JP6550857B2 - Twist ball sheet manufacturing method, twist ball type electronic paper manufacturing method, twist ball sheet - Google Patents

Description

  The present invention relates to a method of manufacturing a twist ball sheet excellent in display characteristics.

  In recent years, display media called electronic paper have 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-hue spherical particles (twist ball) has attracted attention from the viewpoint of excellent outdoor visibility and low power consumption (Patent Document 1) 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. Also, in general, the twisting ball layer 16 in the twisting ball type electronic paper 100 immerses the twisting ball sheet including the curable resin 2 and the twisting 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 conducted various studies to improve the display characteristics of the twist ball type electronic paper based on the display principle of such twist ball type electronic paper, and as a result, the display characteristics of the twist ball type electronic paper It has been found that the improvement is realized by reflecting more light by the twisting ball. Therefore, the inventors of the present invention tried to increase the amount of twist balls 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 contained in the twist ball sheet along with the increase in the amount of twist balls contained in the twist ball sheet. 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 conducted intensive studies to solve the above problems, and as a result, in order to increase the amount of twist balls contained in the twist ball sheet and to prevent the thickness of the twist ball sheet from increasing, When the amount of the cured resin material contained in the twist ball sheet is reduced, 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 We discovered a new problem that the part was exposed from the cured resin 2. As described above, in the twisting ball sheet, when part of the twisting ball is exposed from the cured resin, the twisting ball sheet swells in a solvent and when it is used for a twisting ball type electronic paper, the twisting occurs even if a voltage is applied. There is a problem that the ball does not rotate and the display characteristics are degraded. In addition, in the twist ball sheet, when a part of the twist ball is exposed from the cured resin, the exposed twist ball falls off the twist ball sheet, and the display characteristics are deteriorated when it is used for 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.

  The present inventors, when used in a twist ball type electronic paper, by providing a cured resin layer on the surface where a part of the twist ball is exposed from the cured resin in the twist ball sheet, based on the above-mentioned new problem. 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 comprises, on a support, a curable resin and a twist ball dispersed in the curable resin, and the volume ratio of the curable resin to the twist ball is 2: 3 as a solid content. A twist ball-containing layer forming step of forming a twist ball-containing layer by arranging a twist ball-containing material in the range of -3: 7 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, 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, it is possible to obtain a twist ball-containing layer having a high density of twist balls by mixing the curable resin in the twist ball-containing material and the twist balls 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 sheet excellent in display characteristics can be obtained.

  In the present invention, a third curable resin is disposed on the support before the twist ball-containing layer forming step, and an underlayer is formed by curing the third curable resin. It is preferable that it has a base formation process, and the said twist ball containing layer formation process is a process of forming the said twist ball containing layer on the said foundation layer. It is possible to obtain a higher strength twisted ball sheet.

  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. What is claimed is: 1. A method for producing a twist ball type electronic paper, comprising producing a twist ball type electronic paper comprising: the transparent electrode base material and a twist ball layer disposed between the back electrode base material. The forming step of the twisting ball layer includes, on a support, a curable resin and a twisting ball dispersed in the curable resin, and the volume ratio of the curable resin to the twisting ball is a solid content. 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. Forming a second curable resin on the twist ball-containing layer, and forming a cured resin layer by curing the second curable resin. A cured resin layer forming step, a peeling step of peeling the twist ball-containing layer and the cured resin layer from the support, and a twist ball by swelling the twist ball-containing layer and the cured resin layer in a solvent The present invention provides a method for producing a twist ball type electronic paper characterized by having a swelling step as 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. Further, according to the present invention, by forming the cured resin layer on the twist ball containing layer, it is possible to suppress that a part of the twist ball is exposed from the curable resin contained in the twist ball containing layer. Thereby, a twist ball type electronic paper excellent in display characteristics can be obtained.

  In the present invention, a third curable resin is disposed on the support before the twist ball-containing layer forming step, and an underlayer 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. It is possible to obtain higher strength twist ball type electronic paper.

  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 solid content is in the range of 2: 3 to 3: 7, A second cured resin is formed on the twist ball-containing layer in which a portion of the twist ball is exposed from a cured resin, and the surface of the twist ball-containing layer on which a portion of the twist ball is exposed from the cured resin. And a cured resin layer containing the same.

  According to the present invention, by mixing the cured resin in the twist ball containing layer and the twist ball at a predetermined volume ratio, it is possible to make the twist ball containing layer with a high density of twist balls. Further, according to the present invention, by providing the cured resin layer on the twist ball containing layer, it is possible to suppress the exposure of part of the twist ball from the curable resin contained in the twist ball containing layer. Thereby, it can be set as the twist ball sheet excellent in display characteristics.

  In the present invention, it is preferable to have an underlayer formed on the surface of the twist ball-containing layer opposite to the surface on which the cured resin layer is formed, and containing 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, It is a twist ball type electronic paper which has a twist ball layer arranged between the above-mentioned transparent electrode base material and the above-mentioned back electrode base material, and the above-mentioned twist ball layer was dispersed in hardening resin and the above-mentioned hardening resin. It contains a twist ball and a solvent, and the volume ratio of the cured resin and the twist ball as solid content is in the range of 2: 3 to 3: 7, and a part of the twist 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, by mixing the cured resin in the twist ball containing layer and the twist ball at a predetermined volume ratio, it is possible to make the twist ball containing layer with a high density of twist balls. Further, according to the present invention, by providing the cured resin layer on the twist ball containing layer, it is possible to suppress the exposure of part of the twist ball from the cured resin contained in the twist ball containing layer. Thereby, a twist ball type electronic paper excellent in display characteristics can be obtained.

  In the present invention, it is preferable to have an underlayer formed on the surface of the twist ball-containing layer opposite to the surface on which the cured resin layer is formed, and containing a third cured resin. It is possible to make 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 | seat 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 | seat.

  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. Method for Producing Twisted Ball Sheet The method for producing a twisted ball sheet according to the present invention comprises a curable resin and a twist ball dispersed in the curable resin on a support, and the curable resin as the solid content A twist ball-containing layer is provided by arranging 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. And a second curable resin is disposed on the twist ball-containing layer to form a cured resin layer by curing the second curable resin. It is a manufacturing method characterized by including a layer forming step and a peeling step of peeling the twist ball-containing layer and the cured resin layer from the support.

  The manufacturing method of the twist ball sheet | seat of this invention is demonstrated using figures. FIG. 1 is a schematic process drawing showing an example of the method for producing a twist ball sheet of the present invention. As shown in FIG. 1 (a), the method for producing a twist ball sheet according to the present invention includes a curable resin 2 and a twist ball 1 dispersed in the curable resin 2 on a support 6. 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 according to the present invention, the twist ball-containing material is characterized in that the volume ratio of the curable resin to the twist ball as solid content is in the range of 2: 3 to 3: 7.

  According to the present invention, it is possible to obtain a twist ball-containing layer having a high density of twist balls by mixing the curable resin in the twist ball-containing material and the twist ball at a predetermined volume ratio, which is obtained according to the present invention 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 the twist ball sheet having a low density of twist balls, when light is incident on the twist ball layer formed of the twist ball sheets, the number of twist balls contributing to the reflection of light 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, since the twist ball sheet obtained by the present invention has a high density of twist balls, when light is incident on the twist ball layer composed of the twist ball sheets, many twist balls contribute to light reflection. Become. For these reasons, in the present invention, it is considered that a twist ball sheet having excellent display characteristics can be obtained.

  Also, in a conventional twist ball sheet containing twist balls and a cured resin material, the twist is performed to increase the amount of twist balls in order to increase the density of the twist balls and to prevent the thickness of the twist ball sheets 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 cured resin material is suppressed by increasing the amount of the twist ball contained in the twist ball sheet, there is a problem that a part of the twist ball is exposed from the cured resin. As described above, in the twisting ball sheet, when part of the twisting ball is exposed from the cured resin, the twisting ball sheet swells in a solvent and when it is used for a twisting ball type electronic paper, the twisting occurs even if a voltage is applied. There is a problem that the ball does not rotate and the display characteristics are degraded. In addition, in the twist ball sheet, when a part of the twist ball is exposed from the cured resin, the exposed twist ball falls off the twist ball sheet, and the display characteristics are deteriorated when it is used for 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 a twist ball type electronic paper, the twist ball can be favorably rotated by the application of 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 | seat of this invention is demonstrated.

1. Twist Ball-Containing Layer Forming Step The twist ball-containing layer forming step in the present invention comprises a curable resin and a twist ball dispersed in the curable resin on a support, and the curable resin and the twist ball as a solid content Forming a twist ball-containing layer by arranging 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 is there.

  The thickness of the twist ball-containing layer formed in this step is due to the thick thickness of the twist ball layer composed of the twist ball sheet when the twist ball sheet obtained according to the present invention is used for a twist ball type electronic paper The thickness is preferably such that the display characteristics do not deteriorate. Above all, in the present step, it is preferable that a part of the twist ball contained in the twist ball sheet has a thickness such that it 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, for example, preferably larger than 5 μm, 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, particularly 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 in the above range, when the twist ball sheet obtained according to the present invention is used for a twist ball type electronic paper, the thickness of the twist ball layer composed of the twist ball sheet becomes large. 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 has a step of arranging 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 disposing step and the curing step included in the twist ball containing layer forming step will be described.

(1) Arrangement Step The arrangement step in the twist ball-containing layer formation step is a step of arranging the 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, the 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, immersion pulling method, curtain coating method, die coating Coating methods such as a method, a casting method and a bar coating method can be mentioned.

  Hereinafter, the twist ball containing material and support used in the arrangement process will be described.

(A) Twist Ball-Containing Material The twist ball-containing material used in this step is a material containing a curable resin and a twist ball dispersed in the curable resin. Moreover, the twist ball containing material has a volume ratio of curable resin and twist ball as solid content in the range of 2: 3 to 3: 7. In the present invention, among others, the volume ratio of the curable resin to 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 a 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 works as a display medium when the twist ball sheet obtained according to the present invention is used for a twist ball type electronic paper.

  The twist ball used for the twist ball-containing material is spherical and has two hues of a colored phase / white phase or a different colored phase / colored phase, and has different dipoles having different two hues. 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, the microchannel manufacturing method uses one in which the colored continuous phase and the spherical particle forming phase are in an O / W type or W / O type relationship with each other, and from the first microchannel to which the colored continuous phase is transferred, By discharging two colored continuous phases in sequence into the spherical particle formation phase of the fluid medium flowing to the second microchannel, charging characteristics of two-hue spherical polymer particles and having (±) polarity in electric charge It is a manufacturing method which manufactures the twist ball which is spherical particles.

  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 of different positively and negatively charged polymerizable monomers, transferred to the first microchannel, and then this colored continuous phase is dispersed in the aqueous or oily spherical particulate phase flowing in the second microchannel. The ink is discharged continuously or intermittently. Then, the discharge material discharged into the spherical particle formation phase is sequentially sphericalized into the spherical particle formation phase while being spherical particle formation during a series of discharge, dispersion, and transfer in the microchannel, so 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, and for example, any of black and white, red and white, yellow and white, blue and white, green and white, purple and white, etc. The phase separation hue of two colors selected from "a chromatic phase and a white phase", or the phase separation hue of two colors having a different "colored phase and a colored phase" can be mentioned. The colorant for forming such a hue is not particularly limited as long as it is insoluble or uniformly dispersed in a fluid dispersion medium containing a polymerizable resin component described later, and is appropriately selected and used. 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 add suitably suitably within the range of.

  As the polymerizable resin component or polymerizable monomer used for the twist ball, the chargeability of the twist ball is respectively (-) chargeability depending on the type of functional group or substituent of the polymerizable monomer used for the twist ball. Monomer species which tend to exhibit (+) chargeability can be mentioned. Therefore, in the case where at least two or more of plural kinds of monomers are used as the polymerizable resin component in the present invention, it is preferable to use the same kind of charge, since it is known to tend to exhibit the (+) and It is also possible to suitably use a combination of a plurality of monomers which tend to have a property.

  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 polymerizable monomer having the tendency of (−) chargeability and the polymerizable monomer having the tendency of (+) chargeability, for example, those described in JP-A No. 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 the colored continuous phase in the second microchannel already described above is used in combination with other copolymerizable monomers, Depending on the desired chargeability or electrophoreticity entrusted to the colored resin microparticles, on a weight basis, the monomer tending to be chargeable is preferably in the range of 1% to 100% of all monomers. Copolymer particles with a polymerizable monomer preferably in the range of 5% to 100%, particularly preferably in the range of 10% to 100% are suitably used suitably to provide the desired twist ball can do.

The twist ball is a spherical monodispersed particle, and the average particle diameter thereof is within a range of 1.0 μm to 400 μm, preferably, within a range of 20 μm to 200 μm, and more preferably, 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 uniformity is expressed as a Cv value, and suitably used as a twist ball of monodispersed particles of 20% or less, preferably 5% or less, more preferably 3% or less.
Here, the average particle size is an average particle size by microscopic observation. The average particle size by microscopic observation is obtained, for example, by performing microscopic observation at 100 ×, measuring 100 of the particle sizes of arbitrary particles with image processing software or the like, and averaging the number. The particle diameter refers to the average value of the major and minor axis diameters of the particles.

(Ii) Curable resin The curable resin contained in the twist ball-containing material is used by being mixed with the above-mentioned twist ball, and when using the twist ball sheet obtained by the present invention for a 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 silicone resin, finely crosslinked acrylic resin, finely crosslinked styrene resin, and 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 needed. Examples of other materials include a solvent. When the twist ball-containing material contains a solvent, the twist ball-containing material can be efficiently applied onto the support in the placement step. In addition, about the solvent used for twist ball containing material, since it can be made to be the same as 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), cyclic polyolefin (COP) and the like.

(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. Moreover, when a twist ball containing material contains a solvent as another material, a hardening process is a process of removing the solvent contained in the said twist ball containing material, and hardening the said curable resin.

  The curing step in the present invention is not particularly limited as long as it is a step capable of curing the curable resin contained in the twist ball-containing material. The specific curing step is appropriately selected according to the type of the 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. The above-described heating step and light irradiation step can be performed in the same manner as in a general method, and thus the description thereof is omitted here.

2. Cured Resin Layer Forming Step In the cured resin layer forming step in the present invention, a second curable resin is disposed on the twist ball-containing layer, and the second resin is cured to cure the cured resin layer. 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, a method of forming a cured resin layer by applying a second curable resin on a twist ball containing layer and then curing the second curable resin may be mentioned. 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 process contains 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.

  In addition, the second curable resin used in this step may be the same as or different from the curable resin contained in the twist ball-containing material used in the disposing step described above. In the present invention, the second curable resin constituting the cured resin layer and the curable resin contained in the twist ball-containing material are preferably materials having similar refractive indices, and in particular, the same material. Is preferred. When the twist ball sheet obtained by the present invention is used for a twist ball type electronic paper, it is possible to suppress refraction or reflection of incident light at the interface between the cured resin layer and the twist ball containing layer. The second curable resin is the same as the contents described in the 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, Among them, 0.1 or less is preferable, and 0.05 or less is particularly preferable. 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 multi-wavelength 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. It is preferable that it is the same material among them. When the twist ball sheet obtained by the present invention is swollen and used in a 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 By the difference in the degree of swelling, defects 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, it is preferably 5% or less. 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. The difference in the degree of swelling here is YX (%) where the volume change rate of the twist 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 measure 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 according to the present invention is used for twist ball type electronic paper with the twist ball containing layer side as the visual recognition side. The colorant used in the cured resin layer can be the same as that generally used, and thus the description thereof is omitted here. When the cured resin layer contains, for example, a black colorant, the contrast can be improved when the twist ball sheet obtained according to the present invention is used for a twist ball type electronic paper. When the cured resin layer contains, for example, a white colorant, when the twist ball sheet obtained according to the present invention is used for a 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 or blue, excellent designability can be obtained when the twist ball sheet obtained according to the present invention is used for a twist ball type electronic paper. 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 contained 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. Also, it is possible to suppress the twisting ball from falling off from the twisting ball-containing layer. Furthermore, in the peeling step described later, it is possible to efficiently peel the twist ball-containing layer from the support. 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. 1 (b), the point to the distance _{t 2.}

  The cured resin layer formed in this step can be confirmed, for example, by observing the cross section of the twist ball sheet using 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 The interface with the cured resin layer which does not have can be confirmed.

3. Peeling Step The peeling step in the present invention is a step of peeling the twist ball-containing layer and the cured resin layer from the support.

  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) Base Layer Forming Step In the twist ball sheet manufacturing method of the present invention, the third curable resin is disposed on the support before the twist ball containing layer forming step, and Having a base layer forming step of forming a base layer by curing the curable resin of 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 has a base layer forming step, the twisting 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.

  Further, in the case where the method for producing a twist ball sheet of the present invention has a base layer forming step, as shown in FIG. 2A, the third curable resin 7 ′ is disposed on the support 6. And an underlayer forming step of forming the underlayer 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 ′. Further, as shown in FIG. 2C, a second step of forming a cured resin layer 11 by disposing a second curable resin 11 ′ and curing the second curable resin 11 ′. And further, as shown in FIG. 2D, it has a peeling step of peeling the twist ball-containing layer 10 and the cured resin layer 11 from the support 6.

  The base layer forming step in the present invention is not particularly limited as long as it is a step of disposing the third curable resin on the support and curing the third curable resin to form the base layer. 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 process contains a third curable resin. The underlayer is preferably a layer containing only the third curable resin. Here, "containing only the third curable resin" means that the twist ball is not contained.

  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. The specific reason and other explanations for the third curable resin can be the same as those for the second curable resin described in the above section “2. 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. The specific thickness of the underlayer is, for example, preferably in the range of 10 μm to 150 μm, and 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 twist ball sheet is used as a twist ball layer of a twist ball type electronic paper, swelling in which the twist ball sheet is caused to swell by being immersed 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 step can be the same as the contents described in the section "B. Method for manufacturing twist ball type electronic paper" described later, and thus the description thereof is omitted here.

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 type electronic paper comprising a back electrode substrate having a back electrode formed on the substrate and a twist ball layer disposed between the transparent electrode substrate and the back electrode substrate 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 having a volume ratio of the curable resin to the twist ball in the range of 2: 3 to 3: 7 as 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 it a twist ball layer by making the above-mentioned cured resin layer swell by making it immerse in a solvent.

  The manufacturing method of the twist ball type electronic paper of this invention is demonstrated using figures. FIG. 3 is a schematic flow chart showing an example of the method for producing the twist ball type electronic paper of the present invention. As shown in FIG. 3D, the method of manufacturing the twist ball type electronic paper according to the present invention includes 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 of manufacturing a twist ball type electronic paper 100 having a back electrode base 4 having a base 4 b and a back electrode 4 a formed on the back base 4 b 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 a pair of sealing films 15a is formed from the opening 14 using a stripping tool R such as a roller. , 15b, and after the gas g and the excess solvent 1 are discharged, as shown in FIG. 3C, the sealing portion 13 is formed to close the opening. Subsequently, by disposing the back electrode substrate 4 on the surface of the twist ball layer 16 opposite to the surface on which the transparent electrode substrate 3 is disposed, the twist ball type electronic paper 100 can be obtained. In FIG. 3D, the back electrode spacer layer 41 having a via hole provided so that the back electrode base material 4 further overlaps 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 twisting ball layer forming step of forming the twisting ball layer includes a twisting ball sheet forming step of forming a twisting ball sheet, and a swelling step of causing the twisting ball sheet to be dipped and swollen in a solvent. 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 contains twist balls and a curable resin at a predetermined volume ratio, and a cured resin layer is formed on the twist ball-containing layer. Thus, a twist ball type electronic paper excellent in display characteristics can be obtained. The specific reason can be the same as the contents described in the above-mentioned section “A. Manufacturing method of twist 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 comprises a curable resin and a twist ball dispersed in the curable resin on a support, and the curable resin and the twist as a solid content A twist ball-containing material having a volume ratio of 2: 3 to 3: 7 is disposed to form a twist ball-containing layer by curing the curable resin contained in the twist ball-containing material. 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 It is a process which has the swelling process made into a twist ball layer by making it immerse in a solvent and making it swell.

  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, particularly preferably in the range of 100 μm to 700 μm, and particularly preferably in the range of 200 μm to 500 μm. If the thickness of the twist ball layer is smaller than the above range, the twist ball may not rotate well. When the thickness of the twist ball layer is larger than the above range, the driving voltage may be high.

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 the contents described in the above-mentioned "A. Method for manufacturing twist ball sheet". Therefore, the description here is omitted.
Hereinafter, each configuration of the swelling step and the twist ball type electronic paper will be described.

1. Swelling Step The swelling step in the present invention is a step of immersing and twisting a twist ball sheet in a solvent.

  The swelling step in the present invention is not particularly limited as long as the twist ball sheet obtained in the above-described twist ball sheet forming step can be immersed in a solvent to be swollen. 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 smooth rotation of the twist balls contained in the twist ball sheet. The material used for such a solvent is not particularly limited as long as the material can smoothly rotate the twist ball, and examples thereof include dimethyl silicone oil, isoparaffinic solvent, and linear paraffinic solvent, dodecane, Linear alkanes such as tridecane are mentioned.

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

(1) Twist Ball Layer The twist ball layer in the present invention is obtained by the above-mentioned twist ball layer forming step. 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 sealed and used 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. 3 (d), the twist ball containing layer 2 side in the twist ball layer 16 may be viewed side, although not shown, the cured resin layer 11 side is viewed in the twist ball layer. It may be on the side. In addition, about the twist ball sheet which comprises a twist ball layer and a twist ball layer, suppose that it is the same as that of the content described in the said "1. twist ball layer formation process" and the "A. manufacturing method of a 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 the present invention supports a transparent electrode. The transparent substrate may be a rigid transparent substrate, or may be a flexible transparent substrate.

  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. Further, as the glass, soda lime glass, non-alkali glass, quartz glass and the like can be mentioned.

  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, for example, preferably 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 the transparent substrate when the twist 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, and, 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, A carbon nanotube, a graphene, etc. are mentioned.

  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 Configurations The transparent electrode substrate in the present invention is not particularly limited as long as it has the above-described transparent substrate and transparent electrode, and necessary configurations can be appropriately selected and added. As such a configuration, for example, an auxiliary electrode, a wiring and the like can be mentioned.

(D) Method of Forming a Transparent Electrode Substrate As a method of forming a transparent electrode substrate used in the present invention, for example, a method of disposing a transparent electrode on a transparent substrate after film formation of a transparent electrode may be mentioned. .

  A general electrode deposition method can be used for the film deposition method of the transparent electrode. 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 a method of arranging a transparent electrode on a transparent substrate include a method of directly forming a transparent electrode on a transparent substrate, and a method of bonding a transparent substrate and a transparent electrode using an adhesive layer. . A well-known thing can be used about the adhesive used for an adhesion layer.

(3) Back Electrode Substrate The back electrode substrate used in the present invention is a member having a back substrate and a back electrode formed on the back substrate.
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 an insulating property.

  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 is not necessary to have transparency.

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

(B) Back electrode The back electrode in the present invention is used as a display electrode when the twist ball type electronic paper obtained by the present invention performs fixed information display, 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, “a pattern shape corresponding to information displayed on the twist ball type electronic paper” corresponds not only to the same shape as 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 it is conductive and can display information by using a twist ball layer described later by applying a voltage to the back electrode. As materials used for such a back electrode, for example, metals such as Au, Al, Ag, Ni, Cu, etc., transparent conductors such as ITO, SnO ₂ , ZnO: Al, etc., conductive agents mixed with solvent or 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 the 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 surface base material, and when the back surface electrode has the back electrode insulating layer, it may be formed on the wiring electrode insulating layer. The material of the wiring insulating layer can be the same as the material used for the back electrode insulating layer described above, and thus the description thereof is omitted here.

(D) Method of Forming Back Electrode Substrate As a method of forming the back electrode substrate used in the present invention, there may be mentioned, for example, a method of forming the back electrode and then arranging the back electrode on the back substrate. .

  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 a sputtering method, a vacuum evaporation method, a CVD method, a coating method, 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 may have at least the twist ball layer, the transparent electrode base material and the back electrode base material described above. Such a twist ball type electronic paper may have, for example, a sealing film as another configuration.

  In the present invention, the twist ball type electronic paper has a sealing film for sealing the transparent electrode base material, the back electrode base material and the twist ball layer, whereby the water resistance and moisture resistance of the twist ball type electronic paper are obtained. 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 manufacturing 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 manufacturing a twist ball type electronic paper having a transparent electrode base, a back electrode base and a twist ball layer.

  In the twist ball type electronic paper obtained by the present invention, the transparent substrate of the transparent electrode substrate, the transparent electrode and the twist ball layer may be arranged in this order, and the transparent electrode of the transparent electrode substrate and the transparent substrate 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 The drive voltage of the twist ball can be made smaller than in the case of

  In the twist ball type electronic paper obtained by the present invention, the back substrate of the back electrode substrate, the back electrode and the twist ball layer may be arranged in this order, and the back electrode and back substrate of the back electrode substrate The material and the twist ball layer may be arranged in this order. For example, when the back substrate of the back electrode substrate, the back electrode and the twist ball layer are arranged in this order, the back electrode of the back electrode substrate, the back substrate and the twist ball layer are arranged in this order The drive voltage of the display medium can be made smaller than in the case of 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 becomes easy.

C. Twisted Ball Sheet The twisted ball sheet of the present invention comprises a cured resin, and a twist ball dispersed in the cured resin, and the volume ratio of the cured resin to the twist ball is 2: 3 to 3: 7 as solid content. Formed on the surface of the twist ball-containing layer in which a part of the twist ball is exposed from the cured resin, and the part of the twist ball exposed from the cured resin of the twist ball-containing layer 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. Moreover, the twist ball content layer has a volume ratio of hardened resin and twist ball as solid content in the range of 2: 3 to 3: 7. In the present invention, among others, the volume ratio of the cured resin and the twist ball is preferably in the range of 3: 5 to 1: 2. By setting the volume ratio of the cured resin to the twist ball contained in the twist ball-containing layer within the above range, the density of the twist ball in the twist ball-containing layer can be increased, and the thickness of the twist ball-containing layer is It is possible to suppress the thickening. Therefore, when the twist ball sheet of the present invention is used for a twist ball type electronic paper, it is possible to obtain excellent display characteristics. The volume ratio of the cured resin to the twist ball contained in the twist ball-containing layer is measured by measuring the size (longitudinal, horizontal, height) of the object using a general-purpose length measurement method. be able to. For example, it can measure using a ruler, a micrometer, a microscope or the like.

  Further, in the present invention, it is preferable to have an undercoat layer formed on the surface of the twist ball-containing layer opposite to the surface on which the cured resin layer is formed, and containing a third 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 a twist ball type electronic paper. When using a twist ball sheet for a 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, drying or heat treatment is performed to remove the solvent, thereby measuring the volume ratio of the cured resin to the twist ball contained in the twist ball-containing layer. be able to. The drying or heating temperature and the drying or heating time in the above drying or heat treatment are appropriately adjusted in accordance with the type of the solvent to be removed, and the like. 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 measure 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 and a transparent electrode substrate having a transparent electrode formed on the above transparent substrate, a back substrate and the above back substrate A twist 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 a volume ratio of the cured resin and the twist ball as solid content is in a range of 2: 3 to 3: 7, and the curing A part of the twist ball is exposed from the cured resin of the twist ball containing layer in which a part of the twist ball is exposed from the resin and the twist ball containing layer It is characterized in that it has a cured resin layer formed on the exposed surface and containing a second cured resin.

  According to the present invention, by mixing the cured resin in the twist ball containing layer and the twist ball at a predetermined volume ratio, it is possible to make the twist ball containing layer with a high density of twist balls. Further, according to the present invention, by providing the cured resin layer on the twist ball containing layer, it is possible to suppress the exposure of part of the twist ball from the cured resin contained in the twist ball containing layer. Thereby, a twist ball type electronic paper excellent in display characteristics can be obtained.

  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 twist ball type electronic paper of the present invention can be used, for example, by being attached to an advertising medium installed in an outdoor environment. Advertising media include billboards, advertising towers, building walls, vehicles and the like.

  The twist ball type electronic paper of the present invention can be the same as the contents described in the above-mentioned "B. Method of manufacturing twist ball type electronic paper" and "C. twist ball sheet", so Description is omitted.

  The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. 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 formation process)
A twist ball having an average particle diameter of about 100 μm was prepared, which has a black and positively charged black phase and a white and negatively charged white phase. 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 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.

(Cured resin layer formation process)
A second curable resin, which is a thermoplastic resin, was applied to the surface of the obtained twist ball-containing layer by an applicator, and then heated and cured at 100 ° C. conditions. Thus, 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. Thus, a 165 μm thick twist ball sheet was obtained.

Comparative Examples 1 and 2
In the twist ball-containing material, the volume ratio of the curable resin to the twist ball as a solid content is within a predetermined range as shown in Table 1, and in the twist ball content layer, the solid content as a cured resin and the twist ball The volume ratio of H was a predetermined range as shown in Table 1. Furthermore, a twist ball sheet was obtained in the same manner as in the 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)
The density of the twist balls in the twist ball-containing layer was measured for the twist ball sheets obtained in Examples 1 to 4 and Comparative Examples 1 and 2. The density (filling ratio or hiding ratio) of the twisting ball in the twisting ball-containing layer is determined by observing the plane of the twisting ball-containing layer using a microscope and obtaining a twist ball area and a cured resin area from the obtained plane image. 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.
◎: The density of the twist ball was higher than the evaluation of 、, and the plane of the twist ball-containing layer was uniformly covered by the twist ball.
Good: The density of the twist ball was high, and the plane of the twist ball-containing layer was uniformly covered 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 concealed 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 without any exposure of the twist ball 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, from Examples 1 to 4 and Comparative Examples 1 and 2, the following was found. The twist ball sheet obtained in Examples 1 to 4 was able to increase the density of the twist ball. 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 a defect such as the falling off of the twisting ball from the twisting ball-containing layer, and to efficiently separate the twisting ball-containing layer from the support despite the increase in the density of the twisting ball. 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 surface electrode 4b ... Back surface base material 4 ... Back surface 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)

A twist ball comprising a curable resin and a twist ball dispersed in the curable resin, wherein a volume ratio of the curable resin and the twist ball as a solid content is in a range of 2: 3 to 3: 7. Preparation process to prepare the contained material,
An arrangement step of arranging the twist ball-containing material prepared in the preparation step on a support;
And a curing step of curing the curable resin in the twist ball-containing material disposed on the support by the placement step, and from the cured resin obtained by curing the curable resin by these steps. A twist ball-containing layer forming step of forming a twist ball-containing layer in which a part of the twist ball is exposed;
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;
And a peeling step of peeling the twist ball-containing layer and the cured resin layer from the support. Prior to the twist ball-containing layer forming step, there is provided a base layer forming step of forming a base layer by disposing a third curable resin on the support and curing the third curable resin. And
The method for manufacturing 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 substrate, a back electrode substrate having a back electrode formed on the back substrate, and the transparent electrode substrate A method of manufacturing a twist ball type electronic paper, comprising: manufacturing a twist ball type electronic paper having a material and a twist ball layer disposed between the back electrode base materials,
A twist ball layer forming step of forming the twist ball layer;
A twist ball comprising a curable resin and a twist ball dispersed in the curable resin, wherein a volume ratio of the curable resin and the twist ball as a solid content is in a range of 2: 3 to 3: 7. Preparing the material to be contained;
An arrangement step of arranging the twist ball-containing material prepared by the preparation step on a support;
A curing step of curing the curable resin in the twist ball-containing material disposed on the support by the placement step, and from the cured resin obtained by curing the curable resin by these steps. A twist ball-containing layer forming step of forming a twist ball-containing layer in which a part of the twist ball is exposed;
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 a method of producing a twisted ball type electronic paper comprising a swelling step of immersing the twisted ball-containing layer and the cured resin layer in a solvent to cause the twisted ball layer to swell. Prior to the twist ball-containing layer forming step, there is provided a base layer forming step of forming a base layer by disposing a third curable resin on the support and curing the third curable resin. And
The method for producing a 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 solid content is in a range of 2: 3 to 3: 7, and from the cured resin A twist ball containing layer in which a part of the twist ball is exposed,
A twist ball sheet formed on the surface of the twist ball-containing layer on which a part of the twist ball is exposed from the cured resin, and a cured resin layer containing a second cured resin.   The twist according to claim 5, characterized in that it is formed on the surface of the twist ball-containing layer opposite to the surface on which the cured resin layer is formed, and has an underlayer 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.   The twist according to claim 7, characterized in that it has an undercoat layer formed on the surface opposite to the surface on which the cured resin layer is formed, of the twist ball-containing layer and including a third cured resin. Ball-type electronic paper.