JP2006106452A - Forming method of original plate for forming single particle film and single particle film and electrophoresis display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide forming methods of an original plate for forming a single particle film by arranging particles and the single particle film wherein particles using the original plate come close to each other and to provide an electrophoresis display device wherein high quality display is made possible. <P>SOLUTION: In the original plate having a base body and a plurality of recessed parts arranged in one surface of the base body, relations of d≤D≤1.5d, d≤P and 0.1d≤S≤1.5d are satisfied when an aperture diameter of the recessed part, arrangement pitch of the recessed parts, depth of the recessed part and average particle diameter are defined as D (μm), P (μm), S (μm) and d (μm), respectively. The particles are transferred onto an adhesive layer of a thermally shrinkable film in a single particle film state using the original plate, the thermally shrinkable film is thermally shrunk to form a transfer sheet and the particles on the adhesive layer of the transfer sheet are transferred to a body to be formed to form the single particle film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an original plate for making particles into a single particle film, for example, an original plate for making particles having an average particle diameter in the range of 10 to 100 μm into a single particle film, and a single particle film using this original plate. The present invention relates to a forming method and an electrophoretic display device using a microcapsule containing electrophoretic particles and a dispersion medium as an electrophoretic display element.

Examples of a method for forming a single particle film by arranging particles on the surface of the object to be formed include, for example, a method in which particles are dispersed on an object to be formed on which an adhesive layer has been previously formed and scraped with a blade. There is a method in which the liquid is uniformly applied on the object to be formed and dried.
In addition, as a method of forming a single particle film with a desired pattern, a photothermal conversion layer is provided on a substrate, and a coating liquid in which particles are dispersed in a binder is uniformly applied on the photothermal conversion layer to form a particle layer. There is a method using a formed transfer sheet. In this method, a laser beam is applied to a desired part from the substrate side, or heat is supplied by a thermal head, with the transfer sheet placed on the formed body so that the particle layer contacts the formed body. To do. As a result, the binder is melted in the particle layer at the above-mentioned part, and the particles are transferred together with the binder in a desired pattern onto the object to be formed.

On the other hand, in recent years, a microcapsule containing electrophoretic particles and a dispersion medium is sandwiched between two electrodes as an electrophoretic display element, and a voltage is applied to the electrophoretic display element, so that the electrophoretic particles move inside the microcapsule. An electrophoretic display device using a phenomenon of electrophoresis toward electrodes having different polarities has been developed (Patent Documents 1 and 2). In this electrophoretic display device, an electrophoretic display element layer is formed by uniformly applying a coating liquid in which microcapsules are dispersed on an electrode and drying it.
In the electrophoretic display device as described above, color display can be performed by using microcapsules of each color of yellow, cyan, and magenta as the dispersion medium and sandwiching each color between the electrodes.
JP 2002-357853 A Japanese Patent Laid-Open No. 2002-333643

  However, in the conventional method of forming a single particle film, the inside is different, such as particles made of a uniform material having an average particle diameter in the range of 10 to 100 μm, or microcapsules containing electrophoretic particles and a dispersion medium. It has been difficult to arrange particles including substances having an average particle diameter in the range of 10 to 100 μm in a single particle film state in which the particles are close to the surface of the formed body. For example, in the preparation stage of a coating liquid in which microcapsules are dispersed, the treatment is performed in an aqueous solution in order to facilitate the dispersion and emulsification of electrophoretic particles and the production of microcapsules. As appropriate, polyvinyl alcohol and other water-soluble polymer materials are included. Therefore, the coating liquid containing microcapsules is a water-based thixotropic solution. For this reason, coating characteristics are poor, bubbles are likely to be mixed, and it is difficult to arrange the microcapsules without causing defects. Met. When the microcapsules constituting the electrophoretic display element layer have an arrangement defect, there is a problem that the image quality is deteriorated.

In addition, in the method using the conventional transfer sheet, it is possible to transfer a particle having an average particle diameter in the range of 10 to 100 μm onto the object to be formed in a desired pattern to form a single particle film. It was impossible to transfer and form a single particle film composed of different particles in a desired pattern. This is because the step existing between the already formed single particle film and the object to be formed prevents the single particle film made of different particles from being transferred in close proximity.
Further, in the method using the conventional transfer sheet, sagging of the binder transferred together with the particles in a molten state occurs, and it is difficult to form a single particle film with a high-definition pattern. Thus, it has been a hindrance when a single particle film made of different particles is formed adjacently.

The above-mentioned problem is that the average particle diameter is in the range of 10 to 100 μm, such as particles made of a uniform material, particles containing different substances inside such as microcapsules containing electrophoretic particles and a dispersion medium, etc. The problem with all particles in
Further, the conventional method for forming a single particle film using a transfer sheet has a problem that when the binder is brought into a molten state, the particles are also heated, and depending on the particles, thermal damage occurs. In addition, in a single particle film formed in a desired pattern, there is a problem that, for example, the particles cannot be brought into close contact by being deformed under pressure because the binder exists between the particles.
The present invention has been made in view of the above circumstances, and an original plate for arranging particles to form a single particle film, a method for forming a single particle film in which particles using the original plate approach, and An object of the present invention is to provide an electrophoretic display device capable of high-quality display.

In order to achieve such an object, the present invention, in an original plate for disposing particles in a single particle film state, has a substrate and a plurality of recesses arranged on one surface of the substrate, Between the opening diameter D (μm) of the recesses, the arrangement pitch P (μm) of the recesses, the depth S (μm) of the recesses, and the average particle diameter d (μm), d ≦ D ≦ 1.5d , D ≦ P and 0.1d ≦ S ≦ 1.5d.
As another aspect of the present invention, the adhesive layer is provided in the recess.

  Further, the present invention provides a master for arranging particles in a single particle film state, and has a base and a plurality of through holes arranged in the base, each having a hole diameter D (μm), Between the arrangement pitch P (μm) of the through holes, the thickness T (μm) of the substrate, and the average particle diameter d (μm), d ≦ D ≦ 1.5d, d ≦ P, 0.1d ≦ S ≦ The configuration is such that the relationship of 1.5d is established.

The method for forming a single particle film of the present invention includes a step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate, and one of the heat shrinkable films. Forming a pressure-sensitive adhesive layer on the surface, transferring the particles placed on the original plate onto the pressure-sensitive adhesive layer in a single particle film state, and heating the heat-shrinkable film to heat-shrink to form a substrate And a step of causing the particles on the adhesive layer to approach each other.
As another aspect of the present invention, the original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d.
As another aspect of the present invention, the original plate is configured to have an adhesive layer in the recess.

In the method for forming a single particle film of the present invention, an adhesive layer is formed on one surface of the heat-shrinkable film, an original plate having a plurality of through holes arranged in a substrate is disposed on the adhesive layer, Placing the particles in the through holes of the original plate, then removing the original plate and disposing the particles in a single particle film state on the adhesive layer; and heating and shrinking the heat-shrinkable film Forming a base material, and making the particles on the adhesive layer approach each other.
As another aspect of the present invention, the original plate has a hole diameter D (μm) of the through holes, an arrangement pitch P (μm) of each through hole, a thickness T (μm) of the substrate, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d.

As another aspect of the present invention, the heat shrinkable film is configured to be a uniaxial shrinkable heat shrinkable film.
As another aspect of the present invention, the array of particles in the base material is a stripe array in which the particles are in contact with each other along the heat shrink direction of the heat-shrinkable film. It was set as the structure where a particle | grain non-arrangement area | region exists in the width | variety of the integral multiple of the width | variety.

  The method for forming a single particle film of the present invention includes a step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate, and one of the heat shrinkable films. On the surface, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion layer, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion foam layer and an adhesive layer are formed in this order. Or a step of forming a pressure-sensitive adhesive layer having photothermal conversion foamability, a step of transferring particles placed on the original plate in a single particle film state onto the pressure-sensitive adhesive layer, and the heat-shrinkable film And heat shrinking to form a substrate and bringing the particles on the adhesive layer closer together.

As another aspect of the present invention, the original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d.
As another aspect of the present invention, the original plate is configured to have an adhesive layer in the recess.

  Further, the method for forming a single particle film of the present invention comprises forming a foam layer and an adhesive layer in this order on one surface of a heat-shrinkable film and laminating them, or alternatively, a photothermal conversion layer, a foam layer and an adhesive layer. Forming and laminating in order, or forming and laminating a photothermal conversion foam layer and an adhesive layer in this order, or forming an adhesive layer having photothermal conversion foamability, and a plurality of through holes arranged in the substrate Placing the original plate on the adhesive layer, placing the particles in the through-holes of the original plate, and then removing the original plate and disposing the particles on the adhesive layer in a single particle film state; The heat shrinkable film is heated and thermally contracted to form a base material, and a step of bringing the particles on the adhesive layer closer to each other is provided.

As another aspect of the present invention, the original plate has a hole diameter D (μm) of the through holes, an arrangement pitch P (μm) of each through hole, a thickness T (μm) of the substrate, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d.
As another aspect of the present invention, the heat shrinkable film is a biaxial shrinkable heat shrinkable film.
As another aspect of the present invention, the arrangement of the particles in the transfer sheet is a close-packed hexagonal lattice arrangement or a simple cubic lattice arrangement.

The method for forming a single particle film of the present invention includes a step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate, and one of the heat shrinkable films. Forming a pressure-sensitive adhesive layer on the surface, transferring the particles placed on the original plate onto the pressure-sensitive adhesive layer in a single particle film state, and heating the heat-shrinkable film to heat-shrink to form a substrate At the same time, the method includes a step of preparing a transfer sheet by bringing the particles on the adhesive layer close to each other, and a step of transferring the particles on the adhesive layer of the transfer sheet onto a body to be formed.
As another aspect of the present invention, the original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d.
As another aspect of the present invention, the original plate is configured to include an adhesive layer in the recess.

In the method for forming a single particle film of the present invention, an adhesive layer is formed on one surface of the heat-shrinkable film, an original plate having a plurality of through holes arranged in a substrate is disposed on the adhesive layer, Placing the particles in the through holes of the original plate, then removing the original plate and disposing the particles in a single particle film state on the adhesive layer; and heating and shrinking the heat-shrinkable film A structure comprising: forming a base material; bringing a particle on the pressure-sensitive adhesive layer closer to produce a transfer sheet; and transferring a particle on the pressure-sensitive adhesive layer of the transfer sheet onto a body to be formed It was.
As another aspect of the present invention, the original plate has a hole diameter D (μm) of the through holes, an arrangement pitch P (μm) of each through hole, a thickness T (μm) of the substrate, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d.

As another aspect of the present invention, the heat shrinkable film is configured to be a uniaxial shrinkable heat shrinkable film.
As another embodiment of the present invention, the particle arrangement in the transfer sheet is a stripe arrangement in which the particles are in contact with each other along the heat shrink direction of the heat-shrinkable film, and a stripe arrangement is provided between the stripe arrangements. It was set as the structure where a particle | grain non-arrangement area | region exists in the width | variety of the integral multiple of the width | variety.
As another aspect of the present invention, a plurality of types of transfer sheets having different particle types are prepared, and the stripe-shaped array of particles is transferred onto the object for each transfer sheet.

  The method for forming a single particle film of the present invention includes a step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate, and a heat shrinkable film. On one surface, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion layer, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion foam layer and an adhesive layer are formed in this order. Forming and laminating in order, or forming a pressure-sensitive adhesive layer having photothermal conversion foamability, transferring the particles placed on the original plate in a single particle film state onto the pressure-sensitive adhesive layer, and heat shrinkage Forming a substrate by heating and shrinking the adhesive film to make a transfer sheet by bringing the particles on the adhesive layer closer to each other; Installed and opposed, opposite to the particle placement surface of the substrate of the transfer sheet By supplying light and / or heat to the desired part from the surface, the particles protrude in the direction of the formed body by foaming of the foam layer, the photothermal conversion foam layer or the photothermal conversion foaming adhesive layer of the part And a step of transferring the particles onto the object to be formed to form a single particle film with a desired pattern.

As another aspect of the present invention, the original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d.
As another aspect of the present invention, the original plate is configured to include an adhesive layer in the recess.

  Further, the method for forming a single particle film of the present invention comprises forming a foam layer and an adhesive layer in this order on one surface of a heat-shrinkable film and laminating them, or alternatively, a photothermal conversion layer, a foam layer and an adhesive layer. Forming and laminating in order, or forming and laminating a photothermal conversion foam layer and an adhesive layer in this order, or forming an adhesive layer having photothermal conversion foamability, and a plurality of through holes arranged in the substrate Placing the original plate on the adhesive layer, placing the particles in the through-holes of the original plate, and then removing the original plate and disposing the particles on the adhesive layer in a single particle film state; A step of heating the heat-shrinkable film to heat-shrink to form a base material and making a particle on the adhesive layer approach to make a transfer sheet; The substrate particles of the transfer sheet are opposed to each other with a gap therebetween. Light and / or heat is supplied to a desired part from the surface opposite to the installation surface, and the particles are covered by foaming of the foam layer, the photothermal conversion foam layer, or the photothermal conversion foaming adhesive layer at the part. And a step of projecting in the direction of the forming body and transferring the particles onto the forming body to form a single particle film with a desired pattern.

As another aspect of the present invention, the original plate has a hole diameter D (μm) of the through holes, an arrangement pitch P (μm) of each through hole, a thickness T (μm) of the substrate, and an average particle diameter d (μm). And d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d.
As another aspect of the present invention, the heat shrinkable film is a biaxial shrinkable heat shrinkable film.

As another aspect of the present invention, the arrangement of the particles in the transfer sheet is a close-packed hexagonal lattice arrangement or a simple cubic lattice arrangement.
As another aspect of the present invention, a plurality of types of transfer sheets having different particle types are prepared, and a single particle film is formed in a desired pattern on the formed body for each transfer sheet.

The present invention also provides an electrophoretic display device having an electrophoretic display element layer between electrodes, wherein at least one of the electrodes has a predetermined pattern shape and is a plurality of electrically independent pattern electrodes. The electrophoretic display element layer is an electrophoretic display element in which electrophoretic particles and a dispersion medium are housed in microcapsules, and is brought into a single particle film state on the pattern electrode by the above-described method of forming a single particle film. The color of the dispersion medium of the electrophoretic display element is different for each pattern electrode of each system.
As another aspect of the present invention, the color of the dispersion medium of the electrophoretic display element is at least three kinds of blue, red, and yellow.

  According to the present invention, it is possible to reliably place particles one by one in the recesses or through holes formed in the original plate. In addition, the particles disposed using the original plate on the adhesive layer provided in the heat-shrinkable film are in a single-particle film state, and the heat-shrinkable film is heat-shrinked to provide a single-particle film in which the particles are close to each other. A substrate is obtained. In addition, the particles disposed using the original plate on the adhesive layer provided on the heat-shrinkable film are in a single-particle film state, and the heat-shrinkable film is heat-shrinked to provide a single-particle film in which the particles are close to each other. A transfer sheet is obtained, and the single particle film on the transfer sheet is transferred to an object to be formed, so that a single particle film can be formed. It is possible to form a single particle film with a fine pattern, and it is also possible to make the particles press-deform and adhere to each other, and because the particles are not placed in the melted binder, the particles receive Thermal damage can be minimized.

  In addition, by using a uniaxially shrinkable heat-shrinkable film as the heat-shrinkable film, the particles are arranged in stripes, and between each stripe-like arrangement, the particle non-width is a width that is an integral multiple of the stripe-like arrangement width. It is possible to obtain a base material or a transfer sheet having an arrangement region, and by using such a transfer sheet, a plurality of types of transfer sheets having different particle types are produced, and each transfer sheet has a stripe shape on the formed body. By transferring the arrayed particles, a striped single particle film can be formed adjacent to the already formed striped single particle film.

In addition, when a biaxial shrinkable heat shrinkable film is used as the heat shrinkable film and the transfer sheet can be foamed, only the particles at the desired site are projected and transferred to the object. Therefore, the single particle film can be formed in a desired pattern adjacent to the already formed single particle film.
In addition, on a plurality of electrically independent pattern electrodes of the electrophoretic display device, an electrophoretic display element in which the color of the dispersion medium is different for each pattern electrode is formed as a single particle film by the method for forming a single particle film of the present invention. The electrophoretic particles of the electrophoretic display element are electrophoresed in the microcapsule toward the electrodes having different charges by applying a voltage to the electrophoretic display element layer by the pattern electrode. Color display using the phenomenon becomes high quality with no unevenness.

Embodiments of the present invention will be described below with reference to the drawings.
[Original for forming single particle film]
FIG. 1 is a longitudinal sectional view showing an embodiment of the original plate of the present invention. As shown in FIG. 1, the original plate 1 of the present invention has a base 2 and a plurality of recesses 3 provided on the surface 2 a side of the base 2.

The concave portion 3 constituting the original 1 has a spherical shape, a circular opening diameter D (μm) of the concave portion 3, an arrangement pitch P (μm) of the concave portions 3, a depth S (μm) of the concave portion 3, and a single particle Between the average particle diameter d (μm) of the particles 100 forming the film, d ≦ D ≦ 1.5d, preferably d ≦ D ≦ 1.4d, d ≦ P, 0.1d ≦ S ≦ 1.5d, preferably 0.25d ≦ S ≦ 1.25d. When the above relationship is established among the opening diameter D of the recesses 3, the arrangement pitch P of the recesses 3, the depth S of the recesses 3, and the average particle diameter d of the particles 100, a coating solution containing particles, etc. Is applied to the original plate 1 and the excess coating solution is removed with a blade or the like, the particles can be reliably placed one by one in each recess 3. The lower limit of the arrangement pitch P in the relationship between the arrangement pitch P (μm) of the recesses 3 and the average particle diameter d (μm) of the particles 100 is d ≦ P, but the upper limit is not particularly limited and will be formed. Can be appropriately set according to the pattern shape of the single particle film, the required distance of each particle 100, and the like. Therefore, for example, there may be a region of P = d and a region of P = 5d in the original 1, and a region of P = 2d and a region where the recess 3 is not formed (or P May be present).
In the present invention, the average particle diameter d of the particles 100 is measured according to JIS Z2500.

  FIG. 2 is a longitudinal sectional view showing another embodiment of the original plate of the present invention. As shown in FIG. 2, the original plate 11 includes a base 12 and a plurality of through holes 13 provided in the base 12.

  The through-holes 13 constituting the original plate 11 are through-holes having a circular cross section, the hole diameter D (μm), the arrangement pitch P (μm) of each through-hole 13, the thickness T (μm) of the substrate 12, and a single particle film Between the average particle diameter d (μm) of the particles 100 to be formed, d ≦ D ≦ 1.5 d, preferably d ≦ D ≦ 1.4 d, d ≦ P, 0.1 d ≦ T ≦ 1 .5d, preferably 0.25d ≦ T ≦ 1.25d. The above relationship is established among the hole diameter D of the through holes 13, the arrangement pitch P of the through holes 13, the thickness T of the base body 12, and the average particle diameter d of the particles 100. When the original plate 11 is arranged, a coating solution containing particles is applied to the original plate 11, and the excess coating solution is removed by a blade or the like, the particles can be surely placed in each through-hole 13 one by one. it can. Also in this original plate 11, the lower limit of the arrangement pitch P in the relationship between the arrangement pitch P (μm) of each through-hole 13 and the average particle diameter d (μm) of the particles 100 is d ≦ P, but the upper limit is particularly limited. Rather, it can be appropriately set according to the pattern shape of the single particle film to be formed, the required distance of each particle 100, and the like. Therefore, for example, there may be a region of P = 2d and a region of P = 10d in the original plate 11, and a region of P = 2d and a region where the through hole 13 is not formed (or A region where P is extremely large).

  In the example shown in FIG. 2, the through hole 13 has the same hole diameter on both surfaces of the base 12, but is not limited thereto. That is, it is only necessary that the pore diameter of each surface of the substrate 12 satisfies the above relationship with the average particle diameter, and when only the pore diameter of the surface to which the particles are supplied satisfies the above relationship with the average particle diameter, There is no problem if the pore diameter is larger. Further, the inner wall surface shape of the through hole 13 is not particularly limited.

  For example, as shown in FIG. 3, the recesses 3 in the original plate 1 of the present invention can be a close-packed hexagonal lattice array having a pitch P set in the above range. Moreover, the through-holes 13 in the original plate 11 of the present invention can be a simple cubic lattice array having a pitch P set in the above-mentioned range, for example, as shown in FIG. The arrangement of the recesses 3 and the through holes 13 is merely an example, and the recesses 3 may take a simple cubic lattice arrangement, and the through holes 13 may take a close-packed hexagonal lattice arrangement, or other arrangements.

  The bases 2 and 12 constituting the original plates 1 and 11 are made of glass plate, aluminum, copper, chromium, invar, super invar, 42 iron nickel alloy, kovar, tool steel (SKD11), etc., polyimide, fluororesin Further, organic materials having heat resistance such as polyether ether ketone, polyether sulfone, polysulfone can be used. Further, for the purpose of improving the durability in the repeated use of the original plate, a thin film of chromium, nickel, silicon carbide, titanium nitride or the like may be formed at least on the surfaces 2a and 12a side. Further, the thickness of the base 2 is not particularly limited, and can be appropriately set in consideration of, for example, a material used in a range of 50 μm to 10 mm.

Further, the formation of the recesses and the through holes in the substrate can be performed by an electroforming method, a sand blast method, an excimer laser method, a dry method such as an ion beam method, or a wet method such as an etching solution immersion method.
In addition, the shape of the opening part of the recessed part and through-hole which comprise an original plate is not limited to circular, A polygon more than a triangle, an ellipse etc. may be sufficient, and the opening diameter of a recessed part and the hole diameter of a through-hole are not uniform. If not, the smallest opening diameter and hole diameter satisfy the above relationship.

[Method of forming single particle film]
Next, the method for forming a single particle film of the present invention will be described.
FIG. 5 is a process diagram showing an embodiment of the method for forming a single particle film of the present invention using the above-described original plate 1 for forming a single particle film of the present invention.
In the present invention, first, the particles 100 are placed one by one in each concave portion 3 of the original 1 (FIG. 5A). The particles 100 are placed in the respective recesses 3 by a blade coating method, for example, a method in which the powder 100 in a dry state is dispersed on the original plate 1 and the unnecessary powder 100 is removed by the blade 5. For example, a method in which a dispersion liquid in which is dispersed is applied onto the original plate 1 and unnecessary powder 100 is removed by the blade 5 can be used. In removing the unnecessary powder 100 by the blade 5, it is preferable to set the gap between the blade 5 and the original plate 1 to be less than the average particle diameter d of the powder 100.

Next, an adhesive layer 23 is formed on the heat-shrinkable film 22 ', and this adhesive layer 23 is brought into contact with the particles 100 placed on the original plate 1 (FIG. 5B). By removing, the particles 100 are transferred onto the adhesive layer 23 in a single particle film state (FIG. 5C).
Next, the heat-shrinkable film 22 ′ is heated and thermally shrunk to form the base material 22, and the transfer sheet 21 is produced by bringing the particles 100 on the adhesive layer 23 close to each other (FIG. 5D).

  For example, as shown in FIG. 6A, the heat shrinkage of the heat-shrinkable film 22 ′ described above is performed by sandwiching (releasing) the transfer sheet 21 between a pair of substrates 25 and 27 having release layers 26 and 28. The mold layers 26 and 28 are sandwiched so as to be on the transfer sheet 21 side, heated in this state, and then cooled. In the transfer base material 21 sandwiched between a pair of substrates 25 and 27, the heat-shrinkable film 22 'is thermally contracted by heating on the release layer 28, and the adhesive layer 23 is tacked by heating. The value drops. Accordingly, the particles 100 move between the heat-shrinkable film 22 ′ and the release layer 26 and approach each other (FIG. 6B). The heating rate during heating is preferably set under mild conditions such that unevenness in the thickness direction does not occur in the heat-shrinkable film 22 '. Then, the particle | grains 100 comprise the single particle film hold | maintained at the adhesion layer 23 by cooling to room temperature.

  Examples of the set of substrates 25 and 27 used for the heat shrink treatment as described above include a glass substrate, a metal substrate, a resin substrate, and an alloy substrate. In addition, the release layers 26 and 28 reduce the frictional resistance that hinders the behavior of the heat-shrinkable film 22 ′ that undergoes heat shrinkage and the behavior of the particles 100 due to heat shrinkage stress in the heating and cooling process. is there. The release layers 26 and 28 include, for example, acrylic ester having a long chain alkyl group, vinyl ester, vinyl ether, acrylic amide, maleic acid derivative, allyl ester, etc., and silicone compounds such as polydimethylsiloxane, fluorine compounds, amino acids, etc. It can form using conventionally well-known materials, such as an alkyd compound and a polyester compound. Note that the release layers 26 and 28 are not necessary when both the substrates 25 and 27 have release properties such as a silicone resin substrate.

Next, the particles 100 held on the transfer sheet 21 are brought into contact with the formed body 31 having the adhesive layer 32 formed on the surface, and then the transfer sheet 21 is peeled off, whereby the particles 100 are formed on the formed body 31. Transfer to form a single particle film (FIG. 5E).
In the above-described embodiment, the object to be formed 31 includes the adhesive layer 32 on the surface, but the adhesive layer 32 is not particularly limited. Moreover, when the to-be-formed body 31 has adhesiveness, or when the particle 100 has adhesiveness (the particle 100 exhibits adhesiveness by heating or the like after the arranging step), it is adhesive. Layer 32 is not necessary.
In the above-described embodiment of the method for forming a single particle film, an example in which the original plate 1 is used is shown. However, in the forming method of the present invention, a single particle film can be formed using the original plate 11. In this case, the original plate 11 is disposed on the adhesive layer 23 of the heat-shrinkable film 22 ′. In this state, particles are placed one by one in the through holes 13, and then the original plate 11 is removed and the heat-shrinkable film 22 is removed. The transfer sheet 21 can be produced by heat-shrinking ′.

  Examples of the heat-shrinkable film 22 ′ used in the above-described method for forming a single particle film of the present invention include a uniaxial shrinkage type having a heat shrinkage rate in the range of 1 to 80%, preferably 10 to 50%, or A biaxially shrinkable heat-shrinkable film can be used. As such a heat-shrinkable film, for example, a uniaxially stretched film such as a vinyl chloride resin or a polyester resin, or a biaxially stretched film can be used. In addition, the thermal shrinkage rate in this invention is calculated from the dimensional change of the film before and behind immersion by immersing a 10 cm square film for 10 second in the water bath set to each temperature in the range of 50-100 degreeC, and shrink | contracting it. 10 cm-the length of one side after immersion (cm) / (10 cm) x 100]. In addition, when a heat shrink film is a uniaxially stretched film, it measures about one side parallel to an extending | stretching direction.

  Examples of the vinyl chloride-based resin include, for example, polyvinyl chloride having a number average polymerization degree of 800 to 2500, preferably 1000 to 1800, and a copolymer mainly composed of vinyl chloride (for example, ethylene-vinyl chloride copolymer, Vinyl acetate-vinyl chloride copolymer, vinyl chloride-halogenated olefin copolymer, etc.) or other compatible resins based on these polyvinyl chlorides or vinyl chloride copolymers (for example, polyester resins, epoxies) Resin, acrylic resin, vinyl acetate resin, urethane resin, acrylonitrile-styrene-butadiene copolymer, partially saponified polyvinyl alcohol, etc.) and the like. These may be used alone or in combination of two or more. Can be used in These vinyl chloride resins may be those obtained by known production methods such as bulk polymerization, emulsion polymerization, suspension polymerization, and solution polymerization.

  Moreover, as said polyester-type resin, dicarboxylic acid components, such as aromatic dicarboxylic acid, those ester formation derivatives, aliphatic dicarboxylic acid, and a polyhydric alcohol component are mentioned as a main component, for example. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and 5-sodium sulfoisophthalic acid. Examples of these ester derivatives include derivatives such as dialkyl esters and diaryl esters. Examples of the aliphatic dicarboxylic acid include dimer acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, and succinic acid. Further, an oxycarboxylic acid such as p-oxybenzoic acid, and a polyvalent carboxylic acid such as trimellitic anhydride or pyromellitic anhydride may be used in combination as necessary.

  Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, dimer diol, propylene glycol, triethylene glycol, 1,4-butanediol, neopentyl glycol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,9-nonanediol, Alkylene glycol such as 1,10-decanediol, ethylene oxide adducts of bisphenol compounds or derivatives thereof, trimethylolpropane, glycerin, pentaerythritol, polyoxytetramethylene glycol, polyethylene glycol, etc. It is below. Moreover, although it is not a polyhydric alcohol, epsilon caprolactone can be used similarly. It is preferable to use one or more of the above dicarboxylic acid components and polyhydric alcohol components in combination.

  The thickness of the above-described heat-shrinkable film 22 ′ can be, for example, in the range of 5 to 200 μm, preferably 20 to 100 μm. If the thickness of the heat-shrinkable film 22 ′ is less than 5 μm, the stress at the time of heat-shrinking is weak, and sufficient access of the particles 100 on the adhesive layer 23 may not be obtained. On the other hand, if it exceeds 200 μm, the approach of the particles may be hindered by heat shrinkage strain in the thickness direction.

  The adhesive layer 23 constituting the transfer sheet 21 by the method for forming a single particle film of the present invention preferably has a tack value at room temperature larger than the tack value at 50 to 100 ° C. The adhesive layer 23 has, for example, a tack value at room temperature of 3 to 32, preferably 5 to 20, and a tack value at 50 to 100 ° C. of 2 to 18, preferably 3 to 12. Can be. As a result, the particles 100 placed on the adhesive layer 23 move on the adhesive layer 23 due to the heat shrinkage stress of the heat-shrinkable film 22 ′ at a temperature at which the heat-shrinkable film 22 ′ causes heat shrinkage. It is possible to approach, and in the closest state, the closest packed state is obtained. In addition, the adhesive layer 23 has a temperature at which the tack value decreases (temperature at which particles can move on the adhesive layer 23 due to thermal shrinkage stress) is equal to or lower than the thermal shrinkage start temperature of the above-described heat-shrinkable film 22 ′. Is preferred.

The tack value in the present invention is based on JIS Z0237, using a ball tack tester (VR-5710) manufactured by Ueshima Seisakusho Co., Ltd. A chrome steel ball having a size of 2 is rolled, and the size of the sphere stopped on the adhesive layer is measured as a tack value.
As a material which comprises the above adhesive layers 23, an adhesive, a photocurable peelable adhesive, etc. can be mentioned, for example.
As the pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, or the like can be used.

  The rubber-based adhesive is a polymer (rubber-like substance) having an elastomer as a base polymer, a low glass transition temperature, and a wide rubber range up to a high temperature. Examples of the elastomer include natural rubber, isoprene rubber, styrene butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, butyl rubber, polyisobutylene, silicone rubber, polyvinyl isobutyl ether, chloroprene rubber, nitrile rubber, Examples thereof include graft rubber, recycled rubber, polyvinyl ether, atactic polypropylene, polyester, polyurethane, butadiene rubber and the like. Moreover, you may contain a tackifier, a softening agent, anti-aging agent, a filler etc. other than said elastomer as a structural component of an adhesive.

  Acrylic adhesives are used to improve co-monomer, crosslinkability and adhesion at high glass transition temperature to give adhesion and cohesion to main monomers such as soft acrylate esters with low glass transition temperature that give tackiness. These functional group-containing monomers are copolymerized. Examples of the main monomer include acrylic monomers such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate-methacrylic acid copolymer.

  The photocurable peelable pressure-sensitive adhesive heats and cools the transfer sheet 21 described above, and is then irradiated with light to impart peelability to the pressure-sensitive adhesive layer 23, and easily transfer the particles to the formed body in the transfer step. The purpose is to make it possible. Examples of the photocurable peelable adhesive include, for example, (meth) acrylic acid alkyl esters such as methyl methacrylate, 2-ethylhexyl methacrylate, ethyl acrylate, and butyl acrylate as main monomers, and emulsifiers and deionized water. It can be obtained by adding a polymerization initiator and emulsion polymerization by a usual means. Moreover, adhesive force can be adjusted by selecting a monomer seed | species. Such an acrylic resin emulsion-based photocurable peelable adhesive is selected with a monomer composition such that the glass transition temperature is less than 0 ° C.

The thickness of the pressure-sensitive adhesive layer 23 is smaller than the average particle size of the target particles 100. For example, when the particles having an average particle size in the range of 10 to 100 μm are targeted, The thickness can be set in the range of about 1 to 5 μm. If the thickness of the pressure-sensitive adhesive layer 23 is less than 1 μm, the particles cannot be placed reliably. If the thickness exceeds 5 μm, sufficient proximity of the particles on the pressure-sensitive adhesive layer 23 during heat shrinkage of the heat-shrinkable film 22 ′. May not be obtained, and the transfer of the particles 100 to the object 31 may be hindered.
Here, the behavior of the particles 100 when the transfer sheet 21 is produced by bringing the particles 100 closer by the heat shrinkage of the heat-shrinkable film 22 ′ will be described with reference to FIGS. 7 and 8.

  FIG. 7A is a diagram showing a case where the array of particles 100 transferred onto the adhesive layer 23 of the heat-shrinkable film 22 ′ using the original 1 is a close-packed hexagonal lattice array having a pitch P. . When a uniaxially shrinkable heat-shrinkable film is used as the heat-shrinkable film 22 ', the heat-shrinkable film 22' is uniaxially shrunk (shrink in the direction of arrow a) as shown in FIG. 7B. ) And particle approach in this shrinking direction causes the particles 100 to have a face-centered cubic lattice arrangement in the produced transfer sheet 21. In addition, when a biaxial shrinkable heat shrinkable film is used as the heat shrinkable film 22 ', as shown in FIG. 7C, the heat shrinkable film 22' is biaxially shrunk (in the direction of arrow a). In the transfer sheet 21 produced, the particles 100 take a close-packed hexagonal lattice arrangement.

  FIG. 8A is a diagram showing a case where the array of particles 100 transferred onto the adhesive layer 23 of the heat-shrinkable film 22 ′ using the original plate 1 is a simple cubic lattice array having a pitch P. When a uniaxially shrinkable heat-shrinkable film is used as the heat-shrinkable film 22 ', the heat-shrinkable film 22' is uniaxially shrunk (shrink in the direction of arrow a) as shown in FIG. 8B. ) And the approach of particles in this shrinking direction occurs, and in the produced transfer sheet 21, the particles 100 take a stripe arrangement. In addition, when a biaxial shrinkable heat shrinkable film is used as the heat shrinkable film 22 ', as shown in FIG. 8C, the heat shrinkable film 22' is biaxially shrunk (in the direction of arrow a). (Shrinkage in the direction of arrow b) and particle approach in two orthogonal directions occur, and in the produced transfer sheet 21, the particles 100 take a simple cubic lattice arrangement.

In the present invention, when the particles 100 take a stripe arrangement in the obtained transfer sheet 21 as shown in FIG. 8B, for example, the particles 100 exist between the stripe arrangements as shown in FIG. 8D. When the width W2 of the particle non-arrangement region 24 to be performed is an integral multiple of the stripe arrangement width W1 (twice in the illustrated example), the particles 100 can be transferred to the object 31 as follows.
First, the transfer sheet 21A holding the particles 100A is produced in the same manner as the transfer sheet 21 described above (FIG. 9A). In this transfer sheet 21A, the particles 100A take a stripe arrangement, and a particle non-arrangement region 24 having a width twice as large as the average particle diameter d of the particles 100A exists between the stripe arrangements. In addition, a transfer sheet 21B (not shown) having the same particle non-arrangement region 24 and holding the particles 100B, and a transfer sheet 21C having the same particle non-arrangement region 24 and holding the particles 100C (see FIG. (Not shown).

Next, the particles 100A held on the transfer sheet 21A are brought into contact with the formed body 31 having the adhesive layer 32 formed on the surface, and then the transfer sheet 21A is peeled off, whereby the particles 100A are formed on the formed body 31. Transfer is performed to form a striped single particle film (FIG. 9B).
Next, the particles 100B held in the stripe shape on the transfer sheet 21B are transferred onto the object 31 to be adjacent to the particles 100A already transferred in the stripe shape (FIG. 9C). At the time of this transfer, the stripe-shaped particles 100A that have already been transferred to the object 31 are located in the particle non-arrangement region 24 of the transfer sheet 21B. Therefore, the stripe-shaped single particle film made of the particles 100B is adjacent to the stripe-shaped single particle film 100A made of the particles 100A without being affected by the step between the already transferred particle 100A and the object 31. Can be formed.

  Next, the particles 100C held in a stripe shape on the transfer sheet 21C are transferred onto the object 31 so as to be adjacent to the particles 100A and 100B that have already been transferred in a stripe shape (FIG. 9D). . Even during this transfer, the stripe-shaped particles 100A and particles 100B that have already been transferred to the forming body 31 are located in the particle non-arrangement region 24 of the transfer sheet 21C, and thus the particles 100A and particles 100B that have already been transferred. A stripe-shaped single particle film composed of the particles 100C can be formed adjacent to the stripe-shaped single particle film 100A composed of the particles 100A and the particles 100B without being affected by a step between the substrate 100 and the formation body 31. .

  In this way, each pattern composed of the three types of particles 100A, particles 100B, and particles 100C can be formed adjacent to each other. In addition, there is no restriction | limiting in the number of the kind of particle | grains in the case of forming a single particle film | membrane using such multiple types of particle | grains. Further, in the above-described example, the particles are arranged in a line to form a single stripe array, but the number of particles in the width direction in the stripe array may be two or more.

Next, a method for forming a single particle film of the present invention using the above-mentioned original plate 11 for forming a single particle film of the present invention will be described.
FIGS. 10-12 is process drawing for demonstrating other embodiment of the formation method of the single particle film of this invention.
In the present invention, first, the photothermal conversion layer 43, the foam layer 44, and the adhesive layer 45 are laminated in this order on the heat-shrinkable film 42 ′ (FIG. 10A).
As the heat-shrinkable film 42 ′, those listed as the heat-shrinkable film 22 ′ in the above embodiment can be used.

The photothermal conversion layer 43 is for efficiently converting light irradiated to a transfer sheet produced in a later process into heat. For example, cyanine-based, polymethine-based, azulenium-based, squalium-based in a resin binder , thiopyrylium, naphthoquinone, organic compounds such as anthraquinone dyes, phthalocyanine, azo, those containing an infrared absorbing dye, such as an organic metal complex of a thioamide compound, or iron oxide (Fe ₂ O _3), lead Dan (Pb ₃ O ₄ ), yellow lead (PbCrO ₄ ), silver red (HgS), ultramarine (Na ₆ Al ₆ Si ₆ O ₂₄ S ₄ ), cobalt oxide (CoO or Co ₃ O ₄ ), titanium dioxide (TiO ₂₎ ), mica coated with titanium _{(TiO 2 / K 2 O ·} 3Al 2 O 3 · 6SiO 2 · 2H 2 O dioxide), strontium chromate (SrCrO _4)), titanium Yi Low (nickel yellow, chrome yellow), iron black (Fe ₃ O _4), molybdate orange _{(PbCrO 4 · nPbMoO 4 · mPbSO} 4 · xAl (OH) 3), molybdenum White (ZnMoO ₄ · ZnO or CaZnMoO ₄ · CaCO ₃ ), Lithopone (BaSO ₄ + ZnS), cadmium red (CdS · nCdSe), bronze powder (copper and zinc alloy), aluminum powder, etc. containing metal oxides or carbon black having an absorption band in the near infrared region Or it can be set as the thin film which consists of the said substance single-piece | unit. As said resin binder, the resin binders mentioned in the above-mentioned foamed layer can be used. Moreover, it is preferable to set content of the photothermal conversion substance contained in a resin binder in the range of 0.1-5 weight part with respect to 100 weight part of resin binders.

  The photothermal conversion layer 43 is formed by dissolving a photothermal conversion substance and, if necessary, a crosslinking agent or the like into the above-mentioned resin binder in an appropriate organic solvent, a mixture of an organic solvent and water, or water. Or a dispersed solution or dispersion is prepared, and this is heat-shrinkable at a desired thickness by a known means such as screen printing, gravure coating, gravure reverse coating, air knife coating, etc. It can be formed by coating on the film 42 'and drying. The thickness of such a photothermal conversion layer 43 can be set, for example, in the range of 1 to 100 μm when the photothermal conversion substance is contained in the resin binder, or when the photothermal conversion layer 43 is a thin film of the photothermal conversion substance. Can be set in the range of 0.001 to 10 μm.

  The above-mentioned foamed layer 44 is obtained by adding a foaming agent and, if necessary, a heat conductive material, a crosslinking agent, etc. to the following resin binder, an appropriate organic solvent, a mixture of an organic solvent and water, or water. A solution or dispersion dissolved in or dispersed in the solution is prepared, and this is heated to a desired thickness by a known means such as screen printing, gravure coating, gravure reverse coating, air knife coating, etc. It can be formed by applying on the conversion layer 43 and drying.

  Examples of the blowing agent to be used include azodicarbonamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, N, N′dinitroso-N, N′dimethylterephthalamide, P-toluenesulfonylhydrazide, hydrazolecarbonamide. , P-toluenesulfonyl azide, acetone-based organic foaming agents such as P-sulfonylhydrazone, inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, etc. A microcapsule etc. are mentioned.

  The above-described thermally expandable microcapsule has a capsule structure in which hydrocarbons that volatilize at a low temperature are included in a wall material made of a thermoplastic resin, and is in an unfoamed state by light irradiation (heating) or the like. Volume expansion of about 150 times occurs. Hydrocarbons encapsulated in thermally expandable microcapsules include aliphatics having fluorine atoms such as methyl chloride, methyl bromide, trichloroethane, dichloroethane, n-hexane, n-pentane, isobutane, isoheptane, neopentane, petroleum ether, freon, etc. Hydrocarbons or complex mixtures of these hydrocarbons can be used.

  The wall material of the thermally expandable microcapsule includes vinylidene chloride, vinyl chloride, acrylonitrile, styrene, polycarbonate, methyl methacrylate, ethyl methacrylate, vinyl acetate polymers, or copolymers and mixtures of these resins. Can be used. Moreover, a crosslinking agent can also be used as needed. The average particle diameter of such thermally expandable microcapsules may be, for example, about 0.1 to 50 μm.

  Examples of the resin binder constituting the foam layer 44 include phenoxy resin, vinyl resins such as polyvinyl acetate, polyacrylic acid ester, and polymethacrylic acid ester, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, polyamide, and polyurethane. Acrylonitrile, vinyl chloride-vinylidene chloride copolymer, acrylonitrile-vinylidene chloride copolymer, and rubber resins such as vulcanized rubber and unvulcanized rubber. Examples of the rubber-based resin include chloroprene rubber, fluorine rubber, silicone rubber, synthetic isoprene rubber, butyl rubber, urethane rubber, styrene-butadiene rubber, ethylene-propylene rubber, polyisoprene rubber, butadiene rubber, nitrile rubber, chlorinated butyl rubber, and the like. And unvulcanized rubber such as synthetic rubber and natural rubber, or vulcanized rubber. Particularly preferable examples include polyester, acrylonitrile, vinyl chloride-vinylidene chloride copolymer, and rubber resin.

In the foam layer 44, when the foaming agent contained is foamed by light irradiation (heating) or the like, it is necessary that the foam layer rises accurately at the boundary between the light irradiated (heated) part and another part. For this reason, the number average molecular weight of the binder resin is preferably 1000 to 30000, preferably 3000 to 25000.
In the case of an organic foaming agent or an inorganic foaming agent, the content of the foaming agent in the foam layer 44 is preferably set in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the resin binder. Moreover, when a foaming agent is a thermally expansible microcapsule, it is preferable to set in the range of 5-80 weight part with respect to 100 weight part of resin binders. When the content of the foaming agent is less than the above range, the foamed layer does not sufficiently foam, and when the content exceeds the above range, the foamed layer is ruptured and an accurate protruding shape cannot be formed.

The thickness of the foaming layer 44 containing the foaming agent and binder resin as described above is higher than the size of the particle 100 during foaming in consideration of the foaming agent used, the content of the foaming agent, the size of the particle 100, and the like. It is desirable to set so that it can protrude, for example, it can set in the range of 1-150 micrometers.
The foam layer 44 is made of a material having excellent thermal conductivity, for example, a metal such as copper, aluminum, tin oxide or molybdenum disulfide, a metal oxide, or a carbonaceous material such as metal sulfide or carbon black. May be included.

  Moreover, the above-mentioned adhesive layer 45 can hold the particles 100 to be transferred, and can transfer the particles when the foam layer 44 protrudes by light irradiation (heating) or the like. Such an adhesive layer 45 can be formed using, for example, a slightly adhesive type or a releasable type adhesive. Moreover, it is good also as transferability of the particle | grains 100 with the adhesion layer 45 making the film breakage | shortage of the adhesion layer 45 favorable. The adhesive layer 45 is formed by preparing a solution or dispersion in which the above-mentioned adhesive substance is dissolved or dispersed in a suitable organic solvent, a mixture of an organic solvent and water, or water. For example, it can be formed by applying on the foamed layer 44 with a desired thickness by a known means such as screen printing, gravure coating, gravure reverse coating, air knife coating, and drying. The thickness of the adhesive layer 45 can be appropriately set in consideration of the adhesiveness of the material to be used, the film cutting property, etc., and can be set, for example, in the range of 1 to 10 μm.

  Next, the original plate 11 of the present invention is placed on the adhesive layer 45 (FIG. 10B), and the particles 100 are placed one by one in the through holes 13 of the original plate 11 (FIG. 10C), and thereafter Then, by removing the original 11, the particles 100 are transferred in a single particle film state onto the adhesive layer 45 (FIG. 10D). The particle 100 is placed in each through-hole 13 by a blade coating method, for example, a method in which the powder 100 in a dry state is dispersed on the original plate 11 and the unnecessary powder 100 is removed by the blade 15. A method of applying a dispersion liquid in which 100 is dispersed onto the original plate 11 and removing unnecessary powder 100 with the blade 15 can be used. In removing the unnecessary powder 100 with the blade 15, it is preferable to set the gap between the blade 15 and the original plate 11 to be less than the average particle diameter d of the powder 100.

  Next, the heat-shrinkable film 42 ′ is heated and thermally shrunk to form the base material 42, and the transfer sheet 41 is produced by bringing the particles 100 on the adhesive layer 45 close to each other (FIG. 11A). The heat shrinkage of the heat shrinkable film 42 ′ can be performed, for example, in the same manner as the heat shrinkage of the heat shrinkable film 22 ′ shown in FIG. The behavior of the particles 100 when the transfer sheet 41 is produced by bringing the particles 100 close to each other by the heat shrinkage of the heat-shrinkable film 42 ′ is the same as described above based on FIGS. 7 and 8.

In the following description of the steps, the transfer sheet 41 described above is manufactured for the three types of particles 100A, 100B, and 100C, and three types of transfer sheets 41A, 41B, and 41C (not shown) are manufactured as an example. .
First, the particle arrangement surface of the transfer sheet 41A holding the particles 100A is opposed to the object 51 with a gap, and desired from the substrate 42 side (the surface opposite to the particle arrangement surface) of the transfer sheet 41A. Light and / or heat is supplied to the region 40A (FIG. 11B).

There is no restriction | limiting in particular in the to-be-formed body 51, In the example of illustration, it has the adhesion layer 53 on the one surface of the board | substrate 52. As shown in FIG.
As will be described later, the facing interval between the transfer sheet 41A and the formed body 51 is an interval at which the particles 100A protruding due to the rising of the foam layer 44 due to foaming can come into contact with the formed body 51, and depends on the transfer sheet used. For example, it can set in the range of 10-110 micrometers.
Laser light is used as the light to be supplied to the desired portion 40 </ b> A, and the supplied light is converted into heat by the photothermal conversion layer 43. Moreover, when supplying heat directly to the desired part 40A, a thermal head, an infrared irradiation device, or the like can be used.

By supplying light and / or heat to the desired part 40A as described above, the foaming agent contained in the foamed layer 44 of the transfer sheet 41A is foamed at the part corresponding to the part 40A. As a result, the foamed layer 44 rises, and the particles 100A protrude in the direction of the body 51 to be in contact with the adhesive layer 53 of the body 51 (FIG. 11C). Thereafter, the transfer sheet 41A is removed, whereby the particles 100A are transferred to the object 51 in a single particle state in a desired pattern.
Next, the particle arrangement surface of the transfer sheet 41B holding the particles 100B is opposed to the formation body 51 on which the particles 100A have already been transferred in a single particle state with a gap, and the transfer sheet 41B side of the substrate 42 Light and / or heat is supplied from the (surface opposite to the particle arrangement surface) to the desired portion 40B (FIG. 12A). This part 40B can be a part adjacent to the above-mentioned part 40A.

The facing distance between the transfer sheet 41B and the object 51, and the supply of light and heat to the desired portion 40B are the same as in the case of the transfer sheet 41A.
In the part 40B to which light and / or heat is supplied, foaming of the foaming agent occurs in the part corresponding to the part 40B in the foam layer 44 of the transfer sheet 41B. As a result, the foamed layer 44 rises, and the particles 100B protrude in the direction of the body 51 to be in contact with the adhesive layer 53 of the body 51 (the part adjacent to the particles 100A already transferred in a single particle state) ( FIG. 12 (B)). Thereafter, by removing the transfer sheet 41B, the particles 100B are transferred to the formation target 51 in a single particle state in a desired pattern.

As described above, only the particle 100B at the desired portion 40B can be projected and transferred to the object 51, so that it is not affected by the step between the already formed particle 100A and the object 51. A single particle film made of particles 100B can be formed in a desired pattern adjacent to the single particle film made of particles 100A.
Next, using the transfer sheet 41C (not shown) of the present invention holding the particles 100C, the transfer of the particles 100A and the particles 100B to which the particles 100B are not transferred is performed by the same operation as the transfer of the particles 100B by the transfer sheet 41B described above. The particles 100C are transferred onto the body 51. Thereby, each pattern which consists of the particle | grains 100A, 100B, 100C of a single particle state can be adjacently formed in the adhesion layer 53 of the to-be-transferred body 51 (FIG.12 (C)).

The method for forming a single particle film described above is an example using three types of particles 100A, 100B, and 100C, but the number of types of particles is not limited. Further, instead of the original plate 11, the original plate 1 may be used.
Moreover, there is no restriction | limiting in particular in the magnitude | size of the particle | grains used as the film-forming object by the formation method of the single particle film | membrane of this invention, For example, it may target the particle | grains in the range whose average particle diameter is 10-100 micrometers. The type of particles is not particularly limited, such as particles made of a uniform material, particles such as capsule elements containing different materials inside, and the like.

In the method for forming a single particle film of the present invention as described above, since the binder is not present in the transferred single particle film, it is possible to form a single particle film with a high-definition pattern. Further, since there is no binder between the transferred particles, the particles can be brought into close contact by being deformed under pressure. Furthermore, since the particles are not placed in the melted binder, the thermal damage received by the particles can be minimized.
In the method for forming a single particle film of the present invention, the transfer sheet does not include the photothermal conversion layer 43, the transfer sheet includes a photothermal conversion foam layer instead of the photothermal conversion layer 43 and the foam layer 44, and the photothermal conversion layer 43. Further, instead of the foamed layer 44 and the adhesive layer 45, those having a photothermal conversion foamable adhesive layer, those having a photothermal conversion layer on the back surface of the substrate 42, and the like can also be used.

  The photothermal conversion foam layer can use the resin binder and the foaming agent as mentioned in the above foam layer 44 as the resin binder and foaming agent, and the photothermal conversion layer 43 can be used as the photothermal conversion substance. The photothermal conversion substance mentioned in the above can be used. The content of the foaming agent in the photothermal conversion foamed layer is in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the resin binder, and the content of the photothermal conversion substance is 0.1 to 5 parts with respect to 100 parts by weight of the resin binder. It is preferable to set each in the range of parts by weight. The thickness of such a photothermal conversion foam layer is set so that it can protrude higher than the size of the particles when foaming, taking into account the foaming agent and photothermal conversion material used, their content, the size of the particles, etc. For example, it can be set in the range of 1 to 150 μm.

Moreover, said light-heat conversion foaming adhesion layer is equipped with all the functions of the above-mentioned foaming layer 44, the light-heat conversion layer 43, and the adhesion layer 45, and a foaming agent and light-heat conversion property in the resin binder which has adhesiveness. It contains substances. As the resin binder having adhesiveness constituting the photothermal conversion foamable adhesive layer, rubber adhesives, acrylic adhesives and the like can be used.
As the rubber-based pressure-sensitive adhesive, it is possible to use a rubber-based polymer (rubber-like substance) having an elastomer as a base polymer, a low glass transition temperature, and a wide rubber range up to a high temperature. Examples of the elastomer include natural rubber, isoprene rubber, styrene butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, butyl rubber, polyisobutylene, silicone rubber, polyvinyl isobutyl ether, chloroprene rubber, and nitrile. Examples thereof include rubber, graft rubber, recycled rubber, polyvinyl ether, atactic polypropylene, polyester, polyurethane, and butadiene rubber. Moreover, you may contain a tackifier, a softening agent, anti-aging agent, a filler etc. other than said elastomer as a structural component of an adhesive.

Acrylic adhesives are adhesives and comonomers that are hard at high glass transition temperatures to give cohesive strength to monomers such as soft acrylates with low glass transition temperatures that provide tackiness, and for improved crosslinking and adhesion. A functional group-containing monomer is copolymerized. As said monomer, acrylic monomers, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, an octyl acrylate-methacrylic acid copolymer, can be mentioned, for example.
Further, as the foaming agent, the foaming agent as exemplified in the above-described foaming layer 44 can be used, and as the photothermal conversion substance, the photothermal conversion substance exemplified in the above-described photothermal conversion layer 43 can be used.

The content of the foaming agent in the photothermal conversion foamable adhesive layer is in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the resin binder having adhesiveness, and the content of the photothermal conversion substance is the resin binder 100 having adhesiveness. It is preferable to set within a range of 0.1 to 5 parts by weight with respect to parts by weight. The thickness of such a photothermal conversion foamable pressure-sensitive adhesive layer can be projected higher than the size of the particles during foaming in consideration of the foaming agent and photothermal conversion material used, their content, the size of the particles, etc. For example, it can be set in the range of 1 to 150 μm.
In the above-described method for forming a single particle film, a heat-shrinkable film is heated and thermally contracted to form a substrate, and particles on the adhesive layer are brought close to produce a transfer sheet. In the present invention, the heat-shrinkable film may be heated and thermally contracted to form a base material, and particles on the adhesive layer may be brought close to form a single particle film on the base material. .

[Electrophoretic display device]
Next, the electrophoretic display device of the present invention will be described.
FIG. 13 is a partial longitudinal sectional view showing an embodiment of the electrophoretic display device of the present invention. In FIG. 13, an electrophoretic display device 71 of the present invention comprises an electrophoretic display element comprising a transparent substrate 72 having a transparent pattern electrode 73 on one surface and a transparent substrate 76 having a transparent pattern electrode 77 on one surface. It is made to face through the layer 80. In the electrophoretic display element layer 80, the electrophoretic display element 81 is arranged between the transparent pattern electrode 73 and the transparent pattern electrode 77 so as to be in a single particle film state with the closest packing as shown in FIG. It is.

  The transparent pattern electrode 73 is composed of three electrically independent transparent pattern electrodes 73Y, 73M, and 73C, and the transparent pattern electrode 77 is also composed of three electrically independent transparent pattern electrodes 77Y, 77M, and 77C. ing. The transparent pattern electrodes 73Y and 77Y face each other via the electrophoretic display element 81Y, the transparent pattern electrodes 73M and 77M face each other via the electrophoretic display element 81M, and the transparent pattern electrodes 73C and 77C face the electrophoretic display element 81C. A transparent substrate 72 and a transparent substrate 76 are disposed so as to face each other.

  As the transparent substrates 72 and 76, for example, a glass substrate, a transparent resin substrate, or the like can be used, and the thickness can be appropriately set in the range of 10 μm to 5 mm, preferably 25 to 200 μm. Note that one of the transparent substrates 72 and 76, that is, the substrate positioned on the back as viewed from the display recognizer, can be an opaque substrate. In this case, as the substrate, an opaque glass substrate in which the other substrate surface different from the electrode surface is roughened or a metal film is deposited, an opaque resin substrate in which a dye or a pigment is kneaded can be used. The electrode formed on the substrate may also be a metal electrode such as Cu, Ag, Au, or Al instead of the transparent electrode as described below.

The transparent pattern electrodes 73Y and 77Y, the transparent pattern electrodes 73M and 77M, and the transparent pattern electrodes 73C and 77C are each connected to a voltage application device (not shown). The charge can be controlled. The transparent pattern electrode as described above is, for example, indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO) or the like, and a general film forming method such as sputtering, vacuum evaporation, or CVD. Can be formed. The line width of each transparent pattern electrode can be set in the range of about 10 to 100 μm, and the gap between the electrodes can be set in the range of about 10 to 100 μm.
Note that the pattern electrode in the present invention is not only a pattern electrode having a fine pattern as described above, but also, for example, a transparent electrode provided on the entire surface of the display screen, and corresponds to a shield part at the periphery of the substrate. The part includes an electrode having a pattern in which no electrode exists.

The electrophoretic display element 81 has electrophoretic particles 82 and a dispersion medium 83 housed in a microcapsule 84, and the average particle diameter can be set in the range of, for example, 10 to 100 μm, preferably 10 to 50 μm. In the illustrated example, a yellow dispersion medium 83Y is used as the dispersion medium 83 for the electrophoretic display element 81Y, a magenta dispersion medium 83M is used as the dispersion medium 83 for the electrophoretic display element 81M, and the electrophoretic display element A cyan dispersion medium 83C is used as the dispersion medium 83 in 81C.
As the electrophoretic particles 82, colored or colorless (white) inorganic pigment particles or organic pigment particles can be used. Inorganic pigment particles include lead white, zinc white, lithopone, titanium dioxide, zinc sulfide, antimony oxide, calcium carbonate, kaolin, mica, barium sulfate, gloss white, alumina white, talc, silica, calcium silicate, cadmium yellow, Cadmium lithopone white, yellow iron oxide, titanium yellow, titanium barium yellow, cadmium orange, cadmium lithopone orange, molybdate orange, bengara, red rose, silver vermilion, cadmium red, cadmium lithopone red, amber, brown iron oxide, zinc Iron chrome brown, chrome green, chromium oxide, pyridiane, cobalt green, cobalt chrome green, titanium cobalt green, bitumen, cobalt blue, ultramarine, cerulean blue, cobalt aluminum chrome blue, Baltic violet, mineral violet, carbon black, iron black, manganese ferrite black, cobalt ferrite black, copper chrome black, copper chrome manganese black, black low-order titanium oxide (titanium black), aluminum powder, copper powder, lead powder, tin powder Zinc powder or the like can be used. Organic pigment particles 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, dinitro Aniline Orange, Pyrazolone Orange, Perinone Orange, Naphthol Red, Toluidine Red, Permanent Carmine, Brilliant Fast Scar Red, Pyrazolone Red, Rhodamine 6G Lake, Permanent Red, Resol Red, Bon Lake Red, Lake Red, Brilliant Carmine, Bordeaux 10B, Naphthol Red, Quinacridone Magenta, Condensed Azo Red, Naphthol Carmine, Perylene Scar Red, Condensed Acetate Scarred, 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, alkali blue toner, indanthrone blue, rhodamine B lake, methyl violet lake, dioxazine violet, naphthol violet and the like can be used. The average particle diameter of the electrophoretic particles 82 is preferably about 20 nm to 1 μm. The electrophoretic particles 82 are not limited to the above.

  The dispersion medium 83 includes, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, dodecylbenzene, and other alkylbenzene derivatives, phenylxylylethane, 1,1-ditolylethane, 1,2-ditolylethane, 1,2-bis. Diallylalkane derivatives such as (3,4-dimethylphenylethane) (BDMF), alkylnaphthalene derivatives such as diisopropylnaphthalene, alkylbiphenyl derivatives such as monoisopropylphenyl, isopropylphenyl and isoamylbiphenyl, hydrogenated tars in various proportions Phenyl derivatives, triallyldimethane derivatives such as dibenzyltoluene, benzylnaphthalene derivatives, phenylene oxide derivatives, diallyalkylene derivatives, allylindane derivatives, polychlorinated biphenyl derivatives Naphthenic hydrocarbons, and the like. Also, aliphatic hydrocarbons such as hexane, cyclohexane, kerosene, isobar, paraffinic hydrocarbons, halogenated hydrocarbons such as chloroform, trichloroethylene, tetrachloroethylene, trifluoroethylene, tetrafluoroethylene, dichloromethane, ethyl bromide, phosphorus Phosphate esters such as tricresyl acid, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, phthalates such as dibutyl phthalate, dioctyl phthalate, diuracil phthalate, dicyclohexyl phthalate, butyl oleate, diethylene glycol Dibenzoate, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, trioctyl trimellitic acid, acetyl triethyl citrate, octyl maleate, male Phosphate, dibutyl acid esters such as ethyl acetate, chlorinated paraffin, N, N-dibutyl-2-butoxy-5-tert-octyl aniline, and the like. The dispersion medium 83 is not limited to the above. Furthermore, in this invention, said dispersion medium can be used individually or in mixture of 2 or more types.

  These dispersion media include Spirit Black (SB, SSBB, AB), Nigrosine Base (SA, SAP, SAPL, EE, EEL, EX, EXBP, EB), Oil Yellow (105, 107, 129, 3G, GGS), Oil Orange (201, PS, PR), Fast Orange, Oil Red (5B, RR, OG), Oil Scarlet, Oil Pink 312, Oil Violet # 730, Macrolex Blue RR, Sumiblast Green G, Oil Brown (GR, 416), Sudan Black X60, Oil Green (502, BG), Oil Blue (613, 2N, BOS), Oil Black (HBB, 860, BS), Bali First Yellow (1101, 1105, 3108, 4120), Bali First Orange( 209, 3210), Bali First Red (1306, 1355, 2303, 3304, 3306, 3320), Bali First Pink 2310N, Bali First Brown (2402, 3405), Bali First Blue (3405, 1501, 1603, 1605, 1607, 2606, 2610), Bali First Violet (1701, 1702), Vari First Black (1802, 1807, 3804, 3810, 3820, 3830) and the like, by appropriately selecting and containing a dye, each color dispersion medium 83Y, 83M , 83C.

  As the wall film material of the microcapsule 84, polyurethane, polyurea, polyurea-polyurethane, urea-formaldehyde resin, melamine-formaldehyde resin, polyamide, polyester, polysulfonamide, polycarbonate, polysulfinate, epoxy, acrylate ester Methacrylic acid ester, vinyl acetate, gelatin and the like can be used. The wall film thickness can be set in the range of 50 nm to 1 μm, and the diameter of the microcapsule 84 can be set in the range of 10 to 100 μm, preferably about 10 to 50 μm. .

The electrophoretic display element layer 80 is such that the electrophoretic display element 81 as described above is arranged as a single particle film in a close-packed state on the transparent pattern electrode 73 and has a uniform thickness. it can.
In the electrophoretic display device 71 of the present invention as described above, the voltage is applied to the electrophoretic display element layer 80 by the transparent pattern electrode 73 (73Y, 73M, 73C) and the transparent pattern electrode 77 (77Y, 77M, 77C). Color display using a phenomenon in which the electrophoretic particles 82 of the electrophoretic display element 81 constituting the electrophoretic display element layer 80 migrate in the microcapsule 84 toward electrodes having different charges is possible. Since the electrophoretic display element 81 constituting the electrophoretic display element layer 80 is disposed so as to be in a single particle film state with the closest packing as shown in FIG. Image display is possible.

  Further, in the electrophoretic display device 71 of the present invention, it is possible to perform display using the color of the portion where the electrophoretic display element layer 80 (transparent pattern electrodes 73 and 77) does not exist as a background color, and high quality display with excellent contrast. It becomes an electrophoretic display device capable of. For example, the electrophoretic display element layer 80 (transparent pattern electrodes 73 and 77) does not exist by using a colored substrate or a light reflecting layer as the colored substrate as the substrate positioned on the back as viewed by the display recognizer. In the part, the color of the substrate can be positively used as the background color.

  In the close-packed arrangement of the electrophoretic display elements 81 shown in FIG. 14, there are gaps between the electrophoretic display elements 81, and such gaps do not contribute to display. In the present invention, by bringing the transparent substrate 82 and the transparent substrate 86 closer so that the distance between the transparent pattern electrodes 73 and 77 is slightly smaller than the average particle diameter of the electrophoretic display element 81, as shown in FIG. The microcapsules 84 constituting the electrophoretic display element 81 are slightly crushed so that the width of the electrophoretic display element 81 (in the direction of arrow a in FIG. 15) is larger than the height, thereby providing a gap between the electrophoretic display elements 81. The number of parts may be reduced.

  Moreover, although the above-described embodiment of the electrophoretic display device can display three colors of Y, M, and C, the electrophoretic display device of the present invention is not limited to this. For example, by forming the electrophoretic display element layer 80 using one type of electrophoretic display element 81 in which the color of the dispersion medium 83 is a desired color, the color of the dispersion medium 83 and the color of the electrophoretic particles 82 are changed. The electrophoretic display device of the single color display used can also be used.

The electrophoretic display device of the present invention uses the above-described original plate for forming a single particle film of the present invention, and forms the single particle film of the present invention (for example, the method shown in FIG. 9 described above, the above-described FIG. 10). ~ The method shown in Fig. 12), an electrophoretic display element layer is formed by disposing an electrophoretic display element on a pattern electrode so as to be in a single particle film state. In the present invention, since no binder exists between the transferred electrophoretic display elements, the microcapsules 84 constituting the electrophoretic display element 81 can be slightly crushed and brought into close contact as described above.
For the microencapsulation of the electrophoretic display element, a conventionally known general microencapsulation technique can be used. Examples of general microencapsulation methods include an interfacial polymerization method using a synthetic reaction, an in-situ polymerization method, and a submerged curing coating method that causes changes in polymer properties. Examples of the physicochemical production method include a coacervation method using phase separation, an interfacial precipitation method (concentration method in liquid, drying method in liquid, secondary emulsion method), a melt separation method, and the like.

  The above interfacial polymerization method is a method in which water-soluble and oil-soluble monomers are selected as two types of monomers that undergo polycondensation or polyaddition reaction, and either is dispersed and reacted at the interface. The above-mentioned in-situ polymerization method is a method in which a reactant (monomer or initiator) is supplied from one or the other of the core materials and reacted on the capsule wall membrane surface. The liquid curing coating method (orifice method) is a method in which a core material is encapsulated in advance with a wall film material, and then the wall film is cured in a curing liquid.

  The above coacervation method can be used in either an aqueous solution system or an organic solvent system. In the aqueous solution system, a simple coacervation method in which phase separation is caused by a decrease in solubility or a complex coacervation method in which phase separation is caused by an electrical interaction can be used. In an organic solvent system, a phase separation phenomenon caused by changes in solubility, temperature, or the like can be used. In addition, the interfacial precipitation method is a method that can be encapsulated under mild conditions without violent reaction or rapid pH change. For example, an aqueous solution in which an electrophoretic display element is dispersed is treated with a hydrophobic polymer. After being dispersed in a solvent solution, it is further dispersed in a protective colloid solution. The melt dispersion method uses a waxy material such as wax or polyethylene as the wall film material, and is a method in which the core material is dispersed in a liquid together with the waxy material under heating and then cooled.

An electrophoretic display element is one in which electrophoretic particles and a dispersion medium are housed in a microcapsule. By applying various basic emulsified oil droplet methods and encapsulation methods as described above, electrophoretic electrophoresis is performed. A display element can be manufactured.
In the above-described embodiment of the electrophoretic display device of the present invention, the electrophoretic display elements 81 are arranged so as to be in a close-packed and single particle film state. The electrophoretic display element 81 may be a single particle film, and is not limited to the closest packed state.

Next, the present invention will be described in more detail by showing more specific examples.
[Example 1]
<Preparation of original plate for forming single particle film>
A borosilicate glass plate (length 100 mm × width 100 mm) having a thickness of 3 mm was used as a substrate, and a chromium thin film (thickness 1000 mm) was formed on the substrate by a vacuum evaporation method to form a substrate.
Next, a photoresist (ZPP1800 manufactured by Nippon Zeon Co., Ltd.) was applied on the chromium thin film. Thereafter, both surfaces of the substrate were exposed through a predetermined photomask and developed to form a resist pattern having a thickness of 2 μm. For the exposure, an ultrahigh pressure mercury lamp was used as the light source, and the irradiation amount was set to 150 mJ / cm ^{2 at} 365 nm. Further, development was performed using a developer (ZTMA-U20 manufactured by Nippon Zeon Co., Ltd.).

Next, the chromium thin film was etched by wet etching using a cerium oxide-based etchant. Thus, an etching mask having a two-layer structure of a chromium thin film and a resist pattern and having a circular opening (diameter 60 μm) was formed on both surfaces of the substrate so that the centers of the circular openings coincided.
Next, the substrate provided with the above-described etching mask is immersed in a hydrofluoric acid-based etchant and etched to form a through hole, and then washed with water, and the resist pattern is removed using a resist stripper. Further, the chromium thin film was removed using a cerium oxide-based etching solution to obtain an original plate A. This original plate A has a structure as shown in FIG. 2, and has a simple cubic lattice arrangement (pitch of 100 μm) as shown in FIG. It was equipped with multiple.

<Formation of single particle film>
Preparation of particles (electrophoretic display element) 12 parts by weight of titanium dioxide particles (average particle size 200 nm), 1.5 parts by weight of a surfactant (polycarboxylic acid derivative (Demol EP manufactured by Kao Corporation)), titanium-based coupling 0.5 parts by weight of the agent (Ajinomoto Fine Techno Co., Ltd. Preneact KRTTS), 1 part by weight of blue anthraquinone dye (Oil Blue G extra) and 85 parts by weight of hexylbenzene are mixed by ultrasonic dispersion, and this mixture is mixed. Was used to prepare a microencapsulated electrophoretic display element A (average diameter of microcapsules of 50 μm) by a gum arabic gelatin-based complex coacervation method to obtain a dispersion-containing liquid.

  In addition, by using a red diazo dye (Oil Red B) instead of the blue anthraquinone dye, a microencapsulated electrophoretic display element B (microcapsule average diameter 50 μm) is prepared, and a dispersion-containing liquid It was.

As a heat-shrinkable film for forming a photothermal conversion layer, a foamed layer, and an adhesive layer, a biaxial shrinkable film (Hispet PS-40S manufactured by Mitsubishi Plastics, Inc.) having a thickness of 30 μm was prepared. On one surface of the film, a photothermal conversion layer coating solution having the following composition was applied by a blade coating method and dried to form a photothermal conversion layer (thickness 5 μm).
(Photothermal conversion layer coating solution)
Acrylic resin (M-2000, manufactured by Soken Chemical Co., Ltd.) 20 parts by weight Polymethine infrared absorbing dye 1 part by weight (IR-820B, manufactured by Nippon Kayaku Co., Ltd.)
・ Toluene / methyl ethyl ketone / butyl acetate: 80 parts by weight

Next, on this photothermal conversion layer, a foam layer coating solution having the following composition was applied by a blade coating method and dried to form a foam layer (thickness 30 μm).
(Foaming layer coating solution)
-Polyester aqueous dispersion: 40 parts by weight (Toyobo Co., Ltd. Bironal MD-1930,
30% solid sentence concentration, number average molecular weight of resin 25000)
・ Effervescent microcapsule: 15 parts by weight (Matsumoto Yushi Seiyaku Co., Ltd. Matsumoto Microsphere F-20VS)
・ Water: 20 parts by weight

Next, an acrylic pressure-sensitive adhesive (Aron S-1601 manufactured by Toa Gosei Co., Ltd.) was applied on the foamed layer by a bar coating method and dried to form an adhesive layer (thickness 3 μm). The tack value of this adhesive layer at 25 ° C. and 100 ° C. was measured under the following measurement conditions. As a result, the tack value at 25 ° C. was 19, and the tack value at 100 ° C. was 10.
(Tack value measurement conditions)
According to JIS Z0237, ball tack tester (VR-57) manufactured by Ueshima Seisakusho Co., Ltd.
10), a measurement sample was set on a glass substrate inclined at 30 °, chrome steel balls of various sizes were rolled, and the size of the spheres that stopped on the adhesive layer was taken as the tack value.

Placement of particles (electrophoretic display element) on original plate A and preparation of transfer sheet Next, the original plate A prepared as described above is placed on the adhesive layer, and the dispersion-containing liquid of the electrophoretic display element A is added. It was applied by a blade coating method. At this time, the gap between the original A and the blade was 20 μm. Thus, one electrophoretic display element A was placed in each opening of the through hole of the original A. Thereafter, the original plate A was removed, and a single particle film (simple cubic lattice arrangement) of the electrophoretic display element A was formed on the adhesive layer.
Similarly, one electrophoretic display element B was placed on the adhesive layer of another heat-shrinkable film to form a single particle film.

For the electrophoretic display elements A and B, the particle filling rate was measured from the particle occupation area ratio by image analysis (the particle filling rate is 100%). As a result, the particle filling rate was 33%. there were.
Next, a set of glass substrates on which a release layer was formed by applying a silicone release agent (SH200 manufactured by Toray Dow Corning Silicone Co., Ltd.) was prepared. Using this glass substrate, a heat-shrinkable film holding the single particle film of the electrophoretic display element A is sandwiched so that the release layers face each other, and a spacer having a thickness of 85 μm is disposed on the peripheral edge of the glass substrate. The gap distance of the glass substrate was made constant.

Next, in a state of being sandwiched between glass substrates, heating was performed from normal temperature to 100 ° C. (temperature increase rate: 10 ° C./min) in an oven, and then the product was taken out of the oven and cooled to room temperature. After cooling, the glass substrate was removed. As a result, a transfer sheet 1A in which the electrophoretic display element A was transferred in a single particle film state onto the adhesive layer was obtained.
Similarly, a transfer sheet 1B in which the electrophoretic display element B was transferred in a single particle film state onto the adhesive layer was produced.
As a result of measuring the particle filling rate of the electrophoretic display elements A and B in the transfer sheets 1A and 1B produced as described above in the same manner as described above, it was confirmed that the particle filling rate was improved to 100%.

Next, 170 indium tin oxide (ITO) vapor deposition films having a width of 50 μm were formed on a PET film having a thickness of 100 μm at a pitch of 60 μm to form electrodes. The stripe-shaped electrodes are connected every other line, and therefore adjacent electrodes are electrically independent. One of these two electrically independent stripe-shaped electrodes was electrode A, and the other was electrode B.
Next, an acrylic pressure-sensitive adhesive (Aron S-1601 manufactured by Toa Gosei Chemical Co., Ltd.) was applied by a bar coating method so as to cover the ITO electrode of this PET film, thereby forming a pressure-sensitive adhesive layer having a thickness of 10 μm.

  Next, the transfer sheet 1A holding the electrophoretic display element A was opposed to the PET film so that the electrophoretic display element A was spaced from the adhesive layer on the ITO electrode by 45 μm. In this state, a laser (semiconductor laser: wavelength 830 nm) was irradiated from the substrate side of the transfer sheet 1A so as to correspond to the stripe-shaped electrode A (irradiation amount 150 mW). By this laser irradiation, the foamed layer at the irradiated part was raised by about 50 μm, and the electrophoretic display element A at that part was in contact with the adhesive layer on the electrode A. Thereafter, the transfer sheet 1A was removed. Thereby, the electrophoretic display element A at the laser irradiation site was transferred in a single particle state onto the stripe-shaped electrode A.

  Next, the transfer sheet 1B holding the electrophoretic display element B is placed on the above PET film (the electrophoretic display element A is already present) so that the electrophoretic display element B is spaced 50 μm from the adhesive layer on the ITO electrode. (Transferred). In this state, a laser (semiconductor laser: wavelength 830 nm) was irradiated from the substrate side of the transfer sheet 1B so as to correspond to the stripe-shaped electrode B (irradiation amount 150 mW). By this laser irradiation, the foamed layer at the irradiated part was raised by about 50 μm, and the electrophoretic display element B at that part was in contact with the adhesive layer on the electrode B. Thereafter, the transfer sheet 1B was removed. As a result, the electrophoretic display element B was transferred onto the stripe-shaped electrode B in a single particle state.

Thus, the electrophoretic display element A and the electrophoretic display element B formed in the single particle state on the electrode A and the electrode B, respectively, are adjacent to each other with a gap of 10 μm or less at the boundary between the electrode A and the electrode B. there were.
Next, the PET film having the electrophoretic display element A and the electrophoretic display element B on the electrode A and the electrode B, respectively, and the PET film having a thickness of 100 μm having the ITO vapor deposition film (common electrode) on the electrophoretic display element. The film was pressure-bonded, and the electrophoretic display elements A and B constituting the single particle film were deformed to adhere to each other while filling the close-packed gap. As a result, an electrophoretic display panel having very few gaps between electrophoretic display elements that do not contribute to display was produced.

  When a DC voltage of ± 20 V is applied between the facing electrode A and the common electrode of the electrophoretic display panel, the electrophoretic particles (titanium dioxide particles) move in the direction of voltage application in the electrophoretic display element, and the applied voltage It was confirmed that clear white / blue display is possible by switching between positive and negative. When a DC voltage of ± 20 V is applied between the electrode B and the common electrode facing each other in the electrophoretic display panel, the electrophoretic particles (titanium dioxide particles) move in the direction of voltage application in the electrophoretic display element, and the applied voltage It was confirmed that clear white / red display was possible by switching between positive and negative.

[Example 2]
First, the transfer sheet 2A (holding the electrophoretic display element A) and the transfer sheet 2B are the same as in Example 1 except that the photothermal conversion layer is not provided on the base material and only the foam layer and the adhesive layer are formed. Up to fabrication of (electrophoretic display element B) was performed.
Next, as in Example 1, electrodes A and B, which are two electrically independent stripe-shaped ITO electrodes, are formed on a PET film having a thickness of 100 μm so as to cover the ITO electrodes. An adhesive layer was formed.

  Next, the transfer sheet 2A holding the electrophoretic display element A was opposed to the PET film so that the electrophoretic display element A was spaced from the adhesive layer on the ITO electrode by 45 μm. In this state, heating was performed from the base material side of the transfer sheet 1A so as to correspond to the stripe-shaped electrode A using a thermal head (TH38200, manufactured by Graphtec Corporation). Due to the heating by the thermal head, the foamed layer at the heated part was raised by about 50 μm, and the electrophoretic display element A at that part was in contact with the adhesive layer on the electrode A. Thereafter, the transfer sheet 2A was removed. Thereby, the electrophoretic display element A was transferred onto the stripe-shaped electrode A in a single particle state.

Next, the transfer sheet 2B holding the electrophoretic display element B was opposed to the PET film so that the electrophoretic display element B was spaced 50 μm from the adhesive layer on the ITO electrode. In this state, the transfer sheet 2B was heated from the base material side so as to correspond to the stripe-shaped electrode B using the thermal head, and then the transfer sheet 2B was removed. As a result, the electrophoretic display element B was transferred onto the stripe-shaped electrode B in a single particle state.
Thus, the electrophoretic display element A and the electrophoretic display element B formed in the single particle state on the electrode A and the electrode B, respectively, are adjacent to each other with a gap of 10 μm or less at the boundary between the electrode A and the electrode B. there were.

Next, an electrophoretic display panel was produced in the same manner as in Example 1.
When a DC voltage of ± 20 V is applied between the facing electrode A and the common electrode of the electrophoretic display panel, the electrophoretic particles (titanium dioxide particles) move in the voltage application direction within the electrophoretic display element, and the applied voltage It was confirmed that clear white / blue display is possible by switching between positive and negative. When a DC voltage of ± 20 V is applied between the electrode B and the common electrode facing each other in the electrophoretic display panel, the electrophoretic particles (titanium dioxide particles) move in the direction of voltage application in the electrophoretic display element, and the applied voltage It was confirmed that clear white / red display was possible by switching between positive and negative.

[Example 3]
<Preparation of original plate for forming single particle film>
A borosilicate glass plate (length 100 mm × width 100 mm) having a thickness of 3 mm was used as a substrate, and a chromium thin film (thickness 1000 mm) was formed on the substrate by a vacuum evaporation method to form a substrate.
Next, a photoresist (ZPP1800 manufactured by Nippon Zeon Co., Ltd.) was applied on the chromium thin film. Thereafter, one surface of the substrate was exposed through a predetermined photomask and developed to form a resist pattern having a thickness of 2 μm. For the exposure, an ultrahigh pressure mercury lamp was used as the light source, and the irradiation amount was set to 150 mJ / cm ^{2 at} 365 nm. Further, development was performed using a developer (ZTMA-U20 manufactured by Nippon Zeon Co., Ltd.).

Next, the chromium thin film was etched by wet etching using a cerium oxide-based etchant. As a result, an etching mask having a two-layer structure of a chromium thin film and a resist pattern and having a circular opening (diameter 60 μm) was formed on the substrate.
Next, the substrate provided with the etching mask is immersed in a hydrofluoric acid-based etching solution to form a recess in the substrate, and then washed with water, and the resist pattern is removed using a resist remover. The chromium thin film was removed using a cerium oxide-based etching solution to obtain an original plate B. This master B has a structure as shown in FIG. 1, and has a concave portion (depth 40 μm) having a circular opening (opening diameter 60 μm) in a simple cubic lattice arrangement (pitch 100 μm) as shown in FIG. It was equipped with multiple.

<Formation of single particle film>
Placement of particles to precursor B (electrophoretic display) Next, the original plate B prepared as described above, dispersion liquid containing electrophoretic display device A (as prepared in Example 1) a blade coating method Was applied. At this time, the gap between the original plate B and the blade was 20 μm. As a result, one electrophoretic display element A was placed in each recess of the original B.
Similarly, one electrophoretic display element B was placed in each recess of another master B.

Preparation of Transfer Sheet A uniaxial shrinkable film (Hishipet LX-10S manufactured by Mitsubishi Plastics, Inc.) having a thickness of 30 μm was prepared as a heat-shrinkable film. On one surface of this film, an acrylic pressure-sensitive adhesive (Aron S-1601 manufactured by Toa Gosei Co., Ltd.) was applied by a bar coating method and dried to form an adhesive layer (thickness 3 μm). The tack value of this adhesive layer at 25 ° C. and 100 ° C. was measured under the same measurement conditions as in Example 1. As a result, the tack value at 25 ° C. was 19, and the tack value at 100 ° C. was 10.
Next, the electrophoretic display element A placed on the original B was transferred onto the adhesive layer. In addition, the electrophoretic display element B placed on the original B was transferred onto the adhesive layer of another heat-shrinkable film.

Next, in the same manner as in Example 1, the heat-shrinkable film was subjected to heat shrinkage, and a transfer sheet 3A in which the electrophoretic display element A was transferred onto the adhesive layer in a single particle film state was produced. In this transfer sheet 3A, a stripe array having a width of 50 μm was present via a particle non-arrangement region having a width of 60 μm.
Similarly, a transfer sheet 3B in which the electrophoretic display element B was transferred in a single particle film state onto the adhesive layer was produced.
Next, similarly to Example 1, electrodes A and B, which are two electrically independent stripe-shaped ITO electrodes, are formed on a PET film having a thickness of 100 μm, and are adhered to cover the ITO electrodes. A layer was formed.

Next, the electrophoretic display element A is formed in a single particle state on the electrode A using the transfer sheet 3A holding the electrophoretic display element A and the transfer sheet 3B holding the electrophoretic display element B, and the electrode B An electrophoretic display element B was formed in a single particle state thereon.
Thus, the electrophoretic display element A and the electrophoretic display element B formed in the single particle state on the electrode A and the electrode B, respectively, are adjacent to each other with a gap of 10 μm or less at the boundary between the electrode A and the electrode B. there were.
Next, an electrophoretic display panel was produced in the same manner as in Example 1.

  When a DC voltage of ± 20 V is applied between the facing electrode A and the common electrode of the electrophoretic display panel, the electrophoretic particles (titanium dioxide particles) move in the voltage application direction within the electrophoretic display element, and the applied voltage It was confirmed that clear white / blue display is possible by switching between positive and negative. When a DC voltage of ± 20 V is applied between the electrode B and the common electrode facing each other in the electrophoretic display panel, the electrophoretic particles (titanium dioxide particles) move in the direction of voltage application in the electrophoretic display element, and the applied voltage It was confirmed that clear white / red display was possible by switching between positive and negative.

[Comparative Example 1]
<Preparation of transfer sheet for single particle film formation>
First, in the same manner as in Example 1, a photothermal conversion layer was formed on a substrate.
Next, a particle layer coating liquid A having the following composition is applied onto the light-to-heat conversion layer by a blade coating method and dried to form a particle layer having a thickness of 50 μm (containing the electrophoretic display element A as particles in a binder). Thus, a comparative transfer sheet A was produced.
(Particle layer coating solution A)
・ Polyvinyl alcohol: 10 parts by weight (PVA3500 manufactured by Wako Pure Chemical Industries, Ltd.)
Water: 90 parts by weight Electrophoretic display element A: 90 parts by weight

Similarly, a comparative transfer sheet B including a particle layer having a thickness of 50 μm (containing the electrophoretic display element B as particles in a binder) was prepared using a particle layer coating solution B having the following composition.
(Particle layer coating solution B)
・ Polyvinyl alcohol: 10 parts by weight (PVA3500 manufactured by Wako Pure Chemical Industries, Ltd.)
Water: 90 parts by weight Electrophoretic display element B: 90 parts by weight

<Formation of single particle film>
In the same manner as in Example 1, electrodes A and B, which are two electrically independent stripe-shaped ITO electrodes, were formed on a PET film having a thickness of 100 μm.
Next, the particle layer (thickness 50 μm) of the comparative transfer sheet A is brought into close contact with the ITO electrode of the PET film, and a laser (semiconductor laser: wavelength 830 nm) is applied to the stripe-shaped electrode A from the base material side of the comparative transfer sheet A. (Irradiation amount 150 mW). Thereafter, the comparative transfer sheet A was removed. Thereby, the electrophoretic display element A was transferred onto the stripe-shaped electrode A together with the binder. However, the binder melted due to heat at the time of transfer, and spread when transferred, and line thickening (width about 100 μm) was observed.

  Next, the comparative transfer sheet B is brought into close contact with the PET film (the electrophoretic display element A has already been transferred) so as to correspond to the stripe-shaped electrode B from the substrate side under the same conditions as described above. Laser irradiation was performed. Thereby, the electrophoretic display element B was transferred onto the stripe-shaped electrode B together with the binder. However, due to the thickening of the line of the electrophoretic display element A that has already been transferred, a binder is also present in part of the electrode B, and the transferred line of the electrophoretic display element B is the line of the electrophoretic display element A. It was in a state of riding on the binder. For this reason, a step of about 10 to 50 μm occurred between the transferred line of the electrophoretic display element B and the already transferred line of the electrophoretic display element A.

Next, on the electrophoretic display element of the PET film provided with the electrophoretic display element A and the electrophoretic display element B on the electrode A and the electrode B, respectively, a thickness of 100 μm including the ITO vapor deposition film (common electrode) is provided. A PET film was pressure bonded to produce an electrophoretic display panel. However, since a binder is present between the electrophoretic display elements, the pressure bonding cannot be performed sufficiently, and a gap remains between the electrophoretic display elements.
When a DC voltage of ± 20 V is applied between the facing electrode A and the common electrode of the above-described electrophoretic display panel, the electrophoretic display panel of the embodiment causes a gap between electrophoretic display elements that do not contribute to display. The contrast was low.
In addition, the above-described pressure bonding is performed under the condition that the binder is in a flexible state by heating. However, due to the step between the electrophoretic display element A and the electrophoretic display element B, the electrophoretic display element B is The electrophoretic display element A was compressed and deformed so as to cover the contrast.

[Comparative Example 2]
Comparative master A was produced in the same manner as in Example 3. This comparative original A was provided with a plurality of concave portions (depth 40 μm) having circular openings (opening diameter 80 μm) in a simple cubic lattice arrangement (pitch 100 μm) as shown in FIG. 4 on one surface.
Next, the dispersion containing liquid of the electrophoretic display element A (prepared in Example 1) was applied to the comparative original plate A produced as described above by a blade coating method. At this time, the gap between the comparative original plate A and the blade was 20 μm. However, the comparative original plate A has a recess in which a plurality of electrophoretic display elements A are placed, and it is difficult to place particles for forming a uniform single particle film.

[Comparative Example 3]
A comparative original plate B was produced in the same manner as in Example 3. This comparative original plate B was provided with a plurality of concave portions (depth 20 μm) having circular openings (opening diameter 60 μm) in a simple cubic lattice arrangement (pitch 100 μm) as shown in FIG.
Next, the dispersion containing liquid of the electrophoretic display element A (prepared in Example 1) was applied to the comparative original plate B produced as described above by a blade coating method. At this time, the gap between the comparative original plate B and the blade was 20 μm. However, the comparative original plate B has a concave portion on which the electrophoretic display element A is not placed, and it is difficult to place particles for forming a uniform single particle film.

  The present invention can be used for various applications in which particles are required to be a single particle film.

It is a schematic sectional drawing which shows one Embodiment of the original plate for single particle film formation of this invention. It is a schematic sectional drawing which shows other embodiment of the original plate for single particle film formation of this invention. It is a figure which shows the example of an arrangement | sequence of the recessed part in the original plate for single particle film formation of this invention. It is a figure which shows the example of an arrangement | sequence of the through-hole in the original plate for single particle film formation of this invention. It is process drawing which shows one Embodiment of the formation method of the single particle film of this invention. It is a figure for demonstrating an example of the heat shrink process of the heat-shrinkable film in the formation method of the single particle film of this invention. It is a figure for demonstrating the behavior of the particle | grains at the time of the heat shrink of the heat-shrinkable film in the formation method of the single particle film of this invention. It is a figure for demonstrating the behavior of the particle | grains at the time of the heat shrink of the heat-shrinkable film in the formation method of the single particle film of this invention. It is process drawing which shows other embodiment of the formation method of the single particle film of this invention. It is process drawing which shows other embodiment of the formation method of the single particle film of this invention. It is process drawing which shows other embodiment of the formation method of the single particle film of this invention. It is process drawing which shows other embodiment of the formation method of the single particle film of this invention. It is a fragmentary longitudinal cross-section which shows one Embodiment of the electrophoretic display device of this invention. It is a plane surface which shows the arrangement | sequence of the electrophoretic display element in the electrophoretic display apparatus of this invention. It is a fragmentary longitudinal cross-section which shows other embodiment of the electrophoretic display device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,11 ... Original plate 2,12 ... Base | substrate 3 ... Concave 13 ... Through-hole 21, 41 ... Transfer sheet 22 ', 42' ... Heat-shrinkable film 22, 42 ... Base material 23 ... Adhesive layer 43 ... Photothermal conversion layer 44 ... Foam layer 45 ... Adhesive layer 31, 51 ... Formed object 71 ... Electrophoretic display device 73 (73Y, 73M, 73C) ... Transparent pattern electrode 77 (77Y, 77M, 77C) ... Transparent pattern electrode 80 ... Electrophoretic display element Layer 81 (81Y, 81M, 81C) ... Electrophoretic display element 82 Electrophoretic particles 83 (83Y, 83M, 83C) ... Dispersion medium 84 ... Microcapsules 100, 100A, 100B, 100C ... Particles

Claims (35)

In the original plate for arranging particles in a single particle film state,
A substrate and a plurality of recesses arranged on one surface of the substrate; an opening diameter D (μm) of the recesses; an arrangement pitch P (μm) of each recess; and a depth S (μm) of the recesses And the average particle diameter d (μm), d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d are satisfied. The original version.   The original plate for forming a single particle film according to claim 1, further comprising an adhesive layer in the recess. In the original plate for arranging particles in a single particle film state,
A substrate and a plurality of through holes arranged in the substrate; the diameter D (μm) of the through holes, the arrangement pitch P (μm) of each through hole, and the thickness T (μm) of the substrate; 1. An original plate for forming a single particle film, wherein the relationship of d ≦ D ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d is established between the particle diameter d (μm). A step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate;
Forming a pressure-sensitive adhesive layer on one surface of the heat-shrinkable film, and transferring the particles placed on the original plate onto the pressure-sensitive adhesive layer in a single particle film state;
And a step of heating the heat-shrinkable film to heat-shrink to form a base material and bringing the particles on the adhesive layer closer to each other.   The original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm), d ≦ D 5. The method for forming a single particle film according to claim 4, wherein relationships of ≦ 1.5 d, d ≦ P, and 0.1 d ≦ S ≦ 1.5 d are established.   The method for forming a single particle film according to claim 4 or 5, wherein the original plate is provided with an adhesive layer in the recess. An adhesive layer is formed on one surface of the heat-shrinkable film, an original plate having a plurality of through holes arranged in a substrate is disposed on the adhesive layer, and particles are placed in the through holes of the original plate, Removing the original plate and disposing the particles in a single particle film state on the adhesive layer;
And a step of heating the heat-shrinkable film to heat-shrink to form a base material and bringing the particles on the adhesive layer closer to each other.   The original plate has d ≦ D between the hole diameter D (μm) of the through holes, the arrangement pitch P (μm) of each through hole, the thickness T (μm) of the substrate, and the average particle diameter d (μm). 8. The method for forming a single particle film according to claim 7, wherein the relationships of ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d are established.   9. The method for forming a single particle film according to claim 4, wherein the heat-shrinkable film is a uniaxial shrinkable heat-shrinkable film.   The array of particles in the base material is a stripe array in which the particles are in contact with each other along the heat shrink direction of the heat-shrinkable film. Between each stripe array, the particles have a width that is an integral multiple of the stripe array width. The method for forming a single particle film according to claim 9, wherein a non-arranged region exists. A step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate;
A foam layer and an adhesive layer are formed and laminated in this order on one surface of the heat-shrinkable film, or a photothermal conversion layer, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion foam layer. And forming an adhesive layer in this order and laminating, or forming an adhesive layer having photothermal conversion foamability,
Transferring the particles placed on the original plate in a single particle film state on the adhesive layer;
And a step of heating the heat-shrinkable film to heat-shrink to form a base material and bringing the particles on the adhesive layer closer to each other.   The original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm), d ≦ D 12. The method for forming a single particle film according to claim 11, wherein the relations of ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d are established.   The method for forming a single particle film according to claim 11, wherein the original plate is provided with an adhesive layer in the concave portion. A foam layer and an adhesive layer are formed and laminated in this order on one surface of the heat-shrinkable film, or a photothermal conversion layer, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion foam layer. And forming an adhesive layer in this order and laminating, or forming an adhesive layer having photothermal conversion foamability,
An original plate having a plurality of through-holes arranged on a substrate is placed on the adhesive layer, particles are placed in the through-holes of the original plate, and then the original plate is removed to make particles single particles on the adhesive layer. Arranging in a film state;
And a step of heating the heat-shrinkable film to heat-shrink to form a base material and bringing the particles on the adhesive layer closer to each other.   The original plate has d ≦ D between the hole diameter D (μm) of the through holes, the arrangement pitch P (μm) of each through hole, the thickness T (μm) of the substrate, and the average particle diameter d (μm). 15. The method for forming a single particle film according to claim 14, wherein the relationships of ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d are established.   16. The method for forming a single particle film according to claim 11, wherein the heat-shrinkable film is a biaxial shrinkable heat-shrinkable film.   17. The method for forming a single particle film according to claim 16, wherein the array of particles in the transfer sheet is a close-packed hexagonal lattice array or a simple cubic lattice array. A step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate;
Forming a pressure-sensitive adhesive layer on one surface of the heat-shrinkable film, and transferring the particles placed on the original plate onto the pressure-sensitive adhesive layer in a single particle film state;
Heat-shrinking the heat-shrinkable film to form a base material, and making a transfer sheet by bringing particles on the adhesive layer close to each other;
Transferring the particles on the pressure-sensitive adhesive layer of the transfer sheet onto an object to be formed, and a method for forming a single particle film.   The original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm), d ≦ D 19. The method for forming a single particle film according to claim 18, wherein the relationship of ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d is established.   The method for forming a single particle film according to claim 18 or 19, wherein the original plate includes an adhesive layer in the recess. An adhesive layer is formed on one surface of the heat-shrinkable film, an original plate having a plurality of through holes arranged in a substrate is disposed on the adhesive layer, and particles are placed in the through holes of the original plate, Removing the original plate and disposing the particles in a single particle film state on the adhesive layer;
Heat-shrinking the heat-shrinkable film to form a base material, and making a transfer sheet by bringing particles on the adhesive layer close to each other;
Transferring the particles on the pressure-sensitive adhesive layer of the transfer sheet onto an object to be formed, and a method for forming a single particle film.   The original plate has d ≦ D between the hole diameter D (μm) of the through holes, the arrangement pitch P (μm) of each through hole, the thickness T (μm) of the substrate, and the average particle diameter d (μm). 21. The method for forming a single particle film according to claim 20, wherein the relationship of ≦ 1.5d, d ≦ P, and 0.1d ≦ T ≦ 1.5d is established.   The method for forming a single particle film according to any one of claims 18 to 22, wherein the heat-shrinkable film is a uniaxial shrinkable heat-shrinkable film.   The arrangement of the particles in the transfer sheet is a stripe arrangement in which the particles are in contact with each other along the heat shrink direction of the heat-shrinkable film, and each stripe arrangement has a width that is an integral multiple of the stripe arrangement width. The method for forming a single particle film according to claim 23, wherein a non-arranged region exists.   25. The method for forming a single particle film according to claim 24, wherein a plurality of types of transfer sheets having different particle types are prepared, and the particles in a stripe arrangement are transferred onto the formed body for each transfer sheet. A step of placing particles in each recess of an original plate having a substrate and a plurality of recesses arranged on one surface of the substrate;
A foam layer and an adhesive layer are formed and laminated in this order on one surface of the heat-shrinkable film, or a photothermal conversion layer, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion foam layer. And forming an adhesive layer in this order and laminating, or forming an adhesive layer having photothermal conversion foamability,
Transferring the particles placed on the original plate in a single particle film state on the adhesive layer;
Heat-shrinking the heat-shrinkable film to form a base material, and making a transfer sheet by bringing particles on the adhesive layer close to each other;
The transfer sheet has a particle-arranged surface facing the object to be formed with a gap, and light and / or heat is supplied to a desired part from the surface of the transfer sheet opposite to the particle-arranged surface of the substrate. The particles are projected in the direction of the formed body by foaming of the foam layer, the photothermal conversion foam layer, or the photothermal conversion foaming adhesive layer, and the particles are transferred onto the form body in a desired pattern. And a step of forming a single particle film.   The original plate has an opening diameter D (μm) of the recesses, an arrangement pitch P (μm) of the recesses, a depth S (μm) of the recesses, and an average particle diameter d (μm), d ≦ D 27. The method for forming a single particle film according to claim 26, wherein the relationship of ≦ 1.5d, d ≦ P, and 0.1d ≦ S ≦ 1.5d is established.   The method for forming a single particle film according to claim 26 or 27, wherein the original plate includes an adhesive layer in the recess. A foam layer and an adhesive layer are formed and laminated in this order on one surface of the heat-shrinkable film, or a photothermal conversion layer, a foam layer and an adhesive layer are formed and laminated in this order, or a photothermal conversion foam layer. And forming an adhesive layer in this order and laminating, or forming an adhesive layer having photothermal conversion foamability,
An original plate having a plurality of through-holes arranged on a substrate is placed on the adhesive layer, particles are placed in the through-holes of the original plate, and then the original plate is removed to make particles single particles on the adhesive layer. Arranging in a film state;
Heat-shrinking the heat-shrinkable film to form a base material, and making a transfer sheet by bringing particles on the adhesive layer close to each other;
The transfer sheet has a particle-arranged surface facing the object to be formed with a gap, and light and / or heat is supplied to a desired part from the surface of the transfer sheet opposite to the particle-arranged surface of the substrate. The particles are projected in the direction of the formed body by foaming of the foam layer, the photothermal conversion foam layer, or the photothermal conversion foaming adhesive layer, and the particles are transferred onto the form body in a desired pattern. And a step of forming a single particle film.   The original plate has d ≦ D between the hole diameter D (μm) of the through holes, the arrangement pitch P (μm) of each through hole, the thickness T (μm) of the substrate, and the average particle diameter d (μm). 30. The method for forming a single particle film according to claim 29, wherein the relationship of ≦ 1.5d, d ≦ P, 0.1d ≦ T ≦ 1.5d is established.   31. The method for forming a single particle film according to claim 26, wherein the heat-shrinkable film is a biaxial shrinkable heat-shrinkable film.   32. The method of forming a single particle film according to claim 31, wherein the particle arrangement in the transfer sheet is a close-packed hexagonal lattice arrangement or a simple cubic lattice arrangement.   The single particle according to any one of claims 26 to 32, wherein a plurality of types of transfer sheets having different particle types are prepared, and a single particle film is formed in a desired pattern on the formed body for each transfer sheet. Method for forming a film. In an electrophoretic display device comprising an electrophoretic display element layer between electrodes,
At least one of the electrodes has a predetermined pattern shape and is a plurality of electrically independent pattern electrodes, and the electrophoretic display element layer contains electrophoretic particles and a dispersion medium in a microcapsule. An electrophoretic display element is arranged so as to be in a single particle film state on the pattern electrode by the method of forming a single particle film according to claim 25 or 33, and the dispersion of the electrophoretic display element is performed. An electrophoretic display device, wherein the color of the medium is different for each pattern electrode of each system.   36. The electrophoretic display device according to claim 35, wherein the color of the dispersion medium of the electrophoretic display element is at least three kinds of blue, red, and yellow.

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