阅读说明：本技术 电泳显示装置和电子设备 (Electrophoretic display device and electronic apparatus ) 是由 中森理夫 于 2018-12-21 设计创作，主要内容包括：一种被设计为选择性地保留电泳粒子并呈现优异的显示特性的电泳显示装置,以及用于实施该电泳显示装置的电子设备。电泳显示装置包括：元件基板,设置为面向相对基板的相对基板,设置在元件基板和相对基板之间的分子X,包含电泳粒子以及分散介质的电泳分散液,其中,电泳分散液设置在相对基板和分子X之间,其中分子X包括具有环状结构的芳族环,例如苯、甲苯、二甲苯等。(An electrophoretic display device designed to selectively retain electrophoretic particles and exhibit excellent display characteristics, and an electronic apparatus for implementing the electrophoretic display device. The electrophoretic display device includes: an element substrate, an opposing substrate disposed to face the opposing substrate, molecules X disposed between the element substrate and the opposing substrate, an electrophoretic dispersion liquid containing electrophoretic particles and a dispersion medium, wherein the electrophoretic dispersion liquid is disposed between the opposing substrate and the molecules X, wherein the molecules X include an aromatic ring having a cyclic structure, such as benzene, toluene, xylene, or the like.)

1. An electrophoretic display device comprising:

a first substrate;

a second substrate disposed to face the first substrate;

a molecule X disposed between the first substrate and the second substrate; and

an electrophoretic dispersion liquid including electrophoretic particles and a dispersion medium, wherein the electrophoretic dispersion liquid is disposed between the first substrate and the molecules X,

wherein the molecule X includes an aromatic ring having a cyclic structure, and the aromatic ring includes any one of benzene, toluene, xylene, mesitylene, pyridine, pyrrole, thiophene, acetophenone, aniline, anisole, benzaldehyde, benzyl alcohol, benzylamine, fluorobenzene, bromobenzene, dibromobenzene, chlorobenzene, dichlorobenzene, phenol, furfural, bromoaniline, nitrobenzene, nitrotoluene, toluidine, naphthalene, anthracene, tetracene, pentacene, benzopyrene, acetone chrysene, pyrene, triphenylene, cardiocyclo-olefin, coronene, and ovalene.

2. An electrophoretic display device as claimed in claim 1, wherein the refractive index of the molecule X is 1.5 to 3.0.

3. An electrophoretic display device as claimed in claim 1 or 2, wherein the molecules X are present in an amount of 1 molecule/10 nm²To 10 molecules/10 nm²Is disposed on the second substrate.

4. An electrophoretic display device as claimed in any one of claims 1 to 3, wherein the electrophoretic particles comprise at least one coloured particle.

5. An electrophoretic display device as claimed in any one of claims 1 to 4, wherein the electrophoretic particles further comprise the molecule X.

6. An electrophoretic display device as claimed in claim 5, wherein the weight fraction of the molecules X comprised in the electrophoretic particles is between 20% and 80%.

7. An electrophoretic display device as claimed in any one of claims 1 to 6, wherein a protective film is provided between the second substrate and the molecules X.

8. An electronic device comprising an electrophoretic display device according to any one of claims 1 to 7.

Technical Field

The invention relates to an electrophoretic display device and an electronic apparatus.

Background

Electrophoretic display devices using particle electrophoresis are known. The electrophoretic display device is advantageous in having portability and low power consumption. In the electrophoretic display device, an image is formed on a display area by applying a voltage between a pixel electrode and a common electrode (having an electrophoretic dispersion liquid containing electrophoretic particles therebetween) facing each other to spatially move the electrophoretic particles such as charged black particles or white particles. Known electrophoretic display devices include, for example, a structure in which a plurality of cells (spaces) are defined by a partition between a pair of substrates, and each cell encloses an electrophoretic dispersion liquid containing electrophoretic particles and a dispersion medium.

More specifically, as such an electrophoretic display device, a device is proposed in which a partition is placed between a common electrode and a pixel electrode respectively disposed on a pair of substrates, and an electrophoretic dispersion is sealed within a cell defined by the pixel electrode, the common electrode, and the partition.

However, when the cell is defined by the pixel electrode, the cell common electrode, and the partition, the electrodes of the pixel electrode and the common electrode directly contact the electrophoretic dispersion liquid. Accordingly, the electrophoretic particles are in contact with at least one of the two electrodes each time an image is formed due to the movement of the electrophoretic particles. As a result, since the electrophoretic particles are adsorbed (adhered) to the electrodes, the electric display characteristics of the electrophoretic display device are significantly reduced.

It is to be noted that the adsorption of the electrophoretic particles may occur not only on the electrodes but also on the constituent material of the separators. As a countermeasure to solve these problems, as described in patent document 1, a countermeasure to suppress adsorption of electrophoretic particles by using a low-polarity material as a constituent material and reducing an attractive force (electrostatic attractive force, van der waals force) between the electrophoretic particles has been performed.

Patent document 1: japanese patent application laid-open (JP-A) No.2017-49552

Disclosure of Invention

However, as a side effect of these measures, there is a problem that retention performance of the electrophoretic particles is lowered. The retention property indicates the degree of retaining a display image in a state where no voltage is applied, in which a voltage is applied between two electrodes to move electrophoretic particles to a display surface to form a display image, and then the application of the voltage is stopped. The configuration with retention property can hold a display image for a long time in a state where no voltage is applied, and the configuration with low retention property can hold a display image for a shorter time than the configuration with high retention property.

The retention properties can be controlled by, for example, increasing the viscosity of the electrophoretic dispersion or continuously applying a voltage. When the viscosity of the electrophoretic dispersion liquid increases, the response time for rewriting a display image becomes long, so that the display performance is degraded. In addition, in the case of a configuration in which a voltage is continuously applied, power consumption increases, and thus it is difficult to apply the configuration to a wearable product limited by an installable power supply.

An object of the present invention is to provide an electrophoretic display device capable of having retention performance for a cell of electrophoretic particles contained in an electrophoretic dispersion liquid and exhibiting excellent display characteristics, and an electronic apparatus.

The electrophoretic display device according to this application example includes: a first substrate, a second substrate disposed to face the first substrate, molecules X disposed between the first substrate and the second substrate, and an electrophoretic dispersion liquid disposed between the first substrate and the molecules X and containing electrophoretic particles and a dispersion medium, wherein the molecules X include an aromatic ring having a cyclic structure, and the aromatic ring includes any one of benzene (phenol), toluene, xylene, mesitylene, pyridine, pyrrole, thiophene, acetophenone, aniline, anisole, benzaldehyde, benzyl alcohol, benzylamine, fluorobenzene, bromobenzene, dibromobenzene, chlorobenzene, dichlorobenzene, phenol, furfural, bromoaniline, nitrobenzene, nitrotoluene, toluidine, naphthalene, anthracene, tetracene, pentacene, benzopyrene, acetone chrysene, pyrene, triphenylene, cardiocyclo-olefin, coronene, and ovalene.

According to this application example, the molecules X disposed between the first substrate and the second substrate have aromatic rings having cyclic structures, and in these cyclic structures, electrons are delocalized. As a result, a bias (polarization) of electron density tends to occur, so that the attraction force of the positively or negatively charged electrophoretic particles becomes stronger.

However, since the attractive force acts slightly stronger than the intermolecular force, the force capable of moving the electrophoretic particles when rewriting the display image by applying a voltage is weak. Therefore, adhesion (adsorption) of the electrophoretic particles can be suppressed, and the retention performance of the electrophoretic particles can be maintained after voltage application, and an electrophoretic display device having excellent display characteristics can be provided.

In the electrophoretic display device described in the application example, it is preferable that the refractive index of the molecule X is 1.5 to 3.0.

According to this application example, since the refractive index of the molecule X is 1.5 to 3.0, polarization tends to occur, and the polarizability can be improved. Therefore, since molecules having a high polarizability are strongly attracted to positively or negatively charged electrophoretic particles, adhesion (adsorption) of the electrophoretic particles can be suppressed, and retention properties of the electrophoretic particles can be maintained after voltage application, so that an electrophoretic display device having excellent display characteristics can be provided.

In the electrophoretic display device described in the application example, the molecules X are preferably arranged on the second substrate at a ratio of 1 molecule/10 nm2 to 10 molecules/10 nm 2.

According to this application example, by adjusting the abundance (abundance) of the molecule X to a ratio of 1 molecule/10 nm2 to 10 molecules/10 nm2, the attraction force between the charged electrophoretic particle and the molecule X having a high polarizability becomes stronger. Accordingly, since the retention property of the electrophoretic particles can be maintained after the voltage is applied, an electrophoretic display device having excellent display characteristics can be provided.

In the electrophoretic display device described in the application example, it is preferable that the electrophoretic particles include at least one color particle.

According to this application example, it is possible to provide an electrophoretic display device capable of performing color display by causing electrophoretic particles to use not only achromatic particles (white particles, black particles) but also chromatic particles.

In the electrophoretic display device described in this application example, preferably, the electrophoretic particles include molecules X.

According to this application example, since pi-pi interaction is performed by the molecules X contained in the electrophoretic particles and the molecules X disposed in the second substrate to apply an attractive force stronger than an intermolecular force, it is possible to suppress adhesion (adsorption) of the electrophoretic particles and maintain the retention property of the electrophoretic particles after voltage application. In addition, since pi-pi interaction is performed even between the electrophoretic particles by the molecules X contained in the electrophoretic particles, the electrophoretic particles may be densely present, so that an electrophoretic display device having display characteristics with high contrast may be provided.

In the electrophoretic display device described in the application example, the weight fraction of the molecules X contained in the electrophoretic particles is preferably 20% to 80%.

According to this application example, since the adhesion (adsorption) of the electrophoretic particles can be suppressed by setting the weight fraction of the molecules X to 20% to 80%, and the retention property of the electrophoretic particles can be maintained after the voltage is applied, an electrophoretic display device having excellent display characteristics can be provided.

In the electrophoretic display device described in the application example, it is preferable that a protective film is provided between the second substrate and the molecules X.

According to this application example, since the protective film is provided between the second substrate and the molecules X, thermal expansion and thermal contraction of the electrophoretic dispersion liquid accompanying temperature change can be solved, so that an electrophoretic display device with high reliability can be provided.

The electronic device according to this application example includes the electrophoretic display device described in the application example.

According to this application example, since an electrophoretic display device having a retention property of electrophoretic particles and having excellent display characteristics is provided, an electronic apparatus having high performance and high reliability can be obtained.

Drawings

The present invention will be described with reference to the drawings, wherein like reference numerals refer to like elements throughout.

Fig. 1 is a perspective view showing an embodiment of an electronic apparatus mounted on an electrophoretic display device according to the present invention.

Fig. 2 is an equivalent circuit diagram showing a first embodiment of an electrical configuration of an electrophoretic display device according to the present invention.

Fig. 3 is a schematic plan view showing a first embodiment of the structure of an electrophoretic display device according to the present invention.

Fig. 4 is a cross-sectional view of a line a-a' of the electrophoretic display device shown in fig. 3.

Fig. 5 is a schematic plan view of the structure of the display region and the peripheral sealing portion of the electrophoretic display device shown in fig. 3.

Fig. 6 is a cross-sectional view of line B-B' of the electrophoretic display device shown in fig. 5.

Fig. 7 is an enlarged plan view illustrating an enlarged portion C of the electrophoretic display device shown in fig. 5.

Fig. 8 is a schematic view of an electrophoretic particle according to the present embodiment.

Fig. 9 is a flowchart illustrating a sequence of steps of a method for manufacturing an electrophoretic display device.

Fig. 10 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 11 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 12 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 13 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 14 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 15 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 16 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 17 is a schematic cross-sectional view for explaining a method of manufacturing the electrophoretic display device shown in fig. 3.

Fig. 18 is a schematic cross-sectional view showing a second embodiment of the structure of an electrophoretic display device according to the present invention.

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following drawings, in order to identify each layer and each member, the ratio of each layer and each member is made different from the actual ratio.

First, before describing an electrophoretic display device according to the present invention, an electronic apparatus (an electronic apparatus according to the present invention) including the electrophoretic display device according to the present invention will be described.

Fig. 1 is a perspective view showing an embodiment of an electronic apparatus mounted on an electrophoretic display device according to the present invention. As shown in fig. 1, the electronic apparatus 100 includes an electrophoretic display device 10 and an interface for operating the electronic apparatus 100. Specifically, the interface is, for example, an operation unit 110 including a switch and the like.

The electronic apparatus 100 includes the electrophoretic display device 10, and is a display module having a display region E. The display region E includes a plurality of pixels, and an image is displayed in the display region E by controlling the pixels with electric power.

The electronic apparatus 100 having the electrophoretic display device 10 is suitable for a watch, a writable device, a smart phone, a tablet terminal, a television, a viewfinder or monitor direct view type video recorder, a car navigation system, a pager, an electronic organizer, an electronic calculator, an electronic newspaper, a word processor, a personal computer, a workstation, a television phone, a POS terminal, a touch screen, etc., in addition to the electronic paper (EPD: electronic paper display) shown in fig. 1.

Next, a first embodiment of the electrophoretic display device 10 (electrophoretic display device according to the present invention) included in the electronic apparatus 100 will be described with reference to fig. 2 to 7.

Fig. 2 is an equivalent circuit diagram showing a first embodiment of an electrical configuration of an electrophoretic display device according to the present invention, fig. 3 is a schematic plan view showing the first embodiment of the structure of the electrophoretic display device according to the present invention, fig. 4 is a cross-sectional view of a line a-a 'of the electrophoretic display device according to the present invention shown in fig. 3, fig. 5 is a schematic plan view of the structure of a display region and a peripheral sealing portion of the electrophoretic display device shown in fig. 3, fig. 6 is a cross-sectional view of a line B-B' of the electrophoretic display apparatus shown in fig. 5, and fig. 7 is an enlarged plan view showing an enlarged portion C of the electrophoretic display device shown in fig. 5. In fig. 5 to 7, the insulating layer, the wiring, the illustrated electrode, and the like are omitted.

As shown in fig. 2, the electrophoretic display device 10 includes a plurality of data lines 12 and a plurality of scan lines 13, and the pixels 11 are arranged in portions where the data lines 12 and the scan lines 13 intersect. Specifically, the electrophoretic display device 10 includes a plurality of pixels 11 arranged in a matrix along data lines 12 and scan lines 13. Each pixel 11 has an electrophoretic dispersion liquid containing electrophoretic particles 34 and a dispersion medium 15 disposed between the pixel electrode 21 and the common electrode 22.

The pixel electrode 21 is connected to the data line 12 via a TFT (transistor) 16. Further, the gate electrode of the TFT16 is connected to the scanning line 13. In addition, fig. 2 is exemplary, and other components, such as a storage capacitor, may be incorporated if desired.

Further, as shown in fig. 3 and 4, the electrophoretic display device 10 includes an element substrate 51 as a first substrate, an opposite substrate 52 as a second substrate disposed to face the element substrate 51, and an electrophoretic layer 33.

The element substrate 51 is provided with, for example, a pixel electrode 21 corresponding to each pixel 11, and the pixel electrode 21 is provided on the first base member 31 made of a transparent glass substrate.

More specifically, as shown in fig. 3 and 4, the pixels 11 (pixel electrodes 21) are formed in a plan view, for example, in a matrix. The pixel electrode 21 is made of a light-transmitting material such as ITO (indium oxide added with tin: indium tin oxide), for example.

A circuit portion (not shown) is provided between the first base member 31 and the pixel electrode 21, including the TFT16 and the like. The TFT16 is electrically connected to each pixel electrode 21 via a contact portion (not shown). Although not shown, in the circuit portion, various wirings (for example, the data line 12 or the scan line 13, or the like) and elements (for example, capacitors) and the like are provided together with the TFT 16. Further, an insulating layer 32 is formed on the entire surface of the first base member 31 including the upper pixel electrode 21.

The element substrate 51 is constituted by the first base member 31, the pixel electrode 21, the insulating layer 32, and the circuit unit.

The common electrode 22 is formed on the second base member 41, and the second base member 41 is included in the opposite substrate 52 and is made of a glass substrate (the electrophoretic layer 33 side in fig. 4). The common electrode 22 is commonly disposed to correspond to the plurality of pixels 11 having translucency. The common electrode 22 uses, for example, a light-transmitting material such as ITO. The opposing substrate 52 includes these second base members 41 and the common electrode 22.

Further, the molecules X are disposed between the element substrate 51 and the opposite substrate 52, and specifically, the molecules X are coated on the common electrode 22, thereby forming the molecule X coating layer 42. The molecular X coating layer 42 formed of the molecules X will be described in detail below.

The electrophoretic layer 33 is disposed between the insulating layer 32 and the molecular X coating layer 42. The electrophoretic layer 33 is composed of an electrophoretic dispersion liquid containing at least one or more electrophoretic particles 34 and a dispersion medium 15, in which the electrophoretic particles 34 are dispersed in the dispersion medium 15. The electrophoretic dispersion liquid (dispersion medium 15 and electrophoretic particles 34) is used to fill a space (region) (divided) defined by the insulating layer 32, the molecular X coating layer 42, and the partition 35 provided on the first base member 31.

As shown in fig. 3, the partition 35 is formed in a grid pattern. The spacer 35 is preferably formed of a transparent material such as acrylic or epoxy. The width of the partition 35 is, for example, 5 μm.

In the embodiment, the structure in which the pixel electrode 21 is provided in each pixel 11 and the partition 35 is provided in each pixel electrode 21 has been described. This is not restrictive, and the partition may be formed in each of a plurality of pixels (for example, every 2 to 20 pixels).

In addition, hereinafter, the area surrounded by the partition 35, the insulating layer 32, and the molecular X coating layer 42 is referred to as a cell 36. Also, a charged electrophoretic layer 33 is included in one cell 36.

Further, the height of the partition 35 is set to be approximately equal to the thickness of the electrophoretic layer 33 defined by the partition 35, for example, preferably not less than 10 μm and not more than 150 μm, more preferably not less than 20 μm and not more than 100 μm, particularly preferably about 30 μm. Thus, display with excellent contrast and white display and black display can be performed by the movement of the electrophoretic particles 34. The electrophoretic particles 34 will be described in detail below.

Further, in the present embodiment, the dispersion medium 15 uses a silicone oil that makes the electrophoretic particles 34 movable at a temperature of about-30 ℃. The viscosity of the silicone oil is, for example, not more than 10 cP. Silicone oil is a low viscosity solvent, and thus, for example, even at low temperatures of about-30 ℃, the electrophoretic particles 34 may migrate between the electrodes at a rate of no more than 500 ms.

As the dispersion medium 15, in addition to the silicone oil, for example, alcohols such as butanol and glycerol, cellosolve such as butyl cellosolve, esters such as butyl acetate, ketones such as dibutyl ketone, pentane, and aliphatic hydrocarbons (liquid paraffin), and nitriles such as acetonitrile can be used.

Further, as shown in fig. 5 and 6, the electrophoretic display device 10 includes a display area E and a frame area E1 surrounding the display area E. The frame region E1 includes a virtual pixel region D (which is a region that does not contribute to the display of the electrophoretic layer 33), a frame spacer 61 disposed outside the virtual pixel region D, and a seal portion 14 positioned outside the frame spacer 61.

In addition, the width of the frame region E1 is, for example, about 1 mm. The width of the dummy pixel region D is, for example, 80 μm. A partition 35a formed in the same shape as the partition 35 provided in the display area E is provided on the display area E side of the dummy pixel area D. The width of the partition walls 35, 35a (the width of the top 35 b) is about not less than 3 μm and not more than 10 μm, and is 5 μm in the present embodiment. The distance between the adjacent spacers 35 and the spacers 35 and 35a is, for example, 150 μm.

Outside the virtual pixel region D, a frame spacer 61 is provided. The frame spacer 61 may block the dispersion medium 15 from flowing outward, and serves to adjust the cell gap and is arranged to surround the virtual pixel region D. In addition, the frame spacer 61 is generally made of the same material as the spacer 35 of the display area E.

The width W1 of the frame spacer 61 is, for example, 100 μm. The height of the frame spacer 61 is, for example, in the range of 10 μm to 50 μm, 33 μm in this embodiment.

In addition, the frame spacer 61 also serves to ensure that the adjacently disposed first seal member 14a does not protrude in the display area E.

In this embodiment, as shown in fig. 6, the seal portion 14 has a first seal material 14a and a second seal material 14 b. The first seal member 14a is used for bonding when the element substrate 51 and the opposing substrate 52 are bonded, and is provided so as to surround the frame spacer 61.

The width W2 of the first sealing material 14a is, for example, 400 μm. The viscosity of the first sealing material 14a is, for example, not less than 300,000Pa · s and not more than 100 ten thousand Pa · s, and preferably about 400,000Pa · s. In the case where the element substrate 51 and the opposing substrate 52 are bonded, the first sealing material 14a having such a viscosity can be kept used to increase the contact area between the element substrate 51 and the opposing substrate 52.

Further, the second sealing member 14b is used for sealing between the element substrate 51 and the opposing substrate 52, and is provided so as to surround the first sealing material 14 a.

The width W3 of the second seal member 14b is, for example, 400 μm. The viscosity of the second sealing member 14b is, for example, not less than 100Pa · s and not more than 500Pa · s, preferably about 400Pa · s. The use of the second sealing member 14b having such a viscosity allows the second sealing member 14b to enter between the element substrate 51 and the opposing substrate 52 around the first sealing member 14 a. Therefore, the adhesive strength of the second sealing member 14b can be improved. Further, it is possible to suppress intrusion of moisture from the outside into the inside through the second seal member 14b and the first seal member 14a, thereby obtaining a reliable seal structure.

In addition, the seal portion 14 may be constituted by a single second seal member 14b except for the case of being provided as separate bodies (as in the case of the first seal member 14a and the second seal member 14 b), the first seal member 14a being omitted depending on the constituent material of the second seal member 14 b.

Next, the molecular X coating layer 42 of this embodiment will be described.

As shown in fig. 6, in the display area E, the molecule X coating layer 42 is disposed between the top 35b of the partition 35 and the opposite substrate 52.

By so doing, a space (cell) partitioned by the molecule X coating layer 42 and the element substrate 51 (specifically, the insulating layer 32) and the partition 35 is formed, and the space (closed space) is filled with the electrophoretic dispersion liquid including the dispersion medium 15 and the electrophoretic particles 34, so that the dispersion medium 15 and the electrophoretic particles 34 cannot move between the adjacent cells 36.

The molecule X coating layer 42 may be formed by depositing a transparent resin material including the molecules X on the opposite substrate 52, or may be formed by modifying to a resin layer formed on the opposite substrate 52.

As a constituent material of the molecule X coating layer 42, a substrate including an aromatic ring of the molecule X and having transparency is preferable, and examples thereof may include polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate-based resins, polyvinyl chloride-based resins, polystyrene-based resins, polyarylate-based resins, polysulfone resins, polybenzimidazole resins, polyphenylene sulfide-based resins, polyimide resins, aramid resins, and the like, and one of them or a combination of at least two of them may be used. Among those, particularly preferred are polyester-based resins and polyarylate-based resins, and the thickness of the substrate is preferably 5 to 100 nm.

It is noted that the aromatic ring of the molecule X includes any one of benzene, toluene, xylene, mesitylene, pyridine, pyrrole, thiophene, acetophenone, aniline, anisole, benzaldehyde, benzyl alcohol, benzylamine, fluorobenzene, bromobenzene, dibromobenzene, chlorobenzene, dichlorobenzene, phenol, furfural, bromoaniline, nitrobenzene, nitrotoluene, toluidine, naphthalene, anthracene, tetracene, pentacene, benzopyrene, acetone chrysene, pyrene, triphenylene, cardiocyclo-olefin, coronene, and ovalene.

Further, after a polyvinyl alcohol (PVA) resin is applied and formed on the opposite substrate 52, the molecules X may be modified by esterifying hydroxyl groups (OH groups) present on the surface formed of the PVA with an acid halide. As the acid halide, for example, thiophene-2-acetyl chloride, phenylacetyl chloride, 2- (2-naphthyl) acetyl chloride, p-tolylacetyl chloride, p-fluorophenylacetyl chloride, bromobenzeneacetyl chloride or 4-chlorophenylacetyl chloride is used to esterify the PVA, so that the molecular X coating layer 42 can be formed. Among them, thiophene-2-acetyl chloride or phenylacetyl chloride is particularly preferable, and the acid halide may include thiophene or phenyl having one molecule X. The acid halide may be applied by spin coating, which is preferably performed in an inert gas (e.g., N2 gas). By doing so, water contained in the atmosphere is inhibited from reacting with Cl molecules contained in phenylacetyl chloride.

As a result, the molecules X provided in the molecule X coating layer 42 have aromatic rings having cyclic structures, and in these cyclic structures, electrons are delocalized. As a result, a bias (polarization) of the electron density tends to occur, so that the attraction force of the positively or negatively charged electrophoretic particles 34 becomes stronger.

However, since the attractive force acts slightly stronger than the intermolecular force, the force capable of moving the electrophoretic particles when rewriting the display image by applying a voltage is weak. Therefore, since the adhesion (adsorption) of the electrophoretic particles 34 can be suppressed and the retention performance of the electrophoretic particles 34 can be maintained after the voltage is applied, the electrophoretic display device 10 having excellent display characteristics can be provided.

Here, when the refractive index of the molecule X is less than 1.5, since the polarizability of the molecule X is reduced, the attractive force to the charged electrophoretic particles 34 is reduced, and the electrophoretic particles 34 are dispersed without being retained over time. In addition, when the refractive index of the molecules X is greater than 3.0, the transmittance is reduced or a color tone is developed, so that the reflectance of the electrophoretic display device 10 is reduced. Therefore, by setting the refractive index of the molecule X to 1.5 to 3.0, the molecule is more likely to be polarized and the polarizability can be increased. The attraction force of the molecules having a high polarizability to the positively or negatively charged electrophoretic particles 34 becomes strong, so that the adhesion (adsorption) of the electrophoretic particles 34 can be suppressed, and the retention property of the electrophoretic particles 34 can be maintained after the voltage is applied.

When the abundance of the molecule X is less than 1 molecule/10 nm2, the attraction force to the electrophoretic particle 34 by the high polarizability of the molecule X becomes small, so that the retention property is not exhibited. In addition, when the abundance of the molecules X exceeds 10 molecules/10 nm2, since the molecules X are densely present, the attraction force to the electrophoretic particles 34 becomes strong. Therefore, although the retention property increases, the responsiveness of the electrophoretic particles 34 decreases when the display image is rewritten. From the above, it was found that by adjusting the abundance of the molecules X to a ratio of 1 molecule/10 nm2 to 10 molecules/10 nm2, the adhesion (adsorption) of the electrophoretic particles 34 can be suppressed and the retention performance of the electrophoretic particles 34 can be maintained.

Furthermore, the abundance of molecule X can be determined by using TOF-SIMS or FT-IR.

Fig. 8 is a schematic diagram showing the electrophoretic particles 34 of the present embodiment. As shown in fig. 8, the electrophoretic particles 34 have core particles 71 and siloxane-based compounds 72 bonded to the surfaces of the core particles.

Next, the electrophoretic particles 34 of the present embodiment will be described. In the present embodiment, as shown in fig. 8, the core particles 71 are charged particles, and include, for example, white or black particles. The white particles are particles including a white pigment such as titanium oxide, zinc oxide, or antimony trioxide, and can be used by, for example, being negatively charged. The black particles are particles including a black pigment such as carbon black, aniline black, titanium black, or copper chromite, and are used, for example, by being positively charged.

In addition, instead of the white particles and the black particles, colored particles having red, green, blue pigments or the like as a forming material may be used. According to this configuration, the electrophoretic display device 10 capable of performing color display by displaying red, green, blue, or the like can be provided.

The electrophoretic particles 34 are suppressed from being very close to the electrophoretic particles 34 by the siloxane-based compound 72 bonded to the surface of the core particles 71, so that the electrophoretic particles are properly dispersed in the dispersion medium 15. In addition, since the siloxane-based compound 72 has a high affinity for the nonpolar or low-polar dispersion medium 15, the dispersibility of the electrophoretic particles 34 in the dispersion medium 15 can be improved. In addition, since the siloxane-based compound 72 increases the dispersibility of the electrophoretic particles 34 in the dispersion medium 15, the area of the surface of the core particles 71 covered with the siloxane-based compound 72 can be reduced. In other words, the area of the region on the surface of the core particle 71 not bonded by the siloxane-based compound 72 can be increased. Therefore, the chargeability of the electrophoretic particles 34 can be improved by sufficiently exhibiting the chargeability of the core particles 71 themselves in this region or introducing a group having a chargeability to this region.

As shown in fig. 8, the siloxane-based compound 72 has a polymeric portion 73 including a molecule X and a siloxane bonding portion 74. The siloxane-based compound 72 can be obtained by polymerizing a bonding moiety having a silane coupling moiety with a monomer having a polymerized moiety 73 including the molecule X. As the organic material of the siloxane bond 74, for example, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like can be used. Among them, 3-methacryloxypropylmethyldiethoxysilane is preferable.

As the monomer having the polymerization moiety 73, styrene, chlorostyrene, methylstyrene, tert-butylstyrene, fluorostyrene can be used, and among them, styrene is preferable.

In addition, since the siloxane-based compound 72 may not be polymerized as long as the siloxane-based compound 72 has a silane coupling moiety and a molecule X, and since the molecule X is contained in the molecule, p-styryl trimethoxysilane or N-phenyl-3-aminopropyltrimethoxysilane may be directly bonded to the core particle 71 without a polymerization reaction, and thus the electrophoretic particle 34 having the molecule X may be obtained.

The obtained siloxane-based compound 72 is subjected to dehydration condensation reaction between a hydrolyzable group derived from a coupling agent and a hydroxyl group on the surface of the core particle 71, whereby the electrophoretic particle 34 can be obtained.

The weight average molecular weight of the siloxane-based compound 72 is preferably about 100 to 100,000, and more preferably about 10,000 to 60,000. By setting the weight average molecular weight within the above range, the length of the molecular structure of the siloxane-based compound 72 can be optimized, and the region that exhibits the chargeability of the core particle 71 itself and into which the polarizing group is introduced can be sufficiently fixed on the surface of the core particle 71, and the electrophoretic particle 34 to which dispersibility derived from a long-chain linear chain structure is sufficiently imparted can be obtained.

The weight average molecular weight of the siloxane-based compound 72 is a weight average molecular weight expressed by polystyrene measured using Gel Permeation Chromatography (GPC).

Therefore, since pi-pi interaction is performed by the molecules X contained in the electrophoretic particles 34 and the molecules X disposed in the second substrate to apply an attractive force stronger than an intermolecular force, it is possible to suppress adhesion (adsorption) of the electrophoretic particles 34 and maintain the retention property of the electrophoretic particles 34 after the voltage is applied. In addition, since pi-pi interaction is performed between the electrophoretic particles 34 by the molecules X contained in the electrophoretic particles 34, the electrophoretic particles 34 may be densely present, so that the electrophoretic display device 10 having display characteristics with high contrast may be provided.

When the weight fraction of the molecules X is less than 20%, the attraction force to the electrophoretic particles 34 by the high polarizability of the molecules X becomes small, so that the retention property is not exhibited. In addition, when the weight fraction of the molecules X exceeds 95%, since the molecules X are densely present, the attraction force to the electrophoretic particles 34 becomes strong. Therefore, although the retention property increases, the responsiveness of the electrophoretic particles 34 decreases when the display image is rewritten. Therefore, since the adhesion (adsorption) of the electrophoretic particles 34 can be suppressed and the retention property of the electrophoretic particles 34 can be maintained after the voltage is applied by setting the weight fraction of the molecules X to 20% to 80%, the electrophoretic display device 10 having excellent display characteristics can be provided.

Next, a manufacturing method for manufacturing the above-described electrophoretic display device 10 will be described.

Fig. 9 is a flowchart illustrating a method of manufacturing an electrophoretic display device in order of steps. Fig. 10 to 17 are schematic cross-sectional views for explaining a method of manufacturing the electrophoretic display device shown in fig. 3. Hereinafter, a method of manufacturing an electrophoretic display device will be described with reference to fig. 9 to 17.

First, a method of manufacturing the element substrate 51 will be described with reference to fig. 9.

First, the TFT16 or the pixel electrode 21 made of a light-transmitting material such as ITO is formed on the first base member 31 made of a transparent material such as glass (step S11). Specifically, the TFTs 16, the pixel electrodes 21, and the like on the first base member 31 are formed by using known film formation, photolithography, and etching techniques. In addition, in the following description using the sectional view, description and illustration such as the TFT16 or the pixel electrode 21 are omitted.

Then, the insulating layer 32 is formed on the first base member 31 (step S12).

A method for forming the insulating layer 32 is not particularly limited, and for example, the insulating layer 32 is formed by forming an insulating resin material into a thin film on the first base member 31 using a coating method such as a spin coating method.

Then, as shown in fig. 10, the partition 35 is formed on the first base member 31 (specifically, the insulating layer 32) (step S13). More specifically, the partition 35 of the display area E and the outermost peripheral partition 35a of the display area E, the frame partition 61 provided on the outside thereof are formed at the same time.

For example, the spacers 35, 35a and the frame spacer 61 may be formed by using a known film forming technique, a photolithography technique, and an etching technique.

Therefore, the partition plates 35, 35a and the frame partition plate 61 are simultaneously formed of the same material, thereby enabling efficient manufacturing. Thus, the element substrate 51 is completed.

In addition, the separator 35 is made of a material insoluble in the dispersion medium 15, and it does not matter whether the material is an organic substance or an inorganic substance. Specifically, examples of the organic material include polyurethane resin, urea resin, acrylic resin, polyester resin, silicone resin, acrylic silicone resin, epoxy resin, polystyrene resin, styrene acrylic resin, polyolefin resin, butyral resin, vinylidene chloride resin, melamine formaldehyde resin, phenol resin, fluorine resin, polycarbonate resin, polysulfone resin, polyether resin, polyamide resin, polyimide resin, and the like. These resins may be used alone, or two or more types of complexing agents may be used.

Next, a method for manufacturing the opposing substrate 52 will be described.

First, the common electrode 22 is formed on the second base member 41 (step S21). More specifically, the common electrode 22 is formed on the entire surface of the second base member 41 made of a translucent material such as a glass substrate by using a known film forming technique. In addition, in the following description with reference to the sectional views, the explanation and illustration of the common electrode 22 will be omitted.

Then, the molecule X coating layer 42 is formed on the common electrode 22 (step S22). As for the method of forming the molecule X coating layer 42, as shown in fig. 11, for example, a resin material is formed into a thin film on the second base member 41 by using a coating method such as spin coating, thereby forming the molecule X coating layer 42.

Further, the molecule X coating layer 42 is obtained by forming a pattern corresponding to the shape of the molecule X coating layer 42 to be formed using an etching method. In addition, the method is not limited to the coating method, and may be formed by using a printing method. Thereby, the opposite substrate 52 is completed.

Next, a method of bonding the element substrate 51 and the opposing substrate 52 will be described with reference to fig. 12 to 17.

First, as shown in fig. 12, the first sealing material 14a is applied to the outer periphery of the frame separator 61 in the atmosphere (step S31).

The material of the first sealing material 14a is, for example, KAYATORON (japan chemical limited), which is a liquid epoxy resin having a relatively high viscosity. The viscosity of the first sealing material 14a is, for example, not less than 300,000Pa · s and not more than 100 ten thousand Pa · s, and preferably 400,000Pa · s. When applied, the width of the first sealing material 14a is a width sufficient to withstand a vacuum, for example, 400 μm.

Then, as shown in fig. 13, an electrophoretic dispersion liquid containing the electrophoretic particles 34 (white particles, black particles) and the dispersion medium 15 made of silicone oil is applied to the display region E on the element substrate 51 (step S32). The coating method uses, for example, a dispenser. Further, a die coater or the like may be applied. Further, the viscosity of the silicone oil is, for example, not more than 10 cP. The amount of the dispersion medium 15 is such that the liquid volume of the interior surrounded by the frame spacer 61 is satisfied when the element substrate 51 and the opposing substrate 52 are joined. In this embodiment, the height of the frame spacer 61 is 33 μm, for example.

Since the frame spacer 61 is formed, the first sealing material 14a can be prevented from entering (diffusing) to the display region E side. Further, the width of the first sealing material 14a may be adjusted to be not wider than a predetermined width. This can sufficiently secure the strength of the first sealing material 14 a.

Then, as shown in fig. 14, bonding of the element substrate 51 and the opposing substrate 52 is started (step S33).

In addition, bonding pressing is performed under a vacuum negative pressure environment to prevent bubbles from entering the unit 36. However, silicone oil has high volatility, and therefore the pressure is set to a low vacuum state lower than the atmospheric pressure. Specifically, the pressure is, for example, 500 Pa.

Then, as shown in FIG. 15, the electrophoretic dispersion liquid composed of the dispersion medium 15 and the electrophoretic particles 34 is sealed between the element substrate 51 and the opposite substrate 52 (first sealing; step S34).

That is, in a low vacuum state, the element substrate 51 and the counter substrate 52 are bonded by the first sealing material 14 a.

The counter substrate 52 is pressed to the element substrate 51 so that the partition 35 is in contact with the molecular X coating layer 42.

When the opposing substrate 52 is pressed onto the element substrate 51, the first sealing material 14a is crushed, and the dispersion medium 15 is pushed into the frame spacer 61 and used to fill the first sealing material 14a side. In this case, the partition 35 provided in the display area E is covered with the molecular X coating layer 42 provided on the opposite substrate 52 side, and thus the dispersion medium 15 can be prevented from moving between the adjacent cells 36.

Thereafter, as shown in fig. 16, when the first sealing material 14a is an ultraviolet curing resin, the first sealing material 14a is irradiated with ultraviolet rays to be cured. Also, if the first sealing material 14a is a thermosetting resin, the first sealing material 14a is cured by heating.

The cell gap when the element substrate 51 and the opposing substrate 52 are joined is on the order of not less than 20 μm and not more than 50 μm, 33 μm in this embodiment. In addition, the width of the first sealing material 14a which is crushed is, for example, not less than 200 μm and not more than 500 μm, and is 400 μm in the present embodiment.

Then, as shown in fig. 17, a second sealing material 14b is formed on the periphery of the first sealing material 14a to be bonded in air (second sealing; step S35).

Specifically, it is important that the second sealing member 14b does not enter moisture, has a relatively low viscosity, and enters a gap, such as acrylic or epoxy. In addition, the viscosity of the second sealing member 14b is lower than that of the first sealing material 14a, and is, for example, not less than 100Pa · s and not more than 500Pa · s, and preferably 400Pa · s. The width of the second sealing member 14b is, for example, 400 μm.

As a method for applying the second sealing member 14b, for example, a dispenser, a die coater, or the like is used. Therefore, as shown in fig. 17, the space sandwiched between the element substrate 51 and the opposing substrate 52 is sealed. Thereafter, the product is cut into a certain shape, if necessary.

Examples of the invention

Next, specific examples of the present invention will be described.

First, methods of preparing samples used in examples and comparative examples are described. In the change in the abundance of the molecules X in the molecule X coating layer 42, after the polyvinyl alcohol resin is applied and formed on the opposite substrate 52, phenylacetyl chloride is applied, and the molecules X can be modified by esterifying hydroxyl groups (OH groups) present on the surface formed of PVA with acid halide. At this time, phenylacetyl chloride was diluted to a concentration of 20 mol% under N2 gas, so that the opposite substrate 52 provided with the molecular X coating layer 42 of examples 3 and 4 and comparative examples 1 and 2 could be prepared, and phenylacetyl chloride was added under N₂The gas was diluted down to a concentration of 90 mol%, so that the opposite substrate 52 provided with the molecular X coating layers 42 of examples 1 and 2 and comparative examples 3 and 4 could be prepared.

Next, a method of preparing the molecules X included in the electrophoretic particles 34 having different weight fractions will be described. In example 1, the siloxane-based compound 72 of the electrophoretic particles 34 was synthesized as follows, 15 mol% of p-styryltrimethoxysilane as a coupling agent for p-1-methoxy-2-propanol and 80 mol% of styrene and 10 mol% of methyl acrylate as polymerization components were dissolved, a polymerization initiator (e.g., dimethyl azodiisobutyrate) was dissolved at 1.5 mol% with respect to the entire polymerization components, oxygen was removed by nitrogen bubbling, and polymerization was performed at 80 ℃. Incidentally, the polymerization initiator was added to all the polymerization components at a ratio of 1.5 mol% 2 hours and 4 hours after the start of the polymerization, and the polymerization was carried out for 6 hours in total. After the polymerization, purification treatment and drying are performed to obtain the siloxane-based compound 72. Then, the obtained siloxane-based compound 72 was added to a mixture including titanium black (black particles) and a liquid medium, heated, stirred, and washed to obtain black particles provided with the molecules X of example 1.

Next, in examples 2 to 4 and comparative examples 3 and 4, in the same manner as in example 1, black particles provided with molecules X were obtained, except that the procedure in which the amounts of styrene and methyl acrylate were added was changed as follows.

Examples 2 and 3: 50 mol% of styrene and 40 mol% of methyl acrylate.

Example 4: 20 mol% of styrene and 60 mol% of methyl acrylate.

Comparative example 3: 90 mol% of styrene and 0 mol% of methyl acrylate.

Comparative example 4: 10 mol% of styrene and 70 mol% of methyl acrylate.

Next, the electrophoretic dispersions used in the examples and comparative examples were prepared by adding the black particles prepared as described above to silicone oil as the dispersion medium 15. Then, the electrophoretic dispersion liquid is filled between the opposing substrate 52 and the element substrate 51 opposing the opposing substrate 52, and the electrophoretic dispersion liquid is sealed between the opposing substrate 52 and the element substrate 51 by the sealing materials 14a and 14 b.

From the above, samples used in the examples and comparative examples were prepared.

Table 1 shows the measurement results of the reflectance in the case of performing black display for each sample prepared above. The black display indicates a state in which the opposite substrate 52 is used as a display surface and the electrophoretic particles 34 are moved to the substrate side. The reflectance was measured by measuring the reflectance (reflectance immediately after driving) immediately after stopping the application of the voltage (by applying the voltage between the counter substrate 52 and the element substrate 51 to display black), and was obtained by measuring the reflectance (reflectance after driving for 5 minutes) again after stopping the application of the voltage for 5 minutes. The reduction rate of the black reflectance after 5 minutes shows the difference between the reflectance immediately after driving and the reflectance after 5 minutes of driving. Here, if the change in reflectance is small, there is a retention property, and if the change in reflectance is large, there is no retention property.

The evaluation criteria are as follows.

A: the reduction in reflectance after 5 minutes was less than 1.5%.

B: the reduction rate of the reflectance after 5 minutes was 1.5% to less than 2%.

C: the reflectance decrease rate after 5 minutes was 2% or more.

D: the reduction rate of the reflectance after 5 minutes is less than 1%, but the response rate is reduced (the moving speed of the particles is reduced and the image rewriting time is long).

TABLE 1

Comparative example 5 is a conventional example, and as a result of an experiment with a material not using an aromatic ring such as molecule X, it was found that the reflectance after 5 minutes of application of a driving voltage was 4.2% black floating (blackening) with respect to the immediate reflectance. On the other hand, in examples 1 and 2, since the proportion of the aromatic rings (molecules) contained in the molecule X coating layer 42 is large, or the proportion of the molecules X contained in the electrophoretic particles 34 is large, pi-pi interaction with the aromatic rings is exhibited, and as a result, it is found that the reflectance is hardly decreased and the retention property is improved. In examples 3 and 4, since the ratio of the aromatic rings (molecules) contained in the molecule X coating layer 42 is reduced, but the weight fraction of the molecules X of the electrophoretic particles 34 is 20% or more, the retention property is maintained and the reduction in reflectance immediately after the voltage application to after 5 minutes is as low as 1.5% or less. In comparative examples 1, 2, and 4, as a result of performance under the condition that the molecules X are not added to the electrophoretic particles 34 (the weight fraction of the molecules X is less than 20%), since the dispersibility of the electrophoretic particles 34 increases, when the application of the voltage is stopped, the electrophoretic particles 34 diffuse, and thus it is found that the degree of retention performance decreases. In comparative example 3, in the case of using a material in which the weight fraction of the molecules X of the electrophoretic particles 34 is increased to 90%, the decrease in reflectance becomes small and the retention property becomes high, but since aggregation occurs between the electrophoretic particles 34, it is found that the response is delayed when rewriting the display image.

Next, a second embodiment of the electrophoretic display device 10 (electrophoretic display device according to the present invention) will be described.

In the present embodiment, as shown in fig. 18, a protective film 37 is provided between the counter substrate 52 and the molecule X coating layer 42. Examples of the material constituting the protective film 37 include rubber materials such as acrylonitrile butadiene rubber (NBR), polyurethane rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene-butadiene rubber, hydrogenated rubber, and nitrile rubber, and one or at least two thereof may be used in combination. Among them, NBR is preferable. As a result, even if a change in the height of the separator 35 or a change in the thickness of the molecule X coating layer 42 occurs, the protective film 37 can absorb these changes, so that the top 35b of the separator 35 can reliably contact the molecule X coating layer 42.

As a method of forming the protective film 37 on the opposing substrate 52, for example, a solution is dissolved in a solvent for dissolving constituent materials, and the solution is uniformly applied to form a thin film. For example, the solution may be applied using a die coater or comma coater. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, or octane; alicyclic hydrocarbons such as cyclohexane or methylcyclohexane; aromatic hydrocarbons such as benzene (alkylbenzene derivatives) having a long-chain alkyl group, such as benzene, toluene, xylene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene, tridecylbenzene, or tetradecylbenzene; aromatic hydrocarbons such as pyridine, pyrazine, furan, pyrrole, thiophene, and methylpyrrolidone; esters such as methyl acetate, ethyl acetate, butyl acetate or ethyl formate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, or cyclohexane; nitriles such as acetonitrile, propionitrile or acrylonitrile; amides such as N, N-dimethylformamide or N, N-dimethylacetamide; carboxylate or other various oils, etc., and these may be used alone or in combination. In this example, toluene was used.

In addition, the elastic modulus of the protective film 37 at room temperature is preferably 0.1MPa to 50MPa, and in the present embodiment, the elastic modulus at room temperature is 20 MPa. By setting the elastic modulus of the protective film 37 within such a range, the elastic modulus of the laminated body, i.e., the protective film 37 and the molecule X coating layer 42 as a whole, is set within an appropriate range, so that the top portion 35b of the separator 35 can contact or intrude into the entire surface of the molecule X coating layer 42, and accompany the thermal expansion and thermal contraction of the electrophoretic layer 33 according to the change in temperature, thereby providing the electrophoretic display device 10a with high reliability.

The average thickness of the protective film 37 is preferably 2.5 μm to 20 μm, and 12.5 μm in the present embodiment. As a result, the top 35b of the separator 35 can reliably intrude into the molecule X coating layer 42 and the protective film 37.

Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, it goes without saying that the present invention is not limited to these examples. The shapes and combinations of constituent members shown in the above examples are merely examples, and various modifications may be made based on design requirements and the like without departing from the gist of the present invention.

Description of the reference numerals

10. 10 a: electrophoretic display device

11: pixel

12: data line

13: scanning line

14: sealing part

14 a: first sealing material

14 b: second sealing material

15: dispersion medium

16: TFT (transistor)

21: pixel electrode

22: common electrode

31: a first base member

32: insulating layer

33: electrophoretic layer

34: electrophoretic particles

35. 35 a: partition board

35 b: top part

36: unit cell

37: protective film

41: second base member

42: molecular X coating layer

51: element substrate

52: counter substrate

61: frame partition

71: core particle

72: siloxane-based compound

73: polymeric moieties

74: siloxane linkage part

100: electronic device

110: operating unit

D: virtual pixel region

E: display area

E1: frame area

W1, W2, W3: width of