JP2007304143A - Image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method and an image forming apparatus in which, when full-color image formation is performed by allowing a toner image formed on a substrate surface to develop colors by subjecting the toner image to exposure for imparting information on color development, toner fusion to the substrate by the exposure is prevented, so that images can stably be obtained over a prolonged period of time. <P>SOLUTION: The image forming method uses a toner which is so controlled that it maintains a coloring or non-coloring state by imparting information on color development, and includes a step of forming a toner image, a step of imparting information on color development, a transfer step and a fixing step, wherein at the step of imparting the information on color development, a substrate which is substantially transparent to light in a wavelength region used for imparting the information on color development is used as a substrate bearing the toner image. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an image forming method and an image forming apparatus using toner capable of developing different colors by exposing light of different wavelengths.

  2. Description of the Related Art Conventionally, in a recording apparatus that obtains a color image by an electrophotographic method, the basic three primary colors are developed according to each image information, and these toner images are sequentially superimposed to obtain a color image. As a specific apparatus configuration, a so-called four-cycle machine that obtains a color image by repeatedly developing each color on a photosensitive drum on which a latent image is formed by an image forming method and transferring them to a transfer member, Alternatively, a tandem machine or the like that includes a photosensitive drum and a developing device for each color image forming unit and transfers a toner image successively and sequentially to obtain a color image by moving a transfer member.

  These are at least common by having a plurality of developing devices for each color. For this reason, in normal color image formation, four developing devices in which black is added to the three primary colors are required, and in the tandem machine, four photosensitive drums are required for each of the four developing devices. An increase in the size and cost of the apparatus is inevitable, for example, a means for matching the synchronization of the forming means is required.

On the other hand, a method for obtaining a color image with a single developing device has been proposed (see, for example, Patent Documents 1 and 2). In these techniques, after a toner image is formed on the image carrier, high-intensity light is irradiated on the image carrier in order to color the toner image. Accordingly, at this time, the image carrier is also heated to absorb the light, and there is a problem that the toner is fused to the image carrier.
JP-A 63-131364 JP 2003-330228 A

The object of the present invention is to solve the above-mentioned problems of the prior art.
That is, according to the present invention, when the toner image formed on the surface of the substrate is exposed to give color development information to develop the color of the toner image to form a full-color image, the toner on the substrate is exposed by the exposure. It is an object of the present invention to provide an image forming method and an image forming apparatus capable of preventing fusion and obtaining images stably over a long period of time.

The above-mentioned subject is achieved by the following present invention. That is, the present invention
<1> An image forming method using a toner that is controlled so as to maintain a colored state or a non-colored state by providing coloring information by light,
A toner image forming step for forming a toner image, a color forming information applying step for applying color forming information by light to the toner image, a transfer step for transferring the toner image to which the color forming information is applied to the surface of a recording medium, and the recording A fixing step of fixing the toner image transferred to the surface of the medium by heat and / or pressure, and a coloring step of coloring the toner image to which the coloring information is given by heating,
In the color forming information providing step, the image forming method uses a substrate that is substantially transparent to light in a wavelength region used for providing the color forming information as the substrate carrying the toner image.

<2> The image forming method according to <1>, wherein in the toner image forming step, a toner image is formed on the surface of the substrate.

<3> The image forming method according to <2>, wherein in the coloring information applying step, the coloring information is applied by the light from the surface of the substrate opposite to the toner image forming surface.

<4> The image forming method according to <3>, wherein the application of color development information by light is performed simultaneously with the formation of the toner image.

<5> The substrate is a photoconductor, and the toner image forming step includes a charging step of charging the surface of the photoconductor, an exposure step of forming an electrostatic latent image on the surface of the photoconductor by exposure, and the electrostatic The image forming method according to <1>, further comprising a developing step of converting the latent image into a toner image with the developer containing the toner.

<6> The substrate is a dielectric, and the toner image forming step includes an ion writing step of forming an electrostatic latent image on the surface of the substrate, and the electrostatic latent image is converted into a toner image by a developer containing the toner. And an image forming method according to <1>.

<7> A photocurable composition comprising a first component and a second component that are present in a state where the toners are isolated from each other and react with each other, and any one of the first component and the second component <1>, wherein the photocurable composition is maintained in a cured or uncured state by providing color development information by light, and the reaction for color development is controlled. An image forming method.

<8> An image forming apparatus using a toner that is controlled to maintain a colored state or a non-colored state by providing coloring information by light,
An image carrier, a toner image forming unit for forming a toner image, a coloring information providing unit for imparting coloring information by light to the toner image, and a transfer for transferring the toner image to which the coloring information is imparted to the surface of the recording medium Means, fixing means for fixing the toner image transferred to the surface of the recording medium by heat and / or pressure, and coloring means for coloring the toner image to which the coloring information is given by heating,
In the image forming apparatus, the substrate carrying the toner image to which the color information by the light is imparted is a substrate that is substantially transparent to the light in the wavelength region used for imparting the color information.

In the image forming apparatus, for example, a toner image is formed on the image carrier by the logical sum of image formation information of four colors of cyan (C), magenta (M), yellow (Y), and black (K), and then The toner image is exposed to light of a wavelength according to color information to give color development information to the toner image, and then the toner image to which color development information is given is transferred and fixed on a recording medium. At the same time, a color image of the toner is performed by heat, whereby a color image is obtained. Therefore, since a full color image can be obtained with one image carrier and one developing device, the apparatus can be greatly reduced in size.
In addition, since the substrate carrying the toner image is substantially transparent to light in the wavelength range used for providing color information, the substrate does not rise in temperature during color information-giving exposure. No toner fusion to the toner can occur and the durability of the apparatus can be improved.

  According to the present invention, when the toner image formed on the surface of the substrate is exposed to give color development information to develop the color of the toner image to form a full color image, the toner on the substrate is exposed by the exposure. An image forming method and an image forming apparatus capable of preventing fusion and obtaining an image stably over a long period of time can be provided.

Hereinafter, the present invention will be described in detail.
An image forming method (image forming apparatus) of the present invention is an image forming method (image forming apparatus) using a toner that is controlled so as to maintain a colored state or a non-colored state by applying coloring information by light, A toner image forming step for forming a toner image, a color forming information applying step for applying color forming information by light to the toner image, a transfer step for transferring the toner image to which the color forming information is applied to the surface of a recording medium, and the recording A fixing step of fixing the toner image transferred to the surface of the medium by heat and / or pressure; and a coloring step of coloring the toner image to which the coloring information is given by heating. As a substrate for supporting a toner image, a substrate that is substantially transparent with respect to light in a wavelength region used for imparting color information is used.

  The toner used in the present invention has a function of maintaining a state in which, for example, when each toner particle is exposed to light of a different wavelength, the color is developed according to the wavelength, or the color is not developed (non-colored). is doing. That is, the toner has a chromogenic substance (and a color developing portion including this) that can develop color by providing color development information by light, and the toner can develop color or non-color by the application of color development information by light. It is controlled to maintain this state.

  Here, the “applying color development information by light” refers to a desired region of a toner image in order to control the color development / non-color development state and the color tone upon color development in units of individual toner particles constituting the toner image. On the other hand, it means that one or more kinds of light having a specific wavelength are selectively given, or no light is given.

  Such a toner is not particularly limited as long as it can exhibit the above functions, and examples thereof include toners described in Patent Documents 1 and 2 and toners preferably used in the present invention described later.

  In the image forming method using the toner, for example, such toner is mounted on one developing device, and image formation of four colors of cyan (C), magenta (M), yellow (Y), and black (K) is performed. An electrostatic latent image is formed on the image carrier by the logical sum of information, and the electrostatic latent image is developed with the toner to form a toner image. For example, the toner image is then irradiated with light having a wavelength corresponding to the color information. Is exposed to give color information to the toner image. Thereafter, the toner image to which the coloring information is given is transferred to a recording medium, and then fixed to the recording medium by heat and pressure. At this time, the color reaction of the toner is performed by the heat, and a color image is obtained.

  Accordingly, since a full color image can be obtained with one image carrier and one developing device, the size of the main body of the image forming apparatus is as close as possible to that of a monochrome printer, and the apparatus can be miniaturized. Become. In addition, since it is not necessary to layer toner for each color when forming a toner image, unevenness of the image surface can be suppressed, the gloss of the image surface can be made uniform, and the toner can be colored with a pigment or the like. Since no agent is used, it is possible to obtain a silver salt-like image.

  As described above, in the conventional image forming method using the same toner as described above, exposure for providing color information is performed on the surface of the image carrier on which the toner image is formed, but the intensity of the exposure is considerably large. In general, the image carrier absorbs exposure light for providing color information, so that the temperature of the image carrier rises during exposure, particularly during repeated use, and the toner softens accordingly, resulting in the toner being imaged. In some cases, it was fused to the carrier.

In the present invention, in order to solve the above-mentioned problem, a substrate that is substantially transparent to light in the exposure wavelength region is used as a substrate for supporting a toner image when performing exposure for providing color information. I found that the problem was solved.
Here, “substantially transparent to light in the exposure wavelength region” means that the absorbance to the light is 0.1 or less. The absorbance is preferably 0.05 or less. The substrate means not only an image carrier at the time of forming a toner image, but also a substrate that carries a toner image when coloring information including them is applied.

  That is, according to the present invention, by using a substantially transparent substrate having an absorbance as defined above for exposure for providing color information, it is possible to suppress an increase in substrate temperature during exposure. In addition, it was found that the temperature rise of the substrate can be prevented not only during one image formation but also in continuous repeated image formation, and toner fusion to the substrate can be prevented.

  Further, as will be described later, by using the above-mentioned base, it is possible to expose the toner image formed on the surface of the base from the back side of the base (the side opposite to the toner image forming surface) for providing color information, Further, by performing exposure for providing color information on the surface of the substrate simultaneously with the formation of the toner image, it is possible to reduce the positional deviation between the formation of the toner image and the application of color information and to prevent image distortion.

In the image forming process to which the present invention is applied, the toner image formation is not particularly limited, so-called electrophotographic process, process of forming an electric latent image with ions on a dielectric (ionography), liquid development, ink jet Any method such as printing is possible.
First, an image forming apparatus (image forming method) for forming a color image by an electrophotographic process using a toner that can control color development or non-color development according to color development information by light, to which the present invention is applied. A brief explanation. The image forming apparatus using the ionography is also described as appropriate since only the toner image forming process described later is different and the other processes are the same.

  FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention. An image forming apparatus shown in FIG. 1 includes a photoconductor (image carrier) 10 used in a normal electrophotographic process, a charging device (charging means) 12, an exposure device (exposure means) 14, a developing device (developing means) 16, a transfer device. An apparatus (transfer means) 18 and a fixing device (fixing means) 22 are provided. Further, in this apparatus, a color information providing device 28 for providing color information to the developed toner image is provided, and the fixing device 22 also serves as a color device (coloring means) for coloring the toner image. Further, a light irradiation device 24 (light irradiation means) for irradiating the recording medium 26 with light for fixing the color development of the toner is provided on the downstream side of the fixing device 22. Reference numeral 20 denotes a cleaner.

In the present invention, since the substrate is a support that carries a toner image when color information is applied, when the color information is applied on the photoconductor as in this apparatus, the photoconductor 10 is This is the substrate in the present invention. However, for example, when the toner image on the photosensitive member is transferred to another support and coloring information is applied on the support, the support becomes the base.
Hereinafter, the configuration of the image forming apparatus of the present invention will be described along each step in image formation.

<Toner image forming step>
When the image carrier (substrate) as shown in FIG. 1 is a photoreceptor 10, the toner image forming means includes a charging device 12 for charging the surface of the photoreceptor, and electrostatic exposure to the surface of the photoreceptor by exposure. An exposure device 14 that forms a latent image and a developing device 16 that converts the electrostatic latent image into a toner image using a developer containing the toner are included.

First, the entire surface of the photoreceptor 10 is charged by the charging device 12.
As the photoreceptor 10, any known one can be used as long as it is substantially transparent to exposure light from the color information providing device 20 described later (hereinafter, sometimes referred to as “transparent photoreceptor”). The transparent photoreceptor used in the present invention will be described below with reference to the drawings.

2 to 6 are schematic views showing a cross section of the photoreceptor 10 used in the present invention. The photosensitive layer having a laminated structure is shown in FIGS. 2 to 4, and the photosensitive layer having a single layer structure is shown in FIGS. In FIG. 2, an undercoat layer 1 is provided on a conductive substrate 4, and a charge generation layer 2 and a charge transport layer 3 are provided thereon. In FIG. 3, a protective layer 5 is further provided on the surface. In FIG. 4, an undercoat layer 1 is provided on a conductive substrate 4, a charge transport layer 3 and a charge generation layer 2 are provided thereon, and a protective layer 5 is provided on the surface. . 2 to 4, the undercoat layer may or may not be provided.

  In FIG. 5, the undercoat layer 1 is provided on the conductive substrate 4, and the charge generation / charge transport layer 6 is provided thereon. In FIG. A protective layer 5 is provided on the surface. The layer structure of the photoreceptor 10 used in the present invention is not particularly limited, but a layer structure including at least a charge generation layer and a plurality of layers having different compositions on the charge generation layer is preferable. For example, when a stacked structure such as a charge generation layer, a charge transport layer, and a protective layer is used, it is possible to achieve functional separation because functional separation is achieved so that each layer has only to satisfy each function.

(Conductive substrate)
Examples of the conductive substrate 4 include glass having a drum shape, sheet shape, plate shape, etc., a material obtained by sputtering ITO on a substrate such as PET, a material obtained by dispersing and applying ITO fine powder in a binder, And those formed with a transparent conductive layer such as those coated with a conductive polymer. The conductive substrate 4 may be subjected to a honing process or the like for the purpose of preventing injection, improving adhesiveness, and preventing interference fringes.

(Underlayer)
As the binder resin contained in the undercoat layer 1, any known resin can be used as long as it can form a good film and can obtain desired characteristics. For example, acetal such as polyvinyl butyral can be used. Resin, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin , Using known polymer resin compounds such as silicone-alkyd resin, phenol resin, phenol-formaldehyde resin, melamine resin, urethane resin, charge transport resin having a charge transport group, or conductive resin such as polyaniline, etc. Can do. Among these, resins that are insoluble in the upper coating solvent are preferably used, and phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, epoxy resins, and the like are particularly preferably used.

  Various additives can be used in the coating liquid for forming the undercoat layer in order to improve electrical characteristics, environmental stability, and image quality. As additives, known materials such as electron transport pigments such as polycyclic condensation systems and azo systems, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents are used. be able to.

  The silane coupling agent is used for surface treatment of metal oxides, but it can also be used as an additive added to a coating solution. Specific examples of the silane coupling agent used here include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (Aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane and the like.

  Examples of the zirconium chelate compounds include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate. , Zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Examples of the titanium chelate compound include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, and titanium lactate ammonium. Examples thereof include salts, titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, and polyhydroxytitanium stearate.

Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like.
These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds.

  As the solvent for preparing the coating solution for forming the undercoat layer, any known organic solvent such as alcohol, aromatic, halogenated hydrocarbon, ketone, ketone alcohol, ether, ester, etc. Can be selected. For example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, Usual organic solvents such as methylene chloride, chloroform, chlorobenzene, and toluene can be used.

  Various organic and inorganic fine particles can also be mixed for the purpose of preventing moire images and improving electrical characteristics. Examples of the resin particles include silicone resin particles and cross-linked PMMA resin particles, and examples of inorganic fine particles include tin oxide, titanium oxide, zinc oxide, and zirconium oxide.

As a dispersion method, known methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used. Further, as the coating method used when the undercoat layer 1 is provided, conventional methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used. The undercoat layer 1 can be set to any thickness as long as desired characteristics can be obtained.

  Furthermore, the thing which was excellent in the long-term stability of an electrical property and carrier block property is obtained by containing the said inorganic fine particle and acceptor property compound. As the acceptor compound, any compound can be used as long as the desired characteristics can be obtained, but quinone compounds such as chloranil and bromoanil, tetracyanoquinodimethane compounds, 2,4,7-trinitrofluorenone. Fluorenone compounds such as 2,4,5,7-tetranitro-9-fluorenone, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, Oxadiazole compounds such as 5-bis (4-naphthyl) -1,3,4-oxadiazole, 2,5-bis (4-diethylaminophenyl) 1,3,4-oxadiazole, xanthone compounds Preferred are electron transport materials such as thiophene compounds and diphenoquinone compounds such as 3,3 ′, 5,5′-tetra-t-butyldiphenoquinone. , In particular compounds having an anthraquinone structure are preferable. Furthermore, acceptor compounds having an anthraquinone structure such as hydroxyanthraquinone compounds, aminoanthraquinone compounds, aminohydroxyanthraquinone compounds, and the like are preferably used, and specific examples include anthraquinone, alizarin, quinizarin, anthralfin, and purpurin.

(Charge generation layer)
The charge generation layer 2 is a layer containing a charge generation material and a binder resin. As the charge generation material, any material can be used as long as it is substantially transparent to all the exposure light for providing coloring information, but it is substantially effective for visible light such as zinc oxide, titanium oxide, and acid value aluminum. Most preferred are those having no absorption.

The fact that the photoreceptor 10 in the present invention is substantially transparent with respect to the color forming information providing light means that the color forming information providing light is light in a wavelength region that the toner absorbs. This means that the adjustment region and the absorption wavelength region of the photoconductor 10 are greatly deviated.
From this viewpoint, in the present invention, the absolute value of the difference between the absorption peak of each toner and the absorption peak of the photoreceptor 10 is preferably 10 nm or more, and more preferably 30 nm or more.

  More specifically, although depending on the wavelength range of exposure for providing color information, when the light absorption wavelength range of the toner is in the visible light range, the absorption wavelength range of the charge generating material is 400 nm or less. Is preferable, and it is more preferable that it is 395 nm or less.

  Further, as the charge generation material, it is preferable that the photosensitive member is highly sensitive to latent image formation exposure when forming an electrostatic latent image, which will be described later, because it can cope with image formation in a wide speed range. Therefore, it is preferable to use a material having a high charge generation efficiency for exposure. For example, regarding the charge generation material in the above wavelength range, it is more preferable to use zinc oxide rather than titanium oxide.

The binder resin can be selected from a wide range of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane.
Preferred binder resins include polyvinyl butyral resins, polyarylate resins (polycondensates of bisphenols and aromatic divalent carboxylic acids, etc.), polycarbonate resins, polyester resins, phenoxy resins, vinyl chloride-vinyl acetate copolymers, polyamides. Resins, acrylic resins, polyacrylamide resins, polyvinyl pyridine resins, cellulose resins, urethane resins, epoxy resins, caseins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, and the like. These binder resins can be used alone or in combination of two or more. The mixing ratio of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10 by mass ratio.

  The charge generation layer 2 can be formed using a coating liquid in which a charge generation material and a binder resin are dispersed in a predetermined solvent. Solvents include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, Examples thereof include chlorobenzene and toluene, and these can be used alone or in combination of two or more. Moreover, as a method for dispersing the charge generating material and the binder resin in the solvent, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. In this dispersion, it is effective that the average particle size of the charge generating material is 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

Further, when forming the charge generation layer 2, use usual methods such as blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method and the like. Can do.
The thickness of the charge generation layer 2 thus obtained is preferably in the range of 0.1 to 5 μm, preferably in the range of 0.2 to 2.0 μm.

(Charge transport layer)
The charge transport layer 3 is formed containing a charge transport material and a binder resin, or is formed containing a polymer charge transport material.
Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds Electron transporting compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore transporting compounds. These charge transport materials can be used alone or in combination of two or more.
Among these, it is preferable to use a triarylamine compound, a benzidine compound, or the like from the viewpoint that there is almost no absorption in the wavelength range of exposure light for providing color information and the charge mobility is high.

  A polymer charge transport material can also be used as the charge transport material. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293, JP-A-8-208820 and the like have a high charge transporting property and are particularly preferable. The polymer charge transport material can be formed by itself, but may be formed by mixing with a binder resin described later.

The binder resin used for the charge transport layer 3 is polycarbonate resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer. , Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly- N-vinyl carbazole, polysilane, etc. are mentioned. Also, as described above, polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can be used.
These binder resins can be used individually by 1 type or in mixture of 2 or more types. The compounding ratio of the charge transport material and the binder resin is preferably 10: 1 to 1: 5 by mass ratio.

  The charge transport layer 3 can be formed using a coating liquid in which a charge transport material and a binder resin are dispersed in a predetermined solvent. Solvents include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and ethylene chloride, tetrahydrofuran and ethyl. Ordinary organic solvents such as cyclic or straight chain ethers such as ether can be used alone or in admixture of two or more.

As a coating method, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. Further, a known surface protective layer may be provided on the charge transport layer.
The thickness of the charge transport layer 3 is preferably in the range of 5 to 50 μm, more preferably in the range of 10 to 30 μm.

On the other hand, when a toner image is formed by ionography, a dielectric is used as an image carrier instead of the photoreceptor 10. For the same reason, it is preferable to use a transparent dielectric as the dielectric.
As the transparent dielectric, a transparent dielectric layer, for example, a transparent plastic such as PET or PC can be used instead of the photosensitive layer in the transparent photoreceptor.

  A known charging means can be used for charging the photoreceptor 10. In the case of the contact method, a roll, a brush, a magnetic brush, a blade, or the like can be used. In the case of non-contact, a corotron, a scorotron, or the like can be used. The charging means is not limited to these.

  Among these, a contact-type charger is preferably used because of its excellent charge compensation capability. In the contact charging method, the surface of the photosensitive member is charged by applying a voltage to a conductive member brought into contact with the surface of the photosensitive member. The shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roll shape, and the like, but a roll-like member is particularly preferable. Usually, a roll-shaped member is comprised from the resistance layer, the elastic layer which supports them, and a core material from the outside. Furthermore, a protective layer can be provided outside the resistance layer as necessary.

As a method for charging the photosensitive member 10 using these conductive members, a voltage is applied to the conductive member. The applied voltage is preferably a DC voltage or a DC voltage superimposed with an AC voltage. As for the voltage range, in the case of charging only with direct current, the absolute value is preferably positive or negative of a desired surface potential of about + 500V, and the value is preferably 100V to 1500V, more preferably 100 to 1000V. When the AC voltage is superimposed, the DC value is approximately the desired surface potential ± 50 V, the AC peak-to-peak voltage (Vpp) is 400 to 1800 V, preferably 800 to 1600 V, and the frequency of the AC voltage is 50 to 20000 Hz. The frequency is preferably 100 to 5000 Hz, and any of sine wave, square wave, and triangular wave can be used.
The charging potential is preferably set in the range of 150 to 1000 V in terms of the absolute value of the potential.

  A known exposure device 14 can be used for forming the electrostatic latent image. As the exposure device 14, for example, a laser scanning system, an LED image bar system, analog exposure means, an ion flow control head, or the like can be used, and the surface of the photoconductor 10 is exposed as indicated by an arrow A in FIG. It is possible. In addition to this, new exposure means developed in the future can be used as long as the effects of the present invention are achieved.

  The wavelength of the light source is in the spectral sensitivity region of the photoconductor 10. As described above, since the photosensitive layer of the photoreceptor 10 has almost no absorption in the wavelength range of the exposure light for providing color information, the exposure used for forming the electrostatic latent image is used. An exposure device 14 having a wavelength range that matches the absorption wavelength range of the photoreceptor is used. For example, in the above example, the absorption wavelength range of the photoconductor 10 is preferably set to 400 nm. Therefore, in accordance with this, it is preferable to use a second harmonic of a 780 nm semiconductor laser as the exposure device 14.

  Exposure to the photoconductor 10 is performed as a logical sum of the image formation information of the four colors at a position where toner described later is developed in the case of reversal development, and at a position other than developing toner in the case of regular development. The exposure spot diameter is preferably in the range of 40 to 80 μm so that the resolution is in the range of 600 to 1200 dpi. As the exposure amount, it is preferable that the post-exposure potential is in the range of about 5 to 30% of the charging potential. However, when changing the toner development amount according to the gradation of the image, the exposure position The exposure amount may be changed according to the development amount every time.

On the other hand, in the case of the ionography, a latent image is formed on the image carrier by an ion writing head (ion writing step). As an ion writing head, for example, an ion flow On / Off control using an image signal (Japanese Patent Laid-Open No. 4-122654), or an ion flow itself is controlled On / Off (Japanese Patent Laid-Open No. 6-99610). Publication) can be used.
In this method, not only a dielectric but also a photosensitive member can be used as the image carrier.

  A known developing device 16 can be used for developing the electrostatic latent image. As a development method, a two-component development method composed of fine particles and toner for carrying a toner called a carrier, or a one-component development method composed of only a toner, and further improvement of other characteristics in these development methods Any developing method in which other constituents may be added can be used.

  Further, depending on the developing method, any one of the developer that develops in contact or non-contact with the photoreceptor 10 or a combination thereof can be used. Furthermore, a hybrid development method combining the one-component development method and the two-component development method can also be used. In addition to this, a new developing means developed in the future can be used as long as the effect of the present invention is achieved.

The toner contained in the developer includes, for example, a color developing portion that can develop a color of Y (Y color developing portion), a color developing portion that can develop a color of M (M color developing portion), and a color developing portion that can develop a color of C color ( (C coloring portion) may be included in one toner particle, or the Y coloring portion, M coloring portion, and C coloring portion may be included separately for each toner.
The toner development amount (the amount of toner attached to the photoreceptor) varies depending on the image to be formed, but it is preferably in the range of 3.5 to 8.0 g / m ² in a solid image, and is preferably 4.0 to 6 More preferably, it is in the range of 0.0 g / m ² .

  In addition, in the formed toner image T, the light for providing coloring information to be described later must spread over the entire irradiated portion, and therefore it is preferable to keep the toner layer thickness below a certain level. Specifically, for example, in a solid image, the toner layer is preferably 3 layers or less, more preferably 2 layers or less. The toner layer thickness is a value obtained by measuring the thickness of the toner layer actually formed on the surface of the photoconductor 10 and dividing this by the number average particle diameter of the toner.

<Coloring information application process>
Next, as shown in FIG. 1, color information by light as indicated by an arrow B is applied to the toner image T thus obtained by a color information applying device 28 as shown in FIG. Note that the position of the color information providing step shown in FIG. 1 is one example, and as will be described later, the color information providing step may be simultaneous with the development step.

  The coloring information providing device 28 may be anything as long as the toner particles to be colored at that time can emit light having a wavelength for developing a specific color with a predetermined resolution and intensity. For example, an LED image bar, a laser ROS, or the like can be used. In addition, it is preferable that the irradiation spot diameter of the light irradiated to the toner image T is adjusted so that it may become the range of 10-300 micrometers so that the resolution of the image formed may be the range of 100-2400 dpi. More preferably, it is in the range of 200 μm.

The wavelength of light (exposure for providing coloring information) provided to maintain the coloring or non-coloring state is determined by the material design of the toner to be used because it needs to be in the wavelength range absorbed by the toner. When using a toner that develops color by light irradiation of a specific wavelength (photochromic toner), when developing yellow (Y color), 405 nm light (λ _A light) is developed in magenta (M color). At this time, 535 nm light (referred to as λ _B light) is emitted to the desired position where the color is generated, and 657 nm light (referred to as λ _C light) is applied to develop cyan (C color).

When the secondary color is developed, the light is combined. When the red (R color) is developed, λ _A light and λ _B light are used. When the green (G color) is developed, λ _A light and When the λ _C light is colored blue (B color), the λ _B light and the λ _C light are respectively applied to the desired positions for color development. Further, when the black color (K color), which is the tertiary color, is developed, the λ _A light, λ _B light, and λ _C light are applied to the desired positions for color development.

On the other hand, in the case of a toner that maintains a non-colored state by irradiation with light of a specific wavelength (light non-colorable type toner), for example, to prevent yellow (Y color) from being colored, 405 nm light (λ _A light) , 535 nm light (λ _B light) to prevent magenta (M color) color development, and 657 nm light (λ _C light) color development to prevent cyan (C color) color development. Irradiate each desired position. Accordingly, λ _B light and λ _C light are generated when Y color is generated, λ _A light and λ _C light are generated when M color is generated, and λ _A light and λ _B light are generated when C color is generated. Each of the desired positions for color development is irradiated.

When the secondary color is developed, the light is combined. When the red (R color) is developed, λ _C light is emitted. When the green (G color) is developed, λ _B light is transformed into blue (B When a color is developed, λ _A light is irradiated to each desired position for the color development. Further, when black (K color) which is a tertiary color is developed, exposure is not performed at a desired position where the color is developed.

For the light from the coloring information applying device 28, a known image modulation method such as pulse width modulation, intensity modulation, or a combination of the two described above can be used as necessary. The exposure amount of light is preferably in the range of 0.05~0.8mJ / cm ^2, and more preferably in the range of 0.1~0.6mJ / cm ^2. Particularly with respect to the exposure amount, exposure required amount is correlated with the amount of toner developed, for example, 0.2～0.4MJ the toner developing amount (solid) of about 5.5g / ^{m 2} / ^{m 2} It is preferable to perform exposure within the above range.

  In the present invention, as shown in FIG. 7, the color forming information imparting exposure may be performed from the back surface (the surface opposite to the toner image forming surface) of the photoreceptor 10. In this way, since the exposure means 28 for providing color information can be installed inside the image carrier, the entire apparatus can be made more compact. In this case, the substrate such as the transparent photoconductor used in the present invention is substantially transparent to the color forming information imparting exposure, so that there is almost no loss even when the toner image T is exposed through the photoconductor 10. The exposure can be performed with the same amount of light as in the case of exposing from the surface side of the photoreceptor 10 as shown in FIG.

  Further, in the present invention, as indicated by the broken line arrow B ′ in FIG. 7, it is preferable to perform color information providing exposure from the back surface of the photoconductor 10 simultaneously with development (toner image formation) on the photoconductor surface. By performing the color information imparting exposure in this way, it is possible to reduce the misalignment between the toner image formation and the color information provision and to prevent image distortion.

  Even in this case, when the photosensitive member 10 is sensitive (absorbed) in the color information providing light wavelength region, the electrostatic latent image formed by the exposure device 14 may be disturbed due to a slight positional shift during exposure. However, since the transparent photosensitive member used in the present invention is almost transparent to the color forming information imparting light, the electrostatic latent image is not disturbed as described above.

  In the present invention, when a transparent photoconductor is used as the substrate, the configuration is not limited to that shown in FIGS. 1 and 7, but the sensitivity wavelength range of the transparent photoconductor, the relationship between latent image formation and development, and the color information providing device. Various configurations can be adopted depending on the arrangement, the position where the color information providing apparatus irradiates the exposure light, and the arrangement of the exposure means for forming the latent image.

Hereinafter, it will be briefly described at what timing and by what position control the exposure for providing the color information is performed.
FIG. 8 is a specific circuit block diagram of the print control unit in the image forming apparatus of the present invention. In the figure, the printer controller 36 includes an OR circuit 40, an oscillation circuit 42, a magenta color control circuit 44M, a cyan color control circuit 44C, a yellow color control circuit 44Y, and a black color control circuit 44K. On the other hand, the exposure unit 38 is composed of an optical writing head 32 and a coloring information applying exposure head 34.

  Image data obtained by converting input RGB signals into CMYK values by an interface (I / F) (not shown) is further transmitted from the interface (I / F) to magenta (M), cyan (C), yellow (Y), and black. The pixel data (K) is output to the OR circuit 40. Here, the logical sum circuit 40 calculates the logical sum of CMYK and outputs it to the optical writing head 32.

  That is, logical sum data including all CMYK pixel data is output to the optical writing head 32, and optical writing is performed on the photosensitive member 10 as described above. Therefore, an electrostatic latent image based on logical sum data including all CMYK pixel data is formed on the peripheral surface of the photoreceptor 10.

  The CMYK pixel data is also supplied to the corresponding magenta color control circuit 44M to black color control circuit 44K, and the color information providing exposure head is synchronized with the oscillation signals fm, fc, fy, and fk output from the oscillation circuit 42. 34. That is, color data corresponding to each of magenta (M), cyan (C), yellow (Y), and black (K) is supplied to the color information providing exposure head 34, and the toner image T developed on the photoreceptor 10 is developed. Corresponding to the above, light of a specific wavelength for maintaining a colored or non-colored state is irradiated. Therefore, a photocuring reaction, which will be described later, occurs in the toner that has received the irradiated light, and color development information is given.

For example, color signal fm outputted from the magenta coloring control circuit 44M irradiates the lambda _B light in the color of the toner to the toner in a state capable of color development of magenta (M) color. In addition, the color development signal fc output from the cyan color development control circuit 44C irradiates the color development portion in the toner with the λ _C light, and makes the toner capable of developing cyan (C) color. Further, the same applies to yellow (Y) and black (K), and the color signals fy and fk output from the yellow color control circuit 44Y and the black color control circuit 44K are transmitted to the color development portion in the toner by the λ _A light or Irradiation with λ _A light, λ _B light, and λ _C light enables a yellow (Y) or black (K) color.

  As described above, the mechanism for forming a full color image has been described with respect to the color information providing step (means) in the present invention. However, the color information providing step in the present invention is a monochromatic color that produces one of yellow, magenta, and cyan. It may be a color information providing step for forming a color image. In this case, only the light of a specific wavelength corresponding to the desired color development among the yellow, magenta, and cyan is emitted from the color development information imparting exposure head 54. Other preferable conditions and the like are the same as those at the time of full-color image formation.

<Transfer process>
The toner to which the color development information is given is then transferred to the recording medium 26 at a time. A known transfer device 18 can be used for transfer. For example, rolls, brushes, blades, and the like can be used for the contact method, and corotron, scorotron, pin corotron, and the like can be used for the non-contact method. Also, transfer by pressure or pressure and heat is possible.

  The transfer bias is preferably in the range of 300 to 1000 V (absolute value), and alternating current (Vpp: 400 V to 4 kV, 400 to 3 kHz) may be superimposed.

<Fixing process and coloring process>
The toner image in a state where it can be colored (or maintained in a non-colored state) is colored as described above when the recording medium 26 is heated by the fixing device 22. A known fixing means can be used as the fixing device 22. For example, a roll or a belt can be selected as the heating member and the pressure member, and a halogen lamp, IH, or the like can be used as the heat source. The arrangement can also correspond to various paper paths, for example, a straight path, a rear C path, a front C path, an S path, a side C path, and the like.

  In the present embodiment, the fixing device 22 serves as both a coloring process and a fixing process, but the coloring process may be provided separately from the fixing process. There is no particular limitation on the position where the color developing device for performing the color developing step is arranged.

  As the color development method, various methods can be considered according to the color development mechanism of the toner particles. Therefore, as the color development device (color development means), for example, the color development-related substance is cured in the toner using light of a different wavelength. Alternatively, a light emitting device that emits specific light by a method such as photolysis or a method that restricts the color, or a pressure device that causes a color to be developed or restricted by a method such as destroying colored particles encapsulated by pressurization. , Etc. can be used.

  However, these chemical reactions that cause color development generally have a slow reaction rate due to migration and diffusion, so it is necessary to give sufficient diffusion energy to any of the above methods. It can be said that the method of promoting the reaction is the best. For this reason, it is preferable to use a fixing device 22 that serves as both the color developing step and the fixing step.

<Other processes>
In this invention, it is preferable to include the light irradiation process which irradiates light to the image obtained through the fixing and coloring process. This makes it possible to decompose or deactivate the reactive substances remaining in the color-development part that has been controlled to be incapable of color development. Can be removed and bleached.
In this embodiment, the light irradiation step is provided after the fixing step. However, in the case of a fixing method that does not heat and melt, for example, pressure fixing in which fixing is performed using pressure, the fixing step is performed after the light irradiation step. Can also be done.

  The light irradiation device 24 is not particularly limited as long as the color development of the toner can be prevented from proceeding further, and a known lamp such as a fluorescent lamp, LED, EL, or the like can be used. Further, the wavelength includes three wavelengths in the light for coloring the toner, the illuminance is preferably in the range of 2000 to 200000 lux, and the exposure time is preferably in the range of 0.5 to 60 sec.

  In addition to these, the above-described image forming method may include a known process used in an electrophotographic process performed using a colorant such as a conventional pigment, for example, after transferring a toner image. A cleaning step for cleaning the surface of the image carrier may be included. As the cleaner 20, a known one can be used, and a blade, a brush, or the like can be used. A so-called cleaner-less process in which the cleaner 20 is removed is also applicable.

  In addition, the transfer process includes a first transfer process in which a toner image is transferred from an image carrier to an intermediate transfer body such as an intermediate transfer belt, and the toner image transferred onto the intermediate transfer body is used as a recording medium. An intermediate transfer method including a second transfer step for transferring may be used.

<Toner to be used>
Next, the toner used in the present invention will be described.
As described above, the toner used in the present invention is a toner that is controlled so as to be able to maintain a colored state or a non-colored state by applying coloring information by light. “Maintaining a colored or non-colored state” is also as described above.

  There are various types of toner having the above functions. For example, the toner disclosed in Patent Document 2 is a plurality of microcapsules having a capsule wall whose substance permeability is changed by an external stimulus. Are dispersed and mixed in a toner resin, and one of two kinds of reactive substances (color dye precursors) mixed with each other to cause a color reaction is contained in the microcapsule and the other. (Developer) is contained in the toner resin outside the microcapsule.

This toner uses a photoisomerized substance that increases the substance permeability when irradiated with light of a specific wavelength as the capsule wall, and when applying light irradiation or ultrasonic waves using this cis-trans transition, Two kinds of reactive substances existing inside and outside the capsule react to develop color.
Therefore, in the case of the toner of this configuration, since the cis-trans transition is a reversible reaction, even if the transition from the trans state to the cis state occurs due to light stimulation and the developer slightly permeates the capsule wall, the printing process When it returns to the trans state, a sufficient color development reaction (density) may not be obtained during color development by heating.

  For this reason, in the present invention, a photocurable composition comprising a first component and a second component that exist in a state of being separated from each other and that develop color when reacted with each other, and any one of the first component and the second component And the photocurable composition is maintained in a cured or uncured state by the application of color development information by light, and the reaction for color development is controlled (hereinafter referred to as “F toner”). In some cases).

As will be described later, in the F toner, since the coloring information imparting mechanism for the toner is not a reversible reaction, the toner to be colored for highlight image formation can be stably colored at a low halftone density. Therefore, it is possible to form a high quality image as seen in current multicolor ink jet printers. In addition, as described above, the coloring information imparting mechanism is not a reversible reaction, and as a result, there is no time restriction until color development by heating. As a result, printing up to a low speed range is possible, that is, it is compatible with a wide speed range. In addition, there is a merit that the placement location of the fixing device or the like where color development is performed by heating is also highly flexible.
The coloring mechanism and simple structure of the F toner will be described below.

As will be described later, the F toner can be colored in one specific color (or can maintain a non-colored state) when color development information by light called a color development portion is imparted to the binder resin. ) It has one or more continuous areas.
FIG. 9 is a schematic view showing an example of the color developing portion in the F toner. FIG. 9A is a cross-sectional view of one color developing portion, and FIG. 9B is an enlarged view of the color developing portion.

  As shown in FIG. 9 (A), the color developing portion 60 is composed of color-forming microcapsules 50 containing color formers of the respective colors and a composition 58 surrounding the color-forming microcapsules 50, as shown in FIG. 9 (B). The composition 58 is photopolymerized with a developer monomer (second component) 54 having a polymerizable functional group that develops color by being close to or in contact with the color former (first component) 52 contained in the microcapsule 50. And an initiator 56.

  As the color former 52 encapsulated in the color developable microcapsules 50 in the color development portion 60 constituting the toner particles, a triaryl leuco compound having excellent color development hue is suitable. As the developer monomer 54 for coloring the leuco compound (electron donating property), an electron accepting compound is preferable. In particular, phenolic compounds are common, and can be appropriately selected from color developers used for heat-sensitive and pressure-sensitive paper. The color former develops color by an acid-base reaction between the electron donating color former 52 and the electron acceptor developer monomer 54.

As the photopolymerization initiator 56, a spectral sensitizing dye that generates a polymerizable radical that is exposed to visible light and serves as a trigger for polymerizing the developer monomer 54 is used. For example, a reaction accelerator of the photopolymerization initiator 56 is used so that the color developing monomer 54 can cause a sufficient polymerization reaction to undergo the three primary color exposures such as R color, G color, and B color. For example, by using an ion complex composed of a spectral sensitizing dye (cation) that absorbs exposure light and a boron compound (anion), the spectral sensitizing dye is photoexcited by exposure and electron-transferred to the boron compound, thereby generating a polymerizable radical. To initiate polymerization.
By combining these materials, a color recording sensitivity of about 0.1 to 0.2 mJ / cm ² can be obtained as the photosensitive color developing portion 60.

  Depending on the presence / absence of light irradiation for color forming information on the color forming part 60 having the above-described configuration, some of the color forming part 60 has a polymer developer compound that has been polymerized and a developer monomer 54 that has not been polymerized. . In the color development unit 60 having the developer monomer 54 that has not been polymerized by a subsequent color development device such as heating, the color developer monomer 54 migrates due to heat or the like, and migrates through the pores of the partition walls of the color developer microcapsule 50. Passes through and diffuses into the color former microcapsules. The developer monomer 54 and the color former 52 diffused in the microcapsule 50 are, as described above, the color former 52 is basic and the developer monomer 54 is acidic, so that the color developer 52 is acid-base. The reaction will cause color development.

  On the other hand, the developer compound that has undergone the polymerization reaction cannot pass through the pores of the partition walls of the microcapsule 50 due to the bulk due to the polymerization in the subsequent color development step by heating or the like, and the color former 52 in the color development microcapsule. Color cannot be developed because it cannot react. Therefore, the chromogenic microcapsule 50 remains colorless. That is, the color developing portion 60 irradiated with the specific wavelength light is colored and exists.

  After color development, the entire surface is exposed again with a white light source at an appropriate stage to polymerize all remaining undeveloped color developing monomer 54 to achieve stable image fixing, and residual spectral sensitizing dye. The ground color is erased by disassembling. Note that the spectral sensitizing dye of the photopolymerization initiator 56 corresponding to the visible light region remains as a ground color until the end. Color phenomenon can be used. In other words, a polymerizable radical is generated by electron transfer from a photoexcited spectral sensitizing dye to a boron compound. This radical causes polymerization of the monomer, while reacting with the excited dye radical to cause color separation of the dye. As a result, the pigment can be decolored.

In the F toner, the color developing portions 60 (for example, coloring in Y color, M color, and C color) that perform such different color development are used as color developing agents other than the color developing agent 52 intended by the respective developer monomers 54. And can be used as one microcapsule in a state where they do not interfere with each other (in a state where they are isolated from each other). In this F toner, the space other than the microcapsules containing the electron-donating color former is filled with the electron-accepting developer and the photocurable composition, and the color-developing portion constituted thereby receives the light. The light receiving efficiency of the toner particles is overwhelmingly higher than that of the toner disclosed in Patent Document 2. Therefore, compared with other toners, for example, the effect of the back exposure can be fully utilized.
In addition, as described above, the coloring information imparting mechanism is not a reversible reaction, and as a result, there is no time restriction until color development by heating. As a result, printing up to a low speed range is possible, that is, it is compatible with a wide speed range. In addition, there is also a merit that the degree of freedom is high with respect to the arrangement place of the fixing device or the like where coloring is performed by heating.

The configuration of the F toner will be further described in detail.
The F toner includes a first component and a second component that exist in a state of being separated from each other as colorable substances (coloring substances) and that develop colors when they react with each other. As described above, color development is facilitated by color development utilizing the reaction of two types of reactive components. The first component and the second component may be pre-colored in a state before color development, but are particularly preferably substantially colorless substances.

In order to facilitate the color development control, two types of reactive components that develop color when reacting with each other are used as the color developing materials. However, these reactive components do not diffuse the substance even when the color development information by light is not given. If they exist in the same easy matrix, spontaneous color development may progress during storage or manufacture of the toner.
For this reason, it is necessary that the reactive component be contained in different matrices (separated from each other) that are difficult to diffuse into each other region unless coloring information is given. is there.

  Thus, in order to inhibit the material diffusion in the state where the color development information by light is not given and prevent spontaneous color development at the time of storage or production of the toner, the first component of the two types of reactive components is Contained in the first matrix, the second component is contained outside the first matrix (second matrix), and between the first matrix and the second matrix, there is diffusion of the substance between the two matrices. When an external stimulus such as heat is applied, a partition wall having a function that enables diffusion of substances between both matrices according to the kind, strength, and combination of the stimulus is provided. Is preferred.

In order to place two types of reactive components in the toner using such a partition wall, it is preferable to use microcapsules.
In this case, the F toner preferably includes, for example, the first component of the two types of reactive components inside the microcapsule and the second component outside the microcapsule. In this case, the inside of the microcapsule corresponds to the first matrix, and the outside of the microcapsule corresponds to the second matrix.

  This microcapsule has a core part and an outer shell covering the core part, and inhibits diffusion of substances inside and outside the microcapsule and external stimulus as long as external stimulus such as heat is not given. In this case, there is no particular limitation as long as it has a function that enables diffusion of substances inside and outside the microcapsule according to the type, strength, and combination of the stimulus. The core part contains at least one of the reactive components.

In addition, the microcapsule may be capable of diffusing substances inside and outside the microcapsule by applying light or applying a stimulus such as pressure, but the substance can be diffused inside and outside the microcapsule by heat treatment (outer shell substance). Particularly preferred are thermoresponsive microcapsules (which increase permeability).
In addition, the substance diffusion inside and outside the microcapsule when a stimulus is applied, from the viewpoint of suppressing a decrease in color density during image formation or suppressing a change in color balance of an image left in a high temperature environment, It is preferably irreversible. Therefore, the outer shell of the microcapsule irreversibly increases its substance permeability due to softening, decomposition, dissolution (compatibility with surrounding members), deformation, etc. by applying heat treatment, light irradiation and other stimuli. It is preferable to have the function of

Next, a preferable configuration when the F toner includes microcapsules will be described.
Such a toner preferably includes a first component and a second component that develop color when they react with each other, a microcapsule, and a photocurable composition in which the second component is dispersed. Examples of the toner include the following three modes.

That is, the F toner includes a first component and a second component that develop color when they react with each other, a photocurable composition, and microcapsules dispersed in the photocurable composition, and the first component is A mode (first mode) in which the second component is contained in the microcapsule and contained in the photocurable composition, a first component and a second component that develop color when reacted with each other, and a photocurable composition A mode in which the first component is included outside the microcapsule and the second component is included in the photocurable composition (second mode), or the first component that develops color when reacted with each other And a second component, one microcapsule containing the first component, and another microcapsule containing a photocurable composition in which the second component is dispersed (third embodiment). It is preferable.
Among these three modes, the first mode is particularly preferable from the viewpoints of stability before giving color development information by light, control of color development, and the like. In the following description of the toner, the toner will be described in detail basically on the assumption of the toner of the first aspect. However, the configuration, material, manufacturing method, and the like of the toner of the first aspect described below will be Of course, the toners of the third and third aspects can also be used / reused.

In addition, it is particularly preferable that the F toner using a combination of the above-described thermoresponsive microcapsule and the photocurable composition is one of the following two types.
(1) Even if the photocurable composition is heat-treated in an uncured state, the material diffusion of the second component contained in the uncured photocurable composition is suppressed, and light is emitted by irradiation with the color forming information providing light. When the heat treatment is performed after the curable composition is cured, a toner of a type that promotes material diffusion of the second component contained in the cured photocurable composition (hereinafter, referred to as “photochromic toner”). is there).
(2) When the photocurable composition is heat-treated in an uncured state (a state where the second component is not polymerized), the material diffusion of the second component contained in the uncured photocurable composition is promoted. When the photocurable composition is cured by irradiation with the color forming information imparting light (after the second component is polymerized), the material diffusion of the second component contained in the cured photocurable composition is caused. The type of toner to be suppressed (hereinafter sometimes referred to as “light non-color developing toner”).

The main difference between the photochromic toner and the non-photochromic toner is in the material constituting the photocurable composition. In the photochromic toner, the photocurable toner has no photopolymerizability. ) Whereas the second component and the photopolymerizable compound are at least included, the photo-non-colorable toner includes at least the second component having a photopolymerizable group in the molecule in the photocurable composition. .
The photocurable composition used in the photochromic toner and the non-photochromic toner preferably contains a photopolymerization initiator, and various other materials are contained as necessary. May be.

  As the photopolymerizable compound and the second component used in the photochromic toner, the interaction between the photocurable composition and the second component in the photocurable composition works in an uncured state. In the photocurable composition, the substance diffusion is suppressed, and the interaction between the two decreases in the state after curing of the photocurable composition (polymerization of the photopolymerizable compound) by irradiation with the color forming information imparting light. A material that facilitates diffusion of the second component is used.

Therefore, in the photochromic toner, before the heat treatment (coloring step), the coloration information imparting light having a wavelength for curing the photocurable composition is irradiated in advance, so that the first color contained in the photocurable composition. The two-component material diffusion becomes easy. Therefore, when the heat treatment is performed, a reaction (coloring reaction) between the first component in the microcapsule and the second component in the photocurable composition occurs due to dissolution of the outer shell of the microcapsule or the like.
On the contrary, the second component is trapped in the photopolymerizable compound even if it is heat-treated without irradiating the color-forming information imparting light having a wavelength for curing the photocurable composition, and comes into contact with the first component in the microcapsule. The reaction between the first component and the second component (coloring reaction) does not occur.

  As described above, in the photochromic toner, the first component and the second component are applied by combining the presence / absence of irradiation with color forming information providing light having a wavelength for curing the photocurable composition and the heat treatment. Can control the color development of the toner.

Further, in the non-photochromic toner, since the second component itself has photopolymerization property, even when irradiated with the color forming information imparting light, the wavelength of this light is not the wavelength that cures the photocurable composition, Since the second component contained in the photocurable composition can be easily diffused, if the heat treatment is performed in this state, the first component in the microcapsule and the photocurable composition are dissolved by dissolution of the outer shell of the microcapsule. Reaction (coloring reaction) with the second component in the composition occurs.
On the contrary, when the coloring information imparting light having a wavelength for curing the photocurable composition is irradiated before the heat treatment, the second components contained in the photocurable composition are polymerized with each other. The material diffusion of the second component contained in the composition becomes difficult. Therefore, the second component cannot be brought into contact with the first component in the microcapsule even when the heat treatment is performed, and the reaction (coloring reaction) between the first component and the second component does not occur.

  As described above, in the non-photochromic toner, the first component and the second component can be applied by combining the heat treatment with the presence / absence of irradiation with color forming information providing light having a wavelength for curing the photocurable composition. Since the reaction (coloring reaction) with the components can be controlled, the color development of the toner can be controlled.

Next, a preferable structure of the F toner will be described in more detail when the toner includes the photocurable composition and microcapsules dispersed in the photocurable composition.
In this case, the toner may have only one color developing portion including a photocurable composition and microcapsules dispersed in the photocurable composition, but preferably has two or more. Here, the “coloring portion” means a continuous region that can develop a specific color when an external stimulus is applied as described above.
When the toner includes two or more coloring portions, only one type of coloring portion that can develop the same color may be included in the toner, but two or more types of coloring that can develop colors different from each other may be included. It is particularly preferable that the part is contained in the toner. The reason is that the color that can be developed by one toner particle is limited to only one type in the former case, but can be two or more in the latter case.

For example, as two or more types of color developing portions capable of developing colors different from each other, a yellow coloring portion capable of developing yellow, a magenta coloring portion capable of developing magenta, and a cyan coloring portion capable of developing cyan Combinations including these are mentioned.
In this case, for example, when only one type of coloring portion is colored by the application of an external stimulus, the toner can be colored in any one of yellow, magenta, and cyan, and any two When various types of coloring portions develop color, the colors developed by these two types of coloring portions can be combined, and various colors can be expressed with a single toner particle.

The control of the color to be developed when the toner includes two or more types of coloring portions that can develop colors different from each other depends on the types and combinations of the first component and the second component included in each type of coloring portion. In addition to making the wavelength different, it can be realized by making the wavelength of light used for curing the photocurable composition contained in each type of color developing portion different.
That is, in this case, since the wavelength of light necessary for curing the photocurable composition contained in the color developing portion differs for each type of color developing portion, a plurality of types having different wavelengths according to the type of color developing portion are used as control stimuli. Coloring information imparting light may be used. In order to make the wavelength of light necessary for curing the photocurable composition contained in the color developing part different, a photopolymerization initiator sensitive to light of a different wavelength is used for each type of color developing part. It is suitable for inclusion in the product.

For example, when the toner includes three types of color-developing parts capable of coloring yellow, magenta, and cyan, the photocurable composition contained in each type of color-forming part has a light wavelength of 405 nm, 532 nm, and If a material that cures in response to any of 657 nm is used, the toner can be colored to a desired color by properly using these three color-developing information-giving lights (lights having specific wavelengths).
The wavelength of the coloring information imparting light can be selected from the visible wavelength, but may be selected from the ultraviolet wavelength.

  The toner used in the present invention may include a base material mainly composed of a binder resin similar to that used in a toner using a colorant such as a conventional pigment. In this case, it is preferable that each of the two or more coloring portions is dispersed as a particulate capsule in the base material (hereinafter, one capsule-like coloring portion may be referred to as a “photosensitive / thermosensitive capsule”). is there). Further, in the base material, a release agent and various additives may be contained in the same manner as a toner using a colorant such as a conventional pigment.

The photosensitive / thermosensitive capsule has a core portion containing a microcapsule and a photocurable composition, and an outer shell covering the core portion, and this outer shell is used in the toner production process and toner storage described later. However, the microcapsules and the photocurable composition in the photosensitive / thermosensitive capsule are not particularly limited as long as they can be stably held so as not to leak out of the photosensitive / thermal capsule.
However, in the present invention, in the toner production process described later, the second component passes through the outer shell and flows out to the matrix outside the photosensitive / thermosensitive capsule, or in the photosensitive / thermosensitive capsule capable of developing other colors. In order to prevent the second component from flowing through the outer shell, it is preferable that the second component contains a water-insoluble material such as a binder resin made of a water-insoluble resin or a release material as a main component.

Next, the toner constituent materials used for the F toner and the materials and methods used for adjusting the toner constituent materials will be described in more detail below.
In this case, at least a first component, a second component, a microcapsule containing the first component, and a photocurable composition containing the second component are used for the toner, and a photopolymerization initiator is contained in the photocurable composition. Is particularly preferable, and various auxiliary agents and the like may be included. Further, the first component may be present in a solid state in the microcapsule (core portion), but may be present together with a solvent.

In the light non-color-forming toner, an electron-donating colorless dye or a diazonium salt compound is used as the first component, and an electron-accepting compound having a photopolymerizable group or a photopolymerizable group is used as the second component. A coupler compound or the like is used. In the photochromic toner, an electron-donating colorless dye is used as the first component, and an electron-accepting compound (“electron-accepting developer” or “developer”) is used as the second component. And a polymerizable compound having an ethylenically unsaturated bond is used as the photopolymerizable compound.
In addition to the above-listed materials, various materials similar to those constituting conventional toners using colorants; binder resins, mold release agents, internal additives, external additives, etc., as necessary It can be used as appropriate. Hereinafter, each material etc. are demonstrated in detail.

-1st component and 2nd component-
As the combination of the first component and the second component, the following combinations (a) to (tu) can be preferably mentioned (in the following examples, the former represents the first component and the latter represents the second component, respectively). .

(A) A combination of an electron-donating colorless dye and an electron-accepting compound.
(A) A combination of a diazonium salt compound and a coupling component (hereinafter appropriately referred to as “coupler compound”).
(C) A combination of an organic acid metal salt such as silver behenate or silver stearate and a reducing agent such as protocatechinic acid, spiroindane or hydroquinone.
(D) A combination of a long-chain fatty acid iron salt such as ferric stearate or ferric myristate and a phenol such as tannic acid, gallic acid or ammonium salicylate.
(E) Organic acid heavy metal salts such as nickel, cobalt, lead, copper, iron, mercury and silver salts such as acetic acid, stearic acid and palmitic acid, and alkali metals or alkaline earth such as calcium sulfide, strontium sulfide and potassium sulfide A combination of a metal sulfide or a combination of the organic acid heavy metal salt and an organic chelating agent such as s-diphenylcarbazide or diphenylcarbazone.

(F) A combination of a heavy metal sulfate such as a sulfate such as silver, lead, mercury or sodium and a sulfur compound such as sodium tetrathionate, sodium thiosulfate or thiourea.
(G) A combination of an aliphatic ferric salt such as ferric stearate and an aromatic polyhydroxy compound such as 3,4-hydroxytetraphenylmethane.
(H) A combination of an organic acid metal salt such as silver oxalate or mercury oxalate and an organic polyhydroxy compound such as polyhydroxy alcohol, glycerin or glycol.
(G) A combination of a ferric salt of a fatty acid such as ferric pelargonate or ferric laurate and a thiocesylcarbamide or isothiocecilcarbamide derivative.
(Co) A combination of a lead salt of an organic acid such as lead caproate, lead pelargonate or lead behenate and a thiourea derivative such as ethylenethiourea or N-dodecylthiourea.

(Sa) A combination of a higher aliphatic heavy metal salt such as ferric stearate or copper stearate and zinc dialkyldithiocarbamate.
(B) Those that form an oxazine dye such as a combination of resorcin and a nitroso compound.
(Su) A combination of a formazan compound and a reducing agent and / or a metal salt.
(C) A combination of a protected dye (or leuco dye) precursor and a deprotecting agent.
(So) A combination of an oxidizing color former and an oxidizing agent.
(Ta) A combination of phthalonitriles and diiminoisoindolines. (A combination that produces phthalocyanine.)
(H) A combination of isocyanates and diiminoisoindolines (a combination that produces a colored pigment).
(Iv) A combination of a pigment precursor and an acid or a base (a combination formed by a pigment).

The first component listed above is preferably a substantially colorless electron-donating colorless dye or a diazonium salt compound.
As the electron-donating colorless dye, conventionally known dyes can be used, and any dye that reacts with the second component and develops color can be used. Specifically, phthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucooramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, pyridine Examples thereof include various compounds such as phosphines, pyrazine compounds, and fluorene compounds.

  In the case of the non-photochromic toner, the second component is a substantially colorless compound having a photopolymerizable group and a site that develops color by reacting with the first component in the same molecule. Any compound that has both functions of reacting with the first component such as an electron-accepting compound having a photopolymer or a coupler compound having a photopolymerizable group to develop a color and reacting with light to be cured and cured. be able to.

  The electron-accepting compound having a photopolymerizable group, that is, a compound having an electron-accepting group and a photopolymerizable group in the same molecule has a photopolymerizable group and is one of the first components. Any colorant can be used as long as it reacts with an electron-donating colorless dye and develops color and can be cured by photopolymerization.

  The electron-accepting developer as the second component in the case of the photochromic toner includes phenol derivatives, sulfur-containing phenol derivatives, organic carboxylic acid derivatives (for example, salicylic acid, stearic acid, resorcinic acid, etc.), and Examples thereof include metal salts thereof, sulfonic acid derivatives, urea or thiourea derivatives, acidic clay, bentonite, novolac resins, metal-treated novolac resins, metal complexes, and the like.

  Further, in the photochromic toner, a polymerizable compound having an ethylenically unsaturated bond is used as a photopolymerizable compound, and this is at least in a molecule such as acrylic acid and a salt thereof, an acrylic ester, and an acrylamide. It is a polymerizable compound having one ethylenically unsaturated double bond.

  Next, the photopolymerization initiator will be described. The photopolymerization initiator can generate radicals by irradiating with color forming information imparting light to cause a polymerization reaction in the photocurable composition, and can accelerate the reaction. The photocurable composition is cured by this polymerization reaction.

The photopolymerization initiator can be appropriately selected from known ones, and includes, among others, a spectral sensitizing compound having a maximum absorption wavelength at 300 to 1000 nm and a compound that interacts with the spectral sensitizing compound. It is preferable that
However, if the compound that interacts with the spectral sensitizing compound is a compound having both a dye part and a borate part having a maximum absorption wavelength at 300 to 1000 nm in the structure, the spectral sensitizing dye is used. It does not have to be.

As the compound that interacts with the spectral sensitizing compound, one or more compounds are appropriately selected from known compounds capable of initiating a photopolymerization reaction with the photopolymerizable group in the second component. Can be used.
By making this compound coexist with the above-mentioned spectral sensitizing compound, it is sensitive to the irradiation light in the spectral absorption wavelength region and can generate radicals with high efficiency. Generation of radicals can be controlled using an arbitrary light source in the outer region.

  The “compound interacting with the spectral sensitizing compound” is preferably an organic borate salt compound, a benzoin ether, an S-triazine derivative having a trihalogen-substituted methyl group, an organic peroxide or an azinium salt compound. Borate salt compounds are more preferred. By using this “compound that interacts with the spectral sensitizing compound” in combination with the spectral sensitizing compound, radicals can be generated locally and effectively in the exposed exposed portion, thereby increasing the sensitivity. Can be achieved.

In addition, the photo-curable composition further promotes the polymerization by a transfer agent such as an oxygen scavenger or a chain transfer agent of an active hydrogen donor as an auxiliary agent for the purpose of promoting the polymerization reaction. Other compounds can also be added.
Examples of the oxygen scavenger include phosphine, phosphonate, phosphite, first silver salt, and other compounds that are easily oxidized by oxygen. Specific examples include N-phenylglycine, trimethyl parbituric acid, N, N-dimethyl-2,6-diisopropylaniline, and N, N, N-2,4,6-pentamethylanilic acid. Furthermore, thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, azides and the like are also useful as polymerization accelerators.

In the F toner, a first component such as an electron-donating colorless dye or a diazonium salt compound is encapsulated in a microcapsule.
A conventionally known method can be used as a microencapsulation method. For example, a method using coacervation of hydrophilic wall forming materials described in U.S. Pat. Nos. 2,800,547 and 2,800,458, U.S. Pat. No. 3,287,154, British Patent No. 990443, Japanese Patent Publication No. 38-19574, No. 42. No. -446, No. 42-771, etc., an interfacial polymerization method described in US Pat. Nos. 3,418,250 and 3,660,304, and an isocyanate polyol wall material described in US Pat. No. 3,796,669 are used. A method using an isocyanate wall material described in US Pat. No. 3,914,511, a method using a urea-formaldehyde system, a urea formaldehyde-resorcinol-based wall forming material described in US Pat. US 402 No. 455, a method using a wall-forming material such as melamine-formaldehyde resin, hydroxybrovir cellulose, etc., Japanese Patent Publication No. 36-9168, Japanese Patent Application Laid-Open No. 51-9079, in situ method by polymerization of monomers, British Patent No. 952807, Electrolytic dispersion cooling method described in U.S. Pat. No. 965074, US Pat. No. 3,111,407, British Patent No. 930422, Spray drying method, JP-B-7-73069, JP-A-4-101858, Examples include the method described in Kaihei 9-263057.

  The microcapsule wall material that can be used is added inside and / or outside the oil droplets. Examples of the material of the microcapsule wall include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, and the like. Among these, polyurethane, polyurea, polyamide, polyester, and polycarbonate are preferable, and polyurethane and polyurea are more preferable. Two or more kinds of the polymer substances can be used in combination.

  The volume average particle size of the microcapsules is preferably adjusted to be in the range of 0.1 to 3.0 μm, and more preferably adjusted to be in the range of 0.3 to 1.0 μm.

The photosensitive / thermosensitive capsule may contain a binder, and this is the same for a toner having one color developing portion.
The binder is the same as the binder used for emulsifying and dispersing the photocurable composition, a water-soluble polymer used for encapsulating the first reactive substance, polystyrene, polyvinyl formal, polyvinyl butyral, poly Acrylic resins such as methyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and their copolymers, solvent-soluble polymers such as phenol resin, styrene-butadiene resin, ethyl cellulose, epoxy resin, urethane resin, or these It is also possible to use a polymer latex. Of these, gelatin and polyvinyl alcohol are preferred. Moreover, you may use the binder resin mentioned later as a binder.

  For the F toner, a binder resin used in conventional toners can be used. For example, in a toner having a structure in which photosensitive / thermal capsules are dispersed in a base material, the binder resin can be used as a main component constituting the base material and a material constituting the outer shell of the photosensitive / thermal capsule. It is not limited to this.

  The binder resin is not particularly limited, and a known crystalline or amorphous resin material can be used. In particular, a crystalline polyester resin having sharp melt properties is useful for imparting low-temperature fixability. In addition, as the amorphous polymer (amorphous resin), a known resin material such as a styrene acrylic resin or a polyester resin can be used, but an amorphous polyester resin is particularly preferable.

  In addition, the F toner may contain other components other than those listed above. Other components are not particularly limited and may be appropriately selected depending on the purpose. For example, various known additives used in conventional toners such as release agents, inorganic fine particles, organic fine particles, and charge control agents. Can be mentioned

Next, a method for manufacturing F toner will be briefly described.
The F toner is preferably prepared using a known wet manufacturing method such as an aggregation coalescence method. In particular, a first component and a second component that develop color when they react with each other, a photocurable composition, and a microcapsule dispersed in the photocurable composition, wherein the first component is contained in the microcapsule. The wet manufacturing method is suitable for producing a toner having a structure in which the second component is contained in the photocurable composition.
The microcapsules used for the toner having the above structure are particularly preferably thermoresponsive microcapsules, but may be microcapsules that respond to other stimuli such as light.

For the production of toner, a known wet manufacturing method can be used. Among the wet manufacturing methods, the maximum process temperature can be kept low, and the toner having various structures can be easily produced. It is particularly preferable to do this.
Compared to conventional toners mainly composed of pigments and binder resins, toners having the above structure contain more photocurable compositions containing low-molecular components as the main component. Although the strength of the particles obtained by the above method tends to be insufficient, the aggregation and coalescence method does not require a high shearing force, and it is preferable to use the aggregation and coalescence method in this respect as well.

In general, the aggregation and coalescence method includes an aggregation step in which a dispersion of various materials constituting a toner is prepared, and then aggregated particles are formed in a raw material dispersion obtained by mixing two or more types of dispersions. And a coalescing step for fusing the agglomerated particles formed on the surface of the agglomerated particles to form a coating layer between the agglomeration step and the fusing step. The adhesion process (coating layer formation process) to form is implemented.
Also in the production of the F toner, although the types and combinations of the various dispersions used as raw materials are different, the toner can be prepared by appropriately combining the adhering step in addition to the aggregation step and the fusion step.

  For example, in the case of a toner having a photosensitive / thermosensitive capsule dispersion structure in a resin, first, (a1) a microcapsule dispersion in which microcapsules containing a first component are dispersed and a photocurable composition containing a second component A first aggregating step for forming first agglomerated particles in a raw material dispersion containing a photocurable composition dispersion in which a product is dispersed; and (b1) a raw material on which the first agglomerated particles are formed. An adhesion step of adding a first resin particle dispersion in which resin particles are dispersed to the dispersion and attaching the resin particles to the surface of the aggregated particles; and (c1) attaching the resin particles to the surface. One or more types of photosensitive materials that can develop colors different from each other through a first fusion step in which a raw material dispersion containing aggregated particles is heated and fused to obtain first fused particles (photosensitive / heat-sensitive capsules).・ Prepare heat-sensitive capsule dispersion .

Subsequently, (d1) second aggregated particles are formed in a mixed solution obtained by mixing the one or more types of photosensitive / thermosensitive capsule dispersion and the second resin particle dispersion in which the resin particles are dispersed. By passing through a second aggregating step and (e1) a second fusing step of heating the mixed solution containing the second agglomerated particles to obtain second fused particles, a photosensitive / thermosensitive capsule dispersion structure is obtained. A toner having the same can be obtained.
In addition, the kind of photosensitive / heat-sensitive capsule dispersion used in the second aggregation step is preferably two or more. Alternatively, the photosensitive / heat-sensitive capsules obtained through the steps (a1) to (c1) may be used as they are as toner (that is, toner including only one color developing portion).

  In the case of producing a toner including only one color developing portion, a release agent dispersion liquid in which a release agent is dispersed in the raw material dispersion liquid in which the first aggregated particles are formed instead of the above-described adhesion step. And adding a first resin particle dispersion liquid in which resin particles are dispersed in a raw material dispersion liquid after passing through the first adhesion process. A second adhesion step of adding resin particles to the surface of the aggregated particles to which the release agent has been added may be carried out.

The volume average particle diameter of the toner that can be used in the present invention is not particularly limited, and can be appropriately adjusted according to the structure of the toner and the type and number of color developing portions contained in the toner.
However, there are about 2 to 4 types of coloring portions that can be developed in different colors contained in the toner (for example, the toner includes three types of coloring portions that can develop colors in yellow, cyan, and magenta) ), The volume average particle diameter corresponding to each toner structure is preferably within the following range.

  That is, for example, when the toner structure is a photosensitive / thermosensitive capsule (color developing part) dispersion structure in the resin, the volume average particle diameter of the toner is preferably in the range of 5 to 40 μm, more preferably in the range of 10 to 20 μm. . The volume average particle size of the photosensitive / thermosensitive capsule contained in the photosensitive / thermosensitive capsule dispersed structure toner having such a particle size is preferably in the range of 1 to 5 μm, preferably in the range of 1 to 3 μm. It is preferable that

  When the volume average particle diameter of the toner is less than 5 μm, the amount of color developing components contained in the toner decreases, so that color reproducibility may deteriorate and image density may decrease. On the other hand, if the volume average particle size exceeds 40 μm, unevenness on the image surface becomes large, and gloss unevenness on the image surface may occur. In addition, the image quality may deteriorate.

  In addition, the photosensitive / thermosensitive capsule dispersion type toner in which a plurality of photosensitive / thermosensitive capsules are dispersed therein has a particle diameter as compared with a small-diameter toner (volume average particle diameter of about 5 to 10 μm) using a conventional colorant. However, since the resolution of the image is determined not by the particle size of the toner but by the particle size of the photosensitive / heat-sensitive capsule, a higher-definition image can be obtained. In addition, since the powder fluidity is also excellent, sufficient fluidity can be ensured even if the amount of the external additive is small, and the developability and cleaning properties can be improved.

  On the other hand, in the case of a toner having only one color developing portion, it is easier to reduce the diameter as compared with the case described above, and the volume average particle diameter is preferably in the range of 3 to 8 μm, and in the range of 4 to 7 μm. Is preferred. When the volume average particle size is less than 3 μm, the particle size is too small, so that sufficient powder fluidity may not be obtained or sufficient durability may not be obtained. If the volume average particle size exceeds 8 μm, a high-definition image may not be obtained.

  In the present invention, in addition to the F toner described above, any toner can be used as long as it is controlled so as to maintain a colored or non-colored state by light irradiation (or by no light irradiation). It can be used regardless of the structure, coloring mechanism, etc.

The toner that can be used in the present invention has a volume average particle size distribution index GSDv of 1.30 or less and a ratio (GSDv / GSDp) of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp is 0. .95 or more is preferable.
More preferably, the volume average particle size distribution index GSDv is 1.25 or less, and the ratio (GSDv / GSDp) of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp is 0.97 or more. Is more preferable.

  When the volume distribution index GSDv exceeds 1.30, the resolution of the image may decrease, and the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp (GSDv / GSDp) is If it is less than 0.95, the toner chargeability may be reduced, the toner may be scattered, fogging, etc. may occur, leading to image defects.

In the present invention, the volume average particle diameter of the toner and the values of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp are measured and calculated as follows.
First, with respect to the divided particle size range (channel) of the toner particle size distribution measured using a measuring device such as Coulter Multisizer II (manufactured by Beckman-Coulter), the smaller diameter side with respect to the volume and number of individual toner particles A cumulative distribution is drawn from the particle size, and the particle size that is 16% cumulative is defined as the volume average particle size D16v and the number average particle size D16p, and the particle size that is 50% cumulative is the volume average particle size D50v and the number The average particle size is defined as D50p. Similarly, particle diameters that are 84% cumulative are defined as volume average particle diameter D84v and number average particle diameter D84p. In this case, the volume average particle size distribution index (GSDv) is defined as (D84v / D16v) ^1/2 and the number average particle size index (GSDp) is defined as (D84p / D16p) ^1/2. Can be used to calculate the volume average particle size distribution index (GSDv) and the number average particle size index (GSDp).

  The volume average particle size of the microcapsules or the photosensitive / thermosensitive capsules can be measured using, for example, a laser diffraction particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).

The toner of the present invention preferably has a shape factor SF1 represented by the following formula (1) in the range of 110 to 130.
SF1 = (ML ² / A) × (π / 4) × 100 (1)
[In the above formula (1), ML represents the maximum length (μm) of toner, and A represents the projected area (μm ² ) of toner. ]

When the shape factor SF1 is less than 110, the toner tends to remain on the surface of the image carrier in the transfer process during image formation. Therefore, it is necessary to remove the residual toner. The cleaning property at the time of cleaning tends to be impaired, and as a result, an image defect may occur.
On the other hand, when the shape factor SF1 exceeds 130, when the toner is used as a developer, the toner may be destroyed due to collision with a carrier in the developing device. At this time, as a result, the amount of fine powder increases or the image carrier surface and the like are contaminated by the release agent component exposed on the toner surface, thereby impairing the charging characteristics. May cause problems.

  The shape factor SF1 was measured as follows using a Luzex image analyzer (manufactured by Nireco Corporation, FT). First, an optical microscope image of the toner dispersed on the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length (ML) and projected area (A) of 50 or more toners are measured. The square of the maximum length and the projected area were calculated, and the shape factor SF1 was obtained from the above equation (1).

<Developer>
The toner used in the present invention may be used as it is as a one-component developer, but in the present invention, it is preferably used as a toner in a two-component developer comprising a carrier and a toner.
Here, from the viewpoint that a color image can be formed with one type of developer, the developer is (1) a color development including the photocurable composition and microcapsules dispersed in the photocurable composition. One type of toner having two or more types of parts, and two or more types of color developing parts contained in the toner can develop colors different from each other, or (2) the photo-curing property Two or more types of toner having one color development portion including a composition and microcapsules dispersed in the photocurable composition are mixed, and the color development portions of the two or more types of toner are mutually connected. It is preferable that the developer is of a type that can develop different colors.

  For example, in the former type of developer, the toner includes three types of color developing portions, and the three types of color developing portions include a yellow color developing portion capable of developing a yellow color and a magenta color forming portion capable of developing a magenta color. In the latter type of developer, a yellow color developing toner that can develop a yellow color, and a magenta color that can develop a magenta color. The toner is preferably contained in the developer in a state where the color developing portion and the cyan color developing toner capable of developing a cyan color are mixed.

The carrier that can be used for the two-component developer is preferably formed by coating the surface of the core material with a resin. The core material of the carrier is not particularly defined as long as the above conditions are satisfied, for example, magnetic metals such as iron, steel, nickel, cobalt, alloys of these with manganese, chromium, rare earth, ferrite, magnetite, etc. From the viewpoint of the surface property of the core material and the resistance of the core material, ferrite, particularly an alloy with manganese, lithium, strontium, magnesium or the like is preferable.
Further, the resin for covering the surface of the core material is not particularly limited as long as it can be used as a matrix resin, and can be appropriately selected according to the purpose.

  The mixing ratio (mass ratio) of the toner of the present invention and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100, and about 3: 100 to 20: 100. The range of is more preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.
<Example 1>
(Photoconductor)
First, a photoreceptor (substrate) used in this example was produced as follows.
A 5% methanol solution of γ-aminopropyltrimethoxysilane was applied to the surface of a transparent conductive film (Tobi Co., Ltd.) obtained by applying ITO on a 125 μm thick PET film and dried at 120 ° C. for 10 minutes to obtain a thick film. An adhesive layer having a thickness of about 0.05 μm was formed.

10 parts by mass of zinc oxide (average particle size: 70 nm, manufactured by Teica, specific surface area value: 15 m ² / g), 0.5 parts by mass of the compound represented by the following structural formula (I) are mixed with 100 parts by mass of methanol, 0.3 parts by mass of 1N hydrochloric acid was added and stirred for 1 hour. Then, after depressurizingly distilling methanol, it heated at 100 degreeC for 1 hour. This was uncooked in a mortar, and a mixture of 10 parts by mass of surface-treated pigment, 10 parts by mass of vinyl chloride / vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar Company) and 200 parts by mass of n-butyl acetate was obtained. The glass beads were used for dispersion for 4 hours in a sand mill. To the obtained dispersion liquid, 175 parts by mass of n-butyl acetate and 180 parts by mass of methyl ethyl ketone were added and stirred to prepare a coating solution for a charge generation layer. This charge generation layer coating solution was applied onto the adhesive layer with an applicator and dried at room temperature to form a charge generation layer having a thickness of 0.2 μm.

Next, 45 parts by mass of N, N-bis (3,4-dimethylphenyl) -biphenyl-4-amine and 55 parts by mass of bisphenol Z polycarbonate resin (molecular weight: 40,000) are added to 800 parts by mass of chlorobenzene and dissolved. Then, a coating liquid for charge transport layer was prepared. This coating solution was applied onto the charge generation layer with an applicator and dried at 130 ° C. for 45 minutes to form a charge transport layer having a thickness of 20 μm.
The endless belt photoreceptor 1 having a diameter of 300 mm was prepared by using the photoreceptor film having the laminated photosensitive layer formed as described above and bonding both ends.

  The absorption edge of the photoconductor is 420 nm, and the absorbance at each wavelength of 465 nm, 532 nm, and 657 nm, which is the wavelength of the coloring information imparting light described later, was measured with a spectrophotometer (Hitachi, U-4000). The absorbance was 0.07, 0.03, and 0.03 in this order.

(toner)
Next, the light non-color developing type F toner in which the light emitting part (photosensitive / heat-sensitive capsule) was dispersed in the binder resin was obtained as follows.

-Preparation of microcapsule dispersion (1)-
In 16.9 parts by mass of ethyl acetate, 8.9 parts of an electron-donating colorless dye (1) capable of developing a yellow color is dissolved, and capsule wall material (trade name: Takenate D-110N, Takeda Pharmaceutical Co., Ltd.) 20 parts by mass and 2 parts by mass of capsule wall material (trade name: Millionate MR200, manufactured by Nippon Polyurethane Industry Co., Ltd.) were added.
The resulting solution was added to a mixed solution of 42 parts by mass of 8% by mass phthalated gelatin, 14 parts by mass of water, and 1.4 parts by mass of a 10% by mass sodium dodecylbenzene sulfonate solution. Emulsified and dispersed at 0 ° C. to obtain an emulsion. Next, 72 parts by mass of a 2.9% tetraethylenepentamine aqueous solution was added to the obtained emulsion and heated to 60 ° C. with stirring. After 2 hours, the electron-donating colorless dye (1) was added to the core. To obtain a microcapsule dispersion (1) having an average particle size of 0.5 μm.
The glass transition temperature of the material constituting the outer shell of the microcapsule contained in this microcapsule dispersion (1) (the material obtained by reacting Takenate D-110N and Millionate MR200 under the same conditions as above). Was 100 ° C.

-Preparation of microcapsule dispersion (2)-
A microcapsule dispersion (2) was obtained in the same manner as in the preparation of the microcapsule dispersion (1) except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (2). The average particle size of the microcapsules in this dispersion was 0.5 μm.

-Preparation of microcapsule dispersion (3)-
A microcapsule dispersion (3) was obtained in the same manner as in the preparation of the microcapsule dispersion (1) except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (3). The average particle size of the microcapsules in this dispersion was 0.5 μm.
The chemical structural formulas of the electron donating colorless dyes (1) to (3) used for the preparation of the microcapsule dispersion are shown below.

—Preparation of Photocurable Composition Dispersion (1) —
100.0 parts by mass (mixing ratio 50:50) of a mixture of electron-accepting compounds (1) and (2) having a polymerizable group and 0.1 part by mass of a thermal polymerization inhibitor (ALI) were added to isopropyl acetate (to water). Was dissolved at 42 ° C. in 125.0 parts by mass to obtain a mixed solution I.
In this mixed solution I, hexaarylbiimidazole (1) [2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′tetraphenyl-1,2′-biimidazole] 18.0 Part by mass, 0.5 part by mass of a nonionic organic dye, and 6.0 parts by mass of an organic boron compound were added and dissolved at 42 ° C. to obtain a mixed solution II.
The above mixed solution II was added to a mixed solution of 300.1 parts by mass of an 8% by mass gelatin aqueous solution and 17.4 parts by mass of a 10% by mass surfactant (1) aqueous solution, and a homogenizer (manufactured by Nippon Seiki Co., Ltd.). ) For 5 minutes at a rotational speed of 10,000, followed by desolvation treatment at 40 ° C. for 3 hours to obtain a photocurable composition dispersion (1) having a solid content of 30% by mass.
In addition, the electron-accepting compound (1) which has a polymeric group used for preparation of a photocurable composition dispersion liquid (1), the electron-accepting compound (2) which has a polymeric group, and thermal polymerization inhibitor (ALI) Structural formulas of hexaarylbiimidazole (1), surfactant (1), nonionic organic dye, and organoboron compound are shown below.

-Preparation of photocurable composition dispersion (2)-
0.6 parts by mass of the following organic borate compound (I), 0.1 part by mass of the spectral sensitizing dye-based borate compound (I) shown below, and the following auxiliary agent (1) for the purpose of increasing sensitivity: 5 parts by mass of the following electron-accepting compound (3) having a polymerizable group was added to a mixed solution of 1 part by mass and 3 parts by mass of isopropyl acetate (solubility of about 4.3% in water).

The obtained solution was mixed with 13 parts by weight of a 13% by weight aqueous gelatin solution, 0.8 part by weight of the following 2% by weight surfactant (2) aqueous solution, and 0.8 part by weight of the following 2% by weight surfactant (3) aqueous solution. And emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) for 5 minutes at a rotational speed of 10,000 rotations to obtain a photocurable composition dispersion (2).
In addition, the electron-accepting compound (3) which has a polymeric group used for preparation of a photocurable composition dispersion liquid (2), adjuvant (1), surfactant (2), and surfactant (3) The structural formula of is shown below.

-Preparation of photocurable composition dispersion (3)-
In place of the spectral sensitizing dye-based borate compound (I), the photocurable composition dispersion liquid (2) was used except that 0.1 part by mass of the spectral sensitizing dye-based borate compound (II) shown above was used. A photocurable composition dispersion (3) was obtained in the same manner as in the preparation.

-Preparation of resin particle dispersion-
Styrene: 460 parts by mass nbutyl acrylate: 140 parts by mass Acrylic acid: 12 parts by mass Dodecanethiol: 9 parts by mass The above components were mixed and dissolved to prepare a solution. Subsequently, an emulsion (monomer) in which 12 parts by weight of an anionic surfactant (manufactured by Rhodia, Dowfax) was dissolved in 250 parts by weight of ion-exchanged water, and the above solution was added and dispersed and emulsified in a flask. Emulsion A) was prepared.
In addition, 1 part of an anionic surfactant (Dowfax, manufactured by Rhodia Co., Ltd.) was dissolved in 555 parts by mass of ion-exchanged water and charged into a polymerization flask. The polymerization flask was sealed, a reflux tube was installed, and the polymerization flask was heated to 75 ° C. with a water bath while being slowly stirred while injecting nitrogen.

Next, a solution obtained by dissolving 9 parts of ammonium persulfate in 43 parts by mass of ion-exchanged water was added dropwise to the polymerization flask through a metering pump over 20 minutes, and then the monomer emulsion A was also added to the metering pump. Over 200 minutes.
Thereafter, the polymerization flask was kept at 75 ° C. for 3 hours while stirring slowly, to complete the polymerization.
As a result, a resin particle dispersion having a median particle diameter of 210 nm, a glass transition point of 51.5 ° C., a weight average molecular weight of 31,000, and a solid content of 42% by mass was obtained.

-Preparation of photosensitive / thermosensitive capsule dispersion (1)-
-Microcapsule dispersion (1): 150 parts by mass-Photocurable composition dispersion (1): 300 parts by mass-Polyaluminum chloride: 0.20 parts by mass-Ion exchange water: 300 parts by mass The above ingredients are mixed. Nitric acid is added to the prepared raw material solution to adjust the pH to 3.5, and after thoroughly mixing and dispersing with a homogenizer (IQA, Ultra Tarrax T50), it is transferred to a flask and stirred with a three-one motor in a heating oil bath. While heating to 40 ° C. and holding at 40 ° C. for 60 minutes, 300 parts by mass of the resin particle dispersion was further added and gently stirred at 60 ° C. for 2 hours. Thus, a photosensitive / thermosensitive capsule dispersion (1) was obtained.
The volume average particle size of the photosensitive / thermosensitive capsules dispersed in this dispersion was 3.53 μm. Further, spontaneous color development of the dispersion was not confirmed during the preparation of this dispersion.

-Preparation of photosensitive / thermosensitive capsule dispersion (2)-
-Microcapsule dispersion (2): 150 parts by mass-Photocurable composition dispersion (2): 300 parts by mass-Polyaluminum chloride: 0.20 parts by mass-Ion exchange water: 300 parts by mass A photosensitive / thermosensitive capsule dispersion (2) was obtained in the same manner as in the preparation of the photosensitive / thermosensitive capsule dispersion (1) except that the components were used.
The volume average particle size of the photosensitive / thermosensitive capsules dispersed in this dispersion was 3.52 μm. Further, spontaneous color development of the dispersion was not confirmed during the preparation of this dispersion.

-Preparation of photosensitive / thermosensitive capsule dispersion (3)-
-Microcapsule dispersion (3): 150 parts by mass-Photocurable composition dispersion (3): 300 parts by mass-Polyaluminum chloride: 0.20 parts by mass-Ion exchange water: 300 parts by mass A photosensitive / thermosensitive capsule dispersion (3) was obtained in the same manner as in the preparation of the photosensitive / thermosensitive capsule dispersion (1) except that the components were used.
The volume average particle size of the photosensitive / thermosensitive capsules dispersed in this dispersion was 3.47 μm. Further, spontaneous color development of the dispersion was not confirmed during the preparation of this dispersion.

Photosensitive / thermosensitive capsule dispersion (1): 750 parts by mass Sensitive / thermosensitive capsule dispersion (2): 750 parts by mass Photosensitive / thermosensitive capsule dispersion (3): a solution in which 750 parts by mass or more of components are mixed. The flask was transferred to a flask, heated to 42 ° C. while heating in the flask, and maintained at 42 ° C. for 60 minutes, and then 100 parts by mass of the resin particle dispersion was further added and gently stirred.
Thereafter, the pH in the flask was adjusted to 5.0 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then heated to 55 ° C. while stirring was continued. During the temperature rise to 55 ° C, the pH in the flask usually drops to 5.0 or lower, but here, an aqueous sodium hydroxide solution is added dropwise to keep the pH from dropping to 4.5 or lower. did. This state was maintained at 55 ° C. for 3 hours.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. Then, it was redispersed in 3 liters of ion exchange water at 40 ° C. in a 5 liter beaker, and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, followed by freeze-drying for 12 hours to obtain toner particles in which photosensitive / thermosensitive capsules were dispersed in a styrene resin. When the particle diameter of the toner particles was measured with a Coulter counter, the volume average particle diameter D50v was 15.2 μm.
Subsequently, 1.0 part by mass of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by mass of the toner particles, and mixed with a sample mill to obtain an externally added toner.

(Developer)
As a carrier, 30% by mass of styrene / acrylic copolymer (number average molecular weight: 23000, weight average molecular weight: 98000, Tg: 78 ° C.) and granular magnetite (maximum magnetization: 80 emu / g, average particle size: 0.5 μm) 70% by mass kneaded, pulverized and classified to a volume average particle size of 100 μm, weighed the toner and the toner concentration to 5% by mass, mixed with a ball mill for 5 minutes, and developed. Got.

(Image formation)
In the image forming apparatus shown in FIG. 1, the endless belt photosensitive member 1 is used as a photosensitive member to make an evaluation image forming device. Further, the developer was loaded into the developing device 16. Further, a scorotron was used as the charging device 12.

  As the exposure device 14, a semiconductor laser having a wavelength of 780 nm capable of forming a latent image with a resolution of 600 dpi and capable of generating second harmonics (wavelength 390 nm) was used. The developing device 16 includes a metal sleeve for developing a two-component magnetic brush and can perform reversal development. The toner charge amount when the developer was loaded in the developing device was about −5 to −30 μC / g.

The color-information providing device 28, the peak wavelength 465 nm (exposure ^{amount: 0.2mJ / cm 2), 532nm} ( exposure ^{amount: 0.2mJ / cm 2), 657nm} ( exposure amount: 0.4mJ / cm ²⁾ light The LED image bar with a resolution of 600 dpi capable of irradiating the image was used, and the point of coloring information was set at a position 5 mm away from the development point on the surface of the photoreceptor. The transfer device 18 includes a semiconductive roll formed by coating a conductive elastic body on the outer periphery of a conductive core material as a transfer roll. The conductive elastic body is made by dispersing two types of carbon black consisting of ketjen black and thermal black in an incompatible blend formed by mixing NBR and EPDM, and has a roll resistance of 10 ^8.5 Ωcm, The Asker C hardness is 35 degrees.

  The fixing device 22 used was a fixing device used in DPC1616 manufactured by Fuji Xerox Co., Ltd., and was arranged at a position 30 cm from the point of coloring information application. Moreover, as the light irradiation means 24, the high-intensity shakasten containing the three wavelengths of the said coloring information provision apparatus was used, and the irradiation width was 5 mm.

The printing conditions were set as follows by the image forming apparatus having the above configuration.
Photoconductor linear velocity: 10 mm / sec.
Charging conditions: The surface potential of the photoconductor was set to −700V.
-Exposure: The exposure was performed with a logical sum of image information for four colors of Y, M, C, and black, and the potential after the exposure was about -50V.
Development bias: A rectangular wave of alternating current Vpp 1.2 kV (3 kHz) is superimposed on direct current −330V.
Developer contact conditions: peripheral speed ratio (development roll / photoreceptor) 2.0, development gap 0.5 mm, developer weight on the development roll 400 g / m ² , toner development amount on the photoreceptor was solid The image was 5 g / m ² .
Transfer bias: DC + 800V applied.
Fixing temperature: The fixing roll surface temperature is set to 180 ° C.
-Light irradiation device illuminance: 130000 lux.

  Under the above conditions, a chart having a gradation image portion was printed for each color of Y, M, C, R, G, B, and K. The coloring information was given to the toner in the combinations shown in Table 1 below (indicating that the toner is colored in a desired color when the LED marked with a circle emits light). In addition, in order to control the color density by the light emission intensity or the light emission time, time width modulation in which the time of one dot is divided into eight is adopted.

(Image evaluation)
The following evaluation was performed about the print sample obtained on the said conditions.
-Color density-
When the image density of the solid image part for each of the colors Y, M, and C was examined with a density measuring device X-Rite 938 (manufactured by X-Rite), the image density was 1.5 or more and sufficient color development was obtained for any color. confirmed.

-Color reproducibility-
For each color of R, G, B, Y, M, and C, the color reproducibility was examined using a 5% to 100% gradation chart in 5% increments. It was excellent.

-Durability-
Under the above conditions, image output was repeated using A4 size recording paper, and durability characteristics were examined. As a result, even when printing was performed up to 1000 sheets, toner fusion did not occur on the surface of the photoreceptor, and no problem occurred on the image.

<Example 2>
In the production of the photoconductor of Example 1, an endless belt photoconductor was similarly prepared except that titanium oxide (average particle size: about 20 nm, TTO-55, manufactured by Ishihara Techno Co.) was used instead of zinc oxide as the charge generation material. 2 was obtained. The absorption edge of this photoconductor was 420 nm, and the absorbance at 465 nm, 532 nm, and 657 nm was 0.08, 0.03, and 0.02, respectively.

  Using the endless belt photoreceptor 2, an image was formed in the same manner as in Example 1, and the same evaluation was performed. As a result, toner fusing and photoconductor defects did not occur, and good images were obtained.

<Example 3>
In the first embodiment, the configuration of the image forming apparatus is the same as that shown in FIG. 7 in which the color forming information providing device 28 is installed inside the photoconductor, and the exposure for providing the color forming information is performed simultaneously with the development as indicated by the arrow B ′. Except for the above, image formation was performed in the same manner as in the example, and the same evaluation was performed.
As a result, the same image quality as in Example 1 was obtained in the initial stage, and toner fusion did not occur even when printing up to 1000 sheets in terms of durability.

<Example 4>
(Production of dielectric)
A 5% methanol solution of γ-aminopropyltrimethoxysilane was applied to the surface of a transparent conductive film (Tobi Co., Ltd.) obtained by applying ITO on a 125 μm thick PET film and dried at 120 ° C. for 10 minutes to obtain a thick film. An adhesive layer having a thickness of about 0.05 μm was formed. Next, a dielectric layer coating solution prepared by adding 55 parts by mass of bisphenol Z polycarbonate resin (molecular weight: 40,000) to 800 parts by mass of chlorobenzene was prepared, and this was applied onto the adhesive layer with an applicator. Was dried for 45 minutes to form a dielectric layer having a thickness of 20 μm.
Using this film, both ends were bonded to produce an endless belt dielectric 1 having a diameter of 300 mm.

  The dielectric material hardly absorbs in any wavelength region, and the absorbances at wavelengths of 465 nm, 532 nm, and 657 nm were 0.09, 0.04, and 0.03, respectively.

(Image formation and evaluation)
As an image forming apparatus, an apparatus for forming a latent image by an ionographic method as shown in FIG. 10 was prepared, and the endless belt dielectric 1 was loaded as the dielectric 30. In FIG. 10, the latent image was formed by an ion flow control head 27 with a control slit formed at the resolution of 600 dpi on the front surface of the corona charger. Reference numeral 25 denotes a surface charge removing means. Other configurations are the same as those of the image forming apparatus shown in FIG.

In Example 1, image formation was performed in the same manner except that the above apparatus was used as the image forming apparatus, and the same evaluation was performed.
As a result, even when a toner image was formed by the ionographic method, a color image having the same effect and good quality was obtained. Further, in terms of durability, toner fusion did not occur even after printing 1000 sheets.

<Comparative Example 1>
In the production of the photoreceptor of Example 1, the Bragg angles (2θ ± 0.2 °) of the X-ray diffraction spectrum using CuKα rays instead of zinc oxide as the charge generation material are at least 7.3 ° and 16.0 °. The endless belt photoreceptor 3 was obtained in the same manner except that hydroxygallium phthalocyanine having diffraction peaks at positions of 24.9 ° and 28.0 ° was used. The absorbance of this photoreceptor at 465 nm, 532 nm, and 657 nm was 0.4, 0.8, and 0.9, respectively.

  Using the endless belt photoreceptor 3, an image was formed in the same manner as in Example 1, and the same evaluation was performed. As a result, there was no particular problem with the initial image, but the toner filmed on the surface of the photosensitive member after 1000 sheets of printing, resulting in unevenness.

<Comparative example 2>
A mixture consisting of 6 parts by mass of Ketjen Black EC (manufactured by Lion Corporation), 100 parts by mass of vinyl chloride / vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar), and 2000 parts by mass of n-butyl acetate was used. Were dispersed in a sand mill for 4 hours. To the obtained dispersion, 1750 parts by mass of n-butyl acetate and 1800 parts by mass of methyl ethyl ketone were added and stirred to prepare a coating solution for a conductive layer. The said coating liquid was apply | coated on 125-micrometer-thick PET film, and the conductive layer was formed.

Next, a dielectric layer coating solution was prepared by adding 55 parts by weight of bisphenol Z polycarbonate resin (molecular weight: 40,000) to 800 parts by weight of chlorobenzene, and this was applied onto the conductive layer with an applicator. Was dried for 45 minutes to form a dielectric layer having a thickness of 20 μm. Using this film, both ends were adhered to produce an endless belt photoreceptor 2 having a diameter of 300 mm.
The absorbances of the dielectrics at wavelengths of 465 nm, 532 nm, and 657 nm were 0.95, 0.95, and 0.95, respectively.

  Using the endless belt dielectric 2, image formation was performed in the same manner as in Example 4, and the same evaluation was performed. As a result, there was no particular problem with the initial image, but the toner filmed on the surface of the photosensitive member after 1000 sheets of printing, resulting in unevenness.

  As described above, in the image forming method (image forming apparatus) for exposing the toner image on the surface of the substrate such as the photoreceptor to the color forming information imparting light, the substrate is substantially transparent to the wavelength range of the color developing information imparting light. By using one, it was possible to obtain a high-quality image without toner fusion even in repeated printing, as compared with the case where a substrate having absorption in the wavelength range was used.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. FIG. 3 is a schematic cross-sectional view illustrating an example of a layer configuration of a photoreceptor. It is a schematic cross section which shows another example of the layer structure of a photoreceptor. It is a schematic cross section which shows another example of the layer structure of a photoreceptor. It is a schematic cross section which shows another example of the layer structure of a photoreceptor. It is a schematic cross section which shows another example of the layer structure of a photoreceptor. It is a schematic block diagram which shows another example of the image forming apparatus of this invention. It is a circuit block diagram of a printing control unit. 2A and 2B are schematic diagrams for explaining a toner color development mechanism, in which FIG. 1A shows a color development portion and FIG. 2B shows an enlarged state thereof. It is a schematic block diagram which shows another example of the image forming apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Undercoat layer 2 Charge generation layer 3 Charge transport layer 4 Conductive base material 5 Protective layer 10 Photoconductor 12 Charging device 14 Exposure device 16 Development device 18 Transfer device 20 Cleaner 22 Fixing device 24 Light irradiation device 25 Surface charge removal means 26 Recording medium 27 Ion flow control head 28 Color information imparting device 34 Color information imparting exposure head 36 Printer controller 38 Exposure unit 40 OR circuit 42 Oscillating circuit 44 Color control circuit 50 Color information imparting exposure 52 Toner layer 54 Image carrier 56 Toner image

Claims (8)

An image forming method using a toner controlled to maintain a colored state or a non-colored state by providing coloring information by light,
A toner image forming step for forming a toner image, a color forming information applying step for applying color forming information by light to the toner image, a transfer step for transferring the toner image to which the color forming information is applied to the surface of a recording medium, and the recording A fixing step of fixing the toner image transferred to the surface of the medium by heat and / or pressure, and a coloring step of coloring the toner image to which the coloring information is given by heating,
In the color forming information providing step, an image forming method characterized in that a substrate that is substantially transparent to light in a wavelength region used for applying color forming information is used as a substrate that carries the toner image.   The image forming method according to claim 1, wherein in the toner image forming step, a toner image is formed on the surface of the substrate.   3. The image forming method according to claim 2, wherein in the color information provision step, the color information is imparted by the light from a surface opposite to a toner image formation surface of the substrate.   The image forming method according to claim 3, wherein the application of the coloring information by the light is performed simultaneously with the formation of the toner image.   The substrate is a photoconductor, and the toner image forming step includes a charging step of charging the surface of the photoconductor, an exposure step of forming an electrostatic latent image on the surface of the photoconductor by exposure, and the electrostatic latent image The image forming method according to claim 1, further comprising: a developing step of forming a toner image with the developer containing the toner.   The substrate is a dielectric, and the toner image forming step includes an ion writing step of forming an electrostatic latent image on the surface of the substrate, and a developing step of converting the electrostatic latent image into a toner image with a developer containing the toner. The image forming method according to claim 1, further comprising:   A first component and a second component that are present in a state where the toners are isolated from each other and react with each other; and a photocurable composition containing any one of the first component and the second component. 2. The toner according to claim 1, wherein the photocurable composition maintains a cured or uncured state by the application of color development information by light, and the reaction for color development is controlled. The image forming method described. An image forming apparatus using toner that is controlled to maintain a colored state or a non-colored state by providing coloring information by light,
An image carrier, a toner image forming unit for forming a toner image, a coloring information providing unit for imparting coloring information by light to the toner image, and a transfer for transferring the toner image to which the coloring information is imparted to the surface of the recording medium Means, fixing means for fixing the toner image transferred to the surface of the recording medium by heat and / or pressure, and coloring means for coloring the toner image to which the coloring information is given by heating,
An image forming apparatus, wherein a substrate carrying a toner image to which color information by light is applied is a substrate that is substantially transparent to light in a wavelength region used for providing the color information.

Images