JP2016191856A - Method for manufacturing twist ball sheet, method for manufacturing twist ball type electronic paper, twist ball sheet and twist ball type electronic paper using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a twist ball sheet excellent in display characteristics.SOLUTION: A method for manufacturing a twist ball sheet is provided, which includes: a twist ball-containing layer forming step of disposing a twist ball-containing material 10 comprising a curable resin 2 and twist balls 1 dispersed in the curable resin 2, in which a volume ratio of the curable resin 2 to the twist balls 1 as a solid content ranges from 2:3 to 3:7, on a support body 6, and then curing the curable resin 2 included in the twist ball-containing material 10 to form a twist ball-containing layer 10; a cured resin layer forming step of disposing a second curable resin on the twist ball-containing layer 10 and curing the second curable resin to from a cured resin layer 11; and a release step of releasing the twist ball-containing layer 10 and the cured resin layer 11 from the support body 6.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a twist ball sheet having excellent display characteristics.

  In recent years, a display medium called electronic paper has attracted attention. Electronic paper has outstanding characteristics such as bendable flexibility, thinness and lightness, and has the outstanding feature of being rewritable. Such electronic paper includes various display methods such as a twisting ball method, an electrophoresis method, and a liquid crystal display method. Among them, twist ball type electronic paper (twist ball type electronic paper) using two-color spherical particles (twist balls) is attracting attention because of its excellent outdoor visibility and low power consumption (Patent Literature). 1).

  As shown in FIG. 3D, the twist ball type electronic paper is usually disposed between the transparent electrode base material 3, the back electrode base material 4, and the transparent electrode base material 3 and the back electrode base material 4. The twist ball layer 16 is configured. In addition, the twist ball layer 16 in the twist ball type electronic paper 100 is usually formed by immersing a twist ball sheet including the curable resin 2 and the twist balls 1 dispersed in the curable resin 2 in the solvent 5. Is obtained. That is, the twist ball layer 16 is a layer in which the cured resin is swollen with the solvent 5. Since the twist ball layer is swollen with the solvent, the twist balls dispersedly disposed in the cured resin rotate and a desired display can be performed. In addition, the code | symbol which is not demonstrated in FIG.3 (d) is mentioned later.

Japanese Patent Laid-Open No. 2015-14812

  By the way, in recent years, with the spread of twist ball type electronic paper, development of twist ball type electronic paper having more excellent display characteristics has been demanded. Here, the display of the twist ball type electronic paper is made possible by the light incident from the transparent electrode substrate side being reflected by the twist ball. The inventors of the present invention have conducted various studies on improving the display characteristics of the twist ball type electronic paper based on the display principle of the twist ball type electronic paper. As a result, the display characteristics of the twist ball type electronic paper have been improved. It has been found that the improvement is realized by reflecting more light by the twisting ball. Accordingly, the inventors of the present invention have attempted to increase the amount of twist ball contained in the twist ball sheet in the manufacture of the twist ball sheet constituting the twist ball layer.

  However, in consideration of the strength of the twist ball layer, it is necessary to increase the amount of the cured resin material included in the twist ball sheet as the amount of the twist ball included in the twist ball sheet increases. The problem of becoming thick has arisen. When the thickness of the twist ball type electronic paper is increased, the drive voltage of the twist ball type electronic paper is increased, and there is a problem that display characteristics of the twist ball type electronic paper are deteriorated.

  The inventors of the present invention, as a result of earnest research to solve the above problems, increase the amount of twist balls contained in the twist ball sheet, and prevent the twist ball sheet from becoming thick, When the amount of the cured resin material contained in the twist ball sheet is suppressed, for example, as shown in FIG. 4, in the twist ball sheet 10 including the twist ball 1 and the cured resin 2 on the support 6, A new problem has been discovered that the portion is exposed from the cured resin 2. In this way, in the twist ball sheet, if a part of the twist ball is exposed from the cured resin, the twist ball sheet is swollen in a solvent and used in the twist ball type electronic paper even if a voltage is applied. There is a problem that the ball does not rotate and the display characteristics deteriorate. In addition, in the twist ball sheet, if a part of the twist ball is exposed from the cured resin, the exposed twist ball falls off from the twist ball sheet, and the display characteristics deteriorate when used in the twist ball type electronic paper. There is a problem of end up.

  The present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a twist ball sheet excellent in display characteristics.

  Based on the above-described new problem, the present inventors have provided a cured resin layer on a surface of a twisted ball sheet where a part of the twisted ball is exposed from the cured resin, thereby being used for twisted ball type electronic paper. It was found that excellent display characteristics can be realized. The present invention has been completed based on such findings.

  That is, the present invention includes a curable resin and a twist ball dispersed in the curable resin on a support, and the volume ratio of the curable resin and the twist ball as a solid content is 2: 3. A twist ball-containing layer forming step of forming a twist ball-containing layer by disposing a twist ball-containing material in a range of ˜3: 7 and curing the curable resin contained in the twist ball-containing material; A cured resin layer forming step of disposing a second curable resin on the twist ball-containing layer and curing the second curable resin to form a cured resin layer, and from the support, There is provided a method for producing a twist ball sheet, comprising a twist ball-containing layer and a peeling step for peeling the cured resin layer.

  According to the present invention, a twist ball-containing layer having a high twist ball density can be obtained by mixing the curable resin and the twist ball in the twist ball-containing material at a predetermined volume ratio. Moreover, according to this invention, by forming a cured resin layer on a twist ball content layer, it can suppress that a part of twist ball is exposed from curable resin contained in a twist ball content layer. Thereby, the twist ball sheet excellent in display characteristics can be obtained.

  In the present invention, prior to the twist ball-containing layer forming step, a third curable resin is disposed on the support, and the base layer is formed by curing the third curable resin. It is preferable to have a formation layer forming step, and the twist ball-containing layer forming step is a step of forming the twist ball-containing layer on the base layer. A twist ball sheet with higher strength can be obtained.

  The present invention also provides a transparent electrode substrate having a transparent substrate and a transparent electrode formed on the transparent substrate, a back electrode substrate having a back substrate and a back electrode formed on the back substrate. And a twisting ball type electronic paper for producing a twisting ball type electronic paper having a twisting ball layer disposed between the transparent electrode base material and the back electrode base material, the twisting ball layer comprising: The twist ball layer forming step to be formed includes a curable resin and a twist ball dispersed in the curable resin on a support, and the volume ratio of the curable resin and the twist ball as a solid content is A twist ball is disposed by arranging a twist ball-containing material in a range of 2: 3 to 3: 7 and curing the curable resin contained in the twist ball-containing material. Twist ball-containing layer forming step of forming a layer containing layer, placing a second curable resin on the twist ball-containing layer, and curing the second curable resin to form a cured resin layer A cured resin layer forming step, a peeling step for peeling the twist ball-containing layer and the cured resin layer from the support, and a twist ball by immersing the twist ball-containing layer and the cured resin layer in a solvent and swelling them. The present invention provides a method for producing twisted ball type electronic paper characterized by having a swelling step of forming a layer.

  According to the present invention, a twist ball-containing layer having a high twist ball density can be obtained by mixing the curable resin and the twist ball in the twist ball-containing material at a predetermined volume ratio. Moreover, according to this invention, by forming a cured resin layer on a twist ball content layer, it can suppress that a part of twist ball is exposed from curable resin contained in a twist ball content layer. Thereby, a twist ball type electronic paper excellent in display characteristics can be obtained.

  In the present invention, prior to the twist ball-containing layer forming step, a third curable resin is disposed on the support, and the base layer is formed by curing the third curable resin. It is preferable to have a formation layer forming step, and the twist ball-containing layer forming step is a step of forming the twist ball-containing layer on the base layer. A twist ball type electronic paper with higher strength can be obtained.

  The present invention includes a cured resin and a twist ball dispersed in the cured resin, wherein the volume ratio of the cured resin and the twist ball as a solid content is in the range of 2: 3 to 3: 7, A twist ball-containing layer in which a part of the twist ball is exposed from a cured resin; and a second cured resin formed on a surface of the twist ball-containing layer in which a part of the twist ball is exposed from the cured resin. There is provided a twisted ball sheet comprising a cured resin layer.

  According to the present invention, the twisted ball-containing layer having a high twisted ball density can be obtained by mixing the cured resin and the twisted ball in the twisted ball-containing layer at a predetermined volume ratio. Moreover, according to this invention, by having a cured resin layer on a twist ball content layer, it can suppress that a part of twist ball is exposed from curable resin contained in a twist ball content layer. Thereby, it can be set as the twist ball sheet excellent in the display characteristic.

  In the present invention, it is preferable that the twist ball-containing layer has a base layer that is formed on a surface opposite to the surface on which the cured resin layer is formed and includes a third cured resin. A twist ball sheet having higher strength can be obtained.

  The present invention includes a transparent substrate and a transparent electrode substrate having a transparent electrode formed on the transparent substrate, a back substrate and a back electrode substrate having a back electrode formed on the back substrate, A twist ball type electronic paper having a twist ball layer disposed between the transparent electrode substrate and the back electrode substrate, wherein the twist ball layer is dispersed in the cured resin and the cured resin. A volume ratio of the cured resin and the twisted ball that includes a twisted ball and a solvent is within a range of 2: 3 to 3: 7 as a solid content, and a part of the twisted ball is exposed from the cured resin. The twist ball-containing layer and the twist ball-containing layer are formed on a surface of the twist ball-containing layer where a part of the twist ball is exposed from the cured resin, and has a cured resin layer containing a second cured resin. To provide a twist ball type electronic paper which is characterized in.

  According to the present invention, the twisted ball-containing layer having a high twisted ball density can be obtained by mixing the cured resin and the twisted ball in the twisted ball-containing layer at a predetermined volume ratio. Moreover, according to this invention, by having a cured resin layer on a twist ball content layer, it can suppress that a part of twist ball is exposed from the cured resin contained in a twist ball content layer. Thereby, it can be set as the twist ball type electronic paper excellent in the display characteristic.

  In the present invention, it is preferable that the twist ball-containing layer has a base layer that is formed on a surface opposite to the surface on which the cured resin layer is formed and includes a third cured resin. It can be set as a twist ball type electronic paper with higher strength.

  The present invention has an effect that a twist ball sheet having excellent display characteristics can be obtained.

It is a schematic process drawing which shows an example of the manufacturing method of the twist ball sheet of this invention. It is a schematic process drawing which shows the other example of the manufacturing method of the twist ball sheet of this invention. It is a schematic process drawing which shows an example of the manufacturing method of the twist ball type electronic paper of this invention. It is a schematic sectional drawing which shows an example of the conventional twist ball sheet.

  Hereinafter, the manufacturing method of the twist ball sheet, the manufacturing method of the twist ball type electronic paper, the twist ball sheet, and the twist ball type electronic paper of the present invention will be described.

A. A method for producing a twist ball sheet The method for producing a twist ball sheet of the present invention comprises a curable resin and a twist ball dispersed in the curable resin on a support, and the curable resin as a solid content. A twist ball-containing layer is formed by disposing a twist ball-containing material having a volume ratio of 2: 3 to 3: 7 with the twist ball and curing the curable resin contained in the twist ball-containing material. A twisted ball-containing layer forming step, and a cured resin layer that is formed by disposing a second curable resin on the twisted ball-containing layer and curing the second curable resin. It is a manufacturing method characterized by having a layer formation process and the peeling process which peels the said twist ball content layer and the said cured resin layer from the said support body.

  The manufacturing method of the twist ball sheet of this invention is demonstrated using figures. FIG. 1 is a schematic process diagram showing an example of a method for producing a twisted ball sheet of the present invention. The twist ball sheet manufacturing method of the present invention includes a curable resin 2 and a twist ball 1 dispersed in the curable resin 2 on a support 6 as shown in FIG. There is a twist ball-containing layer forming step of forming the twist ball-containing layer 10 by disposing the sheet-containing material 10 ′ and curing the curable resin 2 contained in the twist ball-containing material 10 ′. Moreover, as shown in FIG.1 (b), the 2nd curable resin 11 'is arrange | positioned on the twist ball containing layer 10, and the cured resin layer 11 is hardened by hardening 2nd curable resin 11'. And a peeling step of peeling the twist ball-containing layer 10 and the cured resin layer 11 from the support 6, as shown in FIG. 1 (c). In the method for producing a twist ball sheet of the present invention, the twist ball-containing material has a volume ratio of curable resin and twist ball in the range of 2: 3 to 3: 7 as a solid content.

  According to the present invention, by mixing the curable resin and the twist ball in the twist ball-containing material at a predetermined volume ratio, a twist ball-containing layer having a high twist ball density can be obtained. When the twist ball sheet to be used is used for twist ball type electronic paper, excellent display characteristics can be obtained. The reason can be considered as follows. That is, in a twist ball sheet having a low density of twist balls, when light is incident on the twist ball layer formed of the twist ball sheet, the number of twist balls contributing to light reflection is reduced. Therefore, it is considered that it is difficult to obtain excellent display characteristics with a twist ball sheet having a low twist ball density. On the other hand, the twist ball sheet obtained by the present invention has a high density of twist balls, so that when the light enters the twist ball layer composed of the twist ball sheet, many twist balls contribute to the reflection of light. Become. For these reasons, it is considered that a twist ball sheet having excellent display characteristics can be obtained in the present invention.

  In addition, in a conventional twist ball sheet including a twist ball and a cured resin material, in order to increase the density of the twist ball and to increase the amount of the twist ball and to prevent the twist ball sheet from becoming thick, Attempts have been made to reduce the amount of cured resin material contained in the ball sheet. However, when the amount of the twist ball contained in the twist ball sheet is increased to suppress the amount of the cured resin material, there is a problem that a part of the twist ball is exposed from the cured resin. In this way, in the twist ball sheet, if a part of the twist ball is exposed from the cured resin, the twist ball sheet is swollen in a solvent and used in the twist ball type electronic paper even if a voltage is applied. There is a problem that the ball does not rotate and the display characteristics deteriorate. In addition, in the twist ball sheet, if a part of the twist ball is exposed from the cured resin, the exposed twist ball falls off from the twist ball sheet, and the display characteristics deteriorate when used in the twist ball type electronic paper. There is a problem of end up. On the other hand, since the twist ball sheet obtained by the present invention can suppress a part of the twist ball from being exposed from the cured resin contained in the twist ball-containing layer, the twist ball sheet obtained by the present invention is When used in twist ball type electronic paper, the twist ball can be rotated satisfactorily by applying a voltage, and the drop of the twist ball from the twist ball containing layer can be suppressed. Therefore, in the present invention, it is considered that a twist ball sheet having excellent display characteristics can be obtained.

  Hereinafter, each process of the manufacturing method of the twist ball sheet of the present invention is explained.

1. Twist ball-containing layer forming step The twist ball-containing layer forming step in the present invention includes a curable resin and a twist ball dispersed in the curable resin on a support, and the curable resin and the twist ball as solid components. In the step of forming a twist ball-containing layer by disposing a twist ball-containing material having a volume ratio of 2: 3 to 3: 7 and curing a curable resin contained in the twist ball-containing material. is there.

  The thickness of the twist ball-containing layer formed in this step is based on the fact that the twist ball layer composed of the twist ball sheet is thick when the twist ball sheet obtained by the present invention is used for twist ball type electronic paper. The thickness is preferably such that the display characteristics do not deteriorate. In particular, in this step, it is preferable that a part of the twist ball included in the twist ball sheet has a thickness that is exposed from the curable resin. Therefore, the thickness of the twist ball-containing layer is appropriately adjusted according to the particle diameter of the twist ball included in the twist ball-containing layer. For example, the thickness of the twist ball-containing layer is such that a part of the twist ball is exposed from the curable resin, and the length from the surface of the curable resin to the surface of the exposed twist ball is within a predetermined range. Is preferred. Specifically, the height difference of the unevenness on the surface of the curable resin is preferably larger than 5 μm, for example, and more preferably larger than 10 μm. On the other hand, the height difference of the unevenness on the surface of the curable resin is preferably smaller than the diameter of the twist ball, for example, and is preferably not more than the radius of the twist ball.

The specific thickness of the twist ball-containing layer is, for example, preferably in the range of 50 μm to 500 μm, more preferably in the range of 75 μm to 400 μm, and particularly preferably in the range of 100 μm to 300 μm. preferable. When the thickness of the twist ball-containing layer is within the above range, when the twist ball sheet obtained by the present invention is used for the twist ball type electronic paper, the thickness of the twist ball layer constituted by the twist ball sheet is increased. It is possible to suppress the drive voltage from increasing. Here, the thickness of the twist ball-containing layer refers to the distance from the surface of the support on which the twist ball-containing layer is disposed to the surface of the cured resin contained in the twist ball-containing layer. In FIG. 1 (a), refers to the distance _{t 1.}

Specifically, the twist ball-containing layer forming step in the present invention includes an arrangement step of disposing the twist ball-containing material on the support and a curing step of curing the curable resin contained in the twist ball-containing material.
Hereinafter, the arrangement | positioning process and hardening process which a twist ball content layer formation process has are demonstrated.

(1) Arrangement Step The arrangement step in the twist ball-containing layer forming step is a step of arranging a twist ball-containing material on the support.

  Although such an arrangement | positioning process will not be specifically limited if it is a process which can arrange | position a twist ball containing material on a support body, For example, the coating method is mentioned. Specifically, gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, dip pulling method, curtain coating method, die coating Examples of the coating method include a coating method, a casting method, and a bar coating method.

  Hereinafter, the twist ball-containing material and the support used in the arranging step will be described.

(A) Twist ball-containing material The twist ball-containing material used in this step is a material including a curable resin and a twist ball dispersed in the curable resin. The twist ball-containing material has a volume ratio of curable resin to twist ball in the range of 2: 3 to 3: 7 as a solid content. In the present invention, the volume ratio between the curable resin and the twist ball is preferably in the range of 3: 5 to 1: 2. When the volume ratio of the curable resin and the twist ball contained in the twist ball-containing material is within the above range, the density of the twist balls in the twist ball-containing layer composed of the twist ball-containing material can be increased. Moreover, it can suppress that the thickness of a twist ball content layer becomes thick. Therefore, when the twist ball sheet obtained by the present invention is used for twist ball type electronic paper, it is possible to obtain excellent display characteristics.

  Hereinafter, the twist ball and the curable resin contained in the twist ball-containing material will be described.

(I) Twist Ball The twist ball contained in the twist ball-containing material is a material that functions as a display medium when the twist ball sheet obtained by the present invention is used for twist ball type electronic paper.

  The twist ball used for the twist ball-containing material has a spherical shape and has two hues of different color hue / white hue or different hue / color hue, and two different hues have different dipoles. It is preferable.

  Such a twist ball can be the same as the twist ball manufactured by the microchannel manufacturing method proposed in Japanese Patent Application Laid-Open No. 2004-197083, for example.

  Here, in the microchannel manufacturing method, the colored continuous phase and the spherical particleized phase are in an O / W type or W / O type relationship with each other, and from the first microchannel in which the colored continuous phase is transferred, Charging characteristics of two-color spherical polymer particles and having a positive (±) polarity by sequentially discharging two colored continuous phases into the spherical particle phase of the flowing medium flowing in the second microchannel A manufacturing method for manufacturing a twist ball which is a spherical particle.

  In the above microchannel production method, the polymerizability in a colored continuous phase in which an oily or aqueous fluid medium containing a polymerizable resin component is phase-separated into two colors containing a coloring dye or pigment insoluble in this medium. The resin component is formed with different positively and negatively charged polymerizable monomers, transferred to the first microchannel, and this colored continuous phase is then transferred into the aqueous or oily spherical particleized phase flowing in the second microchannel. In addition, the liquid is sequentially or intermittently discharged. Next, the discharged material discharged into the spherical particle phase is successively formed into spherical particles during the spherical particle phase while being converted into spherical particles during a series of discharge, dispersion, and transfer within the microchannel. A twist ball is appropriately prepared by polymerizing and curing the polymerizable resin component in the particulate phase under at least one of UV irradiation and heating.

  The colored continuous phase is a continuous hue divided into two hues, for example, black and white, red and white, yellow and white, blue and white, green and white, purple and white, etc. There can be mentioned two phase separation hues selected from “chromatic hue and white hue”, or two phase separation hues having different “color hue and color hue”. The colorant for forming such a hue is appropriately selected and used without particular limitation as long as it is insoluble or uniformly dispersed in a fluid dispersion medium containing a polymerizable resin component described later. As the colorant, dyes and pigments can be used.

  As such dyes and pigments, for example, those described in Japanese Patent Application Laid-Open No. 2004-197083 can be used, and description thereof is omitted here.

  The addition amount of the dyes and pigments as these colorants is not particularly limited, and the desired color tone varies depending on the use of the colored particles, and the dispersibility in the above-described colored continuous phase, etc. Therefore, in the present invention, it is within the range of 0.1 to 80 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the total polymerizable resin component which is a polymerization and curing component in the colored continuous phase. It can be suitably suitably added within the range.

  As the polymerizable resin component or polymerizable monomer used in the twist ball, the chargeability of the twist ball depends on the type of the functional group or substituent of the polymerizable monomer used in the twist ball. Mention may be made of monomer species that tend to exhibit (+) chargeability. Therefore, in the case where at least two or more kinds of monomers are used as the polymerizable resin component in the present invention, the tendency to show the (+) and (−) chargeability is well known, A plurality of monomers having a tendency to property can be used in combination as appropriate.

  On the other hand, in the polymerizable resin component or polymerizable monomer having in the molecule at least one kind of functional group and substituent, examples of the functional group or substituent include carbonyl group, vinyl group, phenyl group, amino group. Groups, amide groups, imide groups, hydroxyl groups, halogen groups, sulfonic acid groups, epoxy groups and urethane bonds. In this invention, it can use suitably suitably combining the monomer type which has a functional group or a substituent in such a polymerizable monomer individually or in combination of 2 or more types.

  As the (−) chargeable monomer and the (+) chargeable polymerizable monomer, for example, those described in JP-A-2004-197083 can be used. The description in is omitted.

  In the present invention, when such a polymerizable monomer at the time of polymerization of the polymerizable resin component after being discharged as a colored continuous phase to the second microchannel already described above is used in combination with another copolymerizable monomer, Depending on the desired chargeability or electrophoretic properties entrusted to the colored resin fine particles, a monomer having a tendency to be charged on a weight basis is preferably in the range of 1% to 100% of the total monomers, Copolymer particles with a polymerizable monomer preferably within a range of 5% to 100%, particularly preferably within a range of 10% to 100%, are suitably used as appropriate to provide a desired twist ball. can do.

The twist ball is a spherical monodisperse particle having an average particle diameter in a range of 1.0 μm to 400 μm, preferably in a range of 20 μm to 200 μm, more preferably in a range of 50 μm to 50 μm. It can be suitably prepared within the range of 120 μm. In addition, uniform particles with extremely low variation in average particle diameter are appropriately prepared. In the present invention, the homogeneity is expressed as a Cv value, and is suitably used as a twist ball of monodisperse particles of 20% or less, preferably 5% or less, more preferably 3% or less.
Here, an average particle diameter is an average particle diameter by microscopic observation. The average particle diameter by microscopic observation is obtained, for example, by performing microscopic observation at 100 times, measuring 100 particle diameters of arbitrary particles with image processing software, and the like and averaging the number. The particle diameter refers to the average value of the major axis diameter and the minor axis diameter of the particles.

(Ii) Curable resin The curable resin contained in the twist ball-containing material is used by mixing with the above-described twist ball, and when the twist ball sheet obtained by the present invention is used for twist ball type electronic paper. Is preferably a material that can swell the curable resin with a predetermined solvent.

  Examples of the curable resin contained in the twist ball-containing material include a silicone resin, a slightly crosslinked acrylic resin, a slightly crosslinked styrene resin, and a polyolefin resin.

(Iii) Others The twist ball-containing material is not particularly limited as long as it contains at least the twist ball and the curable resin described above, and may contain other materials as necessary. Examples of other materials include a solvent. When the twist ball-containing material contains a solvent, it becomes possible to efficiently apply the twist ball-containing material on the support in the disposing step. In addition, about the solvent used for a twist ball containing material, since it can be made to be the same as that of the solvent generally used, description here is abbreviate | omitted.

(B) Support The support used in this step is a member on which a twist ball-containing material is placed. Although the material of such a support body is not specifically limited, For example, a resin material, glass, etc. are mentioned. Specific examples of the resin material include polyethylene (PE), polycarbonate (PC), polyethylene terephthalate (PET), and cyclic polyolefin (COP).

(2) Curing step The curing step in the present invention is a step of curing the curable resin contained in the twist ball-containing material. Further, when the twist ball-containing material contains a solvent as another material, the curing step is a step of removing the solvent contained in the twist ball-containing material and curing the curable resin.

  The curing step in the present invention is not particularly limited as long as it can cure the curable resin contained in the twist ball-containing material. A specific curing step is appropriately selected according to the type of curable resin contained in the twist ball-containing material. For example, when the curable resin contained in the twist ball-containing material is a thermosetting resin, this step is a heating step, and when the curable resin contained in the twist ball-containing material is a photocurable resin In addition, this process is a light irradiation process. In addition, about the heating process and light irradiation process mentioned above, since it can be the same as that of a general method, description here is abbreviate | omitted.

2. Cured resin layer forming step In the cured resin layer forming step in the present invention, the second curable resin is disposed on the twist ball-containing layer, and the cured resin layer is cured by curing the second curable resin. It is a process of forming.

  The cured resin layer forming step is particularly limited as long as the second curable resin is disposed on the twist ball-containing layer and the cured resin layer is formed by curing the second curable resin. Not. Specifically, for example, there is a method of forming a cured resin layer by applying a second curable resin on the twist ball-containing layer and then curing the second curable resin. In addition, about the coating method and hardening method at this time, it selects suitably according to the kind of 2nd curable resin, and a general method can be used.

  The cured resin layer formed by this step includes a second curable resin. The cured resin layer is preferably a layer containing only the second curable resin. Here, the phrase “including only the second curable resin” refers to not containing a twist ball.

  The second curable resin used in this step may be the same material as the curable resin included in the twist ball-containing material used in the above-described arrangement step, or may be a different material. In the present invention, the second curable resin constituting the curable resin layer and the curable resin contained in the twist ball-containing material are preferably materials having a refractive index close to each other, and the same material among them. Is preferred. When the twist ball sheet obtained by the present invention is used for twist ball type electronic paper, it is possible to suppress the refraction or reflection of incident light at the interface between the cured resin layer and the twist ball containing layer. The second curable resin may be the same as that described in the above section “1. Twist ball layer forming step (1) Arrangement step (a) Twist ball containing material (ii) curable resin”. Since it can do, description here is abbreviate | omitted.

  When the second curable resin constituting the cured resin layer and the curable resin contained in the twist ball-containing material are different materials, for example, the refractive index difference of each is preferably 0.2 or less, Especially, it is preferable that it is 0.1 or less, and it is especially preferable that it is 0.05 or less. The difference in refractive index between the second curable resin constituting the curable resin layer and the curable resin contained in the twisted ball-containing material is within the above range, thereby improving the display characteristics due to the different materials. The influence can be suppressed. Here, the refractive index is a value measured using a multiwavelength Abbe refractometer (manufactured by Atago Co., Ltd.).

  In the present invention, the second curable resin constituting the curable resin layer and the curable resin contained in the twist ball-containing material are materials having a similar degree of swelling that is swollen by a solvent in the swelling step described later. Of these, the same material is preferable. When the twist ball sheet obtained by the present invention is swollen and used for twist ball type electronic paper, the second curable resin constituting the cured resin layer and the curable resin contained in the twist ball-containing material Due to the difference in the degree of swelling, problems such as peeling of the cured resin layer from the twist ball-containing layer can be suppressed. The difference in the degree of swelling between the second curable resin constituting the cured resin layer and the curable resin contained in the twist ball-containing material is, for example, preferably 30% or less, and more preferably 10% or less. In particular, 5% or less is preferable. The difference in the degree of swelling is, for example, preferably −30% or more, more preferably −10% or more, and particularly preferably −5% or more. Note that the difference in the degree of swelling here is Y-X (% when the volume change rate of the twisted ball-containing layer after swelling is X% and the volume change rate of the cured resin layer after swelling is Y%. ) Was defined as the difference in swelling rate. In addition, the volume change rate can measure the magnitude | size (length, width, height) of the target object before and after swelling using a general-purpose length measuring method, respectively. For example, it can be measured using a ruler, a micrometer, a microscope or the like.

  The cured resin layer formed in this step may contain a colorant in addition to the second curable resin. When the cured resin layer contains a colorant, the twist ball sheet obtained by the present invention is used for twist ball type electronic paper with the twist ball-containing layer side as the viewing side. Since the colorant used in the cured resin layer can be the same as that generally used, description thereof is omitted here. When the cured resin layer contains, for example, a black colorant, the contrast can be improved when the twisted ball sheet obtained by the present invention is used for twisted ball type electronic paper. In addition, when the cured resin layer contains, for example, a white colorant, when the twist ball sheet obtained by the present invention is used for twist ball type electronic paper, the light reflectance can be increased, and display Characteristics can be improved. Furthermore, when the curable resin layer contains, for example, a colorant such as red, yellow, and blue, when the twist ball sheet obtained by the present invention is used for twist ball type electronic paper, excellent design properties are obtained. Can be obtained.

The thickness of the cured resin layer formed by this step is a thickness that can cover the twist ball exposed from the cured resin in the twist ball-containing layer and can increase the strength of the twist ball-containing layer. Is preferred. Therefore, the thickness of the cured resin layer is appropriately adjusted according to the particle diameter of the twist ball included in the twist ball-containing layer. For example, the thickness of the cured resin layer is preferably 1 time or less of the particle diameter of the twist ball, more preferably 0.5 times or less, and particularly preferably 0.2 times or less. The thickness of the specific cured resin layer is preferably in the range of 10 μm to 150 μm, more preferably in the range of 15 μm to 100 μm, and particularly preferably in the range of 20 μm to 80 μm. . When the thickness of the cured resin layer is within the above range, when the twist ball sheet obtained by the present invention is used for twist ball type electronic paper, the twist ball can be rotated well by applying a voltage. Moreover, it is possible to prevent the twist ball from falling off from the twist ball-containing layer. Furthermore, the twist ball-containing layer can be efficiently peeled from the support in the peeling step described later. Here, the thickness of the cured resin layer refers to the distance from the surface of the cured resin in the twist ball-containing layer to the surface of the cured resin layer. In FIG. 1B, the distance t ₂ is indicated.

  The cured resin layer formed in this step can be confirmed by observing the cross section of the twisted ball sheet using, for example, a scanning electron microscope (SEM). Specifically, when the second curable resin constituting the cured resin layer and the curable resin contained in the twist ball-containing material are different materials, it is cured when the cross section of the twist ball sheet is observed. The interface between the resin layer and the twist ball-containing layer can be confirmed. On the other hand, when the second curable resin constituting the cured resin layer and the curable resin contained in the twist ball-containing material are the same material, the twist ball contained in the twist ball-containing layer and the twist ball are used. The interface with the cured resin layer that does not have can be confirmed.

3. Peeling process The peeling process in this invention is a process of peeling the said twist ball containing layer and the said cured resin layer from the said support body.

  The peeling process in the present invention is not particularly limited as long as it can peel the twist ball-containing layer and the cured resin layer after the curing process from the support.

4). Other Steps (1) Underlayer Formation Step In the twisted ball sheet manufacturing method of the present invention, the third curable resin is disposed on the support before the twisting ball-containing layer formation step. A base layer forming step of forming a base layer by curing the curable resin 3, and the twist ball-containing layer forming step is a step of forming the twist ball-containing layer on the base layer. Is preferred. When the present invention includes a base layer forming step, the twist ball-containing layer can be efficiently peeled from the support in the peeling step described above. Further, the strength of the twist ball sheet obtained by the present invention can be improved.

  When the method for producing a twisted ball sheet of the present invention includes an underlayer forming step, a third curable resin 7 ′ is disposed on the support 6 as shown in FIG. Then, there is a base layer forming step of forming the base layer 7 by curing the third curable resin 7 ′. Further, as shown in FIG. 2B, a twist ball sheet-containing material 10 ′ including a curable resin 2 and a twist ball 1 dispersed in the curable resin 2 is disposed on the base layer 7. And a twist ball-containing layer forming step of forming the twist ball-containing layer 10 by curing the curable resin 2 contained in the twist ball-containing material 10 ′. Moreover, as shown in FIG.2 (c), the cured resin layer formation process which forms the cured resin layer 11 by arrange | positioning 2nd curable resin 11 'and hardening 2nd curable resin 11'. Further, as shown in FIG. 2 (d), there is a peeling step of peeling the twist ball-containing layer 10 and the cured resin layer 11 from the support 6.

  The undercoat layer forming step in the present invention is not particularly limited as long as the undercoat layer is formed by disposing the third curable resin on the support and curing the third curable resin. Specifically, a method of forming a curable resin layer by applying a third curable resin on a support and then curing the third curable resin can be mentioned. In addition, about the coating method and hardening method at this time, it selects suitably according to the kind of 3rd curable resin, and a general method can be used.

  The underlayer formed by this step contains a third curable resin. The underlayer is preferably a layer containing only the third curable resin. Here, the phrase “including only the third curable resin” refers to not containing a twist ball.

  The third curable resin may be the same material as the curable resin used for the twist ball-containing material and the second curable resin used for the cured resin layer, or may be a different material. In the present invention, the third curable resin is preferably the same material as the curable resin used for the twist ball-containing material and the second curable resin used for the cured resin layer. In addition, about a concrete reason and other description about 3rd curable resin, since it can be made to be the same as that of 2nd curable resin described in the above-mentioned "2. Cured resin layer formation process" section. Explanation here is omitted.

  Regarding the thickness of the foundation layer formed in this step, the twist ball-containing layer can be efficiently peeled from the support in the peeling step, and the strength of the twist ball sheet obtained by the present invention can be improved. It is preferable that the thickness is as large as possible. For example, the thickness of the underlying layer is preferably in the range of 10 μm to 150 μm, more preferably in the range of 15 μm to 100 μm, and particularly in the range of 20 μm to 80 μm. preferable.

  The underlayer formed by this step can be confirmed by observing the cross section of the twisted ball sheet using, for example, a scanning electron microscope (SEM). Specifically, since it can be the same as the second curable resin described in the above-mentioned section “2. Cured resin layer forming step”, description thereof is omitted here.

(2) Swelling step In the present invention, when the obtained twisted ball sheet is used as the twisted ball layer of the twisted ball type electronic paper, in addition to the above steps, the swollen step is performed by immersing the twisted ball sheet in a solvent. You may have a process. Specifically, after the cured resin layer forming step, a swelling step can be performed in which the twist ball-containing layer and the cured resin layer formed on the support are immersed in a solvent to swell. In this case, the swollen twist ball-containing layer and the cured resin layer can be easily peeled from the support due to the difference in the swelling rate between the twist ball-containing layer and the support. On the other hand, after the peeling step, a swelling step can be performed in which the twist ball sheet is immersed in a solvent to swell. The swelling process can be the same as the contents described in the section “B. Method for producing twisted ball type electronic paper” to be described later, and the description here is omitted.

B. Manufacturing method of twist ball type electronic paper The manufacturing method of the twist ball type electronic paper of the present invention includes a transparent base material, a transparent electrode base material having a transparent electrode formed on the transparent base material, a back surface base material and the back surface. A twist ball for producing a twist ball electronic paper having a back electrode base material having a back electrode formed on the base material, and the transparent electrode base material and a twist ball layer arranged between the back electrode base material The twisted ball layer forming step for forming the twisted ball layer includes a curable resin and a twisted ball dispersed in the curable resin on a support, A twist ball-containing material in which the volume ratio of the curable resin to the twist ball is in the range of 2: 3 to 3: 7, A twist ball-containing layer forming step of forming a twist ball-containing layer by curing the curable resin contained in the ball-containing material; a second curable resin is disposed on the twist ball-containing layer; A cured resin layer forming step of forming a cured resin layer by curing the curable resin, a peeling step of separating the twisted ball-containing layer and the cured resin layer from the support, and the twisted ball-containing layer, It is a manufacturing method characterized by having a swelling process which makes a twist ball layer by immersing the above-mentioned cured resin layer in a solvent and swelling.

  The manufacturing method of the twist ball type electronic paper of this invention is demonstrated using figures. FIG. 3 is a schematic process diagram showing an example of a method for producing twisted ball type electronic paper of the present invention. As shown in FIG. 3 (d), the twist ball type electronic paper manufacturing method of the present invention comprises a transparent electrode substrate 3 having a transparent substrate 3b and a transparent electrode 3a formed on the transparent substrate 3b, and a back surface. This is a method for producing a twisted ball electronic paper 100 having a back electrode substrate 4 having a substrate 4b and a back electrode 4a formed on the back substrate 4b, and a twist ball layer 16. The specific manufacturing method is as follows.

  First, as shown to Fig.3 (a), a pair of sealing film 15a, 15b is arrange | positioned on the transparent electrode base material 3, and the opening 14 is provided in a part of outer periphery of the said pair of sealing film 15a, 15b. The sealing part 13 is formed. Next, as shown in FIG. 3 (b), the twist ball layer 16 is disposed between the pair of sealing films 15a and 15b, and the pair of sealing films 15a is opened from the opening 14 using a kicking tool R such as a roller. After the gas g and excess solvent l are discharged to the outside of 15b, as shown in FIG. 3 (c), a sealing portion 13 that closes the opening is formed. Then, the twist ball type electronic paper 100 can be obtained by disposing the back electrode substrate 4 on the surface opposite to the surface on which the transparent electrode substrate 3 of the twist ball layer 16 is disposed. In FIG. 3D, the back electrode base material 4 further has a back electrode spacer layer 41 having via holes provided so as to overlap the back electrode 4a in plan view, the wiring electrode 42, and the wiring electrode insulation. In this example, a layer 43 and a wiring electrode spacer layer 44 are provided, and a connection layer 45 is formed inside the via hole and connects the back electrode 4a and the wiring electrode 42.

  In the present invention, the twist ball layer forming step for forming the twist ball layer includes a twist ball sheet forming step for forming the twist ball sheet, and a swelling step for immersing the twist ball sheet in a solvent to swell. The twist ball sheet forming step can be the same as the content described in the above section “A. Method for producing twist ball sheet”, and thus the description thereof is omitted here.

  According to the present invention, the twist ball-containing material used in the twist ball sheet forming step includes a twist ball and a curable resin in a predetermined volume ratio, and a cured resin layer is formed on the twist ball-containing layer. Thus, it is possible to obtain twist ball type electronic paper having excellent display characteristics. The specific reason can be the same as the contents described in the above-mentioned section “A. Method for producing twisted ball sheet”, and thus the description thereof is omitted here.

  Hereinafter, the twist ball layer forming step in the method for producing the twist ball type electronic paper of the present invention and each structure of the twist ball type electronic paper obtained by the present invention will be described.

1. Twist ball layer forming step The twist ball layer forming step in the present invention includes a curable resin and a twist ball dispersed in the curable resin on a support, and the curable resin and the twist as solid components. A twist ball-containing layer is formed by disposing a twist ball-containing material having a volume ratio of 2: 3 to 3: 7 with the ball and curing the curable resin contained in the twist ball-containing material. Twisted ball-containing layer forming step, a cured resin layer forming step of forming a cured resin layer by disposing a second curable resin on the twisted ball-containing layer and curing the second curable resin A peeling step of peeling the twist ball-containing layer and the cured resin layer from the support, and the twist ball-containing layer and the cured resin layer. It is a process which has a swelling process which makes it a twist ball layer by making it swell in a solvent and swelling.

  The thickness of the twist ball layer formed by the twist ball layer forming step is preferably such a thickness that desired display characteristics can be obtained for the twist ball type electronic paper obtained by the present invention. The thickness of the twist ball layer is, for example, preferably in the range of 50 μm to 1000 μm, more preferably in the range of 100 μm to 700 μm, and particularly preferably in the range of 200 μm to 500 μm. When the thickness of the twist ball layer is smaller than the above range, the twist ball may not be rotated well. Further, when the thickness of the twist ball layer is larger than the above range, the drive voltage may be increased.

The twist ball-containing layer forming step, the cured resin layer forming step, and the peeling step included in the twist ball layer forming step in the present invention are the same as those described in the above section “A. Method for producing twist ball sheet”. Therefore, the description here is omitted.
Hereinafter, each structure of a swelling process and twist ball type electronic paper is explained.

1. Swelling process The swelling process in the present invention is a process in which a twist ball sheet is immersed in a solvent to swell.

  The swelling process in the present invention is not particularly limited as long as the twist ball sheet obtained by the twist ball sheet forming process described above can be swollen by being immersed in a solvent. In the swelling step, a specific method for immersing the twisted ball sheet in a solvent can be the same as a general method, and thus description thereof is omitted here.

  The solvent used in the swelling step is for smoothly rotating the twist ball included in the twist ball sheet. The material used for such a solvent is not particularly limited as long as it can smoothly rotate the twist ball. For example, dimethyl silicone oil, isoparaffinic solvent, and linear paraffinic solvent, dodecane, Examples include linear alkanes such as tridecane.

2. Each composition of twist ball type electronic paper The twist ball type electronic paper obtained by the present invention has at least a twist ball layer, a transparent electrode base material, and a back electrode base material.
Hereinafter, the twist ball layer, the transparent electrode substrate, and the back electrode substrate will be described.

(1) Twist ball layer The twist ball layer in the present invention is obtained by the twist ball layer forming step described above. The twist ball layer in the present invention is obtained by swelling a twist ball sheet. Such a twist ball layer in the present invention is usually used by being sealed by a pair of sealing films and a sealing portion. The specific description is the same as the description of FIG. 3 described above, and thus the description thereof is omitted here.

  In the twist ball layer according to the present invention, a transparent electrode substrate, which will be described later, is disposed on the surface on the viewing side. In the present invention, for example, as shown in FIG. 3D, the twist ball containing layer 2 side in the twist ball layer 16 may be set as the viewing side. Although not shown, the cured resin layer 11 side is viewed in the twist ball layer. It may be on the side. The twist ball layer and the twist ball sheet constituting the twist ball layer are the same as the contents described in the above-mentioned sections “1. Twist ball layer forming step” and “A. Method for producing twist ball sheet”. Therefore, the description here is omitted.

(2) Transparent electrode substrate The transparent electrode substrate used in the present invention is a member having a transparent substrate and a transparent electrode formed on the transparent substrate.
Hereinafter, the transparent substrate and the transparent electrode will be described.

(A) Transparent base material The transparent base material in this invention supports a transparent electrode. As a transparent base material, a rigid transparent base material may be sufficient, or the transparent base material which has flexibility may be sufficient.

  Since the transparent base material in this invention is arrange | positioned at the visual recognition side of twist ball type electronic paper, it has transparency. As specific transparency of the transparent substrate, the transmittance in the visible light region is preferably 80% or more, and more preferably 90% or more. Here, the transmittance | permeability of a transparent base material can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

  As a transparent base material used for this invention, an inorganic material may be included and a resin material may be included. When the transparent substrate includes an inorganic material, examples of the transparent substrate include a glass substrate. Examples of the glass include soda lime glass, non-alkali glass, and quartz glass.

  The thickness of the transparent substrate is not particularly limited as long as a transparent electrode described later can be formed. The thickness of such a transparent substrate is preferably, for example, in the range of 10 μm to 300 μm, more preferably in the range of 15 μm to 100 μm, and particularly preferably in the range of 25 μm to 50 μm. When the thickness of the transparent substrate is smaller than the above range, it may be difficult to form a transparent electrode described later on the transparent substrate. Moreover, when the thickness of a transparent base material is larger than the said range, it may become difficult to drive the twist ball type | mold electronic paper obtained by this invention.

(B) Transparent electrode The transparent electrode in the present invention is usually formed on the entire surface of a transparent substrate when the twisted ball type electronic paper obtained by the present invention performs fixed information display.

  The material of the transparent electrode used in the present invention is not particularly limited as long as it is a conductive material capable of forming a transparent electrode. For example, indium tin oxide (ITO), indium zinc oxide (IZO), Conductive oxides such as tin oxide, zinc oxide, indium oxide, aluminum zinc oxide (AZO), metals such as Au, Ni, Ag, conductive polymers such as polyaniline, polyacetylene, polyalkylthiophene derivatives, polysilane derivatives, Examples thereof include carbon nanotubes and graphene.

  The thickness of the transparent electrode used in the present invention is not particularly limited as long as it can function as a transparent electrode, but is preferably in the range of 15 nm to 200 nm, for example. When the thickness of the transparent electrode is smaller than the above range, it may be difficult to form the transparent electrode with a uniform thickness. In addition, when the thickness of the transparent electrode is larger than the above range, it may take a long time to form the transparent electrode, and the material used for the transparent electrode may increase, resulting in an increase in manufacturing cost. End up.

(C) Other structure The transparent electrode base material in this invention will not be specifically limited if it has the transparent base material and transparent electrode which were mentioned above, A required structure can be selected suitably and can be added. Examples of such a configuration include an auxiliary electrode and wiring.

(D) Formation method of transparent electrode base material As a formation method for forming the transparent electrode base material used in the present invention, for example, a method of arranging the transparent electrode on the transparent base material after forming the transparent electrode can be mentioned. .

  As a method for forming the transparent electrode, a general electrode forming method can be used. For example, a PVD method such as a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, a method of applying a conductive paste, or the like can be given.

  Examples of the method of arranging the transparent electrode on the transparent substrate include a method of directly forming the transparent electrode on the transparent substrate, and a method of bonding the transparent substrate and the transparent electrode together using an adhesive layer. . About the adhesive used for an adhesion layer, a well-known thing can be used.

(3) Back Electrode Base The back electrode base used in the present invention is a member having a back base and a back electrode formed on the back base.
Hereinafter, the back substrate and the back electrode will be described.

(A) Back base material The back base material in this invention supports a back electrode. In addition, the back substrate in the present invention usually has insulating properties.

  The back substrate used in the present invention is not particularly limited as long as the back electrode can be formed on the back substrate. Moreover, as a back surface base material, it may have transparency and it does not need to have transparency.

  As such a back substrate, a flexible substrate is usually used. Further, the back substrate in the present invention may contain an inorganic material or a resin material. Specific examples of the material for the back substrate include the inorganic materials and resin materials described in the section of the transparent substrate described above.

(B) Back electrode When the twist ball type electronic paper obtained by the present invention performs fixed information display, the back electrode is used as a display electrode and is displayed on the twist ball type electronic paper. It is formed in a pattern shape corresponding to the information to be recorded.

  Here, the “pattern shape according to the information displayed on the twist ball type electronic paper” corresponds not only to the shape similar to the individual information displayed on the display surface of the twist ball type electronic paper but also to the background. It includes the shape.

The material of the back electrode is not particularly limited as long as the material has conductivity and can display information using a twist ball layer described later by applying a voltage to the back electrode. Examples of materials used for such a back electrode include metals such as Au, Al, Ag, Ni, and Cu, transparent conductors such as ITO, SnO ₂ , and ZnO: Al, and conductive agents mixed in a solvent or a synthetic resin binder. And conductive paste.

  The thickness of the back electrode in the present invention is not particularly limited as long as the twist ball type electronic paper obtained according to the present invention is thick enough to perform good display. Specifically, the thickness of the back electrode is preferably in the range of 50 nm to 500 μm, more preferably in the range of 100 nm to 100 μm, and particularly preferably in the range of 300 nm to 50 μm.

(C) Other Configurations The back electrode substrate of the present invention is not particularly limited as long as it has a back substrate and a back electrode, and a necessary configuration can be appropriately selected and used. An example of such a configuration is a wiring electrode. The wiring electrode may be formed on the back substrate, and when the back electrode has a back electrode insulating layer, it may be formed on the wiring electrode insulating layer. Note that the material for the wiring insulating layer can be the same as the material used for the above-described back electrode insulating layer, and thus description thereof is omitted here.

(D) Forming method of back electrode base material The forming method for forming the back electrode base material used in the present invention includes, for example, a method of arranging the back electrode on the back base material after forming the back electrode. .

  The back electrode can be formed directly on the back substrate. In this case, as a method for forming the back electrode, for example, using a metal mask such as a metal and a transparent conductor, a pattern is formed on the back substrate by sputtering, vacuum deposition, CVD, coating, or the like. Examples thereof include a method of forming a film, or a method of forming a film by applying a conductive paste in a pattern on a back substrate.

(4) Other Configurations The twist ball type electronic paper obtained by the present invention only needs to have at least the twist ball layer, the transparent electrode substrate, and the back electrode substrate described above. Such twist ball type electronic paper may have a sealing film as another configuration, for example.

  In the present invention, the twist ball type electronic paper has a sealing film that seals the transparent electrode base material, the back electrode base material, and the twist ball layer, so that the water resistance and moisture resistance of the twist ball type electronic paper are improved. Can be improved. Therefore, it is possible to provide a twist ball type electronic paper that is easy to use in an outdoor environment. As a material used for the sealing film, for example, the above-described base material that can be laminated can be used.

3. Others The production method of the twist ball type electronic paper of the present invention is not particularly limited as long as it is a method capable of producing a twist ball type electronic paper having a transparent electrode substrate, a back electrode substrate, and a twist ball layer.

  In the twist ball type electronic paper obtained by the present invention, the transparent electrode substrate, the transparent electrode, the transparent electrode, and the twist ball layer may be arranged in this order. The twist ball layer may be arranged in this order. For example, when the transparent substrate of the transparent electrode substrate, the transparent electrode, and the twist ball layer are arranged in this order, the transparent electrode of the transparent electrode substrate, the transparent substrate, and the twist ball layer are arranged in this order. Compared to the case, the drive voltage of the twist ball can be reduced.

  In addition, the twist ball type electronic paper obtained by the present invention may be arranged such that the back substrate, the back electrode, and the twist ball layer of the back electrode substrate are arranged in this order. The material and the twist ball layer may be arranged in this order. For example, when the back substrate, back electrode, and twist ball layer of the back electrode substrate are arranged in this order, the back electrode, back substrate, and twist ball layer of the back electrode substrate are arranged in this order. Compared to the case, the drive voltage of the display medium can be reduced. On the other hand, for example, when the back electrode of the back electrode substrate, the back substrate, and the twist ball layer are arranged in this order, the connection between the back electrode and the wiring electrode is facilitated.

C. Twist ball sheet The twist ball sheet of the present invention includes a cured resin and a twist ball dispersed in the cured resin, and the volume ratio of the cured resin and the twist ball as a solid content is 2: 3 to 3: 7. A twist ball-containing layer in which a portion of the twist ball is exposed from the cured resin, and a surface of the twist ball-containing layer where a portion of the twist ball is exposed from the cured resin. And a cured resin layer containing a second cured resin.

  The twist ball-containing layer in the present invention is a layer containing a cured resin and a twist ball dispersed in the cured resin. The twist ball-containing layer has a volume ratio of the cured resin and the twist ball in the range of 2: 3 to 3: 7 as a solid content. In the present invention, the volume ratio of the cured resin and the twist ball is preferably in the range of 3: 5 to 1: 2. When the volume ratio of the cured resin and the twist ball contained in the twist ball-containing layer is within the above range, the density of the twist balls in the twist ball-containing layer can be increased, and the thickness of the twist ball-containing layer can be increased. Thickening can be suppressed. Therefore, when the twist ball sheet of the present invention is used for twist ball type electronic paper, excellent display characteristics can be obtained. The volume ratio between the cured resin and the twist ball contained in the twist ball-containing layer is measured by measuring the size (vertical, horizontal, height) of the object using a general-purpose length measuring method. be able to. For example, it can be measured using a ruler, a micrometer, a microscope or the like.

  Moreover, in this invention, it is preferable to have the base layer which is formed on the surface on the opposite side to the surface in which the said cured resin layer was formed of the said twist ball containing layer, and contains 3rd cured resin. This is because the strength of the twist ball sheet can be improved.

  The twist ball sheet of the present invention is used for twist ball type electronic paper. When the twist ball sheet is used for twist ball type electronic paper, the twist ball sheet is swollen with a solvent. The twist ball sheet of the present invention can be the same as the contents described in the above-mentioned section “A. Method for producing twist ball sheet”, and thus the description thereof is omitted here.

  When the twist ball-containing layer in the present invention is swollen by a solvent, the volume ratio of the cured resin and the twist ball contained in the twist ball-containing layer is measured by performing drying or heat treatment and removing the solvent. be able to. The drying or heating temperature and the drying or heating time in the drying or heat treatment are appropriately adjusted according to the type of solvent to be removed. For example, the drying or heating temperature can be in the range of 80 ° C. to 150 ° C., and the drying or heating time can be in the range of 30 minutes to 180 minutes. In addition, about the specific measuring method of a volume ratio, it can measure by measuring the magnitude | size (length, width, height) of a target object using a general-purpose length measuring method, respectively. For example, it can be measured using a ruler, a micrometer, a microscope or the like.

D. Twist ball type electronic paper The twist ball type electronic paper of the present invention is formed on a transparent substrate having a transparent substrate and a transparent electrode formed on the transparent substrate, a back substrate and the back substrate. A twisted ball type electronic paper having a back electrode substrate having a back electrode and a twist ball layer disposed between the transparent electrode substrate and the back electrode substrate, wherein the twist ball sheet is cured A resin, a twist ball dispersed in the cured resin, and a solvent, and the volume ratio of the cured resin and the twist ball as a solid content is in the range of 2: 3 to 3: 7, and the cured A twist ball-containing layer in which a part of the twist ball is exposed from the resin, and a part of the twist ball is exposed from the cured resin of the twist ball-containing layer. It has a cured resin layer formed on the exposed surface and containing a second cured resin.

  According to the present invention, the twisted ball-containing layer having a high twisted ball density can be obtained by mixing the cured resin and the twisted ball in the twisted ball-containing layer at a predetermined volume ratio. Moreover, according to this invention, by having a cured resin layer on a twist ball content layer, it can suppress that a part of twist ball is exposed from the cured resin contained in a twist ball content layer. Thereby, it can be set as the twist ball type electronic paper excellent in the display characteristic.

  In the present invention, it is preferable that the twist ball-containing layer has a base layer that is formed on a surface opposite to the surface on which the cured resin layer is formed and includes a third cured resin. This is because the strength of the twist ball sheet can be improved.

  The twisting ball type electronic paper of the present invention can be used by sticking to an advertising medium installed in an outdoor environment, for example. Examples of the advertising medium include a signboard, an advertising tower, a building wall surface, and a vehicle.

  The twist ball type electronic paper of the present invention can be the same as the contents described in the above-mentioned sections “B. Twist ball type electronic paper” and “C. Twist ball sheet”. Description is omitted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described with reference to examples and comparative examples.

[Examples 1 to 4]
(Twist ball-containing layer forming process)
A twist ball having an average particle diameter of about 100 μm and having a black phase positively charged in black and a white phase negatively charged in white was prepared. This was dispersed in a silicone resin, which is a thermosetting resin, to obtain a twist ball-containing material. At this time, in the twist ball-containing material, the volume ratio of the curable resin and the twist ball as the solid content was adjusted to a predetermined range as shown in Table 1. Next, the obtained twist ball-containing material was applied onto a glass substrate by an applicator, and then the curable resin contained in the twist ball-containing material was heated and cured at 100 ° C. In this way, a twist ball-containing layer (thickness: 140 μm) was obtained. When the surface of the twist ball-containing layer was observed, a part of the twist ball was exposed from the cured resin. In the twist ball-containing layer, the volume ratio of the curable resin and the twist ball as a solid content is shown in Table 1.

(Curing resin layer forming process)
A second curable resin, which is a thermoplastic resin, was applied to the surface of the obtained twisted ball-containing layer with an applicator, and then heated and cured at 100 ° C. Thereby, a cured resin layer (thickness: 25 μm) was obtained.

(Peeling process)
The twist ball-containing layer and the cured resin layer were peeled off from the glass substrate. As a result, a twisted ball sheet having a thickness of 165 μm was obtained.

[Comparative Examples 1 and 2]
In the twist ball-containing material, the volume ratio of the curable resin and the twist ball as a solid content is within a predetermined range as shown in Table 1, and in the twist ball-containing layer, the cured resin and the twist ball as a solid content The volume ratio was within a predetermined range as shown in Table 1. Further, a twist ball sheet was obtained in the same manner as in Example except that the thickness of the twist ball containing layer was 165 μm and the cured resin layer forming step was not performed.

[Evaluation]
(density)
About the twist ball sheet obtained by Examples 1-4 and Comparative Examples 1 and 2, the density of the twist ball in the twist ball containing layer was measured. In addition, the density (filling rate or concealment rate) of the twist ball in the twist ball-containing layer is determined by observing the plane of the twist ball-containing layer using a microscope and from the obtained plane image, the twist ball region and the cured resin region. It was measured by calculating the area ratio. The density was evaluated as follows. The results are shown in Table 1. The density of Comparative Example 2 was not measurable.
A: The density of the twist balls was higher than that of the evaluation of ○, and the plane of the twist ball containing layer was uniformly hidden by the twist balls.
○: The density of the twist ball was high, and the plane of the twist ball-containing layer was uniformly hidden by the twist ball.
X: The density of the twist ball was low, and the plane of the twist ball-containing layer was not uniformly hidden by the twist ball.

(Film quality)
The film quality of the twist ball sheets obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was evaluated. The film quality was evaluated by visually observing the surface of the twist ball sheet. The film quality was evaluated as follows. The results are shown in Table 1.
A: The surface of the twist ball sheet was good without exposure of the twist ball.
◯: The surface of the twist ball sheet was good because the twist ball was not exposed, although there were irregularities.
X: The twist ball sheet could not be formed into a film.

  As shown in Table 1, as a result of evaluating the density and film quality, Examples 2 and 3 are “◎”, Examples 1 and 4 are “◯”, and Comparative Examples 1 and 2 are “x”. Met. That is, the following was found from Examples 1 to 4 and Comparative Examples 1 and 2. The twist ball sheets obtained in Examples 1 to 4 were able to increase the density of the twist balls. On the other hand, the twist ball sheet obtained by Comparative Examples 1 and 2 did not use the curable resin and the twist ball in a predetermined volume ratio, and thus the density of the twist balls could not be increased. Moreover, since the cured resin layer was able to be formed by the cured resin layer formation process, the twist ball sheet obtained by Examples 1-4 could be made into favorable film quality. Therefore, it is possible to suppress the occurrence of problems such as the falling of the twist ball from the twist ball-containing layer, and moreover, the twist ball-containing layer is efficiently peeled from the support despite the increase in the density of the twist balls. I was able to.

DESCRIPTION OF SYMBOLS 1 ... Twist ball 2 ... Curable resin 3a ... Transparent electrode 3b ... Transparent base material 3 ... Transparent electrode base material 4a ... Back electrode 4b ... Back base material 4 ... Back electrode base material 5 ... Solvent 6 ... Support body 7 ... Underlayer DESCRIPTION OF SYMBOLS 10 ... Twist ball content layer 11 ... Cured resin layer 12 ... Twist ball sheet 100 ... Twist ball type electronic paper

Claims (8)

The support contains a curable resin and a twist ball dispersed in the curable resin, and the volume ratio of the curable resin and the twist ball as a solid content is in the range of 2: 3 to 3: 7. A twist ball-containing layer forming step of forming a twist ball-containing layer by disposing a twist ball-containing material, and curing the curable resin contained in the twist ball-containing material;
A cured resin layer forming step of forming a cured resin layer by disposing a second curable resin on the twist ball-containing layer and curing the second curable resin;
A method for producing a twist ball sheet, comprising: a peeling step of peeling the twist ball-containing layer and the cured resin layer from the support. Before the twisting ball-containing layer forming step, there is an underlayer forming step in which a third curable resin is disposed on the support and the underlayer is formed by curing the third curable resin. And
The method for producing a twist ball sheet according to claim 1, wherein the twist ball-containing layer forming step is a step of forming the twist ball containing layer on the underlayer. A transparent electrode substrate having a transparent substrate and a transparent electrode formed on the transparent substrate, a back electrode substrate having a back electrode and a back electrode formed on the back substrate, and the transparent electrode base A twist ball type electronic paper manufacturing method for manufacturing a twist ball type electronic paper having a material and a twist ball layer disposed between the back electrode base material,
The twist ball layer forming step of forming the twist ball layer includes a curable resin and a twist ball dispersed in the curable resin on a support, and the curable resin and the twist ball as solid components. A twist ball-containing layer is formed by disposing a twist ball-containing material having a volume ratio of 2: 3 to 3: 7 and curing the curable resin contained in the twist ball-containing material. Twist ball containing layer forming step, a cured resin layer forming step of forming a cured resin layer by disposing a second curable resin on the twist ball containing layer and curing the second curable resin, A peeling step of peeling the twist ball-containing layer and the cured resin layer from the support, and the twist ball-containing layer and the cured resin layer as a solvent. Method of manufacturing a twist ball type electronic paper is characterized by having a swelling step of the twist ball layer by swelling by immersed. Before the twisting ball-containing layer forming step, there is an underlayer forming step in which a third curable resin is disposed on the support and the underlayer is formed by curing the third curable resin. And
4. The method for producing twist ball type electronic paper according to claim 3, wherein the twist ball containing layer forming step is a step of forming the twist ball containing layer on the underlayer. A cured resin, and a twist ball dispersed in the cured resin, wherein a volume ratio of the cured resin and the twist ball as a solid content is in a range of 2: 3 to 3: 7, and the A twist ball-containing layer in which a part of the twist ball is exposed;
A twisted ball sheet, comprising: a twisted resin layer formed on a surface of the twisted ball-containing layer where a part of the twisted ball is exposed from the cured resin and including a second cured resin.   6. The twist according to claim 5, wherein the twist ball-containing layer is formed on a surface opposite to the surface on which the cured resin layer is formed, and has a base layer containing a third cured resin. Ball seat. A transparent electrode substrate having a transparent substrate and a transparent electrode formed on the transparent substrate, a back electrode substrate having a back electrode and a back electrode formed on the back substrate, and the transparent electrode base A twist ball type electronic paper having a material and a twist ball layer disposed between the back electrode base material,
The twist ball layer includes a cured resin, a twist ball dispersed in the cured resin, and a solvent, and a volume ratio of the cured resin and the twist ball as a solid content is 2: 3 to 3: 7. A twist ball-containing layer in which a portion of the twist ball is exposed from the cured resin, and the twist ball-containing layer formed on a surface of the twist ball that is partially exposed from the cured resin, A twisted ball type electronic paper comprising a cured resin layer containing a second cured resin.   8. The twist according to claim 7, wherein the twisted ball-containing layer is formed on a surface opposite to the surface on which the cured resin layer is formed, and has a base layer containing a third cured resin. Ball-type electronic paper.