JP2003315993A - Photosensitive recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high resolution and low energy consumption photosensitive recording material which can be written with light, has excellent coloring property, and is free of ground coloring. <P>SOLUTION: The photosensitive recording material comprises microcapsules containing at least electrophoretic particles colored in a prescribed color and a dispersion medium colored in a color different from that of the electrophoretic particles and causing thickening or hardening under light. Preferably the electrophoretic particles are electrically charged white particles. The top of a support is coated with the photosensitive recording material to obtain a photosensitive recording medium. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive recording material, a photosensitive recording medium and a recording method using the same, and more particularly to a recording material having a small recording energy, a photosensitive recording medium and a recording method using the same.

[0002]

2. Description of the Related Art Conventionally, methods such as silver salt photography, heat-sensitive recording (heat melting type and sublimation type), electrophotography and ink jet are known as methods for forming a full-color image. Although silver salt photography and thermal recording methods have high image quality, they have the drawback of generating waste such as developer and ink ribbon. Toner is required for the electrophotographic method and ink is required for the inkjet method. Therefore, a self-coloring type recording medium has been studied from the viewpoint of eliminating waste. One is called a light and pressure sensitive method, in which exposed portions cause the cured microcapsules to be cured and non-cured, and thereafter, the microcapsules which are not cured by pressurization are destroyed to give colored encapsulation. An image is obtained by transferring an object to paper or by reacting an encapsulated material that is a dye precursor with a developer (coupler) prepared outside the microcapsules to develop a color. For details, see “Electronic Society of Japan 1992 First Research Meeting Proceedings,” p. 47 (19
92).

In addition, a heat-sensitive TA paper (Fuji Photo Film) has been developed. This is a thermoresponsive capsule containing a dye precursor, a diazonium salt, which is controlled by heat to bring the encapsulated material into contact with a developer (coupler) prepared outside the capsule, an organic base compound, that is, By controlling the reaction, the formation of the dye is controlled. Next, the dye precursor is decomposed by irradiating with ultraviolet rays, and the reaction with the coupler makes it impossible to develop a color, thereby fixing the dye. Ingenuity was applied to the thermo-responsive capsule and diazonium salt to obtain full color. About this, "Printer Materials and Chemicals"
(Kyosuke Takahashi, Masahiro Irie, CMC (199
5)).

Further, JP-A-2000-218944 and JP-A-2000-221692 have devised a light-sensitive and heat-sensitive method and a light-sensitive method using a double capsule.

In the above-mentioned light and pressure sensitive method, since it is necessary to break the capsule by applying pressure, it is not possible to make the capsule into a small particle size, and the breakage deteriorates the resolution and the image quality becomes rough. there were. Further, the thermosensitive TA paper has at least Y, which has different writing energy,
There are drawbacks that the three heat-sensitive layers of M and C and ultraviolet rays having different wavelengths are required for fixing, and since writing is performed by a thermal head and fixing is performed by ultraviolet rays, recording energy is increased. Further, in the conventional self-coloring type recording medium, since the chemical reaction of the color forming material is utilized in the developing step, there is a problem of background color formation and a problem that it is difficult to control color formation to obtain a desired color. there were.

[0006]

SUMMARY OF THE INVENTION In order to solve the above-mentioned drawbacks of the prior art, the present invention is a recording material which is writable by light, has excellent coloring properties and does not cause background coloring, and has high resolution. An object is to provide a light-sensitive recording material with low energy consumption.

[0007]

At least an electrophoretic particle colored with a predetermined color and a dispersion medium colored with a predetermined color different from that of the electrophoretic particle, the dispersion medium being thickened or cured by light are enclosed. This has been achieved by using a photosensitive recording material characterized by containing microcapsules and utilizing development based on the physical manipulation of electrophoretic particle movement by voltage.

The first photosensitive recording material of the present invention comprises at least electrophoretic particles colored in a predetermined color, and a dispersion medium colored in a color different from that of the electrophoretic particles and thickened or cured by light. It is a photosensitive recording material containing microcapsules encapsulating.

The second photosensitive recording material of the present invention is the photosensitive recording material of the first photosensitive recording material, wherein the electrophoretic particles are charged white particles.

The third photosensitive recording material of the present invention is the photosensitive recording material of the first or second photosensitive recording material, wherein the dispersion medium contains a polymerizable compound.

The fourth photosensitive recording material of the present invention is the photosensitive recording material according to the third photosensitive recording material, wherein the polymerizable compound is an acrylic compound.

The fifth photosensitive recording material of the present invention comprises:
The photosensitive recording material of 2, 3 or 4 further comprises a photopolymerization initiator, or a photopolymerization initiator and a wavelength sensitizer.

The sixth photosensitive recording material of the present invention comprises:
In the photosensitive recording material of 2, 3, 4 or 5, the wavelength of 40
It is a photosensitive recording material containing a visible light polymerization initiator or a wavelength sensitizer having an absorption spectrum maximum value in the range of 0 nm to 800 nm.

The seventh photosensitive recording material of the present invention comprises:
2, 3, 4, 5 or 6, a dispersion medium colored at least in any of the three primary colors of cyan, magenta and yellow, or in the three primary colors of red, green and blue; A photosensitive recording material comprising at least three types of microcapsules containing electrophoretic particles colored in a color different from the color.

The eighth photosensitive recording material of the present invention is the same as the seventh photosensitive recording material, and further contains a dispersion medium colored black and electrophoretic particles colored different from the black. A photosensitive recording material containing microcapsules.

A ninth photosensitive recording material of the present invention is the same as the seventh or eighth photosensitive recording material, wherein each of the at least three types of microcapsules has a photopolymerization initiator having an absorption spectrum maximum at a different wavelength, Alternatively, it is a photosensitive recording material containing a photopolymerization initiator and a wavelength sensitizer having an absorption spectrum maximum at a different wavelength.

The first photosensitive recording medium of the present invention comprises the first,
It is a photosensitive recording medium obtained by coating a support with 2, 3, 4, 5, 6, 7, 8 or 9 of a photosensitive recording material.

The first recording method of the present invention is the first, second,
It is a recording method including a step of irradiating the photosensitive recording material of 3, 4, 5, 6, 7, 8, 9 or the first photosensitive recording medium with light, and subsequently applying a voltage.

A second recording method of the present invention is the recording method according to the first recording method, wherein the irradiation light is light having three or more different wavelengths.

A third recording method of the present invention is the recording method of the first or second recording method, further including the step of irradiating light.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

The recording material of the present invention has, for example, as shown in FIG. 1, electrophoretic particles 2 (for example, charged white pigment) colored in a predetermined color and a predetermined color (for example, blue) different from the electrophoretic particles. It is composed of microcapsules 1 which are colored with a dispersion medium 3 which is thickened or hardened by light (for example, a low-viscosity polymerizable compound in which a colored dye is dissolved). In addition, the code | symbol 4 has shown the microcapsule wall. This also includes the case where the microcapsules and the recording material containing the microcapsules look white regardless of whether or not the dispersion medium is colored, and the electrophoretic particles are colored in a color other than white. If necessary, a photopolymerization initiator, a wavelength sensitizer, a charge control agent, a dispersant, a lubricant, a stabilizer, etc. are added to the dispersion medium.

The electrophoretic particles are charged particles, and when a voltage is applied, that is, an electric field is applied,
These particles move according to the direction of the electric field.

The particle size of the microcapsules is controlled by adjusting the size of the dispersion emulsion when emulsifying the liquid in which the electrophoretic particles are dispersed during the production of the microcapsules. The size of the dispersion emulsion is adjusted to a desired size depending on the stirring speed, the viscosity of the dispersion, or the type and amount of the emulsifier and the surfactant. The recording medium of the present invention can be produced by applying the microcapsules thus obtained, together with a binder resin, if necessary, on a support such as paper, glass, or film, and providing a protective layer or the like. .

The basic operation of the recording material thus constructed will be described below. Here, the action of the microcapsule will be described by taking a microcapsule composed of white electrophoretic particles and a dispersion medium colored in blue as an example.

The microcapsules shown in FIG. 2 (a) are in a state where no electric field is applied yet, and the electrophoretic particles 2 are
It exists in a dispersed state in the microcapsules in a uniform state.
Note that, here, the upper side is the observation surface direction of the color of the microcapsules.

When a voltage is applied, an electric field having a direction depending on the polarity of the applied voltage is generated. Here, the direction of the electric field is indicated by E. In the microcapsules placed in this electric field, a downward electric field is generated, and the negatively charged white electrophoretic particles 2 are attracted in the direction of the anode and adhere to the inner wall surface of the capsule wall 4. FIG. 2B shows a state in which the electrophoretic particles are attracted upward and adhered to the inner wall surface of the capsule wall 4 of the microcapsule. Therefore, when the capsule is viewed from the observation direction (above), the color of the colored dispersion medium is hidden behind the electrophoretic particles, and only the white color of the electrophoretic particles is observed.

The portion to be recorded can be selected by irradiating the recording medium with light in advance to increase the viscosity of the dispersion medium or by curing a part or all of the dispersion medium. Then, by applying a voltage and applying an electric field, the electrophoretic particles in the portion not irradiated with light are driven to form an image. Even if the voltage application is stopped in this state, due to the viscosity and holding force of the liquid dispersion medium,
The state of FIG. 2B is maintained for a while. Then, by exposing the entire surface, the viscosity of the dispersion medium is increased or the dispersion medium is cured, and the image can be fixed and fixed.

FIG. 3 shows an example of the color combination of the electrophoretic particles and the dispersion medium in the microcapsule color-developing body in a state after voltage application. In the figure, 2a represents white pigment particles, 2b represents colored pigment particles (including white particles), 3a represents a colorless dispersion medium, and 3b represents a colored dispersion medium. FIG. 3A shows a combination of the white pigment particles 2a and the color dispersion medium 3b, and FIG. 3B shows the color pigment particles 2
b and the colorless dispersion medium 3a, and FIG. 3C shows the combination of the color pigment particles 2b and the color dispersion medium 3b of a different color.

In the present embodiment, in order to realize full-color expression, a plurality of microcapsules having the above-described different expression colors are used. For example, the electrophoretic particles are white, and three or more kinds of different dispersion media are colored yellow, magenta, and cyan (or red, green, and blue), respectively, and further, black if necessary. 4 including the dispersion medium
More than one type of microcapsule can be used.

For each microcapsule, it is preferable to use a dispersion medium that is thickened or cured by different light. For example, as such a dispersion medium, a photopolymerization initiator having a different absorption wavelength region, that is, having a maximum value of an absorption spectrum at a different wavelength, or a polymerizable compound to which a combination of a photopolymerization initiator and a wavelength sensitizer is added To use. The wavelength sensitizer may be the same as or different from the coloring dye of the dispersion medium. Also,
As the wavelength sensitizer, a decolorizable dye that disappears when exposed to light may be used so as not to impair the color of the dispersion medium colored by the dye. A color recording medium can be prepared by mixing a plurality of these capsules and coating them on a support (FIGS. 4 and 5) or by laminating each color separately (FIG. 6).

The recording principle using the recording medium of the present invention will be described with reference to FIG. 7 by taking as an example a recording medium using microcapsules for yellow, magenta and cyan. In addition, in FIG. 7, the electrophoretic particles 2a are white,
Dispersion media colored yellow, magenta and cyan are used. 7A shows an embodiment of the recording medium of the present invention, and FIG. 7B shows a color arrangement when the recording medium is viewed from above.

First, when the recording medium of the present invention is irradiated with visible light of three different wavelengths having image signals, for example, 6R (red light), 6G (green light) and 6B (blue light), the respective lights are irradiated. The dispersion medium in the microcapsules sensitive to viscosities thickens or hardens. In a system using a polymerizable compound, the polymerization reaction of the polymerizable compound starts, and the inclusions thicken or harden. At this time, the unexposed portion has fluidity (FIG. 7C). Further, FIG. 7D shows a color arrangement when the recording medium is viewed from above.

Next, by applying a voltage from outside the capsule, the electrophoretic particles 2 in the microcapsule 2 are applied.
a moves according to the charge polarity of the particle itself (FIG. 7 (e)).

In this state, the recorded image is held for a short time,
Furthermore, by exposing the entire surface, the inside of the entire microcapsule is thickened or cured, and fixed,
Storage stability of image quality can be obtained (FIGS. 7F and 7H).

After the voltage is applied, when observed from the side where the particles have moved, the portion where the electrophoretic particles (for example, white charged particles) are attached looks like the color of the electrophoretic particles 2a (in this case, white), In the capsule of the portion exposed before the application, since the internal dispersion medium is thickened or hardened, the movement of the electrophoretic particles 2a is hindered and the color of the dispersion medium is retained (FIG. 7 (g), (i)). )).

Next, the electrophoretic particles and the electrophoretic phenomenon will be described.

The electrophoretic particles are particles that move in the medium by electrophoresis, and are usually charged particles in the medium.

The electrophoretic phenomenon is that when a specific particle is suspended in a medium (dispersion medium), it is electrically charged, and when an electric field is applied in this state, the charged particle passes through the dispersion medium and opposes. This is a phenomenon of migration (electrophoresis) to the electrode side having electric charges. An electric double layer is formed around the electrophoretic particles. The zeta potential is known as a measurable physical quantity of this electric double layer, but this zeta potential largely depends on the surface material of the electrophoretic particles.

The difference in the electrophoretic mobility of the electrophoretic particles can be adjusted by the properties of the coloring dispersion medium colored in different colors, that is, the dielectric constant, the viscosity, or the material of the electrophoretic particles.

For example, surface treatment with different surface treatment agents can produce electrophoretic particles having different zeta potentials. When a solution in which electrophoretic particles are dispersed is sandwiched between two electrodes and an electric field is applied between the electrodes, the electrophoretic particles are positive or negative of the zeta potential, that is, if the electrophoretic particles have a negative polarity, for example, The electrophoretic particles migrate to the anode side. This electrophoretic mobility (velocity per unit electric field) is represented by μ = (εζ / 6πη). Here, ε and η are the dielectric constant and viscosity of the liquid, respectively, and ζ is the zeta potential of the particles.

Therefore, particles having a large zeta potential are
Electrophoretic mobility is also large and easily moves, and particles having a small zeta potential have small electrophoretic mobility and are difficult to move.

Further, if the viscosity of the coloring dispersion medium is high, the electrophoretic mobility of the electrophoretic particles is low, and if the viscosity is low, the electrophoretic mobility of the electrophoretic particles is high.

When an electric field is applied so that both the electrophoretic particles having high electrophoretic mobility and the electrophoretic particles having small electrophoretic mobility can be sufficiently moved, all the electrophoretic particles in the microcapsules move in the direction of the applied voltage. Move in the appropriate direction. Then, when an electric field is applied to such a degree that the electrophoretic particles having high electrophoretic mobility can move sufficiently, but the electrophoretic particles having low electrophoretic mobility cannot move sufficiently, only the electrophoretic particles having high electrophoretic mobility move. However, the electrophoretic particles having a low electrophoretic mobility cannot move, or even move a little.

Here, if the electrophoretic mobility of the electrophoretic particles dispersed in each color dispersion medium is provided with a distribution, the electrophoretic particles have a large and small electrophoretic mobility and an electric field applied. Depending on the size of the, it is divided into electrophoretic ones and non-electrophoretic ones. For this reason, the area where the electrophoretic particles hide the colored dispersion medium varies depending on the magnitude of the electric field, so that various concentrations can be reproduced. In other words, it is possible to express the gradation by the difference in the voltage value of the applied drive voltage or the application time.

In order to provide the electrophoretic mobility of the electrophoretic particles with a distribution, the electrophoretic particles of different materials may be used to provide the potential distribution, or different surface treatment agents may be used to provide the zeta potential distribution. The particle size may be distributed. Even with the same surface treatment agent, the zeta potential can be changed by changing its concentration. In addition, by adjusting the particle diameter and the material, the electrophoretic mobility can be relatively adjusted and binary gradation can be obtained. Further, the gradation expression by area gradation can also be used for the gradation expression.

The particle size of the microcapsules used in the present invention is theoretically preferably as small as possible in order to realize high resolution, but since it has a structure containing electrophoretic particles, it is actually , About 3 μm or more, about 500 μm
The following is desirable.

The volume median diameter of the electrophoretic particles is preferably 5 to 1000 times, preferably 10 to 500 times. 5 to electrophoretic particles
A microcapsule having a volume median diameter of 1000 times can efficiently develop a color tone due to electrophoretic particles. When the volume median diameter of the microcapsules is smaller than 5 times the volume median diameter of the electrophoretic particles, the reflectance of the electrophoretic particles decreases, and vivid color reproduction tends to be difficult to obtain. On the other hand, when it exceeds 1000 times, the migration distance between the electrophoretic particles and the colored particles becomes long, and the electrophoretic response tends to be remarkably reduced.

The method for producing the microcapsules used in the present invention may be a known microencapsulation method, for example, Ashiro Kondo, “Microcapsules”, Nikkan Kogyo Shimbun (19
In situ polymerization method, interfacial polymerization method, coacervation method, spray drying method, in-liquid drying method, etc. Particularly, the interfacial polymerization method and the in situ polymerization method are preferable. In the production of the microcapsules, the oil phase / water phase emulsion may be prepared and then encapsulated, or the water phase layer / oil phase emulsion may be prepared and then encapsulated.

The material of the microcapsules is urea-formaldehyde resin, melamine resin, polystyrene, styrene-methacrylate copolymer, styrene-acrylate copolymer, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, polyurethane, polyurea, polyamide, polyester. , Polycarbonate, etc., and two or more of these may be used in combination. Of these, gelatin is preferable in terms of transparency of the capsule wall, and melamine resin, urea-formaldehyde resin and the like are preferable in terms of hardness.

The white particles used for the electrophoretic particles used in the present invention include organic materials, inorganic materials, and organic / organic materials.
It is composed of an inorganic composite material.

Specifically, inorganic pigments such as titanium oxide, aluminum oxide, zinc oxide, lead oxide, tin oxide, and zirconium oxide, resin dispersion materials of these inorganic pigments such as polyethylene resin, hollow particles made of organic polymer, Examples thereof include porous particles made of an organic polymer, hollow particles made of an inorganic substance, porous particles made of an inorganic substance, and particles in which white particles having voids are covered with a resin or the like. The white particles having voids inside are the materials (about 1.4 to
1.6) and the refractive index of air in the void (= about 1.
Due to the difference with 0), the light is reflected efficiently and a white color tone is provided.

As the colored particles other than white,
A pigment such as an inorganic pigment or an organic pigment, or an organic compound in which a dye is dispersed can be used.

Examples of the inorganic pigments include cadmium yellow, cadmium lipoton yellow, yellow iron oxide, titanium yellow, titanium barium yellow, cadmium orange, cadmium lipoton orange, molybdate orange, red iron oxide, red tin, silver vermillion, cadmium red, Cadmium lipoton red, amber, brown iron oxide, zinc iron chrome brown, chrome green, chrome oxide, viridian, cobalt green, cobalt chrome green, titanium cobalt green, navy blue, cobalt blue, ultramarine blue, cerulean blue, cobalt aluminum chrome blue,
Cobalt violet, mineral violet, carbon black, iron black, manganese ferrite black, cobalt ferrite black, copper chrome black, copper chrome manganese black, titanium black, aluminum powder,
Copper powder, lead powder, bell powder, zinc powder, etc. may be mentioned.

Examples of the organic pigments include fast yellow, disazo yellow, condensed azo yellow, anthrapyrimidine yellow, isoindoline yellow, copper azomethine yellow, quinophthaloin yellow, benzimidazolone yellow, nickel dioxime yellow, monoazo yellow lake, Dinitroaniline orange, pyrazolone orange, perinone orange, naphthol red,
Toluidine red, permanent carmine, brilliant fast scarlet, pyrazolone red, rhodamine 6G rake, permanent red, resole red,
Bon Lake Red, Lake Red, Brilliant Carmine, Bordeaux 10B, Naphthol Red, Quinacridone Magenta, Condensed Azo Red, Naphthol Carmine, Perylene Scar Red, Condensed Azo Scar Red, Benzimidazolone Carmine, Anthraquinonyl Red, Perylene Red, Perylene Maroon, Quinacridone maroon, quinacridone scarred, quinacridone red, diketopyrrolopyrrole red, benzimidazolone brown,
Phthalocyanine Green, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Alkaline Blue Toner, Indanthrone Blue, Rhodamine B
Examples include lake, methyl violet lake, dioxazine violet, and naphthol violet.

As a common name for organic pigments that are commonly used in Japan,
For yellow, Hansa Yellow, Benzine Yellow, Pigment Yellow 83, Pigment Yellow 110, Pigment Yellow 139 and the like can be used. In red,
Permanent Red, Benzine Orange, Pyrazolone Orange, Vulcano Orange, Orange Lake, Para Red, Lake Red, Toluidine Red, Brillfast Scarlet, Brill Carmine, Brill Scarlet,
Bordeaux, Watch Chan Red (watchhung
red), Resor Red, Bon Maroon, Lake Bold, Rhodamine, Mader Lake, Pigment Red 5
3: 1, Pigment Red 177, Pigment Red 221 and the like can be used. For purple, Rhodamine Lake, Dioxazine Violet, Crystal Violet Lake, Pigment Violet 23, Pigment Violet 37 and the like can be used. In blue, Victoria Pure Blue Lake, Victoria Blue Lake,
Phthalocyanine Blue, Fast Sky Blue, Slane Blue RS, Pigment Blue 15, Pigment
Blue 15: 3, Pigment Blue 15: 6, etc. can be used. For green, diamond green lake, phthalocyanine green, pigment green B, green gold, pigment green 7, pigment green 36 and the like can be used. For black, diamond black, carbon black, and pigment black 7 can be used.

In the present invention, these colored particles can be used in various surface-modified forms. In this case, the surface modification method includes a method of coating various compounds including a polymer on the particle surface, a method of coupling treatment with various coupling agents such as titanate / silane, and a method of graft polymerization treatment. Can be given. Further, these colored particles can be used even in a mechanochemically treated form,
It is also possible to use different particles or particles of the same kind, or as composite particles in which polymer particles or hollow polymer particles are combined.

It is preferable that the electrophoretic particles used in the present invention are white particles, among others, in terms of the degree of freedom in selection regarding the coloring material of the coloring dispersion medium.

The dispersion medium which is thickened or hardened by light used in the present invention is increased by light irradiation due to physical changes such as structure and morphological changes, or chemical changes such as chemical reaction and physicochemical bonding. Examples of the material include viscous, gelling or hardening materials. As an example, a polymerizable compound, and
Examples thereof include a mixture of a polymerizable compound and a polymer compound, a mixture of a polymerizable compound and another solvent, and the like.

Examples of the polymerizable compound include photoradical polymerizable compounds, photocationic polymerizable compounds, and photoanionic polymerizable compounds. Examples of the photo-radical polymerizable compound include acrylic acid esters, acrylamides, methacrylic acid, methacrylic acid esters, methacrylamides, maleic anhydrides, maleic acid esters, styrenes, vinyl ethers, vinyl esters and allyl. Ethers, silicones, acrylic silicones, mercapto silicones, mercapto /
Examples include deacetone-cured silicone and acrylic / dealcohol-cured silicone. Examples of the cationic photopolymerizable compound include an epoxy resin, an oxetane compound, a vinyl ether compound, a 1-propenyl compound, and an epoxy silicone. Examples of the photoanionic polymerizable compound include cyanoacrylate compounds. Among these, acrylic acid esters, methacrylic acid esters, silicones, and acrylic silicones are preferable in view of characteristics, and in particular, acrylic resin has high photosensitivity and flexibility in selection of photosensitizing wavelength by a wavelength sensitizer. Compounds are preferred.

Specific examples of the acrylic acid esters, methacrylic acid esters, silicones and acrylic silicones include 2-butylaminocarbonyloxyethyl acrylate, 2-N, N-dimethylaminoethyl acrylate and 2-t. -Butylaminoethyl acrylate, 2-t-butylaminoethyl methacrylate, 2-
Diethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-dimethylaminopropyl acrylate, 4-2
-Allylaminocarbothionyl carbohydrazonoyl phenyl-3-2-chlorophenyl acrylate, 2-ethylhexyl acrylate, dicyclopentenyloxyethyl acrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexa Monomers such as acrylate, trimethylolpropane triacrylate, dipentaerythritol polyacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polysilane, polysiloxane, dimethylpolysiloxane, acrylic modified polysiloxane, mercapto modified polysiloxane, vinyl modified polysiloxane Oligomers, etc. Alone or can be used in combination of two or more.

As the polymer compound which can be mixed with the dispersion medium, polyester, polyvinyl alcohol,
Polyurethane, polyurea, polyamide, polycarbonate, polyvinyl chloride, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, urea-formaldehyde resin, melamine resin, styrene-methacrylate copolymer, styrene-acrylate copolymer, Gelatin, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, ethylene-vinyl alcohol copolymer, polyacetal, methyl cellulose, ethyl cellulose, carboxymethyl cellulose,
Hydroxypropyl cellulose, phenolic resin, fluororesin, silicone resin, diene resin, polystyrene thermoplastic elastomer, polyolefin thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, polyphenylene ether, polyphenylene sulfide, polyether sulfone, Polyetherketone, polyarylate, aramid,
Polyimide, poly-p-phenylene, poly-p-xylene, poly-p-phenylene vinylene, polyhydantoin, polyparabanic acid, polybenzimidazole, polybenzothiazole, polybenzoxadiazole, polyquinoxaline, arabia gum, casein, styrene- Examples thereof include, but are not limited to, butadiene rubber, polyvinyl acetate, polyacrylic acid ester, ethylene-vinyl acetate copolymer, polyethylene, polystyrene and polypropylene. Moreover, you may each mix individually or in mixture of 2 or more types.

As a solvent that can be mixed with the dispersion medium, aromatic hydrocarbons such as benzene, toluene, xylene, phenylxylylethane and dodecylbenzene,
Diisopropylnaphthalene, aromatic hydrocarbons such as naphthene hydrocarbons, hexane, cyclohexane, kerosene, aliphatic hydrocarbons such as paraffin hydrocarbons, chloroform, trichloroethylene, tetrachloroethylene, trifluoroethylene, tetrafluoroethylene,
Dichloromethane, halogenated hydrocarbons such as ethyl bromide, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, phosphate esters such as tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, phthalate Phthalates such as dicyclohexyl acid, butyl oleate, diethylene glycol dibenzoate, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, dibutyl maleate, ethyl acetate, etc. Carboxylic acid esters, isopropyl biphenyl, isoamyl biphenyl, chlorinated paraffin, diisopropyl naphthalene, 1,1-ditolylethane, 1,
Examples thereof include 2-ditolylethane, 2,4-ditertiaryaminophenol, N, N-dibutyl-2-butoxy-5-t-octylaniline, but are not limited thereto. In addition, each may be used alone or in combination of two or more kinds.

Additives may be used to adjust the dielectric constant of the dispersion medium. In this case, the properties required for the additive are that it has a higher dielectric constant than the dispersion soot and that it does not react with the electrophoretic particles.

The reactivity with the electrophoretic particles cannot be unconditionally stated because it greatly varies depending on the composition of the particles, but as a material that can be used as an additive by paying attention to the dielectric constant, specifically,
The following are suitable.

For example, 1-decanol, acetaldehyde, acetonitrile, acetophenone, aniline, anisole, isobutyl alcohol, isobutyronitrile, ethanethiol, methyl ethyl ketone, ethylene glycol, ethylenediamine, epichlorohydrin, allyl chloride, isobutyl chloride, ethyl chloride. , Propyl chloride, benzyl chloride, methyl chloride, 1-octanol, 2
-Octanone, oleic acid, formic acid, xylene, quinoline, guai alcohol, glycerin, cresol, chlorooctane, chlorotoluene, chloroheptane, chlorobenzene, chloroform, pentyl acetate, diethyl ether, carbon tetrachloride, 1,4-dioxane, cyclo Hexanol, cyclohexanone, cyclopentanol, cyclopentanone, dichloroacetone, dichloroethane,
2,2-dichlorodiethyl ether, dichloroethylene, 1,4-dichlorobutane, dichloropropane, dichlorobenzene, divinyl ether, diphenyl ether, dibutyl ether, dipropyl ether, dibromoethylene, dibromobutane, dibromopropane, dibromoheptane, dimethylamine, Dimethyl ether, isobutyl bromide, isopropyl bromide, ethyl bromide, butyl bromide, propyl bromide, diiodoethylene, diethyl sebacate, dioctyl sebacate, dibutyl sebacate, 1
-Decanol, 1,1,2,2-tetrachloroethane,
Tetrachloroethylene, 1,1,2,2-tetrabromoethane, 1-dodecanol, trichloroacetaldehyde, 1,1,1-trichloroethane, tribromoacetaldehyde, 1,2,3-tribromopropane, toluidine, piperidine, pyridine, butanol , Dioctyl phthalate, dibutyl phthalate, 1,4-butanediol, t-butyl alcohol, propanol, propanediol, 1-bromooctadecane, 1-bromooctane, 1-bromo-2-chloroethane, 1-bromo-2-
Chloroethylene, bromocyclohexane, 1-bromotetradecane, 1-bromodecane, 1-bromotridecane, 2-bromo-2-butene, 1-bromohexadecane, 1-bromohexane, 1-bromoheptane, 1-bromopentadecane, 1 -Bromopentane, bromoform, hexachloro-1,3-butadiene, 1-hexadecanol, 1-hexanol, heptanal, 4-heptanal, 4-heptanone, benzaldehyde, 1-pentanol, 2-pentanone, 3-pentanone , Phosgene, formamide, methylamine, 4-methylcyclohexanol, 2-methylcyclohexanone, 2-methylpyridine, isobutyl iodide, isopropyl iodide, ethyl iodide, butyl iodide, propyl iodide, methyl iodide, 1- Iodine octa , 1-iodo-hexadecane,
Examples thereof include 1-iodohexane, 1-iodopentane, and siloxanes.

Examples of dyes or pigments that can be used for coloring the dispersion medium used in the present invention include basic dyes, oil-soluble dyes, and disperse dyes. Among them, examples of dyes that can be preferably used in the invention are shown below.

The basic dyes include Basic Red 12, Basic Red 27, Basic Violet (Basic Vio).
let) 7, Basic Violet 10, Basic Violet 40, Basic Blue (Basi
c Blue) 1, Basic Blue 7, Basic Blue 26, Basic Blue 77, Basic
Examples include Green (Basic Green) 1 and Basic Yellow (Basic Yellow) 21.

Examples of the oil-soluble dyes include Solvent Red 125 and Solvent Red.
Red 132, Solvent Red 83, Solvent
Red 109, Solvent Blue (Solvent
Blue) 67, Solvent Blue 25, Solvent Yellow 25, Solvent Yellow 89, Solvent Yellow 146
Can be given.

Examples of the disperse dyes include Disperse Red 60, Disperse Red 72, and Disperse Blue (Disperses).
eBlue) 56, Disperse Blue 60, Disperse Yellow (Disperse Yellow)
Other than 60, azo dye, metal complex salt dye, nafur dye, anthraquinone dye, indigo dye, carbonium dye, quinoimine dye, cyanine dye, quinoline dye,
Examples thereof include nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, penolin dyes and phthalocyanine dyes.

Oil-soluble dyes are particularly preferable. Also, these dyes can be used in combination.

Examples of the photopolymerization initiator used in the present invention include a photopolymerization initiator for photoradical polymerization and a photopolymerization initiator for cationic photopolymerization.

Examples of the photopolymerization initiator for photoradical polymerization include aromatic carbonyl compounds, acetophenones, triazines, trichlorotriazines, organic peroxides, organic halides, azo compounds, dye-borate complexes and metals. An arene complex, a dye derivative iodonium salt, a dye derivative alkyl borate, and the like are used.
For example, (η5-2,4-cyclopentadiene-1-
Yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] iron (1+) hexafluorophosphate (1-), 4,4′-tetrakis (t-butyldi) Oxycarbonyl) benzophenone, 2- [7- (1,
3-Dihydro-1,3,3-trimethyl-2H-indole-2-ylidene) -1,3,5-heptadentrienyl] -3H-indolium butyltriphenylborate, 2,4-trichloromethyl (piperonyl) ) -6-Triazine, 2,4,6-tris (trihalomethyl)-
1,3,5-triazine and its 2-position, or its 2- and 4-position-substituted compounds, phthalimidotrihalomethanesulfonate and its compound having a substituent on the benzene ring, and naphthalimidotrihalomethanesulfonate and its compound Examples thereof include compounds having a substituent on the benzene ring.

As the polymerization initiator having sensitivity in the visible light region, a mixture of a titanocene, a metal arene complex and a dye, or a compound which generates a radical by an intramolecular electron transfer reaction accompanying photoexcitation in the visible light region, for example, a cyanine dye Examples thereof include alkyl borate salts of dye derivatives such as butyl triphenyl borate which is a derivative.

Examples of the photopolymerization initiator for cationic photopolymerization include diazonium salts, aromatic onium salts,
Examples include aromatic iodonium salts, sulfonium salts, triphenylsulfonium salts, thioxanthone derivatives, and benzophenone derivatives.

The photopolymerization initiator is used in a proportion of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the polymerizable compound. If it is less than 0.1%, the polymerization reaction tends to be difficult to proceed, and if it exceeds 20%, the sensitivity tends to be hardly improved.

If necessary, such as when polysilane is used as the polymerizable compound, an oxidizing agent such as amine oxide and phosphine oxide may be added together with the photopolymerization initiator for radical polymerization.

In order to adjust the wavelength of the photopolymerization initiator,
A wavelength sensitizer can be used together with the photopolymerization initiator. The wavelength sensitizer used in the present invention may be selected from those that absorb a specific wavelength of the exposure source used. For example, acrylic orange dye, benzofuran dye, merocyanine dye, xanthene dye, cyanine dye, thiazine dye, azine dye, methine dye, oxazine dye, phenylmethane dye, azo dye,
Examples include anthraquinone dyes, pyrazoline dyes, stilbene dyes, quinoline dyes, rhodamine dyes, safranine dyes, malachite green dyes, methylene blue dyes, coumarin dyes, squarylium dyes, and dye derivative alkylborates. For red light, a squarylium dye is preferable, for green light, a cyanine dye or a merocyanine dye is preferable, and for blue light, a coumarin dye or a merocyanine dye is preferable.

The wavelength sensitizing dye and the dye for coloring the dispersion medium may be the same or different. Further, as the wavelength sensitizer used in combination with the photopolymerization initiator, a decolorizable dye whose color disappears upon irradiation with light may be used so as not to impair the color of the dispersion medium colored by the dye.

Further, in the microcapsule of the present invention, in addition to the dispersion medium and the electrophoretic particles, various auxiliary components are appropriately selected for the purpose of controlling the surface charge amount of the electrophoretic particles or enhancing the dispersibility. It is also possible to use it. Surfactants, protective colloid agents and the like can be used as these auxiliary components, but the auxiliary components are not limited thereto.

As the above-mentioned surfactant, a nonionic (nonionic) type surfactant which can be dissolved or mixed in a dispersant in a dispersant, an anionic type surfactant, a cationic type surfactant, and an amphoteric The ionic surfactants of the system surfactants can be used alone or in combination of two or more. Specific examples of these surfactants include the following, but the surfactant used in the present invention is not limited to these.

Examples of the nonionic surfactants include polyoxyethylene nonylphenol ether, polyoxyethylene dinonylphenol ether, polyoxyethylene octylphenol ether, polyoxyethylene styrenated phenol, polyoxypolyoxyethylene bisphenol A and polyoxyethylene nonyl. Phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyalkylene alkylphenol ethers such as nonylphenol ethoxylate, polyoxyethylene, castor oil, polyoxyalkylene block polymer, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene Oleyl ether, polyoxyethylene stearyl ether, and poly Polyoxyalkylene ethers such as xyloxypropylene ether, monool type polyoxyalkylene glycol, diol type polyoxyalkylene glycol, triol type polyoxyalkylene glycol, monool block type polyalkylene glycol, diol block type Polyalkylene glycols and glycols such as random type polyalkylene glycols, primary linear alcohol ethoxylates such as octylphenol ethoxylates, oleyl alcohol ethoxylates, and lauryl alcohol ethoxylates and secondary linear alcohol ethoxylates , And alkyl alcohol ethers such as polynuclear phenol ethoxylate, polyoxyethylene rosin ester, poly Alkoxy polyoxyethylene lauryl ester, polyoxyethylene oleyl ester,
And polyoxyalkylene alkyl esters such as polyoxyethylene stearyl ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan dilaurate, sorbitan dipalmitate, sorbitan distearate, sorbitan sesquilaurate, Sorbitan sesquipalmitate, sorbitan fatty acid esters such as sorbitan sesquistearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan dilaurate, poly Oxyethylene sorbitan dipalmitate, polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan ces Polyoxyethylene sorbitan esters such as laurate, polyoxyethylene sorbitan sesquipalmitate, and polyoxyethylene sorbitan sesquistearate, saturated fatty acid methyl ester, unsaturated fatty acid methyl ester, saturated fatty acid butyl ester, unsaturated fatty acid butyl ester, saturated Fatty acid stearyl ester, unsaturated fatty acid stearyl ester, saturated fatty acid octyl ester, unsaturated fatty acid octyl ester, stearic acid polyethylene glycol ester,
Fatty acid esters such as oleic acid polyethylene glycol ester and rosin polyethylene glycol ester, fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid, myristic acid, and amide compounds of these fatty acids, polyoxyethylene lauryl amine, Polyoxyethylene alkylamines, polyoxyethylene alkylamines such as polyoxyethylene alkylamine ethers, higher fatty acid monoethanolamides such as lauric acid monoethanolamide and coconut fatty acid diethanolamide, higher fatty acid diethanolamides, polyoxyethylene Amide compounds such as stearic acid amide, coconut diethanolamide (1-2 type / 1-1 type), and alkylalkylolamide and alkanolamides, etc. _{R- (CH 2 CH 2 O)} m H (CH 2 C
H ₂ O) _n H and R—NH—C ₃ H ₆ —NH ₂ [R = oleyl octyl dodecyl tetradecyl hexadecyl.
Octadecyl, coconut, beef tallow, soybean, etc.], alkanolamines represented by the general formula R-NH ₂ [R = oleyl.
Octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, coconut, beef tallow, soybean, etc.], a primary amine represented by the general formula R1R2-NH [R1R2 = R = oleyl octyl dodecyl tetradecyl hexadecyl octadecyl coconut・ Beef tallow, soybean, etc.], secondary amines, general formula R1R2R3N [R1, R2, R
3 = oleyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, coconut, beef tallow, soybean, etc.], various synthetic and various natural higher alcohols, acrylic acid compounds, and polycarboxylic acid compounds Examples include polymers, oligomers and the like such as compounds, hydroxy fatty acid oligomers, and modified hydroxy fatty acid oligomers.

Examples of the anionic surfactants include polycarboxylic acid type polymer activators, polycarboxylic acid type anion activators, special fatty acid soaps, carboxylic acid salts such as rosin soaps, castor oil sulfate ester salts, and lauryl. Alcohol sulfate Na salt, lauryl alcohol sulfate amine salt, natural alcohol sulfate Na
Salts and alcoholic sulfuric acid ester salts such as higher alcohol sulfuric acid sodium salt, lauryl alcohol ether sulfuric acid amine salt, lauryl alcohol ether sulfuric acid ester Na salt, synthetic higher alcohol ether sulfuric acid amine salt, synthetic higher alcohol ether Sulfate Na salt, alkyl polyether sulfate amine salt, alkyl polyether sulfate N
a salt, natural alcohol EO (ethylene oxide) addition system sulfate ester amine salt, natural alcohol EO (ethylene oxide) addition system sulfate ester Na salt, synthetic alcohol EO (ethylene oxide) addition system sulfate ester amine salt, synthetic alcohol EO (ethylene oxide) addition system Sulfate Na salt, alkylphenol EO (ethylene oxide) addition type sulfate amine salt, alkylphenol EO (ethylene oxide) addition type sulfate Na salt, polyoxyethylene nonylphenyl ether sulfate amine salt, polyoxyethylene nonylphenyl ether sulfate Na salt , Polyoxyethylene polycyclic phenyl ether sulfate amine salt, and polyoxyethylene polycyclic phenyl ether sulfate Na salt, etc. Acid ester salts, various alkylallylsulfonic acid amine salts, various alkylallylsulfonic acid Na salts, naphthalenesulfonic acid amine salts, naphthalenesulfonic acid Na salts, various alkylbenzenesulfonic acid amine salts, various alkylbenzenesulfonic acid Na salts, naphthalenesulfonic acid condensation And sulfonates such as naphthalene sulfonic acid formalin condensate, polyoxyethylene nonylphenyl ether sulfonic acid amine salt, polyoxyethylene nonyl phenyl ether sulfonic acid Na
Salt, polyoxyethylene special allyl ether sulfonic acid amine salt, polyoxyethylene special allyl ether sulfonic acid Na salt, polyoxyethylene tridecyl phenyl ether sulfonic acid amine salt, polyoxyethylene tridecyl phenyl ether sulfonic acid Na salt, polyoxy Polyoxyalkylene-based sulfonates such as ethylene alkyl ether sulfonate amine salt and polyoxyethylene alkyl ether sulfonate Na salt, dialkyl sulfosuccinate amine salt, dialkyl sulfosuccinate Na salt, polycyclic phenyl polyethoxy sulfosuccinate Amine salt, polycyclic phenyl polyethoxysulfosuccinate Na salt, polyoxyethylene alkyl ether sulfosuccinic acid monoester amine salt, and polyoxyethylene alky Ruthenium sulfosuccinate monoester Na salt and other sulfosuccinate salts, alkyl phosphates, alkoxyalkyl phosphates, higher alcohol phosphates, higher alcohol phosphates, alkylphenol phosphates, aromatic phosphates , Phosphoric acid esters such as polyoxyalkylene alkyl ether phosphoric acid ester, and polyoxyalkylene alkyl allyl ether phosphoric acid ester, and phosphoric acid salts.

Examples of the cationic surfactant include the general formula RN (CH ₃ ) ₃ X [R = stearyl / cetyl / lauryl / oleyl / dodecyl / coconut / soybean / beef tallow / X =
Alkyltrimethylamine-based quaternary ammonium salts represented by halogen, amine, etc., quaternary ammonium salts such as tetramethylamine-based salts and tetrabutylamine salts, general formula (RNH ₃ ) (CH ₃ COO) [R = stearyl cetyl. Lauryl, oleyl, dodecyl, coconut, soybean, beef tallow, etc.], lauryl dimethyl benzyl ammonium salt (halogen, amine salt, etc.), stearyl dimethyl benzyl ammonium salt (halogen, amine salt, etc.), and dodecyl dimethyl benzyl ammonium Benzylamine-based quaternary ammonium salts such as salts (halogen / amine salts, etc.), and general formula R (CH ₃ ) N (C ₂ H ₄ O) _m H (C ₂ H ₄ O) _n · X [R
= Stearyl, cetyl, lauryl, oleyl, dodecyl, coconut, soybean, beef tallow, etc./X=halogen, amine, etc.] and the like.

As the amphoteric surfactant, various betaine type surfactants, various imidazoline type surfactants, β
-Alanine type surfactants, polyoctyl polyaminoethylglycine hydrochloride and the like.

As the protective colloid agent, various protective colloid agents which can be dissolved in the dispersion medium or mixed in a dispersed state can be used. For example,
Examples thereof include, but are not limited to, polyvinyl alcohol, styrene-maleic anhydride copolymer, and partial hydrolysates thereof.

Further, in the recording medium of the present invention, a photosensitive recording material obtained by mixing the capsules for developing each color is coated on a support such as paper, glass and film together with a binder if necessary, It can be obtained by providing a protective layer or the like. The color recording layer obtained by coating is 1
It may be a layer, or two or more color recording layers may be laminated.

The binder material is the same material as the wall material of the microcapsule, or polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl alcohol, polyethylene oxide. , Polypropylene oxide, ethylene-vinyl alcohol copolymer, polyacetal, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, phenol resin, fluororesin, silicone resin, diene resin, polystyrene thermoplastic elastomer, polyolefin thermoplastic elastomer, polyurethane -Based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyphenylene ether, polyphenylene sulphate I de, polyether sulfone, polyether ketone, polyarylate, aramide,
Polyimide, poly-p-phenylene, poly-p-xylene, poly-p-phenylene vinylene, polyhydantoin, polyparabanic acid, polybenzimidazole, polybenzothiazole, polybenzoxadiazole, polyquinoxaline, arabia gum, gelatin, polyvinylpyrrolidone , Casein, styrene-butadiene rubber, polyvinyl acetate, polyacrylic acid ester, ethylene-vinyl acetate copolymer, or a mixture thereof, and various emulsions thereof can be used. In order to effectively apply an electric field to the capsule particles, a material having a dielectric constant equal to or higher than that of the dispersion medium is preferably used as the binder material. It is also possible to add the above-mentioned materials such as alcohol, ketone or carboxylate to the binder material as the dielectric constant adjusting agent.

The recording medium of the present invention may be provided with a protective layer on the color recording layer in order to improve light fastness. The protective layer is preferably coated with an emulsion of a water-soluble polymer or a hydrophobic polymer.

In the present invention, if necessary, an intermediate layer may be provided between the color recording layer and the support or between the laminated color recording layers in order to improve color reproducibility. As these materials, it is preferable to apply an emulsion of a water-soluble polymer or a hydrophobic polymer.

The support used in the present invention is, for example, paper, high quality paper, paper such as coated paper, polyester,
Polyethylene, polypropylene, acetyl cellulose,
In addition to films and resins such as polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, and polyimide, synthetic paper composed of paper and resins, and inorganic materials such as metal and glass. A conductive material may be mixed with these materials, and a material obtained by applying a conductive material or vapor-depositing a metal on these materials can be used. An example is a polyester film with aluminum vapor-deposited.

A bar coater, a roll coater, a blade coater, an air knife coater or the like can be used to coat the support with the photosensitive recording material of the present invention.

In the recording method of the present invention, the light used may be visible light, infrared light, or ultraviolet light, and these photosensitive wavelengths can be adjusted by selecting the material.
In recording on a color recording material using a plurality of electrophoretic microcapsules of the present invention, it is preferable to use light in the wavelength region of 300 nm to 900 nm, from the viewpoint of device and energy consumption, and 400 nm to 800 nm.
More preferably, light in the wavelength range of nm is used. Therefore, it is preferable that the visible light polymerization initiator or the wavelength sensitizer used has the maximum value of the absorption spectrum in the wavelength range of 400 nm to 800 nm.

In the recording method of the present invention, a corona charger, a roller type voltage applying device, a sandwich type electrode or the like can be used as a voltage applying means. However,
The voltage applying means is not limited to these.

In the recording method of the present invention, a halogen lamp, a helium xenon lamp, a mercury xenon lamp, a metal halogen lamp, a fluorescent lamp, a light emitting diode, a semiconductor laser or the like can be used as a light source for exposure. A color filter and an interference filter may be used together to adjust the wavelength and the amount of light. However, the light source is not limited to these.

As a device used for recording using the recording material of the present invention, the voltage applying device and the exposure light source may exist as separate devices as independent processes, but both the voltage applying device and the exposure light source may be present. You may use the printing apparatus which mounted at least.

[0097]

EXAMPLES Example 1 (1) Preparation of Electrophoresis Microcapsules Photopolymerization Initiator (Ciba Geigy, Irgacure 18)
100% of a mixture of neopentyl glycol diacrylate containing 5% of 4) and trimethylolpropane triacrylate, and an oil-soluble dye (CI Solvent B
Lue 35) was dissolved to obtain a blue colored solution. To this solution, pigment-dispersed fine particles (Sekisui Plastics Co., Ltd., Techpolymer MB30X-5 White) 1
0.0 g was added and stirred for about 30 minutes to obtain an electrophoretic particle liquid (A1 liquid). The volume median diameter of the electrophoretic particles was about 5 μm.

Next, a partial hydrolyzate of styrene-maleic anhydride copolymer (trade name: Scripset-520 /
(Manufactured by Monsanto Co., Ltd.) was dissolved in 190 parts of distilled water, and a small amount of sodium hydroxide was added to adjust the pH to 4.6. The solution A1 was added to this solution and emulsified and dispersed. Next, a melamine-formalin initial polycondensate (trade name: Sumirez Resin 613 / was added to this emulsion.
60 parts of Sumitomo Chemical Co., Ltd. was added. System temperature 75 ℃
After stirring for 2 hours at room temperature, the solution was cooled to room temperature to obtain a slurry of microcapsules (B1). The volume median diameter of the microcapsules was about 50 μm.

(2) Recording medium using electrophoretic microcapsules 20 g of electrophoretic microcapsules (B1) prepared above was added to 80 g of a 5% polyvinyl alcohol aqueous solution to prepare a dispersion liquid. This dispersion is subjected to the bar coating method,
It was applied on a 200 μm thick aluminum vapor-deposited polyester film to obtain a recording medium having a photosensitive layer having a dry film thickness of 60 μm.

(3) Recording using the electrophoretic microcapsule type recording medium Hg- was applied to the recording medium prepared in (2) through a mask for blocking light transmission in a pattern composed of lines and planes.
The mask was removed by performing exposure for 10 minutes using a Xe lamp (light intensity at 350 nm, ² mW / cm ² ). Next, a voltage was applied to the recording medium by a roller type voltage applying device. Then, again using the Hg-Xe lamp (light intensity at 350 nm ² mW / cm ² ) on the entire surface,
It was exposed for 0 minutes and fixed. As a result, a recorded image that faithfully reproduces the information of the mask was obtained.

Example 2 (1) Preparation of Electrophoresis Microcapsules Photopolymerization Initiator (IRGACURE 18 manufactured by Ciba-Geigy)
4) 5% of neopentyl glycol diacrylate containing 100% of oil-soluble dye (CI Solvent)
Blue 35) was dissolved to obtain a blue colored solution. In this solution, hollow particles of crosslinked styrene-acrylic copolymer (SX-866A, manufactured by JSR Corporation) 10.
0 g and 5.0 g of oleic acid were added and stirred for about 30 minutes to obtain an electrophoretic particle liquid (A2 liquid). The volume median diameter of the electrophoretic particles in this liquid was about 8 μm.

Separately, 6 parts by weight of a 2% sodium dodecylbenzenesulfonate solution was added to prepare 64 parts by weight of a 6% by weight gelatin aqueous solution. The solution A2 was added to this solution and emulsified and dispersed using a homogenizer. To the obtained emulsion, 64 parts by weight of 6% arabic gum aqueous solution was added, and
Mixed at 0 ° C. 20 parts by weight of warm water of 40 ° C. was added to this solution, several milliliters of 10% acetic acid aqueous solution was dropped, and the solution was cooled to 5 ° C. After that, a few milliliters of 30% formalin was added to this solution, a sodium hydroxide solution was added so that the pH value of the solution was 9, and the temperature rising rate was 1 ° C /
In minutes, the temperature was raised to 50 ° C. The solution was cooled to room temperature to obtain a slurry of microcapsules (B2) having gelatin as a wall material. Volume median diameter of microcapsules is about 55 μm
Met.

(2) Recording medium using electrophoretic microcapsules 20 g of the electrophoretic microcapsules (B2) prepared above was added to 80 g of a 5% polyvinyl alcohol aqueous solution to prepare a dispersion liquid. This dispersion was applied to a 200 μm thick aluminum vapor-deposited polyester film by a bar coating method to obtain a recording medium having a photosensitive layer having a dry film thickness of 70 μm.

(3) Recording using the electrophoretic microcapsule type recording medium The recording medium prepared in (2) is cut out in a pattern composed of lines and planes and passed through a mask which blocks transmission of light. , Hg-Xe lamp (light intensity at 350 nm, ² mW / cm ² ) was used for exposure for 10 minutes to remove the mask. Next, the surface of the recording medium was positively charged by a corona charger. Subsequently, the Hg-Xe lamp (light intensity at 350 nm 2
mW / cm ² ) was used for 10 minutes of exposure and fixing. As a result, a recorded image that faithfully reproduces the information of the mask was obtained.

Example 3 100 g of a mixture of neopentyl glycol diacrylate and 2-ethylhexyl acrylate containing 5% of a photopolymerization initiator (Irgacure 184, manufactured by Ciba-Geigy), which was colored yellow with a coumarin dye, was added to phthalocyanine. -Based pigment (Dainippon Ink and Chemicals, Inc.) 10.0
g were mixed. Then, 2 μm zirconia beads 30
pulverize and disperse with a paint shaker for 2 hours,
An electrophoretic particle solution was obtained. The volume median diameter of the electrophoretic particles was about 1.7 μm. A recording medium was manufactured in the same manner as in Example 1 except for the above.

A Hg-Xe lamp (light intensity at 350 nm, ² mW / cm ² ) was cut through the produced recording medium in a pattern composed of lines and planes and passed through a mask for blocking light transmission. Exposure for 10 minutes,
I removed the mask.

Next, the surface of the recording medium was positively charged by a corona charger. Then, again, an Hg-Xe lamp (light intensity at 350 nm of 2 mW / cm was again applied to the entire surface.
² ) was used to perform exposure for 10 minutes to fix. As a result, a recorded image that faithfully reproduces the information of the mask was obtained.

Example 4 In Example 1, Irgacure 18 manufactured by Ciba-Geigy
Instead of a mixture of neopentyl glycol diacrylate containing 5% of 4 and trimethylolpropane triacrylate, trimethylolpropane triacrylate containing 5% by weight of 2,4-trichloromethyl (piperonyl) -6-triazine and tetrachloroethylene Recording was carried out in the same manner as in Example 1 except that 100 g of the mixture of Example 1 and a squalilium dye (manufactured by Hayashibara Biological Laboratory Co., Ltd.) having an absorption peak at 650 nm were used as the dye for wavelength sensitization and the dye for dispersion medium coloring. A medium was prepared.

The recording medium produced was cut out in a pattern composed of lines and surfaces, and a 300 W halogen lamp was passed through a 300 W halogen lamp to 500 nm through a mask for blocking the transmission of light.
Light that passes through a filter that cuts light of the following wavelengths and an interference filter that has a transmission peak at 650 nm (2 mW / c
m ² ) was used for 10 seconds of exposure, and the mask was removed. Next, with the corona charger, on the surface of the recording medium,
A positive charge was applied. Then, again, 300 over the entire surface
It was fixed by exposing it for 15 seconds using a W halogen lamp. As a result, a recorded image that faithfully reproduces the information of the mask was obtained.

Example 5 (1) Preparation of Electrophoresis Microcapsules for Cyan Color 100 g of a mixture of neopentyl glycol diacrylate and trimethylolpropane triacrylate was added to a dispersion medium for coloring and wavelength sensitizing dye at 660 nm. 1.0 g of a cyanine dye having a specific absorption peak (manufactured by Hayashibara Biochemical Laboratory Co., Ltd.) and 5 g of 2,4-trichloromethyl (piperonyl) -6-triazine as a photopolymerization initiator were dissolved. To this solution, 10.0 g of pigment-dispersed fine particles (volume median particle diameter: 1.5 μm) obtained by mixing titanium dioxide with low-molecular-weight polyethylene (Allied Signal AC-617A) and grinding were added, and stirred for about 30 minutes. hand,
An electrophoretic microcapsule solution (A5C solution) was obtained.

Separately, a styrene-maleic anhydride copolymer (trade name: Scripset-520 / manufactured by Monsanto Co.) was dissolved with a small amount of sodium hydroxide to prepare 5
200 parts by weight of an aqueous solution having a pH of 4.6 was prepared. The A5C solution was added to this solution, and this was emulsified.
Dispersed. Next, a melamine-formalin initial polycondensate (trade name: Sumirez Resin) was added to this emulsion.
613 / Sumitomo Chemical Co., Ltd. 60 parts was added. After stirring the system at 75 ° C. for 2 hours, the solution was cooled to room temperature to obtain a slurry of cyan electrophoretic microcapsules (C). The volume median diameter of microcapsules is about 18
was μm.

(2) In preparation of electrophoretic microcapsules for magenta color (1), instead of the squarylium dye having an optical absorption peak at 660 nm, a merocyanine dye having an optical absorption peak at 540 nm (Hayashibara Biochemical A slurry of magenta electrophoretic microcapsules (M) was obtained in the same manner as above except that the slurry was used. The volume median diameter of the microcapsules was about 20 μm.

(3) In the preparation (1) of the electrophoretic microcapsules for yellow color, instead of the squarylium dye having an optical absorption peak at 660 nm, a coumarin dye having an optical absorption peak at 430 nm (Hayashibara Biochemistry A slurry of yellow electrophoretic microcapsules (Y) was obtained in the same manner except that a laboratory-made product was used. The volume median diameter of the microcapsules was about 18 μm.

(4) Recording medium using electrophoretic microcapsules 20 g of each of the electrophoretic microcapsules Y, M, and C prepared in (1) to (3) above was added to 240 g of a 5% polyvinyl alcohol aqueous solution to form capsules. Were mixed with stirring so that the mixture was uniformly dispersed. This dispersion was applied to a 200 μm thick aluminum vapor-deposited polyester film by a bar coating method to obtain a recording medium having a photosensitive layer having a dry film thickness of 40 μm.

(5) Recording by Electrophoresis Microcapsule Type Recording Medium Next, the result of the image forming experiment using the obtained recording medium will be described.

The obtained recording medium was exposed at 1 mJ / cm ² for each of red light, green light, and blue light emitting diodes (LEDs) having an image signal. After that, voltage 10
An image was obtained by applying a voltage with a roller-type voltage applying device set to 0V. Next, light irradiation with a fluorescent lamp was carried out for 10 seconds to fix. At this time, the image formed on the recording medium is
It was a clear color image.

Example 6 (1) Preparation of electrophoretic microcapsules for black In Example 1 (1), Solvent Red 1 was used as the coloring pigment for the dispersion medium.
1 g of 25, Solvent Blue (Solvent B
lue) 67 g, Solvent Yellow (Solv)
ent Yellow) 25 and 1 g of Irgacure 184 (manufactured by Ciba Geigy) as a photopolymerization initiator were used in the same manner to obtain a slurry of black electrophoretic microcapsules (K). The volume median diameter of the microcapsules was about 22 μm.

(2) Recording medium using electrophoretic microcapsules Electrophoretic microcapsules Y, M, C and electrophoretic microcapsules K produced in the same manner as in Examples 5 (1) to (3) were prepared. Each was added to 20 g and 300 g of a 5% polyvinyl alcohol aqueous solution, and mixed by stirring so that the capsules were uniformly dispersed. This dispersion was applied to a 200 μm thick aluminum vapor-deposited polyester film by a bar coating method to obtain a recording medium having a photosensitive layer having a dry film thickness of 40 μm.

(3) Recording by Electrophoresis Microcapsule Type Recording Medium Next, the result of an image forming experiment using the obtained recording medium will be described.

First, exposure was performed at 1 mJ / cm ² using red light, green light, and blue light LEDs each having an image signal.
Furthermore, in order to control the electrophoretic microcapsules K,
UV light of 350 nm wavelength with image signal 1 mJ / cm
Exposed at ² . After that, a voltage was applied with a roller type voltage applying device set to a voltage of 100 V to obtain an image. Next,
Hg-Xe lamp (light intensity at 350 nm 2 mW / cm
^{In 2} ), it was fixed by exposing it for 15 seconds. At this time, the image formed on the recording medium was a clear color image.

[0121]

According to the first photosensitive recording material of the present invention,
Writing is possible by light because it contains at least microcapsules containing electrophoretic particles colored in a predetermined color and a dispersion medium that is colored in a color different from that of the electrophoretic particles and that is thickened or hardened by light. It is possible to provide a photosensitive recording material having excellent resolution, low color energy consumption, high resolution, and low energy consumption.

According to the second photosensitive recording material of the present invention, in the first photosensitive recording material, since the electrophoretic particles are charged white particles, the contrast with the colored portion after recording is improved. There is an effect of improving the visibility.

According to the third photosensitive recording material of the present invention, in the first or second photosensitive recording material, since the dispersion medium contains a polymerizable compound, physical changes such as structure and morphological changes due to light irradiation. Alternatively, the dispersion medium can be thickened, gelled or cured by a chemical reaction, a chemical change such as a physicochemical bond, or the like.

According to the fourth photosensitive recording material of the present invention, in the third photosensitive recording material, since the polymerizable compound is an acrylic compound, the photosensitivity is high, and the photosensitive wavelength can be selected by a wavelength sensitizer or the like. The effect is that there is freedom.

According to the fifth photosensitive recording material of the present invention, in addition to the first, second, third or fourth photosensitive recording material,
Since it contains a photopolymerization initiator, or a photopolymerization initiator and a wavelength sensitizer, the polymerization reaction by irradiation of light proceeds, and the wavelength sensitizer has the effect of adjusting the wavelength of the photopolymerization initiator. is there.

According to the sixth light-sensitive recording material of the present invention, in the first, second, third, fourth or fifth light-sensitive recording material, visible light polymerization initiation having a maximum value of absorption spectrum in the wavelength range of 400 nm to 800 nm is started. Since it contains an agent or a wavelength sensitizer, it is possible to obtain a photosensitive recording material capable of recording with low energy consumption.

According to the seventh photosensitive recording material of the present invention, in the first, second, third, fourth, fifth or sixth photosensitive recording material,
Encapsulating at least a dispersion medium colored in any of the three primary colors of cyan, magenta, and yellow, or three primary colors of red, green, and blue, and electrophoretic particles colored in a color different from the color of the dispersion medium. Since at least three types of microcapsules are included, full-color expression is possible.

According to the eighth photosensitive recording material of the present invention, in addition to the seventh photosensitive recording material, a dispersion medium colored in black and electrophoretic particles colored in a color different from the black are further added. Full-color expression is possible because it contains microcapsules.

According to the ninth photosensitive recording material of the present invention, in the seventh or eighth photosensitive recording material, at least 3
Since each of the types of microcapsules contains a photopolymerization initiator having an absorption spectrum maximum at a different wavelength, or a photopolymerization initiator and a wavelength sensitizer having an absorption spectrum maximum at a different wavelength, The capsules are sensitive to light of different wavelengths, enabling full-color expression.

According to the first photosensitive recording medium of the present invention, the first, second, third, fourth, fifth, sixth, seventh, eighth or ninth photosensitive recording material is coated on a support. Therefore,
It is possible to provide a recording medium that is writable by light, has excellent coloring properties, does not cause background coloring, and has high resolution and low energy consumption.

According to the first recording method of the present invention,
Since the recording method includes a step of irradiating the photosensitive recording material of 2, 3, 4, 5, 6, 7, 8, 9 or the first photosensitive recording medium with light, and a step of subsequently applying a voltage. It is possible to provide a high-resolution, low-energy recording method that is excellent in color development and has no background color.

According to the second recording method of the present invention, in the first recording method, since the irradiation light is light having three or more different wavelengths, a capsule having sensitivity to light having different wavelengths is used. Using, full color expression is possible.

According to the third recording method of the present invention, the first or second recording method further includes the step of irradiating light, so that the inclusion of microcapsules is further thickened or partially Alternatively, the whole can be cured and fixed.

[Brief description of drawings]

FIG. 1 is a schematic view showing an embodiment of a microcapsule used in the present invention.

FIG. 2 is a schematic diagram showing a state of a microcapsule used in the present invention before and after voltage application.

FIG. 3 is a schematic view showing an example of a microcapsule color developing material used in the present invention.

FIG. 4 is a schematic diagram showing an embodiment of a recording medium of the present invention.

FIG. 5 is a schematic diagram showing an embodiment of a recording medium of the present invention.

FIG. 6 is a schematic view showing an embodiment of a recording medium of the present invention.

FIG. 7 is a schematic diagram illustrating a recording principle using the recording medium of the present invention.

[Explanation of symbols]

1 microcapsule, 1Y yellow microcapsule, 1M magenta microcapsule, 1C cyan microcapsule, 2 electrophoretic particles, 2a white pigment particles, 2b color pigment particles, 3 dispersion medium, 3a colorless dispersion medium, 3b color dispersion medium 4 microcapsule wall, 5 support, 6B blue light, 6R red light, 6G green light, 7 light.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AB00 AC01 AD01 AD03 BC32                       BC42 CA00 CC12 CC13 CC20                       DA10 FA03 FA14 FA30                 2H096 AA00 BA05 BA20 EA02 GA60                       HA03

Claims (13)

[Claims] 1. A photosensitive recording comprising at least a microcapsule containing electrophoretic particles colored in a predetermined color and a dispersion medium colored in a color different from that of the electrophoretic particles and thickened or cured by light. material. 2. The photosensitive recording material according to claim 1, wherein the electrophoretic particles are charged white particles. 3. The photosensitive recording material according to claim 1, wherein the dispersion medium contains a polymerizable compound. 4. The photosensitive recording material according to claim 3, wherein the polymerizable compound is an acrylic compound. 5. The photosensitive recording material according to claim 1, further comprising a photopolymerization initiator, or a photopolymerization initiator and a wavelength sensitizer. 6. The photosensitive recording material according to claim 1, which further comprises a visible light polymerization initiator or a wavelength sensitizer having a maximum absorption spectrum in the wavelength range of 400 nm to 800 nm. 7. A dispersion medium colored at least in any of the three primary colors of cyan, magenta, and yellow, or in the three primary colors of red, green, and blue, and electricity colored in a color different from the color of the dispersion medium. 3. At least three types of microcapsules containing electrophoretic particles are included.
The light-sensitive recording material described in 3, 4, 5 or 6. 8. The photosensitive recording material according to claim 7, further comprising microcapsules containing a dispersion medium colored black and electrophoretic particles colored a color different from the black. 9. Each of the at least three types of microcapsules has a photopolymerization initiator having an absorption spectrum maximum value at a different wavelength, or a photopolymerization initiator and a wavelength increasing agent having an absorption spectrum maximum value at a different wavelength. 9. The photosensitive recording material according to claim 7, which contains a sensitizer. 10. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A photosensitive recording medium obtained by coating the photosensitive recording material according to 8 or 9 on a support. 11. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A recording method comprising: a step of irradiating the photosensitive recording material according to claim 8 or 9 or the photosensitive recording medium according to claim 10 with light; and subsequently applying a voltage. 12. The recording method according to claim 11, wherein the irradiation light is light having three or more kinds of different wavelengths. 13. The recording method according to claim 11, further comprising the step of irradiating with light.