lower than the decomposition temperature of the coating layer resin, and is about 220 ° C. The upper limit temperature is more preferable, and the heating time is preferably 5 minutes to 120 minutes.

<Toner production method>
The method for producing the toner base particles constituting the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a pulverization method, a monomer composition containing a specific polymerizable monomer Polymerization method (suspension polymerization method, emulsion polymerization method) in which water is directly polymerized in water phase, a method of emulsifying or dispersing a specific binder resin solution in an aqueous medium, dissolving in a solvent, removing the solvent and grinding And a melt spray method.

-Grinding method-
The pulverization method is, for example, a method of obtaining the toner base particles by melting, kneading, pulverizing, and classifying the toner material.
In the case of the pulverization method, for the purpose of increasing the average circularity of the toner, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.
The toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel Co., Ltd., TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works, Inc. A manufactured kneader or the like is preferably used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. In this case, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing in a narrow gap between a mechanically rotating rotor and a stator is preferably used. .
In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion by a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

-Suspension polymerization method-
The suspension polymerization method will be described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in an oil-soluble polymerization initiator, a polymerizable monomer, and a surfactant and other solid dispersants are contained. Emulsified and dispersed by an emulsification method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, methacrylic acid, and the like. Functional groups on the surface of toner particles by partially using amide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, acrylates with methacrylates such as dimethylaminoethyl methacrylate, methacrylates, etc. Can be introduced.
Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

-Emulsion polymerization method-
As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer used in the suspension polymerization method.

-Method of emulsifying or dispersing a specific binder resin solution in an aqueous medium-
As a method for emulsifying or dispersing a specific binder resin solution in the aqueous medium, a solution or dispersion of a toner material having at least a binder resin is emulsified or dispersed in an aqueous medium, and the emulsion or dispersion is obtained. After the toner is prepared, the toner is granulated (aqueous granulation). As this method, for example, it includes the following steps (1) to (4).

<< Step (1): Preparation of Solution or Dispersion of Toner Material >>
The solution or dispersion of the toner material is prepared by dissolving or dispersing a toner material such as a colorant and a binder resin in an organic solvent. The organic solvent is removed during or after the toner granulation.

<< Step (2): Preparation of aqueous medium >>
The aqueous medium is not particularly limited and may be appropriately selected from known ones. For example, water, alcohol miscible with water, dimethylformamide, tetrahydrofuran, cellosolves, solvents such as lower ketones, or the like Examples thereof include a mixture thereof. Among these, water is particularly preferable.
The aqueous medium can be prepared, for example, by dispersing a dispersion stabilizer such as resin fine particles in the aqueous medium. The amount of the resin fine particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.5 mass% to 10 mass% is preferable.
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin because an aqueous dispersion of fine spherical resin fine particles can be easily obtained.
In addition, in the aqueous medium, if necessary, from the viewpoint of stabilizing the oil droplets of the solution or dispersion at the time of emulsification or dispersion described later, and sharpening the particle size distribution while obtaining a desired shape, It is preferable to use a dispersant. There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are particularly preferable.

<< Step (3): emulsification or dispersion >>
When the solution or dispersion containing the toner material is emulsified or dispersed in the aqueous medium, the solution or dispersion containing the toner material is preferably dispersed while stirring in the aqueous medium. The dispersion method is not particularly limited, but a batch type emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Aihara Seisakusho), TK Fillmix, TK Pipeline Homomixer (made by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (made by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Fine Crusher (Mitsui Miike Chemical Industries) Co., Ltd.), Capitoron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.) and other continuous emulsifiers, Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer (Nanomizer Co., Ltd.), APV Gaulin High-pressure emulsifiers (made by Gaulin), membrane emulsifiers such as membrane emulsifiers (made by Chilling Industries Co., Ltd.), Bro mixer (Hiyaka Kogyo Co., Ltd.) vibration type emulsifying machine such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.), and the like. Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are particularly preferable from the viewpoint of uniform particle size.
In the case where a modified polyester (prepolymer) capable of reacting with an active hydrogen group-containing compound is included as the binder resin contained in the solution or dispersion, the reaction proceeds during emulsification or dispersion. The reaction conditions are not particularly limited and can be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is 10 minutes to 40 hours is preferable, and 2 hours to 24 hours is more preferable.

<< Step (4): Removal of solvent >>
Next, the organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion. The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere, Examples thereof include a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.

-Addition of inorganic fine particles-
Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above. .
For mixing the additive, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. First, a strong load may be given first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

-Volume average particle diameter and ratio of toner (volume average particle diameter / number average particle diameter)-
The shape, size, etc. of the toner is not particularly limited and can be appropriately selected depending on the intended purpose. (Volume average particle diameter / number average particle diameter).

There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, 3 micrometers-10 micrometers are preferable, and 3 micrometers-8 micrometers are more preferable. When the volume average particle size is less than 3 μm, in the electrophotographic developer, the toner is fused to the surface of the electrophotographic carrier during a long period of stirring in the developing device, and the charging ability of the electrophotographic carrier is reduced. If it exceeds 10 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the electrophotographic developer is carried out, the fluctuation of the toner particle size may increase. is there.
The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25. .
The volume average particle diameter and the ratio between the volume average particle diameter and the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III” manufactured by Beckman Coulter, Inc.). Measurement can be performed with an aperture diameter of 100 μm, and analysis can be performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51).
Specifically, 0.5 mL of 10% by mass surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL glass beaker, and 0.5 g of each toner is added. Add, stir with microspatel, then add 80 mL of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion is measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion is dropped so that the concentration indicated by the apparatus is 8% ± 2%. In this measurement method, it is important that the concentration is 8% ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

  The toner of the present invention can be fixed on a recording medium using a fixing solution containing at least a plasticizer that softens or swells at least a part of the toner, and can be used for various applications. The fixing method of the present invention described below. And a fixing device.

<Fixing solution>
The fixing solution contains a plasticizer that softens or swells at least a part of the toner and a diluent, and further contains other components as necessary. When the fixing solution is used as a foamy fixing solution, the fixing solution is used in the form of foam. The foam-like fixing solution contains a diluent, a foaming agent that makes the fixing solution foam, and a plasticizer that softens or swells at least a part of the toner, and further contains other components as necessary. Do it. In the fixing method of the present invention, it is preferable to use this foamy fixing solution.

<< Plasticizer >>
The plasticizer includes a solid plasticizer that is solid at normal temperature and soluble in a diluent, and further includes a liquid plasticizer that is liquid at normal temperature and is soluble in a diluent as necessary. .

-Solid plasticizer-
The solid plasticizer is not particularly limited as long as it is solid at normal temperature and is soluble in a diluent described later, and can soften the toner in a state dissolved in the diluent. Here, “normal temperature” refers to a temperature achieved without heating or cooling, and is preferably 5 ° C. to 35 ° C. as defined in JIS Z8703, for example. If it is within this normal temperature range, the solid plasticizer is in a solid state. That is, in the foam-type fixing solution, the solid plasticizer is in a molten state because it contains water, but is applied to the unfixed toner, penetrates into the toner, and further penetrates into the toner. When the amount decreases due to vaporization or the like, the solid plasticizer changes to a solid state. In the present invention, attention is paid to the fact that the solid plasticizer changes to a solid state as described above, and by utilizing this characteristic, the toner hardness after application of the fixing solution is increased and the problem relating to tack is solved. In addition, the solid plasticizer exerts its plastic ability with respect to the toner under appropriate conditions at room temperature, and when it loses its plastic ability and becomes a solid state, it hardens itself and contributes to prevention of tack. preferable.

  The solid plasticizer preferably has, for example, a functional group having an affinity such as having a certain compatibility with the toner that is a fixing target. The functional group having affinity here is preferably a case where the functional group contained in the molecule constituting the toner is the same as the functional group contained in the solid plasticizer, and between these functional groups. It means having a functional group capable of a certain interaction. When the functional group contained in the solid plasticizer has a functional group capable of having a certain interaction with the molecules constituting the toner, the solid plasticizer enters between the molecules constituting the toner by the interaction of these functional groups. This is because, as a result, a so-called polymer blend state is formed between the solid plasticizer and the toner, and the solid plasticizer is effective in softening or swelling at least a part of the toner. As a specific example, the solid plasticizer is a polyethylene glycol compound, and the polyethylene glycol contains an ethylene oxide group. The corresponding toner corresponds to a combination containing an ethylene oxide group in the resin molecule. In such a case, an ethylene oxide group is contained in both the solid plasticizer and the toner, thereby improving the compatibility, thereby producing an effect of increasing the compatibility between the two. On the other hand, this concept is based on having a functional group having affinity for both the solid plasticizer and the toner, and is not limited to the ethylene oxide group. As another example, a propylene oxide group is used. Further, it also works effectively when a functional group contained in a known toner is contained in the solid plasticizer.

  Examples of the solid plasticizer include those that exhibit plastic ability under certain conditions in addition to the above-mentioned requirements. Examples include the following.

(1) The plastic ability is exhibited by dissolving in a diluent:
Part having an ethylene oxide group: Among polyethylene glycols, those having a peak molecular weight of 1,000 to 2,000 (2) Even if dissolved in a diluent, the plastic ability is not exhibited, but a small amount of liquid plasticizer described later is present. Parts that exhibit plastic ability Part having ethylene oxide group: Polyethylene glycol having a peak molecular weight of 2,000 to 10,000 (3) Although plastic ability is not exhibited even if dissolved in a diluent, some Those that exhibit plastic ability when heated (for example, about 50 ° C. to 100 ° C.) Part having an ethylene oxide group: Among polyethylene glycols, those having a peak molecular weight of 2,000 to 10,000 Polyoxyethylene monoalkyl Examples of ethers include polyoxyethylene monolauryl ether and polyoxyethylene. Such as mono cetyl ether, and the like.

  When the peak molecular weight of the polyethylene glycol exemplified in the above (1) is less than 1,000, the fixed image may be melted depending on the surrounding environment, and when it exceeds 2,000, the solid state is no longer in the normal temperature state. In a fixing liquid system that does not share the liquid plasticizer described later, sufficient plasticizing ability may not be exhibited. Under such technical significance, the peak molecular weight is preferably 1,000 to 2,000.

  When the peak molecular weight of the polyethylene glycol exemplified in the above (2) exceeds 10,000, it is clearly not in a solid state at room temperature, and thus a grain boundary may occur between toners to be fixed. From such a viewpoint, in the system of the fixing solution that does not share the liquid plasticizer, it is clarified that it is difficult to use when the peak molecular weight is 10,000 or more, and the fixing solution contains water. Is used, the peak molecular weight is 1,000 to 10,000.

  The heating temperature of the solid plasticizer exemplified in the above (3) is not particularly limited as long as the plastic ability can be exhibited, but is preferably 50 ° C to 100 ° C. If the heating temperature is less than 50 ° C., fixing may be insufficient, and if it exceeds 100 ° C., it is uneconomical in terms of energy consumption.

  There is no restriction | limiting in particular as content of the said solid plasticizer, Although it can select suitably according to the objective, It is preferable that it is 5-30 mass% with respect to the mass of a fixing solution. When the content is less than 5% by mass, fixing becomes difficult. When the content exceeds 30% by mass, the viscosity of the fixing solution and the foamy fixing solution increases, and in addition, poor foaming, It lacks stability as foam and causes quality problems.

-Liquid plasticizer-
The liquid plasticizer is not particularly limited as long as it is soluble in a diluent described later and exhibits a plastic ability under a certain condition. The toner may be softened by dissolving or swelling a part thereof, but may be one that exhibits plastic ability when combined with the solid plasticizer. Examples of liquid plasticizers include ester compounds in that they are excellent in solubility or swelling under certain conditions. Among these ester compounds, an aliphatic ester or a carbonate ester is more preferable from the viewpoint that the softening ability of the resin is excellent or the degree of foaming inhibition by the diluent described later is low.

From the viewpoint of safety to the human body, the liquid plasticizer preferably has an acute oral toxicity LD ₅₀ of more than 3 g / kg, more preferably 5 g / kg or more. As the liquid plasticizer, the aliphatic ester is particularly preferable because it is highly safe for the human body as frequently used as a cosmetic raw material.

  In addition, the toner is fixed to the recording medium by a device that is frequently used in a sealed environment, and the liquid plasticizer remains in the toner even after the toner is fixed to the recording medium. It is preferable that the fixing of the ink does not involve generation of a volatile organic compound (VOC) and an unpleasant odor. In this respect, it is preferable that the liquid plasticizer does not contain a volatile organic compound (VOC) and a substance that causes an unpleasant odor. The aliphatic ester is more preferable in that it has a high boiling point, low volatility, and no irritating odor compared to generally used organic solvents (toluene, xylene, methyl ethyl ketone, ethyl acetate, etc.).

  In addition, as a practical odor measurement scale that can measure odors in office environments with high accuracy, the odor index [10 × log (substance odor is felt by sensory measurement) The dilution factor of the substance until it disappears)] may be used as an indicator of odor. The odor index of the aliphatic ester contained in the liquid plasticizer is preferably 10 or less. In this case, an unpleasant odor is not felt in a normal office environment. Furthermore, it is preferable that not only the liquid plasticizer but also other liquids contained in the fixing solution have no unpleasant odor and irritating odor, as with the liquid plasticizer.

-Aliphatic ester-
The aliphatic ester is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include saturated aliphatic esters, aliphatic monocarboxylic acid esters, aliphatic dicarboxylic acid esters, and aliphatic dicarboxylic acid dialkoxys. It may be alkyl.

--Saturated aliphatic ester--
When the aliphatic ester is a saturated aliphatic ester, the storage stability (resistance to oxidation, hydrolysis, etc.) of the liquid plasticizer can be improved. Further, the saturated aliphatic ester has high safety to the human body, and many saturated aliphatic esters can dissolve or swell the resin contained in the toner in a short time such as within 1 second. Furthermore, saturated aliphatic esters can reduce the tackiness of the toner provided on the recording medium. This is presumably because the saturated aliphatic ester forms an oil film on the surface of the dissolved or swollen toner.

In the fixing solution according to the present invention, preferably, the general formula of the saturated aliphatic ester may be a compound represented by R ¹ COOR ² , wherein R ¹ is an alkyl having 11 to 14 carbon atoms. R ² is a linear or branched alkyl group having 1 to 6 carbon atoms. If the number of carbon atoms of R ¹ and R ² is less than the desired range, odor is generated, and if it is greater than the desired range, the resin softening ability is lowered. That is, the saturated aliphatic ester is a compound represented by the general formula R ¹ COOR ² , R ¹ is an alkyl group having 11 to 14 carbon atoms, and R ² is 1 to 6 carbon atoms. In the case of the following linear or branched alkyl group, the solubility or swelling property with respect to the resin contained in the toner can be improved. Moreover, it is preferable that the odor index of the compound represented by the general formula R ¹ COOR ² is 10 or less in that it does not have an unpleasant odor and an irritating odor.

-Aliphatic monocarboxylic acid ester-
Examples of the aliphatic monocarboxylic acid ester include ethyl laurate, hexyl laurate, ethyl tridecylate, isopropyl tridecylate, ethyl myristate, and isopropyl myristate. Many of these aliphatic monocarboxylic acid esters are soluble in oily solvents but not in water. Therefore, when an aliphatic monocarboxylic acid ester is used to form a fixing solution composed of an aqueous solvent, glycols may be contained in the fixing solution as a solubilizing agent described later, and the solution may be dissolved or in the form of a microemulsion.

-Aliphatic dicarboxylic acid ester-
The aliphatic ester may be an aliphatic dicarboxylic acid ester. When the aliphatic ester is an aliphatic dicarboxylic acid ester, the toner can be dissolved or swollen in a shorter time. For example, in high-speed printing of about 60 ppm, it is preferable that the time until the fixing liquid is applied to the unfixed toner on the recording medium and the toner is fixed on the recording medium is within 1 second. When the aliphatic ester is an aliphatic dicarboxylic acid ester, the time required for applying the fixing solution to the unfixed toner or the like on the recording medium and fixing the toner on the recording medium is within 0.1 seconds. It becomes possible to do. Furthermore, since the toner can be dissolved or swollen by adding a smaller amount of the liquid plasticizer, the content of the liquid plasticizer contained in the fixing liquid can be reduced.

In the fixing solution according to the present invention, preferably, the general formula of the aliphatic dicarboxylic acid ester is a compound represented by R ³ (COOR ⁴ ) ₂ , wherein R ³ is an alkylene group having 3 to 8 carbon atoms. And R ⁴ may be a linear or branched alkyl group having 3 to 5 carbon atoms. If the number of carbon atoms in R ³ and R ⁴ is less than the desired range, odor is generated, and if it is greater than the desired range, the resin softening ability decreases.

The aliphatic dicarboxylic acid ester is a compound represented by the general formula R ³ (COOR ⁴ ) ₂ , wherein R ³ is an alkylene group having 3 to 8 carbon atoms, and R ⁴ has 3 or more carbon atoms. In the case of a linear or branched alkyl group of 5 or less, the solubility or swelling property with respect to the toner can be improved. In addition, the odor index of the compound represented by the general formula R ³ (COOR ⁴ ) ₂ is preferably 10 or less from the viewpoint of having no unpleasant odor and irritating odor.

  Examples of the aliphatic dicarboxylic acid ester include 2-ethylhexyl succinate, dibutyl adipate, diisobutyl adipate, diisopropyl adipate, diisodecyl adipate, diethyl sebacate, and dibutyl sebacate. Many of these aliphatic dicarboxylic acid esters are soluble in oily solvents but not in water. For this reason, when an aliphatic dicarboxylic acid ester is used to form a fixing solution composed of an aqueous solvent, glycols may be contained in the fixing solution as a solubilizing agent described later, and the solution may be in the form of a solution or a microemulsion.

-Dialkoxyalkyl aliphatic dicarboxylate-
Furthermore, in the fixing solution according to the present invention, the aliphatic ester is preferably a dialkoxyalkyl aliphatic dicarboxylate. When the aliphatic ester is an aliphatic dicarboxylate dialkoxyalkyl, the fixing property of the toner to the recording medium can be improved.

In the liquid plasticizer contained in the fixing solution according to the present invention, the aliphatic dicarboxylic acid dialkoxyalkyl is a compound represented by the general formula R ⁵ (COOR ⁶ —O—R ⁷ ) ₂ , wherein R ⁵ is the number of carbon atoms. Is an alkylene group having 2 to 8 carbon atoms, R ⁶ is an alkylene group having 2 to 4 carbon atoms, and R ⁷ may be an alkyl group having 1 to 4 carbon atoms. If the number of carbon atoms of R ⁵ , R ⁶ and R ⁷ is less than the desired range, odor is generated, and if it is greater than the desired range, the resin softening ability is lowered.

The aliphatic dicarboxylic acid dialkoxyalkyl is a compound represented by the general formula R ⁵ (COOR ⁶ —O—R ⁷ ) ₂ , wherein R ⁵ is an alkylene group having 2 to 8 carbon atoms, and R ⁶ Is an alkylene group having 2 or more and 4 or less carbon atoms, and R ⁷ is an alkyl group having 1 or more and 4 or less carbon atoms, it is possible to improve the solubility or swelling of the resin contained in the toner. In addition, the odor index of the compound represented by the general formula R ⁵ (COOR ⁶ —O—R ⁷ ) ₂ is preferably 10 or less from the viewpoint of having no unpleasant odor and irritating odor.

Examples of the aliphatic dicarboxylic acid dialkoxyalkyl include diethoxyethyl succinate, dibutoxyethyl succinate, dimethoxyethyl adipate, diethoxyethyl adipate, dibutoxyethyl adipate, diethoxyethyl sebacate and the like. When these aliphatic dicarboxylic acid dialkoxyalkyls are used in an aqueous solvent, glycols are included in the fixing solution as a dissolution aid, if necessary, to form a solution or microemulsion.
Furthermore, as a similar structure of an aliphatic dicarboxylic acid dialkoxyalkyl, the compound represented by the general formula (5) has a high ratio in the molecule of the ether group, so that the solubility in water as a diluent is very high. The fixing solution becomes high and contains a high concentration liquid plasticizer.
^{R 8 (COO- (R 9 -O} ) n-R 10) 2 General Formula (5)
However, n in the general formula (5) is 1 or more and 3 or less, R ⁸ is an alkylene group having 2 to 8 carbon atoms, and R ⁹ is an alkylene group having 1 to 3 carbon atoms. , R ¹⁰ is an alkyl group having 1 to 4 carbon atoms.
Examples of the compound represented by the general formula (5) include diethoxyethoxyethyl succinate, diethoxyethoxyethyl adipate, dimethoxyethoxyethyl succinate, dimethoxymethoxypropyl succinate and the like.

-Carbonate ester-
Examples of the carbonate ester which is an example of the liquid plasticizer include cyclic esters such as ethylene carbonate and propylene carbonate (propylene carbonate), glycerol 1,2-carbonate, 4-methoxymethyl-1,3-dioxolan-2-one and the like. Is mentioned.

  Examples of ester compounds other than the above include citric acid esters such as triethyl citrate, acetyl triethyl citrate, tributyl citrate, and tributyl acetyl citrate; ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate And compounds obtained by esterifying glycols such as monoacetin; compounds obtained by esterifying glycerol such as monoacetin, diacetin, and triacetin.

  The content of the liquid plasticizer is preferably 0.5% by mass to 50% by mass and more preferably 5% by mass to 40% by mass with respect to the mass of the fixing solution. If the content is less than 0.5% by mass, the effect of dissolving or swelling the toner may be insufficient. If the content exceeds 50% by mass, the fluidity of the resin contained in the toner over a long period of time may be obtained. The fixing toner layer may have adhesiveness.

<Foaming agent>
The foaming agent contained in the fixing solution according to the present invention is not particularly limited as long as it can foam the fixing solution, and can achieve excellent foaming properties and foam stability. Examples of foaming agents include saturated or unsaturated fatty acid salts, monoalkyl sulfates, sulfonates such as alkyl polyoxyethylene sulfates, alkyl polyoxyethylene sulfates or alkylbenzene sulfonates, or monoalkyl phosphates. Anionic surfactants such as phosphates.

-Fatty acid salt-
Among the foaming agents, fatty acid salts are most excellent in foam stability and are most suitable as foaming agents for fixing solutions.

  The fatty acid salt is preferably a fatty acid sodium salt, a fatty acid potassium salt or a fatty acid amine salt, and more preferably a fatty acid amine salt. The method for producing these fatty acid salts is not particularly limited. For example, by heating water, adding a fatty acid, then adding triethanolamine, and heating the mixture with stirring for a certain period of time to cause a saponification reaction. It may be manufactured. At this time, by increasing the molar ratio of fatty acid to triethanolamine within the range of 1: 0.5 to 1: 0.9 and the fatty acid ratio, unreacted fatty acid remains after saponification, and the fixing solution Fatty acid and fatty acid amine salt can be mixed therein. The same is possible with sodium and potassium salts.

  The unsaturated fatty acid salt that can be used as the foaming agent is not particularly limited, but an unsaturated fatty acid salt having 18 carbon atoms and 1 to 3 double bonds is preferred. Specific examples include oleate, linoleate and linolenate. Since the reactivity is strong when the double bond is 4 or more, the stability of the fixing solution is poor. You may use the unsaturated fatty acid salt by these unsaturated saturated fatty acids individually by 1 type or in mixture of 2 or more types as a foaming agent. Further, the above saturated fatty acid salt and unsaturated fatty acid salt may be mixed and used as a foaming agent.

  The liquid plasticizer has a strong antifoaming effect, and as the concentration of the liquid plasticizer increases in the fixing solution, the foaming property and foam stability of the fixing solution deteriorates, so it is difficult to foam and the foam breaks immediately. In some cases, it is impossible to obtain a foam-like fixing solution having a low foam density.

  Therefore, in order to eliminate the deterioration of foaming properties when the concentration of the liquid plasticizer in the fixer is increased, various prototypes were made using the type and concentration of anionic surfactant as factors. By using a fatty acid salt having 12 to 18 carbon atoms as a foaming agent and further containing a fatty acid having 12 to 18 carbon atoms in the fixing solution, the foaming property of the fixing solution can be improved even when the concentration of the liquid plasticizer increases. Does not deteriorate. Thereby, a stable foamy fixing solution can be provided.

  Here, in the foaming agent contained in the fixing solution, the number of carbon atoms of the fatty acid salt is 12 to 18 in that the foaming property is superior to the case of simply foaming water. preferable. Specifically, laurate (12 carbon atoms), myristic acid salt (14 carbon atoms), pentadecyl acid (15 carbon atoms), palmitate (16 carbon atoms), margaric acid (17 carbon atoms), stearic acid And a salt (carbon number 18).

  The effect | action of the fatty acid used with the fatty acid salt used as a foaming agent and a liquid plasticizer is demonstrated. When an ester compound is used as the liquid plasticizer, the ester compound has an ester group in the chemical structure, and the fatty acid has a carbonyl group in the chemical structure. From this point, the ester group of the liquid plasticizer and the carbonyl group of the fatty acid show an electrical action in the fixing solution system, which causes an intermolecular bonding action, which is a characteristic of the fixing solution. It is thought to improve foamability and foam stability.

  In the fatty acid salt having 12 to 18 carbon atoms that can be used as the foaming agent, the smaller the number of carbons, the better the foaming property, but the foam stability is poor, and the higher the number of carbons, the foaming property is not so good. Excellent stability. Therefore, a single fatty acid salt may be used as the fatty acid salt, but it is more preferable to mix a plurality of fatty acid salts having 12 to 18 carbon atoms and having different carbon numbers. As a mixing ratio, it is preferable to contain the most myristate (carbon number 14) and to lower the ratio of laurate (carbon number 12) and stearate. More specific fatty acid salt ratios are 0: 6: 3: 1, 0: 4: 3: 1, 1: 5 by mass ratio of laurate: myristate: palmitate: stearate. : 3: 1, 1: 4: 4: 1, etc. are suitable.

  The content of the foaming agent is preferably 0.1% by mass to 20% by mass and more preferably 0.5% by mass to 10% by mass with respect to the mass of the fixing solution. When the content is less than 0.1% by mass, the foamability may be insufficient. When the content is more than 20% by mass, the viscosity of the fixing solution may be increased and the foamability may be reduced. There is.

  By containing a fatty acid having the same carbon number as the foaming agent fatty acid salt in the fixing solution, foamability and foam stability can be maintained even when the concentration of the liquid plasticizer increases. If the concentration of the liquid plasticizer is less than 10% by mass, there is no problem in foaming properties even if no fatty acid is contained. However, when the concentration of the liquid plasticizer is 10% by mass or more, particularly when the concentration of the liquid plasticizer is 30% by mass or more, the fatty acid salt hardly foams and the foamability may deteriorate. Even when the foamability is deteriorated, the foamability can be maintained by containing a fatty acid having the same carbon number as that of the fatty acid salt.

  However, if the content of the fatty acid is too large, the ratio of the fatty acid salt that is a foaming agent is lowered, and foamability may be deteriorated again. In such a case, the number of moles of the fatty acid salt may be equal to or greater than the number of moles of the fatty acid, and the ratio of the fatty acid to the fatty acid salt is 5: 5 to 1: 9. It is good also as a range.

  In addition to the combination of a fatty acid having the same carbon number and a fatty acid salt, for example, the fatty acid salt is amine myristate and the fatty acid is stearic acid, or the fatty acid salt is potassium palmitate and the fatty acid is stearic acid. Like a combination, the carbon number may be a combination of different fatty acid salts and fatty acids in the range of 12-18. By containing a fatty acid having a carbon number in the range of 12 to 18 in the fixing solution, even if a high concentration liquid plasticizer is contained, the foamability is not deteriorated, the foam stability is excellent, and the foaming is extremely low in density. Is possible.

  In addition, in order to prevent deterioration of foaming properties, other anionic surfactants (for example, alkyl ether sulfate (AES)) are used as foaming agents, and further contain a fatty acid having 12 to 18 carbon atoms. May be.

<Diluent>
The diluent contained in the fixing solution according to the present invention is not particularly limited as long as it contains water. For example, water, an aqueous solvent obtained by adding an alcohol or the like to water, and the like are preferable. As water, for example, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used.

  When an aqueous solvent is used as a diluent, a surfactant may be added. In particular, the surface tension of the fixing solution is preferably 20 mN / m to 30 mN / m. Examples of the alcohols include unitary alcohols such as cetanol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, diethylene glycol, and the like in terms of enhancing the stability of bubbles in the foam-like fixing solution and making it difficult to break bubbles. Polyhydric alcohols such as propylene glycol, tripropylene glycol, 1,3-butylene glycol and glycerin are preferred. By containing these unit prices or polyhydric alcohols, it is effective in preventing curling of media such as paper.

  The diluent preferably contains an oil component to form an O / W emulsion or a W / O emulsion for the purpose of improving permeability and preventing curling of a medium such as paper. As this oil component, various known materials can be used. In the case of a diluent containing an oil component, an emulsion may be formed by using a dispersant, and various known materials can be used as the dispersant used to form this emulsion, but sorbitan monooleate And sorbitan fatty acid esters such as sorbitan monosterate and sorbitan sesquiolate, and sucrose esters such as sucrose laurate and sucrose stearate are preferred.

  The method for dispersing the fixing solution in the form of an emulsion using the dispersant is not particularly limited, and various known methods can be used. For example, mechanical stirring such as a homomixer or a homogenizer using rotating blades can be used. And means for applying vibration such as an ultrasonic homogenizer. Among these, a method of applying a strong shear stress to the plasticizer in the fixing solution is preferable.

<Recording medium>
The recording medium is not particularly limited as long as it can fix toner. In particular, the recording medium is preferably a medium having permeability to the fixing solution, and when the medium substrate does not have liquid permeability, a medium having a liquid-permeable layer on the substrate is preferable. There is no restriction | limiting in particular as a form of a recording medium, The solid thing which has a plane and a curved surface other than a sheet form may be sufficient. For example, it may be one in which transparent toner is uniformly fixed on a medium such as paper and the paper surface is protected (so-called varnish coat). The material of the recording medium is not particularly limited and can be appropriately selected according to the purpose. For example, a plastic film such as a sheet for OHP having a general fiber constituting a paper, a cloth, a liquid permeable layer, or the like. , Metals, resins, and ceramics.

<Other ingredients>
<< Solution aid >>
The fixing solution according to the present invention may contain a dissolution aid for the purpose of dissolving the liquid plasticizer in the fixing solution. The dissolution aid is not particularly limited as long as it can dissolve the liquid plasticizer, and examples thereof include polyhydric alcohols. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, and glycerin. Among these, propylene glycol and dipropylene glycol are particularly preferable in that the liquid plasticizer can be dissolved even at a high concentration and the foamability of the foaming agent is not deteriorated.
The content of the polyhydric alcohol is preferably in the range of 1% by mass to 30% by mass with respect to the mass of the fixing solution. If the content exceeds 30% by mass, the foaming property is rather deteriorated, which is not suitable. If the content is less than 1% by mass, when the concentration of the liquid plasticizer in the fixing solution is increased, the liquid plasticizer is added to water as a diluted solution. It may be difficult to dissolve.

<< Foaming agent >>
The fixing solution according to the present invention is foamed and used as a later-described foam fixing solution for fixing toner. When the foam fixing solution is pressed into the toner layer at the coating contact nip portion, When the bubble breaks, the penetration is inhibited. Therefore, the fixing solution according to the present invention may further include a foaming agent for the purpose of suppressing such a phenomenon and improving foam stability. The foaming agent is not particularly limited, but is preferably a fatty acid alkanolamide, and more preferably a fatty acid alkanolamide (1: 1) type in terms of foam stability. The content of the foam increasing agent is preferably 0.01% by mass to 3% by mass with respect to the mass of the fixing solution.

(Fixing method)
The fixing method of the present invention includes a foamy fixing solution generation step, a film thickness adjustment step, and a foamy fixing solution application step, and further includes other steps as necessary.
The fixing device used in the present invention has a foam-like fixing liquid generating means, a foam-like fixing liquid applying means, and a film thickness adjusting means, and further has other means as necessary.

  The fixing method of the present invention can be preferably carried out by the fixing device used in the present invention, the foamy fixer generating step can be performed by a foamy fixer generating means, and the film thickness adjusting step It can be performed by the adjusting means, the foam-like fixing solution applying step can be performed by the foam-like fixing solution applying unit, and the other steps can be performed by the other means.

<Foam Fixer Generation Step and Foam Fixer Generation Unit>
The foamy fixing solution generation step is a step of generating a foamy fixing solution by foaming the fixing solution, and is performed by a foaming fixing solution generating means.

  As shown in FIG. 1, by using the foam-like fixing liquid generating means as the foam-like fixing liquid 114 composed of foam, the bulk density of the fixing liquid can be lowered and the fixing liquid layer on the coating roller 111 can be formed. Since the thickness can be increased and the influence of the surface tension of the fixing liquid can be suppressed, the foamy fixing liquid 114 is uniformly applied to the toner layer on the recording medium 112 while preventing the resin fine particles from being offset to the application roller 111. It can be attached.

  FIG. 2 is a schematic diagram showing a layer configuration example of the foamy fixing solution at the time of application. The liquid 121 shown in FIG. 2 contains a plasticizer and has a foam-like configuration in which bubbles 122 are contained in the liquid. Thus, the bulk density of the fixing liquid 120 can be made extremely low by containing a large amount of the bubbles 122. With this configuration, when the fixing solution is applied, even if it is applied in a large volume state, the bulk density is low and the application weight is small. Can be very low. In addition, the bubble shape in this invention shows the state which the bubble disperse | distributed in the liquid and the liquid was tinged with compressibility.

  There are no particular limitations on the foam fixing solution generation step and the foam fixing solution generation means as long as the fixing solution according to the present invention can be foamed to generate a foam fixing solution. One mode thereof will be described with reference to FIG.

  FIG. 3 is a schematic view showing the configuration of the foamy fixing solution generating means in the fixing device according to the present invention. 3 includes a fixing liquid container 131 for storing the liquid fixing liquid 132 such as the fixing liquid according to the present invention, a liquid transport pipe 134 for transporting the liquid fixing liquid 132, and a liquid. A transport pump 133 that obtains driving for transport, a gas / liquid mixing unit 135 that mixes gas and liquid, and a foam generation unit 138 that foams the liquid fixer 132 to obtain a desired foamy fixer. Have.

  The liquid fixing liquid 132 stored in the fixing liquid container 131 is transported through the liquid transport pipe 134 by the driving force of the transport pump 133 and is sent to the gas / liquid mixing unit 135. The transport pump is not particularly limited as long as it can transport the liquid fixing solution, and can be appropriately selected according to the purpose. For example, a gear pump, a bellows pump, and the like can be mentioned, and a tube pump is preferable. If there is a vibration mechanism or a rotation mechanism such as a gear pump, the fixer bubbles in the pump, and the fixer may be compressible, resulting in a decrease in conveying ability. In addition, the above-mentioned mechanical parts or the like may contaminate the fixer or conversely deteriorate the mechanical parts. On the other hand, since the tube pump is a mechanism that pushes out the liquid in the tube while deforming the tube, the only member in contact with the fixing liquid is the tube. By using a member that has liquid resistance to the fixing liquid, No contamination or deterioration of pump system parts. In addition, since the tube is only deformed, the liquid does not foam, and the conveyance capacity can be prevented from being lowered.

  The gas / liquid mixing unit 135 is provided with an air port 136, a negative pressure is generated in the air port 136 along with the flow of the liquid, and the gas is introduced from the air port 136 into the gas / liquid mixing unit 135. Are mixed. Furthermore, by passing through the microporous sheet 137, large bubbles with uniform bubble diameters can be generated. The pore diameter is preferably 30 μm to 100 μm. The porous member is not limited to the microporous sheet 137 in FIG. 3, and may be a porous member having a continuous foam structure, and may be a sintered ceramic plate, a nonwoven fabric, or a foamed resin sheet having a pore diameter of 30 μm to 100 μm. As another method for generating large bubbles, the liquid fixer supplied from the above-described transport pump and the air from the air port are stirred with a blade-like stirrer, and large bubbles are generated while bubbles are involved in the liquid. A configuration in which a large bubble is generated by bubbling the liquid fixing solution supplied from the above-described transport pump with an air supply pump or the like is also preferable.

  Next, the liquid fixing solution 132 mixed with air is sent to the foam generation unit 138 that obtains a desired foam-like fixing solution. In the foam generation unit 138, a shearing force is applied to the liquid fixing solution 132 mixed with air, and large bubbles are divided into two or more bubbles. The configuration of the bubble generation unit 138 is not particularly limited as long as it can be performed in this way, but the inner cylinder can be rotated with a closed double cylinder, which is larger than a part of the outer cylinder. A configuration may be employed in which a foam-like fixer is supplied and a shear force is received by the rotating cylinder while passing through a gap between the inner rotating cylinder and the outer cylinder (this is a flow path). Due to this shearing force, the large bubbles are changed into minute bubbles, and a foam-like fixing liquid having a desired minute bubble diameter can be obtained from the outlet of the bubbles provided in the outer cylinder. In addition, a spiral groove may be provided in the inner cylinder to increase the liquid transport capability in the cylinder.

  The fixer only needs to be foamed when applied to a toner layer on a recording medium such as paper, and need not be foamed in the fixer container. In the fixing liquid container, it is preferable that the liquid is a liquid not containing bubbles, and a means for forming bubbles in the liquid conveyance path until the liquid is supplied from the container or until the liquid is supplied to the toner layer is preferable. This is because the fixing liquid container is a liquid, and the foamed structure after the liquid is taken out from the container has a great advantage that the container can be downsized.

  The fixer is foamed, and the thickness of the foam-like fixer layer composed of the foamed fixer is foam-like as described later on the entire recording medium surface according to the thickness of the toner layer to be fixed. Adjustment is made in terms of the fixing solution applying means. For example, when a toner is composed and color images and black and white characters are mixed on the recording medium, if the entire surface of the recording medium is applied with a foam-type fixing liquid layer having the same thickness, a fixing failure is not obtained with a thick toner layer such as a color photographic image. In some cases, the image may be missing, or the black-and-white character portion may become sticky and the printed matter may stick to each other. The cause of the problem will be described in detail below.

  In general, in the case of large bubbles of about 0.5 mm to 1 mm, bubbles can be generated relatively easily by simple stirring, etc., and the generation of large bubbles takes less than a few seconds (not longer than 0.1 seconds). can do. Therefore, paying attention to the fact that bubbles that are larger than the desired bubble diameter and that can be visually observed can be easily and quickly obtained, and from about 5 μm to 50 μm quickly from the large bubbles. As a result of diligently studying the method of generating microbubbles, dividing the large foam by applying shear force to the large foam is extremely quick compared to the method of generating microbubbles from the liquid state as described above. It has been found that microbubbles of a desired size can be generated. In this respect, the configuration of the foamy fixing solution generating unit 130 as described above is a preferable mode for realizing this.

  In this way, by combining a large bubble generating part that changes the liquid fixing solution into a liquid having a large bubble diameter and a fine bubble generating part that applies a shearing force to the large bubbles to generate minute bubbles, It is possible to generate a foamy fixing solution having a fine bubble diameter of 5 to 50 μm in a very short time.

  In particular, when the toner has a volume average particle diameter of about 5 μm to 10 μm, the foam of the foam-like fixing liquid 114 can be applied to the toner layer 113 without disturbing the toner layer 113 on the recording medium 112. The diameter range is preferably 5 μm to 50 μm. As shown in FIG. 2, the foam-like fixing liquid 120 composed of the bubbles 122 is composed of a liquid 121 that separates each of the bubbles 122.

<Film thickness adjusting step and film thickness adjusting means>
The film thickness adjusting step in the fixing method of the present invention is a step of forming a foamy fixing solution in a desired thickness on the contact surface of the foaming fixing solution applying unit, and is performed by the film thickness adjusting unit.

  The film thickness adjusting means is not particularly limited as long as the foam fixing solution can be formed to a desired thickness on the contact surface of the foam fixing solution applying means, and can be appropriately selected according to the purpose. Examples include a film thickness adjusting blade and a combination of a blade and a coating roller. Note that aspects of the film thickness adjusting step and the film thickness adjusting means will be described later.

<Foam Fixer Application Step and Foam Fixer Application Means>
The foamy fixing solution application step in the fixing method of the present invention is a step of applying a foamy fixing solution formed in a desired thickness to the toner layer on the medium, and is carried out by a foamy fixing solution application unit.

  4A and 4B are schematic configuration diagrams showing an example of a film thickness adjusting unit and a foamy fixing solution applying unit in the fixing device according to the present invention. The fixing device 140 of the present invention shown in FIG. 4A is a coating for applying the desired fine bubble foam fixing solution generated by the foam fixing solution generator 130 described above to the toner layer constituting the toner or the like. The film thickness of the desired fine bubble foam fixing solution on the roller 141 and the application roller surface is adjusted according to the thickness of the unfixed toner layer on the recording medium, and the optimum film thickness of the foam fixing solution is adjusted. And a pressure roller 143 at a position facing the coating roller 141.

  A recording medium having unfixed toner on the surface passes through a nip portion composed of an application roller 141 and a pressure roller 143. On the other hand, the foamed fixing solution generated by the foamed fixing solution generating means 130 is adjusted in film thickness by the film thickness adjusting blade 142 and disposed on the application roller 141 as a foamed fixing solution layer having a desired thickness. The foam-like fixing liquid layer formed on the application roller 141 in this manner is applied onto the unfixed toner in synchronization with the passage of the recording medium having unfixed toner through the nip portion.

  FIG. 4B is an enlarged schematic view of the application roller 141 and the film thickness adjusting blade 142, and a layer of foam-like fixing liquid is formed on the recording medium on the application roller 141 constituting the foam-like fixing liquid application unit. It is formed through a film thickness adjusting blade 142 which is a film thickness adjusting means according to the thickness of the upper unfixed toner layer. With the film thickness adjusting blade 142 as the film thickness adjusting means, the foam fixing solution has an unfixed toner layer corresponding to the bubble size, foam viscosity, coating pressure and unfixed toner layer thickness. The film thickness of the fixing solution layer is optimized with respect to the permeation time. As described above, the desired fine foam foam fixing solution is composed of a large foam generating section that generates large foam and a small foam generating section that separates large foam with a shearing force to generate micro foam. It is generated by the foamed fixing liquid generating means 130 that is configured to be included, and is dropped from the liquid supply port between the coating roller 141 and the film thickness adjusting blade 142 that is the film thickness adjusting means.

  As shown in FIGS. 5A and 5B, the film thickness of the foam-like fixing solution on the application roller is adjusted using a film thickness adjusting blade 142 provided with a gap as shown in FIG. 5A. When the thickness is made thinner, the gap may be narrowed, and when the film thickness is made thicker as shown in FIG. 5B, the gap may be made wider. The gap is adjusted by using a drivable rotary shaft at the end of the film thickness adjusting blade 142, the thickness of the toner layer, the environmental temperature, etc., as well as the bubble size, the bubble viscosity and the coating application. The optimum film thickness for adjusting the permeation time of the foamy fixing solution in the unfixed toner layer according to the pressure and the layer thickness of the unfixed toner may be adjusted.

  The shape, structure, size and material of the application roller constituting the foam-like fixing liquid application means are not particularly limited as long as the foam-type fixing liquid can be applied, but have a curved surface part at least on a part of its surface. It is preferable.

  The blade for adjusting film thickness may be a wire bar in addition to the blade for adjusting film thickness shown in FIGS. 5A and 5B. The thickness of the foam fixing solution on the application roller is adjusted by the wire bar. As described above, the foam fixing solution is a fine foam generating unit that generates large bubbles and a minute foam that separates the large bubbles with shearing force. It is produced | generated by the foam-like fixing liquid production | generation means which has a foam production | generation part, and is dripped between a film | membrane adjustment wire bar and a coating roller from a liquid supply port. By using the wire bar as the film thickness adjusting means, the uniformity of the foam-like fixing liquid film in the axial direction of the coating roller surface is improved as compared with the blade.

The bulk density of the foamy fixing ^{solution, 0.01g / cm 3 ~0.1g / cm} 3 in the range of about preferably. Furthermore, in order to prevent the occurrence of residual liquid feeling on the medium surface when the fixing solution applied is ^preferably from ^{0.01g / cm 3 ~0.02g / cm 3} , 0.02g / cm 3 or less is more preferable. This is because, as in the application roller 141 of FIGS. 4A and 4B, the foam film of the fixing solution on the surface of the contact applying means is required to be equal to or greater than the thickness of the fine particle layer on the recording medium (the gap between the fine particle layers is In general, the thickness of the foam film is preferably 50 μm to 80 μm. On the other hand, in order not to cause a residual liquid feeling (wet feeling) when the fixing liquid adheres to the recording medium surface, the amount of fixing liquid attached is preferably 0.1 mg / cm ² or less per unit area of the recording medium. . Therefore, as the bulk density of the ^foam, preferably in the range of ^{0.0125g / cm 3 ~0.02g / cm 3} , a density of 0.02 g / cm ³ or less of the foam is more preferable.

  FIG. 6 is a schematic configuration diagram showing the configuration of the fixing device according to the embodiment of the present invention. In the fixing device 140 of the embodiment shown in FIG. 6, the pressure roller 143 may be configured using an elastic porous body (hereinafter also referred to as a sponge material) as an elastic layer. It is necessary to take a timing of the nip time so that the application roller and the toner layer are peeled off after the foamy fixing solution penetrates the toner layer and reaches the medium such as paper. In this respect, the pressure roller 43 made of a sponge material is preferable because it ensures a nip time in the range of 50 milliseconds to 300 milliseconds and can be greatly deformed with a weak pressure.

  The nip time is calculated by nip time = nip width / paper conveyance speed. The paper transport speed can be obtained from design data of the paper transport drive mechanism. For the nip width, a colored paint that does not dry is applied thinly on the entire surface of the application roller, and the recording medium is sandwiched between the application roller 141 and the pressure roller 143 that faces the recording medium (the rollers are not rotated) to color the recording medium. It can be determined by applying paint and measuring the length in the paper conveyance direction at the colored portion (usually colored in a rectangular shape) as the nip width.

  By adjusting the nip width according to the conveyance speed of the recording medium, the nip time needs to be equal to or longer than the toner layer permeation time of the foamy fixing solution. In the example shown in FIG. 6, the pressure roller 143 is made of a sponge material with an elastic layer, so that the distance between the axes of the application roller 141 and the pressure roller 143 is changed according to the conveyance speed of the recording medium, and the nip width is increased. It becomes easy to change. Elastic rubber may be used as the material of the pressure roller 143 instead of the sponge, but the sponge can be deformed with a force weaker than that of the elastic rubber, so that the pressure applied to the application roller 141 is not excessively increased. A long nip width can be secured.

  Note that a plasticizer is contained in the fixing liquid, and if the fixing liquid should adhere to a pressure roller formed of a sponge material, there is a possibility that problems such as softening of the sponge material may occur. Therefore, the resin material of the sponge material is preferably a material that does not soften or swell with respect to the liquid plasticizer. Further, the pressure roller using a sponge material may be configured to be covered with a flexible film. Even if the sponge material is a material that deteriorates with a liquid plasticizer, the sponge roller can be prevented from being deteriorated by covering with a flexible film that does not soften or swell with the liquid plasticizer. There is no restriction | limiting in particular as a sponge material, For example, the porous body of resin, such as polyethylene, a polypropylene, polyamide, is mentioned. Moreover, as long as it has flexibility, there is no restriction | limiting in particular as a flexible film which covers sponge, For example, a polyethylene terephthalate, polyethylene, a polypropylene, a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA) is mentioned, for example. It is done.

  In FIG. 6, when the application roller 141 and the pressure roller 143 using a sponge material are always in contact, the foamy fixing liquid on the application roller 141 is applied to the pressure roller 143 when the recording medium is not conveyed. There is a risk of adhering to and soiling. In order to prevent this, a paper leading edge detection unit (not shown) is provided upstream in the recording medium conveyance direction as viewed from the application roller 141, and the foam-like fixing liquid is applied only from the leading edge of the recording medium to the rear according to the leading edge detection signal. It is preferable to form the foam-like fixing liquid on the application roller 141 at the timing of application.

  In the fixing device 140 shown in FIG. 6, the application roller 141 and the pressure roller 143 using the sponge material are separated from each other during standby, and the leading end of the recording medium is detected only during application by a drive mechanism (not shown). It is also preferable that the application roller 141 and the pressure roller 143 using a sponge material are brought into contact with each other according to the means. The fixing device 140 shown in FIG. 6 also detects the trailing edge of the recording medium, and is configured to separate the application roller 141 and the pressure roller 143 using a sponge material in accordance with the trailing edge detection signal of the recording medium. It is also preferable to do.

  FIG. 7 is a schematic configuration diagram showing another configuration of the fixing device according to the embodiment of the present invention. The fixing device 140 according to the embodiment shown in FIG. 7 uses a pressure belt 144 instead of the pressure roller 143 shown in FIG. A liquid produced by a foam-like fixing liquid producing means 130 comprising a large foam producing part that produces large foams and a fine foam producing part that separates large foams with shearing force to produce fine foams. A foam-like fixing solution having a desired bubble diameter is supplied from a supply port to a supply port of a film thickness adjusting blade 142 which is a film thickness adjusting unit using a tube or the like. Then, by adjusting the gap between the film thickness adjusting blade 142 of the film thickness adjusting means and the application roller 141 to adjust the layer thickness of the foam-like fixing solution on the application roller 141, the optimum film thickness of the foam-like fixing solution is adjusted. Make adjustments. As a material of the pressure belt 144, for example, a member such as a seamless nickel belt, a seamless PET file, or the like coated with a releasable fluororesin such as PFA may be used.

  Thus, in the configuration using the belt, the nip width can be easily widened. Therefore, the configuration using the belt is not limited to FIG. 7, and a configuration in which the application roller is a belt and the pressing unit is not a belt but a roller is preferable. Further, by using at least one of the application side and the pressure side as a belt, the nip width can be easily widened, and an excessive force that causes wrinkles on the paper is not applied. Further, when the nip time and the paper transport speed are the same, the paper transport speed can be increased and high-speed fixing can be performed.

  In addition, the toner fixing device may include a pair of smoothing rollers (hard rollers) that pressurize at least a part of the softened or swollen toner after supplying the fixing liquid of the present invention to the toner. By pressurizing the above softened or swollen toner with a pair of smoothing rollers (hard rollers), the surface of the softened or swollen toner layer can be smoothed to give the toner gloss. Furthermore, by fixing the softened or swollen toner into the recording medium, the fixing property of the toner to the recording medium can be improved.

<Other processes and other means>
<< Heating process and heating means >>
The fixing method of the present invention and the fixing device according to the present invention may further include a heating step and a heating means for heating the toner layer to which the foamy fixing solution is applied. The heating temperature in the heating step and the heating means is not particularly limited as long as sufficient fixing characteristics can be obtained, but for example, 50 ° C to 100 ° C is preferable. If the heating temperature is less than 50 ° C., fixing may be insufficient, and if it exceeds 100 ° C., it is uneconomical in terms of energy consumption.

  As a form of the heating means, a roller or the like may be appropriately selected as long as the above-described aspect can be implemented. When the heating means is constituted by a roller, for example, as shown in FIG. 8, it is constituted by a pressure roller 146 and a pressure roller 148, and a heating medium such as an infrared heater 147 is applied to the roller in contact with the fixing object. It may be provided.

The image forming method of the present invention uses the fixing method of the present invention, and the image forming apparatus of the present invention uses a fixing device that embodies the fixing method of the present invention.
The image forming method of the present invention includes a charging step for uniformly charging the surface of the latent image carrier, an exposure step for exposing the surface of the charged latent image carrier based on image data, and writing an electrostatic latent image, A developer layer having a predetermined layer thickness is formed on the developer carrier by a developer layer regulating member, and the electrostatic latent image formed on the surface of the latent image carrier is developed through the developer layer to be visualized. An electrostatic latent image forming step comprising: a developing step, a transfer step for transferring a visible image on the surface of the latent image carrier to a transfer target, and a fixing step for fixing the visible image on the transfer target. And at least a development process, a transfer process, and a fixing process, and further include other processes appropriately selected as necessary, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like. The fixing step is performed by the fixing method of the present invention.

The image forming apparatus of the present invention includes a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier that is exposed based on image data. Exposure means for writing an electrostatic latent image, developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize it, and a visible image on the surface of the latent image carrier. The image forming apparatus includes at least a transfer unit that transfers to a transfer body and a fixing unit that fixes a visible image on the transfer body. Further, other units appropriately selected as necessary, for example, a charge eliminating unit and a cleaning unit recycling means, it has a control means or the like, the toner has a BET specific surface area of 2.0m ² /g~8.0m ² / g.

The electrostatic latent image can be formed, for example, by uniformly charging the surface of the latent image carrier with a charging unit and then exposing the surface of the latent image carrier imagewise with an exposure unit.
In the formation of a visible image by the development, a toner layer is formed on a developing roller as a developer carrying member, and the toner layer on the developing roller is conveyed so as to be in contact with a photosensitive drum as a latent image carrying member. Thus, the electrostatic latent image on the photosensitive drum is developed. The toner is stirred by the stirring means and mechanically supplied to the developer supply member. The toner supplied from the developer supply member and deposited on the developer carrier is formed into a uniform thin layer by passing through a developer layer regulating member provided to contact the surface of the developer carrier. Furthermore, it is charged. The electrostatic latent image formed on the latent image carrier is developed by attaching the toner charged by the developing means in the developing region to become a toner image.

The transfer of the visible image can be performed, for example, by charging the latent image carrier (photoconductor) using a transfer charger, and can be performed by the transfer unit.
The transferred visible image is fixed by using a fixing device to transfer the visible image transferred to the recording medium, and may be performed each time the toner of each color is transferred to the recording medium. On the other hand, it may be carried out simultaneously at the same time in a state of being laminated.
There is no restriction | limiting in particular as said fixing device, According to the objective, it can select suitably.

Next, the basic configuration of the image forming apparatus (printer) according to the embodiment of the present invention will be further described with reference to FIGS.
FIG. 9 is a schematic diagram showing the configuration of the image forming apparatus according to the embodiment of the present invention. Here, an embodiment applied to an electrophotographic image forming apparatus will be described. The image forming apparatus includes yellow (hereinafter referred to as “Y”), cyan (hereinafter referred to as “C”), magenta (hereinafter referred to as “M”), black (hereinafter referred to as “K”). The color image is formed from the four color toners.

First, a basic configuration of an image forming apparatus (a “tandem type image forming apparatus”) that includes a plurality of latent image carriers and parallels the plurality of latent image carriers in the moving direction of the surface moving member will be described.
This image forming apparatus includes four photosensitive members 1Y, 1C, 1M, and 1K as latent image carriers. Although a drum-shaped photoconductor is taken as an example here, a belt-shaped photoconductor can also be adopted. Each of the photoconductors 1Y, 1C, 1M, and 1K is rotationally driven in the direction of the arrow in FIG. 9 while contacting the intermediate transfer belt 10 that is a surface moving member. Each of the photoconductors 1Y, 1C, 1M, and 1K is rotationally driven in the direction of the arrow in FIG. Each of the photoreceptors 1Y, 1C, 1M, and 1K is obtained by forming a photosensitive layer on a relatively thin cylindrical conductive substrate and further forming a protective layer on the photosensitive layer. An intermediate layer may be provided between the protective layer.

  FIG. 10 is a schematic diagram showing a configuration of the image forming unit 2 in which the photoconductor is disposed. Since the configuration around each of the photoreceptors 1Y, 1C, 1M, and 1K in the image forming units 2Y, 2C, 2M, and 2K is the same, only one image forming unit 2 is illustrated, and a code Y for color coding is shown. , C, M, and K are omitted. Around the photosensitive member 1, along the surface movement direction, a charging device 3 as a charging unit, a developing device 5 as a developing unit, and a toner image on the photosensitive member 1 are transferred to a recording medium or an intermediate transfer member 10. A transfer device 6 as a transfer unit and a cleaning device 7 for removing untransferred toner on the photoreceptor 1 are arranged in this order. Between the charging device 3 and the developing device 5, light is emitted from an exposure device 4 as an exposure unit that performs exposure based on image data on the surface of the charged photoconductor 1 and writes an electrostatic latent image. Space is secured so that it can pass through.

  The charging device 3 charges the surface of the photoreceptor 1 to a negative polarity. The charging device 3 according to the present embodiment includes a charging roller as a charging member that performs charging processing by a so-called contact / proximity charging method. In other words, the charging device 3 charges the surface of the photosensitive member 1 by bringing the charging roller into contact with or close to the surface of the photosensitive member 1 and applying a negative bias to the charging roller. A DC charging bias is applied to the charging roller such that the surface potential of the photoreceptor 1 is −500V.

  Note that a charging bias in which an AC bias is superimposed on a DC bias can also be used. The charging device 3 may be provided with a cleaning brush for cleaning the surface of the charging roller. As the charging device 3, a thin film may be wound around both end portions in the axial direction on the circumferential surface of the charging roller and installed so as to contact the surface of the photoreceptor 1. In this configuration, the surface of the charging roller and the surface of the photoreceptor 1 are extremely close to each other with a distance corresponding to the thickness of the film. Therefore, a discharge is generated between the surface of the charging roller and the surface of the photosensitive member 1 by the charging bias applied to the charging roller, and the surface of the photosensitive member 1 is charged by the discharge.

  An electrostatic latent image corresponding to each color is formed on the surface of the photoreceptor 1 charged in this manner by exposure by the exposure device 4. The exposure device 4 writes an electrostatic latent image corresponding to each color on the photoreceptor 1 based on image information corresponding to each color. In addition, although the exposure apparatus 4 of this embodiment is a laser system, the other system which consists of an LED array and an imaging means can also be employ | adopted.

  The toner replenished into the developing device 5 from the toner bottles 31Y, 31C, 31M, and 31K is conveyed by the supply roller 5b and carried on the developing roller 5a. The developing roller 5 a is conveyed to a developing area facing the photoreceptor 1. Here, the developing roller 5 a moves in the same direction at a linear velocity faster than the surface of the photosensitive member 1 in a region facing the photosensitive member 1 (hereinafter referred to as “developing region”). Then, the toner on the developing roller 5 a supplies the toner to the surface of the photosensitive member 1 while rubbing the surface of the photosensitive member 1. At this time, a developing bias of −300 V is applied to the developing roller 5a from a power source (not shown), thereby forming a developing electric field in the developing region. Then, between the electrostatic latent image on the photoreceptor 1 and the developing roller 5a, an electrostatic force directed toward the electrostatic latent image side acts on the toner on the developing roller 5a. As a result, the toner on the developing roller 5 a adheres to the electrostatic latent image on the photoreceptor 1. By this adhesion, the electrostatic latent image on the photoreceptor 1 is developed into a corresponding color toner image.

  The intermediate transfer belt 10 in the transfer device 6 is stretched around three support rollers 11, 12, and 13 and is configured to endlessly move in the direction of the arrow in FIG. 9. On the intermediate transfer belt 10, toner images on the photoreceptors 1Y, 1C, 1M, and 1K are transferred so as to overlap each other by an electrostatic transfer method. Although there is a configuration using a transfer charger in the electrostatic transfer system, a configuration using a transfer roller 14 that generates less transfer dust is adopted here. Specifically, primary transfer rollers 14Y, 14C, 14M, and 14K as transfer devices 6 are disposed on the back surface of the portion of the intermediate transfer belt 10 that contacts the photoreceptors 1Y, 1C, 1M, and 1K, respectively. Here, a primary transfer nip portion is formed by the portions of the intermediate transfer belt 10 pressed by the primary transfer rollers 14Y, 14C, 14M, and 14K and the photoreceptors 1Y, 1C, 1M, and 1K. When transferring the toner images on the photoreceptors 1Y, 1C, 1M, and 1K onto the intermediate transfer belt 10, a positive bias is applied to each primary transfer roller. As a result, a transfer electric field is formed in each primary transfer nip portion, and the toner images on the photoreceptors 1Y, 1C, 1M, and 1K are electrostatically attached to the intermediate transfer belt 10 and transferred.

  A belt cleaning device 115 for removing toner remaining on the surface of the intermediate transfer belt 10 is provided around the intermediate transfer belt 10. The belt cleaning device 115 is configured to collect unnecessary toner adhering to the surface of the intermediate transfer belt 10 with a fur brush and a cleaning blade. The collected unnecessary toner is transported from the belt cleaning device 115 to a waste toner tank (not shown) by a transport means (not shown).

  Further, a secondary transfer roller 16 is disposed in contact with the portion of the intermediate transfer belt 10 stretched around the support roller 13. A secondary transfer nip portion is formed between the intermediate transfer belt 10 and the secondary transfer roller 16, and transfer paper as a recording member is fed into this portion at a predetermined timing. This transfer paper is accommodated in a paper feed cassette 20 on the lower side of the exposure apparatus 4 in the drawing, and is conveyed to the secondary transfer nip portion by a paper feed roller 21, a registration roller pair 22, and the like. Then, the toner images superimposed on the intermediate transfer belt 10 are collectively transferred onto the transfer paper at the secondary transfer nip portion. At the time of the secondary transfer, a positive bias is applied to the secondary transfer roller 16, and the toner image on the intermediate transfer belt 10 is transferred onto the transfer paper by a transfer electric field formed thereby.

  Fixing is performed on the downstream side of the secondary transfer nip portion in the conveyance direction of the transfer paper by a fixing device that controls the film thickness of the foam-like fixing liquid based on image information from an exposure device (not shown). That is, for the unfixed toner image transferred to the recording member, the film thickness of the foam-like fixing liquid layer is controlled based on image information from an exposure device (not shown) such as a color image or a black solid image. A foam-like fixing solution supplied from a toner fixing device is applied, and an unfixed toner image is formed by a plasticizer that dissolves or swells at least a part of the resin contained in the toner contained in the foam-like fixing solution. And fixing to the recording member. As a result, the toner image placed on the transfer paper is fixed on the transfer paper. Then, the fixed transfer paper is discharged by a paper discharge roller 24 onto a paper discharge tray on the upper surface of the apparatus.

-Fixing method and fixing device by spray method-
[Fixing method and fixing device]
FIG. 11 shows a main configuration of an image forming apparatus such as a copying machine, a printer, a facsimile, or a complex machine thereof. The illustrated one is an electrophotographic tandem color image forming apparatus that directly transfers a toner image on an image carrier onto a recording material sheet without using an intermediate transfer member. It is.

  Reference numeral 10 in FIG. 11 denotes an endless belt-like transport belt. In the illustrated example, the conveyor belt 10 is provided so as to be able to rotate around the driving roller 12 and the driven roller 13 in a counterclockwise direction in the drawing. Of course, the number of rollers that wrap around the conveyor belt 10 is not limited to two, and a roller that adjusts the deviation of the conveyor belt 10 or a tension roller may be provided to hang around three or more rollers. .

  Around the conveyor belt 10, four image forming means 15K for black, magenta, cyan, and yellow are sequentially arranged along the traveling direction of the conveyor belt 10 on a horizontal stretched portion between the driving roller 12 and the driven roller 13. 15M, 15C, and 15Y are installed side by side to configure the tandem image forming device 16. Although not shown in the figure, an exposure device or the like is further provided on the tandem image forming device 16.

  Between the conveyance belt 10 and the tandem image forming device 16, a sheet conveyance path for conveying the sheet 17 as a recording medium is formed from right to left in FIG. A registration roller (not shown) is disposed upstream along the sheet conveyance path, and a fixing device 18 is disposed downstream.

  FIG. 12 shows a schematic configuration of one image forming unit 15 provided in the image forming apparatus shown in FIG. The four image forming means 15K, 15M, 15C, and 15Y have the same configuration as shown in FIG.

  Reference numeral 20 in FIG. 12 denotes a photoconductor that is a drum-shaped image carrier. Around the photosensitive member 20, a developing device 22, a transfer device 23, a cleaning device 24, a static elimination device 25, and the like are arranged in order from the charging device 21 arranged at the upper left in the rotational direction indicated by the arrow in the drawing.

  Here, in the illustrated example, the charging device 21 employs a non-contact charging method that gives uniform negative charging using a charging charger, but a contact charging method using a charging roller may of course be employed. In this example, the developing device 22 uses a two-component developer composed of a positively charged carrier 26 and a negatively charged toner 27, which is carried by a developing sleeve 28 and attaches only the toner 27 to the photosensitive member 20. The electrostatic latent image on the body 20 is visualized.

  In the illustrated example, the transfer device 23 employs a non-contact plus transfer corona charger system and is disposed so as to face the photoconductor 20 with the conveyance belt 10 interposed therebetween. However, in addition to the non-contact corona charger system, the transfer device 23 is electrically conductive. A property brush or a transfer roller can also be used. The cleaning device 24 is provided with a cleaning brush 30 and a cleaning blade 31 as cleaning members. As a result, the toner scraped off by the cleaning brush 30 and the cleaning blade 31 can be recovered and reused by the developing device 22 using a recovery screw (not shown) or a toner recycling device. Moreover, as the static elimination apparatus 25, a static elimination lamp is used, for example.

  Then, along with the clockwise rotation of the photoconductor 20, the surface of the photoconductor 20 is uniformly charged by the charging device 21, and writing light L (Lk, Lm, Lc, Ly in FIG. 11) is emitted by an exposure device (not shown). After irradiation, an electrostatic latent image is formed on each photoconductor 20, and each color toner is attached by a developing device 22 to visualize the electrostatic latent image, and each color monochromatic toner is formed on each photoconductor 20. Form an image.

  The recording material (paper) 17 is transported through a paper transport path, and is fed onto the transport belt 10 by a registration roller in time with each color toner image formed on the photoreceptor 20. Then, as the transport belt 10 travels, the recording material (paper) 17 is further transported, and the monochromatic toner images on the respective photoconductors 20 are sequentially transferred to the transported paper 17 by the transfer device 23, and onto the paper 17. A single color toner image of each color is superimposed to form a composite color image. After the toner image has been transferred, the surface of the photoconductor 20 is cleaned by the cleaning device 24, and then is neutralized by the neutralizing device 25 to be initialized, and is prepared for another image formation starting from the charging device 21 again.

  The negatively charged toner 27 on the paper 17 that forms the composite color image is only electrically attached to the paper 17 at this time, and is separated from the paper 17 when subjected to a strong impact or rubbing. The sheet 17 on which the composite color image is formed is conveyed by the conveying belt 10 and guided to the fixing device 18, where the transferred image is fixed by the fixing device 18 and then discharged to a paper discharge stack unit (not shown).

  As shown in FIG. 11, the fixing device 18 has a spray means 33 for spraying the toner fixing liquid as fixing droplets, and the fixing droplet sprayed by the spray means 33 has a negative polarity of the same polarity as the unfixed toner. A droplet charging unit 34 for applying electric charge, a medium conveying unit 35 for conveying the paper 17 on which unfixed toner is placed, through the atmosphere of the fixing droplet to which electric charge is applied by the droplet charging unit 34, and A recording material charging unit 36 for charging the sheet 17 conveyed by the medium conveying unit 35 to a positive polarity opposite to that of the unfixed toner and the fixed droplets is provided.

FIG. 13 shows an enlarged view of the fixing device 18 shown in FIG.
As can be seen from FIG. 13, the spray means 33 is installed in the spray chamber 38 partitioned by the casing 37, and the toner fixing liquid stored in the fixing liquid storage section (not shown) has the mode value. Spraying is performed as fixing droplets having a droplet diameter of 15 μm or less, and the spray chamber 38 is filled with the fixing droplets.

  As the droplet charging unit 34, an ionizer or the like is used, air ions are sprayed into the spray chamber 38, mixed with the fixing droplet sprayed by the spraying unit 33, and the fixing droplet has the same polarity as the unfixed toner. Charge negatively. Unlike the illustrated example, when the unfixed toner is positively charged, the fixing droplet is also positively charged.

  The medium transport unit 35 includes a plurality of rollers 40 and a transport belt 41 that is wound around the rollers 40 and electrostatically attracts and transports the paper 17. Then, the sheet 17 transferred by the transfer device 23 and carrying the unfixed toner 42 having a negative residual charge as shown in the figure is transported by the transport belt 10 and sent to the fixing device 18, and the medium transport of the fixing device 18 is performed. Subsequently, the toner is conveyed from the right to the left in FIG. 13 by the conveying belt 41 of the means 35 through the atmosphere of the fixing droplets to which the charge is applied by the droplet charging means 34.

  The recording material charging unit 36 includes an electrode 44 disposed on the inner side of the conveyance belt 41 that is wound around the roller 40, and a power supply 45 connected to the electrode 44. Then, a voltage is applied to the electrode 44 disposed inside the transport belt 41 by the power source 45, and the paper 17 transported by the transport belt 41 is charged positively with a polarity opposite to that of the unfixed toner 42 and the fixed droplets. . At this time, of course, the transport belt 41 is formed of a material that does not prevent the paper 17 from being charged. As a result, by sucking from the back side of the paper 17 by Coulomb force, the fixing droplets adhering to the paper 17 penetrate further to the back side of the paper 17, and the liquid concentration is made even more uniform on the front and back of the paper 17. Curling of the sheet 17 can be reduced.

  Note that reference numeral 46 in FIG. 13 denotes a static elimination roller as a static elimination member that neutralizes the paper 17 coming out of the fixing device 18 and, of course, is not limited to a roller and may be a brush or the like.

  As described above, according to the illustrated examples of FIGS. 11 to 13, the fixing droplet sprayed by the spraying unit 33 is given a charge having the same polarity as the unfixed toner 42 on the paper 17 by the droplet charging unit 34. The sheet 17 on which the unfixed toner 42 is placed is conveyed by the medium conveying unit 35 through the atmosphere of the fixing droplets to which the electric charge is applied, and the conveyed sheet 17 is unfixed by the recording material charging unit 36. 42 and the fixing droplet are charged in the opposite polarity, and are forcibly attracted by the Coulomb force, and the unfixed toner 42 and the fixing droplet 53 are adsorbed on the recording material (paper) 17 and fixed on the recording material (paper) 17. Is done.

  When the toner fixing liquid is sprayed by the spraying means 33 as the fixing droplet 53 having a mode droplet diameter of 15 μm or less, the sprayed fixing droplet 53 is uniformly floated in the space as a dry mist, and the paper 17 Therefore, the fixing droplet 53 can be adhered to the sheet 17 without waste, and the fixing liquid can be effectively used and the uneven fixing can be eliminated.

-Fixing method and fixing device using contact means-
[Fixing method and fixing device]
FIG. 14 shows an electrophotographic tandem color image forming apparatus, which uses an intermediate transfer member to temporarily transfer the toner image on the image carrier to the intermediate transfer member, and then intermediate transfer member. This is a medium indirect transfer system in which the upper toner image is secondarily transferred to a recording material.

  FIG. 14 is a schematic configuration diagram of a portion including a fixing device as fixing means of the image forming apparatus according to the present embodiment. In the image forming apparatus of the present embodiment, a fixing device 90 is disposed on the upstream side of the secondary transfer portion in the surface movement direction of the intermediate transfer belt 10. The fixing device 90 includes a supply roller 91 as a fixing liquid supply unit disposed so as to face the surface of the intermediate transfer belt 10 with a small gap. The fixing device 90 is configured to be movable by a driving mechanism (not shown) so that the supply roller 91 can approach or separate from the surface of the intermediate transfer belt 10. A fixing liquid 92 is accommodated in the fixing liquid tank 93 of the fixing device 90, and the supply roller 91 is disposed in the fixing liquid 92. The supply roller 91 is rotationally driven in the direction of the arrow in the drawing when the fixing liquid 92 is applied to the toner. As a result, the fixing liquid 92 is pumped up on the surface of the supply roller 91. The fixing liquid 92 pumped up in this way is regulated by the metering blade 94, and the fixing liquid adhering to the surface of the supply roller 91 is adjusted to an appropriate amount. The fixing solution on the supply roller 91 is conveyed to a position facing the surface of the intermediate transfer belt 10 as the supply roller 91 rotates, and supplies the fixing solution to the surface of the intermediate transfer belt 10.

  Further, when the supply roller 91 is used as a fixing liquid supply unit that supplies the fixing liquid to the toner on the intermediate transfer belt 10, there is a possibility that the toner image carried on the intermediate transfer belt 10 may be disturbed. Therefore, in this embodiment, a supply roller 91 in which a base made of a conductive material is covered with an insulating layer or a high resistance layer is used, and a power source 95 as an electric field forming unit is connected to the supply roller 91. Specifically, for example, a conductive rubber layer formed on a stainless steel core and the surface thereof covered with an insulating PFA tube can be used. With such a configuration, an electric field is formed between the supply roller 91 and the intermediate transfer belt 10 in a direction in which the toner is pressed toward the intermediate transfer belt. By forming such an electric field, the binding force of the toner on the intermediate transfer belt 10 toward the intermediate transfer belt 10 at the liquid supply position can be increased. As a result, the fixing liquid 92 can be supplied to the toner without disturbing the toner image carried on the intermediate transfer belt 10.

  Since the image forming method and the image forming apparatus according to the present invention use the fixing method of the present invention, the permeation time of the fixing solution containing at least a plasticizer that softens or swells at least a part of the toner is short, and it is suitable in a short time. In a softened state, the image is firmly fixed on the recording medium, and a high-quality image can be formed.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Examples 1 to 13)
-Synthesis of polyhydroxycarboxylic acid skeleton-containing resins A-1 to A-13-
Into an autoclave reaction vessel equipped with a thermometer, stirrer, and nitrogen insertion tube, the raw materials shown in Table 1 were put, 1 part by mass of titanium terephthalate was substituted with nitrogen, and then opened at 160 ° C for 10 hours under normal pressure. Ring polymerization was conducted, and the reaction was further carried out at 130 ° C. under normal pressure. The taken-out resin was cooled to room temperature and then pulverized to synthesize polyhydroxycarboxylic acid skeleton-containing resins A-1 to A-13.

* L-lactide: manufactured by Tokyo Chemical Industry Co., Ltd. * D-lactide: manufactured by Musashino Chemical Co., Ltd. * 1,3-PD (1,3-propanediol): manufactured by Tokyo Chemical Industry Co., Ltd. * ε-caprolactone: manufactured by Tokyo Chemical Industry Co., Ltd.

(Examples 1 to 13)
<Preparation of Toners 1 to 13>
-Preparation of aqueous dispersion of resin particles-
In a reaction vessel in which a stir bar and a thermometer are set, 680 parts by mass of water, 15 parts by mass of a sodium salt of an ethylene oxide adduct of methacrylic acid (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 85 styrene Part by weight, 85 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 3 parts by weight of ammonium persulfate were charged and stirred at 4,200 rpm for 1 hour to obtain a white emulsion. Next, the system temperature was raised to 77 ° C. and reacted for 4 hours. Furthermore, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added and aged at 75 ° C. for 6 hours to prepare [Resin Dispersion Liquid 1].
The obtained [Resin Dispersion 1] was measured with a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), and the volume average particle diameter was 50 nm. Further, when a part of [Resin Dispersion 1] was dried to isolate the resin component, the resin component had a glass transition temperature (Tg) of 53 ° C. and a weight average molecular weight (Mw) of 125,000. .

-Preparation of aqueous medium-
800 parts by mass of ion-exchanged water, 200 parts by mass of the above [resin dispersion 1] and 10 parts by mass of sodium dodecylbenzenesulfonate were mixed and stirred, and uniformly dissolved to prepare [Aqueous medium 1].

-Synthesis of polyester resin-
700 parts by mass of bisphenol A ethylene oxide 2-mole adduct and 300 parts by mass of terephthalic acid were charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, at 210 ° C. under normal pressure and nitrogen flow. The condensation reaction was carried out for 10 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 mmHg to 15 mmHg, followed by cooling to synthesize a “polyester resin”. The weight average molecular weight (Mw) of THF-soluble matter of the obtained “polyester resin” was 3,700, acid value 10 mgKOH / g, hydroxyl value 50 mgKOH / g, and glass transition temperature (Tg) 41 ° C.

-Synthesis of polyester prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 660 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 80 parts by mass of bisphenol A propylene oxide 2 mol adduct, 285 parts by weight of terephthalic acid, anhydrous 22 parts by weight of trimellitic acid and 2 parts by weight of dibutyltin oxide were added, reacted at 230 ° C. for 7 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 mmHg to 15 mmHg to synthesize an “intermediate polyester resin”. .
The obtained “intermediate polyester resin” has a number average molecular weight (Mn) of 2,400, a weight average molecular weight (Mw) of 9,800, a peak molecular weight of 3,200, a glass transition temperature (Tg) of 55 ° C., The acid value was 0.4 mgKOH / g, and the hydroxyl value was 51 mgKOH / g.
Next, 390 parts by mass of “intermediate polyester resin”, 90 parts by mass of isophorone diisocyanate, and 550 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe at 100 ° C. By reacting for 6 hours, a “polyester prepolymer” was synthesized.
The obtained “polyester prepolymer” had a free isocyanate content of 1.47% by mass.

-Synthesis of ketimine compounds-
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a “ketimine compound”. The obtained ketimine compound had an amine value of 423 mgKOH / g.

-Preparation of toner material liquids 1-13
In a container equipped with a stirrer, in a blending amount (parts by mass) shown in Table 2, [polyhydroxycarboxylic acid skeleton-containing resins A-1 to A-13], [polyester resin 1], 100 parts by mass of ethyl acetate, A black pigment (carbon black) as a pigment was prepared in a blending amount (parts by mass) shown in Table 2, and stirred at a stirring peripheral speed of 20 m / min for 20 hours to prepare a resin solution. Thereafter, the “polyester prepolymer” was charged in the blending amount (parts by mass) shown in Table 2, and using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feeding speed was 1 kg / hour, the disk peripheral speed was 6 m / second, Three passes were carried out under the condition that 80% by volume of zirconia beads having a particle diameter of 0.5 mm were filled. Further, the “ketimine compound” was added and dissolved in the amount (part by mass) shown in Table 2 to prepare toner material liquids 1 to 13.
Toner material liquids 1 to 13 in Table 2 serve as raw materials for toners 1 to 13 described later.

  Next, 150 parts by weight of “aqueous medium” is put in the container, and “toner material liquids 1 to 13” are stirred at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 100 parts by mass were added and mixed for 10 minutes to obtain each emulsified slurry. Furthermore, 100 parts by mass of the emulsified slurry was charged in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min to obtain each dispersed slurry.

  Next, 100 parts by mass of each dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to each of the obtained filter cakes, and the mixture was mixed at 12,000 rpm for 10 minutes using a TK homomixer, followed by filtration. did. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. 20 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the obtained filter cake, and it mixed for 30 minutes at 12,000 rpm using the TK type | mold homomixer, Then, it filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. To each of the obtained filter cakes, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. After adding 20 mass parts of 10 mass% hydrochloric acid to each obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK type homomixer, a fluorine-type quaternary ammonium salt compound (Furgent F-310). (Manufactured by Neos) was added with a 5% methanol solution so that the fluorine-based quaternary ammonium salt was equivalent to 0.1 part by mass with respect to 100 parts by mass of the solid content of the toner, stirred for 10 minutes, and then filtered. 300 parts by mass of ion-exchanged water was added to each of the obtained filter cakes, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, an operation of filtering was performed twice to obtain each filter cake. Each obtained filter cake was dried at 40 ° C. for 36 hours using a circulating dryer, and sieved with a mesh having an opening of 75 μm to prepare “toner base particles 1 to 13”.

  Next, 100 parts by mass of each toner base particle of the obtained [toner base particles 1 to 13] and 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) as an external additive were added to a Henschel mixer. (Mitsui Mining Co., Ltd.) was used, mixed for 30 seconds at a peripheral speed of 30 m / sec, and subjected to a 1 minute pause treatment for 5 cycles, and then sieved with a mesh having a mesh opening of 35 μm to prepare a toner. 1 to 13 “Toners 1 to 13” were produced.

(Example 14)
-Production of Toner 14-
In Example 1, the layered inorganic mineral montmorillonite (manufactured by Kraton APA Souther Clay Products) 3 which was modified at least partially with a quaternary ammonium salt having a benzyl group was added to “toner material liquid 1” used in the production of toner 1. A part by mass is added. K. “Toner 14” of Example 14 was produced in the same manner as in Example 1 except that the mixture was stirred for 30 minutes using a homodisper (manufactured by Koki Kogyo Co., Ltd.).

(Example 15)
-Production of Toner 15-
In Example 2, the “toner material liquid 2” used in the production of the toner 2 is a layered inorganic mineral montmorillonite (manufactured by Kraton APA Souther Clay Products) 3 at least partially modified with a quaternary ammonium salt having a benzyl group. A part by mass is added. K. “Toner 15” of Example 15 was produced in the same manner as in Example 2 except that the mixture was stirred for 30 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

(Example 16)
-Production of Toner 16-
In Example 3, “Toner 16” of Example 16 was produced in the same manner as in Example 3, except that the methanol solution of the fluorinated quaternary ammonium salt compound was not added.

(Example 17)
-Production of Toner 17-
A mixture of 1,592 parts by mass of terephthalic acid, 82 parts by mass of isophthalic acid, 379 parts by mass of ethylene glycol, and 750 parts by mass of neopentyl glycol is heated in an autoclave at 260 ° C. for 2.5 hours to perform an esterification reaction. It was. Subsequently, 0.273 parts by mass of germanium dioxide as a catalyst was added, the temperature of the system was raised to 280 ° C. in 30 minutes, and the pressure of the system was gradually reduced to 0.1 Torr after 1 hour. Under these conditions, the polycondensation reaction was further continued. After 1.5 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 260 ° C., 50 parts by mass of isophthalic acid and 38 parts by mass of trimellitic anhydride were obtained. Part was added, stirred at 255 ° C. for 30 minutes, and discharged into a sheet. And after fully cooling to room temperature, this was grind | pulverized with the crusher and the polyester resin of the fraction of 1-6 mm of openings was obtained as [resin a-1] using the sieve.

  Next, in a 2 L glass container with a jacket, 200 parts by mass of the above [resin a-1], 35 parts by mass of ethylene glycol mono-n-butyl ether, polyvinyl alcohol (Unitika Ltd., “Unitika Poval” 050G) 0.5 463 parts by mass of a mass% aqueous solution (hereinafter referred to as PVA-1) and N, N-dimethylethanolamine (hereinafter referred to as DMEA) corresponding to 1.2 times the total amount of carboxyl groups contained in the polyester resin were added. When this was stirred at 6,000 rpm using an open system desktop homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd., TK Robotics), no precipitation of resin particles was observed at the bottom of the container, and it was completely suspended It was confirmed that it was in a state. Therefore, this state was maintained, and hot water was passed through the jacket after 10 minutes for heating. Then, when the temperature in the container reached 68 ° C., stirring was set to 7,000 rpm, and the temperature in the container was maintained at 68 ° C. to 70 ° C., and further stirred for 20 minutes, thereby obtaining a milky white uniform aqueous dispersion. And it cooled to room temperature, flowing cold water in the jacket, stirring at 3,500 rpm, it filtered using the stainless steel filter (635 mesh, plain weave), and the filtrate was obtained as "fine particle dispersion w-1." . Almost no resin particles remained on the filter.

  Next, “Toner 17” of Example 17 was produced in the same manner as in Example 1 except that “fine particle dispersion w-1” was used instead of “resin dispersion 1” in Example 1. .

(Example 18)
-Production of Toner 18-
In a reaction vessel in which a stir bar and a thermometer were set, 685 parts by mass of water, 13 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries, Ltd.), 80 parts by mass of styrene , 71 parts by weight of methacrylic acid, 128 parts by weight of butyl acrylate, 15 parts by weight of butyl thioglycolate, and 1 part by weight of ammonium persulfate were stirred for 15 minutes at 400 rpm, and a white emulsion was obtained. It was. This emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Furthermore, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to obtain [fine particle dispersion (w-2)].
The volume average particle diameter of the particles of the obtained [fine particle dispersion (w-2)] was 105 nm. Moreover, the weight average molecular weight (Mw) of the resin part of [fine particle dispersion (w-2)] was 10,000, and the glass transition temperature (Tg) was 40 degreeC.

  Next, in Example 1, except that 5 parts by mass of [fine particle dispersion (w-2)] was dropped at the time of preparation of the emulsified slurry, the emulsified slurry was prepared in the same manner as in Example 1 except that “ Toner 18 "was prepared.

(Example 19)
-Production of Toner 19-
In a 2 liter four-necked flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube, 71 parts by mass of polycaprolactone, 85 parts by mass of a copolyester resin (*), 88 parts by mass of isophorone diisocyanate, 25 parts by mass of methylolpropionic acid and 60 parts by mass of ethyl acetate were added, the temperature was raised to 90 ° C. while stirring in a nitrogen atmosphere, and urethanization reaction was performed at this temperature for 1 hour.
((*) Copolymer polyester resin composed of ethylene glycol (E), neopentyl glycol (N), terephthalic acid (T), and isophthalic acid (I) (copolymerization composition: E / N · T / I = 50/50・ 50/50 (molar ratio)))

Subsequently, 90 parts by mass of ethyl acetate was added dropwise over 30 minutes, and the reaction was further continued at 90 ° C. for 1 hour. Thereafter, it was cooled to 40 ° C. to obtain an NCO-terminated prepolymer. Next, 16 parts by mass of triethylamine was added to the prepolymer for neutralization, and then 500 parts by mass of ion-exchanged water was added. Next, 13 parts by mass of adipic acid dihydrazide and 24 parts by mass of dihydrazide compound (Ajinomoto Co., Inc.) were added to the reaction system, and the mixture was stirred at 50 ° C. for 1 hour. A polyurethane aqueous dispersion was obtained. The solid content of this aqueous resin was 39% by mass.
In a 2 liter four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a nitrogen introduction tube and a dropping funnel, 150 parts by mass of ion-exchanged water, 63 parts by mass of the aqueous polyurethane dispersion synthesized in the above section, The temperature was raised to 80 ° C. over 30 minutes from room temperature. From the dropping funnel, a mixture of 130 parts by mass of ethyl acrylate, 35 parts by mass of styrene, 12 parts by mass of diacetone acrylamide, 2 parts by mass of hydrogen peroxide, and 20 parts by mass of ion-exchanged water was added dropwise over 4 hours. Stirring was continued for 1 hour. Next, 1 part by mass of hydrogen peroxide was added, and stirring was continued at 80 ° C. for 2 hours to complete the graft polymerization reaction, whereby [fine particle dispersion (w-3)] was obtained.

  Next, in Example 1, “Toner” in Example 19 was used in the same manner as in Example 1 except that [Fine particle dispersion (w-3)] was used instead of [Fine particle dispersion (w-1)]. 19 "was produced.

(Example 20)
-Production of Toner 20-
In Example 1, except that 3 parts by mass of glycerin was used instead of 3 parts by mass of ε-caprolactone at the time of synthesis of the polyhydroxycarboxylic acid skeleton-containing resin A-1, the same as in Example 1, “ Toner 20 "was produced.

(Example 21)
-Production of Toner 21-
In Example 1, except that 3 parts by mass of erythritol was used instead of 3 parts by mass of ε-caprolactone when the polyhydroxycarboxylic acid skeleton-containing resin A-1 was synthesized, Toner 21 "was prepared.

(Comparative Example 1)
<Preparation of Toner 17>
-Preparation of black masterbatch-
A pigment having the following composition, a styrene-acrylic resin, and pure water were mixed at a ratio of 1: 1: 0.5 (mass ratio) and kneaded by two rolls. The kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water, thereby producing a black master batch.
[Black Masterbatch prescription]
-Styrene-acrylic resin (FCA-1001-NS, manufactured by Fujikura Kasei Co., Ltd.) ... 100 parts by mass-Black pigment (carbon black) ... 100 parts by mass-Pure water ... 50 parts by mass

Black toner formulation 1 having the following composition was premixed using a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.), and then kneaded using a biaxial kneader (PCM-30 manufactured by Ikegai Co., Ltd.). Next, the mixture was finely pulverized using a supersonic jet pulverizer (Labjet, manufactured by Nippon Pneumatic Industry Co., Ltd.), and then classified by an airflow classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Toner base particles having a diameter of 7 μm were prepared.
Next, 1.0 part by mass of colloidal silica (H-2000, manufactured by Clariant Co., Ltd.) was mixed with 100 parts by mass of the toner base particles using a sample mill to prepare “Toner 17” of Comparative Example 1. .

[Black Toner Formula 1]
Styrene-acrylic resin (FCA-1001-NS, manufactured by Fujikura Kasei Co., Ltd.) ... 92 parts by mass ) ... 1 part by mass

(Comparative Example 2)
-Production of Toner 18-
In Example 1, “Toner 18” of Comparative Example 2 was prepared in the same manner as in Example 1 except that the polyhydroxycarboxylic acid skeleton-containing resin A-1 was not added at the time of toner preparation.

  Next, for each of the obtained toners, the optical purity X of the polyhydroxycarboxylic acid skeleton, the mass% of the polyhydroxycarboxylic acid skeleton with respect to the total amount of the resin, and the weight average molecular weight (Mw) of the polyhydroxycarboxylic acid skeleton are as follows. ), Volume average particle diameter (Dv), and ratio (Dv / Dn). The results are shown in Table 3.

<Measurement of optical purity X of polyhydroxycarboxylic acid skeleton>
Distilled water and NaOH were added to each prepared toner to adjust to pH = 9, and then the polyester component containing polylactic acid was decomposed into monomer units at 50 ° C. for 24 hours. After cooling the obtained solution, it was put into a glass container equipped with a semipermeable membrane, the whole glass container was immersed in a container filled with distilled water for 24 hours, and low molecular weight components were extracted through the semipermeable membrane. Calcium carbonate is added to the obtained aqueous solution containing the low molecular weight component to adjust pH = 7, and then sulfuric acid is added to the filtrate obtained by filtration to precipitate the calcium component as calcium sulfate. A filtrate containing was obtained. The optical purity of the obtained lactic acid was measured using HPLC equipped with an optical resolution column.

<Measurement method of ratio of polyhydroxycarboxylic acid skeleton (PLA) part to total resin amount>
A known chemical analysis can be used for the ratio of the polyhydroxycarboxylic acid skeleton to the total amount of the resin, but in the present invention, a component other than polyhydroxycarboxylic acid has a 1H-NMR method using a dilute solution. Measured by measuring the content ratio of the component from the ratio of the area of the proton peak bonded to the aromatic ring and the area of the proton peak of methyl contained in the lactic acid moiety, and converting the obtained content ratio into a ratio in terms of weight. Went.

<Weight average molecular weight (Mw) of polyhydroxycarboxylic acid skeleton (PLA) part>
The weight average molecular weight (Mw) was measured using GPC for the THF soluble matter of the measurement sample. In addition, as a measuring device, HLC-8120 (manufactured by Tosoh Corporation), as a column, TSKgelGMHXL (2), TSKgelMultiporeHXL-M (1), as a detecting device, a refractive index detector is used, and a measuring temperature is measured. The temperature was 40 ° C., and 100 μL of a 0.25 wt% THF solution of the sample was injected and measured. Further, polystyrene was used as a standard sample for creating a calibration curve.

<Volume average particle diameter (Dv) and ratio (Dv / Dn)>
The volume average particle diameter (Dv) and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) are determined by a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). ) Using an analysis software (Beckman Coulter Multisizer 3 Version 3.51).
Specifically, 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL glass beaker, and 0.5 g of each toner is added. The mixture was stirred with a microspatel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped such that the concentration indicated by the apparatus was 8% ± 2%. In this measurement method, it is important that the concentration is 8% ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

(Example of manufacturing carrier 1)
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (organostraight silicone), 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added and dispersed for 20 minutes with a homomixer. Thus, a coating layer coating solution was prepared. Using a fluidized bed type coating apparatus, the coating layer coating solution was applied to the surface of 1,000 parts by mass of spherical magnetite having a volume average particle size of 50 μm to prepare Carrier 1.

(Example of manufacturing carrier 2)
In a stainless steel container, 60 parts by mass of an acrylic resin solution (manufactured by Hitachi Chemical Co., Ltd., 50% by mass of a solid 3018 solid), 20 parts by mass of a guanamine solution (by Mitsui Cytec Co., Ltd., Mycoat 106, 77% by mass of solids), 120 parts by mass of a silicone resin solution (Toray Dow Corning Co., Ltd., SR2405, solid content 50% by mass), 1.5 parts by mass of an aminosilane coupling agent (Toray Dow Corning Co., Ltd., SH6020, solid content 100% by mass) Then, 50 parts by mass of spherical alumina fine particles having a particle diameter of 0.4 μm are added, diluted with toluene so that the solid content concentration becomes 15% by mass, and then dispersed with a homomixer for 10 minutes to obtain [Coating Layer Solution 1]. Prepared.

Next, 3000 parts by mass of ferrite powder (saturation magnetic moment of 65 emu / g at 1 k gauss) was used as a core material, and the [Coating layer liquid 1] was applied using a rolling fluid coating apparatus and dried. The obtained carrier was baked by standing at 120 ° C. for 60 minutes in an electric furnace, and after cooling, the ferrite powder bulk was pulverized using a sieve having an opening of 90 μm to obtain [Carrier 2].
When the particle size distribution of the obtained [Carrier 2] was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 39 μm, the number average particle size (Dn) was 33 μm, and Dw / Dn. Was 1.17. Further, after the alumina fine particles are cut with FIB (focused ion beam) to produce a cross section of the alumina fine particles, the average thickness (h) of the coating layer is measured using a transmission electron microscope (TEM) and a scanning transmission electron microscope (STEM). And the average particle diameter (D) and D / h of the alumina fine particles were calculated as average values obtained by observing fine particle cross-sections of 50 points or more, and the average thickness (h) of the coating layer was 0.43 μm. The average particle diameter (D) of the fine particles was 0.39 μm, and D / h was 0.91.

(Example of manufacturing carrier 3)
In a stainless steel container, acrylic resin solution (Hitaroid 3018, solid content 50% by mass) 30 parts by mass, guanamine solution (Mitsui Cytec Co., Ltd., Mycoat 106, solid content 77% by mass) 10 parts by mass 60 parts by mass of a silicone resin solution (manufactured by Toray Dow Corning, SR2405, solid content 50% by mass), 1 part by mass of an aminosilane coupling agent (manufactured by Toray Dow Corning, SH6020, solid content 100% by mass), 80 parts by mass of spherical alumina fine particles having a particle diameter of 0.5 μm are added, diluted with toluene so that the solid content concentration becomes 15% by mass, and then dispersed for 10 minutes with a homomixer to prepare [Coating Layer Liquid 2] did.
Next, 3,000 parts by mass of ferrite powder (saturation magnetic moment 65 emu / g at 1 k gauss) is used as a core material, and the above [Coating layer liquid 2] is applied using a rolling fluid coating device and dried. did. The obtained carrier was baked by standing at 120 ° C. for 60 minutes in an electric furnace, and after cooling, the ferrite powder bulk was pulverized using a sieve having an opening of 90 μm to obtain [Carrier 3].
When the particle size distribution of the obtained [Carrier 3] was measured with a Microtrac particle size distribution analyzer (model HRA9320-X100), the weight average particle size (Dw) was 41 μm, the number average particle size (Dn) was 35 μm, and Dw / Dn. Was 1.17. Further, after the alumina fine particles are cut with FIB (focused ion beam) to produce a cross section of the alumina fine particles, the average thickness (h) of the coating layer is measured using a transmission electron microscope (TEM) and a scanning transmission electron microscope (STEM). And the average particle diameter (D) and D / h of the alumina fine particles were calculated as average values obtained by observing fine particle cross-sections of 50 points or more, and the average thickness (h) of the coating layer was 0.22 μm. The average particle diameter (D) of the fine particles was 0.51 μm, and D / h was 2.32.

-Production of developer-
Each developer of Examples 1 to 21 and Comparative Examples 1 and 2 was prepared by mixing 5 parts by mass of each of the produced toners 1 to 23 and 95 parts by mass of the carrier 1.
In addition, 7 parts by weight of toner 1 and 100 parts by weight of [Carrier 2] are added to a 2 L stainless steel container, and the container is a type of tumbler mixer (Willy et Bacofen (WAB)) that is stirred and rolled. The two-component developer of Example 22 was prepared by uniformly mixing at 48 rpm for 5 minutes.
Further, a two-component developer of Example 23 was produced in the same manner as Carrier 2 except that [Carrier 3] was used instead of [Carrier 2].

(Production Example 1)
<Fixing solution preparation>
-Liquid containing plasticizer-
・ Ion-exchanged water as dilution solvent: 53% by mass
・ Diethoxyethoxyethyl succinate as a liquid plasticizer (Higher Alcohol Industry Co., Ltd.): 10% by mass
・ Propylene carbonate as liquid plasticizer ... 20% by mass
・ Propylene glycol as thickener: 10% by mass
-Palm fatty acid diethanolamide (1: 1) type (Matsumoto Yushi Seiyaku Co., Ltd., Marpon MM) ... 0.5% by mass as a foaming agent
・ Amine palmitate as foaming agent: 2.5% by mass
・ Amyristate amine as foaming agent: 1.5% by mass
・ Amine stearate as foaming agent: 0.5% by mass
-POE (20) lauryl sorbitan as a dispersant (manufactured by Kao Corporation, Rheodor TW-S120V) ... 1% by mass
-Polyethylene glycol monostearate as a dispersant (manufactured by Kao Corporation, Emanon 3199) ... 1% by mass
The dispersant was used to promote the solubility of the plasticizer in the diluent solvent. The fatty acid amine was synthesized from fatty acid and triethanolamine.

  First, at the above component ratio, the plasticizer was removed at a liquid temperature of 120 ° C. and mixed and stirred to prepare a solution. Next, a plasticizer was mixed, and a fixing solution (stock solution before forming) in which the plasticizer was dissolved was prepared using an ultrasonic homogenizer.

<Coating device>
-Large bubble generation part-
It produced based on FIG.
-Liquid fixer storage container: Bottle made of polyethylene terephthalate (PET) resin-Liquid transport pump: Tube pump (tube inner diameter 2mm, tube material: silicone rubber)
・ Transport flow path: Silicone rubber tube with an inner diameter of 2 mm ・ Microporous sheet for creating large bubbles: # 400 stainless steel mesh sheet (opening approx. 40 μm)

-Microbubble generator-
It produced based on FIG.
The inner cylinder of the double cylinder is fixed to the rotation shaft and is rotated by a rotation drive motor (not shown). The material of the double cylinder was polyethylene terephthalate (PET) resin.
・ Outer cylinder inner diameter: 10 mm, outer cylinder length: 120 mm
・ Outer diameter of inner cylinder: 8 mm, length of inner cylinder: 100 mm
-The rotation speed was variable in the range of 1,000 rpm to 2,000 rpm.

-Fixer application means-
It produced based on FIG. A foam-like fixing solution was prepared using the micro-bubble generating unit that generates the micro-bubbles and supplied to the liquid film thickness control blade. The gap between the liquid film thickness control blade and the application roller was 25 μm and 40 μm.
Pressure roller: A polyurethane foam material (trade name: “Color Foam EMO”, manufactured by INOAC) having a diameter of 50 mm was formed by using an aluminum alloy roller (diameter 10 mm) as a core metal.
・ Coating roller: Stainless steel (SUS) roller (diameter 30mm) coated with PFA resin
・ Blade for film thickness control: A 1 mm thick parallel glass was bonded to an aluminum alloy support plate, and the gap between the coating roller and the glass surface could be controlled in the range of 10 μm to 100 μm with the glass surface facing the coating roller. .
-Paper transport speed: 150 mm / s

  Next, using each of the obtained toner and each developer, the penetration time of the fixing liquid into the toner layer and the fixing property were evaluated as follows. The results are shown in Table 4.

<Spent property (carrier contamination)>
Each developer is put in an electrophotographic printer (Ricoh Co., Ltd., IpsioColor CX8800) from which the fixing device is removed, and an image chart of 20% image area is set to an image density of 1.4 ± 0.2 on PPC paper. While controlling the toner concentration, the developer after running 150,000 sheets was extracted, and an appropriate amount of developer was put into a gauge with a mesh having a mesh size of 32 μm, and air blowing was performed to separate the toner and the carrier. 1.0 g of the obtained carrier was put into a 50 mL glass bottle, 10 mL of chloroform was added, and the mixture was shaken 50 times and allowed to stand for 10 minutes. Thereafter, the supernatant chloroform solution was placed in a glass cell, and the transmittance of the chloroform solution was measured using a turbidimeter, and evaluated according to the following criteria.
[Evaluation criteria for carrier contamination]
A: Transmittance 95% or more B: Transmittance 85% or more and less than 95% C: Transmittance 75% or more and less than 85% D: Transmittance less than 75%

<Penetration time of fixer into toner layer>
As shown in FIG. 15, the upper electrode 61 is viewed on the contact applying means surface and the lower electrode 62 is viewed on the recording medium, and the foam-like fixing liquid layer 63 is formed on the upper electrode 61. A toner layer 64 was formed thereon. And the contact timing of electrodes arrange | positions the load detection load cell 65 under the lower electrode 62, and applies a voltage between upper and lower electrodes. When the upper electrode 61 was brought into contact with the lower electrode 62, the load detection load cell 65 detected the load of the upper electrode 61 and determined the contact start point. Thereafter, when the foamy fixing solution 63 passed through the toner layer 64 and reached the lower electrode 62, a current flowed between the electrodes, and the applied voltage value changed. The toner layer permeation time was determined by measuring the timing from the detection of the weighted detection load cell 65 to the start of voltage change at this time.
Foam fixing liquid layer: A foam layer having an average foam diameter of 20 μm, a bulk density of 0.05 g / cm ³ and a thickness of 40 μm was formed on the upper electrode.
Toner layer: formed on the lower electrode so as to have a thickness of about 30 μm.
-The upper electrode and the lower electrode were made of the same material and SUS304 was used. The upper electrode was fixed to the linear stage, and was brought into contact with the lower electrode at a pressure of 0.03 kgf / cm ² (pressure during application).
In order to prevent electrolysis of the fixing solution between the electrodes, the applied voltage between the voltages was set to 0.8V.
The penetration time was evaluated according to the following criteria, and B or higher was made practical.
[Evaluation criteria for penetration time]
A: Penetration time less than 50 ms B: Penetration time between 50 ms and less than 150 ms C: Penetration time between 150 ms and less than 250 ms D: Penetration time greater than 250 ms

<Evaluation of fixability>
Each developer is loaded into an electrophotographic printer (Ricoh Co., Ltd., IpsioColorCX8800) with the fixing device removed, and an unfixed toner image of halftone (setting after fixing ID = 0.25) is formed. 6 is applied to the PPC paper using the fixing device shown in FIG. 6, and the pressure roller of the sponge and the coating roller are used in the fixing device including the coating device on which the fixing solution obtained in the fixing liquid formulation example is mounted. Fixing was performed at a center distance of 15 mm (nip time 100 ms). The paper conveyance speed at this time was 150 mm / s.
The fixed image is rubbed with a JIS smear cloth (JIS L-0849) using a clock meter (Model 1 manufactured by Atlas Electric Devices), and the output image is rubbed with a JIS smear cloth, and then scanned at a resolution of 600 dpi × 600 dpi. Was captured and imaged. The background paper portion on which the toner is not transferred is gradation 0, the portion on which the toner is printed is gradation 255, the portion where the gradation is 127 or less is white, and the portion where the gradation is 128 or more is black The binarization process is performed, and the area of the black portion with respect to an arbitrary area of 1 cm × 1 cm is obtained by data processing to obtain an image remaining ratio.
In addition, the evaluation of fixability was made practically B or more.
〔Evaluation criteria〕
A: Image remaining rate of 90% or more B: Image remaining rate of 80% or more and less than 90% C: Image remaining rate of 60% or more and less than 80% D: Image remaining rate of less than 60%

From the results of Table 3 and Table 4, Examples 1 to 23 all use polylactic acid as a binder resin, and both have a short penetration time of the fixing solution, and an appropriate softened state can be obtained in a short time. Therefore, the image was firmly fixed on the substrate (paper), and a good image was obtained.
On the other hand, Comparative Example 1 uses a styrene-acrylic resin as a binder resin, and the result was that the fixing solution was poor because the penetration time of the fixing solution was long and the penetration was not sufficient. .
In Comparative Example 2, when the polyester resin used in the conventional toner is used, the penetration time is shorter than that of the styrene-acrylic resin, but the time required for the penetration is longer than that of the toner using polylactic acid. It became.

  The toner of the present invention has a short permeation time of a fixing solution containing at least a plasticizer that softens or swells at least a part of the toner, so that an appropriately soft toner can be obtained in a short time, and an image is firmly fixed on a recording medium. In addition, since a high-quality image can be formed, it can be suitably used for an electrophotographic forming technique that employs a non-thermal fixing method.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Image formation part 3 Charging device (charging roller)
Reference Signs List 4 exposure device 5 developing device 5a developing roller 5b developer supply roller 5c regulating blade 6 transfer device 7 cleaning device 10 intermediate transfer belt 11, 12, 13 support roller 14 primary transfer roller 16 secondary transfer roller T toner (developer)
15K, 15M, 15C, 15Y Image forming means 17 Paper (recording medium)
DESCRIPTION OF SYMBOLS 18 Fixing device 23 Transfer means 33 Spray means 34 Droplet charging means 35 Medium conveying means 36 Recording material charging means 38 Spray chamber 40 Roller 41 Conveying belt 42 Unfixed toner 44 Electrode 45 Power supply 50 Applying means 53 Fixing droplet 64 Intermediate transfer body 67 Secondary transfer means 69 Primary transfer means 101 Electrostatic latent image carrier 102 Charging means 103 Exposure means 104 Development means 105 Recording medium 107 Cleaning means 108 Transfer means 111 Application roller 112 Recording medium 113 Toner layer 114 Foamed fixing liquid 115 Belt Cleaning device 120 Foam fixing liquid 121 Liquid film boundary 122 Bubble 130 Foam fixing liquid generating means 131 Fixing liquid container 132 Liquid fixing liquid 133 Transport pump 134 Liquid transport pipe 135 Gas / liquid mixing section 136 Air port 137 Microporous sheet 138 Foam Generating unit 140 fixing device 141 applying roller 142 thickness regulation blade 143 pressure roller 144 pressing belt 145 heating means 146 the pressure roller 147 infrared heater 148 pressure roller

JP 2006-133306 A JP 2009-008967 A JP 2008-139504 A

Claims (21)

A toner used for fixing a toner to a recording medium by applying a fixing liquid containing a diluent and a plasticizer that softens or swells at least a part of the toner to the toner on the recording medium,
A toner comprising at least a resin having a polyhydroxycarboxylic acid skeleton and a colorant.   The polyhydroxycarboxylic acid skeleton has an optical purity X (%) in terms of monomer component = | X (L form) -X (D form) | [where X (L form) is an L form ratio in terms of an optically active monomer. The toner according to claim 1, wherein (mol%) and X (D form) represent a D form ratio (mol%) in terms of an optically active monomer].   The toner according to claim 1, wherein the polyhydroxycarboxylic acid skeleton has a weight average molecular weight of 7,000 to 60,000.   The toner according to any one of claims 1 to 3, wherein the polyhydroxycarboxylic acid skeleton is a skeleton obtained by polymerization or copolymerization of a hydroxycarboxylic acid having 3 to 6 carbon atoms.   The toner according to claim 1, further comprising a charge control agent.   The toner according to claim 5, wherein the charge control agent is a fluorine-containing quaternary ammonium salt.   7. The toner according to claim 1, wherein the toner further contains a modified layered inorganic mineral, and the modified layered inorganic mineral is obtained by modifying at least part of ions between layers of the layered inorganic mineral with organic ions. toner.   A toner material solution in which a toner material containing at least a binder resin, a resin having a polyhydroxycarboxylic acid skeleton, a colorant, a charge control agent, and a modified layered inorganic mineral is dissolved or dispersed in an organic solvent is contained in an aqueous medium. The toner according to claim 1, which is obtained by dispersing and granulating. The resin particles (A) containing at least the first resin (a), or the coating (P) containing the first resin (a) is the resin particles (B) containing the second resin (b). Toner deposited on the surface,
The resin particles (B) are particles comprising the toner according to any one of claims 1 to 8,
The toner according to claim 1, wherein the first resin (a) is a polyester resin containing a polybasic acid and a polyhydric alcohol. A toner comprising a first resin (a1) and a second resin (a2) having different glass transition temperatures, and resin particles (B) containing a third resin (b),
The first resin (a1) and the second resin (a2) are both attached to the surface of the resin particles (B),
The first resin (a1) and the second resin (a2) are composed of at least one of a styrene monomer and an acrylic monomer,
The toner according to claim 1, wherein the resin particles (B) are particles made of the toner according to claim 1. A toner having a first resin (a) and resin particles (B) containing a second resin (b),
The first resin (a) is composed of a polyurethane-acrylic polymer composite, and is attached to the surface of the resin particles (B).
The toner according to claim 1, wherein the resin particles (B) are particles made of the toner according to claim 1. A developer comprising the toner according to claim 1 and a carrier.
The carrier has at least a core material and a coating layer containing fine particles on the surface of the core material, and the average particle diameter (D) of the fine particles and the average thickness (h) of the coating layer are 1 <[D / h]. <10,
A developer, wherein the content of the fine particles is 40% by mass to 95% by mass.   The developer according to claim 12, wherein the coating layer contains at least a silicone resin.   The developer according to claim 12, wherein the fine particles in the coating layer are at least one of alumina and surface-treated alumina. In a fixing method in which a fixing liquid containing a plasticizer that softens the toner by dissolving or swelling at least a part of the toner is applied to the toner on the recording medium to fix the toner on the recording medium.
The fixing method according to claim 1, wherein the toner is the toner according to claim 1. A fixing method for fixing toner on a recording medium using the toner according to claim 1,
A foamed fixing solution generating step for producing a foamed fixing solution by foaming a fixing solution containing a diluent containing water, a foaming agent, and a plasticizer;
A film thickness adjusting step for forming the foamy fixer to a desired thickness on the contact surface of the foamy fixer applying means,
A foam-like fixing solution applying step for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
A fixing method comprising the steps of:   The fixing method according to claim 15, wherein the plasticizer is an aliphatic dicarboxylate dialkoxyalkyl. The fixing method according to claim 15, wherein the plasticizer is a compound represented by the following general formula.
R ⁸ (COO— (R ⁹ —O) _n —R ¹⁰ ) ₂
In the general formula, n is 1 to 3, R ⁸ is an alkylene group having 2 to 8 carbon atoms, R ⁹ is an alkylene group having 1 to 3 carbon atoms, R ¹⁰ Is an alkyl group having 1 to 4 carbon atoms. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
Developing the electrostatic latent image using a developer containing toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A fixing step of fixing the transferred image transferred to the recording medium;
An image forming method comprising:
An image forming method, wherein the fixing step is performed by the fixing method according to claim 15. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing a developer containing toner A developing unit that develops the electrostatic latent image using a developer containing toner and forms a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
The fixing unit includes a fixing solution applying unit that applies a fixing solution to a toner layer on a recording medium,
An image forming apparatus, wherein the toner is the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer containing toner to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing toner. A developer container for storing, and developing means for developing the electrostatic latent image with a developer containing toner to form a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
A foaming fixer generating means for generating a foamy fixer by foaming a fixer containing a diluent containing water, a foaming agent, and a plasticizer;
Film thickness adjusting means for forming the foamy fixer on the contact surface of the foamy fixer applying means to a desired thickness;
A foam-like fixing solution applying means for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
An image forming apparatus, wherein the toner is the toner according to claim 1.