JP2008015332A - Conductive toner for electrostatic latent image development, developer for electrostatic latent image development, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive toner for electrostatic latent image development that can form an image without using a toner containing a conventional colorant and easily suppresses fog, toner cloud or the like easily induced in an insulating toner, and to provide a developer for electrostatic latent image development, an image forming method and an image forming apparatus using the above conductive toner for electrostatic latent image development. <P>SOLUTION: The conductive toner for electrostatic latent image development contains a color developing composition that can develop color by applying external stimulus, and a conducting agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive toner for developing an electrostatic latent image used for forming an image by electrophotography such as a copying machine, a developer for developing an electrostatic latent image using the same, an image forming method, and image formation It relates to the device.

In recent years, with the progress of IT and demands for further environmental considerations, there is a need for more compact and lightweight color image output machines for business use that are more space- and resource-saving. For this reason, there has been progress in speeding up and compatibility with plain paper in color image output machines such as inkjet, thermal transfer, and sublimation types, which are basically small and light.
However, on the other hand, although it is not small and light compared to these, the electrophotographic method is still mainstream in office use because of its inherent high-speed output and compatibility with plain paper.

  In electrophotographic image formation, generally, an insulating toner is used, and a method of developing an electrostatic latent image by applying a charge of a predetermined polarity by friction charging the insulating toner is generally widely used. It is used. In such a toner charging method, since the frictional state of the toner varies depending on individual toner particles, a certain amount of charge distribution inevitably exists in the charge amount of the toner charged by friction. For this reason, low-charged toner is separated from a toner carrier such as a developing roll in the developing device, so that a so-called toner cloud drifts in the image forming device, or the image background is soiled by the toner charged to the opposite polarity. There is a problem that the so-called fog is easily generated.

In order to solve such problems, there is a method of using a conductive toner instead of an insulating toner, specifically, a method of injecting a charge into the conductive toner to charge it and using it for development. It is known (see, for example, Patent Document 1).
This method using conductive toner has various advantages because it does not use frictional charging. In particular, the conductive toner easily moves the charge and can give the toner a uniform charge. Therefore, it is possible to prevent the occurrence of fog and toner cloud, and it is difficult to be affected by environmental changes and deterioration over time. This is the biggest feature. In addition, since the method using the conductive toner does not require a frictional charging mechanism, the structure of the developing device is simple, and the size and cost can be reduced.

In addition, as an image forming apparatus for outputting a color image at high speed in electrophotography, an image of a tandem system that includes four image forming units, each of which includes a photoconductor, a developing device, and the like for forming, developing, and transferring a latent image. A forming device is common.
Since this apparatus has an image forming unit for each color, C (cyan), M (magenta), Y (yellow), and K (black) images can be formed almost simultaneously, and the speed can be increased. However, since four image forming units having similar functions are used, this is also a reason why the apparatus cannot be reduced in size and weight.
Therefore, in order to enable the formation of a color image with one image forming unit, a toner that develops a necessary color with one kind of toner particles has been proposed (see, for example, Patent Documents 2 to 5). The color development principle of these toners is basically that a dye precursor and a developer are reacted by an external stimulus corresponding to image information to develop a necessary color.
These toners use a recording paper technique (for example, Patent Document 6) in which an ink layer containing microcapsules responsive to external stimuli such as light and heat is coated in advance. There are various other recording paper technologies that have been previously coated with an ink layer containing microcapsules that are responsive to external stimuli such as light and heat (for example, patent documents). (Refer to 7, 8 etc.)

As a specific example of such toner, the toner described in Patent Document 4 will be described as an example. This toner is a particle formed by dispersing and mixing in a toner resin a plurality of microcapsules having capsule walls whose substance permeability changes in response to an external stimulus. The toner is mixed with each other to cause a color reaction 2 One of the types of reactive substances (each color dye precursor) is contained in the microcapsule, and the other (developer) is contained in the toner resin outside the microcapsule.
In this toner, by using a photoisomerized substance that increases substance permeability when irradiated with light of a specific wavelength as a capsule wall, or by using a capsule wall that is destroyed when an ultrasonic wave with a resonance frequency is applied, When light irradiation or ultrasonic waves are applied, two types of reactive substances existing inside and outside the capsule react to develop color.
For this reason, good full-color image formation can be easily obtained using an apparatus having a simpler configuration than an apparatus including four image forming units such as a tandem system. However, there is no proposal that specifically shows how to prepare these toners.

On the other hand, as a method for producing a toner, in recent years, a production method called a wet production method such as a polymerization method, a submerged drying method, and an aggregation coalescence method, which allows for higher functionality in consideration of the environment, has been put into practical use. (For example, refer to Patent Documents 9 to 13). Since these toner production methods do not require high heat and high share compared to conventional toner production methods such as kneading and pulverization methods, materials that have conventionally been difficult to toner can be used.
JP 2005-70674 A JP-A-2-293869 JP-A-8-106172 JP 2003-330228 A Japanese Patent Laid-Open No. 2004-45660 Japanese Patent No. 2979158 Japanese Patent Laid-Open No. 4-211252 JP 2000-199952 A Japanese Patent Laid-Open No. 61-028957 JP 61-046955 A Japanese Patent No. 3661422 JP-A-11-002922 JP-A-11-002923

  The toner that develops color by the application of external stimuli such as light as described in Patent Document 4 described above is smaller in size and simpler than a conventional toner containing a colorant such as a pigment. Although there is a merit that a good full-color image can be formed by using a light-weight device, no specific manufacturing method is actually described as described above. That is, in reality, a toner that develops color in response to an external stimulus without using a colorant has not been realized.

In addition, in the toner described in Patent Document 4, when the capsule wall of the microcapsule contains a photoisomerization substance, after the image formation, a light stimulus is applied again to close the opening of the capsule wall and stop the progress of color development. You can do that.
However, since the material permeability of the capsule wall composed of a photoresponsive photoisomerization material is controlled by using a photoisomerization reaction, the toner is spontaneously stored when stored for a long period of time. May develop color. In addition to this, since the image is exposed to a light stimulus such as an indoor fluorescent lamp or sunlight after the image formation, it is expected that the capsule wall is opened again depending on the intensity and wavelength of the light. In this way, when microcapsules that may reversibly respond to light stimulation after image formation are included in the image, there is a high possibility that the formed image will be discolored and the color balance will be lost. .

In addition, the increase in the material permeability of the capsule wall using the photoisomerization reaction utilizes the transition from the trans state to the cis state. However, such a reaction is reversible, and a reaction returning from the cis state to the trans state may occur during image formation, so that sufficient color development may not be obtained.
Furthermore, if the capsule wall is broken and colored by external stimuli such as ultrasonic waves, the color balance of the image may be lost because the color develops in a high-temperature environment even after image formation. is there.

  An object of the present invention is to solve the above problems. That is, the present invention provides an electrostatic latent image developing conductive toner that can form an image without using a conventional toner containing a colorant and can easily suppress fogging, toner cloud, etc. It is an object of the present invention to provide an electrostatic latent image developing developer, an image forming method, and an image forming apparatus using the electrostatic latent image developing conductive toner.

The above object is achieved by the present invention described below. That is, the present invention
<1>
A conductive toner for developing an electrostatic latent image, comprising a color-developing composition capable of color development upon application of an external stimulus and a conductive agent.

<2>
The curable composition is present in a state of being separated from each other, and includes a first component and a second component that develop color when they react with each other, and a photocurable composition including any one of the first component and the second component. The conductive toner for developing an electrostatic latent image according to <1>, comprising a composition.

<3>
<2 including microcapsules dispersed in the photocurable composition, wherein the first component is contained in the microcapsule and the second component is contained in the photocurable composition <2 > The conductive toner for developing an electrostatic latent image.

<4>
The conductive toner for developing an electrostatic latent image according to <3>, wherein the microcapsule is a heat-responsive microcapsule capable of diffusing substances inside and outside the microcapsule by heat treatment.

<5>
The electrostatic capsule according to <3>, wherein the microcapsule has a core portion including the first component and an outer shell covering the core portion, and the outer shell is made of a thermoplastic material. Conductive toner for developing latent images.

<6>
When the photocurable composition is in an uncured state, a non-colorable state is maintained,
The photocurable composition is cured irreversibly from the uncolorable state to the colorable state by curing the photocurable composition by irradiation with light of a specific wavelength for curing the photocurable composition. The conductive toner for developing an electrostatic latent image according to <2>.

<7>
The conductive toner for developing electrostatic latent images according to <6>, wherein the photocurable composition contains the second component and a photopolymerizable compound.

<8>
The first component and the second component are reacted by heating after irreversibly controlling to the colorable state by curing the photocurable composition by irradiation with light of the specific wavelength. <6> The conductive toner for developing an electrostatic latent image according to <6>, wherein the toner is developed.

<9>
Maintaining a colorable state when the photocurable composition is in an uncured state,
The photocurable composition is cured irreversibly from the colorable state to the noncolorable state by curing the photocurable composition by irradiation with light of a specific wavelength for curing the photocurable composition. The conductive toner for developing an electrostatic latent image according to <2>.

<10>
The electroconductive composition for developing an electrostatic latent image according to <9>, wherein the photocurable composition contains the second component, and the second component has a photopolymerizable group in its molecule. toner.

<11>
The electrostatic latent image developing conductive material according to <9>, wherein the photocurable composition is heated in an uncured state to cause the first component and the second component to react and develop color. Toner.

<12>
<1>, characterized in that it comprises two or more color-forming parts containing a color-forming composition capable of developing color by application of external stimulus, and the two or more color-forming parts can develop colors different from each other. Conductive toner for electrostatic latent image development.

<13>
The two or more coloring portions include a yellow coloring portion capable of developing in yellow, a magenta coloring portion capable of developing in magenta color, and a cyan coloring portion capable of developing in cyan color <1 > The conductive toner for developing an electrostatic latent image.

<14>
The conductive toner for developing an electrostatic latent image according to <1>, wherein the conductive agent includes at least one conductive agent selected from titanium oxide, tin oxide, and ITO.

<15>
A developer for developing an electrostatic latent image, comprising a color-forming composition capable of color development by application of an external stimulus and a conductive agent, and containing a conductive toner.

<16>
A charging step for charging the surface of the image carrier, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier, a charge injection step for injecting charges into conductive toner, and a charge injection for the electrostatic latent image A development process for developing the conductive toner to form a toner image; a color development information application process for irradiating the toner image with color development information application light corresponding to color component information of image information; and recording the toner image on a recording medium A transfer step of transferring to the surface, and a fixing color forming step of forming an image by fixing the toner image transferred to the surface of the recording medium and irradiated with the color forming information imparting light to heat and pressurize and color.
A photocurable composition comprising a first component and a second component which are present in a state where the conductive toner is isolated from each other and react with each other, and any one of the first component and the second component One or more color-developing parts containing a product, and containing a conductive agent,
The image forming method, wherein the image information imparting light includes light having a specific wavelength for curing the photocurable composition contained in each of the one or more kinds of color forming portions.

<17>
<16> The image forming method according to <16>, further comprising a light irradiation step of irradiating the image obtained through the fixing and coloring step with light.

<18>
An image carrier, a charging unit that charges the surface of the image carrier, a latent image forming unit that forms an electrostatic latent image on the surface of the image carrier, a charge injection unit that injects charges into conductive toner, and the electrostatic Developing means for developing a latent image with the conductive toner into which electric charge has been injected to form a toner image; color information providing means for irradiating the toner image with color information providing light corresponding to color component information of image information; Transfer processing means for transferring the toner image to the surface of the recording medium, and fixing coloring for forming the image by heating and pressurizing and coloring the toner image transferred to the surface of the recording medium and irradiated with the color forming information providing light. Means,
A photocurable composition comprising a first component and a second component which are present in a state where the conductive toner is isolated from each other and react with each other, and any one of the first component and the second component One or more color-developing parts containing a product, and containing a conductive agent,
The image forming apparatus, wherein the image information providing light includes light having a specific wavelength for curing the photocurable composition included in each of the one or more types of coloring portions.

<19>
<18> The image forming apparatus according to <18>, further comprising a light irradiation unit configured to irradiate the image obtained through the fixing and coloring step with light.

  As described above, according to the present invention, an image can be formed without using a conventional toner containing a colorant, and electrostatic latent image development that easily suppresses fogging, toner cloud, and the like that are likely to occur in an insulating toner. Conductive toner, and electrostatic latent image developing developer, image forming method, and image forming apparatus using the electrostatic latent image developing conductive toner.

(Conductive toner for electrostatic latent image development)
The conductive toner for developing an electrostatic latent image according to the present invention (hereinafter sometimes abbreviated as “toner”) includes a color forming composition capable of color development by application of an external stimulus and a conductive agent.
Therefore, the toner of the present invention can form an image without using a conventional toner containing a colorant, and it is easy to suppress fog, toner cloud, and the like that are likely to occur in an insulating toner.

The toner of the present invention has conductivity. Specifically, the conductivity means a resistivity (having a charge injection electric field of 10 ¹⁰ Ω · cm or less in order to facilitate charge injection, 10 ⁹ Ω · cm or less is preferable, and 10 ⁸ Ω · cm or less is more preferable, although the lower limit of the resistivity is not particularly limited, but is preferably 10 ¹¹ Ω · cm or more in a developing electric field in order to retain a charged charge. Here, the resistivity was measured by the following method: a cell having a diameter of 30 mm and a thickness of 3 mm was filled with toner, a voltage of 1000 V to 10000 V was applied to the upper and lower surfaces, and the flowing current was measured by a volume resistance meter R8340 (manufactured by Advantest). ) To calculate (see JP 2005-345996).

  In addition, the color forming composition constitutes a color developing part containing this as a main component, and the toner of the present invention contains one or more color developing parts. Here, in the present invention, the “coloring part” means a substantially continuous region that can develop a specific color when an external stimulus is applied. Note that the conductive agent may be contained in any position in the toner, and may be added inside or outside the toner particles.

The chromogenic composition includes a chromogenic component that directly contributes to color development by applying an external stimulus. The color-forming component may be colored in advance before color development, but is particularly preferably a substantially colorless substance. The color-forming component preferably includes two or more components that develop color when reacted with each other, and particularly preferably includes a first component and a second component that develop color when reacted with each other. As described above, when the color is developed using the reaction of two or more kinds of components, the color development can be easily controlled.
In the case where the color forming component is composed of two or more types, basically, it is preferable that all types of color forming components are contained in the color developing portion, but at least one type is disposed outside the color developing portion. May be.

Hereinafter, the case where a color forming component is used will be described in more detail.
Control of the chromogenic component from the non-colored state to the colored state during image formation is performed by applying an external stimulus. Here, the type of external stimulus is not particularly limited, and various physical, chemical, and mechanical stimuli such as light irradiation, heat treatment, application of ultrasonic waves, and pressurization can be used. Good.
However, in the present invention, the external stimulus is a coloring stimulus that develops a coloring component in a colorable state and the coloring component that is not provided with the coloring stimulus can be colored or cannot be colored. It is preferable that the control stimulus includes a control stimulus for controlling to a proper state.
In this case, it is preferable that the control stimulus is irradiation with light of a specific wavelength (hereinafter sometimes referred to as “coloring information imparting light”), and the coloring stimulus is a heat treatment.

In the present invention, in order to facilitate color control, it is preferable to use two or more types of components that develop color when they react with each other as the color forming component. However, these components can be used even when no external stimulus is applied. If they exist in the same matrix that can be easily diffused, spontaneous color development may occur during storage or production of the toner.
For this reason, it is preferable that these components are contained in different matrices that are difficult to diffuse into each other's regions unless an external stimulus is applied.
Thus, in order to inhibit substance diffusion in a state where no external stimulus is applied and prevent spontaneous color development during storage or manufacture of toner, at least one of the two or more types of components must be added. In the first matrix, the remaining types of components are included outside the first matrix (second matrix), and both are provided between the first matrix and the second matrix unless an external stimulus is applied. In addition to inhibiting the diffusion of substances between the matrices, when an external stimulus is applied, it has a function that allows the substance to diffuse between both matrices depending on the type, intensity, and combination of the stimuli. Preferably, a matrix of 3 (usually a membrane) is provided.

In order to arrange each type of component in the toner using such three matrices, it is preferable to use microcapsules.
In this case, in the toner of the present invention, at least one component of two or more components is contained in the microcapsule, and the remaining components are contained outside the microcapsule. Moreover, when two or more types of components consist of a 1st component and a 2nd component, it is especially preferable that any one is contained in a microcapsule and the other is contained outside a microcapsule. In this case, the inside of the microcapsule corresponds to the first matrix, the outer shell of the microcapsule corresponds to the third 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 the diffusion of substances inside and outside the microcapsule unless an external stimulus is applied, and when an external stimulus is applied. Is not particularly limited 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 stimuli. The core portion includes at least one component of two or more components.
In addition, the microcapsule may be capable of diffusing substances inside and outside the microcapsule by applying light irradiation or 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 case where the color forming component includes a first component and a second component that develop colors when they react with each other as two or more types of components will be described.
In this case, the color-forming composition exists in a state of being isolated from each other, and includes a first component and a second component that develop color when they react with each other, and a photocurable composition that includes any one of the first component and the second component. It is particularly preferable that the composition contains a composition.
The toner containing such a color-forming composition includes (1) light of a specific wavelength that maintains a state in which color development is impossible when the photo-curable composition is in an uncured state and cures the photo-curable composition. A type that is irreversibly controlled from a non-colorable state to a colorable state by curing the photocurable composition by irradiation (hereinafter sometimes referred to as “photochromic toner”); 2) Maintaining a colorable state when the photocurable composition is in an uncured state, and coloring is possible by curing the photocurable composition by irradiation with light of a specific wavelength for curing the photocurable composition. There is a type that is irreversibly controlled from a non-colorable state to a non-colorable state (hereinafter sometimes referred to as “light non-colorable toner”). Details of these two types of toner will be described later.

A color-forming composition comprising a first component and a second component that are present in a state of being separated from each other and that develop color when they react with each other, and a photocurable composition including any one of the first component and the second component In the case of using a microcapsule in the toner using the toner, (1) the microcapsule dispersed in the photocurable composition is contained, the first component is contained in the microcapsule, and the second component is photocurable. Aspects included in the composition (hereinafter sometimes referred to as “first aspect”), (2) the second component is contained in the microcapsule, and the first component is contained in the photocurable composition. Aspect (hereinafter sometimes referred to as “second aspect”), or (3) both the first component and the second component are each contained in the microcapsule, and the photocurable composition comprises the first component or One of the microphones containing the second component Aspects contained in the capsule is preferably any one of (hereinafter sometimes referred to as "third aspect").
However, among these three modes, the first mode is particularly preferable. In the following description of the toner of the present invention, the toner will be described in more detail basically on the assumption of the toner of the first aspect. However, the configuration, material, manufacturing method, etc. of the toner of the first aspect described below are Of course, the toner of the second aspect and the third aspect can also be used / reused.

Here, it is particularly preferable that the microcapsule is a thermoresponsive microcapsule capable of diffusing substances inside and outside the microcapsule by heat treatment. In this case, the photocurable composition is cured by irradiation with color forming information providing light. In this case, as the external stimulus, a combination including the presence / absence of irradiation of coloring information imparting light (giving control stimulus) and heat treatment (giving coloring stimulus) can be used.
That is, in this case, the external stimulus applied to control the reaction between the first component and the second component (color reaction control) reacts with the first component and the second component in a state where they can react (color development). Reaction) and the reaction between the first component and the second component (color reaction) before the color stimulus is applied to a state where color development is possible or a state where color development is impossible when the color stimulus is applied. A control stimulus to be controlled, irradiation of coloring information imparting light is used as the control stimulus, and heat treatment is used as the coloring stimulus.

  The heat-responsive microcapsule (hereinafter sometimes simply referred to as “microcapsule”) is composed of a core portion including a first component and an outer shell covering the core portion. It is preferable that the material constituting the outer shell is made of a heat-responsive material capable of diffusing substances inside and outside the microcapsule by heat treatment. In this case, the heat-responsive material used as the outer shell of the microcapsule is decomposed and softened by heat treatment, compatible with surrounding members, etc., and after the heat treatment is finished, the outer shell structure is decomposed and lost. Materials that can be destroyed and maintained permanently (irreversibly) easily diffused inside and outside the microcapsules (for example, thermally decomposable materials that decompose by heating, thermoplastic materials such as thermoplastic resins, and heating It is preferable to use a heat-soluble material that is compatible with surrounding members.

  When the microcapsules as described above are used as the toner, if the same type of microcapsules are substantially dispersed in one region, the region becomes a color developing portion, and a plurality of types of microcapsules are contained in the matrix. When the microcapsules are dispersed in a mixed state, each microcapsule becomes a color developing portion.

-Light non-colorable toner-
Next, the light non-color developing toner will be described in more detail.
As described above, the photo-non-colorable toner maintains a state in which color development is possible when the photo-curable composition is in an uncured state, and the photo-curing composition is irradiated with light of a specific wavelength that cures the photo-curable composition. By curing the composition, the toner has a function of being irreversibly controlled from a colorable state to a noncolorable state.
In order to achieve such a function, the second component contained in the photocurable composition is preferably a substance having a photopolymerizable group in the molecule. In addition to this, it is more preferable to include a photopolymerization initiator, and other components may be further included as necessary.

Here, in the photo-non-colorable toner, since the second component itself has photopolymerization property, the wavelength of this light should be a wavelength that cures the photo-curable composition even when irradiated with the color-forming information imparting light. For example, the state in which the second component contained in the photocurable composition is easily diffused can be maintained. Therefore, in this state, if the substance permeability of the microcapsule outer shell is increased by applying a coloring stimulus such as heat treatment, the reaction between the first component in the microcapsule and the second component in the photocurable composition (color development). Reaction) is possible (color development is possible).
On the other hand, when the photocurable composition is cured by irradiating the color forming information providing light having a wavelength for curing the photocurable composition, the second components contained in the photocurable composition are polymerized. Therefore, the material diffusion of the second component contained in the photocurable composition becomes extremely difficult. Therefore, even when a stimulus that increases the material permeability of the microcapsule shell in this state is applied, the second component cannot contact the first component in the microcapsule, The state where the reaction (coloring reaction) between the first component and the second component is impossible (the state where coloring cannot be performed) is maintained.

In addition, since the curing reaction of the photocurable composition is irreversible, once it is controlled to a state in which coloring is impossible, this state is maintained permanently.
Therefore, for example, in the case where a thermoresponsive microcapsule is used as the microcapsule, if the photocurable composition is cured by irradiating the color forming information imparting light to control the toner to a state in which the color cannot be developed, Subsequently, even if the heat treatment increases the material permeability of the thermoresponsive microcapsule shell, the first component and the second component cannot react. Therefore, for example, if the color of the toner before color development is colorless and transparent, this state is stably maintained.
On the other hand, if the photocurable composition is heat-treated in an uncured state, that is, in a state where the toner can develop color, the material permeability of the thermoresponsive microcapsule shell increases, and the first component and the second component react with each other. In addition, the toner is colored in a predetermined color, and this colored state can be stably maintained.

In the light non-color-developing toner described above, the coloring reaction between the first component and the second component causes the photocurable composition to be in an uncured state (coloring information providing light having a wavelength for curing the photocurable composition). It is controlled by a substantially one-step process of increasing the material permeability of the outer shell of the microcapsule by applying a coloring stimulus such as heat treatment in a state where the irradiation process is not performed).
Therefore, it is easy to control the color development reaction, and it is easy to secure the color density during image formation and to suppress the change in color balance after image formation. In addition, by making the increase in the material permeability of the outer shell of the microcapsule irreversible, more precise control becomes possible. Furthermore, since the gradation of the color density can be controlled by the degree of curing (polymerization) of the photocurable composition, which is an irreversible reaction, the gradation control of the color density is very easy.
Also, if you do not want to develop color in the toner, cure the photocurable composition by irradiating the coloring information application light before increasing the material permeability of the microcapsule shell by applying a coloring stimulus such as heat treatment. By doing so, it is possible to stably maintain a state in which coloring is impossible.

  On the other hand, the color development reaction of the toner using the photoresponsive bimolecular film as the capsule wall described in Patent Document 4 is also made possible by a color irradiation reaction (substance diffusion) by light irradiation, and then the substance by heating. It consists of a two-stage process that reacts by promoting diffusion, and color control is complicated. Furthermore, in the toner described in Patent Document 4, since the first stage process is reversible, the second stage color reaction continues to be greatly affected by the first stage process. It is difficult to control the color development reaction. Therefore, the color density during image formation varies.

-Photochromic toner-
Next, the photochromic toner will be described in more detail.
As described above, the photochromic toner maintains a state in which color development is impossible when the photocurable composition is in an uncured state, and the photocurable composition is irradiated with light of a specific wavelength that cures the photocurable composition. It is a type of toner having a function of irreversibly controlling from a state in which color development is impossible to a state in which color development is possible by curing the product.
In order to achieve such a function, it is preferable that the photocurable composition contains at least a second component (not having photopolymerizability) and a photopolymerizable compound. In addition to this, it is more preferable to include a photopolymerization initiator, and other components may be further included as necessary.

  Here, as the photopolymerizable compound and the second component used in the photochromic toner, an interaction acts between the photocurable composition and the photocurable composition in an uncured state. The diffusion of the two components is suppressed, and the interaction between the two decreases in the state after curing (polymerization of the photopolymerizable compound) due to the irreversible curing reaction of the photocurable composition by the irradiation of the coloring information imparting light. Thus, a material that facilitates material diffusion of the second component in the photocurable composition is used (details of these materials constituting the photocurable composition will be described later).

Accordingly, in the photochromic toner, when the color forming information imparting light is not irradiated and the photocurable composition is in an uncured state, the second component remains trapped in the photopolymerizable compound. Therefore, even when a stimulus that increases the material permeability of the microcapsule shell in this state is applied, the second component cannot contact the first component in the microcapsule, The state where the reaction (coloring reaction) between the first component and the second component is impossible (the state where coloring cannot be performed) is maintained.
On the other hand, when the photocurable composition is cured by irradiating the color forming information providing light having a wavelength for curing the photocurable composition, the material diffusion of the second component contained in the photocurable composition is easy. It becomes. Therefore, if the substance permeability of the outer shell of the microcapsule is increased by applying a coloring stimulus such as heat treatment in this state, the reaction between the first component in the microcapsule and the second component in the photocurable composition ( (Coloring reaction) is possible (coloring is possible).

In addition, since the curing reaction of the photocurable composition is irreversible, once it is controlled to be in a colorable state, this state is maintained permanently.
Therefore, for example, when a thermoresponsive microcapsule is used as the microcapsule, the photocurable composition is cured by irradiating the color forming information imparting light to control the toner to a colorable state. When the heat treatment is performed, the material permeability of the heat-responsive microcapsule outer shell increases, the first component and the second component react, the toner develops a predetermined color, and this colored state can be stably maintained. On the other hand, the photocurable composition will remain in an uncured state unless irradiated with color forming information imparting light that cures the photocurable composition, and heat treatment is performed to pass the substance through the thermoresponsive microcapsule shell. Even if the property increases, the first component and the second component cannot react. Therefore, for example, if the color of the toner before color development is colorless and transparent, this state is stably maintained.

In the photochromic toner described above, the color development reaction between the first component and the second component is as follows: (1) Curing of the photocurable composition by irradiation with color forming information providing light having a wavelength for curing the photocurable composition. And (2) a two-step process of increasing the material permeability of the microcapsule shell by applying a coloring stimulus such as heat treatment.
On the other hand, the color development reaction of the toner using the photoresponsive bimolecular film as the capsule wall described in Patent Document 4 is also made possible by a color irradiation reaction (substance diffusion) by light irradiation, and then the substance by heating. It consists of a two-step process that promotes diffusion and reacts.

However, the first-stage process (curing of the photocurable composition) for determining whether or not to control from a state in which color development is impossible to a state in which color development is possible is irreversible in the photochromic toner. In the toner described in Patent Document 4, the first stage process (photoisomerization reaction of bimolecular film) is reversible.
Therefore, in the toner described in Patent Document 4, since the first stage process is reversible, the second stage color reaction continues to be greatly affected by the first stage process. It is difficult to control the color development reaction. Therefore, the color density during image formation varies.

  On the other hand, the photo-colorable toner can control the color development reaction in the second stage without being affected by the process in the first stage, so that it is easy to control the color reaction and ensure the color density at the time of image formation, It is easy to suppress changes in color balance after image formation. In addition, by making the increase in the material permeability of the outer shell of the microcapsule irreversible, more precise control becomes possible. Furthermore, since the gradation of the color density can be controlled by the degree of curing (polymerization) of the photocurable composition, which is an irreversible reaction, the gradation control of the color density is very easy.

As the photochromic toner, a type using a photopolymerizable compound having a property of trapping the second component when the photocurable composition is in an uncured state as described above (hereinafter referred to as “the photopolymerizable compound”). Photopolymerization containing a decolorization reactive group that inhibits the color development reaction between the first component and the second component by reacting with the first component in the molecule. May be of a type using an organic compound (hereinafter, sometimes referred to as “second photochromic toner”).
In the second photochromic toner, for example, when a thermoresponsive microcapsule is used as the microcapsule, when the color forming information imparting light having a wavelength for curing the photocurable composition is irradiated, Since the composition is cured (that is, the photopolymerizable compound containing a decoloring reactive group is polymerized), the color reaction between the first component and the second component is (heated by polymerization) even if the heat treatment is subsequently performed. Since it is not hindered by the decoloring reactive group), it can develop color. On the other hand, when the heat treatment is performed without irradiating the color forming information providing light having a wavelength for curing the photocurable composition, the decoloring reactive group reacts with the first component, and the first component and Color development is not possible because the color development reaction with the second component is inhibited.
Thus, even in the second photochromic toner, when the photocurable composition is in an uncured state, the non-colorable state is maintained, and photocuring is performed by irradiation with light having a characteristic wavelength that cures the photocurable composition. By curing the sexual composition, it is controlled from an uncolorable state to a colorable state.

<Toner structure>
Next, regarding a preferred structure of the toner used in the developer of the present invention, in the case where the color developing portion of the toner includes the above-described photocurable composition and microcapsules dispersed in the photocurable composition. The case where the toner includes only one coloring portion and the case where two or more coloring portions are included will be described below.

-Toner structure of toner containing only one color development part-
When the toner includes only one color developing portion, the color developing portion is preferably covered with a protective layer in order to ensure durability and storage stability as the toner.
Such a toner has a core layer and a surface layer covering the core layer, the core layer is composed of (one) color-developing portion, and the surface layer includes a resin (so-called core-shell structure). It is preferable.

In addition, the color development part can develop a specific color when an external stimulus is applied, but the yellow color development part capable of color development in yellow, the magenta color development part capable of color development in magenta, or the color development in cyan Any one of the possible cyan coloring portions is preferred.
In this case, when forming an image, for example, a yellow toner that can develop a yellow color in a coloring portion, a magenta toner that can develop a magenta color in a coloring portion, and a cyan toner that can develop a cyan color in a coloring portion. By using it, various colors can be expressed.

The control of the color to be developed when an image is formed by combining two or more kinds of toners capable of developing colors different from each other, such as a combination of the yellow toner, the magenta toner, and the cyan toner described above, In addition to making the types and combinations of the first component and the second component contained in the toner of this type different, the light used for curing the photocurable composition contained in the color developing portion of each type of toner This can be realized by using different wavelengths.
That is, in this case, since the wavelength of light necessary for curing the photocurable composition contained in the toner differs for each type of toner, a plurality of types of color development information having different wavelengths according to the type of toner are used as control stimuli. The imparted light may be used. In order to change the wavelength of light necessary for curing the photocurable composition contained in the toner, a photopolymerization initiator that is sensitive to light having a different wavelength for each type of toner is contained in the photocurable composition. It is preferable to contain it.

For example, when a yellow toner, a magenta toner, and a cyan toner are used in combination, the photocurable composition contained in each type of toner responds to a light wavelength of 405 nm, 532 nm, or 657 nm. If a material that cures in this way is used, the color information imparting light (light having a specific wavelength) of these three different wavelengths is properly used, and the toner image formed using these three types of toner is colored to a desired color. Can be made.
The wavelength of the coloring information imparting light can be selected from the visible wavelength, but may be selected from the ultraviolet wavelength or infrared wavelength. By selecting the wavelength of the coloring information imparting light from the ultraviolet region rather than from the visible region, it has the merit that the beam diameter can be easily reduced due to the short wavelength (high definition is possible). As a light source having such a wavelength, there is a wavelength conversion solid SHG laser (converting a fundamental wavelength to ½) or a gas laser.
In addition, by selecting the wavelength of the coloring information imparting light from the infrared region instead of the visible region, there is an advantage that the light emitting element itself is inexpensive and a high output can be easily obtained as is conventionally known.

As described above, the toner preferably has a core layer composed of a color-developing portion and a surface layer that covers the core layer and contains a resin. However, a conventional colorant may be used as the resin contained in the surface layer. It is particularly preferable to use an amorphous resin such as an amorphous polyester resin used as a binder resin for toner. When an amorphous resin is not used, the charging characteristics may be insufficient or sufficient durability may not be obtained.
The surface layer may have a single-layer structure composed only of a resin layer containing a resin. However, the resin layer provided to constitute the outermost surface layer of the toner and one or more layers provided inside the resin layer The multilayer structure which consists of may be sufficient. The layer structure in the case where the surface layer has a multilayer structure is not particularly limited, but if necessary, a release agent layer including a resin layer and a release agent provided inside the resin layer. It is good also as composition which consists of.

  The thickness of the resin layer constituting the surface layer is preferably at least 0.2 μm or more, and more preferably 0.4 μm or more. If the thickness of the resin layer is less than 0.2 μm, sufficient durability may not be obtained. From the viewpoint of durability, it is preferable that the thickness of the resin layer is large. However, if the thickness of the resin layer is too large, the content of the coloring component in the toner is reduced, and a sufficient image density is obtained. Since it may not be obtained, it is preferably 0.7 μm or less in practice.

Moreover, when an amorphous resin is used for the resin layer, the glass transition temperature is preferably in the range of 45 to 65 ° C, and more preferably in the range of 50 to 60 ° C.
When the glass transition temperature is lower than 40 ° C., the storage stability of the toner may be deteriorated. When the glass transition temperature is higher than 40 ° C., both the application of coloring stimulus and the fixing are performed at the time of image formation. Even if the heat treatment is performed, in order to melt the toner, the fixing temperature must be set high, and the energy consumption may increase.

-Toner structure of toner containing more than one color development-
When the toner includes two or more color developing portions, only one type of color developing portion capable of developing the same color may be included in the toner, but two or more types of color developing portions capable of developing different colors from each other may be included. Is particularly preferably contained in the toner. In this case, the color that can be developed by one toner particle is limited to only one type in the former case, but may be two or more types 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 one of yellow, magenta, or 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.

In addition, when two or more types of color forming portions capable of developing colors different from each other are included in the toner, the color to be developed is controlled by the types of the first component and the second component included in each type of color developing portion. In addition to making the combination different, it can be realized by making the wavelength of light used for curing the photocurable composition contained in each type of color developing part different.
That is, in this case, since the wavelength of light necessary for curing the photocurable composition contained in the color developing portion differs depending on the type of the color developing portion, a plurality of types having different wavelengths according to the type of the color developing portion are used as control stimuli. The color development 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 portions that can develop colors of yellow, magenta, and cyan, the photocurable composition contained in each type of color-developing portion has a light wavelength of 405 nm, 532 nm, If a material that cures in response to any of 657 nm is used, the toner can be colored in a desired color by properly using these three different colors of colored information imparting light (light having a specific wavelength). .
The wavelength of the coloring information imparting light can be selected from the visible wavelength, but may be selected from the ultraviolet wavelength or infrared wavelength. By selecting the wavelength of the coloring information imparting light from the ultraviolet region rather than from the visible region, it has the merit that the beam diameter can be easily reduced due to the short wavelength (high definition is possible). As a light source having such a wavelength, there is a wavelength conversion solid SHG laser (converting a fundamental wavelength to ½) or a gas laser.
In addition, by selecting the wavelength of the coloring information imparting light from the infrared region instead of the visible region, there is an advantage that the light emitting element itself is inexpensive and a high output can be easily obtained as is conventionally known.

The toner 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 in the base material in the form of particles. These coloring portions dispersed in the form of particles are formed in advance as capsule-like particles when the toner is produced. It is particularly preferable that one colored portion composed of capsule-like particles (hereinafter, referred to as “photosensitive / heat-sensitive capsule”). 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 or 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. In the above, there is no particular limitation as long as the microcapsules and the photocurable composition in the photosensitive / thermosensitive capsule 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 permeating through the outer shell, it preferably contains a water-insoluble material such as a binder resin made of a water-insoluble resin or a release material as a main component. It is particularly preferable to use a water-insoluble resin such as a polymer or polyester.

Here, when a water-insoluble resin is used as a material constituting the outer shell of the photosensitive / heat-sensitive capsule, when the water-insoluble resin is a crystalline resin, its melting point is in the range of 40 to 80 ° C. Is preferable, and it is more preferable to be within the range of 50 to 70 ° C. When the water-insoluble resin is an amorphous resin, the glass transition temperature is preferably in the range of 40 to 80 ° C, and more preferably in the range of 50 to 70 ° C.
When the melting point or glass transition temperature is below the above range, the outer shell may be softened by heating in the toner production process, and when the melting point or glass transition temperature is above the above range, image formation is performed. Sometimes, even if heat treatment that combines coloring application and fixing is performed, the outer shell does not soften, so coloring becomes difficult or the fixing temperature must be set higher, and energy consumption is reduced. Sometimes it gets bigger.

In addition to the above-described aspect in which the color developing portion is dispersed in the base material (hereinafter, sometimes referred to as “color developing portion dispersed structure”), the toner has a color of at least one of two or more color developing portions. It is preferable that the portion has an adjacent structure so as to form an interface with at least one other color forming portion (hereinafter, the color forming portion constituting the interface with at least one other color forming portion is referred to as , Sometimes referred to as “photosensitive / thermosensitive layer”).
Examples of such an embodiment include (1) a photosensitive / thermosensitive layer forming a core layer and one or more photosensitive / thermosensitive layers sequentially stacked on the core layer so as to cover the core layer. Aspect (hereinafter sometimes referred to as “concentric circular structure”), or (2) an aspect in which the cross section obtained when the toner is cut from a predetermined direction is composed of two or more photosensitive / thermosensitive layers laminated in a strip shape (Hereinafter, it may be referred to as a “stripe structure”) or (3) a cross section obtained when the toner is cut from a predetermined direction is divided into a fan shape from the center of the toner. A mode in which the area is composed of a photosensitive / thermosensitive layer (hereinafter, sometimes referred to as “fan structure”).
In any of the concentric circular structure, the stripe structure, and the fan structure, an intermediate layer containing a material constituting the outer shell of the above-described photosensitive / thermosensitive capsule is provided between two adjacent photosensitive / thermosensitive layers so as to form an interface. Is particularly preferably provided. Further, the intermediate layer may contain various additives as in the case of a toner using a colorant such as a conventional pigment, and a release agent can be used if necessary. Further, it is preferable that a coating layer containing a binder resin is provided on the outermost surface of these three kinds of toners.

FIG. 1 is a schematic cross-sectional view showing an example in which the toner includes a base material and a coloring portion dispersed in the base material, and FIG. 2 is a concentric structure of the toner. 3 is a schematic cross-sectional view showing an example of the case, FIG. 3 is a schematic cross-sectional view showing an example of the case where the toner structure is a stripe structure, and FIG. 4 is a case where the toner structure is a fan structure. It is the schematic cross section shown about an example.
1-4, 10, 12, 14, and 16 are toners, 20 is a first color developing unit, 22 is a second color developing unit, 24 is a third color developing unit, 26 is a base material, and 30 is a first color forming unit. The photosensitive / thermosensitive layer, 32 represents a second photosensitive / thermosensitive layer, and 34 represents a third photosensitive / thermosensitive layer. 1 to 4 show only the main part of the toner. The intermediate layer provided between two adjacent photosensitive and heat-sensitive layers, the coating layer provided on the outermost surface of the toner, and the like are described. It is omitted.

Here, the toner 10 shown in FIG. 1 has three types of coloring portions 20, 22, 24 dispersed in a base material 26, and each can develop colors, for example, yellow, magenta, and cyan. In FIG. 1, for convenience of explanation, only one color developing portion of each type is shown, but it is preferable that two or more types are included for each type.
Further, the toner 12 shown in FIG. 2 includes a first photosensitive / thermosensitive layer 30 that forms a core layer, and a second photosensitive / thermosensitive layer that is sequentially stacked on the first photosensitive / thermosensitive layer 30 that forms the core layer. The toner 14 shown in FIG. 3 includes a belt-like second photosensitive / heat-sensitive layer 32 and a belt-like shape in which the second photosensitive / heat-sensitive layer 32 is disposed on both sides. The toner 16 shown in FIG. 4 is divided into three regions that are divided into three sections in a fan shape with the central portion of the toner 16 as a base point. The first photosensitive / thermosensitive layer 30 and the third photosensitive / thermosensitive layer 34. Is composed of three photosensitive / thermosensitive layers 30, 32, and 34. In the toners 12, 14, and 16 shown in FIGS. 2 to 4, each of the three photosensitive / thermosensitive layers 30, 32, and 34 can color, for example, yellow, magenta, and cyan.

  In addition, a toner having a structure in which a coloring portion is dispersed in a base material or a concentric structure can be produced by using, for example, an aggregation and coalescence method described later, a concentric structure, a stripe structure, or The toner having a fan structure can be manufactured using a wet manufacturing method using a microreactor.

<Toner constituent materials for non-color-generating toner>
Next, the toner constituent materials used when the toner is a non-photo-colorable toner, and the materials and methods used for adjusting the respective toner constituent materials will be described in more detail below.
In this case, in addition to the conductive agent, at least a color forming composition including a first component, a second component, a microcapsule including the first component, and a photocurable composition including the second component is used for the toner, The photocurable composition particularly preferably contains a photopolymerization initiator, and may contain various auxiliary agents. Further, the first component may be present in a solid state in the microcapsule (core portion), but may be present together with a solvent.
As the first component, an electron-donating colorless dye or a diazonium salt compound is used, and as the second component, an electron-accepting compound having a photopolymerizable group or a coupler compound having a photopolymerizable group is used. .
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).

-1st component-
As a 1st component used for this invention enumerated above, a substantially colorless electron-donating colorless dye or a diazonium salt compound is preferable.

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. Specific examples thereof are shown below, but the electron-donating colorless dye that can be used in the present invention is not limited thereto.
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.

  Examples of the phthalide compounds include US Reissued Patent No. 23,024, US Pat. Nos. 3,491,111, 3,491,112, 3,491,116, and 3, 509,174, specifically, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-diethylamino-o-butoxy) Phenyl) -4-azaphthalide, 3- (p-diethylamino-o-butoxyphenyl) -3- (1-pentyl-2-methylindol-3-yl) -4-azaphthalide, 3- (p-dipropylamino- o-methylphenyl) -3- (1-octyl-2-methylindol-3-yl) -5-aza (or -6-aza, or -7-aza) phthalide.

  Examples of the fluorane compound include U.S. Pat. Nos. 3,624,107, 3,627,787, 3,641,011, 3,462,828, and 3,681. , 390, 3,920,510, 3959,571, specifically, 2- (dibenzylamino) fluorane, 2-anilino-3-methyl-6 -Diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6 -N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isobu Ruaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluorane, 2-anilino-3-methyl-6-pi Peridinoaminofluorane, 2- (o-chloroanilino) -6-diethylaminofluorane, 2- (3,4-dichloroanilino) -6-diethylaminofluorane and the like can be mentioned.

  Examples of thiazine compounds include benzoyl leucon methylene blue and p-nitrobenzyl leucomethylene blue.

  Examples of the leucooramine compound include 4,4′-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucooramine, N-2,4,5-trichlorophenylleucooramine and the like. .

  Examples of the rhodamine lactam compound include rhodamine-B-anilinolactam and rhodamine- (p-nitrino) lactam.

  Examples of spiropyran compounds include compounds described in U.S. Pat. No. 3,971,808, and specific examples include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran 3,3′-. Examples include dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo) spiropyran, 3-propyl-spiro-dibenzopyran, and the like.

  Examples of the pyridine-based and pyrazine-based compounds include compounds described in US Pat. Nos. 3,775,424, 3,853,869, and 4,246,318.

  Examples of the fluorene compound include compounds described in Japanese Patent Application No. 61-240989.

When a full-color image is formed with toner, it is particularly preferable to use an electron-donating colorless dye for each coloring dye of cyan, magenta, and yellow.
As the cyan, magenta and yellow coloring dyes, the respective dyes described in US Pat. No. 4,800,149 can be used. Further, as the electron donating colorless dye for yellow coloring dye, the dyes described in U.S. Pat. No. 4,800,148 can also be used. The dyes described in No. -53542 can also be used.

As the amount of the electron-donating colorless dye used, for example, when the toner has a structure as illustrated in FIGS. 1 to 4, 0.01 to 0.01 in the photosensitive / thermal capsule (or photosensitive / thermal layer). preferably ^{3g / m 2, 0.1~1g / m} 2 is more preferable. If the amount used is less than 0.01 g / m ² , a sufficient color density may not be obtained. If it exceeds 3 g / m ² , formation of a photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer) is formed. Can be difficult. The same applies to a toner including only one color developing portion.

Examples of the diazonium salt compound include compounds represented by the following formula.
Ar-N ₂ ⁺ X ^-
[Wherein, Ar represents an aromatic ring group, and X ⁻ represents an acid anion. ]

  This diazonium salt compound is a compound that develops a color by coupling reaction with a coupler by heating or decomposes by light. The maximum absorption wavelength of these can be controlled by the position and type of the substituent in the Ar portion.

  In the above formula, Ar represents a substituted or unsubstituted aryl group. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbamide group, a sulfonyl group, a sulfamoyl group, a sulfonamide group, a ureido group, A halogen group, an amino group, a heterocyclic group, a nitro group, a cyano group and the like can be mentioned, and these substituents may be further substituted.

  Moreover, as an aryl group, a C6-C30 aryl group is preferable, for example, a phenyl group, 2-methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- ( 2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 2,4,6 -Trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2-ethylhexyloxy) phenyl group, 3,4-dichlorophenyl Group, 3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group,

  3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4-benzylphenyl Group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3-acetylphenyl group 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5-butoxyphenyl group, 4- (N-benzyl-N-methylamino)- And 2-dodecyloxycarbonylphenyl group.

  Further, these groups may be further substituted with an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group, or the like.

The maximum absorption wavelength λ _max of the diazonium salt compound used in the present invention is preferably 450 nm or less, and more preferably 290 to 440 nm, from the viewpoint of effects. The diazonium salt compound used in the present invention is preferably a diazonium salt compound having 12 or more carbon atoms, a solubility in water of 1% by mass or less and a solubility in ethyl acetate of 5% by mass or more.

  Specific examples of the diazonium salt compound that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

  The diazonium salt compounds may be used alone or in combination of two or more according to various purposes such as hue adjustment.

The amount of the diazonium salt compound used is, for example, 0.01 to 3 g / m in the photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer) when the toner has the structure illustrated in FIGS. ² is preferable, and 0.02 to 1.0 g / m ² is more preferable. When the amount used is less than 0.01 g / m ² , sufficient color developability may not be obtained. When the amount used exceeds 3 g / m ² , the sensitivity may be lowered or may be performed as necessary after fixing. It may be necessary to lengthen the time of light irradiation. The same applies to a toner including only one color developing portion.

-Second component-
The second component used in the present invention 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, and an electron accepting compound having a photopolymerizable group or Any material can be used as long as it has both functions of reacting with the first component such as a coupler compound having a photopolymerizable group to develop color and reacting with light to polymerize and cure.

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.
Examples of the electron-accepting compound include 3-halo-4-hydroxybenzoic acid described in JP-A-4-226455, methacryloxyethyl ester of benzoic acid having a hydroxy group described in JP-A-63-173682, Acryloxyethyl ester, ester of benzoic acid having hydroxy group and hydroxymethyl styrene described in JP-A-59-83893, JP-A-60-141588, and JP-A-62-99190, hydroxystyrene described in European Patent No. 29323, Examples thereof include compounds that can be synthesized with reference to N-vinylimidazole complexes of zinc halides described in Kaikai 62-1667077 and 62-16708, and electron-accepting compounds described in 63-317558.
Of these compounds having an electron-accepting group and a polymerizable group in the same molecule, 3-halo-4-hydroxybenzoic acid esters represented by the following general formula are preferred.

[Wherein, X represents a halogen atom, among which a chlorine atom is preferred. Y represents a monovalent group having a polymerizable ethylene group. Among them, an aralkyl group, an acryloyloxyalkyl group or a methacryloyloxyalkyl group having a vinyl group is preferable, and an acryloyloxyalkyl group having 5 to 11 carbon atoms or a carbon number 6-12 methacryloyloxyalkyl groups are more preferred. Z represents a hydrogen atom, an alkyl group or an alkoxyl group. ]

  Examples of the 3-halo-4-hydroxybenzoic acid ester include 3-chloro-4-hydroxybenzoic acid vinylphenethyl ester, 3-chloro-4-hydroxybenzoic acid vinylphenylpropyl ester, and 3-chloro-4-hydroxy. Benzoic acid- (2-acryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-acryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (3-acryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (3 -Methacryloyloxypropyl Ester,

  3-chloro-4-hydroxybenzoic acid- (4-acryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (4-methacryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (5 -Acryloyloxypentyl) ester, 3-chloro-4-hydroxybenzoic acid- (5-methacryloyloxypentyl) ester, 3-chloro-4-hydroxybenzoic acid- (6-acryloyloxyhexyl) ester, 3-chloro-4 -Hydroxybenzoic acid- (6-methacryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (8-acryloyloxyoctyl) ester, 3-chloro-4-hydroxybenzoic acid- (8-methacryloyloxyoctyl) Examples include esters.

  Examples of the compound having the electron accepting group and the photopolymerizable group in the same molecule include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid, zinc β-methacryloxyethoxysalicylate, β-acryloxyethoxysalicylic acid. Zinc, vinyloxyethyloxybenzoic acid, β-methacryloxyethylorcerinate, β-acryloxyethylorcerinate, β-methacryloxyethoxyphenol, β-acryloxyethoxyphenol,

  β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate, hydroxystyrene sulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl-p-hydroxybenzoate , Methacryloxymethylphenol, acryloxymethylphenol, methacrylamidepropanesulfonic acid, acrylamidepropanesulfonic acid, β-methacryloxyethoxy-dihydroxybenzene, β-acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β-methacryloxy Propanecarboxylic acid,

  γ-acryloxypropyl-α-hydroxyethyloxysalicylic acid, β-hydroxyethynylphenol, β-methacryloxyethyl-p-hydroxycinnamate, β-acryloxyethyl-p-hydroxycinnamate, 3,5 distyrene sulfone Acid amidophenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid, acrylic acid, methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid,

  3-β-hydroxyethoxyphenol, β-methacryloxyethyl-p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate, β′-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoate Acid, β-acryloxyethyloxycarbonylhydroxybenzoic acid, N, N′-di-β-methacryloxyethylaminosalicylic acid, N, N′-di-β-acryloxyethylaminosalicylic acid, N, N′-di- Preferable examples include β-methacryloxyethylaminosulfonylsalicylic acid, N, N′-di-β-acryloxyethylaminosulfonylsalicylic acid, and metal salts thereof (for example, zinc salts).

  The electron-accepting compound having the photopolymerizable group is used in combination with the electron-donating colorless dye. In this case, the amount of the electron-accepting compound used is preferably 0.5 to 20 parts by mass and more preferably 3 to 10 parts by mass with respect to 1 part by mass of the electron-donating colorless dye used. If the amount is less than 0.5 parts by mass, a sufficient color density may not be obtained. If the amount exceeds 20 parts by mass, it is difficult to lower the sensitivity and form a photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer). It may become. The same applies to a toner including only one color developing portion.

  The coupler compound having a photopolymerizable group can react with the diazonium salt compound that is a photopolymerizable group and is one of the first components to develop a color, and can be photopolymerized and cured. Anything can be used. The coupler compound forms a dye by coupling with a diazo compound in a basic atmosphere and / or a neutral atmosphere, and a plurality of types can be used in combination according to various purposes such as hue adjustment. Specific examples of the coupler compound are shown below, but the invention is not limited thereto.

The coupler compound is used in combination with a diazonium salt compound. The amount of the coupler compound used is, for example, 0.02 to 5 g / m ^{2 in the} photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer) when the toner has the structure illustrated in FIGS. From the point of an effect, 0.1-4 g / m < ² > is more preferable. When the addition amount is less than 0.02 g / m ² , color developability may be inferior, and when it exceeds 5 g / m ² , formation of a photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer) becomes difficult. There is. The same applies to a toner including only one color developing portion.

  The amount of the coupler compound used is preferably 0.5 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 1 part by mass of the diazonium salt compound. If the amount used is less than 0.5 parts by mass, sufficient color developability may not be obtained, and if it exceeds 20 parts by mass, formation of a photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer) becomes difficult. There is a case.

  The coupler compound can be used by adding a water-soluble polymer together with other components and solid-dispersing with a sand mill or the like, but it can also be emulsified with an appropriate emulsification aid and used as an emulsion. Here, the method for solid dispersion or emulsification is not particularly limited, and can be appropriately selected from known methods. Details of the method are described in JP-A-59-190886, JP-A-2-141279, and JP-A-7-17145.

  For the purpose of accelerating the coupling reaction, it is preferable to use an organic base such as a tertiary amine, piperidine, piperazine, amidine, formamidine, pyridine, guanidine, or morpholine.

  Examples of the organic base include N, N′-bis (3-phenoxy-2-hydroxypropyl) piperazine, N, N′-bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine, N , N′-bis [3- (p-methoxyphenoxy) -2-hydroxypropyl] piperazine, N, N′-bis (3-phenylthio-2-hydroxypropyl) piperazine, N, N′-bis [3- ( (β-naphthoxy) -2-hydroxypropyl] piperazine, N-3- (β-naphthoxy) -2-hydroxypropyl-N′-methylpiperazine,

  Piperazines such as 1,4-bis {[3- (N-methylpiperazino) -2-hydroxy] propyloxy} benzene, N- [3- (β-naphthoxy) -2-hydroxy] propylmorpholine, 1,4- Morpholines such as bis [(3-morpholino-2-hydroxy) propyloxy] benzene and 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, N- (3-phenoxy-2-hydroxy Propyl) piperidine, piperidines such as N-dodecylpiperidine, triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine, 4-hydroxybenzoic acid 2-N-methyl-N-benzylaminoethyl ester, 4-hydroxybenzoic acid 2- N, N-di-n-butylaminoethyl ester , 4- (3-N, N- dibutyl-amino propoxy) benzenesulfonamide, 4- (2-N, N- dibutyl-amino-ethoxycarbonyl) phenoxy acetic acid amide. The said organic base may be used independently and may be used in combination of 2 or more types.

  These are disclosed in JP 57-123086, JP 60-49991, JP 60-94381, JP 7-228731, JP 7-235157, JP 7-235158. Etc. are described.

  The amount of the organic base used is not particularly limited, but is preferably 1 to 30 mol with respect to 1 mol of the diazonium salt.

  Further, for the purpose of promoting the color development reaction, a color development aid can be added. Examples of the coloring aid include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, sulfonamide compounds, and the like. These compounds are considered to have a high color density because they have a function of reducing the melting point of the coupler compound or the basic substance or improving the heat permeability of the microcapsule wall (outer shell).

-Photopolymerization initiator-
Next, the photopolymerization initiator used in the present invention 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.

Examples of known photopolymerization initiators include those described in US Pat. No. 4,950,581 (column 20, line 35 to column 21, line 35). Further, for example, triazines described in EP-A-137452, DE-A-2718254, DE-A-2243621, US Pat. No. 4,950,581 (column 14, line 60 to column 18, line 44); 2,4 And triazine compounds such as trihalomethyltriazine such as -bis (trichloromethyl) -6- (4-stilphenyl) -s-triazine.
When the photopolymerization initiator is used in a hybrid system, in addition to the free radical curing agent, a cationic photopolymerization initiator can also be used. Examples of the cationic photopolymerization initiator include peroxide compounds such as benzoyl peroxide and the peroxide described in US Pat. No. 4,950,581 (column 19, lines 17 to 25); US Pat. No. 4,950,581 (No. Aromatic sulfonium or iodonium salt described in column 18, line 60 to column 19, line 10); (η ⁶ -isopropylbenzene)-(η ⁵ -cyclopentadienyl) -iron (II) hexafluorophosphate, etc. Preferred examples include cyclopentadienyl-arene iron (II) complex salts.

  Further, examples of the dye / boron compound include those described in JP-A-62-143044, JP-A-1-138204, JP-A-6-505287, JP-A-4-261406, and the like. It is done.

  The spectral sensitizing compound having the maximum absorption wavelength at 300 to 1000 nm is preferably a spectral sensitizing dye having a maximum absorption wavelength in this wavelength region. High sensitivity can be obtained by selecting a desired arbitrary dye from the spectral sensitizing dyes in the wavelength region and adjusting the photosensitive wavelength so as to be suitable for the light source used for the irradiation of the color forming information imparting light.

  The spectral sensitizing dye can be appropriately selected from known compounds, and includes, for example, the following patent publications relating to “compounds that interact with spectral sensitizing compounds” and “Research Disclosure, Vol. 200, 1980”. December 2000, Item 20036 "and" Sensitizer "(p.160-p.163, Kodansha; Katsumi Tokumaru, Nobu Okawara, ed., 1987) and the like.

  Specifically, 3-ketocoumarin compounds described in JP-A-58-15603, thiopyrylium salts described in JP-A-58-40302, naphthothiazoles described in JP-B-59-28328 and JP-A-60-53300. Examples include merocyanine compounds, merocyanine compounds described in JP-B-61-9621, JP-A-62-2842, JP-A-59-89303, and JP-A-60-60104.

  Further, the dyes described in “Functional dye chemistry” (1981, CMC Publishing Co., p.393 to p.416), “Coloring materials” (60 [4] 212-224 (1987)), and the like are also included. Specific examples include cationic methine dyes, cationic carbonium dyes, cationic quinoneimine dyes, cationic indoline dyes, and cationic styryl dyes.

  Examples of the spectral sensitizing dye include coumarin (including ketocoumarin or sulfonocoumarin) dye, melostyryl dye, oxonol dye, hemioxonol dye, etc .; non-ketopolymethine dye, triarylmethane dye, xanthene dye, anthracene dye Non-keto dyes such as rhodamine dyes, acridine dyes, aniline dyes, azo dyes; non-ketopolymethine dyes such as azomethine dyes, cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes, hemicyanine dyes, styryl dyes; Examples include quinoneimine dyes such as dyes, oxazine dyes, thiazine dyes, quinoline dyes, and thiazole dyes.

  By appropriately using the spectral sensitizing dye, the spectral sensitivity of the photopolymerization initiator used for the toner can be obtained in the ultraviolet to infrared region. Moreover, the various spectral sensitizing dyes may be used alone or in combination of two or more.

  The amount of the spectral sensitizing compound used is, for example, when the toner has the structure illustrated in FIGS. 1 to 4, the total weight of the material constituting the photosensitive / thermal capsule (or photosensitive / thermal layer). On the other hand, 0.1-5 mass% is preferable and 0.5-2 mass% is more preferable. The same applies to a toner including only one color developing portion.

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. Examples of the compound that interacts with the spectral sensitizing compound include organic borate salt compounds and the following compounds.

  Benzophenone, 4,4-bis (dimethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzylanthraquinone, 2-tert -Butyl anthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide from CIBA, etc. Aromatic ketones such as bisacylphosphine oxides;

  Benzoin and benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin phenyl ether; 2- (o-chlorophenyl) -4,5-diphenylimidazole duplex, 2- (o-chlorophenyl) -4, 5-di (m-methoxyphenyl) imidazole duplex, 2- (o-fluorophenyl) -4,5-diphenylimidazole duplex, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,6-triarylimidazole duplexes such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole duplexes; polyhalogens such as carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone Compound; JP 59-133 No. 28, JP-B-57-1819, JP-B-57-6096, compounds described in U.S. Patent No. 3,615,455;

  2,4,6-tris (trichloromethyl) -S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6-bis (trichloromethyl) -S- S-triazine derivatives having a trihalogen-substituted methyl group described in JP-A No. 58-29803, such as triazine and 2- (P-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine;

  Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditertiary-butyldiperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, Tertiary butyl peroxybenzoate, a, a′-bis (tertiary butyl peroxyisopropyl) benzene, dicumyl peroxide, 3,3 ′, 4,4′-tetra- (tertiary butyl peroxycarbonyl) benzophenone, etc. An organic peroxide described in JP-A-59-189340;

  Azinium salt compounds described in US Pat. No. 4,743,530; tetramethylammonium salt of triphenylbutyrate borate, tetrabutylammonium salt of triphenylbutyrate borate, tetramethylammonium salt of tri (P-methoxyphenyl) butyrateborate, etc. Examples of the organic boron compounds described in Japanese Patent No. 023587; other diaryliodonium salts and iron allene complexes.

A combination of two or more compounds is also known, and these can also be used in the toner.
Examples of the combination of two or more compounds include, for example, a combination of 2,4,5-triarylimidazole dimer and mercaptobenzoxazole, and the like, 4,4′- described in US Pat. No. 3,427,161. A combination of bis (dimethylamino) benzophenone, benzophenone and benzoin methyl ether, benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromerchi) -6- (4′-) described in US Pat. No. 4,239,850. A combination with a methoxyphenyl) -triazole, a combination of a dialkylaminobenzoate and a dimethylthioxanthone described in JP-A-57-23602, a 4,4′-bis (JP-A-59-78339, Dimethylamino) benzophenone and benzophenone and polyhalogenated methylation The combined three types of sets of objects, and the like.

  Among them, a combination of 4,4′-bis (diethylamino) benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, or 4,4′-bis (diethylamino) benzophenone and 2, A combination with 4,5-triarylimidazole dimer is preferred.

  Among the above-mentioned “compounds that interact with the spectral sensitizing compound”, organic borate salt compounds, benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group, organic peroxides or azinium salt compounds are preferable. 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.

  Examples of the organic borate salt compounds include organic borate compounds described in JP-A-62-143044, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710 and the like (hereinafter referred to as “borate compounds”). Or a spectral sensitizing dye-based borate compound obtained from a cationic dye (hereinafter sometimes referred to as “borate compound II”). Specific examples of the borate compound I are listed below, but the present invention is not limited thereto.

In the present invention, it is described in the above-mentioned “functional dye chemistry” (1981, CMC Publishing Co., p.393-p.416), “coloring material” (60 [4] 212-224 (1987)), and the like. Spectral sensitizing dye-based organic borate compounds (borate compounds II) that can be obtained from the above cationic dyes can also be mentioned.
This borate compound II is a compound having both a dye part and a borate part in its structure, absorbs light source energy effectively by the light absorption function of the dye part, and polymerizes by the radical releasing function of the borate part at the time of exposure. It has three functions of accelerating the reaction and decoloring the coexisting spectral sensitizing compound.

  Specifically, any cationic dye having a maximum absorption wavelength in a wavelength region of 300 nm or more, preferably in a wavelength region of 400 to 1100 nm can be suitably used. Among these, cationic methine dyes, polymethine dyes, triarylmethane dyes, indoline dyes, azine dyes, xanthene dyes, cyanine dyes, hemicyanine dyes, rhodamine dyes, azamethine dyes, oxazine dyes or acridine dyes are preferable, and cationic cyanine dyes are preferable. A dye, a hemicyanine dye, a rhodamine dye, or an azamethine dye is more preferable.

  The borate compound II obtained from the organic cationic dye can be obtained using an organic cationic dye and an organic boron compound anion with reference to the method described in European Patent No. 223,587A1.

  Specific examples of the borate compound II obtained from the cationic dye are given below, but the invention is not limited to these.

  The borate compound II is a multifunctional compound as described above. However, from the viewpoint of obtaining high sensitivity and sufficient decoloring property, the photopolymerization initiator in the present invention includes a spectral sensitizing compound, It is preferable that the compound that interacts with the spectral sensitizing compound is appropriately combined. In this case, as the photopolymerization initiator, a photopolymerization initiator (1) in which the spectral sensitizing compound and the borate compound I are combined, or a photopolymerization initiator in which the borate compound I and the borate compound II are combined. (2) is more preferable.

At this time, the use ratio of the spectral sensitizing dye and the organic borate compound present in the photopolymerization initiator is increased as needed, and light is carried out as necessary after color development by heat treatment during fixing during image formation. This is very important in obtaining sufficient decoloring properties (deactivation, decomposition, etc. of unreacted components) by light irradiation in the irradiation process.
In the case of the photopolymerization initiator (1), in the photopolymerization initiator, in addition to the ratio of spectral sensitizing compound / borate compound I required for the photopolymerization reaction (= 1/1: molar ratio), further in the toner It is particularly preferable to add the borate compound I in an amount necessary for sufficiently decoloring the remaining spectral sensitizing compound in view of obtaining sufficient sensitivity and decoloring performance.
That is, the ratio of spectral sensitizing dye / borate compound I is preferably used in the range of 1/1 to 1/50, more preferably in the range of 1 / 1.2 to 1/30. It is most preferable to use in the range of 1 / 1.2 to 1/20. If the ratio is less than 1/1, sufficient polymerization reactivity and decoloring property cannot be obtained, and if it exceeds 1/50, formation of a photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer) becomes difficult. Since there are cases, it is not preferable.

  Further, in the case of the photopolymerization initiator (2), it is sufficient to use the borate compound I and the borate compound II in combination so that the borate portion has an equimolar ratio or more with respect to the dye portion. This is particularly preferable in terms of obtaining high sensitivity and decoloring performance. The ratio of borate compound I / borate compound II is preferably used in the range of 1/1 to 50/1, more preferably in the range of 1.2 / 1 to 30/1. It is most preferable to use within the range of / 1 to 20/1. If the ratio is less than 1/1, the generation of radicals is small and sufficient polymerization reactivity and decoloring performance cannot be obtained. If it exceeds 50/1, sufficient sensitivity cannot be obtained, which is not preferable.

  The total amount of the spectral sensitizing dye and the organic borate compound in the photopolymerization initiator should be used in the range of 0.1 to 10% by mass with respect to the amount of the compound having the photopolymerizable group (second component). It is more preferable to use in the range of 0.1 to 5% by mass, but it is most preferable to use in the range of 0.1 to 1% by mass. If the amount used is less than 0.1% by mass, the effects of the present invention cannot be obtained. If the amount used exceeds 10% by mass, the storage stability of the toner decreases and the photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer). ) May be difficult to form. The same applies to a toner including only one color developing portion.

-Auxiliary-
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.

-Microcapsules and microencapsulation-
In the present invention, a first component such as an electron-donating colorless dye or a diazonium salt compound is used in a microcapsule.
A conventionally known method can be used as a microencapsulation method. For example, a method utilizing coacervation of hydrophilic wall forming materials described in US Pat. Nos. 2,800,547 and 2,800,458, US Pat. No. 3,287,154, British Patent No. 990443, Japanese Patent Publication No. 38-19574, and 42- No. 446, No. 42-771, etc., a method by polymer precipitation described in US Pat. Nos. 3,418,250 and 3,660,304, a method using an isocyanate polyol wall material described in US Pat. No. 3,796,669, US A method using an isocyanate wall material described in Japanese Patent No. 3914511, a method using a urea-formaldehyde system and a urea formaldehyde-resorcinol-based wall forming material described in US Pat. Nos. 4001140, 4087376, and 4089802, US Pat. To 4025455 A method using a wall-forming material such as melamine-formaldehyde resin and hydroxybrovir cellulose, an in situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079, British Patent No. 952807 No. 965074, electrolytic dispersion cooling method, U.S. Pat. No. 3,111,407, British Patent No. 930422, spray drying method, JP-B-7-73069, JP-A-4-101858, JP-A-9-263057. And the like.

  The method for microencapsulation is not limited to these, but in the present invention, in particular, an oil phase prepared by dissolving or dispersing the first component in a hydrophobic organic solvent serving as the core of the capsule is used. , Mixed with an aqueous phase in which water-soluble polymer is dissolved, emulsified and dispersed by means such as a homogenizer, and then heated to cause a polymer formation reaction at the oil droplet interface to form a microcapsule wall of the polymer substance It is preferable to employ an interfacial polymerization method. The interfacial polymerization method can form capsules with a uniform particle size within a short time, and can obtain a toner excellent in raw storage stability.

  In the present invention, the preferred microcapsule is a capsule at room temperature only when contact between the substance inside and outside the capsule is hindered by the substance isolating action of the microcapsule wall (outer shell), and heat and / or pressure is applied above a certain value. It is possible to contact the inside and outside substances. This phenomenon can be freely controlled as a change in the physical properties of the capsule by appropriately selecting the material of the microcapsule wall, the substance contained in the core of the microcapsule, the additive, and the like.

  The material of the microcapsule wall that can be used in the present invention is added inside and / or outside the oil droplets. Examples of the material for 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.

  Examples of the water-soluble polymer include gelatin, polyvinyl pyrrolidone, and polyvinyl alcohol.

  For example, when polyurethane is used as the microcapsule wall material, a polyisocyanate and a second substance (for example, polyol, polyamine) that reacts therewith to form a microcapsule wall are used as a water-soluble polymer aqueous solution (aqueous phase) or capsule. After mixing in an oily medium (oil phase) to be converted, emulsifying and dispersing in water, and heating, a polymer formation reaction occurs at the oil droplet interface to form a microcapsule wall.

  US Pat. Nos. 3,281,383, 3,773,695, 3,793,268, JP-B-48-40347, JP-A-49-24159, JP-A-48-80191 are exemplified as the polyvalent isocyanate and the polyol and polyamine which are reacted with the polyvalent isocyanate. 48-84086 can also be used.

  In the present invention, when forming a microcapsule containing the first component, the first component to be included may be present in the capsule in a solution state or in a solid state. When the first component is encapsulated in a solution state, the first component, such as an electron-donating colorless dye or a diazonium salt compound, may be encapsulated in an organic solvent.

In general, the organic solvent can be appropriately selected from high-boiling solvents such as phosphate ester, phthalate ester, acrylic acid ester, methacrylic acid ester, other carboxylic acid ester, fatty acid amide, alkylated biphenyl, Alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diallylethane, compounds solid at room temperature, oligomer oil, polymer oil, and the like are used.
Specifically, JP-A-59-178451, JP-A-59-178455, JP-A-59-178457, JP-A-60-242894, JP-A-63-85633, JP-A-6-194825, JP-A-7-13310 and the like. Examples thereof include organic solvents described in JP-A Nos. 7-13311 and 9-106039 and Japanese Patent Application No. 62-75409. Further, when encapsulating, a so-called oilless capsule may be used without using the organic solvent. As the usage-amount of the said organic solvent, 1-500 mass parts is preferable with respect to 100 mass parts of electron-donating colorless dyes.

  In addition, when the solubility of the first component such as an electron-donating colorless dye or diazonium salt compound to be encapsulated in the organic solvent is low, a low-boiling solvent having high solubility is also used as an auxiliary solvent. You can also. On the other hand, the low boiling point solvent can be used without using the organic solvent. Examples of the low boiling point solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like.

  For the aqueous phase in which the oil phase is emulsified and dispersed, an aqueous solution in which a water-soluble polymer is dissolved is used. After the oil phase is introduced into the aqueous phase, it is emulsified and dispersed by means such as a homogenizer. The water-soluble polymer has an action as a protective colloid that can make the dispersion uniform and easy, and an emulsified and dispersed aqueous solution. It also acts as a dispersion medium that stabilizes. Here, a surfactant can be added to at least one of the oil phase and the aqueous phase in order to more uniformly emulsify and disperse to obtain a more stable dispersion.

  The water-soluble polymer contained as the protective colloid can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers.

As the anionic polymer, any of natural and synthetic polymers can be used, and examples thereof include those having a linking group such as —COO— or —SO ₂ —. Specifically, natural products such as gum arabic, alginic acid, and bectin; gelatin derivatives such as carboxymethyl cellulose and phthalated gelatin; semi-synthetic products such as sulfated starch, sulfated cellulose, and lignin sulfonic acid; maleic anhydride (hydrolysis) And synthetic products such as copolymers, acrylic acid (methacrylic acid) polymers and copolymers, vinylbenzenesulfonic acid polymers and copolymers, and carboxy-modified polyvinyl alcohol.

  Examples of nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose. Examples of amphoteric polymers include gelatin. Of these, gelatin, gelatin derivatives, and polyvinyl alcohol are preferable. The water-soluble polymer is used as an aqueous solution of 0.01 to 10% by mass.

  The surfactant can be appropriately selected from known surfactants for emulsification. For example, anionic or nonionic surfactants can act as protective colloids as described above and precipitate. And those that do not cause aggregation can be appropriately selected and used. Specific examples include sodium alkylbenzene sulfonate, sodium alkyl sulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (for example, polyoxyethylene nonylphenyl ether), and the like. As addition amount of the said surfactant, 0.1 mass%-5 mass% are preferable with respect to the oil phase weight, and 0.5 mass%-2 mass% are more preferable.

  All the components including the first component can be used as a solid dispersion by means of a sand mill or the like together with, for example, a water-soluble polymer, a sensitizer and other coloring aids. An emulsified dispersion obtained by dissolving in a slightly soluble or insoluble high-boiling organic solvent and then mixing it with a polymer aqueous solution (aqueous phase) containing a surfactant and / or a water-soluble polymer as a protective colloid and emulsifying with a homogenizer or the like. It is preferable to use it as a product. In this case, if necessary, a low boiling point solvent can be used as a dissolution aid. Further, all the components including the first component can be emulsified and dispersed separately, or mixed in advance and then dissolved in a high boiling point solvent and / or a low boiling point solvent and emulsified and dispersed. . The particle size of the emulsified dispersion formed by emulsifying and dispersing is preferably 1 μm or less.

  Emulsification / dispersion is a means of using an oil phase containing the above-mentioned components and a surfactant and / or a protective colloid for fine-particle emulsification such as high-speed stirring and ultrasonic dispersion, such as a homogenizer, Manton Gory, It can be easily carried out using a known emulsifying device such as a sonic disperser, a dissolver, or a teddy mill.

  After emulsification, the emulsion is heated to 30 to 70 ° C. for the purpose of promoting the microcapsule wall formation reaction. Further, during the reaction, in order to prevent the capsules from aggregating, it is necessary to add water to reduce the collision probability between the capsules or to perform sufficient stirring. On the other hand, a dispersion for preventing aggregation can be added separately during the reaction. As the end point of the microcapsule wall formation reaction, the generation of carbon dioxide gas is observed as the polymerization reaction proceeds, and the end of the generation can be regarded as an approximate end point. Usually, microcapsules enclosing the first component can be obtained by performing the reaction for several hours.

  The volume average particle size of the microcapsules is preferably adjusted to be in the range of 0.1 to 3 μm, and more preferably adjusted to be in the range of 0.3 to 1.0 μm. When the volume average particle size of the microcapsules is less than 0.1 μm, the color density and the like may become a problem relatively because of the thickness of the outer shell. Further, when the volume average particle size exceeds 3.0 μm, dispersion in the toner particles becomes non-uniform, and color development may vary.

As the material constituting the outer shell of the microcapsule, the above-described thermoplastic resin such as urethane can be used. As these thermoplastic resin materials, known amorphous resins and crystalline resins can be used.
Here, when an amorphous resin is used, the glass transition temperature thereof is preferably in the range of 90 to 200 ° C, and more preferably in the range of 100 to 150 ° C. When the glass transition temperature is lower than 90 ° C., the outer shell may be softened by heating in the toner production process. When the glass transition temperature is higher than 200 ° C., both the coloring stimulus and the fixing are performed at the time of image formation. Even if heat treatment is performed, the outer shell does not soften, so that color development becomes difficult, or the fixing temperature must be set higher, and energy consumption may increase.
Moreover, when using crystalline resin, it is preferable that the melting | fusing point exists in the range of 90-200 degreeC, and it is more preferable that it exists in the range of 100-150 degreeC. When the melting point is out of the above range, the same problem as when an amorphous resin is used may occur.

-Binder-
In the toner having the structure illustrated in FIGS. 1 to 4, a binder may be contained in the photosensitive / thermosensitive capsule (or the photosensitive / thermosensitive layer). The same applies to a toner including only one color developing portion.
As the binder, the same binder as used for emulsifying and dispersing the photocurable composition, a water-soluble polymer used for encapsulating the first component, polystyrene, polyvinyl formal, polyvinyl butyral, polymethyl acrylate, Solvent-soluble polymers such as acrylic resins such as polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and their copolymers, phenol resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, urethane resins, or these polymers Latex can also be used. Of these, gelatin and polyvinyl alcohol are preferred. Moreover, you may use the binder resin mentioned later as a binder.

-Surfactant etc.-
In the toner having the structure illustrated in FIGS. 1 to 4, various surfactants are used for photosensitive / thermosensitive capsules (or photosensitive / thermosensitive layers) and intermediate layers for various purposes such as emulsification and dispersion. Also good. The same applies to a toner including only one color developing portion.
Examples of the surfactant include nonionic surfactant saponin, polyethylene oxide, polyethylene oxide derivatives such as polyethylene oxide alkyl ether, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate. Anionic surfactants such as esters, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylenalkylkil ethers, amphoteric surfactants such as alkylbetaines, alkylsulfobetaines, And cationic surfactants such as aliphatic or aromatic quaternary ammonium salts.

  Furthermore, additives such as dyes, ultraviolet absorbers, plasticizers, fluorescent brighteners, curing agents, antistatic agents and the like can be used as necessary. Specific examples of the additive are described in “Research Disclosure, Vol. 176” (December 1978, Item 17643) and “Same Vol. 187” (November 1979, Item 18716).

-Curing agent-
In the toner having the structure illustrated in FIGS. 1 to 4, a curing agent may be used in combination with each layer such as a photosensitive / thermosensitive capsule (or photosensitive / thermosensitive layer) and an intermediate layer. The same applies to a toner including only one color developing portion.
As the curing agent, for example, a “gelatin curing agent” used in the production of a photographic light-sensitive material is useful. For example, aldehyde-based compounds such as formaldehyde and glutaraldehyde, the reactivity described in US Pat. No. 3,635,718, etc. Halogen compounds, compounds having reactive ethylenically unsaturated groups described in US Pat. No. 3,635,718, aziridine compounds described in US Pat. No. 3,017,280, epoxy compounds described in US Pat. No. 3,091,537, etc. Halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, vinyl sulfones described in US Pat. No. 3,642,486 and US Pat. No. 3,687,707, and vinyl sulfone breakers described in US Pat. No. 3,841,872. , US special It includes Ketobiniru acids according to No. 3,640,720. Further, chromium alum, zirconium sulfate, boric acid and the like can be used as the inorganic curing agent.

  Among them, 1,3,5-triacroyl-hexahydro-s-triazine, 1,2-pispinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamido) ethane, Compounds such as 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenimino-s-triazine and boric acid are preferred. As addition amount of the said hardening | curing agent, 0.5-5 mass% is preferable with respect to the amount of binders.

-Conductive agent-
A conductive agent is used to impart conductivity to the toner of the present invention. The conductive agent is not particularly limited as long as it is a known conductive material, but it is a conductive material having high transparency to light having a wavelength in the visible light range in that it does not affect the color tone when the toner is colored. It is particularly preferable to use an agent or a conductive agent colored in white.
Examples of the conductive agent that can be suitably used in the present invention include titanium oxide, tin oxide, and ITO (indium tin oxide).
When a conductive agent is internally added to the toner, the conductive agent is preferably contained in an amount of 1% by mass or more, and more preferably 3% by mass or more. When the addition amount of the conductive agent is less than 1% by mass, it may be impossible to obtain the resistivity required for the conductive toner. In addition, although the upper limit of the addition amount of a electrically conductive agent is not specifically limited, It is preferable that it is 10 mass% or less from a practical viewpoint, such as ensuring sufficient addition amount of another component.
When a conductive agent is externally added to the toner, it is preferable to add the conductive agent at a ratio of 0.1 to 3 parts by weight with respect to 100 parts by weight of the toner, and 0.3 to 3.0 parts by weight. It is more preferable to externally add at a ratio of parts by mass. When the external additive amount of the conductive agent with respect to 100 parts by mass of the toner is less than 0.3 parts by mass, it may not be possible to obtain the resistivity required for the conductive toner. Is likely to occur. It is possible to use both internal and external additives.
Moreover, when using the electrically conductive agent which consists of inorganic materials, such as a titanium oxide, it is suitable for the particle size to exist in the range of 0.03-0.6 micrometer.

-Binder resin-
As the toner, a binder resin used in a conventional toner can be used. For example, in the case of a toner having a structure in which photosensitive / thermosensitive capsules are dispersed in a base material as illustrated in FIG. 1, the binder resin is a material that constitutes the main component of the base material or the outer shell of the photosensitive / thermal capsule. In addition, in a toner having a structure having two or more layered coloring portions such as a concentric structure, a stripe structure, and a fan structure as illustrated in FIGS. 2 to 4, a coating layer that covers the outermost surface of the toner, Although it can utilize as a material which comprises the intermediate | middle layer provided between two adjacent color development parts, 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.
When the toner including only one color developing portion has a core-shell structure, a binder resin used in conventional toners can be used for the surface layer. In addition, when using for a surface layer, an amorphous resin, especially an amorphous polyester resin are suitable. When the binder resin is contained in the photocurable composition, either the amorphous resin or the crystalline resin, or both can be used. It is useful to use a crystalline polyester resin having sharp melt properties.

In the present invention, the “crystalline polyester resin” refers to a resin having a clear endothermic peak instead of a stepwise endothermic amount change in differential scanning calorimetry (DSC). Moreover, in the case of the polymer which copolymerized the other component with respect to the said crystalline polyester main chain, when another component is 50 mass% or less, this copolymer is also called crystalline polyester resin.
The crystalline polyester resin and all other polyester resins are synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In the present invention, a commercially available product may be used as the polyester resin, or an appropriately synthesized product may be used.

  Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid Aromatic dicarboxylic acids such as dibasic acids such as, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.

  Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  The polyvalent carboxylic acid component preferably contains a dicarboxylic acid component having a sulfonic acid group in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above. The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, when the entire resin is emulsified or suspended in water to produce fine particles, if a sulfonic acid group is present, it can be emulsified or suspended without using a surfactant as described later.

  Examples of the dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. The divalent or higher carboxylic acid component having a sulfonic acid group is contained in an amount of 0 to 20 mol%, preferably 0.5 to 100 mol%, based on all carboxylic acid components constituting the polyester. When the content is low, the temporal stability of the emulsified particles deteriorates, while when it exceeds 10 mol%, the crystallinity of the polyester resin may be lowered. In addition, when the toner is produced by the aggregation and coalescence method described later, there may be a problem that after the aggregation, the process of fusing the particles is adversely affected and it becomes difficult to adjust the toner diameter.

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

  As the polyhydric alcohol component, an aliphatic diol is preferable, and a linear aliphatic diol having 7 to 20 carbon atoms in the main chain portion is more preferable. When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. Further, when the number of carbon atoms is less than 7, when the polycondensation with aromatic dicarboxylic acid is performed, the melting point becomes high and fixing at low temperature may be difficult. On the other hand, when the number exceeds 20, it is difficult to obtain practical materials. easy. The carbon number is more preferably 14 or less.

  Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester that can be used in the toner include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecane Examples include, but are not limited to, diol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

  Among the polyhydric alcohol components, the content of the aliphatic diol component is preferably 80 mol% or more, and more preferably 90% or more. When the content of the aliphatic diol component is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. is there.

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

  The method for producing the crystalline polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. They are manufactured using different types of monomers.

  The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction is carried out while reducing the pressure in the reaction system as necessary to remove water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable that the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component.

  The crystalline polyester resin particle dispersion can be prepared by adjusting the acid value of the resin or by emulsifying and dispersing it using an ionic surfactant.

  Catalysts that can be used in the production of the crystalline polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compounds: Phosphorous acid compounds, phosphoric acid compounds, amine compounds, and the like, and specific examples include the following compounds.

  For example, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium Tetrapropoxide, titanium tetraisoproxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, naphthenic acid Zirconium, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Sufaito, tris (2, 4-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  As melting | fusing point of crystalline resin, Preferably it is 50-110 degreeC, More preferably, it is 60-90 degreeC. When the melting point is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. When the melting point is higher than 110 ° C., sufficient low-temperature fixing cannot be obtained as compared with the conventional toner. There is a case.

  A crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.

  On the other hand, crystalline vinyl resins include amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, and (meth) acrylic acid. Decyl, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate And vinyl resins using long-chain alkyl and alkenyl (meth) acrylic acid esters. In the present specification, the description “(meth) acryl” means to include both “acryl” and “methacryl”.

  In addition, as the amorphous polymer (amorphous resin), a known resin material can be used, but an amorphous polyester resin is particularly preferable. The amorphous polyester resin used in the present invention is obtained mainly by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols.

  When an amorphous polyester resin is used, it is advantageous in that a resin particle dispersion can be easily prepared by adjusting the acid value of the resin or by emulsifying and dispersing using an ionic surfactant. .

  Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and other aromatic carboxylic acids, maleic anhydride, fumaric acid, succinic acid, alkenyl Examples thereof include aliphatic carboxylic acids such as succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polyvalent carboxylic acids can be used alone or in combination. Of these polyvalent carboxylic acids, it is preferable to use aromatic carboxylic acids, and in order to take a crosslinked structure or a branched structure in order to ensure good fixability, tricarboxylic or higher carboxylic acids (trimerits) It is preferable to use an acid or an acid anhydride thereof in combination.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin, and other aliphatic diols, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct. One or more of these polyhydric alcohols can be used. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferable, and among these, aromatic diols are more preferable. In order to secure good fixing properties, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol in order to take a crosslinked structure or a branched structure.

  In addition, monocarboxylic acid and / or monoalcohol is further added to the polyester resin obtained by polycondensation of polycarboxylic acid and polyhydric alcohol to esterify the hydroxyl group and / or carboxyl group at the polymerization terminal. The acid value of the polyester resin may be adjusted. Examples of the monocarboxylic acid include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, etc., and examples of the monoalcohol include methanol, ethanol, propanol, octanol, 2-ethylhexanol, trifluoroethanol, Examples include trichloroethanol, hexafluoroisopropanol, and phenol.

  The polyester resin can be produced by subjecting the polyhydric alcohol and polyhydric carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid, if necessary, a catalyst, and blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heat at 150 to 250 ° C. to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant Can be manufactured.

  Examples of the catalyst used for the synthesis of this polyester resin include esterification catalysts such as organic metals such as dibutyltin dilaurate and dibutyltin oxide, and metal alkoxides such as tetrabutyl titanate. The amount of such a catalyst added is preferably 0.01 to 1.00% by mass relative to the total amount of raw materials.

  The amorphous polymer that can be used in the toner preferably has a mass average molecular weight (Mw) of 5,000 to 1,000,000 as determined by gel permeation chromatography (GPC) method of tetrahydrofuran (THF) soluble content. The molecular weight (Mn) is preferably from 2,000 to 10,000, the molecular weight distribution Mw / Mn is preferably from 1.5 to 100, and more preferably from 2 to 60.

  When the mass average molecular weight and the number average molecular weight are smaller than the above ranges, while being effective for low-temperature fixability, not only the hot offset resistance is remarkably deteriorated, but also the glass transition temperature of the toner is lowered. The storage stability such as toner blocking may be adversely affected. On the other hand, if the molecular weight is larger than the above range, the hot offset resistance can be sufficiently provided, but the low-temperature fixability is deteriorated and the oozing of the crystalline polyester phase present in the toner is inhibited, so that the document storage stability is reduced. May be adversely affected. Therefore, it becomes easy to satisfy both the low-temperature fixability, the hot offset resistance, and the document storage stability by satisfying the above conditions.

  In the present invention, the molecular weight of the resin is measured with a THF solvent by using a TOSol GPC / HLC-8120, a Tosoh column / TSKgel SuperHM-M (15 cm), and a monodisperse polystyrene standard sample. The molecular weight was calculated using the prepared molecular weight calibration curve.

  The acid value of the polyester resin (the number of mg of KOH required to neutralize 1 g of resin) is easy to obtain the molecular weight distribution as described above, and is easy to ensure the granulation property of the toner particles by the emulsion dispersion method. From the standpoint of maintaining good environmental stability (charging stability when temperature / humidity changes) of the obtained toner and the like, it is preferably 1 to 30 mg KOH / g. The acid value of the polyester resin can be adjusted by controlling the carboxyl group at the terminal of the polyester according to the blending ratio of the raw polyhydric carboxylic acid and polyhydric alcohol and the reaction rate. Or what has a carboxyl group in the principal chain of polyester is obtained by using trimellitic anhydride as a polyvalent carboxylic acid component.

  A styrene acrylic resin can also be used as a known amorphous polymer. Examples of monomers that can be used in this case include styrenes such as styrene, parachlorostyrene, and α-methylstyrene: methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and lauryl acrylate. And esters having vinyl groups such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and the like: Vinyl nitriles such as acrylonitrile and methacrylonitrile: Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether: Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone: Polyolefins such as ethylene, propylene and butadiene: Single amount And a copolymer obtained by combining two or more of these, or a mixture thereof. Furthermore, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl It is also possible to use a condensation resin, a mixture of these with the vinyl resin, or a graft polymer obtained when a vinyl monomer is polymerized in the presence of these resins.

  In the case of polyester, the resin particle dispersion can be prepared with a disperser such as a homogenizer by adjusting the acid value of the resin and using a neutralized amine, and the amorphous polymer is prepared using a vinyl monomer. In this case, emulsion polymerization can be carried out using an ionic surfactant or the like to prepare a resin particle dispersion, and in the case of other resins, those that are oily and soluble in a solvent with relatively low solubility in water If the resin is dissolved in those solvents, the resin is dispersed in water with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte in water, and then the solvent is evaporated by heating or decompression to evaporate the solvent. A particle dispersion can be prepared. Further, the amorphous resin is advantageous in that a resin particle dispersion can be easily prepared by emulsifying and dispersing in water.

  The particle diameter of the resin particle dispersion thus obtained can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

  The glass transition temperature of the amorphous polymer that can be used in the present invention is preferably 35 to 100 ° C., and 50 to 80 ° C. from the viewpoint of the balance between storage stability and toner fixing property. More preferred. When the glass transition temperature is less than 35 ° C., the toner tends to be blocked during the storage or in the developing machine (a phenomenon in which toner particles are aggregated into a lump). On the other hand, if the glass transition temperature exceeds 100 ° C., the fixing temperature of the toner becomes high, which is not preferable.

  The softening point of the amorphous polymer is preferably in the range of 80 to 130 ° C. More preferably, it is the range of 90-120 degreeC. When the softening point is 80 ° C. or lower, the toner and the image stability of the toner after fixing and during storage are significantly deteriorated. On the other hand, when the softening point is 130 ° C. or higher, the low-temperature fixability is deteriorated.

  The softening point of the amorphous polymer was measured by a flow tester (manufactured by Shimadzu Corporation: CFT-500C), preheating: 80 ° C./300 sec, plunger pressure: 0.980665 MPa, die size: 1 mmφ × 1 mm, heating rate: 3 The intermediate temperature between the melting start temperature and the melting end temperature under the condition of 0.0 ° C./min.

-Release agent-
The toner may contain a release agent if necessary. A mold release agent is generally used for the purpose of improving mold release properties.
Examples of the release agent that can be used for the toner are not particularly limited. Minerals such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, microcrystalline wax, Fischer-Tropsch wax, and petroleum wax Natural gas waxes and their modified products, low molecular weight polyolefins such as polyethylene, polypropylene, polybutene, silicones that show a softening point upon heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc. Fatty acid amides, carnauba wax, rice wax, candelilla wax, plant waxes such as tree wax and jojoba oil, and animal waxes such as beeswax. Formulation As a higher alcohol or a mixture thereof to 10 carbon atoms is 18, and there may be mentioned higher fatty acid monoglyceride or mixture thereof having 16 to 22 carbon atoms, it can be used in combination of these things.

-Other additives-
The toner may contain other components other than those listed above. The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include various known additives used in conventional toners such as inorganic fine particles, organic fine particles, and charge control agents. In addition, since the toner itself develops color, a colorant such as a pigment used in conventional toners is basically unnecessary, but in order to finely adjust the color tone when it is developed, A small amount of a known colorant can also be used.
The charge control agent is used for the purpose of improving and stabilizing the chargeability. As the charge control agent, various commonly used charge control agents such as quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments can be used. In the case of producing a toner by the aggregation coalescence method described later, a material that is difficult to dissolve in water is preferable from the viewpoint of controlling ionic strength that affects the stability of aggregated particles formed in a solution and reducing wastewater contamination.

  When inorganic fine particles are added to the toner as a charge control agent, examples of such inorganic fine particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate and other external additives on the normal toner surface. All inorganic fine particles used as can be mentioned. In this case, these inorganic fine particles can be used by being dispersed in a solvent using an ionic surfactant, a polymer acid, a polymer base or the like.

  Also, for the purpose of imparting fluidity and improving cleaning properties, after drying in the same way as normal toner, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester and silicone are flow aids. As a cleaning aid, it can be added to the toner surface by shearing in a dry state.

Inorganic oxide fine particles added to the toner include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na _{2. O,} it can be exemplified _{ZrO 2, CaO · SiO 2,} K 2 O · (TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , and the like. Of these, silica fine particles and titania fine particles are particularly preferable. It is desirable that the surface of the inorganic oxide fine particles is previously hydrophobized. This hydrophobization treatment is more effective for improving the powder fluidity of the toner, as well as the environmental dependency of charging and the resistance to carrier contamination.

  The hydrophobic treatment can be performed by immersing the inorganic oxide fine particles in a hydrophobic treatment agent. Although there is no restriction | limiting in particular as said hydrophobic treatment agent, For example, a silane coupling agent, silicone oil, a titanate coupling agent, an aluminum coupling agent, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, silane coupling agents are preferable.

  As the silane coupling agent, for example, any one of chlorosilane, alkoxysilane, silazane, and a special silylating agent can be used. Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltriethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N- ( Trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane , Γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercapto Examples thereof include propyltrimethoxysilane and γ-chloropropyltrimethoxysilane. The amount of the hydrophobizing agent varies depending on the kind of the inorganic oxide fine particles and cannot be generally defined, but is usually about 1 to 50 parts by mass with respect to 100 parts by mass of the inorganic oxide fine particles.

-Toner particle size, shape, etc.-
The volume average particle diameter of the toner is not particularly limited, and can be adjusted as appropriate 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, when the toner includes three types of coloring portions that can develop colors of yellow, cyan, and magenta) ), The volume average particle diameter corresponding to each toner structure is preferably within the following range.
That is, when the toner structure illustrated in FIG. 1 is a color developing portion dispersion structure, the toner is preferably within a range of 5 to 40 μm, and more preferably within a range of 10 to 20 μm. Further, the volume average particle size of the photosensitive / thermosensitive capsule contained in the color developing portion-dispersed toner having such a particle size is preferably in the range of 1 to 5 μm, and in the range of 1 to 3 μm. It is preferable.
When the volume average particle size is less than 5 μm, the amount of color developing component 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 diameter exceeds 40 μm, the unevenness of the image surface becomes large, uneven glossiness of the image surface may occur, and the image quality may deteriorate.

  In addition, the color development part dispersion type toner in which a plurality of photosensitive / thermosensitive capsules are dispersed therein has a larger particle diameter than 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.

  In the case of a concentric, stripe, or fan structure toner as illustrated in FIGS. 2 to 4, the formation of photosensitive / thermosensitive capsule particles is considered as compared with a color developing portion dispersion structure toner. Since there is no need, it is easy to reduce the diameter. The volume average particle diameter of the toner is preferably in the range of 3 to 40 μm, and more preferably in the range of 5 to 15 μm. When the volume average particle size is less than 3 μm, it may be difficult to produce the toner itself. On the other hand, if the volume average particle size exceeds 40 μm, the unevenness of the image surface becomes large, uneven glossiness of the image surface may occur, and the image quality may deteriorate.

On the other hand, in the case of a toner including only one color developing portion, the volume average particle diameter is preferably in the range of 3 to 8 μm, and more preferably in the range of 4 to 7 μm. 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.
Note that the toner described in Patent Document 4 in which a plurality of color developing portions (microcapsules MCy, MCm, MCc) capable of coloring cyan, magenta, and yellow are contained in a toner resin matrix in a dispersed manner is currently used. In comparison with the conventional toner having a volume average particle size of about 2 to 10 μm using the colorant, it is unavoidable that the particle size of the toner must be increased. However, since the toner including only one color developing portion contains only one color developing portion in the toner, it is easy to control the volume average particle size to the same level or lower than that of the conventional toner. For this reason, when designing an image forming process or device, existing processes and devices are applied almost as they are for matters related to the volume average particle diameter of the toner (for example, the amount and composition of external additives). In addition to having the advantage of being able to do so, it is also possible to obtain a higher definition image when the diameter is smaller than in the past.

Further, the toner 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. It 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 Multimizer II (manufactured by Beckman Coulter, Inc.), the volume and number of individual toner particles from the small diameter side. A cumulative distribution is drawn, 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 average. The 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. At this time, 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). In the present invention, “volume average particle diameter” means a value of D50v unless otherwise specified.

Further, the toner preferably has a shape factor SF1 represented by the following formula (1) within a range of 110 to 130.
Formula (1) SF1 = (ML ² / A) × (π / 4) × 100

[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 performance at the time of cleaning tends to be impaired, resulting in image defects.
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, fine powder may increase as a result, and problems such as generation of fog due to fine powder may occur.

  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 spread 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 toners are measured. The square of the length and the projected area were calculated, and the shape factor SF1 was obtained from the above equation (1).

<Toner constituent materials of photochromic toner>
Next, the toner constituent materials used when the toner is a photochromic toner, and the materials and methods used when adjusting the respective toner constituent materials will be described in more detail below.
In this case, in addition to the conductive agent, the toner contains a first component, a second component, a microcapsule containing the first component, a color forming composition containing a photocurable composition containing the second component and a photopolymerizable compound. Is preferably used, and the photocurable composition particularly preferably contains a photopolymerization initiator (or photopolymerization initiator system), and may contain a spectral sensitizing dye, various auxiliary agents, and the like. . 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 photochromic toner, an electron-donating colorless dye is used as the first component, and an electron-accepting compound (referred to as “electron-accepting developer” or “developer”) is used as the second component. In the case of the first photochromic toner, 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.

-Polymerizable compound having an ethylenically unsaturated bond (photopolymerization compound)-
The polymerizable compound having an ethylenically unsaturated bond that can be used in the present invention is a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule.
For example, acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, itaconic esters; styrenes; Vinyl ethers; vinyl esters; N-vinyl heterocycles; aryl ethers; allyl esters can be used. Among these, a polymerizable compound containing a hetero atom having at least one lone pair in the molecule is preferable.

The heteroatom having a lone electron pair here refers to each atom such as oxygen, nitrogen, sulfur, phosphorus, and halogen. Specifically, those having an ester bond, an amide bond, a carbonyl bond, a thiocarbonyl bond, an ether bond, a thioether bond, and a group such as amine, alcohol, thioalcohol, phosphine, and halogen are included. Among these, polymerizable having an ethylenically unsaturated bond having at least one ester bond, amide bond, amine, carbonyl bond and / or ether bond in the molecule, which has a strong interaction with an electron-accepting developer. A compound is preferable, and a compound having a photopolymerizable ester bond or amide bond is particularly preferable.
In order to make the polymerization efficiency (curing speed) advantageous, a polymerizable compound having a plurality of ethylenically unsaturated double bonds in the molecule is preferable. For example, a polyvalent compound such as trimethylolpropane or pentaerythritol is preferable. Examples include alcohol acrylates and methacrylates; and acrylate or methacrylate terminated epoxy resins, acrylate or methacrylate terminated polyesters, and the like.

  Specific examples of particularly preferred compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate and diethylene glycol. And dimethacrylate. As the molecular weight of these polymerizable compounds, those having a molecular weight of about 100 to about 5000 can be used, but those that are difficult to thermally diffuse in microcapsules containing an electron-donating colorless dye are more preferable, and the molecular weight is 200. The above compounds are particularly useful.

-Photopolymerization initiator (or photopolymerization initiator system)-
As the photopolymerization initiator suitably used in the present invention, one or a combination of two or more compounds can be selected from the compounds capable of initiating photopolymerization of the compound containing an ethylenically unsaturated bond. it can.
Preferable specific examples of the photopolymerization initiator include the following compounds. Aromatic ketones: for example, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylamino Acetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers: such as benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2,4,5-triarylimidazole dimer: for example 2- (o- Lorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; and polyhalogen compounds, such as Carbon tetrabromide, phenyl tripromomethyl sulfone, phenyl trichloromethyl ketone, and description in JP-A-53-133428, JP-B-57-1819, JP-B-57-6096, and US Pat. No. 3,615,455 And S-triazine derivative having a trihalogen-substituted methyl group described in JP-A-58-29803 : For example, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6-bis (trichloromethyl) -S-triazine, compounds such as 2- (P-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine. And organic peroxides described in, for example, JP-A-59-189340: methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditertiary butyl diperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tertiary butyl peroxybenzoate, a, a′-bis (tertiary butyl peroxyisopropyl) benzene, dicumyl peroxide, 3,3 ′ , 4,4′-tetra- (tertiarybutylperoxycarbonyl) benzophenone, and the like; and azinium salt compounds described, for example, in US Pat. No. 4,743,530; Boron compounds: for example, tetramethylammonium salt of triphenylbutyrate borate, tetrabutylammonium salt of triphenylbutyrate borate, tetramethylammonium salt of tri (P-methoxyphenyl) butyrate borate; other diaryl iodonium salts and iron allene complexes In the photosensitive and thermosensitive recording material field, a well-known photopolymerization initiator can be usefully used.

Further, as a photopolymerization initiator system, a combination of two or more kinds of compounds is known, and those combinations can also be used in the present invention.
Examples of the combination of two or more compounds include a combination of 2,4,5-triarylimidazole dimer and mercaptobenzoxazole, etc., 4,4′- described in US Pat. No. 3,427,161. A combination of bis (dimethylamino) benzophenone and benzophenone or benzoin methyl ether, benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6- (4′-) described in US Pat. No. 4,239,850 A combination of methoxyphenyl) -triazole, a combination of dialkylaminobenzoate and dimethylthioxanthone described in JP-A-57-23602, and 4,4′-bis (JP-A-59-78339) Dimethylamino) benzophenone, benzophenone and polyhalogenated compounds It can be mentioned three kinds combination of Le compounds.

More preferable examples include 2,4,5-triarylimidazole dimer and organoboron compound.
The content of the photopolymerization initiator is preferably 0.01 to 20% by mass and more preferably 0.2 to 15% by mass based on the total weight of the photocurable composition, and the most preferable content is 1 -10 mass%. If it is less than 0.01% by mass, the sensitivity is insufficient, and if it exceeds 10% by mass, an increase in sensitivity may not be expected.

-Spectral sensitizing dye-
The photocurable composition may contain a spectral sensitizing dye for adjusting the photosensitive wavelength in addition to the polymerizable compound having an ethylenically unsaturated bond and the photopolymerization initiator.
As the spectral sensitizing dye, various compounds known in the field of light and heat sensitive recording materials can be used. Examples of spectral sensitizing dyes can be found in the patents described in the above mentioned photopolymerization initiators, Research Disclosure, Vol. 200, December 1980, Item 20036, “Sensitizer” (Katsuaki Tokumaru and Shin Okawara / Edited Kodansha 1987), pages 160-163, etc. can be referred to. Specific examples of spectral sensitizing dyes include, for example, 3-ketocoumarin compounds in JP-A-58-15503, thiopyrylium salts in JP-A-58-40302, and JP-B-59-28328. No. 60-53300 discloses naphthothiazole merocyanine compounds, and JP-B Nos. 61-9621, 62-3842, JP-A Nos. 59-89303 and 60-60104 disclose merocyanine compounds, respectively. ing. With these spectral sensitizers, the spectral sensitivity of the photopolymerization initiator can be extended to the visible range. In the above example, the trihalomethyl-S-triazine compound is taken as the photopolymerization initiator, but it may be combined with other photopolymerization initiators.
Spectral sensitizing dyes include keto dyes coumarin (including ketocoumarin or sulfonocoumarin) dyes, melostyryl dyes, oxonol dyes and hemioxonol dyes, non-keto dyes non-ketopolymethine dyes, anthracene dyes, rhodamine dyes, Examples include acridine dyes, aniline dyes and azo dyes, cyanine, hemicyanine and styryl dyes as non-ketopolymethine dyes.

-Auxiliary-
Further, in the photocurable composition, as an auxiliary agent for further promoting the polymerization, a reducing agent such as an oxygen scavenger and a chain transfer agent of an active hydrogen donor, and other components that promote the polymerization in a chain transfer manner. These compounds can also be used in combination.
Oxygen scavengers that have been found useful are phosphines, phosphonates, phosphites, stannous salts and other compounds that are readily oxidized by oxygen. For example, N-phenylglycine, trimethylbarbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N-2,4,6-pentamethylaniline and the like. Further, thiols, thioketones, trihalomethyl compounds, loffin dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides and the like as described below are also useful as polymerization accelerators.

  In addition to these compounds, a thermal polymerization inhibitor can be added to the photocurable composition as necessary. A thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the photocurable composition, thereby improving chemical stability during preparation or storage of the photocurable composition. Can be increased. Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol 2,6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine and the like. A preferable addition amount of the thermal polymerization inhibitor is 0.001 to 5 mass%, more preferably 0.01 to 1 mass%, based on the total weight of the photocurable composition. If it is less than 0.001% by mass, the thermal stability is poor, and if it exceeds 5% by mass, the sensitivity is lowered.

  In addition, you may use a photocurable composition enclosed in a microcapsule as needed. For example, it can be encapsulated in microcapsules with reference to European Patent No. 023587 and the above patent.

-Electron accepting developer (second component)-
Examples of the electron-accepting developer include phenol derivatives, sulfur-containing phenol derivatives, organic carboxylic acid derivatives (eg, salicylic acid, stearic acid, resorcinic acid, etc.), and metal salts thereof, sulfonic acid derivatives, urea, or thiourea Derivatives and the like, acidic clay, bentonite, novolac resin, metal-treated novolac resin, metal complex and the like can be mentioned.
Examples of these are described in Paper Pulp Technology Times (1985), pages 49-54 and 65-70, as well as JP-B-40-9309, 45-14039, JP-A-52-140483, 48-51510, 57-210886, 58-87089, 59-11286, 60-176795, 61-95988, and the like.

Examples of these compounds include 2,2′-bis (4-hydroxyphenyl) propane, 4-t-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, 1,1′- as phenolic compounds. Bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1,1′-bis (3-chloro-4-hydroxyphenyl) -2-ethylbutane, 4, 4′-sec-isooctylidene diphenol, 4,4′-sec-butylidene diphenol, 4-tert-octylphenol, 4-p-methylphenylphenol, 4,4′-methylcyclohexylenephenol, 4,4 '-Isopentylidenephenol, benzyl p-hydroxybenzoate and the like.
Salicylic acid derivatives include 4-pentadecyl salicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di (tert-octyl) salicylic acid, 5-octadecylsalicylic acid, 5-α- (p-α- Methylbenzylphenyl) ethylsalicylic acid, 3-α-methylbenzyl-5-tert-octylsalicylic acid, 5-tetradecylsalicylic acid, 4-hexyloxysalicylic acid, 4-cyclohexyloxysalicylic acid, 4-decyloxysalicylic acid, 4-dodecyloxysalicylic acid 4-pentadecyloxysalicylic acid, 4-octadecyloxysalicylic acid, and the like, and zinc, aluminum, calcium, copper, and lead salts thereof.
These electron accepting compounds can be used alone or in combination of two or more. The amount of the electron-accepting compound used is preferably in the range of 10 to 4000% by mass, particularly preferably 100 to 2000% by mass, based on the electron-donating colorless dye.

-Electron donating colorless dye (first component)-
As electron-donating colorless dyes, conventionally known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucooramine compounds, rhodamine lactam compounds, triphenylmethane compounds Various compounds such as compounds, triazene compounds, spiropyran compounds, and fluorene compounds can be used.
Specific examples of phthalides include US Reissued Patent No. 23,024, US Patent Nos. 3,491,111, 3,491,112, 3,491,116 and Specific examples of fluoranes are described in U.S. Pat. Nos. 3,624,107, 3,627,787, 3,641,011, and 3,462,828. No. 3,681,390, No. 3,920,510, No. 3,959,571, specific examples of spirodipyrans are described in US Pat. No. 3,971,808, Examples of pyrazine compounds are US Pat. Nos. 3,775,424, 3,853,869, 4,246,318, and specific examples of fluorene compounds include Japanese Patent Application No. 61-240989. It is described in.

If some of these are disclosed, the triarylmethane compounds include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide and 3,3-bis (p-dimethylaminophenyl) phthalide. 3- (p-dimethylaminophenyl) -3- (l, 3-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide Diphenylmethane compounds include 4,4′-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucooramine, N-2,4,5-trichlorophenylleucooramine, and the like. , Xanthene compounds include rhodamine-B-anilinolactam, rhodamine- (p-nitrino) lactam, 2- ( Dibenzylamino) fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N -Isoamylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-anilino-3-methyl-6 -N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-tetrahydrofurfurylaminofluorane, 2-anilino- 3-methyl-6-piperidinoaminofluorane, 2- (o-chloroanilino) -6-diethylaminofluora 2- (3,4-dichloroanilino) -6-diethylaminofluorane, etc., and thiazine compounds include benzoyl leucomethylene blue and p-nitrobenzyl leucomethylene blue, and spiro compounds include 3-methyl- Spiro-dinaphthopyrans, 3-ethyl-spiro-dinaphthopyrans 3,3′-dichloro-spiro-dinaphthopyrans, 3-benzylspiro-dinaphthopyrans, 3-methyl-naphtho (3-methoxy-benzo) -spiropyrans, 3-propyl-spiros -Dibenzopyran and the like.
In particular, when used in a full-color recording material, U.S. Pat. No. 4,800,149 is used as an electron-donating colorless dye for cyan, magenta, and yellow, and U.S. Pat. No. 4,800,148 is used as a yellow coloring type. JP, 63-53542, etc. can be referred to as a cyan color developing type.

-Microcapsules and microencapsulation-
When the electron-donating colorless dye is microencapsulated, it can be prepared by a known method in the field of photosensitive and heat-sensitive recording materials.
For example, a method using coacervation of a hydrophilic wall forming material as shown 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. Interfacial polymerization methods such as those found in US Pat. Nos. 4,446 and 42-771, methods based on polymer precipitation found in US Pat. Nos. 3,418,250 and 3660304, and isocyanate polyol wall materials found in US Pat. No. 3,796,669. A method using an isocyanate wall material found in U.S. Pat. US special Method using wall forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose found in No. 4025455, in situ by polymerization of monomers found in Japanese Patent Publication Nos. 36-9168 and 51-9079 And the electrolytic dispersion cooling method found in British Patent Nos. 952807 and 965074, and the spray drying method found in US Pat. No. 3,111,407 and British Patent No. 930422. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall (outer shell) after emulsifying a substance that becomes the core of the microcapsule.

As a method for forming a microcapsule wall, the effect is particularly great when a microencapsulation method by polymerization of a reactant from the inside of an oil droplet is used. That is, it is possible to obtain capsules that are preferable as a toner having a uniform particle diameter and excellent raw storage properties within a short time.
For example, when polyurethane is used as a microcapsule wall material, a polyvalent isocyanate and, if necessary, a second substance that reacts therewith to form a microcapsule wall (for example, polyol, polyamine) are mixed in an oily liquid to be encapsulated and mixed with water. By emulsifying and dispersing, and then raising the temperature, a polymer formation reaction is caused at the oil droplet interface to form a microcapsule wall. At this time, an auxiliary solvent having a low boiling point and a strong dissolving power can be used in the oily liquid. In this case, the polyisocyanate used, and the polyol and polyamine which react with the polyisocyanate are U.S. Pat. Nos. 3,281,383, 3,773,695, 3,793,268, JP-Bs 48-40347, 49-24159, -80191 and 48-84086, and they can also be used.

  Examples of the polyvalent isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4′-diisocyanate. 3,3′-dimethoxy-4,4′-biphenyl-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, xylylene-1,4-diisocyanate, 4,4′-diphenylpropane diisocyanate, tri Methylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4 Diisocyanates such as diisocyanates, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, triisocyanates such as toluene-2,4,6-triisocyanate, 4,4′-dimethyldiphenylmethane-2,2 ′, 5,5 Tetraisocyanate such as' -tetraisocyanate, adduct of hexamethylene diisocyanate and trimethylolpropane, adduct of 2,4-tolylene diisocyanate and trimethylolpropane, adduct of xylylene diisocyanate and trimethylolpropane, tolylene diisocyanate and There are isocyanate prepolymers such as adducts of hexanetriol.

  Examples of the polyol include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers. The following polyols described in JP-A-60-49991 are also used. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 2, 3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl-1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl- 1,5-pentanediol, 1,4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-phenylpropylene glycol, 1,1,1-trimethylolpropane, hexanetriol, penta Erythritol, pentaerythrito Ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4-di (2-hydroxyethoxy) benzene, condensation product of aromatic polyhydric alcohol such as resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene Glycol, m-xylylene glycol, α, α′-dihydroxy-p-diisopropylbenzene, 4,4′-dihydroxy-diphenylmethane, 2- (p, p′-dihydroxydiphenylmethyl) benzyl alcohol, bisphenol A and ethylene oxide Examples of adducts include bisphenol A and adducts of propylene oxide. The polyol is preferably used at a hydroxyl group ratio of 0.02 to 2 moles per mole of isocyanate groups.

  Polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylene. Examples include diamine, diethylene, triamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and an amine adduct of an epoxy compound. Polyvalent isocyanate can also react with water to form a polymeric material.

When making the microcapsules, a water-soluble polymer can be used, and the water-soluble polymer may be any of a water-soluble anionic polymer, nonionic polymer, and amphoteric polymer. The anionic polymer may be a natural one or a synthetic one, and examples thereof include those having —COO— or —SO ₂ — group. Specific anionic natural polymers include arabic gum, alginic acid, pectin and the like, and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose and lignin sulfonic acid. Synthetic products include maleic anhydride (including hydrolyzed) copolymers, acrylic acid (including methacrylic acid) polymers and copolymers, vinyl benzene sulfonic acid polymers and copolymers. And carboxy-modified polyvinyl alcohol.

Nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of amphoteric compounds include gelatin. These water-soluble polymers are used as an aqueous solution of 0.01 to 10% by mass.
The volume average particle size of the microcapsules is preferably adjusted to be in the range of 0.1 to 3 μm, and more preferably adjusted to be in the range of 0.3 to 1.0 μm. When the volume average particle size of the microcapsules is less than 0.1 μm, the color density and the like may be relatively problematic due to the thickness of the outer shell. When the volume average particle size exceeds 3.0 μm, the dispersion in the toner particles becomes non-uniform, and the color development may vary.

As the material constituting the outer shell of the microcapsule, the above-described thermoplastic resin such as urethane can be used. As these thermoplastic resin materials, known amorphous resins and crystalline resins can be used.
Here, when an amorphous resin is used, the glass transition temperature thereof is preferably in the range of 90 to 200 ° C, and more preferably in the range of 100 to 150 ° C. When the glass transition temperature is lower than 90 ° C., the outer shell may be softened by heating in the toner production process. When the glass transition temperature is higher than 200 ° C., both the coloring stimulus and the fixing are performed at the time of image formation. Even if heat treatment is performed, the outer shell does not soften, so that color development becomes difficult, or the fixing temperature must be set higher, and energy consumption may increase.
Moreover, when using crystalline resin, it is preferable that the melting | fusing point exists in the range of 90-200 degreeC, and it is more preferable that it exists in the range of 100-150 degreeC. When the melting point is out of the above range, the same problem as when an amorphous resin is used may occur.

-Solvent (used in microcapsules)-
The electron donating colorless dye may be present in a solution state in the microcapsule or may be present in a solid state. When a solvent is used in combination, the amount of the solvent used in the capsule is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the electron donating colorless dye.

  A natural oil or a synthetic oil can be used in combination as a solvent used in the present invention. Examples of these solvents include, for example, cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffin, naphthene oil, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene and 1-phenyl 1-xylyl ethane, 1- Diarylethanes such as phenyl 1-p-ethylphenylethane, 1,1′-ditolylethane and the like. Phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, etc.), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (eg tributyl acetylcitrate), benzoic acid Esters (octyl benzoate), alkylamides (eg diethyl lauryl amide), fatty acid esters (eg dibutoxyethyl succinate, dioctyl acetate), trimesic acid esters (eg tributyl trimesate), ethyl acetate, butyl acetate Lower alkyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve Seteto, there is cyclohexanone and the like. Further, at the time of microencapsulation, a volatile solvent may be used in combination as an auxiliary solvent for dissolving the electron donating colorless dye. Examples of this type of solvent include ethyl acetate, butyl acetate, methylene chloride and the like.

-UV absorber-
As the toner, an ultraviolet absorber can be used as necessary for the purpose of improving the light resistance of the image. For example, in the case of a toner having a structure in which the color developing portion is dispersed in the base material as illustrated in FIG. 1, the ultraviolet absorber is added to the material constituting the outer shell of the color developing portion. In a toner having a structure having two or more layered color forming portions such as a concentric structure, a stripe structure, and a fan structure as exemplified in the above, a coating layer covering the outermost surface of the toner and a gap between two adjacent color forming portions Although it can be added to the intermediate layer to be provided, it can also be added to other portions (for example, the coloring portion) as necessary. Similarly, in a toner including only one color developing portion, an ultraviolet absorber can be used at any location in the toner as necessary. When the toner has a core-shell structure, an ultraviolet absorber is added to the surface layer. It is suitable to add.
In addition, as an ultraviolet absorber, compounds known in the industry such as benzotriazole compounds, cinnamic acid ester compounds, aminoarylidenemalon nitrile compounds, benzophenone compounds, and the like can be used.

-Water-soluble polymer-
In the present invention, the dispersion of the photocurable composition and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer. The water-soluble polymer that can be preferably used in the present invention is 25. A compound that dissolves 5% by mass or more in water at 0 ° C. is preferable. Specifically, gelatin, gelatin derivatives, proteins such as albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sodium alginate, starches (modified starch) Sugar derivatives such as gum arabic, polyvinyl alcohol, hydrolyzate of styrene-maleic anhydride copolymer, carboxy-modified polyvinyl alcohol, polyacrylamide, saponified product of vinyl acetate-polyacrylic acid copolymer, polystyrene sulfone And synthetic polymers such as acid salts. Of these, gelatin and polyvinyl alcohol are preferred.

-Binder-
In the toner having the structure illustrated in FIGS. 1 to 4, a binder may be included in the color development portion. The same applies to a toner including only one color developing portion.
Binders include the above water-soluble polymers and polystyrene, polyvinyl formal, polypinyl butyral, acrylic resins: for example, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and their copolymers, phenol resins, styrene Solvent-soluble polymers such as ptadien resin, ethyl cellulose, epoxy resin, urethane resin, or latex of these polymers can be used. Of these, gelatin and polyvinyl alcohol are preferred. Moreover, you may use the binder resin mentioned later as a binder.

-Surfactant-
In the toner having the structure exemplified in FIGS. 1 to 4, various surfactants may be used in the color developing portion for various purposes such as emulsification and dispersion. The same applies to a toner including only one color developing portion.
Examples of surfactants include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide alkyl ethers such as polyethylene ether derivatives, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N -Anionic surfactants such as acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethyne alkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, fatty or aromatic Cationic surfactants such as genus quaternary ammonium salts can be used as necessary.

-Solvent (microcapsule dispersion, photocurable composition dispersion)-
When the toner is prepared by a wet manufacturing method such as an aggregation and coalescence method described later, a dispersion liquid in which microcapsules are dispersed or a dispersion liquid in which a photocurable composition is dispersed is prepared. Solvents used for the preparation of these dispersions include water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, methyl cellosolve, 1-methoxy-2-propanol; Solvents: for example, methylene chloride, ethylene chloride; ketones: for example acetone, cyclohexanone, methyl ethyl ketone; esters: for example, methyl acetate cellosolve, ethyl acetate, methyl acetate; It is done. Among these, water is particularly preferable.

-Others-
In addition to the materials described above, the same conductive agent, binder resin, release agent, and other additives used for the photochromic toner as those described above for the photochromic toner can be used. . Further, the toner particle size, shape, and the like can be the same as those of the non-color-developing toner.
In addition, the materials listed for the light-colorable toner may be used for the light non-colorable toner, and the materials listed for the light non-colorable toner may be used as long as the color development characteristics and color control are not adversely affected. You may use for a photochromic toner.

<Toner production method>
Next, a method for producing the toner of the present invention will be described. The toner of the present invention is preferably prepared using a known wet manufacturing method such as an aggregation coalescence method. The wet manufacturing method is particularly suitable in the case where the toner has a configuration that develops a color utilizing at least the material diffusion during heating (for example, when two or more kinds of components described above are contained in different matrices). is there. If the wet manufacturing method is used, the maximum process temperature in the production of toner can be kept low, and it is easy to prevent color development in the toner manufacturing process.
From the viewpoint of preventing color development in the toner manufacturing process, the maximum process temperature when the wet manufacturing method is used is preferably 90 ° C. or less, and more preferably 80 ° C. or less. However, if the process temperature is too low, it is difficult to produce the toner itself, and therefore the maximum process temperature is preferably 40 ° C. or higher.

The use of the wet manufacturing method includes, in particular, the first and second components that develop color when they react with each other, the photocurable composition, and the microcapsules dispersed in the photocurable composition, It is suitable for production of a toner having a structure in which the first component is contained in the microcapsule and the second component is contained in the photocurable composition.
The microcapsule used for the toner having the above structure is particularly preferably a thermoresponsive microcapsule, but may be a microcapsule that responds to other stimuli such as light.

In the present invention, a known wet manufacturing method can be used, but among the wet manufacturing methods, the maximum process temperature can be kept low, and toners having various structures as exemplified in FIGS. 1 and 2 can be easily produced. For this reason, it is particularly preferable to use the aggregation coalescence method.
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.
Next, a toner production method using the aggregation and coalescence method will be described in more detail. In general, the aggregation and coalescence method includes an aggregation process 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.
In a toner using a colorant such as a conventional pigment, a release agent dispersion is used in addition to the resin particle dispersion and the colorant dispersion as needed in the aggregation process. A particle dispersion (which may be the same as or different from the resin particle dispersion used in the aggregation step) is used.

Also in the production of toner, although the types and combinations of the various dispersions used as raw materials are different, the toner can be produced by appropriately combining the adhering step in addition to the aggregation step and the fusion step.
Hereinafter, a manufacturing method using the aggregation and coalescence method of the toner having the color developing portion dispersion structure illustrated in FIG. 1 and the toner toner having the concentric structure illustrated in FIG. 2 will be described in detail.

<Method for Producing Toner Having Colored Portion Dispersion Structure>
First, a manufacturing method using the aggregation and coalescence method of toner having a coloring portion dispersion structure will be described.
In this case, first, a raw material containing (a1) a microcapsule dispersion in which microcapsules containing a first component are dispersed and a photocurable composition dispersion in which a photocurable composition containing a second component is dispersed. A first agglomeration step for forming first agglomerated particles in the dispersion; and (b1) a first resin particle dispersion in which resin particles are dispersed in the raw material dispersion in which the first agglomerated particles are formed. Adding a liquid to attach the resin particles to the surface of the aggregated particles; (c1) heating and fusing the raw material dispersion containing the aggregated particles having the resin particles attached to the surface; Through the first fusing step of obtaining the fused particles (photosensitive / thermosensitive capsules), two or more kinds of photosensitive / thermosensitive capsule dispersions capable of developing colors different from each other are prepared.

Subsequently, (d1) second aggregated particles are formed in a mixed solution obtained by mixing the two or more types of photosensitive / thermosensitive capsule dispersion and the second resin particle dispersion in which the resin particles are dispersed. A toner having a color developing portion dispersion structure 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. Can be obtained.
The photosensitive / thermosensitive capsule dispersion used in the second aggregating step may be one type, and the photosensitive / thermosensitive capsule obtained through the steps (a1) to (c1) includes only one color developing portion as it is. It can also be used as a toner. Moreover, in each process, the dispersion liquid containing another component can also be used together as needed.

-Adjustment of various dispersions-
Hereinafter, a method for adjusting various dispersions used in the toner manufacturing method using the above-described aggregation and coalescence method will be described.
The resin particle dispersion is prepared by dispersing resin particles prepared by emulsion polymerization or the like in a solvent using an ionic surfactant. Alternatively, the resin is dissolved in a soluble solvent and adjusted by phase inversion emulsification.

Examples of the dispersion medium in the resin particle dispersion include an aqueous medium and an organic solvent.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together. In the present invention, it is preferable to add and mix a surfactant in the aqueous medium. Although it does not specifically limit as surfactant, For example, anionic surfactants, such as sulfate ester type, sulfonate type, phosphate ester type, soap type; amine salt type, quaternary ammonium salt type, etc. Nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and the like.
Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. Among these, ionic surfactants such as anionic surfactants and cationic surfactants are preferable.
Examples of the organic solvent include ethyl acetate and toluene, which are appropriately selected according to the binder resin.

In addition, the release agent particle dispersion can disperse the release agent in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, and can be heated to the melting point or higher and subjected to strong shearing. It adjusts by atomizing with an apparatus.
As a device for fine dispersion by the above mechanical means, Menton Gorin high-pressure homogenizer (Gorin), continuous ultrasonic homogenizer (Nippon Seiki Co., Ltd.), Nanomizer (Nanomizer), Microfluidizer (Mizuho Industrial Co., Ltd.) Company), Harrell type homogenizer, Slasher (Mitsui Mining Co., Ltd.), Cavitron (Eurotech Co., Ltd.) and the like.

As the microcapsule dispersion, an emulsion obtained by dispersing microcapsules prepared by using various microencapsulation methods as described above in a solution containing a water-soluble binder or the like can be used.
In addition, the photocurable composition dispersion is prepared by adding a surfactant to a resin component such as a water-soluble binder and a solvent component such as water to various components constituting the photocurable composition, followed by strong shearing. It can be obtained by micronizing with an apparatus that can be applied.

  The particle size of the fine particles contained in the various dispersions excluding the microcapsule dispersion is preferably 1 μm or less in order to easily adjust the toner diameter and the particle size distribution to desired values. More preferably, it is in the range of ˜300 nm.

-(A1) First aggregation step-
In the first aggregation step, a raw material dispersion containing a microcapsule dispersion in which microcapsules containing the first component are dispersed and a photocurable composition dispersion in which a photocurable composition containing the second component is dispersed First aggregated particles are formed in the liquid.
In the first aggregating step, after adding an aggregating agent to the raw material dispersion, the fine particles in the raw material dispersion are aggregated by heating as necessary to form first aggregated particles.
The heating temperature may be raised from room temperature to 40 ° C., and further to around 60 ° C. if necessary.

Aggregated particles are formed by adding a flocculant at room temperature under stirring with a rotary shearing homogenizer or the like to make the pH of the raw material dispersion acidic (pH = about 2 to 4).
The flocculant used in the first flocculation step is preferably a surfactant having a polarity opposite to that of the surfactant used as the dispersant added to the raw material dispersion, that is, an inorganic metal salt or a metal complex having a valence of 2 or more. Can be used. In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide, and the like. Examples thereof include inorganic metal salt polymers.
Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is divalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

-(B1) Adhering step-
In the attaching step, the first resin particle dispersion in which the resin particles are dispersed is added to the raw material dispersion in which the first aggregated particles are formed, and the resin particles are attached to the surface of the aggregated particles. Thereby, the coating layer corresponding to the outer shell portion of the photosensitive / thermosensitive capsule can be formed.

  The coating layer can be formed by additionally adding the first resin particle dispersion to the dispersion in which the aggregated particles (core particles) are formed in the aggregation step. The binder resin component used for the first resin particle dispersion may be either a crystalline resin or an amorphous resin, and a release agent dispersion may be used in combination with the first resin particle dispersion. Further, a release agent dispersion may be used instead of the first resin particle dispersion.

  A surfactant can be used for emulsion polymerization of the binder resin, dispersion of various fine particle components, aggregation of the fine particles, stabilization of the aggregated particles, and the like. Specifically, sulfate surfactants, sulfonates, phosphates, soaps and other anionic surfactants, amine salts, quaternary ammonium salts and other cationic surfactants, polyethylene glycols, It is also effective to use a nonionic surfactant such as an alkylphenol ethylene oxide adduct system or a polyhydric alcohol system. Can be used

-(C1) First fusion step-
In the first fusing step, the raw material dispersion containing the agglomerated particles with the resin particles attached to the surface thereof is heated and fused to obtain first fused particles (photosensitive / heat-sensitive capsules).
In the first fusion step, the pH of the suspension containing the agglomerated particles obtained through the first agglomeration step and the adhering step is set to a range of about 6.5 to 8.5, so that the progress of aggregation is progressed. After stopping, the aggregated particles are fused by heating.
The heating is performed at a temperature equal to or higher than the glass transition temperature or melting point of the binder resin (and / or the release agent) used for forming the coating layer.

The heating temperature is set to such an extent that the material constituting the outer shell of the microcapsule is dissolved and the outer shell structure is not lost, and generally the heat resistance of the material constituting the outer shell of the microcapsule, The temperature is determined in consideration of the temperature at which the material forming the outer shell of the photosensitive / thermosensitive capsule can be fused, but in general, it is preferably in the range of 40 to 90 ° C, and in the range of 50 to 80 ° C. More preferably, it is within.
When the heating temperature exceeds 90 ° C., the outer shell of the microcapsule may disappear and color may develop. Further, when the heating temperature is less than 40 ° C., sufficient fusion is not performed, and the photosensitive / thermosensitive capsule particles may be decomposed in a later step.

-(D1) Second aggregation step-
The above steps (a1) to (c1) are carried out for each kind of photosensitive / thermosensitive capsule (colorable color) dispersed in the toner, and two or more kinds of photosensitive / thermosensitive capsules capable of developing colors different from each other. Prepare the dispersion.
Subsequently, in the second aggregating step, the second agglomerated particles are mixed in a mixed solution obtained by mixing two or more kinds of photosensitive / thermosensitive capsule dispersions and the second resin particle dispersions in which the resin particles are dispersed. Form. In addition, a dispersion liquid of other components such as a release agent dispersion liquid can be added to the above mixed solution as necessary.
The second aggregating step is also basically performed in the same manner as the first aggregating step except that the composition of the liquid used for the agglomeration is different. That is, after adding an aggregating agent to the mixed dispersion liquid, the photosensitive / thermosensitive capsule particles and resin particles being mixed are aggregated by heating to form second aggregated particles. In addition, after the formation of the second agglomerated particles, or after the formation is completed, a resin particle dispersion liquid in which amorphous resin particles are dispersed is added, and the surface of the second agglomerated particles is made of amorphous resin particles. It is preferable to coat.
The heating temperature is preferably a temperature at which the amorphous resin particles can be fused to each other or other materials by heating. Specifically, the glass transition temperature of the amorphous resin particles. A temperature higher by several to tens of degrees Celsius is preferable.

-(E1) Second fusion step-
In the second fusing step, the mixed solution containing the second agglomerated particles is heated to obtain second fusing particles (wet toner).
In the second fusion step, the pH of the suspension containing the agglomerated particles obtained through the second agglomeration step is adjusted to a range of about 6.5 to 8.5 to stop the agglomeration, The aggregated particles are fused by heating.
The heating is performed at a temperature equal to or higher than the glass transition temperature or the melting point of the binder resin used for forming the second aggregated particles.

The heating temperature depends on the heat resistance of the material forming the outer shell of the microcapsule, the heat resistance of the material forming the outer shell of the photosensitive / thermosensitive capsule, and the binder resin used for forming the second aggregated particles. Although it is determined in consideration of the temperature at which fusion is possible, generally it is preferably in the range of 40 to 90 ° C, more preferably in the range of 50 to 70 ° C.
When the heating temperature exceeds 90 ° C., the outer shell of the microcapsule disappears and the color develops, or the second component dispersed in the photosensitive / thermal capsule capable of developing one color is outside the photosensitive / thermal capsule. In some cases, it diffuses or diffuses into a photosensitive / thermosensitive capsule capable of developing in other colors, and sufficient color development cannot be obtained during image formation.
Further, when the heating temperature is less than 40 ° C., sufficient fusion is not performed, and the toner particles may be decomposed in subsequent processes such as washing and drying.

  When a conductive agent is internally added to the toner, the toner can be added at an arbitrary timing when performing the above-described series of steps. Specifically, various dispersions used in the first and second aggregation processes and dispersions used to form a coating layer on the aggregated particles obtained in the first and second aggregation processes. It is possible to add a conductive agent to the toner by adding a conductive agent therein or adjusting and using a dispersion liquid in which the conductive agent is dispersed.

-Cleaning, drying process, etc.-
After passing through the second fusion step, desired toner particles are obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In consideration of charging properties, the washing step should be sufficiently substituted and washed with ion-exchanged water. Is desirable. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity. In addition, various external additives as described above including a conductive agent can be added to the toner particles after drying as necessary.

<Method for producing toner having concentric structure>
Next, a manufacturing method using a method of aggregating and uniting toner having a concentric structure will be described.
In this case, first, (a2) a first photocurable composition in which a first microcapsule dispersion in which microcapsules containing a first component are dispersed and a photocurable composition containing a second component are dispersed. A first aggregating step of forming first agglomerated particles in a raw material dispersion containing the dispersion, and (b2) a first in which resin particles are dispersed in the raw material dispersion in which the agglomerated particles are formed. An adhesion step of adding a resin particle dispersion to attach the resin particles to the surface of the aggregated particles; and (c2) heating and fusing the raw material dispersion containing the aggregated particles having the resin particles adhered to the surface thereof. Then, the photosensitive / thermosensitive capsule dispersion liquid is prepared through the first fusion step for obtaining the photosensitive / thermosensitive capsule.

  Subsequently, (d2) a second microcapsule dispersion in which microcapsules containing the first component are dispersed and a photocurable composition containing the second component are dispersed in the photosensitive / thermosensitive capsule dispersion. A photosensitive / thermosensitive layer is formed on the surface of the photosensitive / thermosensitive capsule by forming a photosensitive / thermosensitive layer capable of developing a color different from that of the photosensitive / thermosensitive capsule. A layer forming step; (e2) adding a second resin particle dispersion in which resin particles are dispersed to the raw material dispersion after the photosensitive / thermosensitive layer forming step; A coating layer forming step of forming a coating layer by adhering resin particles; and (f2) a raw material dispersion containing second agglomerated particles in which the resin particles are adhered to the surface of the photosensitive / thermosensitive layer to form a coating layer The second fusion step to obtain fused particles by heating By going through, it is possible to obtain a toner having a concentric structure.

In the case of producing a toner having a concentric structure including three or more kinds of coloring portions capable of developing colors different from each other, (d2) a photosensitive / thermosensitive layer forming step, (e2) a coating layer forming step, and (f2) The process of sequentially performing the second fusion step in this order is repeated one more time. Thereby, two or more photosensitive / thermosensitive layers formed through the respective photosensitive / thermosensitive layer forming steps and photosensitive / thermosensitive capsules can have different colors.
In each step, a dispersion containing other components can be used in combination as necessary. For example, in the first aggregation step, the adhesion step, the photosensitive / thermosensitive layer forming step, and the coating layer forming step, a release agent. A dispersion may be used.

Next, each step will be described in more detail. First, the method for adjusting various dispersions used in each step is the same as that for producing a toner having a color development portion dispersion structure.
The steps (a2) to (c2) can also be performed basically in the same manner as the steps (a1) to (c1) described above. However, only one type of photosensitive / heat-sensitive capsule dispersion is prepared through the steps (a2) to (c2).

In the subsequent (d2) photosensitive / thermosensitive layer forming step and (e2) coating layer forming step, the photosensitive / thermosensitive capsule particles to be the core layer (core particles) are combined with the photosensitive / thermosensitive layer and the coating layer. The steps can be performed in the same manner as the steps (a1) and (b1) except that the layers are sequentially stacked. As a result, photosensitive / thermosensitive capsule particles are used as a core layer, and second aggregated particles are obtained in which the photosensitive / thermosensitive layer and the coating layer are sequentially laminated so as to cover the core layer.
Note that (e2) the coating layer formed in the coating layer forming step is a surface layer that covers the surface of the toner when it is finally used as a toner, or an intermediate layer provided between two adjacent photosensitive and thermosensitive layers. It is what constitutes a layer. Here, when this coating layer constitutes a surface layer when used as a toner, it is particularly preferable that a resin particle dispersion using an amorphous resin is used in the (e2) coating layer forming step.

(F2) The second fusion step can also be performed basically in the same manner as the above-described step (e1). The heating temperature in the second fusion step was carried out by repeating the heat resistance of the material constituting the outer shell of the microcapsule, the outer shell of the photosensitive / thermosensitive capsule, and ((d2) to (f2) two or more times. In this case, it is determined in consideration of the heat resistance of the material forming the intermediate layer and the temperature at which the binder resin used for forming the second aggregated particles can be fused. It is preferably within the range of 90 ° C, and more preferably within the range of 50 to 80 ° C.
When the heating temperature exceeds 90 ° C., the outer shell of the microcapsule disappears and the color develops, or it is dispersed in the color developing part (photosensitive / thermosensitive capsule and / or photosensitive / thermosensitive layer) capable of developing one color. Color developing part (photosensitive / thermosensitive capsule and / or photosensitive / thermosensitive layer) in which the second component diffuses out of the color developing part (photosensitive / thermosensitive capsule and / or photosensitive / thermosensitive layer) or can develop colors in other colors. In some cases, sufficient color development cannot be obtained during image formation.
Further, when the heating temperature is less than 40 ° C., sufficient fusion is not performed, and the toner particles may be decomposed in subsequent processes such as washing and drying.

When a conductive agent is internally added to the toner, the toner can be added at an arbitrary timing when performing the above-described series of steps. Specifically, a conductive agent is added to the dispersion liquid used in the photosensitive / thermosensitive layer formation process and the coating layer formation process, or the dispersion liquid in which the conductive agent is dispersed is used by adjusting the dispersion liquid. It is possible to add an agent internally.
After the series of steps described above, a toner can be obtained by performing a washing and drying step and the like as described above.

(Developer for developing electrostatic latent images)
The developer for developing an electrostatic latent image of the present invention (hereinafter sometimes referred to as “developer”) is not particularly limited as long as it contains the toner of the present invention, but is usually used as a one-component developer. It is done.

(Image forming method and image forming apparatus)
Next, an image forming method and an image forming apparatus using the toner (or developer) of the present invention will be described.
The image forming method of the present invention is applied to a known electrophotographic image forming method equipped with a charge injection type developing system using a conductive toner, and an external stimulus is applied to the toner in order to control the color development of the toner. It will not specifically limit if the process to provide is added. For example, if the conductive toner used is a non-photo-colorable toner as described above in which the color development is controlled by the application of light and heat as an external stimulus, or the photo-colorable toner, control the color development. The step of irradiating light for the purpose of and the step of applying heat are provided, and the latter step can be carried out using a conventional fixing step. In addition, if the toner uses external stimuli other than the combination of light and heat, a step of applying these stimuli is provided.

  In the case where a non-photo-colorable toner or a toner whose color is controlled by applying light and heat stimulus, such as a photo-colorable toner, is used as the conductive toner, the image forming method of the present invention is performed on the surface of the image carrier. A charging step for charging the electrostatic latent image, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier, a charge injection step for injecting charges into conductive toner, and the conductive material into which the electrostatic latent image has been injected. A developing process for developing a toner image by forming a toner image, a coloring information applying process for irradiating the toner image with a coloring information applying light corresponding to color component information of the image information, and transferring the toner image to the surface of the recording medium. It is preferable to include a transfer step and a fixing color forming step in which the toner image transferred to the surface of the recording medium and irradiated with the color forming information imparting light is heated and pressed to fix and color the toner image to form an image. The image forming apparatus of the present invention includes an image carrier and means for carrying out the above steps (charging means, latent image forming means, charge injection means, coloring information providing means, transfer means, fixing coloring means). It is preferable.

In the image forming method including such steps, as the conductive toner, the first component and the second component that exist in a state of being separated from each other and develop colors when reacted with each other, the first component, and the second component It is particularly preferable to use a toner having one or more color-forming portions including a photocurable composition containing any one of the components and containing a conductive agent. In this case, the color information imparting light used in the color information imparting step includes light of a specific wavelength that cures the photocurable composition contained in each of the one or more color developing parts contained in the toner.
Further, “irradiation with color forming information imparting light” refers to a desired area of a toner image in order to control color development / non-color development in individual toner particle units constituting the toner image and to control the color tone upon color development. On the other hand, it means that one or more kinds of light having a specific wavelength for curing the photocurable composition is applied, or no light is applied.

  In the above-described image forming method, in the color information providing step, each toner particle constituting the toner image is irradiated with light having a specific wavelength corresponding to the color component information of the image information. For each type, the transition to the cured state or the uncured state of the photocurable composition is maintained, and the state is controlled so that color can be developed or not developed for each type of color developing portion. Subsequently, only the color-developing portion in a state capable of color development is selectively colored by heating in the fixing color development step performed after the transfer step, so that a monotone or color image corresponding to the image information can be obtained. From the viewpoint of color development of toner by applying external stimuli (control stimulus and color stimulus), the color information providing step corresponds to the control stimulus and the fixing color step corresponds to the color stimulus.

The image obtained through the fixing and coloring process preferably includes a light irradiation process for irradiating light, and the image forming apparatus preferably includes a light irradiation unit for performing this light irradiation process. As a result, it is possible to decompose or deactivate the first component, the second component, or the spectral sensitizing dye that is used as necessary, in the color developing portion that is controlled in a state where color development is impossible. Later fluctuations in color balance and unnecessary coloring can be more reliably suppressed.
In addition to this, 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 of cleaning the surface of the image carrier with a cleaning blade or the like may be included. 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.

Further, in the image forming method using the toner of the present invention, only one type of developer needs to be used for the formation of a full color image. This is unnecessary and can be downsized to the same level as a conventional monochrome type copying machine.
In addition, since it is not necessary to stack toner for each color when forming a toner image, unevenness on the image surface can be suppressed, and gloss uniformity on the image surface is good. Furthermore, since a colorant such as a pigment is not used, an image close to a silver salt can be obtained.

The development step is performed after injecting electric charge into the toner of the present invention and charging it (so-called charge injection development). For this reason, charging variation between toner particles can be suppressed as compared with development by the frictional charging method, and it is possible to easily prevent the occurrence of a toner cloud and a fog that are problematic in the case of the frictional charging method.
When a color image is formed with a conventional toner containing a colorant, various colors are reproduced by superimposing different color toners. However, in development using a conductive toner containing a colorant, the toners are superimposed. In other words, there is a problem that it cannot cope with colorization. However, in the image forming method of the present invention, (1) it is possible to develop colors different from each other so that the color developing portion included in the toner to be used is composed of, for example, three types of yellow color developing portion, magenta color developing portion and cyan color developing portion. Even when two or more types of color developing parts are included, or (2) the toner contains only one type of color developing part, a cyan color developing toner capable of developing cyan as a developer, and magenta coloring capable of developing magenta A developer containing a mixture of two or more types of toner capable of developing colors different from each other, such as a developer including a mixture of three types of toner, a yellow color developing toner capable of developing yellow, When used, a color image can be formed without overlapping toner for each color when forming a color image.

  Any method can be used for the charge injection development carried out in the present invention as long as it is a known charge injection development. For example, after charge is injected into a toner by a charge injection means (toner charging means), The charged toner is conveyed to the image carrier side by a developing roll, and an electrostatic latent image on the image carrier is converted into a conductive toner by utilizing a potential difference formed between the toner carrier and the image carrier. Can be developed. When the toner is charged, the toner is patterned and charged so as to correspond to the image information, and the patterned and charged toner is conveyed to the image carrier side by the developing roll. It is also possible to transfer onto the image carrier using a potential difference formed therebetween. In this case, the latent image forming step can be omitted.

Next, details of each step will be described.
In the charging step, the entire surface of the image carrier is charged by charging means.
Any known image carrier (photosensitive member) can be used. For example, an inorganic photosensitive layer such as Se or a-Si, or a single or multilayer organic photosensitive layer is formed on a conductive substrate. In the case of a belt-shaped photoconductor, a transparent resin such as PET or PC can be used as a substrate, and the thickness is determined by design matters such as the diameter and tension of a roll on which the belt-shaped photoconductor is stretched, and is approximately 10 to 500 μm. Range. Other layer configurations are the same as in the drum.

  In the color development information providing step, when the color development information application light is irradiated from the back surface of the photoconductor (inside the photoconductor), a transparent photoconductor having the substrate as a transparent resin or the like can be used. In the case of a transparent photoconductor, a material transparent to the color information imparting light is used as the photoconductor substrate. For example, glass or plastic material is used as the base material and a conductive layer is formed on the outer surface for electrode formation. However, the base material itself may be subjected to a conductive treatment. In addition, when not using a transparent photoconductor, base materials, such as metal cylindrical bodies, such as aluminum normally used, and a nickel seamless belt other than the above-mentioned transparent base | substrate can also be used.

Further, as will be described later, since the irradiation of the color forming information imparting light is performed with a considerably stronger intensity than the exposure for normal latent image formation (the amount of energy of the color developing information imparting light is a sensitivity used in a normal electrophotographic process). The exposure amount of the body (approximately 1000 times the ² mJ / m ² ) is necessary), and there is a concern about damage to the photoreceptor. For example, if the photosensitivity of the charge generation layer of the photoreceptor is 1/1000 of the conventional, This is not a problem because it is balanced.

  Further, it is preferable that the surface of the photoconductor has a function of preventing the photoconductor from being deteriorated by the irradiation of the color forming information imparting light. Specifically, only the exposure light for forming the latent image is transmitted to the surface of the photosensitive layer, and the exposure light for providing color information is reflected or absorbed (however, the exposure light for forming the latent image is transmitted). It is effective to provide a surface layer. Examples of the surface layer include a dichroic mirror coat (reflection) and a sharp cut filter (absorption) in which a light absorbing material is dispersed.

  A known charging means can be used for charging. 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 charger is preferably used from the balance between the charge compensation capability and the amount of ozone generated. 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 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. The voltage range is preferably positive or negative with an absolute value of the desired surface potential of about +500 V when charged only with direct current, and the value is 700V to 1500V. 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 700 V in absolute value of the potential.

  A known exposure apparatus can be used for forming the electrostatic latent image. As the exposure apparatus, for example, a laser scanning system, an LED image bar system, an analog exposure means, an ion flow control head, or the like can be used.

  The wavelength of the light source is in the spectral sensitivity region of the photoconductor. Until now, the near-infrared having an oscillation wavelength near 780 nm as the wavelength of the semiconductor laser has been mainstream, but an oscillation wavelength laser in the 600 nm range and a laser having an oscillation wavelength near 400 to 450 nm can be used as a blue laser. . A surface-emitting laser light source capable of multi-beam output is also effective for color image formation.

  In the case of reversal development, the exposure of the photosensitive member is performed at a position where toner is developed as described later, and in the case of regular development, at positions other than the development of toner, image formation information of four colors of cyan, magenta, yellow and black This is done as a logical sum. 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.

A known charge injection type developing device can be used for developing the electrostatic latent image. As the developing method, a one-component developing method consisting only of a conductive toner can be used, and another constituent material may be added to improve other characteristics.
Further, depending on the developing method, any one of the developer that performs development with or without contact with the developer, or a combination thereof can be used.

As the toner contained in the developer, for example, a color developing portion (Y color developing portion) capable of developing yellow color, a color developing portion capable of developing magenta color (M color developing portion), and a color developing portion capable of developing cyan 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 .

  Further, in the formed toner image, since the color forming information imparting light has to spread over the entire irradiated portion, 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.

  When the toner is a photothermal stimulation response type toner that can develop color in response to light and heat, such as the non-photo-colorable toner and the photo-colorable toner described above, the color information imparting light is applied to the toner image. Irradiated.

  Any device capable of irradiating with light having a predetermined resolution and intensity can be used as the color information-applying light irradiation device as long as the toner particles to be colored at that time can emit light having a wavelength for generating a specific color. For example, an LED image bar, a laser ROS, or the like can be used. The irradiation spot diameter of the light applied to the toner image is preferably adjusted so as to be in the range of 10 to 300 μm so that the resolution of the formed image is in the range of 100 to 2400 dpi. It is more preferable to set the range.

The wavelength of light used to maintain the colored or non-colored state is determined by the material design of the toner used. For example, when using a toner that develops color when irradiated with light of a specific wavelength (photochromic toner), yellow 405 nm light (referred to as λ _A light) for color development (Y color), 535 nm light (referred to as λ _B light) for cyan (C color) color development for magenta (M color) When irradiating, light of 657 nm (referred to as λ _C light) is irradiated to each desired position for color development.

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.

Even in the case of a photothermal stimulation response type toner other than the non-photo-colorable toner or the photo-colorable toner, the color information providing step is performed using light in a wavelength region to which the toner is sensitive.
For example, a toner using a microcapsule that does not use a photocurable composition, such as a photochromic or non-photochromic toner, and whose material permeability is controlled by an external stimulus (for example, a toner shown in Patent Document 4) ), The outer shell includes a photoresponsive microcapsule composed of a bimolecular film (bimolecular cumulative film) containing a photoisomerized substance that isomerizes upon irradiation with light of a specific wavelength. For this reason, the color development in the fixing color development process can be controlled by irradiation with color development information imparting light in accordance with the type of photoisomerization substance contained in the outer shell of the photoresponsive microcapsule.

For the light emitted from the color information-applying light irradiation device, 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.

  As described above, the mechanism in the case of forming a full-color image in the coloring information providing step in the present invention has been described. However, the coloring information providing step in the present invention forms a monocolor image that develops one of yellow, magenta, and cyan. It may be a coloring information providing step for the purpose. In this case, only the color information providing light corresponding to the desired color of the yellow, magenta and cyan is emitted from the color information providing light irradiation device. Other preferable conditions and the like are the same as those at the time of full-color image formation. Further, it may be transparent to the toner image carrier, and color information imparting light may be irradiated from the back side.

The timing of irradiating the color forming information applying light is not particularly limited as long as it is from the end of the development process to the execution of the fixing color forming process, and may be performed on the toner image formed on the photoconductor. Alternatively, a transfer process may be performed after the development process, and may be performed on the toner image transferred onto the intermediate transfer member or the recording medium.
However, when the color information-imparting light is irradiated after the transfer, it is necessary to perform the post-development process and before the transfer process because of the smoothness of the surface of the recording medium and the intermediate transfer body and the accuracy of the color development position of the desired image. Desirable above.
At this stage, the toner image remains in an original color tone that has not yet been developed. If the toner image is, for example, dye-sensitized, the toner image has only the color tone of the dye.

  The details of the coloring information providing step performed when using the photothermal stimulation responsive toner capable of color development by applying a light stimulus and a heat stimulus have been described above, but other stimuli other than the light stimulus (for example, a pressure stimulus) The toner is controlled from the colorable state to the non-colorable state or from the non-colorable state to the colorable state by applying the toner, and has a function of developing color when heated in the colorable state. In this case, in the color information providing step, the other stimulus can be used to give color information to the toner.

  After completion of the development process, the toner to which the color forming information imparting light is irradiated as necessary is transferred to a recording medium in a lump. A known transfer device 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.

  The transfer process may transfer the toner image directly from the photoreceptor to the recording medium. However, the transfer process transfers the toner image from the image carrier to an intermediate transfer body such as an intermediate transfer belt. An intermediate transfer method including one transfer step and a second transfer step of transferring the toner image transferred onto the intermediate transfer member onto a recording medium may be used.

A conventionally known fixing means can be used in the fixing coloring process. 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.
When the toner is a non-photo-colorable toner or a photo-colorable toner, the toner that has been controlled so as to be capable of color development in the color development information applying step is colored by heating during fixing.

If an infrared absorber is added to the toner, fixing color development can be performed using a known light fixing means. As this light irradiating means, a conventional optical fixing device (flash fixing device) used for fixing a light fixing toner containing a colorant and an infrared absorber can be used.
Light sources used as light irradiation means include ordinary halogen lamps, mercury lamps, flash lamps, infrared lasers, etc. Among them, the most suitable because the flash lamps can save energy by being fixed instantaneously. It is. Here, it is preferable that emission energy of the flash lamp is in the range of 1.0~7.0J / cm ^2, and more preferably in the range of 2~5J / cm ^2.

Here, the emission energy per unit area of flash light indicating the lamp intensity of xenon is expressed by the following equation (2).
Formula (2) S = ((1/2) × C × V ² ) / (u × L) × (n × f)
In the above formula (2), n is the number of lamps that emit light at once (f), f is the lighting frequency (Hz), V is the input voltage (V), C is the capacitor capacity (F), u is the process transport speed (cm) / S), L represents the effective light emission width of the flash lamp (usually the maximum paper width, cm), and S represents the energy density (J / cm ² ).

  The light fixing method is preferably a delay method in which a plurality of flash lamps emit light with a time difference. This delay system is a system in which a plurality of flash lamps are arranged, each lamp is delayed by about 0.01 to 100 ms, light is emitted, and the same portion is illuminated a plurality of times. As a result, the light energy can be divided and supplied to the toner image by one light emission, so that the fixing condition can be made mild, and both the void resistance and the fixing property can be achieved.

Here, when flash emission is performed on the toner a plurality of times, the emission energy of the flash lamp indicates the total amount of emission energy given to the unit area for each emission.
In the present invention, the number of flash lamps is preferably in the range of 1-20, and more preferably in the range of 2-10. Moreover, it is preferable that each time difference between several flash lamps is the range of 0.1-20 msec, and it is more preferable that it is the range of 1-3 msec.
Further, it is preferable that one single luminous energy by the light emission of the flash lamp is in the range of 0.1 to 1 J / cm ^2, and more preferably in the range of 0.4~0.8J / cm ² .

  If photofixing is carried out, at the same time as fixing and color development, decomposition and deactivation of coloring components such as spectral sensitizers and photopolymerization initiators remaining in the toner and components capable of coloring in an uncolored state are also possible. Since it can accelerate, the implementation of the light irradiation process performed after heat fixing can be omitted.

  When the fixing coloring process is performed by heat fixing, it is preferable to further perform a light irradiation process for irradiating light on the image obtained through the fixing coloring process. This makes it possible to decompose and deactivate the color-developing component in an uncolored state, and coloring components such as a spectral sensitizer and a photopolymerization initiator that are added as necessary remain in the toner. Even in such a case, since these components can be decomposed and deactivated, fluctuations in color balance after image formation can be more reliably suppressed, and background colors can be removed and bleached.

  The light irradiation device used in the light irradiation step 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. The wavelength includes a wavelength 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. A known cleaner can be used, and a blade, a brush, or the like can be used. In addition, a so-called cleaner-less process in which the cleaner is removed is also applicable.

A known recording medium can be used as a recording medium to be used for forming an image. However, an electrically insulating medium made of resin, wax, oil alone or a combination thereof is applied to at least one surface of the substrate in an amount of 0.3 to 50 g / Using a recording medium on which a toner image-receiving surface having a volume specific resistance of 3 × 10 ¹³ Ω · cm or more is applied with a coating amount of m ² , during transfer, corona discharge is applied from the back surface of the recording medium, It is preferable to electrostatically transfer the toner image to a recording medium. Thereby, it is possible to obtain an image with a sharper outline.

  Here, as a substrate, paper made of ordinary cellulose fiber, for example, high-quality paper, tracing paper, etc .: resin film such as transparent film, mat-treated film, foam-treated film, etc .: manufactured by artificial fiber papermaking Synthetic papers, non-woven fabrics, cloths, etc .: metal foils, metal sheets, etc .: can be freely selected and used depending on the application, but it is not necessary to be conductive, and for normal copying Is most preferably paper.

Toner image-receiving surface of an electrically insulating medium composed of resin, wax, oil alone or a combination thereof with a coating amount of 0.3 to 50 g / m ² and a volume resistivity of 3 × 10 ¹³ Ω · cm or more. The recording medium on which the toner image is formed can improve the image density as compared with the recording medium not provided with such a toner image-receiving surface, and suppresses the broadening of the contour, so that the toner image before transfer on the photosensitive layer can be suppressed. It is possible to maintain the same edge cutting quality as in the above.

For the toner image receiving surface, a medium such as resin, wax, oil, or a combination thereof is used so that the volume specific resistance is 3 × 10 ¹³ Ω · cm or more, particularly preferably in the range of 10 ¹⁴ to 10 ¹⁵ Ω · cm. It is formed by applying to at least the surface of the substrate by means such as coating, impregnation or temporary adhesion. In particular, a resin sheet that satisfies the above specific resistance condition may itself be a base and may also be a toner image-receiving surface of conductive or semiconductive toner.
In addition, it is possible to dehumidify a sheet having high hygroscopicity by heating or the like immediately before transfer so that the sheet has a desired resistance value range, but generally the resistance of the recording medium is influenced by the atmosphere such as humidity as much as possible. It is desirable that the resistance range is not deviated.

  Therefore, it is preferable to apply a medium such as a resin, wax, fats and oils, or an insulating agent alone or in combination to at least the surface of the base sheet. Examples of the resin having such characteristics include olefin resins such as ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polybutadiene ethylene-propylene copolymer, butadiene-styrene copolymer: acrylic resin: polyvinyl acetate, vinyl butyral. And vinyl resins such as vinyl chloride resin: melamine resin, epoxy resin, alkyd resin, unsaturated polyester resin, urea resin, rosin, copal and other thermoplastic or thermosetting resins, natural rubber, natural resin and the like. In addition to the above resins, natural oils such as linseed oil, tung oil, soybean oil, sardine oil: synthesis of alkylbenzene oils such as silicon oil, molybdenum oil, polycyclic aromatic oil, dodecylbenzene oil, mineral oil, fluorinated synthetic oil, etc. Oils, minerals, liquid paraffin, petroleum jelly, polyethylene wax, microcrystalline wax, beeswax, montan wax, carnauba wax, and other waxes can also be suitably used.

  The above-mentioned electrically insulating medium such as resin, electrically insulating oil and wax can be applied to the substrate surface in the form of an organic solvent solution or an aqueous dispersion (emulsion). Coating method is air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, cast coater spray coater, curtain coater, calendar coater, extrusion coater, etc. A conventionally known method by combination can be used.

The resin, electrical insulating oil, wax, and the like are particularly preferably provided as thin layers as possible so as not to greatly change the properties such as the texture of the substrate. The coating amount varies considerably depending on the type of electrically insulating medium such as resin, electrically insulating oil and wax, but the non-volatile component is preferably 0.3 to 50 g / m ^2, particularly preferably 0.5 to ²⁰ g / m ² . When the coating amount is 0.3 g / m ² or less, it becomes difficult to make the sheet surface sufficiently electrically insulating, and faithful transfer of conductive or semiconductive magnetic toner cannot be obtained. That is, when the coating amount is 0.3 g / m ² or less, a copy image with a sharp outline, that is, without sharpness at the edge of the image may be formed.

On the other hand, if the coating amount exceeds 50 g / m ² , the material of the substrate of the recording medium is greatly changed, and it becomes difficult to handle the sheet in the copying apparatus, and it is particularly difficult to peel the recording medium from the surface of the recording body. The characteristics desirable as a recording medium are lost. In particular, when the substrate is paper, the amount of coating must be reduced because it is necessary to maintain toner retention, writing characteristics, stamping characteristics, and texture of the paper as a recording medium.

In order to improve toner retention, writing characteristics, stamping characteristics, and texture of the recording medium, titanium dioxide, silica powder, zinc oxide, magnesium silicate, barium sulfide, barium carbonate, carbonic acid are included in the coating composition described above. Benzidine yellow, yellow lead, cyanine blue, sky blue, rose bengal, brilliant carmine 6B, rose for the purpose of obtaining white materials such as calcium, zinc sulfide, lead white, alumina white, clay and colored recording media Coloring agents or dyes such as Juanal lake can be added at a rate of 10 to 200 parts by weight per 100 parts by weight of resin, oil guard or wax.
In addition, dryers and inhibitors may be added to adjust the drying rate after being applied to the sheet surface.
The viscosity of the viscous material obtained by mixing the resin, oil or the like and an additive such as pigment can be arbitrarily selected and used depending on the coating method, the texture of the recording medium, and the like.
The toner image receiving surface may be provided only on one side of the substrate or on both sides for the purpose of transferring on both sides.

Next, specific examples of the image forming apparatus of the present invention will be described in more detail with reference to the drawings.
FIG. 5 is a schematic diagram showing an example of the image forming apparatus of the present invention. As shown in FIG. 5, the image forming apparatus has a photosensitive drum 100 as an image carrier that is driven to rotate at a predetermined speed in the direction of the arrow, and around the photosensitive drum 100. A charging device 110 for charging the surface of the photosensitive drum 100 to a predetermined potential, an exposure device 120 as a latent image writing unit for forming an electrostatic latent image on the photosensitive drum 100, and the photosensitive drum 100. A developing device 130 that develops the electrostatic latent image formed thereon to form a toner image, and a color information providing light irradiation that irradiates the toner image developed on the photosensitive drum 100 with color information providing light. A transfer device 140 serving as a transfer unit that transfers the toner image irradiated with the coloring information imparting light onto the recording paper 180; and a cleaning device 1 that cleans the toner remaining on the surface of the photosensitive drum 100. 0 and are sequentially arranged.

  That is, as shown in FIG. 5, the developing device 130 includes a developing device housing 131, and the developer G containing the conductive toner 200 is accommodated in the developing device housing 131. The developing device housing 131 is provided with a developing opening 132 at a position facing the photosensitive drum 100, and a developing roll 133 as a toner carrier is disposed in the developing opening 132. ing. A predetermined developing bias voltage is applied to the developing roll 133 so that a developing electric field acts on the developing area between the photosensitive drum 100 and the developing roll 133. In addition, an intermediate toner carrying roll 134 is disposed inside the developing housing 131 on the back side of the developing roll 133 so as to face the developing roll 133 and is opposed to the intermediate toner carrying roll 134. In addition, a toner supply roll 135 as a toner supply member / charge injection member is provided.

The toner supply roll 135 as the toner supply member / charge injection member performs charge injection on the conductive toner 200.
As the toner supply roll 135, a foamed urethane foam roll imparted with conductivity, a roll coated with a urethane foam imparted with conductivity, or the surface is polished or blasted. A conductive roll made of metal or the like is used.
Further, the toner supply roll 135 is disposed in contact with the intermediate toner carrying roll 134 or opposed to the toner supply roll 135 through a minute gap so as to improve the charge injection property to the conductive toner 200.

  Further, as the intermediate toner carrying roll 134, for example, a conductive roll having an insulating surface with a thickness of about 5 μm to 100 μm or a semiconductive roll is used. The intermediate toner carrying roll 134 is constituted by, for example, an aluminum roll whose surface is anodized, a conductive roll whose surface is covered with an insulating tube, or an elastic roll. Further, the intermediate toner carrying roll 134 is rotationally driven or driven in a direction in which the surface moves in the direction opposite to the moving direction of the surface of the developing roll 133. The toner supply roll 134 is rotationally driven or driven in a direction in which the surface moves in the direction opposite to the moving direction of the surface of the intermediate toner carrying roll 134.

  Further, the developing roll 133 is composed of a conductive roll having a conductive surface made of an aluminum cylindrical member or the like in order to prevent charging history and realize low potential development. Further, the developing roll 133 is rotationally driven or driven in a direction in which the surface moves in the same direction as the moving direction of the surface of the photosensitive drum 100.

  Further, a charge injection bias voltage that forms a high electric field for injecting charges into the conductive toner 200 by a power supply for charge injection (not shown) between the toner supply roll 135 and the intermediate toner carrying roll 134. Is applied. As the charge injection bias voltage, for example, a voltage corresponding to the charging polarity of the toner (for example, a negative polarity) and a voltage of about 100 V to 1000 V is used.

  Further, a toner transfer bias voltage that forms an electric field for transferring the conductive toner 200 is applied between the intermediate toner carrying roll 134 and the developing roll 133 by a toner transfer power supply (not shown). ing. As the toner transfer bias voltage, for example, a voltage (for example, negative polarity) corresponding to the charging polarity of the toner and a voltage of about 100 V is used.

  Further, as shown in FIG. 5, the transfer device 140 is provided with a transfer roll (not shown) opposed to the photoconductor drum 100, for example, and a transfer bias voltage is applied to the transfer roll, thereby the photoconductor. A transfer electric field is applied between the drum 100 and the transfer roll, and the toner image on the photosensitive drum 100 is electrostatically transferred to the recording paper 180 as a recording medium.

Next, the operation of the image forming apparatus according to this embodiment will be described.
When the image forming process is started, first, the surface of the photosensitive drum 100 is charged by the charging device 110, and then the exposure device 120 writes an electrostatic latent image on the charged photosensitive drum 100, and the developing device 130. Develops the electrostatic latent image to form a toner image.

Subsequently, the coloring information providing light irradiating device 160 irradiates the toner image with coloring information providing light corresponding to the image information. Thereafter, the toner image on the photoconductive drum 100 is conveyed to a transfer portion and electrostatically transferred onto a recording paper 180 as a recording medium by the transfer device 140. Thereafter, the toner image transferred onto the recording paper 180 is colored together with fixing by heat and pressure by a fixing color developing device (not shown), and subsequently irradiated with light by a light irradiation means (not shown).
The toner remaining on the photosensitive drum 100 is removed by the cleaning device 150.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example. In the following examples, “part” and “%” are “mass”, respectively.
Part "," mass% ". In the following toner preparation, the preparation of the photocurable composition dispersion and the series of toner preparations using the dispersion were all performed in the dark.

<< Example 1 >>
<Preparation of microcapsule dispersion>
-Preparation of microcapsule dispersion (1)-
In 16.9 parts by mass of ethyl acetate, 8.9 parts by mass of an electron-donating colorless dye (1) capable of developing yellow color is dissolved. Further, a 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. Subsequently, 72 mass parts of 2.9 mass% tetraethylenepentamine aqueous solution was added to the obtained emulsion, and it heated at 60 degreeC, stirring, and after 2 hours passed, electron donating colorless dye (1) was cored. A microcapsule dispersion (1) having an average particle size of 0.5 μm contained in the part was obtained.
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 liquid (2) was obtained in the same manner as in the preparation of the microcapsule dispersion liquid (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 liquid (3) was obtained in the same manner as in the preparation of the microcapsule dispersion liquid (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>
—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 organic borate compound (29) (borate compound II) shown above, 0.1 part by mass of the spectral sensitizing dye-based borate compound (26) (borate compound II) shown above, and high sensitivity The following electron acceptor having a polymerizable group in a mixed solution of 0.1 part by mass of the following auxiliary agent (1) for the purpose of conversion to 3 parts by mass of isopropyl acetate (solubility in water of about 4.3%) 5 parts by mass of the active compound (3) was added.
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) having a polymerizable group used for the preparation of the photocurable composition dispersion (2), the auxiliary agent (1), the surfactant (2), and the 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 (26), the photocurable composition dispersion was used except that 0.1 parts by mass of the spectral sensitizing dye-based borate compound (28) (borate compound II) shown above was used. A photocurable composition dispersion (3) was obtained in the same manner as in the case of preparing the liquid (2).

<Adjustment of resin particle dispersion>
・ Styrene: 460 parts by mass
N butyl acrylate: 140 parts by mass
-Acrylic acid: 12 parts by mass
・ Dodecanethiol: 9 parts by mass
Titanium oxide (TAF500J, anatase type, particle size 50 nm, manufactured by Fuji Titanium Industry Co., Ltd.): 4.0 parts by mass The above components were mixed and dissolved to prepare a solution. Subsequently, an emulsion obtained by adding 12 parts by weight of an anionic surfactant (manufactured by Dow Chemical Co., Ltd., Dowfax) in 250 parts by weight of ion-exchanged water, adding the solution and dispersing and emulsifying in a flask (single amount) Body emulsion A) was prepared.
Further, 1 part by mass of an anionic surfactant (manufactured by Rhodia, Dowfax) 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 by mass of ammonium persulfate in 43 parts by mass of ion-exchanged water was dropped into the polymerization flask through a metering pump over 20 minutes, and then the monomer emulsion A was also metered into 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% was obtained.

-Production of Toner A-
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 components were adjusted to pH = 3.5 with nitric acid, thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), then transferred to a flask and heated with an oil bath for heating. While stirring with a three-one motor, the mixture was heated to 42 ° C. and held at 42 ° C. for 60 minutes, and then 150 parts by mass of the resin particle dispersion was further added and stirred gently. Thereafter, the pH in the flask was adjusted to 5.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 55 ° C. while stirring was continued. Furthermore, it hold | maintained at 55 degreeC for 3 hours. During the temperature rising and holding up to 55 ° C., the pH in the flask is usually lowered to 5.0 or less, but here, an aqueous sodium hydroxide solution is added dropwise so that the pH does not become 4.5 or less. Held on.

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, and then freeze-drying for 12 hours to obtain toner particles. In addition, spontaneous color development of the dispersion was not confirmed in the process of granulating the toner particles.
When the particle size of the toner particles was measured with a Coulter Multimizer, the volume average particle size D50v was 4.5 μm.

To 50 parts by mass of the toner particles, 1.5 parts by mass of hydrophobic silica (manufactured by Cabot, TS720) was added and mixed by a sample mill to obtain an externally added toner. This toner A had a volume resistivity of 10 ⁹ Ω · cm when 7 × 10 ⁴ V / cm was applied.

-Production of Toner B-
In the preparation of the toner A, the microcapsule dispersion (2) and the photocurable composition dispersion (2) were used in place of the microcapsule dispersion (1) and the photocurable composition dispersion (1). Were obtained in the same manner as in the preparation of toner A. In addition, spontaneous color development of the dispersion was not confirmed in the process of granulating the toner particles. Further, the volume resistivity of Toner B when 7 × 10 ⁴ V / cm was applied was 10 ⁹ Ω · cm.

-Production of Toner C-
In the preparation of toner A, the microcapsule dispersion (3) and the photocurable composition dispersion (3) were used in place of the microcapsule dispersion (1) and the photocurable composition dispersion (1). Were obtained in the same manner as in the preparation of toner A. In addition, spontaneous color development of the dispersion was not confirmed in the process of granulating the toner particles. The volume resistivity of Toner C when 7 × 10 ⁴ V / cm was applied was 10 ⁹ Ω · cm.

-Production of developer-
The toners A, B and C were mixed at a mass ratio of 1: 1: 1 and stirred with a Henschel mixer to obtain a developer.

-Evaluation-
In the dark place, the developer is introduced into an image forming apparatus (Fuji Xerox Co., Ltd., Docu Print 3530 modified machine) that performs development by charge injection development, and forms a toner image consisting of 10 cm × 10 cm bars and fine lines, An unfixed image (toner image) before transfer and after fixing onto C2 paper (Fuji Xerox Co., Ltd.) was obtained.
Subsequently, this unfixed image is first imagewise exposed using a semiconductor laser beam having a wavelength of 657 nm, then imagewise exposed using a semiconductor laser beam having a wavelength of 532 nm, and further imaged using a semiconductor laser beam having a wavelength of 405 nm. Exposed. Thereafter, the unfixed image was passed through a fixing machine of the copier prepared separately, and the color was developed and fixed. At this time, the fixing temperature of the fixing machine is 180 ° C., and the process speed is 150 mm / sec. Thereafter, the obtained image was irradiated with light for 30 seconds using a high brightness Schaukasten of 58000 lux.

The above-described image output was performed a total of 10 times. As a result, there was no destruction of the toner in the developing machine, and the image, color tone, gradation and the like were stable, and a high-definition full-color image was obtained. Also, there was no problem with fixing properties. In addition, no toner cloud or fog was observed.
Furthermore, an image irradiated with high-brightness shakasten was left for about half a year in a normal lighting environment where a fluorescent lamp was placed on the ceiling. It was found that there was almost no change in color balance.

<< Example 2 >>
-Preparation of microcapsule dispersion (1)-
Dissolving 12.1 parts by mass of electron donating colorless dye (1) in 10.2 parts by mass of ethyl acetate, 12.1 parts by mass of dicyclohexyl phthalate, 26 parts by mass of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.), and millionate A solution to which 2.9 parts by mass of MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added was prepared.
Subsequently, this solution was added to a mixed solution of 5.5 parts by weight of polyvinyl alcohol and 73 parts by weight of water, and emulsified and dispersed at 20 ° C. to obtain an emulsion having an average particle size of 0.5 μm. 80 parts by mass of water was added to the obtained emulsion, heated to 60 ° C. with stirring, and after 2 hours, a microcapsule dispersion in which microcapsules having an electron-donating colorless dye (1) as a core material were dispersed ( 1) was obtained.
The material constituting the outer shell of the microcapsule contained in this microcapsule dispersion (1) (the material obtained by reacting dicyclohexylphthalate, Takenate D-110N and Millionate MR200 under the same conditions as described above) The glass transition temperature was about 130 ° C.

-Preparation of microcapsule dispersion (2)-
A microcapsule dispersion liquid (2) was obtained in the same manner as in the preparation of the microcapsule dispersion liquid (1) except that the electron donating colorless dye (1) was changed to the electron donating colorless dye (2).

-Preparation of microcapsule dispersion (3)-
A microcapsule dispersion liquid (3) was obtained in the same manner as in the preparation of the microcapsule dispersion liquid (1) except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (3).
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)-
In a solution prepared by dissolving 1.62 parts by mass of the photopolymerization initiator (1-a) and 0.54 parts by mass of (1-b) in 4 parts by mass of ethyl acetate, 9 parts by mass of the electron-accepting compound (1) And 7.5 parts by weight of trimethylolpropane triacrylate monomer (trifunctional acrylate, molecular weight of about 300) were added.
The solution thus obtained was mixed with 19 parts by weight of a 15% by weight PVA (polyvinyl alcohol) aqueous solution, 5 parts by weight of water and 2% by weight surfactant (1) 0.8 part by weight of an aqueous solution and 2% by weight surfactant. (2) A photocurable composition dispersion (emulsified at 8000 rpm with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) for 7 minutes by adding 0.8 parts by mass of an aqueous solution) 1) was obtained.

-Preparation of photocurable composition dispersion (2)-
The photopolymerization initiators (1-a) and (1-b) were added to 0.08 parts by mass of the photopolymerization initiator (2-a), 0.18 parts by mass of (2-b), (2-c) 0. Except having changed into 18 mass parts, it carried out similarly to the case where a photocurable composition dispersion liquid (1) was adjusted, and obtained the photocurable composition dispersion liquid (2).

-Preparation of photocurable composition dispersion (3)-
The photocurable composition dispersion liquid (1) was changed except that the photopolymerization initiator (2-b) used in the photocurable composition dispersion liquid (2) was changed to the photopolymerization initiator (3-b). The photocurable composition dispersion liquid (3) was obtained in the same manner as in the case of adjusting.
In addition, the photoinitiator (1-a), (1-b), (2-a), (2-b), (2-c), (3) used for preparation of a photocurable composition dispersion liquid Chemical structural formulas of -b), electron-accepting compound (1), and surfactants (1) to (2) are shown below.

-Preparation of resin particle dispersion (1)-
Styrene: 360 parts by mass nbutyl acrylate: 40 parts by mass Acrylic acid: 4 parts by mass Dodecanethiol: 24 parts by mass Carbon tetrabromide: 4 parts by mass Titanium oxide (TAF500J, anatase type, particle size 50 nm, Fuji Titanium Industry Co., Ltd.): 3.5 parts by mass The above mixed solution was dissolved in 6 parts by mass of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and anionic surfactant. In a flask, 10 parts by weight of an agent (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 560 parts by weight of ion-exchanged water was dispersed and emulsified in a flask, and slowly mixed with ammonium persulfate for 10 minutes. 50 parts by mass of ion-exchanged water in which 4 parts by mass was dissolved was added.
Subsequently, after the flask was purged with nitrogen, the contents were heated in an oil bath while stirring the flask until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thus, a resin particle dispersion (1) (resin particle concentration) in which resin particles having a volume average particle diameter of 200 nm, a glass transition temperature of 50 ° C., a weight average molecular weight (Mw) of 16,200, and a specific gravity of 1.2 are dispersed. : 30%).

-Preparation of photosensitive / thermosensitive capsule dispersion (1)-
Microcapsule dispersion (1) 24 parts by mass Photocurable composition dispersion (1) 232 parts by mass The above was sufficiently mixed and dispersed in a round stainless steel flask using IKA Ultra Turrax T50.
Then, the pH was adjusted to 3 with nitric acid, then 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued for 10 minutes at 6000 rpm with an ultra turrax. The flask was heated to 40 ° C. with gentle stirring in an oil bath for heating.
Here, 60 parts by mass of the resin particle dispersion (1) was gradually added.
Thereby, a photosensitive / heat-sensitive capsule dispersion liquid (1) was obtained.
The volume average particle size of the photosensitive / thermosensitive capsule dispersed in the dispersion was about 2 μm. Moreover, spontaneous color development of the obtained dispersion was not confirmed.

-Preparation of photosensitive / thermosensitive capsule dispersion (2)-
Photosensitive / thermosensitive capsule dispersion, except that the microcapsule dispersion (1) is changed to the microcapsule dispersion (2) and the photocurable composition dispersion (1) is changed to the photocurable composition dispersion (2). Prepared in the same manner as (1) to obtain a photosensitive / thermosensitive capsule dispersion (2). The volume average particle size of the photosensitive / thermosensitive capsule dispersed in the dispersion was about 2 μm. Moreover, spontaneous color development of the obtained dispersion was not confirmed.

-Preparation of photosensitive / thermosensitive capsule dispersion (3)-
Photosensitive / thermosensitive capsule dispersion, except that the microcapsule dispersion (1) is changed to the microcapsule dispersion (3) and the photocurable composition dispersion (1) is changed to the photocurable composition dispersion (3). Prepared in the same manner as (1) to obtain a photosensitive / thermosensitive capsule dispersion (3). The volume average particle size of the photosensitive / thermosensitive capsule dispersed in the dispersion was about 2 μm. Moreover, spontaneous color development of the obtained dispersion was not confirmed.

-Preparation of toner-
Photosensitive / thermosensitive capsule dispersion (1): 80 parts by mass Sensitive / thermosensitive capsule dispersion (2): 80 parts by mass Sensitive / thermosensitive capsule dispersion (3): 80 parts by mass Resin particle dispersion (1) : 80 parts by mass The above was sufficiently mixed and dispersed in a round stainless steel flask using an Ultra Turrax T50 manufactured by IKA.
Next, 0.1 parts by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued for 10 minutes at 6000 rpm with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 20 parts by mass of the resin particle dispersion (1) was gradually added thereto.
Thereafter, the pH of the system was adjusted to 8.5 with a 0.5 mol / l aqueous sodium hydroxide solution, the stainless steel flask was sealed, and heated to 55 ° C. while continuing to stir using a magnetic seal and heated for 10 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Subsequently, the toner (1) having a structure in which three types of photosensitive / heat-sensitive capsules are dispersed in the base material was obtained by vacuum drying for 12 hours.
When the particle diameter at this time was measured with a Coulter Multimizer, the volume average particle diameter D50v was about 15 μm. Further, spontaneous color development of the obtained toner was not confirmed.

Next, 100 parts by mass of the toner (1), 0.3 parts by mass of hydrophobic titania having an average particle diameter of 15 nm and surface-treated with n-decyltrimethoxysilane, and hydrophobic silica having an average particle diameter of 30 nm (NY50, Japan) (Aerosil Co., Ltd.) 0.4 parts by mass was blended for 10 minutes at a peripheral speed of 32 m / s using a Henschel mixer. An additive toner was used as a developer. This externally added toner had a volume resistivity of 10 ¹⁰ Ω · cm when 7 × 10 ⁴ V / cm was applied.

-Evaluation-
In the dark place, the developer is introduced into an image forming apparatus (Fuji Xerox Co., Ltd., Docu Print 3530 modified machine) that performs development by charge injection development, and forms a toner image consisting of 10 cm × 10 cm bars and fine lines, An unfixed image (toner image) before transfer and after fixing onto C2 paper (Fuji Xerox Co., Ltd.) was obtained.
Subsequently, this unfixed image is first imagewise exposed using a semiconductor laser beam having a wavelength of 657 nm, then imagewise exposed using a semiconductor laser beam having a wavelength of 532 nm, and further imaged using a semiconductor laser beam having a wavelength of 405 nm. Exposed. Thereafter, the unfixed image was passed through a fixing machine of the copier prepared separately, and the color was developed and fixed. At this time, the fixing temperature of the fixing machine is 180 ° C., and the process speed is 150 mm / sec. Thereafter, the obtained image was irradiated with light for 30 seconds using a high brightness Schaukasten of 58000 lux.

The above-described image output was performed a total of 10 times. As a result, there was no destruction of the toner in the developing machine, and the image, color tone, gradation and the like were stable, and a high-definition full-color image was obtained. Also, there was no problem with fixing properties. In addition, no toner cloud or fog was observed.
Furthermore, an image irradiated with high-brightness shakasten was left for about half a year in a normal lighting environment where a fluorescent lamp was placed on the ceiling. It was found that there was almost no change in color balance.

-Measurement method of toner particle size and particle size distribution-
For the measurement of toner particle size and particle size distribution, Coulter Multimizer Type II (Beckman-Coulter) was used as the measuring device, and ISOTON-II (Beckman-Coulter) was used as the electrolyte.
As a measurement method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. This was added to 100 to 150 ml of the electrolytic solution. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of particles having an aperture diameter of 2 to 60 μm is measured using the Coulter Multimizer type II with an aperture of 100 μm, The volume average particle size was determined as described above. The number of particles to be measured was 50,000.

-Volume average particle size of fine particles-
The volume average particle size of various fine particles other than toner particles was measured with a laser scattering diffraction particle size distribution analyzer (LS 13 320 manufactured by Beckman-Coulter).

―Measurement method of glass transition temperature of resin and toner―
The glass transition temperatures of various resin materials used for the production of the toner were determined as the temperature of the intersection of the extension line of the base line and the rising line in the endothermic part according to ASTM D3418-8. A differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50) was used for the measurement.

FIG. 3 is a schematic cross-sectional view illustrating an example in which the toner of the present invention includes a base material and a color developing portion dispersed in the base material in a particulate form. FIG. 3 is a schematic cross-sectional view illustrating an example in which the toner of the present invention has a concentric structure. FIG. 4 is a schematic cross-sectional view illustrating an example in which the toner of the present invention has a stripe structure. FIG. 5 is a schematic cross-sectional view illustrating an example in which the toner of the present invention has a fan structure. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention.

Explanation of symbols

10, 12, 14, 16 Toner 20 First color developing part 22 Second color developing part 24 Third color developing part 26 Base material 30 First photosensitive / thermosensitive layer 32 Second photosensitive / thermosensitive layer 34 Third photosensitive・ Thermosensitive layer

Claims (19)

  A conductive toner for developing an electrostatic latent image, comprising a color-developing composition capable of color development upon application of an external stimulus and a conductive agent.   The curable composition is present in a state of being separated from each other, and includes a first component and a second component that develop color when they react with each other, and a photocurable composition including any one of the first component and the second component. The conductive toner for developing an electrostatic latent image according to claim 1, further comprising a composition.   The microcapsule dispersed in the photocurable composition, wherein the first component is contained in the microcapsule and the second component is contained in the photocurable composition. The conductive toner for developing an electrostatic latent image according to 2.   4. The electrostatic latent image developing conductive toner according to claim 3, wherein the microcapsule is a heat-responsive microcapsule capable of diffusing substances inside and outside the microcapsule by heat treatment.   The electrostatic capsule according to claim 3, wherein the microcapsule has a core portion containing the first component and an outer shell covering the core portion, and the outer shell is made of a thermoplastic material. Conductive toner for developing latent images. When the photocurable composition is in an uncured state, a non-colorable state is maintained,
The photocurable composition is cured irreversibly from the uncolorable state to the colorable state by curing the photocurable composition by irradiation with light of a specific wavelength for curing the photocurable composition. The conductive toner for developing an electrostatic latent image according to claim 2.   The electroconductive toner for developing an electrostatic latent image according to claim 6, wherein the photocurable composition contains the second component and a photopolymerizable compound.   The first component and the second component are reacted by heating after irreversibly controlling to the colorable state by curing the photocurable composition by irradiation with light of the specific wavelength. The electroconductive toner for developing an electrostatic latent image according to claim 6, wherein the toner is developed. Maintaining a colorable state when the photocurable composition is in an uncured state,
The photocurable composition is cured irreversibly from the colorable state to the noncolorable state by curing the photocurable composition by irradiation with light of a specific wavelength for curing the photocurable composition. The conductive toner for developing an electrostatic latent image according to claim 2.   The electroconductive composition for developing an electrostatic latent image according to claim 9, wherein the second component is contained in the photocurable composition, and the second component has a photopolymerizable group in its molecule. toner.   10. The electrostatic latent image developing conductive material according to claim 9, wherein the first component and the second component are reacted to develop a color by heating the photocurable composition in an uncured state. Toner.   The two or more color development parts containing the color development composition which can be developed by giving of the above-mentioned external stimulus are included, and these two or more color development parts can develop in mutually different colors. Conductive toner for electrostatic latent image development.   The two or more coloring portions include a yellow coloring portion capable of developing in yellow, a magenta coloring portion capable of developing in magenta color, and a cyan coloring portion capable of developing in cyan color. The conductive toner for developing an electrostatic latent image according to 1.   2. The electrostatic latent image developing conductive toner according to claim 1, wherein the conductive agent includes at least one conductive agent selected from titanium oxide, tin oxide, and ITO.   A developer for developing an electrostatic latent image, comprising a color-forming composition capable of color development by application of an external stimulus and a conductive agent, and containing a conductive toner. A charging step for charging the surface of the image carrier, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier, a charge injection step for injecting charges into conductive toner, and a charge injection for the electrostatic latent image A development process for developing the conductive toner to form a toner image; a color development information application process for irradiating the toner image with color development information application light corresponding to color component information of image information; and recording the toner image on a recording medium A transfer step of transferring to the surface, and a fixing color forming step of forming an image by fixing the toner image transferred to the surface of the recording medium and irradiated with the color forming information imparting light to heat and pressurize and color.
A photocurable composition comprising a first component and a second component which are present in a state where the conductive toner is isolated from each other and react with each other, and any one of the first component and the second component One or more color-developing parts containing a product, and containing a conductive agent,
The image forming method, wherein the image information imparting light includes light having a specific wavelength for curing the photocurable composition contained in each of the one or more kinds of color forming portions.   The image forming method according to claim 16, further comprising a light irradiation step of irradiating the image obtained through the fixing and coloring step with light. An image carrier, a charging unit that charges the surface of the image carrier, a latent image forming unit that forms an electrostatic latent image on the surface of the image carrier, a charge injection unit that injects charges into conductive toner, and the electrostatic Developing means for developing a latent image with the conductive toner into which electric charge has been injected to form a toner image; color information providing means for irradiating the toner image with color information providing light corresponding to color component information of image information; Transfer processing means for transferring the toner image to the surface of the recording medium, and fixing coloring for forming the image by heating and pressurizing and coloring the toner image transferred to the surface of the recording medium and irradiated with the color forming information providing light. Means,
A photocurable composition comprising a first component and a second component which are present in a state where the conductive toner is isolated from each other and react with each other, and any one of the first component and the second component One or more color-developing parts containing a product, and containing a conductive agent,
The image forming apparatus, wherein the image information providing light includes light having a specific wavelength for curing the photocurable composition included in each of the one or more types of coloring portions.   The image forming apparatus according to claim 18, further comprising a light irradiation unit configured to irradiate the image obtained through the fixing and coloring step with light.

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